CN86104775A - The preparation of polyolefin adhesive - Google Patents
The preparation of polyolefin adhesive Download PDFInfo
- Publication number
- CN86104775A CN86104775A CN 86104775 CN86104775A CN86104775A CN 86104775 A CN86104775 A CN 86104775A CN 86104775 CN86104775 CN 86104775 CN 86104775 A CN86104775 A CN 86104775A CN 86104775 A CN86104775 A CN 86104775A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- chlorinated polypropylene
- polypropylene iii
- acrylate
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention carries out free radical grafting copolymerization with Chlorinated Polypropylene III and vinyl cyanide, acrylate and obtains in solution, polyolefine (polypropylene, polyethylene etc.) is had the novel adhesive of the ability of gluing than strong rubber.Can reach 55kg/cm to the gluing shearing resistance of polypropylene-polypropylene
2, also be used for polypropylene-steel, bonding between polypropylene-aluminium and the above-mentioned metal.Be characterized in that the reaction times short, technology is simple, and product does not need can directly use through separation and purification.
Description
The invention provides and carry out free radical grafting copolymerization by Chlorinated Polypropylene III and acrylate, vinyl cyanide and close reaction, preparation has the method for the tackiness agent of strong bonding strength to polyolefin polymers material and goods thereof.The tackiness agent that is provided is nonpolar, difficult bonding polypropylene material (as sheet material, finished product, film etc.) to the surface, has good adhesive effect.To other materials such as metal, rubber, leather, synthetic leather, timber, good cementability is arranged also simultaneously.Also can be used as coating and metal oil resistant tectum.It is a kind of range of application novel adhesive comparatively widely.
Polypropylene is that production is bigger at present, uses one of wider general-purpose plastics.But owing to do not have polar group in the polypropylene molecule, the material surface adsorptive power is very poor, and surface tension is little, and being difficult to find can wetting its surperficial tackiness agent.In addition, because polyacrylic fusing point is than higher, melting solder is difficulty relatively, be dissolved in any solvent at normal temperatures again hardly, this just gives the bonding of polypropylene material itself and polypropylene material and other material, brings a lot of difficulties, has limited the broadened application of acrylic plastering to a certain extent.Only find that so far Chlorinated Polypropylene III has reasonable cementability to polypropylene.
Chlorinated Polypropylene III has good ageing-resistant, anti-combustion, performance such as corrosion-resistant, can be dissolved in benzene,toluene,xylene, the tetracol phenixin equal solvent.When chlorinated polypropylene solution and polypropylene material connect when melting, polypropylene surface generation limited swelling, crystallizing field in polypropylene surface and the Chlorinated Polypropylene III, power attracts mutually between polypropylene surface is with the crystallization of identical chemical structure crystalline, thereby demonstrates Chlorinated Polypropylene III to polyacrylic cementability.Usually the chlorinity that is used as the Chlorinated Polypropylene III of tackiness agent is 20-40%.At this moment, the original very high polypropylene of degree of crystallinity, after introducing the chlorine atom and forming Chlorinated Polypropylene III, the crystallization of Chlorinated Polypropylene III is reduced to below 40%.Therefore Chlorinated Polypropylene III has that fusing point (softening temperature) is lower, the characteristics of Yi Rong, and the physical strength of polymkeric substance also reduces because of force of cohesion reduces correspondingly.With the bonding polypropylene material of Chlorinated Polypropylene III, when stressed, the destruction between the glue-line is often taken place.Therefore chlorinated polypropylene adhesive is mainly used in polypropylene film, the hot melt adhesion of the printing-ink of polypropylene articles, coating and two-way drawing-off polypropylene film etc.
In order to improve the force of cohesion of Chlorinated Polypropylene III, people once utilized the activity of chlorine atom in the Chlorinated Polypropylene III, Chlorinated Polypropylene III is connect technological transformation, in polymer molecule, introduce the compound that has polar group, to strengthen the physical strength of Chlorinated Polypropylene III, increase the adhesiveproperties of Chlorinated Polypropylene III to other materials simultaneously, used according to reports grafted monomer has unsaturated carboxylic acid compounds such as esters of acrylic acid, maleic anhydride.And obtained certain effect, main as the poly-third material coating, printing ink, anti-corrosion of metal tectum etc.
It is grafted monomer that the present invention adopts the vinyl cyanide have strong polar group, and introduces a certain amount of esters of acrylic acid unsaturated organic compound, uses the force of cohesion that strengthens polymkeric substance and to the adhesiveproperties of other material, has obtained significant effect.
It is 2-10 ten thousand that the present invention adopts the Chlorinated Polypropylene III molecular weight.Be the polypropylene chlorination in tetracol phenixin with harmonic component, or make that chlorinity is controlled at 30-40% at the aqueous phase suspension chlorination.Then Chlorinated Polypropylene III is dissolved in the solvent, obtains the chlorinated polypropylene solution of proper viscosity, add a certain amount of grafted monomer again, under the initiation of organo-peroxide, free radical grafting copolymerization takes place close reaction.Because Chlorinated Polypropylene III, monomer, solvent can be miscible well,, form Chlorinated Polypropylene III-acrylic ester-acrylonitrile graft copolymer in homogeneous phase so reaction is to carry out rapidly.This grafted chlorinated polypropylene multipolymer through modification to difficult clay soil/polyolefin base polymer materials such as polypropylene, has stronger bonding force, and we are referred to as polyolefin adhesive to it.
Main grafted monomer of the present invention is an acrylate, second grafted monomer be acrylonitrile compound (
R=C
4-C
8).Used raw material and proportioning are as follows:
Chlorinated Polypropylene III: monomer=100: the 1-10(weight ratio)
Monomeric proportioning is:
Vinyl cyanide: acrylate=1: the 1-3(mol ratio)
Organo-peroxide is a peroxidation di-t-butyl, and consumption is 0.1-0.5%, and solvent is toluene, dimethylbenzene etc.
Be reflected under the nitrogen protection and carry out, temperature of reaction is 110-120 ℃, and the reaction times is 3 hours.
Polyolefine glue jelly provided by the present invention except that polyolefins (polypropylene, polyethylene etc.) polymer materials, finished product, film etc. being had stronger adhesiveproperties, also has good cementability to other material.Bonding as metals such as polypropylene and steel, aluminium, metallic substance such as steel, aluminium itself bonding, polypropylene, polyethylene film and paper bonding, and leather, rubber, synthetic leather is bonding or the like.Can reach 55kg/cm to polypropylene-polyacrylic adhesive shear strength
2
Preparation method of the present invention and the available following example explanation of enforcement:
The preparation of preparation method's 1 Chlorinated Polypropylene III-butyl acrylate-acrylonitrile graft copolymer (polyolefin adhesive CT-12)
In 1000 milliliters of three-necked bottles of electric mixer, reflux condensing tube and dropping funnel are housed, add Chlorinated Polypropylene III 100 grams and dimethylbenzene 280 grams, rise moving the stirring, dissolving gradually under heating.In addition, adding in dropping liquid liquid funnel by butyl acrylate and vinyl cyanide mol ratio is 3: 1 mixed solution 1 gram, 20 milliliters of dimethylbenzene and peroxidation di-t-butyl 0.4 gram.
When reactor temperature rises to 80 ℃, under the stirring that keeps, progressively be added dropwise to the mixed solution of butyl acrylate and vinyl cyanide, in 20 minutes, dropwise.Slowly be warming up to 110-120 ℃ then, back flow reaction 2.5-3 hour, then get polyolefin adhesive CT-12, product is a light yellow viscous liquid.
Polyolefin adhesive CT-12 records with standard method of test: polypropylene-polypropylene adhesive shear strength is 55kg/cm, and steel-steel shearing resistance is 107kg/cm.
The preparation of preparation method's 2 Chlorinated Polypropylene IIIs-butyl acrylate-acrylonitrile graft copolymer (polyolefin adhesive CT-24)
According to reaction unit and condition that preparation method 1 is provided, with Chlorinated Polypropylene III 100 grams, butyl acrylate and vinyl cyanide mol ratio are 3: 1 mixed solution 4 grams, in the presence of 0.5 gram peroxidation di-t-butyl, carry out the reaction of free radical grafting copolymerization thing.Get the viscous solution of light yellow polyolefin tackiness agent CT-24.
Polyolefin adhesive CT-24 is through actual measurement, polypropylene-polypropylene adhesive shear strength is 56kg/cm, and polypropylene-steel shearing resistance is 63kg/cm, and polypropylene-aluminium shearing resistance is 68kg/cm, steel-steel shearing resistance is 136kg/cm, and aluminium-aluminium shearing resistance is 83kg/cm.
Polyolefin adhesive provided by the present invention is single-component adhesive easy to use, does not need to add curing agent during use again, as long as adherend spare is coated with gummed, suitable airing, fit together, be heating and curing at a certain temperature then, can reach high-adhesive-strength. Also can be under the cold curing condition, be used for the goods such as bonding leather, rubber, synthetic leather, timber.
Adhesive provided by the present invention under the condition of suitable regulator solution concentration, also can be used as the coating of polypropylene material, metallic article, and the metal protective mulch of anti-gasoline etc.
Claims (4)
1, the present invention is to be raw material with Chlorinated Polypropylene III, vinyl cyanide and acrylate, is initiator with the peroxidation di-t-butyl in solution, carries out free radical grafting copolymerization, prepares the method for polyolefin adhesive.It is characterized in that with the lower molecular weight Chlorinated Polypropylene III be the graft copolymer main chain, is the monomer of graft copolymerization with vinyl cyanide and acrylate.Reaction product does not need to carry out separation and purification, can obtain polyolefin polymers is had the tackiness agent of strong bonding strength.
2, by the described method of claim 1, it is characterized in that the Chlorinated Polypropylene III chlorinity is 30-40%, molecular weight is 2-10 ten thousand.
3, by the described method of claim 1, it is characterized in that reactant ratio is:
Chlorinated Polypropylene III (weight part): monomer (weight part)=100: 1-5
Vinyl cyanide (mole): acrylate (mole)=1: 1-3
4, method according to claim 1, it is characterized by temperature of reaction is 110-120 ℃, the reaction times is 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104775A CN86104775B (en) | 1986-07-14 | 1986-07-14 | Preparation of polyolefin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86104775A CN86104775B (en) | 1986-07-14 | 1986-07-14 | Preparation of polyolefin adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86104775A true CN86104775A (en) | 1988-01-27 |
| CN86104775B CN86104775B (en) | 1988-07-27 |
Family
ID=4802601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86104775A Expired CN86104775B (en) | 1986-07-14 | 1986-07-14 | Preparation of polyolefin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86104775B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123613C (en) * | 1998-12-03 | 2003-10-08 | 中国石化齐鲁石油化工公司 | Hot-fusible high-molecular adhesive and its preparing process |
| CN101357967B (en) * | 2008-09-23 | 2010-11-10 | 西安交通大学 | Polyolefin substrate adhesion promoter and preparation method thereof |
| CN102153912A (en) * | 2011-03-10 | 2011-08-17 | 安徽师范大学 | Single-component glass printing ink |
| 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 |
| CN109280134A (en) * | 2018-09-25 | 2019-01-29 | 中国科学院长春应用化学研究所 | The preparation method of watersoluble chlorinated polypropylerie lotion |
| CN110229277A (en) * | 2019-05-21 | 2019-09-13 | 上海保立佳新材料有限公司 | A kind of CPP/ acrylic acid ester emulsion and aqueous CPP- acryloid cement and preparation method thereof and its application |
-
1986
- 1986-07-14 CN CN86104775A patent/CN86104775B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123613C (en) * | 1998-12-03 | 2003-10-08 | 中国石化齐鲁石油化工公司 | Hot-fusible high-molecular adhesive and its preparing process |
| CN101357967B (en) * | 2008-09-23 | 2010-11-10 | 西安交通大学 | Polyolefin substrate adhesion promoter and preparation method thereof |
| 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 |
| CN102153912A (en) * | 2011-03-10 | 2011-08-17 | 安徽师范大学 | Single-component glass printing ink |
| CN102153912B (en) * | 2011-03-10 | 2013-06-12 | 安徽师范大学 | Single-component glass printing ink |
| CN109280134A (en) * | 2018-09-25 | 2019-01-29 | 中国科学院长春应用化学研究所 | The preparation method of watersoluble chlorinated polypropylerie lotion |
| CN110229277A (en) * | 2019-05-21 | 2019-09-13 | 上海保立佳新材料有限公司 | A kind of CPP/ acrylic acid ester emulsion and aqueous CPP- acryloid cement and preparation method thereof and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN86104775B (en) | 1988-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU614019B2 (en) | High performance pressure-sensitive adhesive polymers | |
| CA1193376A (en) | Production of polyolefin copolymer | |
| US4727120A (en) | Adhesive compositions based on polypropylene modified by grafting an unsaturated monomer | |
| US4880487A (en) | Hot melt adhesives containing poly(p-hydroxystyrene) homopolymers and copolymers and bonding methods employing same | |
| KR0136861B1 (en) | Epoxy acrylate blend pressure sensitive thermosetting adhesives | |
| WO2012112303A1 (en) | Isobutylene copolymer with grafted polymer groups | |
| CN1006552B (en) | Hot melting adhesive for polyolefin | |
| WO2003083005A1 (en) | Rubber-acrylic adhesive formulation | |
| JPS62290706A (en) | Silane-modified ethylene copolymer, its production and adhesive comprising said copolymer | |
| CN105765018A (en) | Pressure-sensitive adhesive mass for low-energy or rough surfaces | |
| CN86104775A (en) | The preparation of polyolefin adhesive | |
| DE19905800A1 (en) | Pressure-sensitive and structural adhesive for the aggressive fixing of parts to be joined, followed by curing in the adhesive joint using thermal energy | |
| US4207220A (en) | Heat curable hot-melt adhesives containing modified polyethylene | |
| DE3783979T2 (en) | ZINC CARBOXYLATE CONTAINING MELTING ADHESIVES. | |
| USRE34122E (en) | Hot melt adhesives containing poly(p-hydroxystyrene) homopolymers and copolymers and bonding methods, employing same | |
| CN1962789A (en) | Chlorinated polypropylene adhesive | |
| US5395894A (en) | Branched block copolymer, procedures for its preparation and use | |
| EP1283251A2 (en) | Aqueous emulsion compositon and adherent composition | |
| JP4559084B2 (en) | Rubber-acrylic adhesive formulation | |
| DE3939454A1 (en) | MOISTURIZABLE PRIMER COMPOSITION | |
| US5473022A (en) | Carboxyl-containing isobutene copolymers | |
| US3784502A (en) | Block copolymer compositions | |
| CA1208388A (en) | Process for producing a storage-stable, miscible curing agent for acrylate resin adhesives | |
| US3282881A (en) | Hot-melt adhesive compositions consisting essentially of ethylene-vinyl acetate and chlorinated terphenyls | |
| US5877259A (en) | Heat sealable adhesive coating composition and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| PB01 | Publication | ||
| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |