阅读说明：本技术 一种水性聚氨酯树脂及其制备方法和应用 (Waterborne polyurethane resin and preparation method and application thereof ) 是由 赵波峰 蒋红梅 孙丽娟 唐劲松 于 2021-10-21 设计创作，主要内容包括：本发明提供一种水性聚氨酯树脂及其制备方法和应用,所述水性聚氨酯树脂的制备原料包括二聚酸聚酯多元醇、二异氰酸酯、扩链剂和催化剂的组合；且所述二聚酸聚酯多元醇的制备原料包括二聚酸、二元醇和复合稳定剂的组合；通过在二聚酸聚酯多元醇的制备原料中添加复合稳定剂,使其酸度更低,分子量分布更窄；进一步在水性聚氨酯树脂的制备原料中添加上述二聚酸聚酯多元醇,在树脂中引入二聚酸分子链,可以使所述水性聚氨酯树脂具有优异的耐水解性、耐候性、耐磨性、耐热性以及力学性能；且可以克服固化速度慢的缺点,成膜后具有高透、高亮和附着力好的特性,满足合成革领域的需求。(The invention provides an aqueous polyurethane resin and a preparation method and application thereof, wherein the preparation raw material of the aqueous polyurethane resin comprises the combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer; the composite stabilizer is added into the raw materials for preparing the dimer acid polyester polyol, so that the acidity of the dimer acid polyester polyol is lower, and the molecular weight distribution of the dimer acid polyester polyol is narrower; the dimer acid polyester polyol is further added into the raw materials for preparing the waterborne polyurethane resin, and a dimer acid molecular chain is introduced into the resin, so that the waterborne polyurethane resin has excellent hydrolysis resistance, weather resistance, wear resistance, heat resistance and mechanical properties; the curing agent can overcome the defect of low curing speed, has the characteristics of high transparency, high brightness and good adhesive force after film forming, and meets the requirements of the synthetic leather field.)

1. The waterborne polyurethane resin is characterized in that raw materials for preparing the waterborne polyurethane resin comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst;

the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer.

2. The aqueous polyurethane resin according to claim 1, wherein the mass percentage of the dimer acid polyester polyol in the raw materials for preparing the aqueous polyurethane resin is 10-40%;

preferably, the number average molecular weight of the dimer acid polyester polyol is 1000-5000;

preferably, the raw materials for preparing the dimer acid polyester polyol comprise the following components in parts by weight:

preferably, the diol comprises any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol or a combination of at least two thereof;

preferably, the catalyst comprises any one or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide or antimony trioxide;

preferably, the composite stabilizer comprises a combination of a phosphate-based heat stabilizer and a phosphite-based heat oxygen stabilizer;

preferably, the phosphate-based heat stabilizer comprises any one of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate or a combination of at least two of the foregoing;

preferably, the phosphite thermal oxygen stabilizer comprises any one of triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetrakis (2, 4-di-tert-butylphenol) -4,4' -biphenylyl diphosphite or a combination of at least two thereof;

preferably, the raw materials for preparing the dimer acid polyester polyol also comprise other dibasic acid;

preferably, the other dibasic acid comprises any one of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid or a combination of at least two thereof;

preferably, the content of other dibasic acids in the raw materials for preparing the dimer acid polyester polyol is 0-50 parts by weight and is not equal to 0.

3. The aqueous polyurethane resin according to claim 1 or 2, wherein the mass ratio of the dimer acid polyester polyol to the diisocyanate is (0.5-2): 1;

preferably, the diisocyanate includes any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate, and more preferably any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.

4. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein the mass ratio of the dimer acid polyester polyol to the chain extender is (5-10): 1;

preferably, the chain extender comprises a hydrophilic chain extender;

preferably, the hydrophilic chain extender comprises any one or a combination of at least two of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or sodium ethylenediamine ethanesulfonate;

preferably, the chain extender comprises an alcohol chain extender;

preferably, the alcohol chain extender comprises any one of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol or ethanolamine or a combination of at least two thereof;

preferably, the chain extender further comprises an amine chain extender;

preferably, the amine chain extender comprises ethylene diamine.

5. The aqueous polyurethane resin according to any one of claims 1 to 4, wherein the mass ratio of the catalyst to the dimer acid polyester polyol is (0.00001 to 0.00005): 1.

6. The aqueous polyurethane resin according to any one of claims 1 to 5, wherein the raw materials for the preparation of the aqueous polyurethane resin further comprise any one or a combination of at least two of a neutralizer, a solvent or other polyols;

preferably, the neutralizing agent comprises any one or a combination of at least two of triethylamine, ammonia water, N-methylmorpholine, N-ethylmorpholine, N-methyldiethanolamine or NaOH;

preferably, the solvent comprises acetone and/or butanone;

preferably, the other polyol comprises any one of or a combination of at least two of tetrahydrofuran ether glycol, polycarbonate glycol or polyester polyol;

preferably, the number average molecular weight of the other polyhydric alcohol is 500-4000;

preferably, the mass percentage of the dimer acid polyester polyol in all polyols in the raw materials for preparing the aqueous polyurethane resin is 50-100% and is not equal to 100%.

7. A preparation method of the waterborne polyurethane as described in any one of claims 1 to 6, wherein the preparation method comprises the following steps:

(1) mixing dimer acid polyester polyol, optional other polyol, optional chain extender and optional catalyst, and adding diisocyanate for reaction to obtain an initial product;

(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent, and adding a catalyst to react to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent to obtain the waterborne polyurethane resin.

8. The preparation method according to claim 7, wherein the temperature of the reaction in the step (1) is 70-95 ℃;

preferably, the reaction of step (1) is carried out under normal pressure conditions;

preferably, the reaction time in the step (1) is 2-4 h;

preferably, the temperature of the mixing in the step (2) is 90-95 ℃;

preferably, the mixing time in the step (2) is 2-3 h;

preferably, the temperature of the reaction in the step (2) is 60-65 ℃;

preferably, the reaction time in the step (2) is 2-3 h.

9. The method according to claim 7 or 8, wherein the temperature of the reaction of step (3) is not higher than 40 ℃;

preferably, the solvent removal in the step (3) is carried out under the condition that the vacuum degree is-0.09 to-0.1 MPa.

10. Use of the aqueous polyurethane resin according to any one of claims 1 to 6 in synthetic leather.

Technical Field

The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a waterborne polyurethane resin and a preparation method and application thereof.

Background

The green and environment-friendly technology has become one of the most concerned topics of people in the world nowadays and also becomes an important index for the development of social economy. At present, in the field of waterborne polyurethane synthesis, the used raw materials are generally derived from petroleum-based non-renewable resources. In order to further protect the natural environment and guarantee the sustainable development of the social economy, the dimer acid derived from renewable resources is a high-quality raw material for replacing adipic acid, and has important application in the field of synthesis of waterborne polyurethane.

Dimer acid has a unique molecular structure, and is increasingly applied to the field of high polymer materials. Polyester polyol with high relative molecular mass, which is synthesized by taking dimer acid, short-molecule diol and the like as raw materials, is used for synthesizing aqueous polyurethane resin, and has good flexibility and higher strength. Dimer acid polyester diols having relatively small molecular weight, which are flexible and rigid, have good solubility, and can impart excellent mechanical properties and thermal stability to polyurethane materials, have been used to prepare polyurethane-urea aqueous dispersions, polyurethane foams, polymeric surfactants, and the like.

CN113265901A discloses a dimer acid-based waterborne polyurethane surface sizing agent, a preparation method and application thereof, belonging to the technical field of surface sizing agent preparation. Mixing dimer acid polyester diol, polycaprolactone diol and diisocyanate for prepolymerization reaction; then adding a hydrophilic chain extender to carry out chain extension reaction; and adding triethylamine for neutralization reaction, and finally adding deionized water for emulsification to obtain the dimer acid-based waterborne polyurethane surface sizing agent. The method not only realizes the high-value utilization of the dimer acid in the field of green environment-friendly coatings, but also provides an environment-friendly, sustainable and economic method for improving the waterproof and oil-proof performance of paper, and the prepared dimer acid-based waterborne polyurethane emulsion can be used as a paper surface sizing agent to obviously improve the waterproof, oil-proof and mechanical properties of paper.

However, since the dimer acid polyester polyol used in the prior art has a wide molecular weight distribution and yet needs to be further reduced in chromaticity and acid value, the waterborne polyurethane prepared by using the dimer acid polyester polyol as a raw material has poor properties, and is difficult to be applied in a large range in the field of synthetic leather.

Therefore, an object of the present invention is to provide an aqueous polyurethane resin which is produced from a dimer acid polyester polyol and has excellent weather resistance, abrasion resistance, heat resistance and mechanical properties.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the waterborne polyurethane resin and the preparation method and the application thereof, wherein the preparation raw material of the waterborne polyurethane resin comprises the combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer; the color and acid value of the dimer acid polyester polyol prepared by using the dimer acid, the dihydric alcohol and the composite stabilizer as raw materials are low, and the comprehensive performance of the waterborne polyurethane resin prepared by using the dimer acid polyester polyol as the raw materials is excellent.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides an aqueous polyurethane resin, wherein the raw materials for preparing the aqueous polyurethane resin comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst;

the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer.

The preparation raw materials of the waterborne polyurethane resin provided by the invention comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer; the dimer acid is derived from renewable resources, so that the environment is protected, and the application of the renewable resources and the renewability of the polyurethane resin are promoted; the addition of the composite stabilizer can limit the generation of byproducts in the whole preparation process of the dimer acid polyester polyol, so that the prepared dimer acid polyester polyol has narrower molecular mass distribution and higher yield; the prepared waterborne polyurethane resin can overcome the defects of low room temperature curing speed, poor water resistance, weather resistance, wear resistance, heat resistance, mechanical property and the like of the traditional waterborne polyurethane; and the paint has the characteristics of high brightness and good adhesive force after film forming, and can meet the requirements in some special application fields.

In the present invention, the catalyst may be selected from BICAT8118 available from leading chemicals in the united states.

Preferably, the mass percentage of the dimer acid polyester polyol in the raw materials for preparing the aqueous polyurethane resin is 10-40%, for example, 15%, 20%, 25%, 30%, 35% or 40%.

Preferably, the number average molecular weight of the dimer acid polyester polyol is 1000 to 5000, such as 1500, 2000, 2500, 3000, 3500, 4000 or 4500.

Preferably, the raw materials for preparing the dimer acid polyester polyol comprise the following components in parts by weight:

wherein the diol may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, or the like.

The dimer acid may be 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, or the like.

The catalyst may be 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, or 0.045 parts by weight, or the like.

The composite stabilizer may be 0.005 parts by weight, 0.007 parts by weight, 0.009 parts by weight, 0.011 parts by weight, 0.013 parts by weight, 0.015 parts by weight, 0.017 parts by weight, 0.019 parts by weight, 0.02 parts by weight, 0.023 parts by weight, 0.026 parts by weight, 0.029 parts by weight or the like.

As a preferred technical scheme, the raw materials for preparing the dimer acid polyester polyol adopted by the invention comprise the combination of specific parts of dihydric alcohol, dimer acid, a catalyst and a composite stabilizer; by adding the composite stabilizer in a specific part in the preparation raw materials, the generation of byproducts in the whole preparation process of the dimer acid polyester polyol can be limited; the addition of the composite stabilizer can reduce the oxidation of dihydric alcohol in the esterification stage; on the other hand, the oxidation of the dimer acid in the polycondensation stage can be reduced, so that the generation of byproducts in the whole preparation process is less, and finally the dimer acid polyester polyol with low acid value and low chroma is obtained; the dimer acid polyester polyol prepared by combining the preparation raw materials has narrower molecular mass distribution and higher yield, so that the dimer acid polyester polyol is more suitable for synthesis of aqueous polyurethane resin.

Preferably, the diol comprises any one of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol, or a combination of at least two thereof.

Preferably, the catalyst comprises any one of or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide, or antimony trioxide.

Preferably, the composite stabilizer comprises a combination of a phosphate-based heat stabilizer and a phosphite-based heat oxygen stabilizer.

Preferably, the phosphate-based heat stabilizer comprises any one of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate or a combination of at least two of the foregoing.

Preferably, the phosphite thermal oxygen stabilizer includes any one of triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetrakis (2, 4-di-t-butylphenol) -4,4' -biphenylyl diphosphite or a combination of at least two thereof.

Preferably, the raw materials for preparing the dimer acid polyester polyol also comprise other dibasic acid.

Preferably, the other dibasic acid comprises any one of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid or a combination of at least two thereof.

The "other dibasic acid" in the present invention means a dibasic acid other than the dimer acid; for example, the other dibasic acid may include any one of succinic acid, glutaric acid, adipic acid, azelaic acid, or sebacic acid, or a combination of at least two thereof.

Preferably, the content of the other dibasic acid in the raw materials for preparing the dimer acid polyester polyol is 0 to 50 parts by weight and is not equal to 0, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.

As a preferred embodiment of the present invention, the dimer acid polyester polyol of the present invention can be prepared by a method comprising the steps of:

(A1) under the protection of inert gas, reacting dihydric alcohol, dimer acid, a composite stabilizer and optionally other dibasic acids at 130-160 ℃ for 3-120 min, heating to 210-250 ℃ at the temperature rise speed of 5-30 ℃/h, and carrying out esterification dehydration reaction for 3-5 h to obtain an intermediate product;

(A2) and (C) mixing the intermediate product obtained in the step (A1) with a catalyst, preserving the temperature at 210-250 ℃ for 30-180 min, and carrying out distillation polycondensation reaction under-0.1-0 Mpa for 2-6 h to obtain the dimer acid polyester polyol with the hydroxyl value of 30-120 mgKOH/g and the acid value of 0.1-1 mgKOH/g.

Preferably, the mass ratio of the dimer acid polyester polyol to the diisocyanate is (0.5-2: 1), such as 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1 or 1.9: 1.

Preferably, the diisocyanate includes any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate, and more preferably any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.

Preferably, the mass ratio of the dimer acid polyester polyol to the chain extender is 5-10: 1, such as 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1 or 9.5: 1.

Preferably, the chain extender comprises a hydrophilic chain extender.

Preferably, the hydrophilic chain extender comprises any one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or sodium ethylenediamine ethanesulfonate or a combination of at least two of the same.

Preferably, the chain extender comprises an alcohol chain extender.

Preferably, the alcohol chain extender comprises any one of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, 3-methyl-1, 5-pentanediol or ethanolamine or a combination of at least two thereof.

Preferably, the chain extender further comprises an amine chain extender.

Preferably, the amine chain extender comprises ethylene diamine.

Preferably, the mass ratio of the catalyst to the dimer acid polyester polyol is 0.00001-0.00005: 1, such as 0.000015:1, 0.00002:1, 0.000025:1, 0.00003:1, 0.000035:1, 0.00004:1 or 0.000045: 1.

Preferably, the raw materials for preparing the aqueous polyurethane resin also comprise any one or a combination of at least two of a neutralizer, a solvent or other polyester polyols.

Preferably, the neutralizing agent comprises any one of triethylamine, ammonia water, N-methylmorpholine, N-ethylmorpholine, N-methyldiethanolamine or NaOH or a combination of at least two of them.

Preferably, the solvent comprises acetone and/or butanone.

Preferably, the other polyol comprises any one of or a combination of at least two of a tetrahydrofuran ether glycol, a polycarbonate glycol or a polyester polyol.

Preferably, the number average molecular weight of the other polyol is 500 to 4000, such as 1000, 1500, 2000, 2500, 3000, 3500 or 4000.

Preferably, the mass percentage of the dimer acid polyester polyol in all polyols in the raw materials for preparing the aqueous polyurethane resin is 50-100% and is not equal to 100%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%.

In a second aspect, the present invention provides a method for preparing the waterborne polyurethane according to the first aspect, wherein the method comprises the following steps:

(1) mixing dimer acid polyester polyol, optional other polyol, optional chain extender and optional catalyst, and adding diisocyanate for reaction to obtain an initial product;

(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent, and adding a catalyst to react to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent to obtain the waterborne polyurethane resin.

Preferably, the reaction temperature in step (1) is 70-95 ℃, such as 72 ℃, 74 ℃, 76 ℃, 79 ℃, 82.5 ℃, 84 ℃, 86.5 ℃, 89 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃ or 94.5 ℃.

Preferably, the reaction of step (1) is carried out under atmospheric conditions.

Preferably, the reaction time in step (1) is 2-4 h, such as 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h or 3.8 h.

Preferably, the temperature of the mixing in step (2) is 90-95 ℃, such as 90.5 ℃, 91 ℃, 91.5 ℃, 92 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃ or 94.5 ℃.

Preferably, the mixing time in step (2) is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9 h.

Preferably, the temperature of the reaction in step (2) is 60 to 65 ℃, such as 60.5 ℃, 61 ℃, 61.5 ℃, 62 ℃, 62.5 ℃, 63 ℃, 63.5 ℃, 64 ℃ or 64.5 ℃.

Preferably, the reaction time in the step (2) is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9 h.

Preferably, the reaction in step (3) is carried out at a temperature of not higher than 40 deg.C, such as 39 deg.C, 38 deg.C, 37 deg.C, 36 deg.C, 35 deg.C, 30 deg.C, 25 deg.C, 20 deg.C, 15 deg.C, 10 deg.C or 5 deg.C, etc.

Preferably, the solvent removal in step (3) is carried out under a vacuum of-0.09 to-0.1 MPa (e.g., -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, or-0.01, etc.).

As a preferable technical scheme of the invention, the preparation method of the waterborne polyurethane resin comprises the following steps:

(1) mixing dimer acid polyester polyol, optionally other polyols, optionally a chain extender and optionally a catalyst, adding diisocyanate, and reacting at normal pressure and 70-95 ℃ for 2-4 h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent at 90-95 ℃ for 2-3 h, adding a catalyst, and reacting at 90-95 ℃ for 2-3 h to obtain an intermediate product;

(3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer at the temperature of not higher than 40 ℃, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent under the condition of-0.09 to-0.1 MPa to obtain the waterborne polyurethane resin.

In a third aspect, the invention provides a use of the aqueous polyurethane resin according to the first aspect in synthetic leather.

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

(1) the preparation raw materials of the waterborne polyurethane resin provided by the invention comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer; the raw material for preparing the waterborne polyurethane resin takes dimer acid polyester polyol extracted from renewable resources as a raw material, and is beneficial to promoting the application of the renewable resources and the renewability of the waterborne polyurethane resin.

(2) According to the waterborne polyurethane resin provided by the invention, dimer acid molecular chains are introduced into polyurethane molecular chains and resin components, so that the waterborne polyurethane resin has excellent hydrolysis resistance, weather resistance, wear resistance, heat resistance and mechanical properties; the waterborne polyurethane resin overcomes the defects of low room-temperature curing speed, poor water resistance and mechanical property and the like of the traditional waterborne polyurethane, has the characteristics of high brightness and good adhesive force after film forming, and can meet the requirements in some special application fields.

(3) The waterborne polyurethane resin provided by the invention has good comprehensive performance, has the advantages of environmental friendliness, no toxicity, no harm, safe transportation and the like, and belongs to an environment-friendly polyurethane product.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 150g of dimer acid polyester polyol (with a number average molecular weight of 2000), 150g of polytetrahydrofuran ether glycol (with a number average molecular weight of 2000), 5g of DMPA and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of dicyclohexylmethane diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 6g of methyl propylene glycol, 3g of ethanolamine and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) for reaction for 30min, adding 677g of water for high-speed dispersion, immediately adding 4.5g of ethylenediamine for reaction for 30min after dispersion is finished, and removing the acetone at 50 ℃ and-0.1 MPa for 30min to obtain the waterborne polyurethane resin.

Example 2

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 300g of dimer acid polyester polyol (with the number average molecular weight of 2000), 5g of DMPA and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of dicyclohexylmethane diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 6g of methyl propylene glycol, 3g of ethanolamine and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) for reaction for 30min, adding 677g of water for high-speed dispersion, immediately adding 4.5g of ethylenediamine for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 MPa for 30min to obtain the waterborne polyurethane resin.

Example 3

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 190g of dimer acid polyester polyol (number average molecular weight of 3000), 80g of polycarbonate diol (number average molecular weight of 2000), 40g of polypropylene oxide ether glycol (number average molecular weight of 2000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of isophorone diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 5g of DMPA, 7g of 1, 6-hexanediol and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) to react for 30min, adding 710g of water to disperse at high speed, immediately adding 6.87g of ethylenediamine to react for 30min after the dispersion is finished, and removing the acetone for 30min at 50 ℃ and-0.09 MPa to obtain the waterborne polyurethane resin.

Example 4

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 150g of dimer acid polyester polyol (with the number average molecular weight of 3000), 80g of polycarbonate diol (with the number average molecular weight of 2000), 80g of polypropylene oxide ether glycol (with the number average molecular weight of 2000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of isophorone diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 5g of DMPA, 7g of 1, 6-hexanediol and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 16g of a 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) to react for 30min, adding 710g of water to disperse at a high speed, immediately adding 6.87g of ethylenediamine to react for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 MPa for 30min to obtain the waterborne polyurethane resin.

Example 5

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 210g of dimer acid polyester polyol (with the number average molecular weight of 3000), 100g of polycarbonate diol (with the number average molecular weight of 2000) and 2g of antioxidant Chinox 1010 at 50 ℃ for 20min, adding 105g of toluene diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 2g of trimethylolpropane, 8g of DMPA and 18g of methyl propylene glycol at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 6.03g of triethylamine at 40 ℃ for 5min, then adding 683g of water for high-speed dispersion, immediately adding 3g of ethylenediamine and 2g of hydrazine hydrate for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.

Example 6

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 210g of dimer acid polyester polyol (with the number average molecular weight of 3000), 100g of polytetrahydrofuran diol (with the number average molecular weight of 2000) and 2g of Chinox 1010 at 50 ℃ for 20min, adding 80g of toluene diisocyanate and 30g of diphenylmethane 4, 4-diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 10g of DMPA, 150g of acetone and 23g of hexanediol at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 7.54g of triethylamine at 40 ℃ for 5min, then adding 702g of water for high-speed dispersion, immediately adding 2.7g of ethylenediamine and 2g of hydrazine hydrate for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and under the condition of-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.

Example 7

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 200g of dimer acid polyester polyol (number average molecular weight of 3000), 80g of polycarbonate diol (number average molecular weight of 2000), 14g of polyethylene glycol monomethyl ether (number average molecular weight of 1000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 90g of isophorone diisocyanate and 31g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 4g of ethanolamine, 150g of acetone and 21g of 1.4-butanediol at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) reacting the intermediate product obtained in the step (2) with 20g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) at 40 ℃ for 30min, then adding 678g of water for high-speed dispersion, immediately adding 2g of ethylenediamine for reacting for 30min after the dispersion is finished, and removing acetone for 30min at 50 ℃ and-0.09 Mpa to obtain the waterborne polyurethane resin.

Example 8

The preparation method of the waterborne polyurethane resin comprises the following steps:

(1) stirring 200g of dimer acid polyester polyol (with the number average molecular weight of 4000), 110g of polytetrahydrofuran ether glycol (with the number average molecular weight of 2000) and 14g of polyethylene glycol monomethyl ether (with the number average molecular weight of 1000) at 50 ℃ for 20min, adding 2g of Chinox 1010, 80g of toluene diisocyanate and 40g of diphenylmethane 4, 4-diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;

(2) mixing the initial product obtained in the step (1), 10g of DMPA, 20g of 1, 4-butanediol, 150g of acetone and 2g of trimethylolpropane at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;

(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 7.54g of triethylamine at 40 ℃ for 5min, adding 723g of water for high-speed dispersion, immediately adding 30g of amino-terminated silicone oil and 2g of ethylenediamine for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and under the condition of-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.

Comparative example 1

An aqueous polyurethane resin is JF-PDY-850H available from Huafeng corporation.

Comparative example 2

An aqueous polyurethane resin which is different from example 1 in that no dimer acid polyester polyol is added in step (1) and the amount of polytetrahydrofuran ether glycol added is 300g, and the other conditions and steps are the same as those in example 1.

Comparative example 3

An aqueous polyurethane resin which is different from example 1 in that step (1) replaces 150g of dimer acid polyester polyol and 150g of polytetrahydrofuran ether glycol with 300g of polycarbonate glycol, and the other conditions and steps are the same as those of example 1.

And (3) performance testing:

(1) 100% modulus, breaking strength and elongation: naturally air-drying the waterborne polyurethane resin into a resin film with the thickness of about 1mm, baking the resin film for 30min at the temperature of 120 ℃, cutting the resin film into a sample piece with the thickness of 2.5 multiplied by 3.5cm, clamping the sample piece on an Shimadzu electronic universal test machine for testing, wherein the model of the machine is as follows: AGS-X-10kN, Shimadzu instruments Inc.

The aqueous polyurethanes obtained in examples 1 to 8 and comparative examples 1 to 3 were tested according to the test method (1) described above, and the test results are shown in table 1:

TABLE 1

	100% modulus/MPa	Breaking strength/MPa	Elongation/percent
				Example 1	3.3	47	730
Example 2	3.6	53	760
				Example 3	4.1	51	740
Example 4	4.0	49	760
				Example 5	3.5	54	820
Example 6	3.4	59	790
				Example 7	4.5	48	720
Example 8	4.3	52	740
				Comparative example 1	4.8	28	590
Comparative example 2	3.1	38	860
				Comparative example 3	5.2	58	620

As can be seen from the data in table 1: the modulus, the breaking strength and the elongation of the waterborne polyurethane resin prepared by using the dimer acid polyester polyol as the raw material are between those of the waterborne polyurethanes provided in the comparative examples 2 and 3, which shows that the modulus, the breaking strength and the elongation of the waterborne polyurethane provided by the invention are relatively balanced, and the physical property requirement of the synthetic leather fabric is met.

Preparing to-be-detected waterborne polyurethane resin synthetic leather: taking 100g of the waterborne polyurethane resin obtained in each of examples 1-8 and comparative examples 1-3, adding 8g of waterborne color paste, and thickening the waterborne color paste to the viscosity of about 5000cps by using a thickening agent; defoaming for 30min by using a washing machine, coating release paper with the thickness of about 0.2mm by blade coating, and drying in an oven at about 100 ℃ for 10min to obtain a waterborne polyurethane film; and (2) performing blade coating on the prepared waterborne polyurethane film by using the prepared waterborne middle layer foaming resin (JF-PDY-519 HY manufactured by Huafeng corporation) with the thickness of 0.35mm, completely drying in an oven at 120 ℃, then coating a layer of waterborne adhesive (JF-PDY-P521H manufactured by Huafeng corporation) on the surface of the waterborne middle layer foaming resin, wherein the blade coating thickness is 0.15mm, finally attaching the Huafeng FA microfiber substrate, drying and removing release paper to obtain the waterborne polyurethane resin synthetic leather to be measured.

(2) Folding endurance at 25 ℃: cutting the to-be-tested waterborne polyurethane resin synthetic leather into a sample piece with the thickness of 7 multiplied by 4.5cm, clamping the sample piece on a normal-temperature folding-resistant machine for testing, wherein the model of the machine is as follows: GT-7071-BN, high-speed rail detection instruments (Dongguan), Inc.

(3) Folding endurance at-15 ℃: cutting the to-be-tested waterborne polyurethane resin synthetic leather into a sample piece with the thickness of 7 multiplied by 4.5cm, clamping the sample piece on a low-temperature bending machine, setting the temperature to be-15 ℃, and testing. The machine model is as follows: GT-7006-V30, high-speed rail detection instruments (Dongguan), Inc.

(4) Wear resistance: cutting the waterborne polyurethane resin synthetic leather to be measured into a wafer with the diameter of 11cm, clamping the sample wafer on a machine, setting a grinding wheel to be H-18, setting the weight to be 750 grams, and setting the model of the machine: GT-7012-T, high-speed rail detection instruments (Dongguan), Inc.

(5) Anti-sticking property: putting the waterborne polyurethane resin synthetic leather to be measured on a clean glass plate, covering a layer of glass plate on the waterborne polyurethane resin synthetic leather, pressing a 3Kg weight, placing the glass plate in a 60 ℃ oven, and taking out the glass plate after 1 hour; cut out into strips of 3cm width and tested in tension in a tensile machine. A machine: shimadzu electronic universal tester, model: AGS-X-10 kN.

(6) And (3) jungle aging: putting the waterborne polyurethane resin synthetic leather to be measured on a clean glass plate, covering a layer of glass plate on the waterborne polyurethane resin synthetic leather, pressing a 3Kg weight, placing the glass plate in a 60 ℃ oven, and taking out the glass plate after 1 hour; cut into a sample strip with the width of 3cm, clamped on a constant temperature and humidity machine according to the specification, set the temperature at 70 ℃ and the humidity at 95%, and tested. The machine model is as follows: MHX-225QK, Shanghai Taichi science and technology, Inc.

The prepared waterborne polyurethane synthetic leather to be tested is tested according to the test methods (2) to (6), and the test results are shown in table 2:

TABLE 2

As can be seen from the data in table 2: the synthetic leather prepared by the waterborne polyurethane synthesized by using the dimer acid polyester polyol as the raw material has obviously improved normal-low temperature bending, abrasion resistance and anti-sticking property.

Specifically, the normal-temperature folding resistance of the synthetic leather prepared from the waterborne polyurethane obtained in the embodiments 1 to 8 is 31 to 38 ten thousand; the low-temperature folding resistance is 5.5-8 ten thousand; the wear resistance is 900-1250 Kg; the anti-adhesion test is free of adhesion or slight adhesion; and (5) carrying out jungle aging test for 3-4.5 weeks.

Comparing example 1 with comparative examples 1 to 3, it can be found that the weather resistance, wear resistance, anti-sticking property and jungle aging test result of the waterborne polyurethane synthesized without adding dimer acid polyester polyol as a raw material are poor.

The applicant states that the invention is illustrated by the above examples to a waterborne polyurethane and its preparation method and application, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.