CN115058225A

CN115058225A - Bi-component solvent-free polyurethane adhesive for textile fabric compounding and preparation method thereof

Info

Publication number: CN115058225A
Application number: CN202210891825.1A
Authority: CN
Inventors: 丛小雨; 张泽绮
Original assignee: Jiangsu Huada New Material Co ltd
Current assignee: Jiangsu Huada New Material Co ltd
Priority date: 2022-07-27
Filing date: 2022-07-27
Publication date: 2022-09-16

Abstract

The invention relates to the field of polyurethane adhesives, and particularly discloses a bi-component solvent-free polyurethane adhesive for textile fabric compounding and a preparation method thereof. The polyurethane adhesive comprises a component A and a component B, wherein the component A comprises 25-60 parts of polyether polyol, 15-80 parts of polyester polyol and 10-55 parts of isocyanate, and the component B comprises 0-50 parts of polyether polyol and 40-100 parts of polyester polyol, based on the total weight of the two-component solvent-free polyurethane adhesive. The application provides a bi-component solvent-free polyurethane adhesive for textile fabric compounding and a preparation method thereof, which are used for improving the cohesiveness and environmental protection of the adhesive.

Description

Bi-component solvent-free polyurethane adhesive for textile fabric compounding and preparation method thereof

Technical Field

The invention relates to the field of polyurethane adhesives, in particular to a bi-component solvent-free polyurethane adhesive for textile fabric compounding and a preparation method thereof.

Background

In order to improve the performances of textile fabrics such as water washing resistance and moisture permeability, textile fabric raw materials are generally combined with films such as TPU, PVC and PTFE. The textile fabric mainly comprises raw materials such as terylene, chinlon, spandex, cotton and the like. The textile fabric compounding is to compound the film material and the single-woven or blended fabric together by using an adhesive.

Currently, the adhesives mainly used include two-component solvent-based adhesives and one-component solvent-free moisture-curable polyurethane adhesives. The single-component solvent-free moisture-curing polyurethane adhesive is mainly a liquid adhesive, needs to be bonded by air and moisture curing in materials in the using process, and can cause poor bonding of the adhesive due to uncontrollable moisture content; the bi-component solvent type polyurethane adhesive contains organic solvent, and the organic solvent is easy to volatilize in the preparation process, thereby causing the problem of environmental pollution.

In view of the above-mentioned related art, the inventors of the present invention have considered that there is a need to develop a polyurethane adhesive having both high adhesion and green environmental characteristics.

Disclosure of Invention

In order to improve the caking property and the environmental protection property of the adhesive at the same time, the application provides a bi-component solvent-free polyurethane adhesive for compounding textile fabrics and a preparation method thereof.

In a first aspect, the application provides a two-component solvent-free polyurethane adhesive for textile fabric compounding, which adopts the following technical scheme:

the two-component solvent-free polyurethane adhesive for compounding the textile fabric comprises a component A and a component B, wherein the component A comprises 25-60 parts of polyether polyol, 15-80 parts of polyester polyol and 10-55 parts of isocyanate, and the component B comprises 0-50 parts of polyether polyol and 40-100 parts of polyester polyol by total weight of the two-component solvent-free polyurethane adhesive.

By adopting the technical scheme, the two-component solvent-free polyurethane adhesive is prepared according to the polyether diol, the polyester diol and the isocyanate in a specific ratio. Compared with the adhesive in the prior art, the adhesive avoids the condition of poor bonding caused by moisture curing when a single-component solvent-free moisture curing type polyurethane adhesive is used, and simultaneously avoids the problem of environmental pollution caused by volatilization of toxic solvents when a two-component solvent type adhesive is used. Therefore, the adhesive improves the bonding property and the environmental protection property of the adhesive at the same time, and the two-component solvent-free polyurethane adhesive can firmly bond the film material and the textile fabric together and has excellent bonding property even under severe conditions.

In a particular embodiment, the polyether polyol comprises a polyoxyethylene glycol.

By adopting the technical scheme, the polyoxyethylene glycol is used as a soft chain, and has no side group and more methylene, so that the polyoxyethylene glycol can provide better crystallinity for the bi-component solvent-free polyurethane adhesive, and the cohesive force and the adhesive force of the adhesive layer are improved, thereby improving the adhesive property of the adhesive

In a particular embodiment, the polyether polyol further comprises at least one of a polyoxybutylene glycol and a polyoxypropylene glycol.

By adopting the technical scheme, when the polyether polyol further comprises at least one of polyoxybutylene glycol and polyoxypropylene glycol, the disadvantage of poor water resistance of polyoxyethylene glycol can be improved due to good water resistance of polyoxybutylene glycol and polyoxypropylene glycol, so that the bonding property of the polyurethane adhesive for textile fabric compounding after washing is improved in a specific practical embodiment, and the polyester polyol comprises the following components in parts by weight: 1060-1100 parts of polybasic acid, 405-660 parts of polyol and 0.1-0.5 part of polyester catalyst; the polybasic acid is at least one of adipic acid, dimer acid and hydrogenated dimer acid; the polyalcohol is at least one of dihydric alcohol, hydrogenated dihydric alcohol, 1,6 hexanediol, neopentyl glycol, 1, 4-cyclohexanediol and 2-methyl-1, 3 propanediol; the polyester catalyst is at least one of tetrabutyl titanate and tetraisobutyl titanate.

By adopting the technical scheme, the inventor finds that when the polybasic acid, the polyhydric alcohol and the polyester catalyst are selected and the ratio of the polybasic acid, the polyhydric alcohol and the polyester catalyst is controlled within the range, the prepared polyester polyol improves the bonding property of the two-component solvent-free polyurethane adhesive, and the polyurethane adhesive prepared in the solvent-free environment has excellent elasticity and water resistance. This is probably because adipic acid, dimer acid and hydrogenated dimer acid have a highly branched structure, an amorphous dimer structure and an ultra-long carbon chain structure, and when dimer alcohol, hydrogenated dimer alcohol, 1,6 hexanediol, neopentyl glycol, 1, 4-cyclohexanediol and 2-methyl-1, 3-propanediol have a branched structure, the reaction of the above-mentioned polybasic acid and polyhydric alcohol improves the flexibility, adhesiveness, water resistance and migration resistance of the polyurethane adhesive.

In addition, in the condensation stage of the polyester polyol, the reaction rate is slowed due to the overlarge viscosity of the reaction system, and the proportion of the polybasic acid, the polyhydric alcohol and the polyester catalyst is controlled within the range, so that the reaction rate is accelerated, and the yield of the polyester polyol is improved.

In a specific embodiment, the polyester polyol is prepared as follows:

s1, uniformly stirring the polyol, the polybasic acid and the polyester catalyst to obtain a mixed solution;

s2, heating the mixed solution to 135-145 ℃, performing stable dehydration, continuing heating to 185-195 ℃, and performing vacuum pumping to obtain a dehydrated mixture;

s3, continuously heating the dehydrated mixture to 205-215 ℃ for ester exchange reaction, and when the final acid value of the reaction product is 0.1-0.3mgKOH/g and the hydroxyl value is 55-57mgKOH/g, reducing the pressure and the temperature to obtain the polyester diol.

By adopting the technical scheme, the method enables the chain initiation and chain growth reactions to reach balance under the condition of stirring and heating in the presence of the polyester catalyst, discharges water generated in the reaction process through the dehydration step, and terminates the chain under the condition of temperature rise so as to finish the polycondensation reaction. Finally, the polyol and the polybasic acid are subjected to ester exchange reaction, and the acid value and the hydroxyl value of the final product are measured so as to ensure the viscosity and the reactivity of the prepolymer polyol. Finally, carrying out treatments such as pressure reduction, temperature reduction and the like to obtain the polyester diol. The method is simple to operate and simple and convenient in reaction process.

In a specific possible embodiment, the isocyanate is at least one of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, 4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and 1, 5-naphthalene diisocyanate.

By adopting the technical scheme, when isocyanate is used as a hard segment part in the adhesive, isocyanate can be given so as to react with an organic matter with an active group to generate the polyurethane adhesive. The isocyanate influences the rigidity and the strength of the adhesive, and the diphenylmethane diisocyanate, the liquefied diphenylmethane diisocyanate and the 1, 5-naphthalene diisocyanate have rigid aromatic rings, so that the cohesive energy of a hard segment is increased, the strength is high, and the adhesive has better peel strength; 4, 4-dicyclohexyl methane diisocyanate and hexamethylene diisocyanate have excellent hydrolysis resistance and wear resistance, and meanwhile, the transparency is good, and the cohesiveness of the adhesive after washing is improved.

In a specific embodiment, the component A further comprises the following components in parts by weight: 0.01-0.5 part of catalyst 1, wherein the catalyst 1 is at least one of dibutyltin dilaurate, stannous octoate, zinc isooctoate and bismuth isooctanoate.

By adopting the technical scheme, when the catalyst 1 is added to catalyze the reaction, the catalyst 1 and the isocyanate form a coordinate bond, so that the isocyanate has polarity, isocyanate groups in the isocyanate have lower activation energy, the isocyanate is more easily reacted with hydroxyl, the obtained component A has better reaction activity, and the component A is conveniently reacted with the component B to obtain the polyurethane adhesive.

In a specific embodiment, the component B also comprises the following components in parts by weight: 0.01-0.2 parts of catalyst 2, wherein the catalyst 2 is at least one of 1, 2-bis (dimethylaminoethoxy) ethane, N-methyl dicyclohexylamine, 1, 4-dimethyl piperazine, dimorpholinoethyl ether and dimorpholintriethyl ether.

By adopting the technical scheme, when the catalyst 2 is added into the component B, the reaction rate of the polyester polyol and the polyether polyol is accelerated, and the chain extension and crosslinking rate of the component B and the component A during mixing is improved.

In a specific embodiment, the weight ratio of the A component to the B component is 2 (1-3).

By adopting the technical scheme, when the weight ratio of the component A to the component B is 2 (1-3), the adhesive property of the double-component solvent-free polyurethane adhesive is improved, and the adhesive has better adhesive effect.

In a second aspect, the application provides a preparation method of a bi-component solvent-free polyurethane adhesive for textile fabric compounding, which adopts the following technical scheme.

A preparation method of a bi-component solvent-free polyurethane adhesive for compounding textile fabrics comprises the following steps,

preparation of component A: according to the proportion, polyether polyol and polyester polyol are uniformly mixed to obtain mixed alcohol A; heating the mixed alcohol A to 120 ℃ at 100 ℃, adjusting the water content of the mixed alcohol A to 0-0.02%, cooling the mixed alcohol A to 50-80 ℃, adding a catalyst 1 and isocyanate, and carrying out heat preservation reaction to obtain a pretreatment component A; heating the pretreatment component A to 90-100 ℃, and discharging bubbles to obtain a component A;

the preparation steps of the component B are as follows: according to the proportion, polyether polyol and polyester polyol are uniformly mixed to obtain mixed alcohol B; heating the mixed alcohol B to 120 ℃ below zero, adjusting the water content of the mixed alcohol B to 0-0.02%, cooling the mixed alcohol B to 70-90 ℃, adding the catalyst 2, and uniformly stirring to obtain a pretreatment component B; and (3) heating the pretreatment component B to 90-100 ℃, and discharging bubbles and materials to obtain the component B.

And mixing the component A and the component B to obtain the bi-component solvent-free polyurethane adhesive for compounding the textile fabric.

By adopting the technical scheme, in the preparation of the component A, the temperature of the mixed alcohol A is raised to adjust the water content, so that the addition of the catalyst 1 and the isocyanate is facilitated, the NCO end blocking is prepared, the free isocyanate in the system is obtained, and the storage stability of the component A is prolonged. The temperature of the mixed alcohol A is reduced, which is beneficial to the better reaction of the mixed alcohol A and isocyanate after the catalyst 1 and the isocyanate are added. By adopting the method, the operation for preparing the component A is simple, and the preparation success rate is high; meanwhile, the component A prepared according to the proportion of the invention also has excellent cohesiveness, and the peel strength of the polyurethane adhesive is improved.

In the preparation process of the component B, after the component B is mixed, the temperature is raised to adjust the water content, the polycondensation reaction is started, and meanwhile, the water generated in the reaction process is removed; cooling the reaction, adding a catalyst 2, and accelerating the chain growth reaction rate of polyether polyol and polyester polyol by the catalyst 2; then raising the reaction temperature, starting a chain termination reaction to stop the polycondensation reaction, and preparing the component B by the preparation method, wherein the reaction process is rapid; meanwhile, the component B prepared according to the proportion has excellent adhesiveness, and the adhesive force of the polyurethane adhesive is enhanced.

After the component A and the component B are mixed, a large number of active isocyanate groups are contained in the component A and react with hydroxyl groups in the component B to form aminomethyl acid value groups, so that the binding force between the polyurethane adhesive and the textile fabric is improved. Meanwhile, ester groups in the component B can form good hydrogen bonds and van der Waals force with a base material, and the acting force strengthens the bonding force between the polyurethane adhesive and the textile fabric, so that the polyurethane adhesive has better bonding strength.

In summary, the present application includes at least one of the following beneficial technical effects:

1. the double-component solvent-free polyurethane adhesive provided by the application has better adhesive and green environmental protection property;

2. according to the component proportion provided by the application, the prepared polyurethane adhesive has excellent adhesive strength;

3. the preparation method is simple to operate, the reaction process is simple and convenient, and the bi-component solvent-free polyurethane adhesive obtained by the preparation method has better adhesive and environmental protection.

Detailed Description

In the present application, at least one of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, 4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and 1, 5-naphthalene diisocyanate is used as an isocyanate raw material; at least one of dibutyltin dilaurate, stannous octoate, zinc isooctanoate and bismuth isooctanoate is used as a raw material of the catalyst 1; the two-component solvent-free polyurethane adhesive with excellent adhesiveness can be prepared by using at least one of 1, 2-bis (dimethylaminoethoxy) ethane, N-methyldicyclohexylamine, 1, 4-dimethylpiperazine, dimorpholinoethyl ether and dimorpholintriethyl ether as a raw material of the catalyst 2.

The present application will be described in further detail with reference to examples, preparations and comparative examples.

Preparation examples of polyester polyols

The polyester polyol is prepared from the following polybasic acid, polyhydric alcohol and polyester catalyst by adjusting the reaction temperature and the dehydration speed, wherein the polybasic acid comprises: at least one of adipic acid, dimer acid, and hydrogenated dimer acid; the polyhydric alcohol includes: at least one of a diol, a hydrogenated diol, 1,6 hexanediol, neopentyl glycol, 1, 4-cyclohexanediol, and 2-methyl-1, 3 propanediol; the polyester catalyst comprises: at least one of tetrabutyl titanate and tetraisobutyl titanate.

The following will explain preparation example 1 as an example.

Preparation example 1

In this example, the polyester polyol comprises the following components: 405g of neopentyl glycol, 530g of adipic acid, 530g of dimer acid and 0.1g of tetrabutyltitanate.

In this example, the polyester polyol was prepared as follows:

neopentyl glycol, adipic acid, dimer acid and tetrabutyl titanate are sequentially added into a reaction kettle, the mixture is uniformly stirred, the temperature of the reaction kettle is raised to 135-fold-material 145 ℃, the temperature is raised to 140 ℃ in the embodiment, and the temperature is kept constant for 3 hours. Keeping the temperature of the top of the rectifying tower at 110 ℃, passing the mixed liquid through the rectifying tower, then heating the temperature in the reaction kettle to 185-195 ℃, in the embodiment, heating to 190 ℃, starting a vacuum pump and starting timing, controlling the vacuum degree to slowly increase, meanwhile, continuously heating to 205-215 ℃, in the embodiment, heating to 210 ℃ for transesterification, and introducing nitrogen to take away the excessive polyhydric alcohol and the small molecular alcohol. After vacuumizing for 5h, detecting the acid value and the hydroxyl value of the sample, sampling once every 2h until the final acid value of the sample is 0.1-0.3mgKOH/g, the final acid value is 0.2mgKOH/g, the hydroxyl value is 55-57mgKOH/g, the hydroxyl value is 56.0mgKOH/g in the embodiment, recovering the normal pressure, reducing the reaction system to 140 ℃, discharging and storing to obtain the polyester diol.

Preparation examples 2 to 3

As shown in Table 1, preparations 2 to 3 were different from preparation 1 in that: the raw materials for preparing the polyester diol have different proportions.

TABLE 1

Sample(s)	Neopentyl glycol/g	Adipic acid/g	Dimer acid/g	Tetrabutyl titanate/g
					Preparation example 2	530	540	540	0.15
Preparation example 3	660	550	550	0.2

Preparation example 4

The difference between the preparation example and the preparation example 3 is that: no dimer acid was included and the amount of adipic acid used was 1100 g.

Preparation example 5

The difference between the preparation example and the preparation example 4 is that: the neopentyl glycol was used in an amount of 330g, including 330g of 1, 4-cyclohexanediol.

Preparation example 6

The difference between the preparation example and the preparation example 3 is that: the neopentyl glycol was used in an amount of 330g, and 330g of 1, 4-cyclohexanediol was also included.

Examples

The following description will be given by taking example 1 as an example.

Example 1

The embodiment provides a bi-component solvent-free polyurethane adhesive for textile fabric compounding, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2 (1-3).

This example provides a composition A comprising 25g of a polyether polyol, 70g of a polyester polyol and 45g of an isocyanate; the polyether polyol is ethylene oxide dihydric alcohol, the polyester polyol in the component A is the polyester polyol of the preparation example 1, and the isocyanate is diphenylmethane diisocyanate;

this example provides a B-side comprising 100g of a polyester polyol. The polyester polyol in the component B is at least one of the polyester polyols in the preparation examples, and the polyester polyol in the embodiment is 50g of each of the two polyester polyols of the preparation examples 1 and 2.

A preparation method of a bi-component solvent-free polyurethane adhesive for textile fabric compounding comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 110 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; then reducing the temperature of the mixture in the reaction device to 65 ℃, adding diphenylmethane diisocyanate, controlling the reaction temperature at 70 ℃, and reacting for 4 hours to ensure that the NCO content tends to be stable; and finally, keeping the temperature at 100 ℃, simultaneously vacuumizing until no bubbles exist in the system, and discharging to obtain the component A.

Preparation of the component B:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 110 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; and finally, keeping the temperature at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

And respectively storing the component A and the component B, and when the adhesive is used, uniformly mixing the component A and the component B to obtain the double-component solvent-free polyurethane adhesive.

Examples 2 to 6

Examples 2-6 differ from example 1 in the feed composition, as shown in Table 2.

TABLE 2

Example 7

Example 7 differs from example 3 in that:

the polyester diol in the component B is any one of the preparation examples, and the polyester diol in the embodiment is 100g of the polyester diol in the preparation example 1.

Example 8

Example 8 differs from example 3 in that:

the polyether diol in the component A is polyoxyethylene diol and polyoxybutylene diol, and the use amounts of the polyoxyethylene diol and the polyoxybutylene diol are respectively 25g and 30 g.

Example 9

Example 9 differs from example 3 in that:

the polyether diol in the component A is polyoxyethylene diol, polyoxybutylene diol and polyoxypropylene diol, and the use amounts of the polyoxyethylene diol, the polyoxybutylene diol and the polyoxypropylene diol are respectively 10g, 20g and 25 g.

Example 10

Example 10 differs from example 3 in that:

the isocyanate in the component A is selected from diphenylmethane diisocyanate and liquefied diphenyl, and the use amounts of the diphenylmethane diisocyanate and the liquefied diphenyl are respectively 10g and 25 g.

Example 11

Example 11 differs from example 3 in that:

the starting material for component A also included 0.01g of catalyst 1, catalyst 1 in this example being dibutyltin dilaurate.

The preparation of the component A comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; then, reducing the temperature in the reaction device to 50 ℃, firstly adding dibutyltin dilaurate, then adding diphenylmethane diisocyanate, controlling the reaction temperature in the reaction device at 90 ℃, and reacting for 3 hours to ensure that the NCO content tends to be stable; and finally, keeping the temperature in the reaction device at 90 ℃, simultaneously vacuumizing until no bubbles exist in the system, and discharging to obtain the component A.

Example 12

Example 12 differs from example 11 in that: the amount of catalyst 1 added was 0.25 g.

Example 13

Example 13 differs from example 11 in that: the amount of catalyst 1 added was 0.5 g.

Example 14

Example 14 differs from example 11 in that:

the catalyst 1 is dibutyltin dilaurate and stannous octoate, and the dosage of the dibutyltin dilaurate and the stannous octoate is 0.005g respectively.

Example 15

Example 15 differs from example 3 in that:

the raw materials of the component B also comprise: 0.01g of catalyst 2, catalyst 2 in this example being 1, 2-bis (dimethylaminoethoxy) ethane.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; keeping the temperature in the reaction device at 80 ℃, adding 0.01g of 1, 2-bis (dimethylaminoethoxy) ethane, stirring for 0.8h, finally keeping the temperature in the reaction device at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Example 16

Example 16 differs from example 15 in that: the amount of catalyst 2 added was 0.1 g.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; keeping the temperature in the reaction device at 80 ℃, adding 0.1g of 1, 2-bis (dimethylaminoethoxy) ethane, stirring for 0.5h, finally keeping the temperature in the reaction device at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Example 17

Example 17 differs from example 15 in that: the amount of catalyst 2 added was 0.2 g.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; keeping the temperature in the reaction device at 90 ℃, adding 0.2g of 1, 2-bis (dimethylaminoethoxy) ethane, stirring for 1h, finally keeping the temperature in the reaction device at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Example 18

Example 18 differs from example 15 in that: catalyst 2 in this example was 1, 2-bis (dimethylaminoethoxy) ethane and N-methyldicyclohexylamine, and 1, 2-bis (dimethylaminoethoxy) ethane and N-methyldicyclohexylamine were used in an amount of 0.005 g.

Example 19

Example 19 differs from example 3 in that: the raw materials of the component A also comprise: 0.01g of catalyst 1, catalyst 1 being dibutyltin dilaurate; the raw materials of the component B also comprise: catalyst 2, 0.01g, catalyst 2 was 1, 2-bis (dimethylaminoethoxy) ethane.

The preparation of the component A comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; then, reducing the temperature in the reaction device to 50 ℃, firstly adding 0.01g of dibutyltin dilaurate, then adding diphenylmethane diisocyanate, controlling the reaction temperature in the reaction device to be 90 ℃, and reacting for 3 hours to ensure that the NCO content tends to be stable; and finally, keeping the temperature in the reaction device at 90 ℃, simultaneously vacuumizing until no bubbles exist in the system, and discharging to obtain the component A.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into another reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.01 percent; keeping the temperature in the reaction device at 90 ℃, adding 0.01g of 1, 2-bis (dimethylaminoethoxy) ethane, stirring for 1h, finally keeping the temperature in the reaction device at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Example 20

Example 20 differs from example 1 in that: the preparation method of the bi-component solvent-free polyurethane adhesive for textile fabric compounding in this embodiment is,

the preparation of the component A comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of a mixture in the reaction device to 0; then reducing the temperature in the reaction device to 50 ℃, adding diphenylmethane diisocyanate, controlling the reaction temperature in the reaction device at 50 ℃, and reacting for 3 hours to ensure that the NCO content tends to be stable; and finally, keeping the temperature in the reaction device at 90 ℃, simultaneously vacuumizing until no bubbles exist in the system, and discharging to obtain the component A.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into another reaction device, heating to 100 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0; and finally, keeping the temperature in the reaction device at 100 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Example 21

Example 21 differs from example 1 in that: the preparation method of the bi-component solvent-free polyurethane adhesive for textile fabric compounding in this embodiment is,

the preparation of the component A comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into a reaction device, heating to 120 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.02%; then reducing the temperature in the reaction device to 80 ℃, adding diphenylmethane diisocyanate, controlling the reaction temperature in the reaction device at 90 ℃, and reacting for 5 hours to ensure that the NCO content tends to be stable; and finally, keeping the temperature in the reaction device at 110 ℃, simultaneously vacuumizing until no bubbles exist in the system, and discharging to obtain the component A.

The preparation of the component B comprises the following steps:

firstly, putting ethylene oxide dihydric alcohol and polyester dihydric alcohol which are well proportioned into another reaction device, heating to 120 ℃, uniformly stirring and vacuumizing to reduce the water content of the mixture in the reaction device to 0.02%; and finally, keeping the temperature in the reaction device at 110 ℃, vacuumizing until no bubbles exist in the system, and discharging to obtain the component B.

Comparative example

Comparative example 1

Comparative example 1 is a commercial adhesive model HDP-2310.

Comparative example 2

Comparative example 2 differs from example 3 in that the polyester polyols in both component a and component B are replaced with equal amounts of 1, 4-butanediol adipate diol.

Comparative example 3

Comparative example 3 differs from example 3 in that the ethylene oxide diol in the feed is replaced with an equal amount of polytetrahydrofuran diol.

Performance detection

The following bond strength and viscosity tests were performed on the two-component solvent-free polyurethane adhesives provided in examples 1-21 of the present application and comparative examples 1-3, and the test data are shown in tables 3 and 4.

The specific test method comprises the following steps: adhering the adhesive between polyester fabric and TPU with the thickness of 0.06mm, curing for different times in the environment with the temperature of 23 ℃ and the humidity of 35%, and then carrying out various tests. The adhesive coating weights of the terylene cloth and the TPU are both 6g/m ² 。

The peel strength test method comprises the following steps: peel strength of TPU film having a width of 15mm, tensile machine speed 200mm/min, unit: n, final data for each test used the average of 5 sets of data totals.

The water washing strength test conditions are as follows: and (3) putting the finished cloth which is bonded and cured for a certain time into water at the temperature of 60 ℃, washing for 40 minutes, drying for 10 minutes in an environment at the temperature of 100 ℃, and then testing the peel strength.

The viscosity test method comprises the following steps: the viscosity of the polyurethane adhesive is tested by adopting a rotary viscometer, and the working principle of the rotary viscometer is as follows: the rotating drum is driven by a synchronous micromotor to rotate in the fluid to be measured at a certain speed, the rotating drum generates hysteresis under the action of the viscous force of the fluid, an elastic element connected with the rotating drum generates certain torsion in the reverse direction of the rotation, and the sensor measures the torsional stress, so that the viscosity value of the fluid is obtained.

TABLE 3

TABLE 4

The greater viscosity and lower peel strength of comparative example 1 compared to example 3, and the lower overall performance of the product of comparative example 1, demonstrate the better adhesion performance of the two-component solvent-free polyurethane adhesive of the present application.

The viscosity of comparative example 2 was high and the peel strength was low as compared with example 3, and the poly-1, 4-butylene adipate diol used in comparative example 2 did not exert excellent adhesive effects in the a-component and the B-component, indicating that the polyester polyol prepared according to the formulation systems of preparation examples 1 and 2 could improve the adhesive property of the polyurethane adhesive.

Compared with example 3, comparative example 2 of comparative example 3 has higher viscosity and lower peel strength, and polytetrahydrofuran diol in comparative example 3 cannot perform a good polycondensation reaction with polyester polyols prepared in preparation examples 1 and 2, which shows that polyether polyol used in the examples and polyester polyol prepared in preparation examples 1 and 2 have a special synergistic reaction effect, so that the polyurethane adhesive provided by the application has excellent bonding effect.

From the peel strength and viscosity results of examples 1-6, the two-component solvent-free polyurethane adhesive of the present application has good adhesion, with example 3 being the preferred example.

The peel strength in example 7 is higher than that in comparative example 1, and the viscosity in example 7 is lower than that in comparative example 1, compared to comparative example 1, indicating that only one polyester diol in the B component can still provide good adhesion properties to the polyurethane adhesive.

Compared with comparative example 1, the peel strength of examples 8-9 is higher than that of comparative example 1, and the viscosity of examples 8-9 is similar to that of example 3, which shows that the use of a plurality of polyether diols in component A helps to improve the cohesion and adhesion of the polyurethane adhesive.

The peel strength and viscosity of example 10 are similar to example 3 compared to example 3, indicating that the polyurethane adhesive still has excellent adhesion properties after the addition of various isocyanates.

Compared with the example 3, the peel strength of the examples 11 to 19 is obviously improved, and the viscosity of the examples 11 to 19 is similar to that of the example 3, which shows that the addition of the catalyst 1 to the component A and the addition of the catalyst 2 to the component B can improve the reaction rate and the activity of the component A and the component B, so that the polyurethane adhesive has better adhesive property.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The two-component solvent-free polyurethane adhesive for compounding the textile fabric is characterized by comprising a component A and a component B, wherein the component A comprises 25-60 parts of polyether polyol, 15-80 parts of polyester polyol and 10-55 parts of isocyanate, and the component B comprises 0-50 parts of polyether polyol and 40-100 parts of polyester polyol.

2. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein: the polyether polyol comprises a polyoxyethylene glycol.

3. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 2, wherein: the polyether polyol further comprises at least one of polyoxybutylene glycol and polyoxypropylene glycol.

4. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein the polyester polyol comprises the following components in parts by weight: 1060-1100 parts of polybasic acid, 405-660 parts of polyol and 0.1-0.5 part of polyester catalyst; the polybasic acid is at least one of adipic acid, dimer acid and hydrogenated dimer acid; the polyalcohol is at least one of dihydric alcohol, hydrogenated dihydric alcohol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanediol and 2-methyl-1, 3-propanediol; the polyester catalyst is at least one of tetrabutyl titanate and tetraisobutyl titanate.

5. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 4, wherein the polyester polyol is prepared according to the following method:

6. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein: the isocyanate is at least one of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, 4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and 1, 5-naphthalene diisocyanate.

7. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein the component A further comprises the following components in parts by weight: 0.01-0.5 part of catalyst 1, wherein the catalyst 1 is at least one of dibutyltin dilaurate, stannous octoate, zinc isooctoate and bismuth isooctanoate.

8. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein the component B further comprises the following components in parts by weight: 0.01-0.2 parts of catalyst 2, wherein the catalyst 2 is at least one of 1, 2-bis (dimethylaminoethoxy) ethane, N-methyl dicyclohexylamine, 1, 4-dimethyl piperazine, dimorpholinoethyl ether and dimorpholintriethyl ether.

9. The two-component solvent-free polyurethane adhesive for textile fabric compounding of claim 1, wherein: the weight ratio of the component A to the component B is 2 (1-3).

10. A preparation method of bi-component solvent-free polyurethane adhesive for textile fabric compounding is characterized by comprising the following steps,

the preparation steps of the component B are as follows: according to the proportion, polyether polyol and polyester polyol are uniformly mixed to obtain mixed alcohol B; heating the mixed alcohol B to 120 ℃ below zero, adjusting the water content of the mixed alcohol B to 0-0.02%, cooling the mixed alcohol B to 70-90 ℃, adding the catalyst 2, and uniformly stirring to obtain a pretreatment component B; heating the pretreatment component B to 90-100 ℃, and discharging bubbles to obtain a component B;