CN108373900B - Waterborne polyurethane adhesive and preparation method thereof - Google Patents

Waterborne polyurethane adhesive and preparation method thereof Download PDF

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CN108373900B
CN108373900B CN201810192148.8A CN201810192148A CN108373900B CN 108373900 B CN108373900 B CN 108373900B CN 201810192148 A CN201810192148 A CN 201810192148A CN 108373900 B CN108373900 B CN 108373900B
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cyclohexane
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isocyanatomethyl
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CN108373900A (en
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李满林
胡赞军
刘志军
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GUANGDONG TAIQIANG TECHNOLOGY INDUSTRY CO.,LTD.
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Shenzhen Taiqiang Chemicals Co ltd
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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
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/70—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
    • C08G18/757—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 at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the field of adhesives, in particular to a water-based polyurethane adhesive which is prepared from the following components in percentage by weight: 20-30% of dihydric alcohol; 30-50% of diisocyanate and the balance of water; wherein the dihydric alcohol is one or a mixture of cyclohexane dihydric alcohol, 1, 6-hexanediol and D-glucitol; the diisocyanate is composed of at least one cis-isocyanate and at least one trans-isocyanate in 1, 3-cis bis (isocyanatomethyl) cyclohexane, 1, 3-trans bis (isocyanatomethyl) cyclohexane, 1, 4-cis bis (isocyanatomethyl) cyclohexane and 1, 4-trans bis (isocyanatomethyl) cyclohexane.

Description

Waterborne polyurethane adhesive and preparation method thereof
Technical Field
The invention relates to the field of chemical industry, in particular to a water-based polyurethane adhesive and a preparation method thereof.
Background
The application and research of the domestic waterborne polyurethane adhesive are still in the beginning stage. The Riming chemical research institute develops an external crosslinking type cationic aqueous dispersion adhesive J I961 which can be used for bonding ABS/nylon, PVC/PE foam, canvas/metal, glass fiber reinforced plastic/PS foam and the like. The research work in the aspect is carried out successively by the Chenguang research institute, the university of Anhui and Shanxi chemical research institute, from the viewpoint of product structure, the emulsion type is mainly adopted, the water solubility is inferior, the raw materials are mostly polyether polyol and TDI, and the preparation method is generally a self-emulsifying, carboxylic acid type and anionic system. However, the application level of the water-based adhesive is not high, a plurality of manufacturers are provided, the variety is single, and a large number of commodities are not on the market.
The polyurethane adhesive for high-grade vehicles in China is basically imported at present, the technical scales of independent development of several families in China are small, equipment and processes are behind than foreign matters, the product performance is poorer than foreign matters, and the polyurethane adhesive is not competitive with imported products of large foreign companies at present. Therefore, the development and industrialization of the high-performance water-based polyurethane adhesive for the vehicle can improve the competitiveness of the vehicle adhesive industry in China.
Therefore, in the present stage, research is focused on realizing localization of the high-grade automotive polyurethane adhesive and improving the adhesive strength and curing speed of the high-grade automotive polyurethane adhesive. Moreover, most domestic polyurethane adhesives can exert a better initial adhesion effect only by heating at normal temperature, which is very inconvenient in industrial application.
Disclosure of Invention
The invention aims to provide a waterborne polyurethane adhesive and a preparation method thereof, the waterborne polyurethane adhesive has the advantages of high bonding strength and high curing speed, and the defect that the traditional polyurethane adhesive can exert the primary bonding effect only at high temperature is overcome.
The technical scheme provided by the invention is as follows: the waterborne polyurethane adhesive is prepared from the following components in percentage by weight:
20-30% of dihydric alcohol;
30-50% of diisocyanate and the balance of water;
wherein the dihydric alcohol is one or a mixture of cyclohexane dihydric alcohol, 1, 6-hexanediol and D-glucitol;
the diisocyanate is composed of at least one cis-isocyanate and at least one trans-isocyanate in 1, 3-cis bis (isocyanatomethyl) cyclohexane, 1, 3-trans bis (isocyanatomethyl) cyclohexane, 1, 4-cis bis (isocyanatomethyl) cyclohexane and 1, 4-trans bis (isocyanatomethyl) cyclohexane.
The waterborne polyurethane adhesive is prepared from the following components in percentage by weight:
23-28% of dihydric alcohol;
35-45% of diisocyanate and the balance of water.
In the above aqueous polyurethane adhesive, the weight ratio of cis-isocyanate to trans-isocyanate in the diisocyanate is 1: 1-1: 2.
the waterborne polyurethane adhesive is prepared from the following components in percentage by weight:
23-25% of dihydric alcohol;
37-43% of diisocyanate;
3-5% of isomeric alcohol polyoxyethylene ether;
and the balance water;
the molar mass of the isomeric alcohol polyoxyethylene ether is between 430 and 500 g/mol; the number of EO repeating units is between 5 and 7.
Meanwhile, the invention also discloses a preparation method of the waterborne polyurethane adhesive, which comprises the following steps:
step 1: mixing dihydric alcohol, isomeric alcohol polyoxyethylene ether and water, and adding diisocyanate in a dropwise manner for 2-3h at a reaction temperature of 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender, and continuing to react for 1-2h at constant temperature;
and step 3: adding a pH regulator and water to regulate the pH value and solid content of the system;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 0.5-1h at constant temperature.
In the preparation method of the aqueous polyurethane adhesive, in the step 2, the hydrophilic chain extender is dimethylolpropionic acid or N-methylpyrrolidone; the amount of which is 3-4% by weight of the diisocyanate.
In the preparation method of the waterborne polyurethane adhesive, the pH regulator is triethanolamine.
In the preparation method of the aqueous polyurethane adhesive, the amount of the ethylenediamine used in the step 4 is 1-1.5% of the weight of the diisocyanate.
Has the advantages that:
the continuous composite synthesis method adopted by the invention introduces an internal emulsification mechanism, searches out a synthesis process of a continuous feeding method, and prepares a series of high-solid-content waterborne polyurethane emulsions. And the relationship between the experimental process and the particle size of the emulsion, the molecular chain structure, the coating performance and the application of the waterborne polyurethane is discussed. And preparing the polyurethane aqueous dispersion with high bonding strength and high curing speed according to the actual use requirement of the emulsion type adhesive. The method has obvious innovation in the preparation process of the waterborne polyurethane.
In the invention, hydrophilic isomeric alcohol ether is used as a functional monomer, which can improve the initial adhesion of the product while improving the hydrophilicity of the product.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.
Example one
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (cyclohexane dihydric alcohol) and water, and adding diisocyanate (1, 3-cis-bis (isocyanatomethyl) cyclohexane: 1, 4-trans-bis (isocyanatomethyl) cyclohexane: 1) in a dropwise manner, wherein the dropwise addition time is 2.5 hours, and the reaction temperature is 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 0.5-1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 20 parts by weight;
40 parts by weight of diisocyanate;
1.5 parts of hydrophilic chain extender;
0.4 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
Example 2
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (1, 6-hexanediol) and water, and adding diisocyanate (1, 3-cis-bis (isocyanatomethyl) cyclohexane: 1, 4-trans-bis (isocyanatomethyl) cyclohexane: 1: 2) in a dropwise manner for 2 hours at the reaction temperature of 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 1h at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 25 parts by weight;
50 parts by weight of diisocyanate;
2 parts of hydrophilic chain extender;
0.7 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
Example 3
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (D-glucitol) and water, and adding diisocyanate (1, 4-cis-bis (isocyanatomethyl) cyclohexane: 1, 3-trans-bis (isocyanatomethyl) cyclohexane: 1: 1.5) in a dropwise manner, wherein the dropwise addition time is 3 hours, and the reaction temperature is 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 30 parts by weight;
30 parts by weight of diisocyanate;
1 part by weight of hydrophilic chain extender;
0.4 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
Example 4
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (D-glucitol), Lutensol TO-5 (Basff) and water, and adding diisocyanate (1, 4-cis-bis (isocyanatomethyl) cyclohexane: 1, 3-trans-bis (isocyanatomethyl) cyclohexane: 1: 1.5) in a dropwise manner for 3 hours at the reaction temperature of 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 25 parts by weight;
40 parts by weight of diisocyanate;
5 parts by weight of Lutensol TO-5 (basf);
1.4 parts of hydrophilic chain extender;
0.4 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
Example 5
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (cyclohexane dihydric alcohol), Lutensol TO-7 (Basff) and water, and adding diisocyanate (1, 3-cis-bis (isocyanatomethyl) cyclohexane: 1, 4-trans-bis (isocyanatomethyl) cyclohexane ═ 1: 1) in a dropwise manner for 3h at the reaction temperature of 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 24 parts by weight;
38 parts by weight of diisocyanate;
3 parts by weight of Lutensol TO-7 (basf);
1.3 parts of hydrophilic chain extender;
0.42 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
Comparative example 1
The preparation method of the waterborne polyurethane adhesive comprises the following steps:
step 1: mixing dihydric alcohol (cyclohexane dihydric alcohol) and water, and adding hexamethylene diisocyanate in a dropwise manner for 2.5h at a reaction temperature of 40-45 ℃;
step 2: adding a proper amount of hydrophilic chain extender (N-methyl pyrrolidone), and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator (triethanolamine) and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding a proper amount of ethylenediamine for chain extension reaction, and reacting for 0.5-1h at constant temperature.
In the reaction step, the use amount of each material is as follows:
a dihydric alcohol: 20 parts by weight;
40 parts by weight of diisocyanate;
1.5 parts of hydrophilic chain extender;
0.4 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
The application effect is as follows:
the application effect 1: (same drying time, different drying temperature)
Directly spraying glue on the bonding surface of leather (meeting GB/T16799) at the ambient temperature of 25 ℃ and the relative humidity of 75%, airing for 3min, folding the bonding surface of the leather, heating and drying for 15min at different drying temperature conditions, and testing the peeling strength of the initially bonded T according to the GB/T2791-1995 standard.
Figure GDA0002768643280000071
Tests show that the examples 1 to 5 show excellent initial adhesion effect, and the initial adhesion effect is effectively improved.
The application effect 2: (same drying temperature, different drying time)
Directly spraying glue on the bonding surface of leather (meeting GB/T16799) at the ambient temperature of 25 ℃ and the relative humidity of 75%, airing for 3min, folding the bonding surface of the leather, heating and drying at different temperatures under the drying temperature condition of 40 ℃, and testing the initial bonding T peel strength according to the GB/T2791-plus 1995 standard.
Figure GDA0002768643280000081
Tests show that the initial adhesion of the samples 1 to 5 can exert the maximum effect in a short time, and the initial adhesion time is effectively improved.
Application effect 3: (Room temperature, time of standing after different adhesions)
Directly spraying the glue on the bonding surface of the leather (meeting GB/T16799) at the ambient temperature of 23 ℃ and the relative humidity of 75%, airing for 3min, folding the bonding surface of the leather, drying without heating, and testing the initial bonding T peel strength according to the GB/T2791 + 1995 standard according to the time lapse of the placement after bonding at room temperature.
Figure GDA0002768643280000082
Figure GDA0002768643280000091
It was found through testing that the examples 1 to 5 exhibited initial adhesion capable of exhibiting excellent initial adhesion effect at normal temperature.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (2)

1. The water-based polyurethane adhesive is characterized by comprising the following preparation methods:
step 1: mixing dihydric alcohol, Lutensol TO-5 and water, and adding diisocyanate in a dropwise manner for 3h at a reaction temperature of 40-45 ℃;
step 2: adding a hydrophilic chain extender, and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding ethylenediamine to carry out chain extension reaction, and reacting for 1h at constant temperature;
the dihydric alcohol is D-glucitol, the diisocyanate is a combination of 1, 4-cis bis (isocyanatomethyl) cyclohexane and 1, 3-trans bis (isocyanatomethyl) cyclohexane, and the weight ratio of the 1, 4-cis bis (isocyanatomethyl) cyclohexane to the 1, 3-trans bis (isocyanatomethyl) cyclohexane is 1: 1.5; the hydrophilic chain extender is N-methyl pyrrolidone; the pH regulator is triethanolamine;
the using amount of each material is as follows:
a dihydric alcohol: 25 parts by weight;
40 parts by weight of diisocyanate;
lutensol TO-55 weight parts;
1.4 parts of hydrophilic chain extender;
0.4 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
2. The water-based polyurethane adhesive is characterized by comprising the following preparation methods:
step 1: mixing dihydric alcohol, Lutensol TO-7 and water, and adding diisocyanate in a dropwise manner for 3h at a reaction temperature of 40-45 ℃;
step 2: adding a hydrophilic chain extender, and continuing to react for 2 hours at constant temperature;
and step 3: adding a pH regulator and water to regulate the pH value of the system to be neutral and the solid content to be 48 percent;
and 4, step 4: adding ethylenediamine to carry out chain extension reaction, and reacting for 1h at constant temperature;
the dihydric alcohol is cyclohexane dihydric alcohol, the diisocyanate is a combination of 1, 3-cis bis (isocyanatomethyl) cyclohexane and 1, 4-trans bis (isocyanatomethyl) cyclohexane, and the weight ratio of the 1, 3-cis bis (isocyanatomethyl) cyclohexane to the 1, 4-trans bis (isocyanatomethyl) cyclohexane is 1: 1; the hydrophilic chain extender is N-methyl pyrrolidone; the pH regulator is triethanolamine;
the using amount of each material is as follows:
a dihydric alcohol: 24 parts by weight;
38 parts by weight of diisocyanate;
lutensol TO-73 weight parts;
1.3 parts of hydrophilic chain extender;
0.42 part by weight of ethylenediamine;
the water is proportioned until the total amount of all materials is 100 parts by weight.
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US5250651A (en) * 1992-10-30 1993-10-05 Minnesota Mining And Manufacturing Company Crosslinked polyether polyol sealant
KR101111990B1 (en) * 2002-10-31 2012-02-17 다우 글로벌 테크놀로지스 엘엘씨 Polyurethane dispersion and articles prepared therefrom
CN104087235B (en) * 2014-07-08 2016-08-31 新纶科技（常州）有限公司 A kind of Aqueous Polyurethane Adhesives and preparation method thereof
MX2017007329A (en) * 2014-12-05 2017-10-20 Basf Se Aqueous adhesive dispersion containing polyurethanes and ethoxylated fatty alcohols.

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