CN106753160A - Aqueous polyurethane Flock Adhesive and preparation method thereof - Google Patents
Aqueous polyurethane Flock Adhesive and preparation method thereof Download PDFInfo
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- CN106753160A CN106753160A CN201611073164.2A CN201611073164A CN106753160A CN 106753160 A CN106753160 A CN 106753160A CN 201611073164 A CN201611073164 A CN 201611073164A CN 106753160 A CN106753160 A CN 106753160A
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- diisocyanate
- aqueous polyurethane
- reaction system
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- chain extender
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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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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/721—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
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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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
- C09J175/08—Polyurethanes from polyethers
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of aqueous polyurethane Flock Adhesive and preparation method thereof, aqueous polyurethane Flock Adhesive is prepared using the component for including following weight portion：15~30 parts of diisocyanate, 40~60 parts of polymer polyatomic alcohol, 20~40 parts of benzoic anhydride polyester polyol, 10~20 parts of water-soluble poly ester polyol, 0.01~0.15 part of catalyst, 0.5~1.5 part of non-hydrophilic chain extender, 0.5~1.5 part of hydrophilic chain extender, 70~100 parts of water, diisocyanate is selected from toluene di-isocyanate(TDI), 1, 6 hexamethylene diisocyanates, IPDI, diphenyl methane 4, 4 diisocyanate, double-hexyl methane diisocyanate, in tetramethylxylylene diisocyanate at least two, polymer polyatomic alcohol is selected from the adipic acid type PEPA of number-average molecular weight 1000~3000, polycaprolactone, makrolon, at least one in PPG.The present invention has good water-wash resistance, firmness and solvent resistance, and safety and environmental protection, product has good pliability and feel.
Description
Technical field
The present invention relates to flocking glue of polyurethane and preparation method thereof.
Background technology
Flocking is the technology decorated to base material commonly used in textile industry.Implanted article has its significant spy
Point：Third dimension is strong, bright in luster, soft touch, magnificent warmth, using flocking technique formed pattern image it is true to nature, flocking produce
The features such as product also have heat-holding dampproof, rub resistance.It is adhesive as the topmost auxiliary agent of electrostatic spinning, initial in the market
Static flocking adhesive product is essentially the several types such as solvent borne polyurethane, polybutadiene emulsion, acroleic acid resin, recently as
The raising of people's environmental consciousness, increasing environmental requirement is it is also proposed to adhesive, and environment-friendly aqueous resin is gluing
Agent becomes study hotspot.
Due to the superperformance and environmentally friendly feature of water-base resin adhesive, obtained extensively in fields such as coating, fabric, buildings
Using in terms of the exploitation of flocking adhesive, China is in textile, plastics, rubber, metal porcelain, paper, transfer printing
Many flock binders Deng process exploitation.
The problem of presence has that firmness is poor, water repelling property is poor, feel is poor, breathable moisture permeability difference etc., and also part is gluing
There is the shortcomings of use is dangerous, baking temperature is too high in agent.
At present, domestic many electrostatic spinning factories all select esters of acrylic acid as adhesive, are washed with hydrolysis, resistance to dry
Wipe, cheap advantage occupies the 90% of whole Flock Adhesive market glue consumption, but it is poor to there is low temperature flexibility, solvent resistant
Property is not good, and the shortcomings of hot sticky cold crisp, and aqueous polyurethane can just make up these shortcomings.In the prior art, aqueous polyurethane
The water resistance of Flock Adhesive, wearability be not good, it is impossible to meets the application demand in actual industrial production.
Chinese patent CN104151504A disclose a kind of aqueous polyurethane grafted water polyacrylic acid emulsion and its
Preparation method, by the cooperation of the optimum choice and reaction process of emulsifying agent, from the emulsifying agent of compounding, in increased emulsifying agent
Carbon chain lengths, make two kinds of emulsions stablize in the course of the polymerization process it is compatible concurrently life be copolymerized into PUA emulsions, solve and enter PU and PA
The problem of demulsifying phenomenon is easily produced during row reaction, compared with the emulsion that aqueous PU and aqueous PA is compounded, the water of aqueous PU grafting
Property PA emulsions as Flock Adhesive combination property more preferably.
Chinese patent CN101857791A discloses a kind of aqueous polyurethane static flocking adhesive and preparation method, selects hexichol
Two kinds of reactive isocyanate groups synergies of dicyclohexylmethane diisocyanate and IPDI, introduce Linear Double hydroxyl
Alkylsiloxane, from anionic hydrophilic group dimethylolpropionic acid, obtains the cold-resistant, aqueous polyurethane of excellent solvent resistance
Static flocking adhesive.Aqueous PU described in reported above is still that carboxylic acid is hydrophilic chain extender, during the reaction of such hydrophilic chain extender
Between it is long, production efficiency is not high；The volatilization of nertralizer amine therein, causes that pH's is unstable, and the catalyzing hydrolysis of carboxyl are made
With influence polyurethane emulsion bin stability；The hydrophily of carboxylate is relatively poor, and usage amount is big, must influence the resistance to of product
Fastness is washed, also the aqueous polyurethane dispersion of more difficult synthesis of high solid content, the dry high energy consumption of application process mesoglea.
Chinese patent CN101343525A discloses a kind of " water used in the product of imitation leather electrostatic real leather embedding fiber
Property adhesive and preparation method thereof ", the application for a patent for invention is a kind of Compound waterborne adhesive, with polyurethane as shell, with poly-
Acrylate is the interpenetrating network polymer emulsion of core, then synthesize it is a kind of can close carboxyl in aqueous polyurethane containing epoxy radicals
Acrylate polymer emulsion, the two carries out chemical blend with certain proportion.It is fine that it is only used for imitation leather electrostatic real leather embedding
Dimension product, is not suitable for various fibre fluffs, also without cold-resistant, solvent resistance.
The content of the invention
First purpose of the invention is to provide a kind of aqueous polyurethane Flock Adhesive, with lacking of overcoming prior art to exist
Fall into.
Second object of the present invention is to provide the preparation method of above-mentioned Flock Adhesive.
Aqueous polyurethane Flock Adhesive of the present invention, is prepared from using the component for including following weight portion：
It is different that described diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate, isophorone two
Cyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate (HMDI), tetramethyl
Base XDI (TMXDI)) at least two；
The preferably mixture of IPDI (IPDI) and hexamethylene diisocyanate；
IPDI:Hexamethylene diisocyanate=1:0.2~5；
Preferably：
IPDI:Hexamethylene diisocyanate=1:0.5~2；
Described polymer polyatomic alcohol is selected from the adipic acid type PEPA of number-average molecular weight 1000~3000, gathers in oneself
At least one in ester, makrolon, PPG；Wherein, the small molecular alcohol in described PEPA synthesis material
Selected from 2- methyl isophthalic acids, ammediol, BDO, 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- trimethyl -1 are 3- pentanediols, new
One or more in pentanediol, 1,6- hexylene glycols, 1,4-CHDM, diethylene glycol；
Preferably, described adipic acid type PEPA be selected from poly adipate succinic acid ester (PBA), polyadipate oneself two
Alcohol ester (PHA), polyneopentyl glycol adipate (PNA), polybutyleneadipate-neopentyl glycol copolyesters (PBNA), gather oneself two
One or more in sour hexylene glycol-neopentyl glycol copolyesters (PHNA)；
Described PPG is at least one in polypropylene glycol or polytetramethylene ether diol；
Described benzoic anhydride polyester polyol is the PEPA based on the hexylene glycol of phthalic anhydride -1,6；
Described water-soluble poly ester polyol is the PEPA for being grafted with sulfonate groups；
Described catalyst is selected from environment-friendly type organo-bismuth class catalyst, such as
Described non-hydrophilic chain extender is selected from 2- methyl isophthalic acids, ammediol, BDO, 3- methyl isophthalic acids, 5- penta 2
Alcohol, 2,2,4- trimethyl -1, at least one in 3- pentanediols, neopentyl glycol or 1,6- hexylene glycol；
Described hydrophilic chain extender is ethylenediamine base ethyl sulfonic acid sodium；
The weight solid content of above-mentioned aqueous polyurethane Flock Adhesive is 45%-55%；
The preparation method of aqueous polyurethane Flock Adhesive of the present invention, comprises the following steps：
(1) in an inert atmosphere, by polymer polyatomic alcohol, water-soluble poly ester polyol, benzoic anhydride polyester polyol, two isocyanides
Acid esters and partial catalyst, 80 DEG C of -100 DEG C of reaction 1-2h, obtain prepolymerization reaction system；
Described inert gas can be used such as nitrogen etc.；
(2) and then, the temperature of the prepolymerization reaction system is down to less than 60 DEG C, acetone is added, when being cooled to 25 DEG C
Viscosity is 2500-6000cP, is subsequently adding non-hydrophilic chain extender and residual catalyst, and 55 DEG C~75 DEG C reaction 0.5-2h are obtained
To chain extending reaction system；
Wherein, the amount of catalyst has no particular limits in above-mentioned steps (1) and step (2), and those skilled in the art can
The consumption of catalyst in empirically determined step (1), and the use of catalyst in step (2) is calculated according to catalyst total amount
Amount；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, hydrophilic chain extender reaction 1-5min is added, and is added water
Emulsification, obtains polyaminoester emulsion, and solvent is sloughed in vacuum distillation, obtains final product the product that weight solid content is 45%-55%.
Aqueous polyurethane Flock Adhesive of the present invention is widely used in electrostatic spinning, such as flocked pile leather field.
Compared with prior art, beneficial effects of the present invention are as follows：
The present invention uses the PEPA and ethylenediamine base ethyl sulfonic acid sodium that are grafted with sulfonate groups as the poly- ammonia of offer
The hydrophilic structure of ester, with the prior art using the aqueous polyurethane Flock Adhesive of carboxylic acid type hydrophilic group compared with because without carboxylic
Base, with good water-wash resistance, firmness and solvent resistance, it is not necessary to using the strong triethylamine class nertralizer of excitant,
Using safety and environmental protection, technical process simplifies, and improves production efficiency.Product will not cause polyaminoester emulsion because of the volatilization of nertralizer
PH changes cause unstable, and the water-wash resistance that carboxyl has obvious acid-catalyzed hydrolysis characteristic, product can be reduced substantially.Sulphur
The hydrophilic efficiency high of hydrochlorate, consumption is few, can prepare high solid product, can reduce Product transport cost, improve product construction
During rate of drying, reducing energy consumption.Because hydrophile content is less, the water-wash resistance of product can be significantly improved.Sulfonate
The highly polar adhesive force improved with base material, the firmness of product is had outstanding performance.From phthalic anhydride polyurethane polyol, Neng Gouti
The water resistance of high product, solvent resistance and firmness, while assigning product good pliability and feel.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Technical staff makes according to the present invention in actual applications improvement and tune
It is whole, still fall within protection scope of the present invention.
Following examples of the invention use following raw materials according：
Adipic acid type PEPA：
PBA, poly adipate succinic acid ester, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
PHA, polyadipate hexylene glycol ester, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
PNA, polyneopentyl glycol adipate, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
PBNA, polybutyleneadipate-neopentyl glycol copolyesters, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/
mol；
PHNA, polyadipate hexylene glycol-neopentyl glycol copolyesters, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/
mol；
PTMEG, polytetramethylene ether diol, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
Water-soluble poly ester polyol BY3301, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
Benzoic anhydride polyester polyol HF8356, hydroxyl value 56mg KOH/g, number-average molecular weight 2000g/mol；
Catalyst, leading chemistry
Hydrophilic chain extender, Degussa A95；
Below the raw material in the following examples do not mentioned is commercially available.
Embodiment 1
(1) under drying nitrogen protection, by the PBA of the 230g after vacuum dehydration, the IPDI of 25g,
The 1 of 50g, hexamethylene-diisocyanate, the HF8356 of 100g, the BY3301 of 55g, 0.02g'sIt is added to reaction
In container, under mechanical stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, acetone is added, and viscosity when being cooled to 25 DEG C is
5000cP, is subsequently adding the BDO and 0.03g of 2.5gUnder mechanical stirring, control temperature is 60
2h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, adds the A95 reactions of hydrophilic chain extender 3.5g
2min, then add the water emulsification dispersion of 500g, the polyaminoester emulsion of milky white blueing light is obtained, solvent is sloughed in vacuum distillation, is obtained final product solid
Content is 50% product.
Embodiment 2
(1) under drying nitrogen protection, by the PBNA of PBA, 100g of the 100g after vacuum dehydration, the isophorone of 25g
Diisocyanate, the 1 of 60g, hexamethylene-diisocyanate, the HF8356 of 150g, the BY3301 of 50g, 0.05g's
It is added in reaction vessel, under mechanical stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
4000cP, is subsequently adding the BDO and 0.05g of 6.0gUnder mechanical stirring, control temperature is 65
2h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 2.5g reacts 4min,
Again plus 520g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
50% product.
Embodiment 3
(1) under drying nitrogen protection, by the PNA of the 200g after vacuum dehydration, the IPDI of 30g,
The 1 of 100g, hexamethylene-diisocyanate, the HF8356 of 100g, the BY3301 of 50g, 0.05g'sIt is added to reaction
In container, under mechanical stirring, 95 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
2500cP, is subsequently adding 1, the 6- hexylene glycols and 0.1g of 7.0gUnder mechanical stirring, control temperature is 70
2h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 3.0g reacts 4min,
Again plus 480g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
52% product.
Embodiment 4
(1) under drying nitrogen protection, by the PHA of the 230g after vacuum dehydration, the IPDI of 50g,
The 1 of 50g, hexamethylene-diisocyanate, the HF8356 of 150g, the BY3301 of 75g, 0.03g'sIt is added to reaction
In container, under mechanical stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
6000cP, is subsequently adding the neopentyl glycol and 0.1g of 4.5gUnder mechanical stirring, control temperature is at 75 DEG C
Lower reaction 2h, obtains chain extending reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 4.5g reacts 2min,
Again plus 680g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
46% product.
Embodiment 5
(1) under drying nitrogen protection, by the PHNA of PHA, 100g of the 100g after vacuum dehydration, the isophorone of 40g
Diisocyanate, the 1 of 60g, hexamethylene-diisocyanate, the HF8356 of 100g, the BY3301 of 65g, 0.05g's
It is added in reaction vessel, under mechanical stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
4500cP, is subsequently adding the neopentyl glycol and 0.05g of 2.0gUnder mechanical stirring, control temperature is at 70 DEG C
Lower reaction 1h, obtains chain extending reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 3.5g reacts 4min,
Again plus 550g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
48% product.
Embodiment 6
(1) under drying nitrogen protection, by the PTMEG of the 200g after vacuum dehydration, the isophorone diisocyanate of 40g
Ester, the 1 of 80g, hexamethylene-diisocyanate, the HF8356 of 100g, the BY3301 of 85g, 0.1g'sIt is added to anti-
Answer in container, under mechanical stirring, 90 DEG C of reaction 2.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
3000cP, is subsequently adding 1, the 6- hexylene glycols and 0.15g of 7.0gUnder mechanical stirring, control temperature is 70
1h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 5.0g reacts 5min,
Again plus 610g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
46% product.
Embodiment 7
(1) under drying nitrogen protection, by the PTMEG of PBA, 50g of the 150g after vacuum dehydration, the isophorone of 30g
Diisocyanate, the 1 of 70g, hexamethylene-diisocyanate, the HF8356 of 120g, the BY3301 of 70g, 0.03g's
It is added in reaction vessel, under mechanical stirring, 90 DEG C of reaction 2h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
4000cP, is subsequently adding the BDO and 0.06g of 3.5gUnder mechanical stirring, control temperature is 70
1h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 4.0g reacts 3min,
Again plus 545g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
48% product.
Embodiment 8
(1) under drying nitrogen protection, by the PTMEG of PHA, 100g of the 100g after vacuum dehydration, the isophorone of 55g
Diisocyanate, the 1 of 55g, hexamethylene-diisocyanate, the HF8356 of 100g, the BY3301 of 80g, 0.07g's
It is added in reaction vessel, under mechanical stirring, 90 DEG C of reaction 2h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when adding acetone to be cooled to 25 DEG C is
5000cP, is subsequently adding the BDO and 0.1g of 2.5gUnder mechanical stirring, control temperature is 70
1h is reacted at DEG C, chain extending reaction system is obtained；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, plus the A95 of hydrophilic chain extender 5.0g reacts 5min,
Again plus 595g water emulsification dispersion, obtain the polyaminoester emulsion of milky white blueing light, solvent is sloughed in vacuum distillation, is obtained final product solid content and is
46% product.
Comparative example 1
This comparative example is on the basis of embodiment 1, BY3301 and hydrophilic chain extender A95 to be replaced by dihydromethyl propionic acid
Generation：
(1) under drying nitrogen protection, by the PBA of the 285g after vacuum dehydration, the IPDI of 25g,
The 1 of 50g, hexamethylene-diisocyanate, the HF8356 of 100g, 0.02g'sIt is added in reaction vessel, in machinery
Under stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when addition acetone is reduced to 25 DEG C is about
5000cP, is subsequently adding the BDO and 10.0 dihydromethyl propionic acid 0.03g of 2.5gStirred in machinery
Mix down, control temperature reacts 5h at 60 DEG C, obtains chain extending reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, adds the triethylamine react 30min of 7.5g, then add
The water emulsification dispersion of 900g, obtains the polyaminoester emulsion of milky white blueing light, and solvent is sloughed in vacuum distillation, and it is 35% to obtain final product solid content
Product.
Comparative example 2
This comparative example is on the basis of comparative example 1, the moiety content of HF8356 to be substituted by PBA：
(1) under drying nitrogen protection, by the PBA of the 325g after vacuum dehydration, the IPDI of 25g,
The 1 of 50g, hexamethylene-diisocyanate, the HF8356 of 60g, 0.02g'sIt is added in reaction vessel, in machinery
Under stirring, 90 DEG C of reaction 1.5h of temperature obtain prepolymerization reaction system；
(2) above-mentioned prepolymerization reaction system temperature is reduced to less than 60 DEG C, and viscosity when addition acetone is reduced to 25 DEG C is about
5000cP, is subsequently adding the BDO and 10.0 dihydromethyl propionic acid 0.03g of 2.5gStirred in machinery
Mix down, control temperature reacts 5h at 60 DEG C, obtains chain extending reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, adds the triethylamine react 30min of 7.5g, then add
The water emulsification dispersion of 900g, obtains the polyaminoester emulsion of milky white blueing light, and solvent is sloughed in vacuum distillation, and it is 35% to obtain final product solid content
Product.
Embodiment 1-8 and comparative example 1-2 gained aqueous polyurethane emulsions are thickened with Europe anthracene Ji thickener Gel ALA, is glued
Degree reaches about 2000cP, then with coating machine on fabric coating, contrast test is carried out after Drying and cooling, as a result such as table 1.
Table 1
Note：GB/T 8629-2001 are pressed in washing fastness detection《Textile Test home washings and drying program》, it is wear-resisting
Property detection press GB/T 21196-2007《The measure of textile Martindale's method fabric abrasion resistance》.
In sum, in the embodiment of the present invention, using the PEPA and ethylenediamine base second that are grafted with sulfonate groups
Sodium sulfonate simplifies as the structure for providing polyurethane hydrophilic, production process, and production efficiency is improved, the poly- ammonia of phthalic anhydride of introducing
Ester polyol, assigns product good pliability and feel, and the water-wash resistance of product, firmness have detailed excellent compared with other products
Gesture.
Under the teaching of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that the present invention is cited
Or each raw material for enumerating or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention, and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. aqueous polyurethane Flock Adhesive, it is characterised in that be prepared from using the component for including following weight portion：
Described diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate, isophorone diisocyanate
Ester (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate (HMDI), durol
Dimethylene diisocyanate (TMXDI)) at least two；
Described polymer polyatomic alcohol be selected from the adipic acid type PEPA of number-average molecular weight 1000~3000, polycaprolactone,
At least one in makrolon, PPG.
2. aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that described diisocyanate is different Fo Er
The mixture of ketone diisocyanate (IPDI) and hexamethylene diisocyanate.
3. aqueous polyurethane Flock Adhesive according to claim 2, it is characterised in that IPDI:1,6-
Hexamethylene diisocyanate=1:0.2~5.
4. aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that described PEPA synthesis material
In small molecular alcohol be selected from 2- methyl isophthalic acids, ammediol, BDO, 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- trimethyls-
One or more in 1,3- pentanediol, neopentyl glycol, 1,6- hexylene glycols, 1,4-CHDM, diethylene glycol.
5. aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that described adipic acid type PEPA
Selected from poly adipate succinic acid ester (PBA), polyadipate hexylene glycol ester (PHA), polyneopentyl glycol adipate (PNA), gather oneself
One kind in diacid butanediol-neopentyl glycol copolyesters (PBNA), polyadipate hexylene glycol-neopentyl glycol copolyesters (PHNA) or
It is various.
6. aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that described PPG is poly- the third two
At least one in alcohol or polytetramethylene ether diol；
Described benzoic anhydride polyester polyol is the PEPA based on the hexylene glycol of phthalic anhydride -1,6；
Described water-soluble poly ester polyol is the PEPA for being grafted with sulfonate groups.
7. aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that described catalyst has selected from environment-friendly type
Machine bismuth class catalyst.
8. the aqueous polyurethane Flock Adhesive according to any one of claim 1~7, it is characterised in that described non-hydrophilic
Chain extender is selected from 2- methyl isophthalic acids, ammediol, BDO, 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- trimethyl -1,3- penta
At least one in glycol, neopentyl glycol or 1,6- hexylene glycol；
Described hydrophilic chain extender is ethylenediamine base ethyl sulfonic acid sodium.
9. the preparation method of aqueous polyurethane Flock Adhesive according to claim 1, it is characterised in that comprise the following steps：
(1) in an inert atmosphere, by polymer polyatomic alcohol, water-soluble poly ester polyol, benzoic anhydride polyester polyol, diisocyanate
And partial catalyst, reaction, obtain prepolymerization reaction system；
(2) and then, the temperature of the prepolymerization reaction system is down to less than 60 DEG C, add acetone, cooling is subsequently adding non-hydrophilic
Property chain extender and residual catalyst, reaction obtains chain extending reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced, hydrophilic chain extender reaction is added, emulsification is added water, polyaminoester emulsion is obtained,
Solvent is sloughed in vacuum distillation, obtains final product described aqueous polyurethane Flock Adhesive.
10. method according to claim 9, it is characterised in that (1) in an inert atmosphere, by polymer polyatomic alcohol, water-soluble
Property PEPA, benzoic anhydride polyester polyol, diisocyanate and partial catalyst, 80 DEG C -100 DEG C reaction 1-2h, obtain pre-polymerization
Reaction system；
(2) and then, the temperature of the prepolymerization reaction system is down to less than 60 DEG C, add acetone, viscosity when being cooled to 25 DEG C
It is 2500-6000cP, is subsequently adding non-hydrophilic chain extender and residual catalyst, 55 DEG C~75 DEG C reaction 0.5-2h is expanded
Chain reaction system；
(3) above-mentioned chain extending reaction system temperature is reduced to less than 50 DEG C, hydrophilic chain extender reaction 1-5min is added, and adds water breast
Change.
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| CN110699030A (en) * | 2019-10-11 | 2020-01-17 | 汕头市鑫源化工科技有限公司 | Electrostatic flocking adhesive and preparation method thereof |
| CN112227083A (en) * | 2020-09-30 | 2021-01-15 | 京准化工技术(上海)有限公司 | Fabric water pressure resistance improver and preparation method thereof |
| CN112745795A (en) * | 2020-12-28 | 2021-05-04 | 辽宁恒星精细化工有限公司 | Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
| CN114892421A (en) * | 2021-06-26 | 2022-08-12 | 上海九裕纺织科技有限公司 | Production process based on flocking on film and application thereof |
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| CN107190511B (en) * | 2017-06-19 | 2019-06-21 | 福建南鼎纺织科技有限公司 | A kind of AS resin modified polyurethane resin textile slurry and preparation method thereof |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
| CN109651582A (en) * | 2018-11-27 | 2019-04-19 | 上海华峰新材料研发科技有限公司 | Water-based polyurethane ink binder and preparation method thereof |
| CN109651582B (en) * | 2018-11-27 | 2022-02-01 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane ink binder and preparation method thereof |
| CN110699030A (en) * | 2019-10-11 | 2020-01-17 | 汕头市鑫源化工科技有限公司 | Electrostatic flocking adhesive and preparation method thereof |
| CN110699030B (en) * | 2019-10-11 | 2022-03-15 | 汕头市鑫源化工科技有限公司 | Electrostatic flocking adhesive and preparation method thereof |
| CN112227083A (en) * | 2020-09-30 | 2021-01-15 | 京准化工技术(上海)有限公司 | Fabric water pressure resistance improver and preparation method thereof |
| CN112745795A (en) * | 2020-12-28 | 2021-05-04 | 辽宁恒星精细化工有限公司 | Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method |
| CN112745795B (en) * | 2020-12-28 | 2022-07-15 | 辽宁恒星精细化工有限公司 | Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method |
| CN114892421A (en) * | 2021-06-26 | 2022-08-12 | 上海九裕纺织科技有限公司 | Production process based on flocking on film and application thereof |
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