阅读说明：本技术 一种高阻燃性汽车革用无溶剂聚氨酯树脂及其制备方法 (Solvent-free polyurethane resin for high-flame-retardancy automobile leather and preparation method thereof ) 是由 石磊 纪尚超 沈连根 于 2021-01-07 设计创作，主要内容包括：本发明公开了一种高阻燃性汽车革用无溶剂聚氨酯树脂及其制备方法。A组分和B组分按质量比为2∶3～3∶2经低压浇注机高速搅拌混合后涂覆于离型纸上,然后在高温下烘干从而制备而成,其中A组分由异氰酸酯改性的二元醇、羟基改性聚磷酸铵、改性氢氧化铝、小分子扩链剂、胺类催化剂、金属催化剂和流平剂制备而成；B组分由含异氰酸酯端基的预聚物和抗氧化剂制备而成。本发明的高阻燃性汽车革用无溶剂聚氨酯树脂具有快速成型的特点,且不含任何有机溶剂,工艺效果稳定,导热系数低,柔软度可达6.0以上,同时,本发明所用的阻燃材料引入到聚氨酯中,可在增强汽车革阻燃性的同时提高聚氨酯树脂耐磨、柔软等物性。(The invention discloses a solvent-free polyurethane resin for high-flame-retardancy automobile leather and a preparation method thereof. The component A and the component B are stirred and mixed at a high speed by a low-pressure casting machine according to the mass ratio of 2: 3-3: 2, then coated on release paper, and then dried at a high temperature to prepare the composition, wherein the component A is prepared from isocyanate modified dihydric alcohol, hydroxyl modified ammonium polyphosphate, modified aluminum hydroxide, a small molecular chain extender, an amine catalyst, a metal catalyst and a leveling agent; the component B is prepared from prepolymer containing isocyanate end groups and an antioxidant. The solvent-free polyurethane resin for the high-flame-retardancy automobile leather has the characteristic of quick forming, does not contain any organic solvent, has stable process effect and low heat conductivity coefficient, and has the softness of more than 6.0.)

1. The solvent-free polyurethane resin for the high-flame-retardancy automobile leather is characterized by being prepared by coating a component A and a component B on release paper after being stirred and mixed at a high speed by a low-pressure casting machine according to the mass ratio of 2: 3-3: 2, and then drying at a high temperature of 110-130 ℃, wherein the component A comprises the following components in parts by mass:

wherein the structural formula of the hydroxyl modified ammonium polyphosphate is as follows:

the component B comprises the following components in percentage by mass:

150-250 parts of diisocyanate

2-3 parts of antioxidant

30-60 parts of polytetrahydrofuran ether glycol.

2. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the isocyanate modified dihydric alcohol is prepared by mixing the following components in percentage by mass:

the isocyanate is any one or a mixture of IPDI, HDI and carbodiimide modified MDI; the polyether diol is one or more of polyethylene glycol and polypropylene glycol with the molecular weights of 1000, 1500, 2000 and 2500, and the chain extender is one or more of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol; the catalyst is one of stannous octoate and dibutyltin dilaurate.

3. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the hydroxyl modified ammonium polyphosphate is prepared from the following components in percentage by mass:

80 portions of ammonium polyphosphate

20-30 parts of 3-aminopropanol

The molecular weight of the ammonium polyphosphate is 1000-2500.

4. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the modified aluminum hydroxide is prepared from the following components in parts by mass:

100 portions of aluminum hydroxide

2-5 parts of stearic acid

The aluminum hydroxide is 1000-1500 meshes of aluminum hydroxide powder.

5. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the micromolecular chain extender is selected from any one or a mixture of a plurality of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methylpropanediol and dipropylene glycol.

6. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the amine catalyst is any one of triethylene diamine, N-bis (dimethylaminopropyl) isopropanolamine and N- (dimethylaminopropyl) diisopropanolamine; the metal catalyst is any one or a mixture of organic tin and organic bismuth.

7. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the isocyanate is any one or a mixture of more of MDI, TDI, MDI-50, HDI-100 and dicyclohexylmethane diisocyanate; the antioxidant is selected from one or a mixture of more of antioxidant 264, antioxidant 1076 and triphenyl phosphite.

8. The solvent-free polyurethane resin for high flame retardancy automobile leather according to claim 1, wherein: the polytetrahydrofuran diol is one or a mixture of several of PTMEG-1000, PTMEG-1500, PTMEG-2000 and PTMEG-3000.

9. The solvent-free polyurethane resin for highly flame-retardant automobile leather according to any one of claims 1 to 8, wherein: the method comprises the following steps: (1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 20-30 parts of 3-aminopropanol into an ethylene glycol solution, slowly stirring uniformly, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare 5% -8% slurry, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 2-5 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then performing suction filtration, drying at 100-120 ℃ after filtering, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(2) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65-85 ℃, stirring for 3-5h, detecting the moisture content to be 5000-9000ppm, cooling to 40 ℃, adding an amine catalyst, a metal catalyst and modified aluminum hydroxide, stirring for 1.5-2 h at constant temperature, detecting the hydroxyl value and the moisture content again, obtaining the component A after qualification, and sealing and packaging for later use.

(3) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol, heating to 80-85 ℃, stirring at a constant temperature for 3-6h until the content m of a detected value of-NCO groups is controlled to be qualified after being controlled to be more than 8% and less than 10% in percentage by weight, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 2: 3-3: 2 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-.

Technical Field

The invention belongs to the technical field of industrial semi-finished products and synthetic leather, and particularly relates to a solvent-free polyurethane resin for high-flame-retardancy automobile leather and a preparation method thereof

Background

Because of the excellent characteristics of softness, cold resistance, water resistance, moisture permeability and heat preservation, the polyurethane synthetic leather is widely applied to automobile products of domestic and foreign high-end brands such as galloping, BMW, popular, Audi, red flags and the like, has unique advantages particularly in the aspects of (seat cushion leather, steering wheel, interior decoration leather) and the like, and is considered to be a perfect substitute of natural leather and attracts much attention. However, the traditional polyurethane has the problem of release of DMF and other toxic gases in the production and taking processes. With the increasing importance of the environmental protection of products at home and abroad, the requirements of upstream brands on low VOC (volatile organic compounds) production of polyurethane are gradually strict, and even no DMF (dimethyl formamide) is released, so that downstream enterprises gradually start to improve and optimize the traditional polyurethane production process.

Compared with the traditional polyurethane, the solvent-free polyurethane does not add a solvent harmful to a human body in the production process, is a novel polyurethane synthetic leather preparation technology developed based on the combination of the production process of the solvent-based polyurethane synthetic leather and the production process of a two-component workpiece, has the advantages of low energy consumption, no organic solvent release in the production process, safety, environmental protection and the like, and the finished leather almost has no VOC (volatile organic compound) residue, so the solvent-free polyurethane is pursued by consumers.

Polyurethane synthetic leather is a flammable material, generates a large amount of harmful gas during combustion, and has great potential safety hazard when being used for automobile seats and decorative materials. At present, reports on how to improve the flame retardant property of the solvent-free polyurethane synthetic leather are few. The invention patent CN106008892A discloses that flame-retardant hydrolysis-resistant solvent-free polyurethane synthetic leather resin is prepared by adding additive flame retardant and reactive flame retardant into hydroxy A component, thereby solving the dual requirements of synthetic leather on flame retardant property and hydrolysis resistance. The patent has the following problems: the detection results of the examples show that the solvent-free polyurethane is attached to the base cloth after being filmed, the flame retardant effect is greatly different, the flame retardant is not uniformly dispersed in the solvent-free layer, the content of the flame retardant is low, and the flame retardant effect is not ideal.

The invention patent CN107503168A discloses that a solvent-free polyurethane layer is prepared by adding a compound flame retardant of red phosphorus and aluminum hydroxide into a polyol A component system, so that the flame retardant property of the solvent-free synthetic leather is improved. Although the flame retardant performance is improved to a certain extent, the problems of poor dispersibility and compatibility and the like caused by large addition amount of the flame retardant still exist. The hydroxyl modified ammonium polyphosphate is used as a phosphorus flame retardant material, can be combined with polyurethane in a chemically irreversible manner, has good compatibility with the polyurethane, and can improve the performance of the polyurethane to a certain extent, particularly the performances of heat resistance, wear resistance, flame retardance and the like. The nanometer aluminum hydroxide is used as a nanometer filling material, has a certain reinforcing flame-retardant effect on the product, but has larger addition amount when in use, is easy to agglomerate in an organic phase matrix and has poorer compatibility, so that the method is undoubtedly an effective way for processing the surface of the aluminum hydroxide by adopting the related technology. The automobile leather is different from general synthetic leather, and has very high requirements on flame retardance and the like, so how to achieve the high flame retardance effect by utilizing hydroxyl modified ammonium polyphosphate and modified aluminum hydroxide has very important significance.

Based on the situation, the invention provides the solvent-free polyurethane resin for the high-flame-retardancy automobile leather and the preparation method thereof, and the solvent-free polyurethane resin can effectively solve the problems.

Disclosure of Invention

The invention aims to provide a solvent-free polyurethane resin for high-flame-retardancy automobile leather and a preparation method thereof, so that the problem of consideration of both environmental protection performance and special functionality in the use process of automobile leather seats and decorative materials is solved.

The technical scheme of the invention is as follows

A solvent-free polyurethane resin for high-flame-retardancy automobile leather is prepared by coating a component A and a component B which are mixed at a high speed by a low-pressure casting machine according to a mass ratio of 2: 3-3: 2 on release paper, and drying at a high temperature of 110-130 ℃;

wherein the component A comprises the following components in percentage by mass:

60-90 parts of isocyanate modified dihydric alcohol

5-20 parts of hydroxyl modified ammonium polyphosphate

5-30 parts of modified aluminum hydroxide

5-10 parts of micromolecular chain extender

0.01-1 part of amine catalyst

0.01-1 part of metal catalyst

Flatting agent BYK-UV 35105-10 parts

The structural formula of the hydroxyl modified ammonium polyphosphate is as follows:

wherein the component B comprises the following components in percentage by mass:

150-250 parts of diisocyanate

2-3 parts of antioxidant

30-60 parts of polytetrahydrofuran ether glycol

In a further scheme, the isocyanate modified dihydric alcohol is prepared from the following components in parts by mass:

isocyanate 100 parts

220-300 parts of polyether glycol

10-15 parts of chain extender

01-2 parts of catalyst

The isocyanate is any one or a mixture of IPDI, HDI and carbodiimide modified MDI; the polyether diol is one or more of polyethylene glycol and polypropylene glycol with the molecular weights of 1000, 1500, 2000 and 2500, and the chain extender is one or more of ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol; the catalyst is one of stannous octoate and dibutyltin dilaurate.

In a further scheme, the molecular weight of the hydroxyl modified ammonium polyphosphate is 1000, 1500, 2000 and 2500, and the hydroxyl modified ammonium polyphosphate is obtained by modifying ammonium polyphosphate with 3-aminopropanol;

ammonium polyphosphate is used as a phosphorus and nitrogen-containing intumescent flame retardant, has high nitrogen and phosphorus contents and good flame retardant effect, and simultaneously has good thermal stability and good high-temperature resistance mechanical property; when the polyurethane is applied to solvent-free polyurethane, the flame retardance of the polyurethane can be improved, the heat resistance, wear resistance and other properties of the polyurethane can be improved, and a polyurethane high polymer material with excellent properties is developed.

In a further scheme, the mesh number of the modified aluminum hydroxide is 1000, and the modified aluminum hydroxide is obtained by modifying aluminum hydroxide nano powder with stearic acid.

Further, the small molecular chain extender is selected from any one or a mixture of a plurality of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methylpropanediol and dipropylene glycol.

In a further scheme, the amine catalyst is any one of triethylene diamine, N-bis (dimethylaminopropyl) isopropanolamine and N- (dimethylaminopropyl) diisopropanolamine.

Further, the metal catalyst is a delayed organic catalyst, is any one or a mixture of organic tin and organic bismuth, and preferably any one or more of TEGOKAT 722, BICAT8108 and Borchi Kat 24.

Preferably, the leveling agent is selected from any one or a mixture of BYK-UV3510, BYK-UV3500, TEGO Flow300, TEGO Rad 2200N and TEGO Rad 2100.

In a further scheme, the diisocyanate is any one or a mixture of more of MDI, TDI, MDI-50, carbodiimide modified MDI, HDI-100 and dicyclohexylmethane diisocyanate.

In a further scheme, the antioxidant is selected from any one or a mixture of several of antioxidant 264, antioxidant 1076 and triphenyl phosphite.

In a further scheme, the polytetrahydrofuran diol is selected from any one or a mixture of PTMEG-1000, PTMEG-1500, PTMEG-2000 and PTMEG-3000.

The invention also provides a preparation method of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather, which comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly, pouring 20-30 parts of 3-aminopropanol into an ethanol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 90 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(1) Preparing modified aluminum hydroxide:

100 parts of aluminum hydroxide ultrafine powder and deionized water are mixed to prepare 5% -8% slurry, the slurry is poured into a reaction kettle, the temperature is controlled to be 40-80 ℃, 2-5 parts of glycol diluted stearic acid are added, the mixture is stirred for 4-8 hours at constant temperature, then suction filtration is carried out, and the modified aluminum hydroxide can be prepared after the filtration and drying at the temperature of 100-120 ℃.

(2) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65-85 ℃, stirring for 3-5h, detecting the moisture content to be 5000-9000ppm, cooling to 40 ℃, adding an amine catalyst, a flatting agent and modified aluminum hydroxide powder, stirring for 1.5-2 h at constant temperature, detecting the hydroxyl value and the moisture content again, obtaining the component A after qualification, and sealing and packaging for later use.

(3) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol, heating to 80-85 ℃, stirring at a constant temperature for 3-6h until the content m of a detected value of-NCO groups is controlled to be qualified after being controlled to be more than 8% and less than 10% in percentage by weight, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 2: 3-3: 2 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the solvent-free polyurethane resin for the automobile leather with high flame retardancy is prepared by utilizing a solvent-free polyurethane synthesis production process of a semi-prepolymer method, respectively synthesizing a component A with modified ammonium polyphosphate and a component B of a prepolymer, and then mixing the components A and B to perform a series of reactions; the synthesis processing has the beneficial effects that toxic organic solvent is not required to be added, the direct reaction forming is realized, and the environment is protected; the method also shows that the addition of the modified ammonium polyphosphate reduces the degree of soft and hard segment microphase separation, and simultaneously combines the excellent flame retardant and heat resistance of the ammonium polyphosphate and the synergistic reinforcing and flame retardant effects of the nano metal aluminum hydroxide, so that the design of the high flame retardant solvent-free polyurethane resin for the automobile leather can be finally realized.

(2) According to the invention, hydroxyl modified ammonium polyphosphate is introduced into the component A as one of the chain extension components, and further reacts with the prepolymer of the component B, so that the modified structure of the ammonium polyphosphate can be embedded in the polyurethane structure, and the flame retardance of the solvent-free polyurethane is improved by a chemical modification method.

(3) The invention introduces the nano aluminum hydroxide into the solvent-free polyurethane, has certain reinforcing flame retardant effect, can be uniformly distributed in the polyurethane after surface modification, improves the flame retardant property of the solvent-free polyurethane resin by a physical blending mode, and further solves the requirements of the automobile leather on high flame retardant property and high wear resistance.

(4) On the basis of the synthesis of solvent-free polyurethane, the invention well balances the contradiction between the improvement of flame retardant property caused by high-content filling and the reduction of physical and mechanical properties by a method of combining physical modification and chemical modification and by utilizing the synergistic effect of organic in-situ flame retardant and inorganic filling flame retardant.

Drawings

Fig. 1 is an SEM image of a solvent-free synthetic leather (a) containing ammonium polyphosphate filler particles and a block copolymer solvent-free synthetic leather (b) containing surface-modified aluminum hydroxide and hydroxyl-modified ammonium polyphosphate;

FIG. 2 is a diagram of the appearance of a solvent-free polyurethane resin for automobile leather, which contains surface modified aluminum hydroxide (mAI (OH)3) (a), block copolymerized hydroxyl modified ammonium polyphosphate (HAPP) (b) and a compound modification of mAI (OH)3 and HAPP (c).

Detailed Description

The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto, and all equivalent changes or modifications made in accordance with the spirit of the present invention should be covered thereby.

Example 1

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

the component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

Polytetrahydrofuran ether glycol 50 parts

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether diol

13 parts of chain extender (1, 4-butanediol)

The polyether diol is polypropylene glycol product with molecular weight of 1000 produced by Tianjin neutralization Shengtai chemical Co.

Preferably, the modified ammonium polyphosphate is prepared from the following components in percentage by mass:

80 portions of ammonium polyphosphate

26 parts of 3-aminopropanol

300 parts of ethanol solution

Ammonium polyphosphate with a molecular weight of 1000 produced by Jinan Taxing chemical Co., Ltd is selected as the ammonium polyphosphate HT-208 product, and IPA product of Shanghai Senxu chemical engineering Co., Ltd is selected as the 3-aminopropanol.

Preferably, the modified aluminum hydroxide is prepared from the following components in parts by mass:

100 portions of aluminum hydroxide

Stearic acid 4 parts

The aluminum hydroxide powder is AH-1 product with the mesh number of 1000 of New Material Co, Yuejiang, and stearic acid is 1801 product of chemical industry of Jinan Duckweed.

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3:1

The polytetrahydrofuran ether glycol is selected from polytetrahydrofuran ether glycol product with molecular weight of 2000 produced by Zhengzhou Borilan trade company Limited.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 2

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

Modified aluminium hydroxide 5 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 3

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

Modified aluminium hydroxide 5 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 4

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

Modified aluminium hydroxide 5 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 5

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

5 parts of modified ammonium polyphosphate

10 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 6

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

10 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 7

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

10 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 8

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

10 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

230 portions of polyether glycol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 9

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

5 parts of modified ammonium polyphosphate

15 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 10

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

15 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the small molecular chain extender is 1, 4-butanediol or dipropylene glycol, and the weight ratio of the small molecular chain extender to the dipropylene glycol is 2:1 are mixed.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 11

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

15 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 12

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

15 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 13

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

5 parts of modified ammonium polyphosphate

20 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 14

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

20 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to a ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be 8% by weight and less than 10% by weight, and then obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed in a low-pressure casting machine according to the mass fraction of 1:1.15 is cast and coated on release paper, and is dried in an oven at the temperature of 110-.

Example 15

A solvent-free polyurethane resin for high-flame-retardancy automobile leather is prepared by mixing a component A and a component B according to a mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

20 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

230 portions of polyether glycol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 16

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

20 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 17

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

5 parts of modified ammonium polyphosphate

Modified aluminium hydroxide 25 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

230 portions of polyether glycol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 18

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

Modified aluminium hydroxide 25 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 19

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

Modified aluminium hydroxide 25 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 20

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

Modified aluminium hydroxide 25 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

230 portions of polyether glycol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the small molecular chain extender is 1, 4-butanediol or dipropylene glycol, and the weight ratio of the small molecular chain extender to the dipropylene glycol is 2:1 are mixed.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 21

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

5 parts of modified ammonium polyphosphate

30 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 22

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

10 portions of modified ammonium polyphosphate

30 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the small molecular chain extender is 1, 4-butanediol or dipropylene glycol, and the weight ratio of the small molecular chain extender to the dipropylene glycol is 2:1 are mixed.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 23

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

15 parts of modified ammonium polyphosphate

30 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Example 24

A solvent-free polyurethane resin for high flame-retardant automobile leather is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3,

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

20 portions of modified ammonium polyphosphate

30 portions of modified aluminum hydroxide

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

13 parts of chain extender (1, 4-butanediol)

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method comprises the following steps:

(1) preparing hydroxyl modified ammonium polyphosphate:

in the nitrogen atmosphere, firstly pouring 26 parts of 3-aminopropanol into an ethylene glycol solution, slowly and uniformly stirring, then adding 80 parts of ammonium polyphosphate, gradually heating to 80 ℃, and treating for 2-3 hours by using a condensation reflux device; after cooling to room temperature, the product is filtered, washed with ethanol, dried, filtered and the like to obtain the hydroxyl modified ammonium polyphosphate.

(2) Preparing modified aluminum hydroxide:

mixing 100 parts of aluminum hydroxide nano powder and deionized water to prepare slurry with the concentration of 7%, pouring the slurry into a reaction kettle, controlling the temperature to be 40-80 ℃, adding 4 parts of glycol-diluted stearic acid, stirring at constant temperature for 4-8 h, then carrying out suction filtration, drying at 100-120 ℃ after filtration, and screening through a screen plate of 1000 meshes to obtain the modified aluminum hydroxide.

(3) Preparation of component A:

adding isocyanate modified dihydric alcohol, a micromolecular chain extender and hydroxyl modified ammonium polyphosphate into a reaction kettle, heating to 65 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, cooling to 50 ℃, adding an amine catalyst, a flatting agent, a metal catalyst and modified aluminum hydroxide powder, stirring for 1.5h at constant temperature, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(4) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding liquid diisocyanate and an antioxidant into the reaction kettle, uniformly stirring, adding the dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(4) The preparation of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather comprises the following steps:

the solvent-free A, B component which is fully mixed by the mass fraction of 1:1.15 in a low-pressure casting machine is cast and coated on release paper, and is dried in an oven at the temperature of 110-130 ℃ to prepare the solvent-free polyurethane resin for the high-flame-retardancy automobile leather.

Comparative example

The invention also provides a comparative example of the solvent-free polyurethane resin for the high-flame-retardancy automobile leather, namely, hydroxyl modified ammonium polyphosphate and modified aluminum hydroxide are removed in the scheme of example 2, and the concrete steps are as follows:

the paint is prepared by mixing a component A and a component B according to the mass ratio of 3: 2-2: 3;

the component A is prepared from the following components in parts by mass:

isocyanate modified diol 75 parts

8 parts of micromolecular chain extender

0.4 part of amine catalyst

0.4 part of metal catalyst

Leveling agent BYK-UV351010 parts

The component B is prepared from the following components in parts by mass:

180 parts of diisocyanate (carbodiimide modified MDI)

Antioxidant 2.5 parts

50 parts of polytetrahydrofuran ether glycol (PTMEG2000)

The isocyanate modified dihydric alcohol in the component A comprises the following components in parts by mass:

isocyanate (IPDI)100 parts

250 portions of polyether dihydric alcohol (PPG1000)

Chain extender (ethylene glycol) 13 parts

Preferably, the micromolecular chain extender is formed by mixing 1, 4-butanediol and dipropylene glycol according to the ratio of 2: 1.

Preferably, the amine catalyst is selected from low-odor N, N-bis (dimethylaminopropyl) isopropanolamine products of Dow corporation, USA.

Preferably, the metal catalyst is a delayed organic catalyst, and a BICAT8108 product produced by Jiaxing standing grain chemical company Limited is selected.

Preferably, the antioxidant is selected from antioxidant 264 and antioxidant 1076 of Younging group of Germany, and the ratio is 3: 1.

The preparation method of the solvent-free polyurethane resin for synthetic leather comprises the following steps:

(1) preparation of component A:

adding isocyanate modified dihydric alcohol and 1, 4-butanediol into a reaction kettle, heating to 85 ℃, stirring for 3h, detecting the water content to be 5000-9000ppm, then cooling to 50 ℃, adding an amine catalyst and a flatting agent, stirring for 1.5h at constant temperature of a metal catalyst, detecting the hydroxyl value and the water content again, obtaining the component A after the components are qualified, and sealing and packaging for later use.

(2) Preparation of component B:

removing water in a reaction kettle by introducing nitrogen into the reaction kettle, adding carbodiimide modified MDI and an antioxidant into the reaction kettle, uniformly stirring, adding dehydrated polytetrahydrofuran ether glycol 2000, heating to 80 ℃, stirring at a constant temperature for 3 hours until the content m of a detected value of-NCO groups is controlled to be more than 8% and less than 10% by weight, and obtaining a component B, and sealing and packaging for later use.

(3) Preparation of solvent-free polyurethane resin:

the solvent-free A, B component which is fully mixed in a low-pressure casting machine according to the mass fraction of 3: 2-2: 3 is cast and coated on release paper, and is dried in an oven at the temperature of 110-.

In order to better embody the benefits of the present invention, the following performance tests were performed on the solvent-free polyurethane resins for high flame retardant automobile leather obtained in examples 1 to 24 of the present invention and the solvent-free polyurethane resin obtained in the comparative example, and the test results are described as follows:

note: the hand feeling hardness is detected by a hardness tester, and the higher the value is, the softer the hand feeling is; the limit oxygen index is tested by an oxygen index tester, and the high oxygen index indicates that the material is not easy to burn; a low oxygen index indicates that the material is readily combustible. Generally, the oxygen index is less than 22% and belongs to flammable materials, the oxygen index is between 22% and 27% and belongs to flame-retardant materials, and the oxygen index is more than 27%.

The data in the table show that the synthetic leather processed by the high-flame-retardancy solvent-free polyurethane resin has slightly better hand feeling than the comparative example, the peel strength is reduced, but the flame-retardancy is greatly improved. The technology is proved to be capable of greatly improving the flame retardant property of the synthetic leather on the premise of not changing the property of the original solvent-free synthetic leather. And the technology can be applied to the field of automotive leather with higher requirement on flame retardant property.

The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.