CN110606934A - Environment-friendly water-based anionic polyurethane adhesive and preparation method thereof - Google Patents
Environment-friendly water-based anionic polyurethane adhesive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Abstract
In the preparation process of the water-based adhesive, a large amount of organic solvents (such as acetone, butanone and the like) are needed to reduce the viscosity of a reaction system, the later-stage solvent recovery not only increases the complexity of the process and the manufacturing cost, but also influences the product quality, and meanwhile, the large amount of the organic solvents in the preparation process increases the VOCs content of shoe materials. In order to solve the problems, the invention provides a preparation method of an environment-friendly water-based anionic polyurethane adhesive, which adopts dendritic polyamidoamine as a chain extender, and does not need or needs a small amount of acetone to reduce the viscosity of a system; the dendritic polyamidoamine does not need to be dissolved in a nonvolatile organic solvent, so that the use of the organic solvent in the synthesis process is reduced, and the pollution to the environment can be reduced to the minimum; the synthesized environment-friendly water-based anionic polyurethane adhesive emulsion has small particle size and good permeability and adhesive force to base materials.
Description
Technical Field
The invention belongs to the field of high polymer chemical materials, relates to a water-based polyurethane adhesive, and particularly relates to an environment-friendly water-based anionic polyurethane adhesive and a preparation method thereof.
Background
In the preparation process of the water-based adhesive, a large amount of organic solvents (such as acetone, butanone and the like) are needed to reduce the viscosity of a reaction system, and the solvent recovery in the later period not only increases the complexity of the process and the manufacturing cost, but also influences the product quality. For the use and treatment of acetone, domestic patents report, for example, CN108179001A discloses a waterborne environment-friendly polyurethane adhesive and a manufacturing process and application thereof, wherein 7.5 parts of acetone is added in the preparation method to reduce the viscosity of the material, and then the reaction kettle is subjected to rotary evaporation to remove the acetone; the waterborne polyurethane disclosed in CN102516920A and the preparation method thereof also add a large amount of acetone for reducing viscosity, and then rotationally evaporate and recover the acetone.
At present, the requirement on environmental protection is higher and higher, and the following problems exist when the waterborne polyurethane adhesive is used as the adhesive for third-generation shoes: firstly, the non-degradable material in the shoe material shoe glue aggravates white pollution; secondly, the use of a large amount of organic solvent in the preparation process increases the VOCs content of the shoe material. In order to solve the above problems, the use of organic solvents or the content of organic solvents, particularly acetone, should be reduced as much as possible during the development of aqueous polyurethanes.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly water-based anionic polyurethane adhesive, which reduces the viscosity of a prepolymer and reduces or even avoids the use of an organic solvent.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an environment-friendly aqueous anionic polyurethane adhesive mainly comprises the following steps:
(1) mixing one or more diisocyanate with dihydric alcohol, and reacting under the action of a catalyst to form a polyurethane prepolymer;
(2) dendritic polyamidoamine and an anionic hydrophilic chain extender are sequentially added into the polyurethane prepolymer, and then neutralized into salt by triethylamine, and the environment-friendly water-based anionic polyurethane adhesive is obtained by dispersion and emulsification.
In the method, the dendritic macromolecule-dendritic polyamidoamine is added as a chain extender, so that polar groups can be effectively introduced, the viscosity of the polyurethane prepolymer is reduced, and the use of organic solvents is greatly reduced.
Dendrimers (dendrimers) refer to organic molecules with a branched structure. The dendritic structure is divided into two types, one type is an ideal perfect dendritic structure, and generally, if no special description is provided, all dendritic molecules refer to perfect structures; also an organic molecule is a defective dendritic structure, which is commonly referred to as a hyperbranched molecule. In 1978, Vogtle et al reported that a branch distribution structure was obtained by an iterative method for the first time, and proposed the idea of repeated synthesis for the first time; in 1979, Denkewelter synthesizes dendritic macromolecules based on l-lysine for the first time, and the performance of the dendritic macromolecules is characterized; tomalia of DOW chemical company and Newkome of California's institute of technology proposed the dendrimer concept in 1985 and synthesized two different dendrimers separately.
The structure of the dendrimer has the following characteristics:
a) precise molecular structure: can be strictly controlled at the molecular level, and the molecular weight dispersion coefficient is approximately 1;
a) high geometric symmetry: structural uniformity;
b) a large number of functional groups: the versatility;
c) the molecule has an inner cavity: host-guest chemistry and molecular catalysis;
d) the molecular weight has controllability: derived from its synthesis;
e) the molecules themselves have a nanometer size: spherical structures, several to tens of nanometers.
Dendritic macromolecules have brought some excellent performance characteristics due to structural characteristics:
a) good fluid mechanical property, which is beneficial to molding processing; can be used as rheology modifier;
b) a unique viscosity behavior, with the intrinsic viscosity showing a maximum as the molecular weight increases;
c) easy film formation, a great deal of research has been conducted in the field of film science;
d) the multifunctionality is caused by the existence of a large number of functional groups on the surface;
e) is not easy to crystallize and is determined by the highly branched structure;
f) unique density and distribution, with minimal density as molecular weight increases;
g) a unique refractive index increase, which is found to be at a maximum with increasing molecular weight;
h) good thermal stability.
Under the condition of the same molecular weight, the dendritic polyamidoamine adopted by the invention has smaller hydrodynamic volume and smaller viscosity than linear macromolecules, and organic solvents such as acetone and the like are not needed or are added in a small amount in the chain extension process to reduce the viscosity of the system.
Preferably, the molecular weight of the dendritic polyamidoamine is 500-2500. The molecular weight is large, the end group density is small, and the reaction activity is low, so the molecular weight is selected to be between 500 and 2500.
Preferably, the dendritic polyamidoamine is dendritic hydroxyl-terminated polyamidoamine or dendritic amino-terminated polyamidoamine. In the synthesis process, hydroxyl-terminated dendritic macromolecules or dendritic amino-terminated polyamidoamines are used as chain extenders, so that the viscosity of polyurethane prepolymers can be reduced, polar groups can be effectively introduced, and the use of organic solvents is further reduced.
Preferably, the first generation dendrimer OHTD1 or the second generation dendrimer OHTD2 has the following structure:
the dendritic polyamidoamine is dendritic hydroxyl-terminated polyamidoamine of more branches such as 3 branches, 6 branches, 8 branches and the like; or a higher generation dendritic hydroxyl-terminated polyamidoamine; or a great number of polar functional groups, such as carboxyl, amino, sulfonic acid and the like, are connected on the outer surface of the dendritic polyamidoamine. The external surface is connected with a large number of polar functional groups, so that the overall polarity of the dendritic molecules can be effectively increased, namely the water solubility is improved, and the use of organic solvents is reduced.
Preferably, the dispersion and emulsification step is to dissolve ethylenediamine in deionized water to prepare an ethylenediamine solution, and then disperse, chain extend and emulsify the polyurethane prepolymer in the ethylenediamine solution. If ethylene diamine is added for chain extension before neutralization, the product viscosity will be very high, and a large amount of organic solvent is required to reduce the viscosity. Therefore, the chain extension reaction of the ethylenediamine is controlled to be carried out in water and is placed after the neutralization step, the use of organic solvents can be effectively reduced, and the environmental protection requirement is met.
Preferably, the particle size of the emulsion in the environment-friendly water-based anionic polyurethane adhesive is less than 40 nm. The emulsion has the particle size of below 40nm, good stability and stronger adhesive force.
Preferably, the diisocyanate is isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI);
preferably, the dihydric alcohol is a degradable dihydric alcohol, such as polycaprolactone dihydric alcohol and polylactic acid dihydric alcohol.
Preferably, the diisocyanate and the diol are added by a peristaltic pump, which is effective to keep the feeding rate consistent.
Preferably, the catalyst is dibutyltin dilaurate or bismuth isooctanoate;
preferably, the anionic hydrophilic chain extender is: one of dimethylolpropionic acid, dihydroxybutyric acid, diaminobenzoic acid, tartaric acid, 1, 4-butanediol-2-sodium sulfonate, 1, 3-dicarboxybenzenesulfonic acid sodium salt or ethylenediamine ethanesulfonic acid sodium salt. .
Preferred weak bases are triethylamine or NH4OH。
The invention has the following advantages and beneficial effects:
in the synthesis process of the environment-friendly water-based anionic polyurethane adhesive, dendritic polyamidoamine is used as a chain extender, and the system does not need or needs a small amount of acetone to reduce the viscosity; the dendritic polyamidoamine does not need to be dissolved in a nonvolatile organic solvent, so that the use of the organic solvent in the synthesis process is reduced, and the pollution to the environment can be reduced to the minimum; the synthesized environment-friendly water-based anionic polyurethane adhesive emulsion has small particle size and good permeability and adhesive force to base materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 60g of polycaprolactone diol (Mn is 3000) into a 250mL three-neck flask, adding 0.078g of bismuth isooctanoate, adding a mixture of 1.74g of toluene diisocyanate and 6.66 g of isophorone diisocyanate by using a peristaltic pump, and heating to 80 ℃ for reaction for 2 hours;
(2) adding 0.375g of dendritic hydroxyl-terminated polyamide-amine OHTD1, and reacting for 2 h; adding 1.5g of 2, 2-dimethylolpropionic acid, continuing to react for 2 hours, cooling to 40 ℃, adding 1.13g of triethylamine for neutralization, and reacting for 1 hour; dissolving 0.36g of ethylenediamine in 120g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive. The synthesized anionic polyurethane adhesive emulsion has small particle size (less than 40nm), strong permeability and strong adhesive property.
In the synthesis process of the polyurethane adhesive, by introducing the dendritic hydroxyl-terminated polyamide-amine with low viscosity, high polarity and good water solubility, the system does not need to be dissolved in a difficult-to-volatilize organic solvent, and does not need volatile organic solvents such as acetone and the like to reduce the viscosity, and the organic solvent is not used in the whole process, so that the pollution to the environment can be minimized, and the preparation method is an excellent preparation method for obtaining an environment-friendly anionic polyurethane adhesive product.
Example 2
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 60g of polycaprolactone diol (Mn is 3000) into a 250mL three-neck flask, adding 0.042g of dibutyltin dilaurate, then adding a mixture of 8.88g of isophorone diisocyanate and 3.36g of hexamethylene diisocyanate by using a peristaltic pump, and heating to 80 ℃ for reaction for 2 hours;
(2) adding 5.04g of dendritic hydroxyl-terminated polyamidoamine OHTD2, and reacting for 2 h; adding 1.77g of 2, 2-dimethylolbutyric acid, continuing to react for 2 hours, cooling to 40 ℃, adding 1ml of ammonia water for neutralization, and reacting for 1 hour; dissolving 0.72g of ethylenediamine in 100g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive.
Example 3
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 40g of polycaprolactone diol (Mn ═ 2000) into a 250mL three-necked flask, adding 0.066g of dibutyltin dilaurate, then adding a mixture of 13.32g of isophorone diisocyanate and 3.48g of dicyclohexylmethane diisocyanate by using a peristaltic pump, and heating to 80 ℃ for reaction for 2 hours;
(2)5.50g of dendritic hydroxyl-terminated polyamidoamine (OHTD1), reaction for 2 h; 2.25g of diaminobenzoic acid, reacting for 2 hours, cooling to 40 ℃, adding 1.54g of triethylamine for neutralization, and reacting for 1 hour; dissolving 0.72g of ethylenediamine in 100g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive.
Example 4
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 20g of polycaprolactone diol (Mn is 1000) into a 250mL three-neck flask, adding 0.042g of dibutyltin dilaurate, adding 22.22g of dicyclohexylmethane diisocyanate by using a peristaltic pump, and heating to 80 ℃ to react for 2 hours;
(2) 8.16g of dendritic hydroxyl-terminated polyamidoamine (OHTD1) is added for reaction for 2 h; 2.58g of ethylenediamine ethanesulfonic acid sodium salt, reacting for 2 hours, cooling to 40 ℃, adding 1.76 triethylamine for neutralization, and reacting for 1 hour; dissolving 0.86g of ethylenediamine in 60g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive.
Example 5
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 40g of polylactic acid dihydric alcohol (Mn ═ 2000) into a 250mL three-neck flask, adding 0.023g of dibutyltin dilaurate, then adding 13.32g of isophorone diisocyanate by a peristaltic pump, heating to 80 ℃ and reacting for 2 hours;
(2) adding 5.04g of dendritic amino-terminated polyamidoamine for reaction for 2 h; 1.76g of tartaric acid, reacting for 2 hours, cooling to 40 ℃, adding 1.33 triethylamine for neutralization, and reacting for 1 hour; dissolving 0.54g of ethylenediamine in 100g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive.
Example 6
The preparation method of the environment-friendly anionic polyurethane adhesive comprises the following steps:
(1) adding 40g of polycaprolactone diol (Mn ═ 2000) into a 250mL three-neck flask, adding 0.055g of dibutyltin dilaurate, adding a mixture of 8.88g of isophorone diisocyanate and 6.72g of hexamethylene diisocyanate by using a peristaltic pump, and heating to 80 ℃ for reaction for 2 hours;
(2) adding 9.42g of dendritic amino-terminated polyamidoamine for reaction for 2 h; adding 2.25g of 1, 4-butanediol-2-sodium sulfonate, reacting for 2 hours, cooling to 40 ℃, adding 1.54g of triethylamine for neutralization, and reacting for 1 hour; dissolving 0.72g of ethylenediamine in 100g of deionized water to prepare an ethylenediamine solution, mechanically stirring at a high speed, and emulsifying the prepolymer in the diethylamine solution to obtain the anionic polyurethane adhesive.
Example 7
The structural properties of the anionic polyurethane adhesives prepared in examples 1 to 6, including molecular weight, PDI, solid content, viscosity, particle size, potential, initial adhesion PU/PVC, are characterized, and the structural properties of the anionic polyurethane adhesives are detailed in Table 1.
TABLE 1 structural Properties of anionic polyurethane Adhesives
Viscosity: measured using an NDJ-8T viscometer.
The patent application No. CN106189994 discloses an environment-friendly waterborne polyurethane adhesive for artificial leather and a preparation method thereof, the adhesive film viscosity is 51634mPa & s, and the peeling strength (PU/PVC) is only 4.21 KN/m.
The patent CN105732939 discloses a waterborne polyurethane adhesive, a preparation method and a waterborne polyurethane adhesive, the peeling strength is only 2.55-3.10 KN/m.
The invention adopts dendritic amino-terminated polyamide amine to synthesize the environment-friendly anionic polyurethane adhesive, the particle size of the emulsion is below 40nm and between 10nm and 30nm, and the stability of the emulsion is good; the peel strength (PU/PVC) is higher than 6KN/m, which is higher than that of the materials given in the two patents, and shows stronger adhesion.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the environment-friendly water-based anionic polyurethane adhesive is characterized by mainly comprising the following steps:
1) mixing one or more diisocyanate with dihydric alcohol, and reacting under the action of a catalyst to form a polyurethane prepolymer;
2) dendritic polyamidoamine and an anionic hydrophilic chain extender are sequentially added into the polyurethane prepolymer, and then neutralized into salt by triethylamine, and the environment-friendly water-based anionic polyurethane adhesive is obtained by dispersion and emulsification.
2. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive according to claim 1, wherein the molecular weight of the dendritic polyamidoamine is 500-2500.
3. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive as claimed in claim 1, wherein the dendritic polyamidoamine is dendritic hydroxyl-terminated polyamidoamine or dendritic amino-terminated polyamidoamine.
4. The method for preparing environment-friendly aqueous anionic polyurethane adhesive according to claim 1, wherein the dendritic hydroxyl-terminated polyamidoamine is OHTD1 or OHTD2, and the molecular structure is as follows:
5. the method for preparing the environment-friendly aqueous anionic polyurethane adhesive as claimed in claim 1, wherein the step of dispersing and emulsifying comprises dissolving ethylenediamine in deionized water to prepare an ethylenediamine solution, and then dispersing, chain extending and emulsifying the polyurethane prepolymer in the ethylenediamine solution.
6. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive as claimed in claim 1, wherein the particle size of the emulsion in the environment-friendly aqueous anionic polyurethane adhesive is below 40 nm.
7. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive according to claim 1, wherein the diisocyanate is isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), dicyclohexylmethane diisocyanate (HMDI).
8. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive according to claim 1, wherein the dihydric alcohol is a degradable dihydric alcohol, such as polycaprolactone dihydric alcohol and polylactic acid dihydric alcohol.
9. The method for preparing the environment-friendly aqueous anionic polyurethane adhesive according to claim 1, wherein the catalyst is dibutyltin dilaurate or bismuth isooctanoate.
10. The preparation method of the environment-friendly aqueous anionic polyurethane adhesive as claimed in claim 1, wherein the anionic hydrophilic chain extender is: one of dimethylolpropionic acid, dihydroxybutyric acid, diaminobenzoic acid, tartaric acid, 1, 4-butanediol-2-sodium sulfonate, 1, 3-dicarboxybenzenesulfonic acid sodium salt or ethylenediamine ethanesulfonic acid sodium salt.
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| CN112708104A (en) * | 2020-12-25 | 2021-04-27 | 合肥科天水性科技有限责任公司 | Heat-resistant and water-resistant waterborne polyurethane resin and preparation method thereof |
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