CN108530603B - Mica modified waterborne polyurethane emulsion, adhesive and preparation method thereof - Google Patents
Mica modified waterborne polyurethane emulsion, 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
- C08G18/28—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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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- 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
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Abstract
The invention discloses a mica modified waterborne polyurethane emulsion, an adhesive and a preparation method thereof. Pre-polymerizing oligomer polyol and diisocyanate, adding KH-580 modified mica, adding a carboxylic acid type hydrophilic monomer, a chain extender and a cross-linking agent after reaction, adding acetone for viscosity reduction, neutralizing, dispersing and emulsifying, and removing the acetone by reduced pressure distillation to obtain the mica modified waterborne polyurethane emulsion. And adding the obtained emulsion into auxiliaries such as a water-based thickening agent, a flatting agent, a defoaming agent, a plasticizer and the like to prepare the mica modified water-based polyurethane adhesive. The invention improves the water resistance, mechanical property and bonding strength of the waterborne polyurethane adhesive, and is suitable for bonding shoe materials and leather. The adhesive prepared by the invention has excellent hardness, adhesive force, peeling strength, water resistance and the like after being formed into a film. The pencil hardness is 3H at most, the adhesive force can reach 0 grade at most, the water absorption rate can reach 3.3% at least, and the peel strength is 205-220N/2.5 cm.
Description
Technical Field
The invention relates to the field of aqueous adhesives, and particularly relates to a mica modified aqueous polyurethane emulsion, a mica modified aqueous polyurethane adhesive and a preparation method thereof.
Background
The Waterborne polyurethane is a polyurethane system which takes water instead of an Organic solvent as a dispersion medium, also called water-dispersed polyurethane, water-system polyurethane or water-based polyurethane, the Waterborne polyurethane takes water as a solvent, has the advantages of no pollution, safety, reliability, excellent mechanical properties, good compatibility, easy modification and the like, and is widely applied to Coatings, adhesives, fabric Coatings and finishing agents, leather finishing agents, paper surface treating agents and fiber surface treating agents in recent years, at present, the polyurethane adhesives are widely applied to the shoe industry by virtue of excellent adhesive properties of the polyurethane adhesives, but most of the polyurethane adhesives for domestic shoes mainly adopt solvent type, toxic and harmful Organic solvents easily cause environmental pollution and damage human life safety, while the environmentally-friendly Waterborne polyurethane adhesives for domestic shoes mainly adopt water as a dispersion medium, have the advantages of adjustable hardness, low temperature resistance, good flexibility, small flame retardance, small environmental pollution, no pollution to human environment and life safety factors, and the development and application of environmentally-friendly Waterborne polyurethane adhesives for shoes are the future main trend (Sudipta M, Krishmania N.Synthesis and the environmental protection of polyurethane adhesives for shoes, No. 3532. the adhesive has the disadvantages of low water-based adhesive property, good water resistance, good property of polyurethane adhesive property, good property of polyurethane adhesive for polyurethane adhesive materials for China, good environmental protection and low-property of polyurethane adhesive materials [ 12. No. 23. No. 13, No. 2. No. 1.
Disclosure of Invention
The invention aims to provide a mica modified waterborne polyurethane emulsion, an adhesive and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the mica modified waterborne polyurethane emulsion comprises the following steps:
step 1, dropwise adding diisocyanate into anhydrous oligomer polyol, stirring, dropwise adding a catalyst, and reacting at 80-85 ℃ for 1-2 hours to obtain a first intermediate, wherein the weight ratio of the oligomer polyol to the polyisocyanate is 1800-2400: 1200-1500;
step 2, mixing mica and a first intermediate, stirring and reacting to obtain a second intermediate, wherein the total mass of oligomer polyol, diisocyanate, polyhydroxycarboxylic acid, small molecular diol monomer and cross-linking agent is the total amount, and the weight ratio of the mica (mica for short) of gamma-mercaptopropyltriethoxysilane (KH-580 modification) to the total amount is 6-14: 50;
step 3, cooling the second intermediate to 60-70 ℃, adding dry polyhydroxycarboxylic acid, and reacting for 2-3 hours to obtain a third intermediate;
step 4, dropwise adding a micromolecular dihydric alcohol monomer into the third intermediate, adding an organic solvent to reduce the viscosity until the solution is colorless, heating to 70-80 ℃, and reacting for 1-2 hours to obtain a fourth intermediate;
step 5, dropwise adding a cross-linking agent into the fourth intermediate, and reacting at 60-70 ℃ for 2-3 hours to obtain a fifth intermediate;
step 6, cooling the fifth intermediate to 20-35 ℃, adding organic amine to neutralize and salify under a stirring state, and reacting for 0.5-1 hour to obtain a sixth intermediate;
and 7, adding water into the sixth intermediate, shearing and emulsifying, controlling the shearing speed to be 2000-3000 r/min, reacting for 0.5-1 hour, and performing rotary evaporation to remove the organic solvent to obtain the mica modified waterborne polyurethane emulsion.
In the step 1, the number average molecular weight of the oligomer polyol is 1000-4000, and the oligomer polyol is selected from one or two of polycaprolactone diol, poly (hexanediol adipate) diol, polytetrahydrofuran diol, hydroxyl-terminated polybutadiene and hydroxyl-terminated polybutadiene-acrylonitrile.
In step 1, the diisocyanate is selected from one or more of norbornane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethylm-xylylene diisocyanate, and 2-methylpentane diisocyanate.
In the step 1, the catalyst is stannous octoate or dibutyltin dilaurate.
In the step 2, the mass ratio of diisocyanate, polyhydroxy carboxylic acid, micromolecular dihydric alcohol and cross-linking agent is 720-2600: 430 to 650: 160-360: 400-600.
In step 3, the polyhydroxy carboxylic acid is selected from one or two of dimethylol propionic acid and dimethylol butyric acid.
In the step 4, the small molecular diol monomer is selected from one or more of 2-methyl-2, 4-pentanediol, TCD tricyclo-diol, trimethyl pentanediol, methyl propanediol, 1, 6-hexanediol and neopentyl glycol; the organic solvent is selected from one or more of acetone, butanone and N-methyl pyrrolidone.
In the step 5, the cross-linking agent is selected from one of triethanolamine, pentaerythritol and glycerol;
in the step 6, the organic amine is selected from one of triethylamine, ammonia water and sodium hydroxide, and the molar ratio of the organic amine to the polyhydroxycarboxylic acid is 1: 1.
The invention also provides the mica modified waterborne polyurethane emulsion prepared by the preparation method.
Further, the invention provides an adhesive based on the mica modified waterborne polyurethane emulsion, which comprises the following components in parts by weight:
80-110 parts of mica modified waterborne polyurethane emulsion,
0.1 to 0.3 part of water-based thickening agent,
0.15 to 0.25 part of water-based leveling agent,
0.2 to 0.4 part of water-based defoaming agent,
4-7 parts of a plasticizer,
14-26 parts of talcum powder,
2-6 parts of titanium dioxide powder,
0.2 to 0.8 portion of fumed silica,
3-8 parts of a water-based curing agent.
Furthermore, the invention provides a preparation method of the mica modified waterborne polyurethane adhesive, which comprises the following steps:
adding 0.1-0.3 part by weight of water-based thickener, 0.15-0.25 part by weight of water-based leveling agent, 0.2-0.4 part by weight of water-based defoamer, 4-7 parts by weight of plasticizer, 14-26 parts by weight of talcum powder, 2-6 parts by weight of titanium dioxide and 0.2-0.8 part by weight of fumed silica into 80-110 parts by weight of mica-modified water-based polyurethane emulsion, stirring, adding 3-8 parts by weight of water-based curing agent, and stirring for 10-20 minutes to obtain the mica-modified water-based polyurethane adhesive.
The aqueous thickener is selected from one of Borchi Gel L W44, Borchi Gel L75N, BENAQUA 4000 and BENAQUA 1000.
The aqueous leveling agent is selected from one of BYK-361N, BYK-359, BYK-356 and BYK-350.
The water-based defoaming agent is selected from one of BYK-019, BYK-021, BYK-024, BYK-093 and BYK-1730.
The plasticizer is selected from one of dimethyl phthalate, diethyl phthalate and dibutyl phthalate.
The waterborne curing agent is selected from one of waterborne polyisocyanate curing agents Desmodur DN, Bayhydur3100, Bayhydur XP2487/1, Bayhydur XP2547 and Bayhydur XP 2451.
Compared with the prior art, the invention has the following advantages:
according to the invention, the aqueous polyurethane emulsion is modified by mica, and the prepared mica modified aqueous polyurethane adhesive has strong adhesive force, good adhesive property, improved film forming property, and improved water resistance and mechanical property. The mica modified waterborne polyurethane emulsion is matched with other additives to obtain the waterborne polyurethane adhesive which has excellent stripping force and tensile strength. The mica modified waterborne polyurethane adhesive prepared by the invention is particularly suitable for the fields of shoe materials, packaging films, leather and the like. Experimental results show that the adhesive prepared by the method has excellent hardness, adhesive force, peeling strength, water resistance and the like after being formed into a film. The pencil hardness is 3H at most, the adhesive force can reach 0 grade at most, the water absorption rate can reach 3.3% at least, and the peel strength is 205-220N/2.5 cm.
Detailed Description
In order to better understand the present invention, the following embodiments are further described in detail. The scope of the invention is not limited to the embodiments shown.
Comparative example 1: unmodified waterborne polyurethane adhesives
(1) Synthesis of aqueous polyurethane emulsion
Raw materials:
| polycaprolactone diol | 10.54g |
| Hydroxyl-terminated polybutadiene | 8.10g |
| Xylylene diisocyanate | 20.87g |
| Dibutyl tin dilaurate | 0.2g |
| KH-580 modified mica | 0 |
| Dimethylolpropionic acid | 3g |
| TCD tricyclic diols | 3.05g |
| Acetone (II) | 15ml |
| Pentaerythritol | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
The preparation method comprises the following steps: adding polycaprolactone diol, 2000-hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid to react for 2 hours, heating to 75 ℃, adding TCD tricyclic diol to react for 1.5 hours, and adding 15ml of acetone to reduce the viscosity of a reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the waterborne polyurethane emulsion.
(2) Synthesis of aqueous polyurethane adhesive
According to the method, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added into 100g of waterborne polyurethane emulsion to obtain the waterborne polyurethane adhesive.
Comparative example 2: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 2:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
| polycaprolactone diol | 10.54g |
| Hydroxyl-terminated polybutadiene | 8.10g |
| Xylylene diisocyanate | 20.87g |
| Dibutyl tin dilaurate | 0.2g |
| KH-580 modified mica | 2g |
| Dimethylolpropionic acid | 3g |
| TCD tricyclic diols | 3.05g |
| Acetone (II) | 15ml |
| Pentaerythritol | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
The preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 2gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Comparative example 3: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total weight is 4:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
| polycaprolactone diol | 10.54g |
| Hydroxyl-terminated polybutadiene | 8.10g |
| Xylylene diisocyanate | 20.87g |
| Dibutyl tin dilaurate | 0.2g |
| KH-580 modified mica | 4g |
| Dimethylolpropionic acid | 3g |
| TCD tricyclic diols | 3.05g |
| Acetone (II) | 15ml |
| Pentaerythritol | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
The preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 4gKH-580 modified mica, and reacting for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Comparative example 4: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 16:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
| polycaprolactone diol | 10.54g |
| Hydroxyl-terminated polybutadiene | 8.10g |
| Xylylene diisocyanate | 20.87g |
| Dibutyl tin dilaurate | 0.2g |
| KH-580 modified mica | 16g |
| Dimethylolpropionic acid | 3g |
| TCD tricyclic diols | 3.05g |
| Acetone (II) | 15ml |
| Pentaerythritol | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
The preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 16gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Comparative example 5: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 18:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
the preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 18gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Example 1: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 6:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
the preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 6gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Example 2: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 8:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
the preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 8gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Example 3: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 10:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
the preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 10gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Example 4: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 12:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
the preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 12gKH-580 modified mica, and reacting for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
Example 5: mica modified waterborne polyurethane adhesive (the weight ratio of mica to the total amount is 14:50)
(1) Synthesis of mica modified aqueous polyurethane emulsion
Raw materials:
| polycaprolactone diol | 10.54g |
| Hydroxyl-terminated polybutadiene | 8.10g |
| Xylylene diisocyanate | 20.87g |
| Dibutyl tin dilaurate | 0.2g |
| KH-580 modified mica | 14g |
| Dimethylolpropionic acid | 3g |
| TCD tricyclic diols | 3.05g |
| Acetone (II) | 15ml |
| Pentaerythritol | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
The preparation method comprises the following steps: adding polycaprolactone diol, 2000 hydroxyl-terminated polybutadiene 2000 and xylylene diisocyanate into a three-neck flask, adding dibutyltin dilaurate to react for 2 hours at 82 ℃ to obtain a polyurethane prepolymer, adding 14gKH-580 modified mica to react for 2 hours. Cooling to 65 ℃, adding dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding TCD (trichloro-dimethyl-benzene) diol for reaction for 1.5h, and adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless and can be stirred smoothly. And adding pentaerythritol, reacting for 2.5h, cooling to 20 ℃, adding triethylamine, performing neutralization reaction for 0.5h, adding deionized water, shearing, emulsifying, reacting for 0.5h, and performing rotary evaporation to remove acetone to obtain the mica modified waterborne polyurethane emulsion.
(2) Synthesis of mica modified waterborne polyurethane adhesive
According to the method, per 100g of mica modified waterborne polyurethane emulsion, 0.2g of waterborne thickener Borchi Gel L W44, 0.2g of waterborne flatting agent BYK-361N, 0.3g of waterborne defoamer BYK-019, 6g of plasticizer dimethyl phthalate, 18g of talcum powder, 4g of titanium dioxide, 0.7g of fumed silica and 5g of waterborne curing agent Bayhydur3100 are added to obtain the mica modified waterborne polyurethane adhesive.
The aqueous polyurethane adhesives obtained in comparative examples 1 to 5 and examples 1 to 5 were prepared into films.
Preparation of film samples: and (3) casting the aqueous polyurethane emulsion into a film in a polytetrafluoroethylene mold, wherein the film thickness is about 1mm, naturally drying for 48h, placing the film in a vacuum oven, drying the film in vacuum at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
Table 1 results of adhesive film property test of comparative examples 1 to 5 and examples 1 to 5:
| sample name | Hardness of | Adhesion (grade) | Water absorption (%) | Peel strength (N/2.5cm) |
| Comparative example 1 | 4B | 4 | 19.2 | 67 |
| Comparative example 2 | 3B | 3 | 18.4 | 74 |
| Comparative example 3 | HB | 3 | 18.2 | 83 |
| Comparative example 4 | HB | 3 | 18.8 | 90 |
| Comparative example 5 | 3B | 3 | 19.6 | 82 |
| Example 1 | 3H | 0 | 4.5 | 205 |
| Example 2 | 3H | 0 | 4.2 | 213 |
| Example 3 | 3H | 0 | 3.3 | 220 |
| Example 4 | 3H | 0 | 3.5 | 209 |
| Example 5 | 3H | 0 | 4.7 | 190 |
As can be seen from the above table, after the aqueous polyurethane adhesive is modified by mica, the performance after coating is obviously improved, and the aqueous polyurethane adhesive has excellent hardness, adhesive force, peel strength, water resistance and the like. The pencil hardness is 3H at most, the adhesive force can reach 0 grade at most, the water absorption rate can reach 3.3% at least, and the peel strength is 205-220N/2.5 cm.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the mica modified waterborne polyurethane emulsion is characterized by comprising the following steps:
step 1, dropwise adding diisocyanate into anhydrous oligomer polyol, stirring, dropwise adding a catalyst, and reacting at 80-85 ℃ for 1-2 hours to obtain a first intermediate, wherein the weight ratio of the oligomer polyol to the diisocyanate is 18.64: 20.87;
step 2, mixing and stirring mica and a first intermediate for reaction by taking the total mass of oligomer polyol, diisocyanate, polyhydroxycarboxylic acid, small molecular diol monomer and cross-linking agent as the total amount and the weight ratio of KH-580 modified mica to the total amount of 6-14: 50 to obtain a second intermediate;
step 3, cooling the second intermediate to 60-70 ℃, adding dry polyhydroxycarboxylic acid, and reacting for 2-3 hours to obtain a third intermediate;
step 4, dropwise adding a micromolecular dihydric alcohol monomer into the third intermediate, adding an organic solvent to reduce the viscosity until the solution is colorless, heating to 70-80 ℃, and reacting for 1-2 hours to obtain a fourth intermediate;
step 5, dropwise adding a cross-linking agent into the fourth intermediate, and reacting at 60-70 ℃ for 2-3 hours to obtain a fifth intermediate;
step 6, cooling the fifth intermediate to 20-35 ℃, adding organic amine to neutralize and salify under a stirring state, and reacting for 0.5-1 hour to obtain a sixth intermediate;
and 7, adding water into the sixth intermediate, shearing and emulsifying, controlling the shearing speed to be 2000-3000 r/min, reacting for 0.5-1 hour, and performing rotary evaporation to remove the organic solvent to obtain the mica modified waterborne polyurethane emulsion.
2. The method according to claim 1, wherein in step 1, the number average molecular weight of the oligomer polyol is 1000 to 4000, the oligomer polyol is one or two selected from polycaprolactone diol, polyhexamethylene adipate diol, polytetrahydrofuran diol, hydroxyl-terminated polybutadiene, and hydroxyl-terminated polybutadiene-acrylonitrile, the diisocyanate is one or more selected from norbornane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethylm-xylylene diisocyanate, and 2-methylpentane diisocyanate, and the catalyst is stannous octoate or dibutyltin dilaurate.
3. The preparation method according to claim 1, wherein in the step 2, the mass ratio of the diisocyanate, the polyhydroxycarboxylic acid, the small molecular diol and the crosslinking agent is 20.87: 3: 3.05: 3.31.
4. the method according to claim 1, wherein in step 3, the polyhydroxycarboxylic acid is one or two selected from dimethylolpropionic acid and dimethylolbutyric acid.
5. The method according to claim 1, wherein in step 4, the small molecule diol monomer is selected from one or more of 2-methyl-2, 4-pentanediol, TCD tricyclo diol, trimethylpentanediol, methylpropanediol, 1, 6-hexanediol, and neopentyl glycol; the organic solvent is selected from one or more of acetone, butanone and N-methyl pyrrolidone.
6. The method of claim 1, wherein in step 5, the cross-linking agent is selected from one of triethanolamine, pentaerythritol, and glycerol; in the step 6, the organic amine is selected from triethylamine or ammonia water, and the molar ratio of the organic amine to the polyhydroxycarboxylic acid is 1: 1.
7. The mica-modified aqueous polyurethane emulsion prepared by the preparation method according to any one of claims 1 to 6.
8. The adhesive is characterized by comprising the following components in parts by weight:
80-110 parts of mica modified waterborne polyurethane emulsion as described in claim 7,
0.1 to 0.3 part of water-based thickening agent,
0.15 to 0.25 part of water-based leveling agent,
0.2 to 0.4 part of water-based defoaming agent,
4-7 parts of a plasticizer,
14-26 parts of talcum powder,
2-6 parts of titanium dioxide powder,
0.2 to 0.8 portion of fumed silica,
3-8 parts of a water-based curing agent.
9. The method for preparing the adhesive according to claim 8, characterized by comprising the following steps:
adding 0.1-0.3 part by weight of water-based thickener, 0.15-0.25 part by weight of water-based leveling agent, 0.2-0.4 part by weight of water-based defoamer, 4-7 parts by weight of plasticizer, 14-26 parts by weight of talcum powder, 2-6 parts by weight of titanium dioxide and 0.2-0.8 part by weight of fumed silica into 80-110 parts by weight of mica-modified water-based polyurethane emulsion, stirring, adding 3-8 parts by weight of water-based curing agent, and stirring for 10-20 minutes to obtain the adhesive.
10. The method as claimed in claim 9, wherein the aqueous thickener is selected from the group consisting of Borchi Gel L W44, Borchi Gel L75N, BENAQUA 4000 and BENAQUA 1000, the aqueous leveling agent is selected from the group consisting of BYK-361N, BYK-359, BYK-356 and BYK-350, the aqueous defoamer is selected from the group consisting of BYK-019, BYK-021, BYK-024, BYK-093 and BYK-1730, the plasticizer is selected from the group consisting of dimethyl phthalate, diethyl phthalate and dibutyl phthalate, and the aqueous curing agent is selected from the group consisting of aqueous polyisocyanate curing agents Desmodur DN, Bayhydur 24XP 87/1, Bayhydur XP2547 and Bayhydur XP 2451.
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