CN106753161A - Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof - Google Patents

Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof Download PDF

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Publication number
CN106753161A
CN106753161A CN201611095770.4A CN201611095770A CN106753161A CN 106753161 A CN106753161 A CN 106753161A CN 201611095770 A CN201611095770 A CN 201611095770A CN 106753161 A CN106753161 A CN 106753161A
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polyol
heat resistant
resistant type
component polyurethane
type pvc
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Inventor
沈建峰
纪尚超
石磊
李寿伟
沈连根
徐欣欣
武锦峰
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JIAXING HEXIN CHEMICAL INDUSTRY CO LTD
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JIAXING HEXIN CHEMICAL INDUSTRY CO LTD
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Priority to CN201611095770.4A priority Critical patent/CN106753161A/en
Publication of CN106753161A publication Critical patent/CN106753161A/en
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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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids

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

Abstract

A kind of compound dual-component polyurethane adhesives of heat resistant type PVC, host is a kind of base polyurethane prepolymer for use as, and the constituent of its raw material is：Oligomer polyol, hydroxyl vinyl chloride-vinyl acetate resin, chain extender, polyisocyanates, catalyst A and solvent, its mass ratio is 100: (5~20): (0~20): (10~30): (0~0.05): (300~800), 1000~20000cps/25 DEG C of viscosity, solid content 20~50%；Curing agent is the base polyurethane prepolymer for use as of the terminal isocyanate group that polyisocyanates is synthesized with polyol by pre-polymerization method, 10~15wt% of isocyanate group content, solid content 70~80%.Due to containing hydroxyl vinyl chloride-vinyl acetate resin, having good affinity to PVC base, the product initial adhesive strength being made is high, and plasticizer-resistant effect is good, while good peel strength is reached, with tear load very high, and with heat resistance very high.

Description

Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof
Technical field
The present invention relates to polyurethane material field, and in particular to a kind of compound two-component polyurethane adhesives of heat resistant type PVC Stick and preparation method thereof.
Background technology
Polyurethane adhesive refers to contain carbamate groups (- NHCOO-) or NCO in strand The adhesive of (- NCO-), polyurethane adhesive has an activity and polarity of height, and the base material containing active hydrogen, such as foam, The porous materials such as plastics, timber, leather, fabric, paper, ceramics, and any surface finish such as metal, glass, rubber, plastics material Material has excellent chemical adhesive power.Many PVC products, such as water wing, window advertising, plastics swimming pool etc., are required for using glue Stick, and polyurethane adhesive is widely used with its excellent performance, but polyurethane adhesive on the market, it is general Store-through in the not good problem of heat resistance, make need to the presence of the product of heat resistant requirements when peel off the variety of problems such as decline, degumming.
The content of the invention
It is an object of the invention to provide a kind of compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof, The adhesive is mainly used in making the product of heat resistant requirements PVC, reaches the application requirement of product.
The compound dual-component polyurethane adhesives of this heat resistant type PVC include host and curing agent, and host is a kind of poly- ammonia Ester performed polymer, the constituent of its raw material is：Oligomer polyol, hydroxyl vinyl chloride-vinyl acetate resin, chain extender, polyisocyanates, catalysis Agent A and solvent, its mass ratio are 100: (5~20): (0~20): (10~30): (0~0.05): (300~800), its performance Index is：1000~20000cps/25 DEG C of viscosity, solid content 20~50%；The curing agent is polyisocyanates and polyhydroxy The base polyurethane prepolymer for use as of the terminal isocyanate group that compound is synthesized by pre-polymerization method, its isocyanate group content be 10~ 15wt%, solid content is 70~80%.
The host of polyurethane adhesive of the invention mainly constitutes adhesive by oligomer polyol, hydroxyl vinyl chloride-vinyl acetate resin The hard section of soft section, small molecule polyol or amine (chain extender) and polyisocyanates composition adhesive, catalyst, solvent are constituted.Make Used time, take 100 parts of host, 0.5~20 part of curing agent and appropriate solvent are mixed, and are stirred, you can for PVC film with The dry-lamination process of other materials.This polyurethane adhesive to PVC base due to containing hydroxy chloride vinegar resin component, having Good affinity, the product initial adhesive strength being made is high, and plasticizer-resistant effect is good, while good peel strength is reached, With tear load very high.Because of the introducing of hydroxyl vinyl chloride-vinyl acetate resin, the spatial configuration of molecules of resin is changed, make it have Heat resistance very high, surveys its peel strength still very high at 80 DEG C.
Specific embodiment
The compound dual-component polyurethane adhesives of this heat resistant type PVC include host and curing agent, and host is a kind of poly- ammonia Ester performed polymer, the constituent of its raw material is：Oligomer polyol, hydroxyl vinyl chloride-vinyl acetate resin, chain extender, polyisocyanates, catalysis Agent A and solvent, its mass ratio are 100: (5~20): (0~20): (10~30): (0~0.05): (300~800), its performance Index is：1000~20000cps/25 DEG C of viscosity, solid content 20~50%；The curing agent is polyisocyanates and polyhydroxy The base polyurethane prepolymer for use as of the terminal isocyanate group that compound is synthesized by pre-polymerization method, its isocyanate group content be 10~ 15wt%, solid content is 70~80%.
In this compound dual-component polyurethane adhesives of heat resistant type PVC, the oligomer polyol in host is by binary Acid and polyalcohol carry out PEPA obtained in polyesterification reaction, above-mentioned binary acid and polyalcohol in the presence of catalyst B Mass ratio be 1: (0.5~2)；Wherein, described binary acid is that adipic acid and terephthalic acid (TPA) are mixed with any mass ratio Mixture；Described polyalcohol is two or more in ethylene glycol, diglycol, 1,4- butanediols arbitrarily comparing The mixed mixture of example；The catalyst B is tetraisopropyl titanate.
In this compound dual-component polyurethane adhesives of heat resistant type PVC, the oligomer polyol in adhesive host is also May include poly- ε-oneself in alcohol, PPG, poly- carbon polyol, polyester polyethers polyols blend, the poly- carbon polyols blend of polyester One or more.
In this compound dual-component polyurethane adhesives of heat resistant type PVC, the chain extender in adhesive host can be small point Sub- polyalcohol or amine such as 1,4- butanediols (1,4-BG), ethylene glycol (EG), diglycol (DEG), ethylenediamine (EA), second One or more mixture in glycol amine (MEA), different Fo Er diamines (IPDA)；Described solvent be ketone, ethers, One or more mixture in esters solvent；The catalyst A be dibutyl tin laurate, triethylene diamine, One or more mixtures in tetramethyl diethylenetriamines；The polyisocyanates is that 4,4 '-diphenyl methane two is different One or more mixture in cyanate (MDI), Carbodiimide-Modified MDI, toluene di-isocyanate(TDI) (TDI).
In this compound dual-component polyurethane adhesives of heat resistant type PVC, the isocyanates in curing agent can be 4,4 '-two In methylenebis phenyl isocyanate, Carbodiimide-Modified MDI, toluene di-isocyanate(TDI) (TDI) one or more Mixture；Described polyol is one or two in trimethylolpropane or 1,2,6- hexanetriols or glycerine Mixture above.
This heat resistant type PVC is combined with the preparation method of dual-component polyurethane adhesive, can be following steps：
(1) preparation of PEPA：By binary acid and polyalcohol under composite catalyst B effects, under nitrogen protection Polyesterification reaction is carried out in 140 DEG C~250 DEG C, reaction to acid number is reduced to below 1mgKOH/g, and hydroxyl value is 30~200mgKOH/g When stop reaction, be obtained PEPA；
(2) preparation of adhesive host：Hydroxyl vinyl chloride-vinyl acetate resin is dissolved in partial solvent, gained is prepared with step (1) PEPA, chain extender, isocyanates add reactor together, be warmed up to 50~80 DEG C of fully reactions；Add portion Divide solvent dilution, be dividedly in some parts remaining isocyanates until viscosity meets the requirements；It is eventually adding small molecule polyol and residue Solvent terminating reaction, is cooled to 35~40 DEG C of dischargings；
(3) preparation of curing agent：Polyisocyanates and polyol are reacted at 45~90 DEG C, polyisocyanates It is 2~3.5 with the mol ratio of polyalcohol:1, the content of NCO is between 10%~15% in control curing agent.
With reference to example, the invention will be further described, but protection scope of the present invention is not limited to this.It is each to implement In example in raw material used, from the product purchased from German company Solter, the trade mark is VM-390 to hydroxyl vinyl chloride-vinyl acetate resin；Polyethers is more First alcohol produces polytetrahydrofuran polyol, molecular weight 2000 for Japan；Remaining material is self-control.
Embodiment 1：
First, PEPA 1 is prepared：
822gAA, 385gEG and 5g catalyst tetrabutyl titanate are mixed, being heated to 210 DEG C under nitrogen protection is gathered Esterification, reacts 18Hr, and reaction is stopped when acid number 0.3mgKOH/g, hydroxyl value are 56mgKOH/g, and 960g polyester polyols are obtained Alcohol.
2nd, PEPA 2 is prepared：
370gAA, 247gPTA, 160gEG, 370gDEG and 5g catalyst tetrabutyl titanate are mixed, under nitrogen protection Being heated to 240 DEG C carries out polyesterification reaction, reacts 20Hr, stops when acid number is 0.3mgKOH/g, hydroxyl value is 225mgKOH/g anti- Should, PEPA 960g is obtained.
3rd, polyurethane adhesive host is prepared：
(1) 20g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 40gMEK (butanone), what is prepared with 150g after stirring and dissolving is poly- Ester polyol 1,20g PEPAs 2 are put into reactor together, are slowly heated to 50 DEG C, and stirring is well mixed it.
(2) 20gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) add catalyst dibutyltin dilaurylate 0.03g, according to its viscosity be dividedly in some parts 12.3gMDI, 240gETAC (ethyl acetate), 240gMEK (butanone), regulation viscosity is to 3200mPa.s/25 DEG C
(4) 0.5gEG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 710.3g, its 3200mPa.s/25 DEG C of viscosity, solid content 29.78%.
4th, curing agent is prepared：
During TDI 100g and acetic acid second vinegar 48.86g put into reactor, 0.5Hr is stirred under the conditions of 50 DEG C, progressively dripped Plus three antelope methylpropane 25.66g, 8HR is reacted, polyisocyanic acid vinegar is 3 with the mol ratio of polyalcohol:1, obtain 174.40g solidifications Agent, its isocyanate group content (NCO) is 14.59%, and solid content is 72.25%.
Embodiment 2：
First, PEPA 3 is prepared：
697gAA, 476gBG and 5g catalyst tetrabutyl titanate are mixed, being heated to 220 DEG C under nitrogen protection is gathered Esterification, reacts 16Hr, and reaction is stopped when acid number 0.3mgKOH/g, hydroxyl value are 56mgKOH/g, and PEPA is obtained 961g。
2nd, polyurethane adhesive host is prepared：
(1) 20g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 40gMEK (butanone), what is prepared with 145g after stirring and dissolving is poly- Ester polyol 3, PEPA 2 prepared by 25g embodiments 1 is put into reactor together, is slowly heated to 50 DEG C, and stirring makes It is well mixed.
(2) 22gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) add catalyst dibutyltin dilaurylate 0.03g, according to its viscosity be dividedly in some parts 12.5gMDI, 160gETAC (ethyl acetate), 325gMEK (butanone), regulation viscosity is to 2530mPa.s/25 DEG C
(4) 0.5gEG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 706.8g, its 2530mPa.s/25 DEG C of viscosity, solid content 30.13%.
Embodiment 3：
First, PEPA 4 is prepared：
505gAA, 216gPTA, 230gEG, 230gDEG and 5g catalyst tetrabutyl titanate are mixed, under nitrogen protection Being heated to 230 DEG C carries out polyesterification reaction, reacts 18Hr, stops when acid number is 0.3mgKOH/g, hydroxyl value is 112mgKOH/g anti- Should, PEPA 960g is obtained.
2nd, polyurethane adhesive host is prepared：
(1) 20g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 40gMEK (butanone), made with 120g embodiments 2 after stirring and dissolving Standby PEPA 3,25g PEPAs 4 manufactured in the present embodiment, 30g polytetrahydrofuran polyols (molecular weight 2000, Japan produces) put into reactor together, slowly it is heated to 50 DEG C, stirring is well mixed it.
(2) 18gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) add catalyst dibutyltin dilaurylate 0.03g, according to its viscosity be dividedly in some parts 10.3gMDI, 180gETAC (ethyl acetate), 200gMEK (butanone), regulation viscosity is to 5615mPa.s/25 DEG C
(4) 0.5gEG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 608.9g, its 5615mPa.s/25 DEG C of viscosity, solid content 34.38%.
Embodiment 4：
First, PEPA 5 is prepared：
831gAA, 375gEG and 5g catalyst tetrabutyl titanate are mixed, being heated to 210 DEG C under nitrogen protection is gathered Esterification, reacts 16Hr, and reaction is stopped when acid number 0.4mgKOH/g, hydroxyl value are 38mgKOH/g, and PEPA is obtained 961g。
2nd, polyurethane adhesive host is prepared：
(1) 15g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 30gMEK (butanone), the polyester prepared with 75g after stirring and dissolving Polyalcohol 5, PEPA 3 prepared by 80g embodiments 2, puts into reactor together, is slowly heated to 50 DEG C, and stirring makes It is well mixed.
(2) 20gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) catalyst dibutyltin dilaurylate 0.03g is added, 9.3gMDI, 200gETAC is dividedly in some parts according to its viscosity (ethyl acetate), 280gMEK (butanone), regulation viscosity is to 7530mPa.s/25 DEG C
(4) 0.5gEG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 713.6g, its 7530mPa.s/25 DEG C of viscosity, solid content 29.67%.
Embodiment 5：
First, PEPA 6 is prepared：
708gAA, 460gBG and 5g catalyst tetrabutyl titanate are mixed, being heated to 220 DEG C under nitrogen protection is gathered Esterification, reacts 16Hr, and reaction is stopped when acid number 0.3mgKOH/g, hydroxyl value are 38mgKOH/g, and PEPA is obtained 961g。
2nd, polyurethane adhesive host is prepared：
(1) 30g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 60gMEK (butanone), what is prepared with 180g after stirring and dissolving is poly- Ester polyol 6, PEPA 2 prepared by 10g embodiments 1 is put into reactor together, is slowly heated to 50 DEG C, stirring It is well mixed it.
(2) 16gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) catalyst dibutyltin dilaurylate 0.03g is added, 8.5gMDI, 150gETAC is dividedly in some parts according to its viscosity (ethyl acetate), 160gMEK (butanone), regulation viscosity is to 10380mPa.s/25 DEG C
(4) 0.5gBG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 598.6g, its 10380mPa.s/25 DEG C of viscosity, solid content 39.86%.
Embodiment 6：
Prepare polyurethane adhesive host：
(1) 25g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 50gMEK (butanone), what is prepared with 160g after stirring and dissolving is poly- Ester polyol 3, PEPA 1 prepared by 20g embodiments 1 is put into reactor together, is slowly heated to 50 DEG C, stirring It is well mixed it.
(2) 20gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) add catalyst dibutyltin dilaurylate 0.03g, according to its viscosity be dividedly in some parts 14.3gMDI, 235gETAC (ethyl acetate), 160gMEK (butanone), regulation viscosity is to 9780mPa.s/25 DEG C.
(4) 0.5gBG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 653.8g, its 9780mPa.s/25 DEG C of viscosity, solid content 35.32%.
Embodiment 7：
Prepare polyurethane adhesive host：
(1) 15g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 30gMEK (butanone), made with 180g embodiments 5 after stirring and dissolving Standby PEPA 6, PEPA 4 prepared by 20g embodiments 3, puts into reactor together, is slowly heated to 50 DEG C, stirring is well mixed it.
(2) 15gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) catalyst dibutyltin dilaurylate 0.03g is added, 7.2gMDI, 210gETAC is dividedly in some parts according to its viscosity (ethyl acetate), 200gMEK (butanone), regulation viscosity is to 1020mPa.s/25 DEG C.
(4) 0.5gBG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 648.7g, its 1020mPa.s/25 DEG C of viscosity, solid content 35.25%.
Embodiment 8：
Prepare polyurethane adhesive host：
(1) 30g hydroxyl vinyl chloride-vinyl acetate resins are taken, is well mixed with 60gMEK (butanone), made with 150g embodiments 5 after stirring and dissolving Standby PEPA 6, PEPA 4 prepared by 30g embodiments 3,30g polytetrahydrofuran polyols (molecular weight 2000, day This product) put into reactor together, slowly it is heated to 50 DEG C, stirring is well mixed it.
(2) 16gMDI is put into, 75 DEG C are warming up to, is reacted 1 hour.
(3) add catalyst dibutyltin dilaurylate 0.03g, according to its viscosity be dividedly in some parts 10.2gMDI, 330gETAC (ethyl acetate), 320gMEK (butanone), regulation viscosity is to 2870mPa.s/25 DEG C.
(4) 0.5gBG is added, is reacted 1 hour at 70 DEG C, terminate its reaction, finally obtain adhesive host 928.3g, its 2870mPa.s/25 DEG C of viscosity, solid content 25.16%.
Above-mentioned 8 enumerated polyurethane adhesive embodiment test results are as shown in the table
Solvent described in table can be any solvent that MEK (butanone), ETAC (ethyl acetate) or client use
Can be seen that polyurethane adhesive is combined with excellent bonding force to PVC screen cloths by the test result in table, Instant peel strength is also higher under the conditions of 80 DEG C, meets heat resistant requirements, can carry out industry production.

Claims (6)

1. a kind of compound dual-component polyurethane adhesives of heat resistant type PVC, including host and curing agent, it is characterised in that the master Agent is a kind of base polyurethane prepolymer for use as, and the constituent of its raw material is：Oligomer polyol, hydroxyl vinyl chloride-vinyl acetate resin, chain extender, polyisocyanate Cyanate, catalyst A and solvent, its mass ratio are 100: (5~20): (0~20): (10~30): (0~0.05): (300~ 800), its performance indications is：1000~20000cps/25 DEG C of viscosity, solid content 20~50%；The curing agent is polyisocyanic acid The base polyurethane prepolymer for use as of the terminal isocyanate group that ester and polyol are synthesized by pre-polymerization method, its isocyanate group content is 10~15wt%, solid content is 70~80%.
2. compound dual-component polyurethane adhesives of heat resistant type PVC as claimed in claim 1, it is characterised in that described is gluing Oligomer polyol in agent host is as obtained in binary acid and polyalcohol carry out polyesterification reaction in the presence of catalyst B The mass ratio of PEPA, above-mentioned binary acid and polyalcohol is 1: (0.5~2)；Wherein, described binary acid be adipic acid and The mixture that terephthalic acid (TPA) is mixed with any mass ratio；Described polyalcohol is ethylene glycol, diglycol, 1,4- fourths two Two or more in alcohol is with the mixed mixture of arbitrary proportion；The catalyst B is tetraisopropyl titanate.
3. compound dual-component polyurethane adhesives of heat resistant type PVC as claimed in claim 2, it is characterised in that described is gluing Oligomer polyol in agent host also include poly- ε-oneself in alcohol, PPG, poly- carbon polyol, the mixing of polyester polyethers it is polynary One or more of the poly- carbon polyols blend of alcohol, polyester.
4. compound dual-component polyurethane adhesives of heat resistant type PVC as claimed in claim 3, it is characterised in that described is gluing Chain extender in agent host is one or more the mixture in small molecule polyol or amine；Described solvent is ketone One or more mixture in class, ethers, esters solvent；The catalyst A is dibutyl tin laurate, three second One or more mixtures in alkene diamines, tetramethyl diethylenetriamines；The polyisocyanates is 4,4 '-diphenylmethyl One or more mixed in alkane diisocyanate (MDI), Carbodiimide-Modified MDI, toluene di-isocyanate(TDI) (TDI) Compound.
5. compound dual-component polyurethane adhesives of heat resistant type PVC as claimed in claim 4, it is characterised in that the curing agent In isocyanates be 4,4 '-methyl diphenylene diisocyanate, Carbodiimide-Modified MDI, toluene di-isocyanate(TDI) (TDI) In one or more mixture；Described polyol be trimethylolpropane or 1,2,6- hexanetriols or One or more mixture in person's glycerine.
6. the heat resistant type PVC described in claim 4 or 5 is combined the preparation method for using dual-component polyurethane adhesive, and its feature exists It is in step：
(1) preparation of PEPA：By binary acid and polyalcohol under composite catalyst B effects, under nitrogen protection in 140 DEG C~250 DEG C carry out polyesterification reaction, reaction to acid number is reduced to below 1mgKOH/g, stops when hydroxyl value is 30~200mgKOH/g Reaction, is obtained PEPA；
(2) preparation of adhesive host：Hydroxyl vinyl chloride-vinyl acetate resin is dissolved in partial solvent, with gathering obtained by step (1) preparation Ester polyol, chain extender, isocyanates are added in reactor together, are warmed up to 50~80 DEG C of fully reactions；Add part molten Dilution agent, is dividedly in some parts remaining isocyanates until viscosity meets the requirements；It is eventually adding small molecule polyol and residual solvent Terminating reaction, is cooled to 35~40 DEG C of dischargings；
(3) preparation of curing agent：Polyisocyanates and polyol are reacted at 45~90 DEG C, polyisocyanates with it is many The mol ratio of first alcohol is 2~3.5:1, the content of NCO is between 10%~15% in control curing agent.
CN201611095770.4A 2016-12-02 2016-12-02 Compound dual-component polyurethane adhesives of heat resistant type PVC and preparation method thereof Pending CN106753161A (en)

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CN109267352A (en) * 2018-09-04 2019-01-25 温州大学新材料与产业技术研究院 A kind of high solid low viscosity mirror face synthetic leather inorganic agent and preparation method thereof
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CN115923291A (en) * 2022-12-20 2023-04-07 佛山市彩龙镀膜包装材料有限公司 Alcohol-resistant BOPP aluminized film and preparation method thereof
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CN108148533A (en) * 2018-01-23 2018-06-12 佛山市加恩新材料有限公司 A kind of hot melt adhesive for being used for the outer transfer technique of film and preparation method thereof
CN108148533B (en) * 2018-01-23 2021-01-29 佛山市加恩新材料有限公司 Hot melt adhesive for off-film transfer printing technology and preparation method thereof
CN109267352A (en) * 2018-09-04 2019-01-25 温州大学新材料与产业技术研究院 A kind of high solid low viscosity mirror face synthetic leather inorganic agent and preparation method thereof
CN109321196A (en) * 2018-09-30 2019-02-12 山东诺威新材料有限公司 Anti-skid surface dual-component polyurethane adhesive and preparation method thereof
CN112194777A (en) * 2020-10-12 2021-01-08 浙江华峰合成树脂有限公司 Polyurethane surface layer resin for PVC sole injection molding and preparation method thereof
CN115923291A (en) * 2022-12-20 2023-04-07 佛山市彩龙镀膜包装材料有限公司 Alcohol-resistant BOPP aluminized film and preparation method thereof
CN115923291B (en) * 2022-12-20 2023-09-15 佛山市彩龙镀膜包装材料有限公司 Alcohol-resistant BOPP aluminized film and preparation method thereof
CN117264528A (en) * 2023-09-27 2023-12-22 科顺防水科技股份有限公司 Single-component polyurethane waterproof coating and preparation method and structure thereof
CN117264528B (en) * 2023-09-27 2024-04-16 科顺防水科技股份有限公司 Single-component polyurethane waterproof coating and preparation method and structure thereof
CN117801657A (en) * 2023-11-24 2024-04-02 广东裕田霸力科技股份有限公司 Dermis treating agent and preparation method thereof

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Application publication date: 20170531