阅读说明：本技术 一种喷涂型阻燃聚氨酯组合料及其制备方法与使用方法 (Spraying type flame-retardant polyurethane composite material and preparation method and use method thereof ) 是由 赵超斌 杨庆云 于 2021-07-13 设计创作，主要内容包括：本发明公开了一种喷涂型阻燃聚氨酯组合料,其包括如下重量份的组分：聚酯多元醇50～80份、阻燃聚醚多元醇5～15份、异氰酸酯20～50份、交联剂5～10份、催化剂0.1～1份、扩链剂5～12份、发泡剂3～10份和泡沫稳定剂0.5～1份；所述阻燃聚醚多元醇包括阻燃聚醚多元醇POP3628H和阻燃级聚醚多元醇YB-3028,按质量比计,所述阻燃聚醚多元醇POP3628H与阻燃级聚醚多元醇YB-3028的质量比1:1～3:1。本发明聚氨酯组合料中引入了阻燃聚醚多元醇,将阻燃元素稳定地结合到聚氨酯基体中,并通过对阻燃聚醚多元醇的种类及配比进行优化筛选,显著提高了聚氨酯的阻燃性能,以及降低了阻燃聚氨酯泡沫材料的制备成本,阻燃稳定性好,能持久保持阻燃效果,且对聚氨酯的物理性能无不良影响。(The invention discloses a spraying type flame-retardant polyurethane composite material which comprises the following components in parts by weight: 50-80 parts of polyester polyol, 5-15 parts of flame-retardant polyether polyol, 20-50 parts of isocyanate, 5-10 parts of a cross-linking agent, 0.1-1 part of a catalyst, 5-12 parts of a chain extender, 3-10 parts of a foaming agent and 0.5-1 part of a foam stabilizer; the flame-retardant polyether polyol comprises flame-retardant polyether polyol POP3628H and flame-retardant polyether polyol YB-3028, and the mass ratio of the flame-retardant polyether polyol POP3628H to the flame-retardant polyether polyol YB-3028 is 1: 1-3: 1. The flame-retardant polyether polyol is introduced into the polyurethane combined material, the flame-retardant elements are stably combined into the polyurethane matrix, and the type and the proportion of the flame-retardant polyether polyol are optimized and screened, so that the flame-retardant property of the polyurethane is obviously improved, the preparation cost of the flame-retardant polyurethane foam material is reduced, the flame-retardant stability is good, the flame-retardant effect can be kept for a long time, and no adverse effect is caused on the physical property of the polyurethane.)

1. The spraying type flame-retardant polyurethane composite material is characterized by comprising the following components in parts by weight: 50-80 parts of polyester polyol, 5-15 parts of flame-retardant polyether polyol, 20-50 parts of isocyanate, 5-10 parts of a cross-linking agent, 0.1-1 part of a catalyst, 5-12 parts of a chain extender, 3-10 parts of a foaming agent and 0.5-1 part of a foam stabilizer; the flame-retardant polyether polyol comprises flame-retardant polyether polyol POP3628H and flame-retardant polyether polyol YB-3028, and the mass ratio of the flame-retardant polyether polyol POP3628H to the flame-retardant polyether polyol YB-3028 is 1: 1-3: 1.

2. The spray-type flame retardant polyurethane composition according to claim 1, wherein the polyester polyol is a mixture of polycaprolactone polyol and aromatic polyester polyol, the polycaprolactone polyol has a hydroxyl value of 50 to 60(mg KOH/g), the aromatic polyester polyol has a viscosity of 400 to 600mPa.s under a test condition of 60 ℃, a melting point of 40 to 50 ℃, a hydroxyl value of 50 to 120(mg KOH/g), a viscosity of 800 to 5500mPa.s under a test condition of 25 ℃, and a functionality of 2 or more.

3. The spray-type flame retardant polyurethane composite material according to claim 2, wherein the polyester polyol comprises the following components in percentage by mass: 30 to 70 percent of polycaprolactone polyol and 30 to 70 percent of aromatic polyester polyol.

4. The sprayable flame retardant polyurethane composition of claim 1, wherein the isocyanate comprises at least one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), HDI (hexamethylene diisocyanate), MDI (diphenylmethane diisocyanate), HMDI (dicyclohexylmethane diisocyanate).

5. The sprayable flame retardant polyurethane composition of claim 1, wherein the crosslinking agent is at least one of triethanolamine, diethanolamine, and glycerol.

6. The sprayable flame retardant polyurethane composition of claim 1, wherein the catalyst comprises an organometallic compound comprising at least one of tetraphenyltin, stannous octoate, dibutyltin dilaurate, bismuth naphthenate, bismuth isooctanoate, bismuth laurate, zinc isooctanoate.

7. The sprayable flame retardant polyurethane composition of claim 1, wherein the chain extender is at least one of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, and 1, 3-propanediol.

8. The sprayable flame retardant polyurethane composition of claim 1, wherein the foam stabilizer is a polysiloxane-polyether copolymer and the blowing agent is water.

9. A preparation method of the spray-type flame-retardant polyurethane composite material according to any one of claims 1 to 8, characterized by comprising the following steps:

(1) putting polyester polyol, flame-retardant polyether polyol, a cross-linking agent, a catalyst, a chain extender, a foaming agent and a foam stabilizer into a reaction kettle, and uniformly stirring and mixing to obtain a component A;

(2) isocyanate is taken as component B;

(3) and respectively sealing and storing the component A and the component B to obtain the spraying type flame-retardant polyurethane combined material.

10. The use method of the spray-type flame retardant polyurethane composition according to any one of claims 1 to 8, comprising: and (3) uniformly mixing the component A and the component B under the action of high pressure, atomizing and spraying in a low-pressure mode, and quickly foaming and forming to obtain the flame-retardant polyurethane foam material.

Technical Field

The invention belongs to the technical field of polyurethane, and particularly relates to a spraying type flame-retardant polyurethane composite material, and a preparation method and a use method thereof.

Background

The polyurethane is mainly used for preparing various soft, hard and semi-hard foam plastics, has various excellent properties such as shock absorption, heat insulation, sound absorption, wear resistance, high elasticity and the like, and is widely applied to the fields of petroleum, chemical pipelines, refrigeration, heat preservation and insulation of buildings and the like, and various cushions, backrest materials, decoration materials and the like of vehicles and furniture. However, the oxygen index of the conventional polyurethane foam is only 16.5, which is close to the candle oxygen index of 15.01, and belongs to the category of flammable materials. When the polyurethane foam is burned, a large amount of reaction heat, combustible gas, and toxic gas such as nitrogen oxide, hydrogen cyanide, etc. are emitted.

In order to improve the flame retardant property of polyurethane foam plastics, the existing method mainly uses an additive flame retardant. However, the additive flame retardant has the defects of easy migration, incapability of maintaining the flame retardant effect for a long time, damage to the physical properties (such as tensile strength, tear strength and the like) of the foam and the like. Therefore, in the field with high requirements on flame retardant performance, the additive flame retardant is difficult to meet the use requirements.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a spraying type flame-retardant polyurethane composite material, and a preparation method and a use method thereof.

In order to realize the purpose, the technical scheme adopted by the invention is as follows:

a spraying type flame-retardant polyurethane composite material comprises the following components in parts by weight: 50-80 parts of polyester polyol, 5-15 parts of flame-retardant polyether polyol, 20-50 parts of isocyanate, 5-10 parts of a cross-linking agent, 0.1-1 part of a catalyst, 5-12 parts of a chain extender, 3-10 parts of a foaming agent and 0.5-1 part of a foam stabilizer, wherein the flame-retardant polyether polyol comprises flame-retardant polyether polyol POP3628H and flame-retardant polyether polyol YB-3028, and the mass ratio of the flame-retardant polyether polyol POP3628H to the flame-retardant polyether polyol YB-3028 is 1: 1-3: 1.

The polyurethane combined material formula system uses the flame-retardant polyether polyol to replace an additive flame retardant, and stably combines flame-retardant elements into a polyurethane matrix, so that adverse effects of the flame retardant on materials are avoided, the flame retardant performance and the flame retardant stability of the polyurethane are improved, and the compatibility of the components is also improved.

The flame-retardant polyether polyol POP3628H has the dual functions of flame retardance, opening of holes of polymer polyether and the like, has the foam oxygen index of more than 30 percent and the smoke density of less than 60 percent, has better flame retardance, does not contain halogen, phosphorus, antimony and other elements, has low viscosity, and has better compatibility with additives such as a catalyst, a foaming agent, a foam stabilizer and the like. The flame retardant grade polyether polyol YB-3028 also has flame retardant property, although the flame retardant property is lower than that of the flame retardant polyether polyol POP36 3628H, the use cost is lower. Through experimental research, the inventor of the application finds that the flame-retardant polyether polyol POP36 3628H and the flame-retardant polyether polyol YB-3028 are combined and used according to the mass ratio of 1: 1-3: 1, so that the flame retardant property of the polyurethane material can be obviously improved, the oxygen index of the polyurethane material is obviously increased, and the overall cost of the flame-retardant polyether polyol can be reduced.

Preferably, the mass ratio of the flame-retardant polyether polyol POP3628H to the flame-retardant polyether polyol YB-3028 is 1.5: 1-2.5: 1. When the flame-retardant polyether polyol POP36 3628H and the flame-retardant polyether polyol YB-3028 are used in combination according to the proportion, the flame-retardant property of the polyurethane material is better.

Preferably, the mass ratio of the flame-retardant polyether polyol POP3628H to the flame-retardant polyether polyol YB-3028 is 2: 1. When the flame-retardant polyether polyol POP3628H and the flame-retardant polyether polyol YB-3028 are used in combination according to the mixture ratio, the flame-retardant property of the polyurethane material is the best.

Preferably, the polyester polyol is a mixture of polycaprolactone polyol and aromatic polyester polyol.

Preferably, the hydroxyl value of the polycaprolactone polyol is 50-60 (mg KOH/g), the viscosity under the test condition of 60 ℃ is 400-600 mPa.s, and the melting point is 40-50 ℃.

Preferably, the hydroxyl value of the aromatic polyester polyol is 50-120 (mg KOH/g), the viscosity under the test condition of 25 ℃ is 800-5500 mPa.s, and the functionality is more than or equal to 2.

The polyester polyol affects the soft segment polarity and the soft and hard state poly-aggregate structure of the polyurethane elastomer molecules, and therefore, the kind, structure, number average molecular weight, etc. of the polyester polyol have a large influence on the performance of the polyurethane. The polycaprolactone Polyol (PCL) with the parameters is linear aliphatic polyester, has narrow number average molecular weight distribution and better thermal stability, and can improve the mechanical property and the chemical property of polyurethane. The aromatic polyester polyol with the parameters contains rigid benzene rings in molecular chains, so that the strength and the heat resistance of the polyurethane can be improved, and the flame retardance of the polyurethane can be further improved. The inventors of the present application have found through experimental studies that the mechanical properties (e.g., tensile strength, tear resistance, elasticity, etc.) and chemical properties (e.g., heat resistance, cold resistance, chemical corrosion resistance, etc.) of a polyurethane material can be significantly enhanced by using a polycaprolactone polyol having the above-mentioned parameters in combination with an aromatic polyester polyol as a base material of a polyurethane foam.

Preferably, the polyester polyol consists of the following components in percentage by mass: 30 to 70 percent of polycaprolactone polyol and 30 to 70 percent of aromatic polyester polyol. When the polyester polyol consists of the components in mass ratio, the mechanical property and the chemical property of the polyurethane material are better.

Preferably, the polyester polyol consists of the following components in percentage by mass: 50% of polycaprolactone polyol and 50% of aromatic polyester polyol. When the polyester polyol consists of the components in mass ratio, the mechanical property and the chemical property of the polyurethane material are the best.

Preferably, the isocyanate comprises at least one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), HDI (hexamethylene diisocyanate), MDI (diphenylmethane diisocyanate), HMDI (dicyclohexylmethane diisocyanate).

Preferably, the cross-linking agent is at least one of triethanolamine, diethanolamine, and glycerol.

Preferably, the catalyst comprises an organometallic compound. Preferably, the organic metal compound is at least one of tetraphenyl tin, stannous octoate, dibutyltin dilaurate, bismuth naphthenate, bismuth isooctanoate, bismuth laurate and zinc isooctanoate.

Preferably, the chain extender is at least one of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, and 1, 3-propanediol.

Preferably, the foam stabilizer is a polysiloxane-polyether copolymer.

Preferably, the blowing agent is water.

The invention also provides a preparation method of the spray type flame-retardant polyurethane composite material, which comprises the following steps:

(1) putting polyester polyol, flame-retardant polyether polyol, a cross-linking agent, a catalyst, a chain extender, a foaming agent and a foam stabilizer into a reaction kettle, and uniformly stirring and mixing to obtain a component A;

(2) isocyanate is taken as component B;

(3) and respectively sealing and storing the component A and the component B to obtain the spraying type flame-retardant polyurethane combined material.

The invention also provides a using method of the spraying type flame-retardant polyurethane composite material, which comprises the following steps: and (3) uniformly mixing the component A and the component B under the action of high pressure, atomizing and spraying in a low-pressure mode, and quickly foaming and forming to obtain the flame-retardant polyurethane foam material. For example, the component A and the component B are respectively injected into a spray gun by using a pneumatic airless sprayer, are uniformly mixed in a mixing chamber under the action of high pressure, and are atomized and sprayed in a low-pressure mode and are rapidly foamed and molded.

Compared with the prior art, the invention has the beneficial effects that: the components of the polyurethane combined material have good compatibility, the flame-retardant polyether polyol is introduced into a formula system, the flame-retardant elements are stably combined into a polyurethane matrix, and the type and the proportion of the flame-retardant polyether polyol are optimized and screened, so that the flame-retardant property of the polyurethane is obviously improved, the preparation cost of the flame-retardant polyurethane foam material is reduced, the flame-retardant stability is good, the flame-retardant effect can be kept for a long time, and no adverse effect is caused on the physical property of the polyurethane. The invention also optimizes and screens the basic materials of the polyurethane composite material, and uses the polycaprolactone polyol and the aromatic polyester polyol with specific parameters in a combined way, thereby obviously enhancing the mechanical property and the chemical property of the polyurethane.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. The methods employed in the examples of the present invention are conventional in the art and the equipment used is commercially available unless otherwise specified, and "parts" are referred to as "parts by weight".

Some of the raw materials used in the examples were purchased from the following sources:

(1) the flame-retardant polyether polyol POP3628H is purchased from International trade company, Inc. in Zhang Jia gang bonded tax district;

(2) the flame-retardant grade polyether polyol YB-3028 is purchased from Jiangyin Yongbang chemical Co., Ltd;

(3) polycaprolactone polyol, model PCL2000, available from general biotechnology ltd, hua, science & specialty;

(4) aromatic polyester polyol, model CP-2055, available from Nanjing Kangplast chemical Co., Ltd;

(5) foam stabilizer, model HY-193, available from Shanghai Hui research materials, Inc.;

(6) the additive type flame retardant is triisopropylphenyl phosphate 35 and the type flame retardant ippp35, which are purchased from Shandong Daihou chemical Co., Ltd.

Examples 1 to 3

Examples 1-3 provide a spray-type flame retardant polyurethane composition, the formulation composition of which is shown in table 1.

Comparative examples 1-2 provide a spray-coating type polyurethane composite material, the formulation composition of which is shown in table 1.

TABLE 1

Component (in parts)	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						PCL2000	25	32	40	32	32
CP-2055	25	32	40	32	32
						POP3628H	7.5	5	2.5	-	-
YB-3028	7.5	5	2.5	-	-
						ippp35	-	-	-	-	10
MDI	20	35	50	35	35
						Triethanolamine	10	8	5	8	8
Stannous octoate	0.8	0.5	0.3	0.5	0.5
						1, 3-propanediol	5	8	12	8	8
Water (W)	5	8	10	8	8
						HY-193	1	0.8	0.5	0.8	0.8

Note: in the table, "-" indicates that the component was not added.

The use method of the polyurethane composite material comprises the following steps: putting polyester polyol, flame-retardant polyether polyol (or an additive flame retardant), a cross-linking agent, a catalyst, a chain extender, a foaming agent and a foam stabilizer into a reaction kettle, and stirring and mixing uniformly at room temperature to obtain a component A; isocyanate is taken as component B; and respectively injecting the component A and the component B into a spray gun of a pneumatic airless sprayer, uniformly mixing in a mixing chamber under the action of high pressure, atomizing and spraying in a low-pressure mode, and quickly foaming and forming to form a layer of continuous, compact and seamless polyurethane foam material.

Polyurethane foam samples with the same specification were prepared from the polyurethane compositions of examples 1 to 3 and comparative examples 1 to 2 by the above-described methods, and the performance of each sample was tested, and the test results are shown in table 2.

The method for each test item is as follows:

1. oxygen index: testing according to GB/T2406.2-2009

2. Coefficient of thermal conductivity: testing was performed according to GB/T3399-;

3. tensile strength: testing according to GB/T528-2009;

4. tear strength: testing according to GB/T529 and 2008;

5. rebound resilience: testing according to GB/T6670-;

6. dimensional stability: GB/T8811-1988 (-30 ℃, 48h (-0.6%); 70 ℃, 48h (0.9%))

TABLE 2

As can be seen from the data in Table 2, after the POP3628H and the YB-3028 are added into the polyurethane composite material, the oxygen index of the foam material obtained by foaming is obviously improved, the flame retardant property is enhanced, and the mechanical property is better. When the additive flame retardant is added, the flame retardant property of the foam material is reduced, and the mechanical property is also reduced.

The influence of the component composition and the component proportion of the flame-retardant polyether polyol on the performance of the polyurethane composition is researched, and test groups 1-9 in Table 3 are designed. The flame-retardant polyether polyols of test groups 1 to 9 were prepared into polyurethane composite materials according to the formula of example 2 (the total weight of the flame-retardant polyether polyols is 10 parts, and the other components are the same as in example 2), and the polyurethane composite materials were prepared into polyurethane foam materials according to the method, and then performance tests were performed, with the test results shown in table 4.

TABLE 3

Group of	Component composition and component mass ratio of flame-retardant polyether polyol
		Test group 1	POP3628H
Test group 2	YB-3028
		Test group 3	POP3628H+YB-3028，POP3628H:YB-3028＝0.5:1
Test group 4	POP3628H+YB-3028，POP3628H:YB-3028＝1:1
		Test group 5	POP3628H+YB-3028，POP3628H:YB-3028＝1.5:1
Test group 6	POP3628H+YB-3028，POP3628H:YB-3028＝2:1
		Test group 7	POP3628H+YB-3028，POP3628H:YB-3028＝2.5:1
Test group 8	POP3628H+YB-3028，POP3628H:YB-3028＝3:1
		Test group 9	POP3628H+YB-3028，POP3628H:YB-3028＝3.5:1

TABLE 4

As can be seen from the data in Table 4, the combined use of POP3628H and YB-3028 can obviously improve the oxygen index of the polyurethane material, so that the flame retardant property of the polyurethane material is better. Meanwhile, the combination ratio of POP3628H and YB-3028 also has influence on the performance of the material, especially has the greatest influence on the oxygen index; when the mass ratio of POP3628H to YB-3028 is 1: 1-3: 1, the flame retardant property of the material is better; when the mass ratio of POP3628H to YB-3028 is 2:1, the flame retardant property of the material is optimal.

The influence of the component composition and the component proportion of the polyester polyol on the performance of the polyurethane composition is researched, and test groups 10-16 in Table 5 are designed. The polyester polyols of test groups 10 to 16 were prepared into polyurethane composite materials according to the formula of example 2 (the total weight parts of the polyester polyols are 64 parts, and the other components are the same as those of example 2), and the polyurethane composite materials were prepared into polyurethane foam materials according to the method, and then performance tests were performed, with the test results shown in table 6.

TABLE 5

Group of	The components of polyester polyol and the mass percentage of the components
		Test group 10	PCL2000
Test group 11	CP-2055
		Test group 12	20％PCL2000+80％CP-2055
Test group 13	30％PCL2000+70％CP-2055
		Test group 14	50％PCL2000+50％CP-2055
Test group 15	70％PCL2000+30％CP-2055
		Test group 16	80％PCL2000+20％CP-2055

TABLE 6

As can be seen from the data in Table 6, when PCL2000 and CP-2055 are used in combination, the properties, especially the mechanical properties, of the polyurethane material can be remarkably improved. Meanwhile, the combination ratio of PCL2000 and CP-2055 also has influence on the performance of the material, especially has the greatest influence on the tensile strength, the tear strength and the rebound resilience; in the polyester polyol, when the mass percentage of PCL2000 and CP-2055 are respectively 30-70%, the tensile strength, tear strength and rebound resilience of the material are excellent; when the PCL2000 and the CP-2055 are respectively 50 percent in mass percentage, the tensile strength, the tear strength and the rebound resilience of the material are optimal.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.