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CN109266267A - A kind of novel acrylic ester modified aqueous polyurethane binder - Google Patents

A kind of novel acrylic ester modified aqueous polyurethane binder Download PDF

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Publication number
CN109266267A
CN109266267A CN201811129301.9A CN201811129301A CN109266267A CN 109266267 A CN109266267 A CN 109266267A CN 201811129301 A CN201811129301 A CN 201811129301A CN 109266267 A CN109266267 A CN 109266267A
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acrylate
parts
polyurethane binder
novel
modified
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Inventor
周超
江龙
赵赫
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Changchun University of Technology
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Changchun University of Technology
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Priority to CN201811129301.9A priority Critical patent/CN109266267A/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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • 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
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • 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
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A kind of novel acrylic ester modified aqueous polyurethane binder, it is characterized in that the binder is using the pure and mild polyisocyanates reaction of polyether polyols, obtain Waterborne Polyurethane Prepolymer, it reacts to obtain aqueous polyurethane acrylate with acrylic monomers or methacrylic acid monomer under emulsifier, initiator effect, lotion is obtained, which is acrylic ester modified water-soluble polyurethane binder.The invention also discloses the preparation method and application of the binder.Compared with the prior art, the advantages of the present invention are as follows: there is more excellent environmental-protecting performance, while also increasing in terms of oxidation resistance and ageing resistance, the invention and glue film, paper products have good adhesive property.

Description

A kind of novel acrylic ester modified aqueous polyurethane binder
Technical field
The present invention relates to a kind of binders, further relate to the preparation method of the binder.
Background technique
Waterborne polyurethane binders have environmentally friendly, nontoxic, gluing validity period is long, saves resource etc. using water as decentralized medium Advantage is widely used in the bonding of building, automobile, house decoration, packaging, printing, leather, craftwork etc..Aqueous polyurethane is viscous Tie agent it is external oneself through obtaining very big development, wherein the companies such as Bayer, BASF develop a series of aqueous polyurethane bonding Agent.The country starts late, and is in developing stage, and the present invention has extensive prospect.Currently, domestic waterborne polyurethane binders are deposited There are slow drying speed, initial adhesion force is small and poor water resistance the disadvantages of, especially adhesion strength is low has seriously affected it and has answered extensively With.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of novel acrylic ester modified aqueous polyurethane binder, energy Disadvantages mentioned above existing for waterborne polyurethane binders is solved, enough to solve prior art problem.
Technical solution of the invention is as follows:
Novel acrylic ester modified aqueous polyurethane binder, wherein each component weight fraction ratio is as follows:
25~65 parts of polyether polyol,
20~50 parts of polyisocyanates,
10~30 parts of acrylate/methacrylate,
5~20 parts of castor oil,
12~19 parts of chain extender,
5~9 parts of emulsifier,
5~9 parts of initiator,
4~8 parts of salt forming agent,
30~50 parts of deionized water,
Preferably, the polyether polyol is selected from Polyoxyethylene glycol, polyoxypropyleneglycol, polypropylene oxide triol Or one or more of polytetrahydrofuran diol.
Preferably, the polyether polyol number-average molecular weight is 1000~3000.
Preferably, the polyisocyanates monomer is selected from hexamethylene diisocyanate, dicyclohexyl methyl hydride two In isocyanates, benzene dimethylene diisocyanate, isophorone diisocyanate or tetramethyl xylylene diisocyanate One or more.
Preferably, the acrylate/methacrylate monomer is selected from methyl acrylate, ethyl acrylate, third One or more of olefin(e) acid butyl ester, 2- methyl methacrylate and ethyl 2-methacrylate.
Preferably, the chain extender is selected from ethylene glycol, 1.4- butanediol, 1.6- hexylene glycol, diglycol, two One of hydroxymethyl propionic acid, half rouge of dihydroxy, ethylenediamine base ethanesulfonic acid sodium, diethylenetriamine or methyl diethanolamine are several Kind.
Preferably, the emulsifier is selected from lauryl sodium sulfate, 2- acrylamido -2- methyI-oropvD sulfuric acid One or more of sodium salt and 2- acrylamido -2- methyI-oropvD ammonium sulfate.
Preferably, the initiator is in dibutyl tin dilaurate, potassium peroxydisulfate and azodiisobutyronitrile It is one or more of.
Preferably, the salt forming agent is selected from one or more of triethylamine, hydrochloric acid, acetic acid kind propylene oxide.
The present invention also provides a kind of preparation methods of novel acrylic ester modified aqueous polyurethane binder, include the following:
Step 1: polyether polyol, isocyanate-monomer, castor oil, chain extender and catalyst are added in four-hole boiling flask, 50 1~3h is reacted under the conditions of~90 DEG C, obtains prepolymer；
System: being cooled to rapidly 30~50 DEG C by step 2, and salt forming agent is added and reacts 10~20min, deionized water is then added 30~60min of high-speed stirred, obtains Waterborne Polyurethane Prepolymer；
Step 3: emulsifier, initiator, acrylate/methacrylate monomer is added, reacts 90 under the conditions of 45~55 DEG C ~120min obtains acrylic ester modified water-soluble polyurethane lotion, as novel acrylic ester modified aqueous polyurethane binder.
The beneficial effects of the present invention are: a kind of novel acrylic ester modified aqueous polyurethane binder of the present invention, passes through third The introducing of olefin(e) acid ester/methacrylate monomers, effectively shortens the curing time of Aqueous Polyurethane Adhesives at room temperature, simultaneously Significantly improve its adhesive property, wide market.
Specific embodiment
To further appreciate that the present invention, preferred embodiment of the invention is described With reference to embodiment, but It should be appreciated that these descriptions are only further explanation advantages and features of the invention, not to the limitation of patent requirements.
Example 1
1. by 26 grams of isophorone diisocyanate (IPDI) with 40 grams through dehydration polytetrahydrofuran ether glycol (PTMG, 2000) it is added in the 500ml three-necked flask at 80 DEG C equipped with agitating paddle, condenser pipe and nitrogen protection, 0.02 gram of February is added Dilaurylate is used as initiator, keeps the temperature 40~50 minutes at 70~80 DEG C.
2. 7 grams of 2,2- dihydromethyl propionic acids are added, react 2 hours, acetone can be used during reaction and adjust viscosity.
3. cooling, makes temperature in three-necked flask are as follows: 40~48 DEG C, triethylamine is added and a small amount of deionized water neutralizes.
4. after being uniformly dispersed, 7 grams of lauryl sodium sulfate and 5 grams of potassium peroxydisulfates are added, and the reaction was continued 30 minutes.
5. 20 grams of butyl acrylates are added after 30 minutes and the temperature was then adjusted to 60 DEG C, react 2 hours.
6. after 2 hours, obtaining novel acrylic ester modified aqueous polyurethane binder.
Example 2
1. by 26.3 grams of toluene di-isocyanate(TDI)s (TDI) with 40 grams through dehydration polytetrahydrofuran ether glycol (PTMG, 2000) it is added in the 500ml three-necked flask equipped with agitating paddle, condenser pipe and nitrogen protection, 0.02 gram of tin dilaurate two is added Butyl tin is used as initiator, stirs 40~50 minutes at 90 DEG C.
2. 5 grams of 2,2- dihydromethyl propionic acids are added, react 1 hour, acetone can be used during reaction and adjust viscosity.
3. 50 DEG C of additions 7 grams of lauryl sodium sulfate, 5 grams of azodiisobutyronitriles and 30 grams of hydroxy-ethyl acrylates are cooled to, 80 DEG C are warming up to, is reacted two hours
4. being cooled to 40 DEG C, being added in triethylamine and a small amount of deionized water and dispersing, it is poly- to obtain novel acrylic ester modified water-soluble Urethane binder.
Example 3
1. by 43 grams of isophorone diisocyanate (IPDI) with 40 grams through dehydration polytetrahydrofuran ether glycol (PTMG, 1000) it is added in the 500ml three-necked flask at 80 DEG C equipped with agitating paddle, condenser pipe and nitrogen protection, 0.02 gram of February is added Dilaurylate is used as initiator, keeps the temperature 40~50 minutes at 70~80 DEG C.
2. 7 grams of 2,2- dihydromethyl propionic acids are added, react 2 hours, acetone can be used during reaction and adjust viscosity.
3. cooling, makes temperature in three-necked flask are as follows: 40~48 DEG C.
4. 10 grams of 2- hydroxyethyl methacrylates are added, and the reaction was continued 30 minutes.
5. 7 grams of lauryl sodium sulfate, 5 grams of azodiisobutyronitriles and 30 grams of hy-droxybutyls are added simultaneously after 30 minutes The temperature was then adjusted to 60 DEG C, react 2 hours.
6. after 2 hours, being cooled to 40 DEG C of addition triethylamines and a small amount of deionized water neutralizing, after being uniformly dispersed, obtain new Type acrylic ester modified water-soluble polyurethane binder.
Example 4
1. by 26 grams of isophorone diisocyanate (IPDI) with 40 grams through dehydration polytetrahydrofuran ether glycol (PTMG, 2000) it is added in the 500ml three-necked flask at 80 DEG C equipped with agitating paddle, condenser pipe and nitrogen protection, 0.02 gram of February is added Dilaurylate is used as initiator, keeps the temperature 40~50 minutes at 70~80 DEG C.
2. 7 grams of 2,2- dihydromethyl propionic acids and 6 grams of 1-4 butanediols are added, react 2 hours, third can be used during reaction Ketone adjusts viscosity.
3. cooling, makes temperature in three-necked flask are as follows: 40~48 DEG C, triethylamine is added and a small amount of deionized water neutralizes.
4. after being uniformly dispersed, be added 7 grams of 2- acrylamido -2- methyI-oropvD sodium sulphate and 5 grams of potassium peroxydisulfates after Continuous reaction 30 minutes.
5. 15 grams of 2- methyl methacrylates and 10 grams of methyl acrylates are added after 30 minutes and the temperature was then adjusted to 60 DEG C, it reacts 2 hours.
6. after 2 hours, obtaining novel acrylic ester modified aqueous polyurethane binder.

Claims (10)

1.一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征是包含以下成分，其中各组分重量份数比如下：A novel acrylate-modified aqueous polyurethane binder characterized by comprising the following components, wherein the weight fraction of each component is as follows: 聚醚多元醇 25～65份，Polyether polyol 25 to 65 parts, 多异氰酸酯 20～50份，20 to 50 parts of polyisocyanate, 丙烯酸酯/甲基丙烯酸酯 10～30份，10 to 30 parts of acrylate/methacrylate, 蓖麻油 5～20份，Castor oil 5 to 20 parts, 扩链剂 12～19份，12 to 19 parts of chain extender, 乳化剂 5～9份，5 to 9 parts of emulsifier, 引发剂 5～9份，5 to 9 parts of the initiator, 成盐剂 4～8份，4 to 8 parts of salt forming agent, 去离子水 30～50份，30 to 50 parts of deionized water, 该粘结剂采用聚醚多元醇和多异氰酸酯反应，得到水性聚氨酯预聚体，在乳化剂、引发剂作用下与丙烯酸单体或甲基丙烯酸单体作反应得到聚氨酯丙烯酸酯，获得乳液，该乳液即为丙烯酸酯改性水性聚氨酯粘结剂。The binder is reacted with a polyether polyol and a polyisocyanate to obtain an aqueous polyurethane prepolymer, which is reacted with an acrylic monomer or a methacrylic acid monomer under the action of an emulsifier or an initiator to obtain a urethane acrylate, thereby obtaining an emulsion. It is an acrylate-modified waterborne polyurethane binder. 2.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯二醇、聚氧化丙烯三醇或聚四氢呋喃二醇中的一种或几种。The novel acrylate-modified waterborne polyurethane binder according to claim 1, wherein the polyether polyol is selected from the group consisting of polyoxyethylene diol, polyoxypropylene diol, and polyoxypropylene. One or more of a triol or a polytetrahydrofuran diol. 3.根据权利要求1或2所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的聚醚多元醇数均分子量为1000～3000。The novel acrylate-modified waterborne polyurethane binder according to claim 1 or 2, wherein the polyether polyol has a number average molecular weight of from 1,000 to 3,000. 4.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的多异氰酸酯类单体选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或四甲基苯二甲基二异氰酸酯中的一种或几种。The novel acrylate-modified waterborne polyurethane binder according to claim 1, wherein the polyisocyanate monomer is selected from the group consisting of hexamethylene diisocyanate and dicyclohexylmethane diisocyanate. One or more of benzene dimethylene diisocyanate, isophorone diisocyanate or tetramethyl dimethyl dimethyl diisocyanate. 5.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的丙烯酸酯/甲基丙烯酸酯单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、2-甲基丙烯酸甲酯和2-甲基丙烯酸乙酯中的一种或几种。The novel acrylate-modified waterborne polyurethane adhesive according to claim 1, wherein the acrylate/methacrylate monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, and butyl acrylate. One or more of ester, 2-methyl methacrylate and 2-ethyl methacrylate. 6.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的扩链剂选自乙二醇、1.4-丁二醇、1.6-己二醇、一缩二乙二醇、二羟甲基丙酸、二羟基半脂、乙二胺基乙磺酸钠、二乙烯三胺或甲基二乙醇胺中的一种或几种。The novel acrylate-modified waterborne polyurethane binder according to claim 1, wherein the chain extender is selected from the group consisting of ethylene glycol, 1.4-butanediol, and 1.6-hexanediol. One or more of diethylene glycol, dimethylolpropionic acid, dihydroxy half fat, sodium ethylenediamine ethanesulfonate, diethylenetriamine or methyldiethanolamine. 7.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的乳化剂选自十二烷基硫酸钠、2-丙烯酰胺基-2-甲基-丙基硫酸钠盐和2-丙烯酰胺基-2-甲基-丙基硫酸铵盐中的一种或几种中的一种或几种。7. A novel acrylate-modified aqueous polyurethane binder according to claim 1 wherein said emulsifier is selected from the group consisting of sodium lauryl sulfate and 2-acrylamido-2-methyl. One or more of one or more of sodium propyl sulfate and 2-acrylamido-2-methyl-propyl ammonium sulfate. 8.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的引发剂选自二月桂酸二丁基锡、过硫酸钾和偶氮二异丁腈中的一种或几种。The invention relates to a novel acrylate-modified waterborne polyurethane binder according to claim 1, wherein the initiator is selected from the group consisting of dibutyltin dilaurate, potassium persulfate and azobisisobutyronitrile. One or several. 9.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂，其特征在于，所述的成盐剂选自三乙胺、盐酸、醋酸种环氧丙烷中的一种或几种。The acrylate-modified water-based polyurethane binder according to claim 1, wherein the salt-forming agent is one selected from the group consisting of triethylamine, hydrochloric acid, and acetic acid propylene oxide. Several. 10.根据权利要求1所述的一种新型丙烯酸酯改性水性聚氨酯粘结剂的制备方法，其特征在于，包括如下：10 . The method for preparing a novel acrylate modified waterborne polyurethane adhesive according to claim 1 , comprising the following steps: 步骤一：在四口烧瓶中加入聚醚多元醇、异氰酸酯单体、蓖麻油、扩链剂和催化剂，在50～90℃条件下反应1～3h，得到预聚物；Step 1: adding a polyether polyol, an isocyanate monomer, a castor oil, a chain extender and a catalyst to a four-necked flask, and reacting at 50 to 90 ° C for 1 to 3 hours to obtain a prepolymer; 步骤二：将体系迅速降温至30～50℃，加入成盐剂反应10～20min，然后加入去离子水高速搅拌30～60min，得到水性聚氨酯预聚体；Step 2: The system is rapidly cooled to 30-50 ° C, and the salt forming agent is added for 10-20 min, and then deionized water is added for high speed stirring for 30-60 min to obtain an aqueous polyurethane prepolymer; 步骤三：加入乳化剂、引发剂、丙烯酸酯/甲基丙烯酸酯单体，在45～55℃条件下反应90～120min,得到丙烯酸酯改性水性聚氨酯乳液，即为丙烯酸酯改性水性聚氨酯粘结剂。Step 3: adding an emulsifier, an initiator, an acrylate/methacrylate monomer, and reacting at 45-55 ° C for 90-120 min to obtain an acrylate-modified water-based polyurethane emulsion, which is an acrylate-modified water-based polyurethane adhesive. Conjunction.
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CN109837021A (en) * 2019-02-27 2019-06-04 徐超 A kind of metallic conduit gap makes up agent
CN109957365A (en) * 2019-03-11 2019-07-02 江苏大力士投资有限公司 A kind of high-elastic retractility jointing adhesive and preparation method thereof
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