1. The polyurethane adhesive is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (8-15);

the component A comprises the following raw materials in parts by weight:

10-20 parts of castor oil based polyether polyol

20-30 parts of aromatic polyol

6-12 parts of aliphatic polyol

3-8 parts of polyester polyol with functionality of more than 2

Chain extender 1-5 parts

0.3 to 0.8 portion of antioxidant

0.02-0.1 part of catalyst

25-35 parts of environment-friendly solvent

0-1 part of end capping agent

8-12 parts of isocyanate;

the component B comprises the following raw materials in parts by weight:

8-12 parts of diisocyanate derivatives.

2. The polyurethane adhesive as claimed in claim 1, wherein the castor oil based polyether polyol has a molecular weight of 2000-3000, a functionality of 2-4, and a hydroxyl value of 50-100 mgKOH/g.

3. The polyurethane adhesive as claimed in claim 1, wherein the aromatic polyol is selected from terephthalic acid, phthalic anhydride, succinic acid, sebacic acid, adipic acid, ethylene glycol butanediol, pentanediol, bio-based propylene glycol, and diethylene glycol, and has a molecular weight of 3000-4000, a functionality of 2, and a hydroxyl value of 24-40mg KOH/g.

4. The polyurethane adhesive as claimed in claim 1, wherein the aliphatic polyol is selected from adipic acid, succinic acid, diethylene glycol, ethylene glycol and propylene glycol, has a molecular weight of 2500-.

5. The polyurethane adhesive of claim 1, wherein the polyester polyol with functionality greater than 2 is selected from the group consisting of adipic acid, diethylene glycol, propylene glycol, trimethylolpropane, and glycerol, and has a hydroxyl value of 50 to 60 mgKOH/g.

6. The polyurethane adhesive as claimed in claim 1, wherein the chain extender is one or more selected from the group consisting of ethylene glycol, butylene glycol, propylene glycol, pentylene glycol, hexylene glycol, aromatic diols, and alcohol amine diols; the antioxidant is one or a combination of several of an ultraviolet absorbent and a hindered amine light stabilizer; the catalyst is one or a combination of several of tertiary amine catalysts and organic bismuth catalysts.

7. The polyurethane adhesive of claim 1, wherein the environmentally friendly solvent is one or a combination of dimethyl carbonate, dibutyl phthalate, and n, n-diethylformamide; the capping agent includes a 2-functional compound, the 2-functional compound including propylene glycol, ethylene glycol, and/or butylene glycol.

8. The polyurethane adhesive of claim 1, wherein the isocyanate is one or more selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, isocyanate derivatives, and hexamethylene diisocyanate.

9. The polyurethane adhesive of claim 1, wherein the diisocyanate derivative is one or more selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isooctanoic acid, benzoic acid, polyester polyol, glycerol, trimethylolpropane, and ethyl acetate.

10. The method of any one of claims 1-9, comprising the steps of:

(1) preparation of component A

Weighing castor oil-based polyether polyol, aromatic polyol, aliphatic polyol, polyester polyol with the functionality of more than 2, a chain extender and an antioxidant according to a metering ratio, putting the materials into a reactor, stirring and mixing, then adding isocyanate weighed according to the metering ratio, stirring and mixing uniformly, adding a catalyst, detecting the viscosity, adding an environment-friendly solvent weighed according to the metering ratio for diluting when the viscosity reaches 40-50 ten thousand cps/50 ℃, detecting the viscosity after diluting, adding a capping agent when the viscosity reaches 1-2 ten thousand cps/25 ℃, and mixing uniformly to obtain a component A;

(2) preparation of component B

Dissolving glycerol, trimethylolpropane, antioxidant and ethyl acetate completely at 40 ℃ to obtain a component B1;

uniformly stirring and mixing toluene isocyanate and diphenylmethane diisocyanate, controlling the temperature to be 35-40 ℃, adding polyester polyol, reacting for 2-3h at the temperature of 80-90 ℃, cooling to 40 ℃, adding the dissolved component B1 for 6-10 times, controlling the reaction temperature to be 50-55 ℃, controlling the temperature to be 50-70 ℃ after dropwise adding, reacting for 6-8h, detecting to reach the required index, cooling to 40-50 ℃, and packaging;

the mass ratio of the glycerol to the trimethylolpropane to the antioxidant to the ethyl acetate to the toluene isocyanate to the diphenylmethane diisocyanate to the polyester polyol is 1-2: 2-5: 1-3: 3-7: 5-13: 6-10;

(3) preparation of polyurethane adhesive

When in use, the component A and the component B are mixed according to the proportion of 100: and (8-15), adding a proper amount of environment-friendly solvent, and uniformly mixing to obtain the required polyurethane adhesive.

Background

In recent years, the national economic level is continuously improved, the living quality of people is obviously improved, the environmental protection consciousness is gradually enhanced, and higher requirements are put forward on the quality of materials used for household articles such as clothes, sofas, curtains, automobile cushions and the like. Materials used for household articles are generally adhered by using a solvent type polyurethane adhesive, but the adhesive has great potential safety hazard due to the fact that a large amount of solvent is used, so that the environment and human bodies are greatly damaged, and in addition, the adhesive has room for improvement in adhesion fastness, water washing resistance and the like.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide a polyurethane adhesive and a preparation method thereof.

In order to achieve the purpose and achieve the technical effect, the invention adopts the technical scheme that:

the polyurethane adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (8-15);

the component A comprises the following raw materials in parts by weight:

10-20 parts of castor oil based polyether polyol

20-30 parts of aromatic polyol

6-12 parts of aliphatic polyol

3-8 parts of polyester polyol with functionality of more than 2

Chain extender 1-5 parts

0.3 to 0.8 portion of antioxidant

0.02-0.1 part of catalyst

25-35 parts of environment-friendly solvent

0-1 part of end capping agent

8-12 parts of isocyanate;

the component B comprises the following raw materials in parts by weight:

8-12 parts of diisocyanate derivatives.

Furthermore, the molecular weight of the castor oil based polyether polyol is 2000-3000, the functionality is 2-4, and the hydroxyl value is 50-100 mgKOH/g.

Furthermore, the aromatic polyol adopts one or a combination of more of terephthalic acid, phthalic anhydride, succinic acid, sebacic acid, adipic acid, ethylene glycol butanediol, pentanediol, bio-based propanediol and diethylene glycol, the molecular weight is 3000-4000, the functionality is 2, and the hydroxyl value is 24-40mg KOH/g.

Furthermore, the aliphatic polyhydric alcohol adopts one or a combination of more of adipic acid, succinic acid, diethylene glycol, ethylene glycol and propylene glycol, the molecular weight is 2500-3000, the functionality is 2, and the hydroxyl value is 35-42mg KOH/g.

Furthermore, the polyester polyol with the functionality of more than 2 adopts one or a combination of more of adipic acid, diethylene glycol, propylene glycol, trimethylolpropane and glycerol, and the hydroxyl value is 50-60 mgKOH/g.

Further, the chain extender is one or a combination of more of ethylene glycol, butanediol, propylene glycol, pentanediol, hexanediol, aromatic diol and alcohol amine diol; the antioxidant is one or a combination of several of an ultraviolet absorbent and a hindered amine light stabilizer; the catalyst is one or a combination of several of tertiary amine catalysts and organic bismuth catalysts.

Further, the environment-friendly solvent is one or a combination of more of dimethyl carbonate, dibutyl phthalate and N, N-diethylformamide; the capping agent includes a 2-functional compound, the 2-functional compound including propylene glycol, ethylene glycol, and/or butylene glycol.

Furthermore, the isocyanate is one or a combination of several of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, isocyanate derivatives and hexamethylene diisocyanate.

Further, the diisocyanate derivative is one or a combination of several of toluene diisocyanate, diphenylmethane diisocyanate, isooctanoic acid, benzoic acid, polyester polyol, glycerol, trimethylolpropane and ethyl acetate.

The invention discloses a preparation method of a polyurethane adhesive, which comprises the following steps:

(1) preparation of component A

Weighing castor oil-based polyether polyol, aromatic polyol, aliphatic polyol, polyester polyol with the functionality of more than 2, a chain extender and an antioxidant according to a metering ratio, putting the materials into a reactor, stirring and mixing, then adding isocyanate weighed according to the metering ratio, stirring and mixing uniformly, adding a catalyst, detecting the viscosity, adding an environment-friendly solvent weighed according to the metering ratio for diluting when the viscosity reaches 40-50 ten thousand cps/50 ℃, detecting the viscosity after diluting, adding a capping agent when the viscosity reaches 1-2 ten thousand cps/25 ℃, and mixing uniformly to obtain a component A;

(2) preparation of component B

Dissolving glycerol, trimethylolpropane, antioxidant and ethyl acetate completely at 40 ℃ to obtain a component B1;

uniformly stirring and mixing toluene isocyanate and diphenylmethane diisocyanate, controlling the temperature to be 35-40 ℃, adding polyester polyol, reacting for 2-3h at the temperature of 80-90 ℃, cooling to 40 ℃, adding the dissolved component B1 for 6-10 times, controlling the reaction temperature to be 50-55 ℃, controlling the temperature to be 50-70 ℃ after dropwise adding, reacting for 6-8h, detecting to reach the required index, cooling to 40-50 ℃, and packaging;

the mass ratio of the glycerol to the trimethylolpropane to the antioxidant to the ethyl acetate to the toluene isocyanate to the diphenylmethane diisocyanate to the polyester polyol is 1-2: 2-5: 1-3: 3-7: 5-13: 6-10;

(3) preparation of polyurethane adhesive

When in use, the component A and the component B are mixed according to the proportion of 100: and (8-15), adding a proper amount of environment-friendly solvent, and uniformly mixing to obtain the required polyurethane adhesive.

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

the invention discloses a polyurethane adhesive and a preparation method thereof, wherein the polyurethane adhesive comprises a component A and a component B, and the mass ratio of the component A to the component B is 100: (8-15); the component A comprises the following raw materials in parts by weight: 10-20 parts of castor oil based polyether polyol, 20-30 parts of aromatic polyol, 6-12 parts of aliphatic polyol, 3-8 parts of polyester polyol with functionality greater than 2, 1-5 parts of chain extender, 0.3-0.8 part of antioxidant, 0.02-0.1 part of catalyst, 25-35 parts of environment-friendly solvent, 0-1 part of end-capping reagent and 8-12 parts of isocyanate; the component B comprises the following raw materials in parts by weight: 8-12 parts of diisocyanate derivatives. According to the polyurethane adhesive and the preparation method thereof provided by the invention, the castor oil-based polyether polyol is prepared by using the natural vegetable oil polyol castor oil, and then the A component is prepared by combining the aromatic polyol, the aliphatic polyol, the polyester polyol with the functionality of more than 2, the chain extender and other additives, the castor oil can be used without being modified by a chemical method, the ester group of the castor oil can be subjected to hydrolysis reaction to generate fatty acid, the biodegradable polyurethane adhesive has biodegradability and wide raw material sources; the component A and the component B are cooperated to prepare the polyurethane adhesive, the fastness and the washing resistance of the product are greatly improved through the component B, compared with the prior art, the chain extender of the component A contains the polyhydric alcohol with the branching degree of more than 2, a network polymer can be formed, the polyurethane adhesive with the required viscosity can be obtained after the addition reaction with the component B, plasticizers, coupling agents and the like are not needed, the used materials are few, no solvent residue is left, the polyurethane adhesive has biodegradability and is more environment-friendly, the smell is low, the harm to a human body is small, DMF (N.N dimethylformamide) is not contained, the unit consumption is low, the yield is high, and the polyurethane adhesive is suitable for household articles such as clothes, sofas, curtains, automobile cushions and the like.

Detailed Description

The following detailed description of the embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention.

Example 1

A method of preparing a polyurethane adhesive comprising the steps of:

(1) preparation of component A

Firstly, adding 10 parts of castor oil-based polyether polyol, 30 parts of aromatic polyester polyol, 7 parts of aliphatic polyol, 3 parts of polyester polyol with the functionality of more than 2, 1 part of chain extender and 0.5 part of antioxidant into a reaction kettle, heating to 55-60 ℃, adding 6.5 parts of toluene diisocyanate, heating to 70-90 ℃, reacting for 2-4h, cooling to 45-60 ℃, adding 2.2 parts of chain extender, adding 4.5 parts of diphenylmethane diisocyanate, heating to 70-90 ℃, reacting for 1-2h, adding 0.02 part of catalyst, continuing to react for 6-8h, cooling to 40-60 ℃, adding 25 parts of environment-friendly solvent, and diluting to obtain a required index, thus obtaining a component A;

(2) preparation of component B

Dissolving glycerol, trimethylolpropane, antioxidant and ethyl acetate completely at 40 ℃ to obtain a component B1;

uniformly stirring and mixing toluene isocyanate and diphenylmethane diisocyanate, controlling the temperature to be 35-40 ℃, adding polyester polyol, reacting for 2-3h at the temperature of 80-90 ℃, cooling to 40 ℃, adding the dissolved component B1 for 6-10 times, controlling the reaction temperature to be 50-55 ℃, controlling the temperature to be 50-70 ℃ after dropwise adding, reacting for 6-8h, detecting to reach the required index, cooling to 40-50 ℃, and packaging;

the mass ratio of glycerol, trimethylolpropane, antioxidant, ethyl acetate, toluene isocyanate, diphenylmethane diisocyanate and polyester polyol is 1: 3: 2: 5: 10: 9.

(3) preparation of polyurethane adhesive

And (3) uniformly mixing 100 parts of the component A and 8 parts of the component B, adding 40-60 parts of the environment-friendly solvent, and uniformly stirring to obtain the polyurethane adhesive for spinning.

Example 2

A method of preparing a polyurethane adhesive comprising the steps of:

(1) preparation of component A

Firstly, adding 15 parts of castor oil based polyether polyol, 28 parts of aromatic polyester polyol, 12 parts of aliphatic polyol, 5 parts of polyester polyol with the functionality of more than 2, 0.3 part of antioxidant and 1.5 parts of chain extender into a reaction kettle, heating to 55-60 ℃, adding 5.5 parts of toluene diisocyanate, heating to 70-90 ℃, reacting for 2-4h, cooling to 45-60 ℃, adding 2.2 parts of chain extender, adding 5.5 parts of diphenylmethane diisocyanate, heating to 70-90 ℃, reacting for 1-2h, adding 0.1 part of catalyst, continuing to react for 6-8h, cooling to 40-60 ℃, adding 28 parts of environment-friendly solvent for dilution, detecting viscosity after dilution is finished, adding 0.5 part of propylene glycol when the viscosity reaches 1-2 ten thousand cps/25 ℃, and uniformly mixing to obtain a component A;

(2) preparation of component B

Dissolving glycerol, trimethylolpropane, antioxidant and ethyl acetate completely at 40 ℃ to obtain a component B1;

uniformly stirring and mixing toluene isocyanate and diphenylmethane diisocyanate, controlling the temperature to be 35-40 ℃, adding polyester polyol, reacting for 2-3h at the temperature of 80-90 ℃, cooling to 40 ℃, adding the dissolved component B1 for 6-10 times, controlling the reaction temperature to be 50-55 ℃, controlling the temperature to be 50-70 ℃ after dropwise adding, reacting for 6-8h, detecting to reach the required index, cooling to 40-50 ℃, and packaging;

(3) preparation of polyurethane adhesive

And (3) uniformly mixing 100 parts of the component A and 12 parts of the component B, adding 40-60 parts of the environment-friendly solvent, and uniformly stirring to obtain the polyurethane adhesive for spinning.

The same as in example 1.

Example 3

A method of preparing a polyurethane adhesive comprising the steps of:

(1) preparation of component A

Firstly, adding 20 parts of castor oil-based polyether polyol, 22 parts of aromatic polyester polyol, 6 parts of aliphatic polyol, 7 parts of polyester polyol with the functionality of more than 2, 0.8 part of chain extender and 0.8 part of antioxidant into a reaction kettle, heating to 55-60 ℃, adding 8.5 parts of toluene diisocyanate, heating to 70-90 ℃, reacting for 2-4h, cooling to 45-60 ℃, adding 4.2 parts of chain extender, adding 2.5 parts of diphenylmethane diisocyanate, heating to 70-90 ℃, reacting for 1-2h, adding 0.05 part of catalyst, continuing to react for 6-8h, cooling to 40-60 ℃, adding 32 parts of environment-friendly solvent for dilution, detecting the viscosity after dilution, adding 0.5 part of ethylene glycol end-capping agent after the viscosity reaches 1-2 ten thousand cps/25 ℃, uniformly mixing, obtaining the component A;

(2) preparation of component B

Dissolving glycerol, trimethylolpropane, antioxidant and ethyl acetate completely at 40 ℃ to obtain a component B1;

uniformly stirring and mixing toluene isocyanate and diphenylmethane diisocyanate, controlling the temperature to be 35-40 ℃, adding polyester polyol, reacting for 2-3h at the temperature of 80-90 ℃, cooling to 40 ℃, adding the dissolved component B1 for 6-10 times, controlling the reaction temperature to be 50-55 ℃, controlling the temperature to be 50-70 ℃ after dropwise adding, reacting for 6-8h, detecting to reach the required index, cooling to 40-50 ℃, and packaging;

(3) preparation of polyurethane adhesive

And (3) uniformly mixing 100 parts of the component A and 12 parts of the component B, adding 40-60 parts of the environment-friendly solvent, and uniformly stirring to obtain the polyurethane adhesive for spinning.

The same as in example 1.

Comparative example 1

The existing commercial products are adopted.

The performance analysis of examples 1-3 and comparative example 1 is shown in table 1.

TABLE 1

The parts of the invention not specifically described can be realized by adopting the prior art, and the details are not described herein.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.