CN1317324C - Production of thermoplastic elastomer - Google Patents
Production of thermoplastic elastomer Download PDFInfo
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- CN1317324C CN1317324C CNB2005100277299A CN200510027729A CN1317324C CN 1317324 C CN1317324 C CN 1317324C CN B2005100277299 A CNB2005100277299 A CN B2005100277299A CN 200510027729 A CN200510027729 A CN 200510027729A CN 1317324 C CN1317324 C CN 1317324C
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- thermoplastic elastomer
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- methacrylate
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Abstract
The present invention provides a preparing method for thermoplastic elastomers, namely that ethylene propylene diene rubber, polyolefine resin and unsaturated carboxylate are blended, and a melt blending method is used under the condition that dicumyl peroxide exists; thus, a thermoplastic elastomer with excellent mechanical properties is made. The present invention has the advantages of simple processes. The thermoplastic elastomer which is made has excellent physical and mechanical properties, and also has good processing properties.
Description
Technical field the present invention relates to a kind of preparation method of macromolecular material, particularly a kind of process for preparation of thermoplastic elastomer.
Background technology dynamic full vulcanization terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastomer (TPV) is that exploitation is the most successful at present, also is to use the most a kind of thermoplastic elastic material.This class Thermoplastic Elastomer, Olefinic can be good at satisfying the loss of weight of trolley part and shockproof requirement, therefore is widely used in the automotive material field, also is widely used in fields such as cable and wire, construction industry and household electrical appliances industry simultaneously.
General polyolefins thermoplastic elastomer by a kind of polyolefine and a kind of rubber crosslinked the forming in linking agent effect lower section.The at present main linking agent that uses has organo-peroxide, Sulfur or other to be used for the vulcanizing agent of traditional vulcanized rubber.All there is different shortcomings in these several vulcanization.Wherein, the organo-peroxide linking agent so cause polyolefinic molecular breakdown easily when reaction, degrades polypropylene because reactive behavior is big, and molecular weight reduces, thereby causes the mechanical property variation of TPV; And the polysulfidic bond poor heat stability in the course of processing that forms during sulfur vulcanization, easy fracture, and also the system smell is big, easy coloring, and processing characteristics is also relatively poor.
In U.S. Patent Publication No. US.3806558, Fisher successfully makes a kind of partial cross-linked thermoplastic elastomer, includes the terpolymer EP rubber of (A) 60～90 weight parts, (B) acrylic resin of 10～40 weight parts.A kind of peroxide vulcanizing agent of this use for avoiding polyacrylic degraded, uses the amount of superoxide less, thereby can only prepare the PP/EPDM thermoplastic elastomer of partial vulcanization, and therefore the mechanical property that obtains is also relatively poor.
In another part U.S. Pat .4130535, employing Sulfurs such as Coran are made the linking agent of rubber phase, TMTD (TMTD) and curing Dibenzo thiazole (MBTS) are as crosslinking coagent and promotor, adopt the method for dynamic crosslinking to make the complete crosslinked EPT rubber blend thermoplastic elastomer of rubber phase, obtain fabulous mechanical property.But this thermoplastic elastomer smell is big, and processing characteristics is relatively poor.Free sulphur in the prescription can produce corrosive nature to copper conductor in addition, thereby has limited its application in cable industry.
In Chinese patent 87108108.3, people such as the quiet hero of clear water of Mitsui Petrochemical Industries Ltd. with (a) contain ethylene/propene mol ratio 50/50～90/10 ethylene-propylene copolymer rubber and (or) ethylene-propylene-non-conjugated diene rubber, (b) olefin series plastic, (c) unsaturated carboxylic acid or derivatives thereof mix, and carries out melt blending in the presence of organo-peroxide.Prepared thermoplastic elastic liquid flowability and formability excellence, the caoutchouc elasticity excellence of molding.But because the unsaturated carboxylic acid boiling point is lower, volatilization causes damage easily when the high temperature dynamic blending, thereby causes the instability of quality product, and unsaturated carboxylic acid also has certain corrodibility to processing units simultaneously.
Summary of the invention the objective of the invention is to solve the not good problem of thermoplastic elastomer mechanical property of peroxide cross-linking system preparation.By introducing salt unsaturated carboxylic acid as a kind of novel additional crosslinker, not only can suppress the Degradation of dicumyl peroxide to polyolefin resin, also rubber phase is had to a certain degree strengthening action, thereby obtain a kind of novel process for preparation of thermoplastic elastomer.
A kind of process for preparation of thermoplastic elastomer of the present invention is as follows:
Step 1: at normal temperatures 100 weight part terpolymer EP rubbers are added in the blending equipment, add 0.1～80 weight part salt unsaturated carboxylic acid and 0.1～5 weight part dicumyl peroxide after 3～10 minutes successively, blend 5～30 minutes, thus make the rubber master batch that contains salt unsaturated carboxylic acid;
Step 2: under 170～210 ℃, 25～500 weight part polyolefin resines are added in the blending equipment, add the rubber master batch that 100.2～185 weight parts contain salt unsaturated carboxylic acid after 2～5 minutes, blend 3～10 minutes, thus obtain a kind of thermoplastic elastomer.
The 3rd monomer of the terpolymer EP rubber that the present invention uses is ethylidene norbornene, and the weight percent of ethylene content is 40～80%, and mooney viscosity is 40～100 under 100 ℃.
The polyolefin resin that the present invention uses is selected from polypropylene, polyethylene or its mixture.
6. the salt unsaturated carboxylic acid of the present invention's use is selected from sodium methacrylate, magnesinm methacrylate, zinc methacrylate, aluminium methacrylate, sodium acrylate, vinylformic acid magnesium, zinc acrylate resin or vinylformic acid aluminium.
The blending equipment that the present invention uses is selected from mill, Banbury mixer, single screw extrusion machine or twin screw extruder.
A kind of process for preparation of thermoplastic elastomer of the present invention is to introduce salt unsaturated carboxylic acid in traditional polyolefin-type thermoplastic elastomer.In the process of high-temperature fusion blend, the polyreaction of self takes place in salt unsaturated carboxylic acid on the one hand under the initiation of dicumyl peroxide, form nanoparticle reinforced rubber phase; Graft reaction also can take place with rubber phase, plastics in salt unsaturated carboxylic acid mutually on the other hand, thereby has strengthened the biphase interface interaction; Salt unsaturated carboxylic acid can effectively reduce the Degradation of superoxide to polyolefin resin simultaneously, thereby the physical and mechanical properties of resulting thermoplastic elastomer also is significantly improved.
A kind of process for preparation of thermoplastic elastomer of the present invention has obviously improved the physical and mechanical properties of the thermoplastic elastomer that adopts the peroxide cross-linking system preparation, wherein the salt unsaturated carboxylic acid of being introduced has played key effect, only the salt unsaturated carboxylic acid of 5 weight parts just can make the tensile strength of thermoplastic elastomer improve 4.6MPa, reaches 10.4Mpa; Elongation at break has also increased more than one times, has reached 410%.Principal feature of the present invention is as follows:
1. effectively reduce the Degradation of superoxide, and unsaturated carboxylic acid salt pair rubber phase there is strengthening action to a certain degree, thereby significantly improved the physical and mechanical properties of thermoplastic elastomer polyolefin resin;
2. therefore the thermoplastic elastomer good fluidity that obtains of the present invention has good processing properties, can use the employed device of common thermoplastics to make its moulding, is suitable for extrusion moulding, calendering formation, injection moulding or the like.
Embodiment
Following examples are that the present invention is further specified, rather than limit the scope of the invention.
In following examples, the tensile property test is all carried out according to ASTM D412 standard, and the tear strength test is all carried out according to ASTM D624 standard, and the shock strength test is all carried out according to ISO 180 standards.
In following examples, Comparative Examples 1,2,3,4 has 1,2,3, the 4 identical preparation technologies with embodiment, and difference only is prescription.
Embodiment 1:
Step 1: according to prescription terpolymer EP rubber is added in the Banbury mixer, add zinc methacrylate and dicumyl peroxide successively according to prescription after 3 minutes, blend at normal temperatures 30 minutes, thus make the rubber master batch that contains zinc methacrylate;
Step 2: under 170 ℃, in Banbury mixer, add polypropylene by component requirements of table 1 prescription, treat its plasticizing after, the rubber master batch that adding contains zinc methacrylate carries out melt blending, operates after 10 minutes discharging.At 200 ℃ of counterdie tablet formings.The physical and mechanical properties of obtained thermoplastic elastomer sees Table 2.From this table as can be seen, behind the adding zinc methacrylate, the tensile strength and the tensile yield of thermoplastic elastomer significantly improve.
Table 1 basic recipe
| Comparative Examples 1 | Embodiment 1 | |
| Terpolymer EP rubber (EP4703 of Du Pont) polypropylene zinc methacrylate dicumyl peroxide | 100 42.86 0 1 | 100 42.86 5 1 |
Table 2 performance
| Comparative Examples 1 | Embodiment 1 | |
| 100% stretches modulus surely, the MPa tensile strength, the MPa tensile yield, the % tear strength, kN/m | 5.0 5.8 180 45 | 5.6 10.4 410 63.8 |
Embodiment 2:
Step 1: by the component requirement of table 3 prescription, other is operated with embodiment 1;
Step 2: by the component requirement of table 3 prescription, other is operated with example 1.The physical and mechanical properties that makes thermoplastic elastomer sees Table 4.From this table as can be seen, behind the adding magnesinm methacrylate, the tensile strength and the tensile yield of thermoplastic elastomer significantly improve.
Table 3 basic recipe
| Comparative Examples 2 | Embodiment 2 | |
| Terpolymer EP rubber (EP4703 of Du Pont) polypropylene magnesinm methacrylate dicumyl peroxide | 100 43 0 1 | 100 43 5 1 |
Table 4 performance
| Comparative Examples 2 | Embodiment 2 | |
| 100% stretches modulus surely, the MPa tensile strength, the MPa tensile yield, the % tear strength, kN/m | 5.0 5.8 180 45 | 5.6 9.6 360 61.3 |
Embodiment 3:
Step 1: by the component requirement of table 5 prescription, other is operated with embodiment 1;
Step 2: by the component requirement of table 3 prescription, other is operated with example 1.The physical and mechanical properties that makes thermoplastic elastomer sees Table 6.From this table as can be seen, behind the adding zinc methacrylate, the tensile strength and the tensile yield of thermoplastic elastomer significantly improve.
Table 5 basic recipe
| Comparative Examples 3 | Embodiment 3 | |
| Terpolymer EP rubber (EP4703 of Du Pont) polypropylene zinc methacrylate dicumyl peroxide | 100 100 0 1 | 100 100 5 1 |
Table 6 performance
| Comparative Examples 3 | Embodiment 3 | |
| Tensile strength, MPa tensile yield, % | 7.4 40 | 13.8 210 |
Embodiment 4:
Step 1: by the component requirement of table 7 prescription, other is operated with embodiment 1;
Step 2: in twin screw extruder, the component requirement adding polyolefin resin of filling a prescription by table 5 carries out melt blending with the rubber master batch that contains zinc methacrylate, and blending temperature is 200 ℃.Extrude pelletizing, injection moulding.The physical and mechanical properties that makes thermoplastic elastomer sees Table 8.From this table as can be seen, behind the adding zinc methacrylate, the shock strength and the tensile yield of thermoplastic elastomer significantly improve.
Table 7 basic recipe
| Comparative Examples 4 | Embodiment 4 | |
| Terpolymer EP rubber (EP4703 of Du Pont) polypropylene zinc methacrylate dicumyl peroxide | 100 400 0 1 | 100 400 10 1 |
Table 8 performance
| Comparative Examples 4 | Embodiment 4 | |
| Shock strength (J/m) yield strength, the MPa tensile strength, the MPa tensile yield, % | 80 21.5 19.8 597 | 360 23.7 27.5 980 |
Claims (5)
1. process for preparation of thermoplastic elastomer is characterized in that the preparation method is as follows:
Step 1: at normal temperatures 100 weight part terpolymer EP rubbers are added in the blending equipment, add 0.1～80 weight part salt unsaturated carboxylic acid and 0.1～5 weight part dicumyl peroxide after 3～10 minutes successively, blend 5～30 minutes makes the rubber master batch that contains salt unsaturated carboxylic acid;
Step 2: under 170～210 ℃, 25～500 weight part polyolefin resines are added in the blending equipment, add the rubber master batch that 100.2～185 weight parts contain salt unsaturated carboxylic acid after 2～5 minutes, blend 3～10 minutes, thus make a kind of thermoplastic elastomer.
2. a kind of process for preparation of thermoplastic elastomer according to claim 1 is characterized in that polyolefin resin is selected from polypropylene, polyethylene or its mixture.
3. a kind of process for preparation of thermoplastic elastomer according to claim 1, the 3rd monomer that it is characterized in that terpolymer EP rubber is an ethylidene norbornene, and the weight percent of ethylene content is 40～80%, and mooney viscosity is 40～100 under 100 ℃.
4. a kind of process for preparation of thermoplastic elastomer according to claim 1 is characterized in that salt unsaturated carboxylic acid is selected from sodium methacrylate, magnesinm methacrylate, zinc methacrylate, aluminium methacrylate, sodium acrylate, vinylformic acid magnesium, zinc acrylate resin or vinylformic acid aluminium.
5. a kind of process for preparation of thermoplastic elastomer according to claim 1 is characterized in that blending equipment is selected from mill, Banbury mixer, single screw extrusion machine or twin screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100277299A CN1317324C (en) | 2005-07-14 | 2005-07-14 | Production of thermoplastic elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100277299A CN1317324C (en) | 2005-07-14 | 2005-07-14 | Production of thermoplastic elastomer |
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| CN1712441A CN1712441A (en) | 2005-12-28 |
| CN1317324C true CN1317324C (en) | 2007-05-23 |
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| CNB2005100277299A Expired - Fee Related CN1317324C (en) | 2005-07-14 | 2005-07-14 | Production of thermoplastic elastomer |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100480286C (en) * | 2006-07-20 | 2009-04-22 | 上海交通大学 | Preparation method of halogen less fire retardant trielement ethylene-propylene rubber |
| CN101560315B (en) * | 2008-04-14 | 2012-08-29 | 上海大裕橡胶制品有限公司 | Modified foaming ethylene propylene diene rubber |
| CN102030866B (en) * | 2010-12-29 | 2012-06-27 | 深圳市科聚新材料有限公司 | Polybasic grafted ethylene propylene diene monomer rubber and preparation method thereof |
| CN106046568A (en) * | 2016-07-19 | 2016-10-26 | 合肥毅创钣金科技有限公司 | Graft modified polyethylene anti-wear and enhanced EPDM rubber sealing strip |
| CN106589490B (en) * | 2016-11-25 | 2019-05-14 | 华南理工大学 | A kind of magnetic rubber and preparation method thereof by salt unsaturated carboxylic acid reinforcement |
| CN109096624B (en) * | 2018-08-30 | 2021-08-10 | 青岛三祥科技股份有限公司 | Rubber composition for automobile hose rubber core and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301738A (en) * | 1988-05-30 | 1989-12-05 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
| JPH0411646A (en) * | 1990-04-27 | 1992-01-16 | Fujikura Ltd | Electrically insulating resin composition |
-
2005
- 2005-07-14 CN CNB2005100277299A patent/CN1317324C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301738A (en) * | 1988-05-30 | 1989-12-05 | Idemitsu Petrochem Co Ltd | Polypropylene resin composition |
| JPH0411646A (en) * | 1990-04-27 | 1992-01-16 | Fujikura Ltd | Electrically insulating resin composition |
Non-Patent Citations (2)
| Title |
|---|
| EPDM/PP共混型热塑性弹体的进展 黄世强 肖汉文等，材料导报，第12卷第3期 1998 * |
| 甲基丙烯酸锌对EPD-M的补强作用 虞宇力 彭宇林等，橡胶工业，第48卷 2001 * |
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Granted publication date: 20070523 Termination date: 20100714 |