CN86104776A - Synthesizing of polypropylene chloride-acrylate adhesive - Google Patents
Synthesizing of polypropylene chloride-acrylate adhesive Download PDFInfo
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- CN86104776A CN86104776A CN 86104776 CN86104776A CN86104776A CN 86104776 A CN86104776 A CN 86104776A CN 86104776 CN86104776 CN 86104776 CN 86104776 A CN86104776 A CN 86104776A CN 86104776 A CN86104776 A CN 86104776A
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- polypropylene
- chlorinated polypropylene
- vinylformic acid
- ester
- reaction
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Abstract
The present invention carries out free radical grafting copolymerization with Chlorinated Polypropylene III and vinylformic acid or its ester to close reaction in solution.Polyolefin polymers material and goods thereof that prepared tackiness agent is difficult bonding to polypropylene, polyethylene etc. have bonding strength preferably, can reach 35kg/cm to the adhesive shear strength of polypropylene-polypropylene material
2Simultaneously, also can be used for the bonding of polypropylene-aluminium, polypropylene-iron.Its process characteristic is that the reaction times is short, and technology is simple, and product does not need can directly use through separation and purification.
Description
The present invention is the method for preparing Chlorinated Polypropylene III-vinylformic acid or its ester graft copolymerization tackiness agent.This tackiness agent is the wider novel adhesive of range of application, is difficult clay soil/polyolefin base polymer such as nonpolar polypropylene, polyethylene material, goods, film etc. for the surface particularly, has good adhesiveproperties.
For the sticking effective tackiness agent of polymkeric substance (as polypropylene, polyethylene etc.) goods of difficulty, people once carried out some research, and the tackiness agent of employing has Resins, epoxy, paracril-phenolic aldehyde, polyhutadiene and Chlorinated Polypropylene III etc.Wherein tackiness agent such as epoxy resin, paracril-phenolic aldehyde, polyhutadiene are relatively poor to finished product adhesivepropertieies such as polypropylene, polyethylene.Though the effect that Chlorinated Polypropylene III is certain to being bonded with of difficult clay soil/polyolefin finished product because the force of cohesion of Chlorinated Polypropylene III itself is less, has considerable influence to bonding strength.So Chlorinated Polypropylene III mainly is applicable to bonding between the lamination of polypropylene film and goods thereof, and to the sheet material and the goods (as injection-molded item etc.) thereof of polypropylene, polyethylene kind, and bonding, unsatisfactory between polypropylene and the metal (as aluminium, steel etc.).
In order further to improve the cementability of Chlorinated Polypropylene III to difficult stick polymer and metal, Japan's appropriate authority and individual had once done a large amount of modification work to Chlorinated Polypropylene III, and resulting goods are used for the coating of polypropylene articles or metal, tectal tackiness agent mostly.1985 the blue or green clear second-class people's report of wood of Japan (spy opens clear 60-13807) the use mixing roll with Chlorinated Polypropylene III and unsaturated carboxylic acid and the sour acid anhydrides of horse, in the presence of organo-peroxide, carry out mixing, extrude by extrusion machine then, and make modified chlorinated polypropylene adhesive.This tackiness agent in use uses basic metal or alkaline-earth metal plasma as linking agent, makes it have adhesiveproperties preferably.
In recent years, we are the activity of chlorine atom in the molecule based on Chlorinated Polypropylene III, adopting cheap Atactic Polypropelene is that raw material carries out chlorination earlier and obtains CAP, use conventional radical copolymerization method then, in solvent, make chlorination random poly-and vinylformic acid or its ester graft copolymerization, this tackiness agent of polyolefin adhesive is in use preferably to have obtained bonding strength, to polypropylene material and finished product thereof, polypropylene material and aluminium, bonding between the metals such as steel, only need be heating and curing at a certain temperature, do not need to add again any linking agent, can obtain higher bonding strength.
The new Chlorinated Polypropylene III that adopts of the present invention be by molecular weight at the Atactic Polypropelene below 100,000, chlorination makes in carbon tetrachloride solvent, chlorinity is 30-40%.The grafted monomer that adopts is (methyl) vinylformic acid or (methyl) esters of acrylic acid (as vinylformic acid, methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, Jia Jibingxisuanyizhi, butyl methacrylate etc.).Chlorinated Polypropylene III (weight part)/its ester of vinylformic acid (weight part)=100: 0.5-25.Organo-peroxide is a peroxidation di-t-butyl 0.1-0.5(weight part), solvent is 300 milliliters of toluene, dimethylbenzene etc.Be reflected under the nitrogen protection and carry out, the reaction solution degree is 110-120 ℃, and the reaction times is 3 hours.
The preparation of tackiness agent of the present invention and enforcement can illustrate with following several examples:
The preparation of preparation method's 1 Chlorinated Polypropylene III-acrylic graft copolymer tackiness agent (CA-8).
In 1000 milliliters of three-necked bottles that agitator, reflux exchanger, logical nitrogen pipe and drips of solution feeder apparatus are housed, add 100 gram Chlorinated Polypropylene IIIs (oxygen level 30-40%), feed nitrogen and under agitation be warming up to 100 ℃ gradually, after treating that Chlorinated Polypropylene III all dissolves, to be dissolved with 20 milliliters of peroxidation two special basic ether 0.2 grams and the acrylic acid xylene solutions of 1.5 grams, in 30 minutes, evenly be added dropwise in the reactor, temperature of reaction is risen to 110-120 ℃ then, keep reaction 3 hours, can make solids content is 27% Chlorinated Polypropylene III-acrylic graft copolymer tackiness agent.
Preparation method's 2 Chlorinated Polypropylene IIIs-butyl methacrylate copolymerized adhesive (CBMA-1)
According to preparation method 1, wherein peroxide tertiary butyl ether consumption is 0.3 gram, and the butyl methacrylate consumption is 2 grams, can make solids content and be about Chlorinated Polypropylene III-butyl methacrylate graft copolymerization tackiness agent of 27%.
Preparation method's 3 Chlorinated Polypropylene IIIs-butyl methacrylate is gathered tackiness agent (CBMA-2)
According to preparation method 1, the peroxidation di-t-butyl consumption is 0.5 gram, and butyl methacrylate 10 gram can make solids content and be Chlorinated Polypropylene III-butyl methacrylate graft copolymerization tackiness agent of 29%.
Preparation method's 4 Chlorinated Polypropylene IIIs-butyl acrylate copolymerized adhesive (CBA-1)
According to preparation method 1, wherein peroxidation di-t-butyl is with being 0.2 gram, and the consumption of butyl acrylate is 1.5 grams, can make solids content and be Chlorinated Polypropylene III-butyl acrylate graft copolymerization tackiness agent of 27%.
Above-mentioned preparation method prepared (CA-8), (CBMA-1), (CBMA-2), (CBA-1) tackiness agent, it is respond well to carry out adhesive test.Test-results such as following table
The adhesive that this method makes is except difficult clay soil/polyolefin goods (polypropylene, polyethylene board, goods, film etc.) are presented good cementability. Once be used for the bonding of polypropylene injection moulding product (100 ℃ of environment for use temperature, water vapour); The metals such as polypropylene articles and steel, aluminium bonding, respond well. The room temperature that also can be used for the films such as polypropylene, polyethylene, polyvinyl chloride and paper is bonding, and polyethylene foams and water paper wall is bonding etc.
Claims (4)
1, the present invention is to be initiator in solution, with the peroxidation di-t-butyl with Chlorinated Polypropylene III and vinylformic acid or its ester, carries out free radical grafting copolymerization and closes reaction.It is characterized in that being the main chain of graft copolymer, being the graft copolymerization monomer preparation Chlorinated Polypropylene III-vinylformic acid, ester gum stick with vinylformic acid or its ester with low-molecular-weight CAP.Reaction product does not need to separate purification.
2, by the described method of claim 1, it is characterized in that the CAP chlorinity is 30-40%, molecular weight is below 100,000.
3, by the described method of claim 1, it is characterized by temperature of reaction is 110-120 ℃, and the reaction times is 3 hours.
4, method according to claim 1 is characterized in that reactant ratio is by weight:
Chlorinated Polypropylene III: vinylformic acid, ester=100: 0.5-25
The product solids content is 20-40%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86104776 CN86104776A (en) | 1986-07-14 | 1986-07-14 | Synthesizing of polypropylene chloride-acrylate adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86104776 CN86104776A (en) | 1986-07-14 | 1986-07-14 | Synthesizing of polypropylene chloride-acrylate adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86104776A true CN86104776A (en) | 1988-01-27 |
Family
ID=4802602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86104776 Pending CN86104776A (en) | 1986-07-14 | 1986-07-14 | Synthesizing of polypropylene chloride-acrylate adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86104776A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858104B (en) * | 2006-06-09 | 2010-12-01 | 广东多正化工科技有限公司 | Polypropylene and polyethylene treating agent |
| CN102086332B (en) * | 2009-12-03 | 2013-05-15 | 立邦涂料（中国）有限公司 | Coating composition for polyolefin substrate and coating and product thereof |
| CN103113789A (en) * | 2011-11-17 | 2013-05-22 | 上海杰事杰新材料(集团)股份有限公司 | Primer for hard-bonding materials and preparation method thereof |
| CN111635485A (en) * | 2020-05-29 | 2020-09-08 | 广州五行材料科技有限公司 | Photosensitive chlorinated polypropylene prepolymer and preparation method and application thereof |
-
1986
- 1986-07-14 CN CN 86104776 patent/CN86104776A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858104B (en) * | 2006-06-09 | 2010-12-01 | 广东多正化工科技有限公司 | Polypropylene and polyethylene treating agent |
| CN102086332B (en) * | 2009-12-03 | 2013-05-15 | 立邦涂料（中国）有限公司 | Coating composition for polyolefin substrate and coating and product thereof |
| CN103113789A (en) * | 2011-11-17 | 2013-05-22 | 上海杰事杰新材料(集团)股份有限公司 | Primer for hard-bonding materials and preparation method thereof |
| CN103113789B (en) * | 2011-11-17 | 2015-11-25 | 上海杰事杰新材料(集团)股份有限公司 | A kind of difficulty silane coupling agent gluing material and preparation method thereof |
| CN111635485A (en) * | 2020-05-29 | 2020-09-08 | 广州五行材料科技有限公司 | Photosensitive chlorinated polypropylene prepolymer and preparation method and application thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |