CN108530603A - Mica modified aqueous polyurethane emulsion, adhesive and preparation method thereof - Google Patents
Mica modified aqueous polyurethane emulsion, adhesive and preparation method thereof Download PDFInfo
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- CN108530603A CN108530603A CN201810348064.9A CN201810348064A CN108530603A CN 108530603 A CN108530603 A CN 108530603A CN 201810348064 A CN201810348064 A CN 201810348064A CN 108530603 A CN108530603 A CN 108530603A
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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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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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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
- C08G18/70—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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- 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
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- Adhesives Or Adhesive Processes (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of mica modified aqueous polyurethane emulsions, adhesive and preparation method thereof.Oligomer polyol and the pre-polymerization of diisocyanate elder generation, the mica that KH 580 is modified is added, carboxylic acid type hydrophilic monomer, chain extender, crosslinking agent are added after reaction, it is glutinous that acetone drop is added, then neutralized, dispersion and emulsion, vacuum distillation removing acetone obtain mica modified aqueous polyurethane emulsion.The auxiliary agents such as water-based thickener, levelling agent, antifoaming agent and plasticizer are added in obtained lotion and are prepared into mica modified aqueous polyurethane adhesive.The present invention improves the water resistance, mechanical property and adhesion strength of Aqueous Polyurethane Adhesives, the bonding being suitable in footwear material and leather.There is excellent hardness, adhesive force, peel strength, water resistance etc. after adhesive film forming prepared by the present invention.Pencil hardness highest 3H, adhesive force can reach 0 grade, and water absorption rate is minimum to can reach 3.3%, and peel strength is 205~220N/2.5cm.
Description
Technical field
The present invention relates to Aqueous Adhesives fields, more particularly to mica modified aqueous polyurethane emulsion, mica modified water-soluble
Adhesive for polyurethane and preparation method thereof.
Background technology
Aqueous polyurethane is to replace organic solvent as the polyurethane system of decentralized medium, poly- ammonia also referred to as water-dispersed using water
Ester, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane is using water as solvent, with pollution-free, safe and reliable, mechanical performance is excellent
Good, the advantages that compatibility is good, easily modified, it is widely used in coating, adhesive, fabric coating and finishing agent, skin in recent years
Remove from office finishing agent, sheet surface treating agent and fiber surface treatment agent.Currently, adhesive for polyurethane is existed with its excellent adhesive property
It is widely used in shoemaking industry.But domestic polyurethane in use for shoes adhesive is most of based on solvent type, poisonous and harmful
Organic solvent easily cause environmental pollution, damage human life safety.And environment-friendly water-based polyurethane adhesive be using water as
Decentralized medium has many advantages, such as that hardness is adjustable, low temperature resistant, flexibility is good, fire-retardant, smell is small, free from environmental pollution.From mankind's ring
Border and life security factor consider that exploitation and application shoes environment-friendly water-based polyurethane adhesive will become the following main flow direction
(Sudipta M,Krishanmurti N.Synthesis and characterization of aqueous
cationomeric polyurethanes and their use as adhesives[J].J.Appl.Polym Sci,
1996,62:1993-2003.).Currently, the shoes of domestic high quality are also few on the market with environment-friendly water-based polyurethane adhesive
See, main cause is that solid content is low, and that there are still initial bonding strengths in use is relatively low, curing rate is slow, to the bonding of non-polar material
Intensity is low, poor mechanical property and (Noble K L.Waterborne polyurethane [J] the shortcomings of poor water resistance
.Progress in Organic Coatings,1997,32(3):131-136)。
Invention content
The purpose of the present invention is to provide a kind of mica modified aqueous polyurethane emulsions, adhesive and preparation method thereof.
In order to achieve the above objectives, this invention takes following technical solutions：
The preparation method of mica modified aqueous polyurethane emulsion, includes the following steps：
Step 1, diisocyanate is added dropwise in anhydrous oligomer polyol, under stirring, catalyst is added dropwise, at 80~85 DEG C
Lower reaction 1~2 hour, obtains the first intermediate, wherein and oligomer polyol and the weight ratio of polyisocyanates be 1800~
2400：1200~1500；
Step 2, with oligomer polyol, diisocyanate, multi-hydroxy carboxy acid, small molecule glycol monomer and crosslinking agent
Gross mass is total amount, by mica (hereinafter referred to as mica) and the total amount of gamma-mercaptopropyltriethoxysilane (KH-580 modifications)
Weight ratio is 6~14:50, mica is reacted with the mixing of the first intermediate, obtains the second intermediate；
Step 3, the second intermediate is cooled to 60~70 DEG C, dry multi-hydroxy carboxy acid is added, reacted 2~3 hours, obtain
To third intermediate；
Step 4, small molecule glycol monomer is added dropwise in third intermediate, and organic solvent is added to reduce viscosity to solution
In colourless, 70~80 DEG C are warming up to, reacts 1~2 hour, obtains the 4th intermediate；
Step 5, crosslinking agent is added dropwise in the 4th intermediate, reacts 2~3 hours, is obtained among the 5th at 60~70 DEG C
Body；
Step 6, the 5th intermediate is cooled to 20~35 DEG C, organic amine is added under stirring and is neutralized into salt, reacts
0.5~1 hour, obtain the 6th intermediate；
Step 7, the 6th intermediate is added into water emulsification pretreatment, shear velocity control is in 2000~3000r/min, reaction 0.5
~1 hour, after rotary evaporation removes organic solvent, obtain the aqueous polyurethane emulsion of mica modification.
In step 1, the number-average molecular weight of the oligomer polyol is 1000~4000, the oligomer polyol
Selected from polycaprolactone diols, polyhexamethylene adipate glycol, polytetrahydrofuran diol, end hydroxy butadiene, terminal hydroxy group
One or both of Polybutadiene-acrylonitrile.
In step 1, the diisocyanate is selected from norbornene alkyl diisocyanate, lysine diisocyanate, naphthalene two
Isocyanates, 4,4 '-diisocyanate of diphenyl methane-, benzene dimethylene diisocyanate, cyclohexane diisocyanate, four
Methylresorcinol dimethylene diisocyanate and 2- methylpentane diisocyanate it is one or more.
In step 1, the catalyst is stannous octoate or dibutyl tin laurate.
In step 2, the diisocyanate, multi-hydroxy carboxy acid, small molecule dihydric alcohol, crosslinking agent mass ratio be 720
~2600：430~650：160~360：400~600.
In step 3, the multi-hydroxy carboxy acid is selected from one or both of dihydromethyl propionic acid and dimethylolpropionic acid.
In step 4, the small molecule glycol monomer is selected from 2- methyl -2,4- pentanediol, TCD tricyclics glycol, front three
Base pentanediol, methyl propanediol, 1,6- hexylene glycols and neopentyl glycol it is one or more；The organic solvent be selected from acetone,
It is one or more in butanone, N-methyl pyrrolidones.
In step 5, the one kind of the crosslinking agent in triethanolamine, pentaerythrite and glycerine；
In step 6, the organic amine be selected from triethylamine, ammonium hydroxide and sodium hydroxide one kind, the organic amine with it is more
Hydroxycarboxylic acid molar ratio is 1:1.
The present invention also provides mica modified aqueous polyurethane emulsions made from above-mentioned preparation method.
Further, the present invention provides the adhesive based on above-mentioned mica modified aqueous polyurethane emulsion, in parts by weight
Meter, including following component：
80~110 parts of mica modified aqueous polyurethane emulsion,
0.1~0.3 part of water-based thickener,
0.15~0.25 part of aqueous levelling agent,
0.2~0.4 part of aqueous defoamer,
4~7 parts of plasticizer,
14~26 parts of talcum powder,
2~6 parts of titanium dioxide,
0.2~0.8 part of gas-phase silica,
3~8 parts of waterborne curing agent.
Further, the present invention provides the preparation method of above-mentioned mica modified aqueous polyurethane adhesive, including following
Step：
In 80~110 parts by weight mica modified aqueous polyurethane emulsions be added 0.1~0.3 parts by weight water-based thickener,
0.15~0.25 parts by weight aqueous levelling agent, 0.2~0.4 parts by weight aqueous defoamer, 4~7 parts by weight of plasticizer, 14~26 weights
Part talcum powder, 2~6 parts by weight titanium dioxides and the stirring of 0.2~0.8 parts by weight gas-phase silica are measured, it is aqueous that 3~8 parts by weight are added
Curing agent stirs 10~20 minutes, obtains mica modified aqueous polyurethane adhesive.
The water-based thickener be selected from Borchi Gel LW44, Borchi Gel L75N, 4000 BENAQUA,
One kind in BENAQUA 1000.
The one kind of the aqueous levelling agent in BYK-361N, BYK-359, BYK-356, BYK-350.
The aqueous defoamer in BYK-019, BYK-021, BYK-024, BYK-093 and BYK-1730 one
Kind.
The plasticizer is in repefral, diethyl phthalate and dibutyl phthalate
One kind.
The waterborne curing agent be selected from aqueous polyisocyanate curing agent Desmodur DN, Bayhydur3100,
One kind in Bayhydur XP2487/1, Bayhydur XP2547 and Bayhydur XP2451.
Compared with prior art, the present invention has the following advantages：
The present invention is modified aqueous polyurethane emulsion by mica, manufactured mica modified aqueous polyurethane adhesive
There is strong adhesive force good adhesive property, film forming to improve, and water resistance and mechanical performance improve.It is modified using mica
Aqueous polyurethane emulsion coordinates with other additives, and obtained water-based polyurethane adhesive has excellent peeling force, stretch-proof
Intensity.Mica modified aqueous polyurethane adhesive produced by the present invention is especially suitable for fields such as footwear material, packing film, leathers.
The experimental results showed that there is excellent hardness, adhesive force, peel strength, water resistance etc. after adhesive film forming prepared by this method.
Pencil hardness highest 3H, adhesive force can reach 0 grade, and water absorption rate is minimum to can reach 3.3%, and peel strength is 205~220N/
2.5cm。
Specific implementation mode
To be best understood from the present invention, the present invention will be described in further detail with reference to the following examples.The present invention claims
The range of protection is not limited to the range of embodiment expression.
Comparative example 1：Unmodified Aqueous Polyurethane Adhesives
(1) synthesis of aqueous polyurethane emulsion
Raw material：
| Polycaprolactone diols | 10.54g |
| End hydroxy butadiene | 8.10g |
| Benzene dimethylene diisocyanate | 20.87g |
| Dibutyl tin laurate | 0.2g |
| The mica that KH-580 is modified | 0 |
| Dihydromethyl propionic acid | 3g |
| TCD tricyclic glycol | 3.05g |
| Acetone | 15ml |
| Pentaerythrite | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtains base polyurethane prepolymer for use as, be cooled to 65
DEG C, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD tricyclic glycol is added, reacts 1.5h, 15ml acetone is added and comes
Viscosity to the solution for reducing reaction system is in colourless and can smoothly stir.Pentaerythrite is added, 2.5h is reacted, is cooled to 20
DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, is eventually adding deionized water emulsification pretreatment, reacts 0.5h, rotary evaporation
After removing acetone, aqueous polyurethane emulsion is obtained.
(2) synthesis of Aqueous Polyurethane Adhesives
According in every 100g aqueous polyurethane emulsions plus 0.2g water-based thickener Borchi Gel LW44,0.2g aqueous flows
Flat agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acid dimethyl ester, 18g talcum powder, 4g titanium whites
Powder, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain Aqueous Polyurethane Adhesives.
Comparative example 2：(weight ratio of mica and total amount is 2 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
| Polycaprolactone diols | 10.54g |
| End hydroxy butadiene | 8.10g |
| Benzene dimethylene diisocyanate | 20.87g |
| Dibutyl tin laurate | 0.2g |
| The mica that KH-580 is modified | 2g |
| Dihydromethyl propionic acid | 3g |
| TCD tricyclic glycol | 3.05g |
| Acetone | 15ml |
| Pentaerythrite | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 2g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Comparative example 3：(weight ratio of mica and total amount is 4 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
| Polycaprolactone diols | 10.54g |
| End hydroxy butadiene | 8.10g |
| Benzene dimethylene diisocyanate | 20.87g |
| Dibutyl tin laurate | 0.2g |
| The mica that KH-580 is modified | 4g |
| Dihydromethyl propionic acid | 3g |
| TCD tricyclic glycol | 3.05g |
| Acetone | 15ml |
| Pentaerythrite | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 4g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Comparative example 4：(weight ratio of mica and total amount is 16 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
| Polycaprolactone diols | 10.54g |
| End hydroxy butadiene | 8.10g |
| Benzene dimethylene diisocyanate | 20.87g |
| Dibutyl tin laurate | 0.2g |
| The mica that KH-580 is modified | 16g |
| Dihydromethyl propionic acid | 3g |
| TCD tricyclic glycol | 3.05g |
| Acetone | 15ml |
| Pentaerythrite | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 16g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Comparative example 5：(weight ratio of mica and total amount is 18 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 18g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Embodiment 1：(weight ratio of mica and total amount is 6 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 6g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Embodiment 2：(weight ratio of mica and total amount is 8 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 8g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Embodiment 3：(weight ratio of mica and total amount is 10 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 10g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Embodiment 4：(weight ratio of mica and total amount is 12 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 12g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
Embodiment 5：(weight ratio of mica and total amount is 14 to mica modified aqueous polyurethane adhesive:50)
(1) synthesis of mica modified aqueous polyurethane emulsion
Raw material：
| Polycaprolactone diols | 10.54g |
| End hydroxy butadiene | 8.10g |
| Benzene dimethylene diisocyanate | 20.87g |
| Dibutyl tin laurate | 0.2g |
| The mica that KH-580 is modified | 14g |
| Dihydromethyl propionic acid | 3g |
| TCD tricyclic glycol | 3.05g |
| Acetone | 15ml |
| Pentaerythrite | 3.31g |
| Triethylamine | 0.92g |
| Deionized water | 130g |
Preparation method：Polycaprolactone diols, 2000 end hydroxy butadienes 2000 and benzene two are added in three-necked flask
Methylene diisocyanate is added dibutyl tin laurate and reacts 2h at 82 DEG C, obtain base polyurethane prepolymer for use as, 14g is added
The mica that KH-580 is modified reacts 2h.65 DEG C are cooled to, dihydromethyl propionic acid is added and reacts 2h, is warming up to 75 DEG C, TCD is added
Tricyclic glycol reacts 1.5h, and viscosity to the solution that 15ml acetone is added to reduce reaction system is in colourless and can smoothly stir.Again
Pentaerythrite is added, reacts 2.5h, is cooled to 20 DEG C, triethylamine is added and carries out neutralization reaction, neutralizes 0.5h, be eventually adding from
Sub- water emulsification pretreatment reacts 0.5h and obtains mica modified aqueous polyurethane emulsion after rotary evaporation removes acetone.
(2) synthesis of mica modified aqueous polyurethane adhesive
According to every 100g micas be modified aqueous polyurethane emulsion in plus 0.2g water-based thickener Borchi Gel LW44,
0.2g aqueous levelling agent BYK-361N, 0.3g aqueous defoamer BYK-019,6g plasticizer phthalic acids dimethyl ester, 18g talcums
Powder, 4g titanium dioxides, 0.7g gas-phase silicas, 5g waterborne curing agent Bayhydur3100, obtain mica modified aqueous polyurethane glue
Glutinous agent.
The Aqueous Polyurethane Adhesives of comparative example 1 to comparative example 5 and embodiment 1 to 5 gained of embodiment are prepared into film forming.
The preparation of membrane sample：By aqueous polyurethane emulsion in Teflon mould casting film-forming, film thickness about 1mm, from
So dry 48h, is placed in vacuum drying oven and is dried under vacuum to constant weight in 60 DEG C, and taking-up is placed in spare in drier.
1 comparative example 1-5 of table and embodiment 1-5 glue film performance test results：
| Sample ID | Hardness | Adhesive force (grade) | Water absorption rate (%) | 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 |
| Embodiment 1 | 3H | 0 | 4.5 | 205 |
| Embodiment 2 | 3H | 0 | 4.2 | 213 |
| Embodiment 3 | 3H | 0 | 3.3 | 220 |
| Embodiment 4 | 3H | 0 | 3.5 | 209 |
| Embodiment 5 | 3H | 0 | 4.7 | 190 |
As can be seen from the above table, Aqueous Polyurethane Adhesives are modified by mica, and performance is significantly improved after film,
With excellent hardness, adhesive force, peel strength, water resistance etc..Pencil hardness highest 3H, adhesive force can reach 0 grade, inhale
Water rate is minimum to can reach 3.3%, and peel strength is 205~220N/2.5cm.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. the preparation method of mica modified aqueous polyurethane emulsion, which is characterized in that include the following steps：
Step 1, diisocyanate is added dropwise in anhydrous oligomer polyol, under stirring, catalyst is added dropwise, it is anti-at 80~85 DEG C
It answers 1~2 hour, obtains the first intermediate, wherein oligomer polyol and the weight ratio of polyisocyanates are 1800~2400：
1200~1500；
Step 2, with total matter of oligomer polyol, diisocyanate, multi-hydroxy carboxy acid, small molecule glycol monomer and crosslinking agent
Amount is total amount, and the weight ratio by the KH-580 micas being modified and total amount is 6~14:50, mica is mixed with the first intermediate and is stirred
Reaction is mixed, the second intermediate is obtained；
Step 3, the second intermediate is cooled to 60~70 DEG C, is added dry multi-hydroxy carboxy acid, reacted 2~3 hours, obtain the
Three intermediates；
Step 4, small molecule glycol monomer is added dropwise in third intermediate, and it is in nothing that organic solvent, which is added, to reduce viscosity to solution
Color is warming up to 70~80 DEG C, reacts 1~2 hour, obtains the 4th intermediate；
Step 5, crosslinking agent is added dropwise in the 4th intermediate, is reacted 2~3 hours at 60~70 DEG C, obtains the 5th intermediate；
Step 6, the 5th intermediate is cooled to 20~35 DEG C, organic amine is added under stirring and is neutralized into salt, reaction 0.5~
1 hour, obtain the 6th intermediate；
Step 7, the 6th intermediate is added into water emulsification pretreatment, in 2000~3000r/min, reaction 0.5~1 is small for shear velocity control
When, after rotary evaporation removes organic solvent, obtain the aqueous polyurethane emulsion of mica modification.
2. preparation method according to claim 1, which is characterized in that in step 1, the number of the oligomer polyol is equal
Molecular weight be 1000~4000, the oligomer polyol be selected from polycaprolactone diols, polyhexamethylene adipate glycol,
One or both of polytetrahydrofuran diol, end hydroxy butadiene, end hydroxy butadiene-acrylonitrile, described two is different
Cyanate is selected from norbornene alkyl diisocyanate, lysine diisocyanate, naphthalene diisocyanate, diphenyl methane -4,4 '-two
Isocyanates, benzene dimethylene diisocyanate, cyclohexane diisocyanate, tetramethyl m-xylylene diisocyanate and
2- methylpentane diisocyanate it is one or more, the catalyst is stannous octoate or dibutyl tin laurate.
3. preparation method according to claim 1, which is characterized in that in step 2, the diisocyanate, polyhydroxy
Carboxylic acid, small molecule dihydric alcohol, crosslinking agent mass ratio be 720~2600：430~650：160~360：400~600.
4. preparation method according to claim 1, which is characterized in that in step 3, the multi-hydroxy carboxy acid is selected from dihydroxy
One or both of methylpropanoic acid and dimethylolpropionic acid.
5. preparation method according to claim 1, which is characterized in that in step 4, small molecule glycol monomer choosing
From 2- methyl -2,4- pentanediol, TCD tricyclics glycol, trimethylpentanediol, methyl propanediol, 1,6- hexylene glycols and neopentyl glycol
It is one or more；The organic solvent is one or more in acetone, butanone, N-methyl pyrrolidones.
6. preparation method according to claim 1, which is characterized in that in step 5, the crosslinking agent is selected from three ethyl alcohol
One kind in amine, pentaerythrite and glycerine；In step 6, the organic amine be selected from triethylamine, ammonium hydroxide and sodium hydroxide one
Kind, the organic amine is 1 with multi-hydroxy carboxy acid's molar ratio:1.
7. mica modified aqueous polyurethane emulsion made from preparation method according to any one of claims 1 to 6.
8. the adhesive of mica modified aqueous polyurethane emulsion according to claim 7, which is characterized in that in parts by weight
Meter, including following component：
80~110 parts of mica modified aqueous polyurethane emulsion,
0.1~0.3 part of water-based thickener,
0.15~0.25 part of aqueous levelling agent,
0.2~0.4 part of aqueous defoamer,
4~7 parts of plasticizer,
14~26 parts of talcum powder,
2~6 parts of titanium dioxide,
0.2~0.8 part of gas-phase silica,
3~8 parts of waterborne curing agent.
9. the preparation method of mica modified aqueous polyurethane adhesive according to claim 8, which is characterized in that including with
Lower step：
In 80~110 parts by weight mica modified aqueous polyurethane emulsions be added 0.1~0.3 parts by weight water-based thickener, 0.15~
0.25 parts by weight aqueous levelling agent, 0.2~0.4 parts by weight aqueous defoamer, 4~7 parts by weight of plasticizer, 14~26 parts by weight are slided
Mountain flour, 2~6 parts by weight titanium dioxides and the stirring of 0.2~0.8 parts by weight gas-phase silica, are added 3~8 parts by weight waterborne curing agents,
Stirring 10~20 minutes, obtains mica modified aqueous polyurethane adhesive.
10. preparation method according to claim 9, which is characterized in that the water-based thickener is selected from Borchi Gel
One kind in LW44, Borchi Gel L75N, 4000 BENAQUA, BENAQUA 1000, the aqueous levelling agent are selected from
One kind in BYK-361N, BYK-359, BYK-356, BYK-350, the aqueous defoamer be selected from BYK-019, BYK-021,
One kind in BYK-024, BYK-093 and BYK-1730, the plasticizer are selected from repefral, phthalic acid
One kind in diethylester and dibutyl phthalate, the waterborne curing agent are selected from aqueous polyisocyanate curing agent
In Desmodur DN, Bayhydur3100, Bayhydur XP2487/1, Bayhydur XP2547 and Bayhydur XP2451
One kind.
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