CN109180900A - A kind of water-based polyurethane and preparation method promoted with PVC artificial leather coating adhesion - Google Patents

A kind of water-based polyurethane and preparation method promoted with PVC artificial leather coating adhesion Download PDF

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Publication number
CN109180900A
CN109180900A CN201810964473.1A CN201810964473A CN109180900A CN 109180900 A CN109180900 A CN 109180900A CN 201810964473 A CN201810964473 A CN 201810964473A CN 109180900 A CN109180900 A CN 109180900A
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parts
water
artificial leather
based polyurethane
leather coating
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范浩军
徐佳丽
颜俊
陈意
孙哲
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Sichuan University
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Sichuan University
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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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/065—Insulating
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    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
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  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The water-based polyurethane and preparation method with PVC artificial leather coating adhesion can be promoted the invention discloses one kind.Using the terminal hydroxy group compound for containing cyano as chain extender, is reacted with isocyanates in the structural unit for being embedded into aqueous polyurethane, improve the adhesive force of aqueous polyurethane Yu PVC artificial leather coating.Meanwhile when water-based polyurethane drying, during emulsion particle mutually merges, zwitterion crosslinked action occurs for the carboxyl for shielding tertiary amine groups and emulsion particle surface inside emulsion particle, further improves its solvent resistance, resistance to bond and hydrolytic resistance.The aqueous polyurethane excellent combination property, and organic solvent is replaced with water, organic solvent pollution can be eliminated from source, there is environment friendly, be particularly suitable as the base resin of the surface treating agent of various flexible PVC materials.

Description

It is a kind of to be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation Method
Technical field
The present invention relates to one kind can promote water-based polyurethane and preparation method with PVC artificial leather coating adhesion, belongs to Synthesis of polymer material technical field.
Background technique
In China, it is (referred to as artificial that people's habit will be known as PVC artificial leather with the artificial leather that polyvinyl chloride resin is raw material production Leather).China is artificial leather production and consumption big country of the world, and by 2017, China's artificial leather, synthetic leather production line and yield were The 2/3 of Gross World Product is occupied, is the industry that plastic industry is given priority to.
Artificial leather is mainly constituted by 3 layers, adhesive layer, middle foaming layer, skin effect layer (surface treating agent).Agent one at table As compounded by polyurethane and special auxiliary agent, be used as artificial leather top layer, it is desirable that have preferable physical property, such as it is water-fast Solution, solvent resistant have good adhesive force etc. with PVC artificial leather coating.
Conventional artificial removes from office surface treatment process and uses solvent type resin, and wherein the volatilization of organic solvent will cause serious ring Border pollution, these solvents are mainly dimethylformamide (DMF), toluene, cyclohexanone, butanone, ethyl acetate and butyl acetate etc.. According to measuring and calculating, in the enterprise for having solvent reclaimer, each artificial leather production line discharges toluene, butanone, acetic acid esters every year 24.5 tons of class solvent.Therefore, artificial leather industry is faced with environmental improvement at high cost, serious waste of resources, environmental pollution for a long time How severe challenge develops water-base resin and substitutes traditional solvent type resin, is the pass for maintaining artificial leather industry sustainable development Key.
But for waterborne polyurethane resin, polyester polyurethane can be divided into according to the type of dihydric alcohol and polyether-type is poly- Urethane.For polyester-type aqueous polyurethane, the ester bond in structure is conducive to be promoted the adhesive force of polyurethane and PVC coating, but Ester bond of intramolecular itself is intolerant to hydrolysis, and the hydrophilic group in aqueous polyurethane can also accelerate this hydrolysis；Polyether-type Aqueous polyurethane hydrolysis is excellent, but solvent resistant and the poor adhesive force that interlayer is applied with PVC, easily occurs when stretching drawing white and roll over white existing As.Therefore, the hydrolytic resistance of agent is difficult to balance with adhesive force at table.
Summary of the invention
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and providing one kind can be promoted and PVC The water-based polyurethane and preparation method of artificial leather coating adhesion.It is the low modulus of the water-based polyurethane, high resiliency, soft without viscous, resistance to Hydrolysis, solvent resistant, and the adhesive force with PVC artificial leather coating is improved, it is suitable as the base resin of agent at PVC table；Using Aqueous polyurethane replaces traditional solvent borne polyurethane as resin at table, can reduce the use of organic solvent, and it is dirty to reduce environment Dye has environment friendly.
(wherein the number of the material is parts by weight) is prepared by following processing step:
(1) preparation of small molecule chain extender N- (2- itrile group ethyl) diethanol amine
50~70 parts of diethanol amine are placed in 250~500 with temperature control, stirring, constant pressure funnel and reflux condensate device In the dry four-hole bottle of ml, lead to nitrogen protection, and be heated to 35~50 DEG C；Then start 40~50 parts of acrylonitrile of dropwise addition, keep temperature Degree is stablized at 50~55 DEG C, is added dropwise within 1~1.5 hour, continues heat preservation 3~5 hours, then vacuum distillation removing remaining third Alkene nitrile to get arrive chain extender N- (2- itrile group ethyl) diethanol amine；
(2) preparation of water-based polyurethane
By 30-80 parts of hydrolysis type dihydric alcohol, 10-20 parts of diisocyanate, 0.1-0.2 parts of trimethylolpropane and catalyst 0.02-0.04 parts of addition reaction vessels are warming up to 75-85 DEG C of reaction 50-70 points under lasting stirring and nitrogen atmosphere protection Clock is added 0.5-3 parts of diethanol amine of small molecule chain extender N- (2- itrile group ethyl), and maintains 75-85 DEG C of reaction 50-70 minutes Performed polymer is made；
2-3 parts of carboxylic short-chain aliphatic dihydric alcohols are dissolved in 5-20 parts of solvents, add 1.8-2.5 parts of triethylamines into Row neutralizes, and is then added into resulting performed polymer, is cooled to 50-55 DEG C of sustained response 3-4 hours, is made containing hydrophilic group Performed polymer；
45 DEG C are cooled to hereinafter, deionized water emulsification is added under high-rate of shear (since system is in alkalinity, COO during this- Ion emulsion particle surface provide hydrophily, and the tertiary amine in chain extender can not be ionized and is shielded in inside emulsion particle), then plus Enter 0.3-0.8 parts of rear crosslinking agents or rear chain extender reacts 2-3 hours at room temperature to get attached with PVC artificial leather coating to that can be promoted The water-base polyurethane emulsion puted forth effort.
Water-based polyurethane solid content is 25%-35%, and the mass fraction of carboxyl is 1.0%-1.5%, and isocyano index is 1.3-1.4。
Hydrolysis type dihydric alcohol be number-average molecular weight be 1000-4000 copolymerization ethyleneoxide propylenenoxide ether glycol, altogether Polyethylene glycol oxide tetrahydrofuran ether glycol, polycarbonate glycol, is copolymerized in propylene oxide tetrahydrofuran ether glycol polypropylene glycol One kind or combinations thereof.
Diisocyanate be different Buddhist diisocyanates,2,4Toluene di-isocyanate(TDI),4,4 , Two isocyanide of diphenyl-methane Acid esters, hexamethylene diisocyanate, paraphenylene diisocyanate or carbodiimides and uretonimine-modified4,4 , Hexichol first One of alkane diisocyanate or combinations thereof.
Catalyst be dibutyl tin laurate, stannous octoate, lauric acid bismuth, bismuth neodecanoate, isooctyl acid bismuth, bismuth naphthenate, Dimethyl cyclohexyl amine orNAny one of dionin quinoline.
Carboxylic short-chain aliphatic dihydric alcohol is any one of dihydromethyl propionic acid or dimethylolpropionic acid.
Rear crosslinking agents or rear chain extender be ethyl orthosilicate,γAminopropyl triethoxysilane,N-(βAminoethyl)-γ- At least one of aminopropyltriethoxy dimethoxysilane, diethylenetriamine and ethylenediamine.
Small molecule chain extenderN-(2Itrile group ethyl) diethanol amine has the following structure formula:
。
Small molecule chain extenderN-(2Itrile group ethyl) diethanol amine specific synthetic route are as follows:
。
Compared with prior art, the present invention having the positive effect that:
(1) water-based polyurethane of the invention withN-(2Itrile group ethyl) diethanol amine as small molecule chain extender, draws in the molecule Highly polar group-CN is entered, has improved the adhesive force of itself and highly polar PVC artificial leather coating, be particularly suitable for PVC artificial leather The base polyurethane resin of agent at table, and-CN heat resistance and solvent resistance are excellent；
(2) water-based polyurethane provided by the invention mutually merges between emulsion particle in the drying process, shields inside emulsion particle Tertiary amine groups and emulsion particle surface carboxyl occur zwitterion crosslinked action, be effectively promoted its adhesive force, resistance to bond and Solvent resistance；Meanwhile zwitterion interacts and loses hydrophily, further improves anti-hydrolytic performance；
(3) present invention usesN-(2Itrile group ethyl) diethanol amine chain extender, terminal hydroxy group symmetrical configuration, reactivity phase Together, be conducive to the progress of chemical reaction and the regulation of polymer performance；
(4) traditional solvent borne polyurethane is substituted as resin at table using aqueous polyurethane of the invention, eliminating from source has Solvent pollution, eliminate safe hidden trouble, economize on resources, improve worker's working environment, improve artificial leather ecological grades and Competitiveness in the international market.
Detailed description of the invention
Fig. 1 is that embodiment 1 usesN-(2Itrile group ethyl) diethanol amine as chain extender and comparative example 1 uses a contracting diethyl Infrared spectrum comparison diagram of the glycol as the aqueous polyurethane of chain extender.Compared with comparative example 1, embodiment 1 is in 2247 cm-1Place There is apparent-CN characteristic absorption peak, shows that chain extender N- (2- itrile group ethyl) diethanol amine has been successfully accessed aqueous poly- ammonia In ester.
Specific embodiment
The present invention is specifically described below by embodiment, is served only for that invention is further explained, no It can be interpreted as limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention Make some nonessential modifications and adaptations.
Embodiment 1:
(1) 30 parts of the polypropylene glycol by number-average molecular weight for 2000, copolymerization propylene oxide tetrahydrofuran ether glycol, number-average molecular weight 20 parts of copolymerization ethylene oxide tetrahydrofuran ether glycol, 9 parts of different Buddhist diisocyanates, hexa-methylene diisocyanate for 1000 0.04 part of 9 parts of ester, 0.2 part of trimethylolpropane and lauric acid bismuth addition reaction vessel, in lasting stirring and nitrogen atmosphere protection Under, it is warming up to 85 DEG C and reacts 1 hour, small molecule chain extender is addedN-(2Itrile group ethyl) 0.9 part of diethanol amine, and maintain 85 DEG C reaction 1 hour obtained performed polymer；
(2) 2.6 parts of dihydromethyl propionic acids are dissolved in 15 parts of acetone, add 2.15 parts of triethylamines and is neutralized, then will It is added in resulting performed polymer, is cooled to 55 DEG C of sustained responses 3 hours, and the performed polymer containing hydrophilic group is made；
(3) 45 DEG C are cooled to hereinafter, 200 parts of deionized water emulsifications, then 0.4 part of addition are added under high-rate of shearN-(βAmmonia Ethyl)-γAminopropyltriethoxy dimethoxysilane reacts 3 hours at room temperature to get attached with PVC artificial leather coating to that can be promoted The water-base polyurethane emulsion puted forth effort.
Embodiment 2
(1) number-average molecular weight is divided equally for 2,000 40 parts of polypropylene glycol, 10 parts of ethylene oxide tetrahydrofuran ether glycol of copolymerization, number Copolymerization ethylene oxide tetrahydrofuran ether glycol 10 part, different Buddhist diisocyanates 14 part, hexa-methylene two of the son amount for 1000 0.04 part of 4 parts of isocyanates, 0.2 part of trimethylolpropane and lauric acid bismuth addition reaction vessel, in lasting stirring and nitrogen gas Under atmosphere protection, it is warming up to 85 DEG C and reacts 1 hour, small molecule chain extender is addedN-(2Itrile group ethyl) 1 part of diethanol amine, and maintain In 85 DEG C of reactions, 1 hour obtained performed polymer；
(2) 2.5 parts of dihydromethyl propionic acids are dissolved in 15 parts of acetone, add 2 parts of triethylamines and neutralized, is then added Enter in resulting performed polymer, be cooled to 55 DEG C of sustained responses 3 hours, the performed polymer containing hydrophilic group is made；
(3) 45 DEG C are cooled to emulsify hereinafter, 180 parts of deionized waters are added under high-rate of shear, 0.1 part of positive silicic acid is then added Ethyl ester, 0.5 part of diethylenetriamine react 2 hours at room temperature to get water base poly- with PVC artificial leather coating adhesion to that can be promoted Urethane lotion.
Embodiment 3:
(1) by number-average molecular weight be 2000 20 parts of polypropylene glycol, 16 parts of polycarbonate glycol,2,4Toluene di-isocyanate(TDI) 7.5 parts, 0.02 part of 2.5 parts of hexamethylene diisocyanate, 0.1 part of trimethylolpropane and dibutyl tin laurate addition reaction Container is warming up to 65 DEG C and reacts 1 hour, small molecule chain extender is added under lasting stirring and nitrogen atmosphere protectionN-(2Itrile group Ethyl) 0.8 part of diethanol amine, and maintain 75 DEG C of reactions, 1 hour obtained performed polymer；
(2) 2.3 parts of dihydromethyl propionic acids are dissolved in 15 parts of acetone, add 1.9 parts of triethylamines and neutralized, then by it It is added in resulting performed polymer, is cooled to 55 DEG C of sustained responses 3 hours, the performed polymer containing hydrophilic group is made；
(3) 45 DEG C are cooled to emulsify hereinafter, 110 parts of deionized waters are added under high-rate of shear, 0.8 part of positive silicic acid is then added Ethyl ester reacts 2 hours at room temperature to get to the water-base polyurethane emulsion that can be promoted with PVC artificial leather coating adhesion.
Embodiment 4:
(1) by number-average molecular weight be 4000 15 parts of polycarbonate glycol, number-average molecular weight be 1000 copolymerization ethylene oxide oxygen 25 parts of propylene ether glycol of change,2,49 parts of toluene di-isocyanate(TDI), 3 parts of hexamethylene diisocyanate, trimethylolpropane 0.2 Part and 0.03 part of addition reaction vessel of dibutyl tin laurate are warming up to 65 DEG C instead under lasting stirring and nitrogen atmosphere protection It answers 1 hour, small molecule chain extender is addedN-(2Itrile group ethyl) 0.7 part of diethanol amine, and maintain 75 DEG C of reactions and be made for 1 hour Performed polymer；
(2) 2.1 parts of dihydromethyl propionic acids are dissolved in 15 parts of acetone, add 1.8 parts of triethylamines and neutralized, then by it It is added in resulting performed polymer, is cooled to 55 DEG C of sustained responses 3 hours, the performed polymer containing hydrophilic group is made；
(3) 45 DEG C are cooled to hereinafter, 120 parts of deionized water emulsifications, then 0.4 part of addition are added under high-rate of shearγAmmonia third Ethyl triethoxy silicane alkane react at room temperature 2 hours to get to can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion cream Liquid.
Comparative example 1:
(1) 30 parts of the polypropylene glycol by number-average molecular weight for 2000, copolymerization propylene oxide tetrahydrofuran ether glycol, number-average molecular weight 20 parts of copolymerization ethylene oxide tetrahydrofuran ether glycol, 9 parts of different Buddhist diisocyanates, hexa-methylene diisocyanate for 1000 0.04 part of 9 parts of ester, 0.2 part of trimethylolpropane and lauric acid bismuth addition reaction vessel, in lasting stirring and nitrogen atmosphere protection Under, it is warming up to 85 DEG C and reacts 1 hour, be added 0.9 part of diglycol, and maintain 85 DEG C of reactions, 1 hour obtained performed polymer；
(2) 2.6 parts of dihydromethyl propionic acids are dissolved in 15 parts of acetone, add 2.15 parts of triethylamines and is neutralized, then will It is added in resulting performed polymer, is cooled to 55 DEG C of sustained responses 3 hours, and the performed polymer containing hydrophilic group is made；
(3) 45 DEG C are cooled to hereinafter, 200 parts of deionized water emulsifications, then 0.4 part of addition are added under high-rate of shearN-(βAmmonia Ethyl)-γAminopropyltriethoxy dimethoxysilane reacts 3 hours at room temperature to get water-base polyurethane emulsion is arrived.
Test result:
(1) PVC base will be coated on after the addition of aqueous polyurethane emulsion obtained by each embodiment and comparative example thickener, levelling agent compounding On material, adhesive force test is carried out according to GB/T 9286-1998 standard after Drying and cooling at 120 DEG C, is as a result evaluated with 0-5 grades, 0 Preferably, 5 grades worst, and for general purposes, preceding three-level is satisfactory for grade；
(2) aqueous polyurethane emulsion obtained by each embodiment and comparative example is first placed in polytetrafluoroethylene (PTFE) template, at room temperature slowly Air-dry, place into 60 DEG C of vacuum ovens drying and no longer change to glue film quality, obtain with a thickness of 3.0mm it is transparent, without gas It steeps, the polyurethane latex film of surfacing, then carries out pliability, viscosity, hydrolytic resistance, solvent resistance test:
According to the mechanical property of ASTM D412-Diec standard test glue film, as a result indicate pliability with 1-5 grades: very soft is 5 Grade, softness are 4 grades, and relatively soft is 3 grades, and harder is 2 grades, and hard is 1 grade；
Resistance to blocking test is carried out according to HG/T 3828-2006 standard, adhesion grade is as a result indicated with A-F, 0-5 indicates surface Grade is damaged, grade is smaller, and antistick characteristic is better；
Hydrolytic resistance test is carried out according to QB/T 4671-2014 standard A method, the guarantor of front and back tensile strength is as a result hydrolyzed with glue film Rate is stayed to carry out quantificational expression；
Film is cut into the cm square of 2 cm × 2, weighing is immersed in 25 DEG C of toluene, is re-weighed after 24 h, to increase weight after immersion Rate indicates solvent resistance.
1 one kind of table can promote the water-based polyurethane the performance test results with PVC artificial leather coating adhesion
Project example Comparative example 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Adhesive force/grade 4 2 2 1 1
Pliability/grade 5 5 4 5 4
Viscosity/grade C-0 B-0 B-0 B-0 B-0
Hydrolytic resistance/% 88 92 94 90 95
Solvent resistance/% 149 121 116 125 109
As shown in Table 1, embodiment 1-4 show with the preferable adhesive force of PVC coating, and form a film it is soft without viscous, hydrolysis, it is resistance to Solvent, excellent combination property.Compared with comparative example 1, adhesive force of the embodiment 1 on PVC is significantly improved, and illustrates point Highly polar group-CN is introduced in son has remarkable result to the adhesive force for improving aqueous polyurethane, simultaneously as the aqueous polyurethane It is mutually merged between emulsion particle in the drying process, the carboxyl for shielding tertiary amine groups and emulsion particle surface inside emulsion particle occurs Zwitterion crosslinked action improves its resistance to bond, hydrolytic resistance and solvent resistance in varying degrees, but since itrile group ethyl exists Molecular side chain, pliability are held essentially constant.

Claims (7)

1. one kind can promote the water-based polyurethane and preparation method with PVC artificial leather coating adhesion, it is characterised in that by such as Lower technique preparation, wherein the number of material is parts by weight:
(1) preparation of small molecule chain extender N- (2- itrile group ethyl) diethanol amine
50~70 parts of diethanol amine are placed in 250~500 with temperature control, stirring, constant pressure funnel and reflux condensate device In the dry four-hole bottle of ml, lead to nitrogen protection, and be heated to 35~50 DEG C；Then start 40~50 parts of acrylonitrile of dropwise addition, keep temperature Degree is stablized at 50~55 DEG C, is added dropwise within 1~1.5 hour, continues heat preservation 3~5 hours, then vacuum distillation removing remaining third Alkene nitrile to get arrive chain extender N- (2- itrile group ethyl) diethanol amine；
(2) preparation of water-based polyurethane
By 30-80 parts of hydrolysis type dihydric alcohol, 10-20 parts of diisocyanate, 0.1-0.2 parts of trimethylolpropane and catalyst 0.02-0.04 parts of addition reaction vessels are warming up to 75-85 DEG C of reaction 50-70 points under lasting stirring and nitrogen atmosphere protection Clock is added 0.5-3 parts of diethanol amine of small molecule chain extender N- (2- itrile group ethyl), and maintains 75-85 DEG C of reaction 50-70 minutes Performed polymer is made；
2-3 parts of carboxylic short-chain aliphatic dihydric alcohols are dissolved in 5-20 parts of solvents, add 1.8-2.5 parts of triethylamines into Row neutralizes, and is then added into resulting performed polymer, is cooled to 50-55 DEG C of sustained response 3-4 hours, is made containing hydrophilic group Performed polymer；
Be cooled to 45 DEG C hereinafter, under high-rate of shear be added deionized water emulsification, then be added 0.3-0.8 parts of rear crosslinking agents or Rear chain extender reacts 2-3 hours at room temperature to get to the water-base polyurethane emulsion that can be promoted with PVC artificial leather coating adhesion.
2. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the water-based polyurethane solid content is 25%-35%, and the mass fraction of carboxyl is 1.0%-1.5%, isocyano Index is 1.3-1.4.
3. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the hydrolysis type dihydric alcohol is the copolymerization ethyleneoxide propylenenoxide that number-average molecular weight is 1000-4000 Ether glycol, copolymerization ethylene oxide tetrahydrofuran ether glycol, polypropylene glycol, polycarbonate glycol, copolymerization propylene oxide tetrahydrofuran One of ether glycol or combinations thereof.
4. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the diisocyanate be different Buddhist diisocyanates,2,4Toluene di-isocyanate(TDI),4,4 , Hexichol Methane diisocyanate, hexamethylene diisocyanate, paraphenylene diisocyanate or carbodiimides and uretonimine-modified4,4 , One of '-diphenylmethane diisocyanate or combinations thereof.
5. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the catalyst be dibutyl tin laurate, stannous octoate, lauric acid bismuth, bismuth neodecanoate, isooctyl acid bismuth, Bismuth naphthenate, dimethyl cyclohexyl amine orNAny one of dionin quinoline.
6. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the carboxylic short-chain aliphatic dihydric alcohol is any in dihydromethyl propionic acid or dimethylolpropionic acid Kind.
7. one kind according to claim 1 can be promoted and the water-based polyurethane of PVC artificial leather coating adhesion and preparation side Method, it is characterised in that the rear crosslinking agents or rear chain extender be ethyl orthosilicate,γAminopropyl triethoxysilane,N-(βAmmonia Ethyl)-γAt least one of aminopropyltriethoxy dimethoxysilane, diethylenetriamine and ethylenediamine.
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