CN1428367A - Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method - Google Patents
Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method Download PDFInfo
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Abstract
The present invention provides an oil-resistant full-vulcanized thermoplastic elastomer and its preparation method. Said elastomer is obtained by blending the oil-resistant powder rubber with crosslinked structure and average grain size of 0.02 micrometer-0.5 micrometer and polyolefin, in which the polyolefine plastic component is formed from polyolefine and modified polyolefine. Said invented thermoplastic elastomer contains small rubber phase grain size, high tensile strength and high extensibility at break.
Description
Technical field
The present invention relates to thermoplastic elastomer, further, the present invention relates to a kind of oil-resistant fully-vulcanized thermoplastic elastomer and this process for preparation of thermoplastic elastomer.
Background technology
Fully sulfurized thermoplastic elastomer is the type material of the development 1980s.It is by elastomerics and rigidity plastics under certain conditions, utilizes the method for dynamic vulcanization technology by mechanical blending to prepare.The rubber phase that this kind thermoplastic elastomer is fully crosslinked on phase is dispersed in the plastics substrate.Prepare fully sulfurized thermoplastic elastomer by dynamic vulcanization process, sulfuration at the simultaneous rubber of material blend, the size of rubber phase mainly rely on mechanical blending shear and chemical crosslink reaction between balance decide, so that the rubber phase particle diameter is difficult to accomplish is very little.This method all has very high requirement to vulcanizing agent, blending temperature, shearing rate, blend time and mutual cooperation etc., so the production technique more complicated, the median size of rubber phase and degree of crosslinking are difficult to control; And the special blending equipment that is applicable to dynamic vulcanization process of these method needs, so the production cost of this method is very high.
The inventor obtains a kind of fully vulcanized powder rubber by great deal of experimental.This kind fully vulcanized powder rubber is by in rubber latex, behind the adding crosslinking coagent, carries out radiation vulcanization, and obtain after spray-dried.This kind powdered rubber and plastics can be made the little fully sulfurized thermoplastic elastomer of a kind of rubber phase median size by rubber plastic blend.Associated patent is seen the applicant's Chinese patent application CN99125530.5 (application on December 3rd, 1999).This method is different from dynamic vulcanization process, uses general rubber plastic blend equipment and does not need special blending equipment, and technology is simple, and processing condition are easy to control, and are good for the particle diameter and the degree of crosslinking controllability of rubber phase.The prepared rubber phase particle diameter of rubber phase particle diameter ratio conventional dynamic vulcanization process of the fully sulfurized thermoplastic elastomer that obtains with this method is much smaller.
But when this method was used to prepare oil-resistant fully-vulcanized thermoplastic elastomer, because the oil-resisting type powdered rubber is incompatible with polyolefine, the physical and mechanical properties of resultant goods was very poor, and its elongation at break is not higher than 50%.
Summary of the invention
In order to prepare oil-resisting type thermoplastic elastomer with good physical mechanical property, the present invention is when the preparation oil-resistant fully-vulcanized thermoplastic elastomer, plastic polymer by in plastic substrate, adding modification or use the modified plastics polymkeric substance as plastic substrate, and improve consistency between rubber and the plastics, reached good effect.
The objective of the invention is for a kind of oil-resistant fully-vulcanized thermoplastic elastomer of excellent performance is provided.This thermoplastic elastomer has mechanical property and excellent oil-proofness preferably, and outward appearance is good and have the well processed formability, and its tension fracture elongation rate can reach more than 100%.
Another object of the present invention provides the preparation method of described oil-resistant fully-vulcanized thermoplastic elastomer.Because solved the compatibility problem that plastics reach rubber phase mutually, resulting thermoplastic elastomer has the favorable mechanical performance.This method is different from dynamic vulcanization process, and it uses general rubber plastic blend equipment and does not need special blending equipment, and processing condition are easy to control, and are good for the particle diameter and the degree of crosslinking controllability of rubber phase.
Oil-resistant fully-vulcanized thermoplastic elastomer of the present invention comprises that following component blend forms:
A. polyolefin plastics component: the mixture group of forming by modified polyolefin or modified polyolefin and polyolefine
Become, wherein modified polyolefin is the graft polyolefin that contains the polarity graft component, and modified polyolefin accounts for
10～100% of mixture total weight amount;
B. the oil-resisting type powdered rubber that has crosslinking structure, its median size are 0.02 μ m～0.5 μ m, and be described
The weight ratio of oil-resisting type powdered rubber and polyolefin plastics component is 30: 70～75: 25;
The disperse phase of oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is that rubber phase is the oil-resisting type powdered rubber with crosslinking structure, and its rubber particles is preferably equal phase structure.This kind oil-resisting type powdered rubber comprises at least a of following rubber: powder nbr rubber, carboxyl butyronitrile powdered rubber and acrylate powder rubber etc.Its gel content is counted 60% weight or higher with weight ratio, and preferred 80% weight or higher, its median size are 0.02 μ m～0.5 μ m, is preferably 0.05 μ m～0.2 μ m.
The oil-resisting type powdered rubber that has crosslinking structure in the oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is the fully vulcanized powder rubber that adopts the Chinese patent application submitted on December 3rd, 1999 according to the applicant 99125530.5 prepared.The full sulfuration of this kind oil-resisting type powdered rubber is by in the rubber latex of oil-resisting type, behind the adding crosslinking coagent, carries out radiation vulcanization, and obtain after spray-dried.Be that need not with separant after a kind of drying is free flowable rubber micro mist.Full sulfuration oil-resisting type powdered rubber with this method preparation comprises: vulcanize powder nbr rubber entirely, vulcanize carboxyl butyronitrile powdered rubber, full propylene sulfide esters of gallic acid powdered rubber entirely.The gel content that should vulcanize the oil-resisting type powdered rubber entirely changes to some extent according to the irradiation dose difference, is preferably 60% weight or higher, and more excellent is 75% weight or higher.Its median size is 0.02 μ m～0.5 μ m, is preferably 0.05 μ m～0.2 μ m.Should complete each particulate that vulcanizes in the oil-resisting type powdered rubber all be homogeneous, promptly single particulate all be a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
The external phase of oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is that plastics can adopt various types of polyolefin plasticss mutually.Wherein modified polyolefin is the graft polyolefin that contains the polarity graft component, grafted monomer is any graftable polar monomer, the preferred polar monomer that can react with oil-resisting type powdered rubber end group or side group is as glycidyl methacrylate, maleic anhydride etc.Percentage of grafting is that the percentage that polarity graft component content (weight) accounts for graft polyolefin weight is 0.1～10%, is preferably 0.1～5%.Polyolefine in polyolefin plastics and the modified polyolefin is optional from polypropylene, polyethylene, comprises its homopolymerization and/or multipolymer.The modified polyolefin plastics are 10%～100% at the content of plastics in mutually by weight percentage, and in this scope, modified polyolefin all can play good compatibilization effect.
The external phase of oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is that the modified polyolefin plastics of plastics in mutually can be commercially available and get, also can be by adopting the formulation of common prior art.
The weight ratio of oil-resisting type powdered rubber and polyolefin plastics component is 30: 70～75: 25 in the oil-resistant fully-vulcanized thermoplastic elastomer of the present invention, it is preferably 40: 60～and 75: 25.
The preparation method of oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is: utilize common melt-blending process in the rubber and plastic processing, with above-described median size be the oil-resisting type powdered rubber of 0.05 μ m～0.2 μ m and polyolefin plastics component with crosslinking structure by rubber plastic blend equipment blend granulation, thereby make oil-resistant fully-vulcanized thermoplastic elastomer.
Have the oil-resisting type powdered rubber of crosslinking structure among this preparation method, its rubber particles is preferably equal phase structure.The gel content of this kind oil-resisting type powdered rubber is counted 60% weight or higher with weight ratio, and preferred 80% weight or higher, median size are preferably 0.05 μ m～0.2 μ m.The weight ratio of oil-resisting type powdered rubber and polyolefin plastics component is 30: 70～75: 25, it is preferably 40: 60～and 75: 25.
The oil-resisting type powdered rubber that has crosslinking structure in the oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is prepared in the Chinese patent application 99125530.5 of submission on December 3rd, 1999 according to the applicant.The full sulfuration of this kind oil-resisting type powdered rubber is by in the oil-resisting type rubber latex, behind the adding crosslinking coagent, carries out radiation vulcanization, and obtain after spray-dried.It is that need not with separant after a kind of drying is free flowable rubber micro mist.The gel content that should vulcanize the oil-resisting type powdered rubber entirely changes to some extent according to the irradiation dose difference, is preferably 60% weight or higher, and more excellent is 75% weight or higher.Its median size is 0.02 μ m～0.5 μ m, is preferably 0.05 μ m～0.2 μ m.Should complete each particulate that vulcanizes in the oil-resisting type powdered rubber all be homogeneous, promptly single particulate all be a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
Polyolefin plastics component among this preparation method can adopt various types of polyolefin plasticss.Wherein modified polyolefin is the graft polyolefin that contains the polarity graft component, grafted monomer is any graftable polar monomer, the preferred polar monomer that can react with oil-resisting type powdered rubber end group or side group is as glycidyl methacrylate, maleic anhydride etc.Percentage of grafting is that the percentage that polarity graft component content (weight) accounts for graft polyolefin weight is 0.1～10%, is preferably 0.1～5%.Polyolefine in polyolefin plastics and the modified polyolefin is optional from polypropylene, polyethylene, comprises its homopolymerization and/or multipolymer.The modified polyolefin plastics are 10%～100% at the content of plastics in mutually by weight percentage, and in this scope, modified polyolefin all can play good compatibilization effect.
The external phase of oil-resistant fully-vulcanized thermoplastic elastomer of the present invention is that the modified polyolefin plastics of plastics in mutually can be commercially available and get, also can be by adopting the formulation of common prior art.
In preparation process, the blending temperature of material is polyolefinic common processing temperature, should select not only guaranteeing the complete fusion of polyolefine but also can not make in the scope of its decomposition.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent of plastic working in right amount.
Employed rubber plastic blend equipment can be mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc. among this preparation method, preferred twin screw extruder.
Oil-resistant fully-vulcanized thermoplastic elastomer of the present invention, owing to having introduced polar monomer grafted polyolefin plastics consistency is improved between its main body plastics polyolefine and the oil-resisting type rubber, tensile strength and elongation at break are greatly improved, elongation at break can reach more than 100%, not only have excellent oil-proofness, and have good appearance and processibility.This preparation method uses general rubber plastic blend equipment, and technology is simple, operation controllability good.Prepared oil-resistant fully-vulcanized thermoplastic elastomer has good performance, is applicable to requirement of industrialized batch production.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in the appended claims.
Embodiment 1
Median size is about the full sulfuration carboxyl butyronitrile powdered rubber of 0.05 μ m, and (trade mark of producing in Lanhua Latex Research and Development Centre is in the carboxyl butyronitrile emulsion of XNBRL, after pressing 3% adding crosslinking coagent Viscoat 295 of carboxyl butyronitrile emulsion dry glue quality, carry out radiation vulcanization, irradiation dose is 2.5Mrad, obtain after spray-dried, gel content is 97.1%) and the polyolefin plastics component with the mixed of weight ratio 60/40, wherein the polyolefin plastics component is that 10% glycidyl methacrylate graft polypropylene (preparation method's face explanation as follows) and weight percentage are 90% polypropylene (the polypropylene trade mark is 1300, Yanshan Petrochemical production) composition by weight percentage.And add 0.2% antioxidant 1076 (productions of Switzerland vapour Ba Jiaji company) of rubber and plastics gross weight, 0.5% anti-aging agent RD (production of German Bayer AG), with the ZSK-25 type twin screw extruder extruding pelletization of German WP company, each section of forcing machine temperature is respectively: 180 ℃, 190 ℃, 190 ℃, 200 ℃, 200 ℃ and 195 ℃ (head temperature).Pellet is made the standard batten with injection moulding, carry out every performance test, the results are shown in Table 1 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Wherein the polyacrylic preparation method of glycidyl methacrylate graft is: per 100 parts of polypropylene add 4 parts of glycidyl methacrylate GMA, 2.9 parts of vinylbenzene and 0.4 part of dicumyl peroxide DCP, 190-200 ℃ of reaction down, its percentage of grafting is about 1.4%; Polypropylene is produced by Qilu Petroleum Chemical Corporation Institute, and the trade mark is QPR01.Glycidyl methacrylate, vinylbenzene and dicumyl peroxide are commercially available.
Embodiment 2
Except that polyolefin component changes into by weight percentage is that 50% glycidyl methacrylate graft polypropylene and weight percentage are that all the other conditions were all identical with embodiment 1 50% polypropylene was formed.The results are shown in Table 1 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 3
Except that polyolefin component change into form by pure glycidyl methacrylate graft polypropylene, all the other conditions are all identical with embodiment 1.The results are shown in Table 1 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 4
Removing that polyolefin component changes into by weight percentage is that 10% maleic anhydride inoculated polypropylene and weight percentage are that all the other conditions were all identical with embodiment 1 outside 90% polypropylene (the polypropylene trade mark is 1300, Yanshan Petrochemical production) was formed.Wherein maleic anhydride inoculated polypropylene is produced by German Hirst company (Hoechst AG.), and the trade mark is Hostaprime HC5, and percentage of grafting is 5%.The results are shown in Table 2 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 5
Except that polyolefin component changes into by weight percentage is that 50% maleic anhydride inoculated polypropylene and weight percentage are that all the other conditions were all identical with embodiment 4 50% polypropylene was formed.The results are shown in Table 2 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Comparative example 1
Median size is about full sulfuration carboxyl butyronitrile powdered rubber (with embodiment 1) and polypropylene (the Yanshan Petrochemical production of 0.05 μ m, the trade mark is 1300) with the mixed of weight ratio 60/40, add 0.2% antioxidant 1076 (production of Switzerland vapour Ba Jiaji company) of rubber and plastics gross weight, 0.5% anti-aging agent RD (German Bayer AG produces) again, with the ZSK-25 type twin screw extruder extruding pelletization of German WP company, each section of forcing machine temperature is respectively: 180 ℃, 190 ℃, 190 ℃, 200 ℃, 200 ℃ and 195 ℃ (head temperature).Pellet is made the standard batten with injection moulding, carry out every performance test, the results are shown in Table 1 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 6
Except that full sulfuration carboxyl butyronitrile powdered rubber and glycidyl methacrylate graft polypropylene by 30/70 the mixed, all the other conditions are all identical with embodiment 3.The results are shown in Table 3 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 7
Except that full sulfuration carboxyl butyronitrile powdered rubber and glycidyl methacrylate graft polypropylene by 40/60 the mixed, all the other conditions are all identical with embodiment 3.The results are shown in Table 3 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 8
Except that full sulfuration carboxyl butyronitrile powdered rubber and glycidyl methacrylate graft polypropylene by 50/50 the mixed, all the other conditions are all identical with embodiment 3.The results are shown in Table 3 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 9
Except that full sulfuration carboxyl butyronitrile powdered rubber and glycidyl methacrylate graft polypropylene by 70/30 the mixed, all the other are all identical with embodiment 3.The results are shown in Table 3 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 10
Except that full sulfuration carboxyl butyronitrile powdered rubber and glycidyl methacrylate graft polypropylene by 75/25 the mixed, all the other are all identical with embodiment 3.The results are shown in Table 3 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 11
Except that the polyacrylic preparation of glycidyl methacrylate graft prescription adds 2 parts of glycidyl methacrylate GMA, 1.5 parts of vinylbenzene and the 0.2 part of dicumyl peroxide DCP for per 100 parts of polypropylene, all the other conditions are all identical with embodiment 3.Obtain the polyacrylic percentage of grafting of glycidyl methacrylate graft and be about 0.3%.The results are shown in Table 4 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Embodiment 12
Except that the polyacrylic preparation of glycidyl methacrylate graft prescription adds 4 parts of glycidyl methacrylate GMA, 2.9 parts of vinylbenzene and the 0.8 part of dicumyl peroxide DCP for per 100 parts of polypropylene, all the other are all identical with embodiment 3.Obtain the polyacrylic percentage of grafting of glycidyl methacrylate graft and be about 2.1%.The results are shown in Table 4 for the oil-resistant fully-vulcanized thermoplastic elastomer that records.
Table 1
| Tensile break strength | 100% tensile modulus | Tension fracture elongation rate | Tensile set | Cubical expansivity in the gasoline * | Shore hardness D | |
| Unit | ????MPa | ????MPa | ????％ | ????％ | ????％ | ?????- |
| Comparative example 1 | ????13.7 | ?????- | ????47 | ????6 | ????24.7 | ????45 |
| Embodiment 1 | ????21.7 | ????18.3 | ????182 | ????60 | ????24.5 | ????47 |
| Embodiment 2 | ????23.9 | ????18.2 | ????205 | ????62 | ????25.0 | ????47 |
| Embodiment 3 | ????23.5 | ????18.0 | ????190 | ????57 | ????24.9 | ????47 |
| Testing standard | ???????????????ASTM?D412-95 | ????ASTM ???D471-79 | ????ASTM ???D2240-97 | |||
*Test condition is: 23 ℃, and 166 hours
Table 2
| Tensile break strength | 100% tensile modulus | Tension fracture elongation rate | Tensile set | Cubical expansivity in the gasoline * | Shore hardness D | |
| Unit | ????MPa | ??MPa | ????％ | ????％ | ????％ | ????- |
| Comparative example 1 | ????13.7 | ???- | ????47 | ????6 | ????24.7 | ????45 |
| Embodiment 4 | ????22.0 | ??18.6 | ????174 | ????57 | ????23.9 | ????49 |
| Embodiment 5 | ????19.9 | ??18.4 | ????120 | ????33 | ????25.8 | ????49 |
| Testing standard | ???????????????????ASTM?D412-95 | ????ASTM ???D471-79 | ????ASTM ???D2240-97 | |||
*Test condition is: 23 ℃, and 166 hours
Table 3
| The rubber plastic blend weight ratio | Tensile break strength | 100% tensile modulus | Tension fracture elongation rate | Tensile set | Cubical expansivity in the gasoline * | Shore hardness D | |
| Unit | ???- | ??MPa | ??MPa | ????％ | ????％ | ????％ | ????- |
| Embodiment 6 | ?30∶70 | ?28.9 | ??27.1 | ????239 | ????99 | ????21.5 | ????59 |
| Embodiment 7 | ?40∶60 | ?27.2 | ??23.9 | ????228 | ????70 | ????23.5 | ????56 |
| Embodiment 8 | ?50∶50 | ?26.2 | ??20.7 | ????211 | ????66 | ????24.4 | ????51 |
| Embodiment 3 | ?60∶40 | ?23.5 | ??18.0 | ????190 | ????57 | ????24.9 | ????47 |
| Embodiment 9 | ?70∶30 | ?20.1 | ??13.9 | ????176 | ????36 | ????27.0 | ????40 |
| Embodiment 10 | ?75∶25 | ?18.0 | ??12.5 | ????171 | ????32 | ????27.2 | ????39 |
| Comparative example 1 | ?30∶70 | ?13.7 | ???- | ????47 | ????6 | ????24.7 | ????45 |
| Testing standard | ???- | ????????????????ASTM?D412-95 | ????ASTM ???D471-79 | ????ASTM ???D2240-97 | |||
*Test condition is: 23 ℃, and 166 hours
Table 4
| The modified polypropene percentage of grafting | Tensile break strength | 100% tensile modulus | Tension fracture elongation rate | Tensile set | Cubical expansivity in the gasoline * | Shore hardness D | |
| Unit | ?????- | ??MPa | ?????MPa | ????％ | ??％ | ????％ | ????- |
| Embodiment 3 | ????1.4％ | ??23.5 | ????18.0 | ????190 | ????57 | ????24.9 | ????47 |
| Embodiment 11 | ????0.3％ | ??23.2 | ????16.5 | ????223 | ????73 | ????26.0 | ????45 |
| Embodiment 12 | ????2.1％ | ??21.7 | ????15.9 | ????201 | ????58 | ????25.2 | ????48 |
| Testing standard | ?????- | ???????????????ASTM?D412-95 | ????ASTM ???D471-79 | ????ASTM ??D2240-97 | |||
*Test condition is: 23 ℃, and 166 hours
Claims (13)
1. oil-resistant fully-vulcanized thermoplastic elastomer comprises that following component blend forms:
A. polyolefin plastics component: be made up of the mixture that modified polyolefin or modified polyolefin and polyolefine are formed, wherein modified polyolefin is the graft polyolefin that contains the polarity graft component, and modified polyolefin accounts for 10～100% of mixture total weight amount;
B. the oil-resisting type powdered rubber that has crosslinking structure, its median size are 0.02 μ m～0.5 μ m, and the weight ratio of described oil-resisting type powdered rubber and polyolefin plastics component is 30: 70～75: 25;
2. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1, the rubber particles that it is characterized in that described oil-resisting type powdered rubber is equal phase structure.
3. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1, the gel content that it is characterized in that described oil-resisting type powdered rubber is 60% weight or higher.
4. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 3, the gel content that it is characterized in that described oil-resisting type powdered rubber is 80% weight or higher.
5. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1, the median size that it is characterized in that described oil-resisting type powdered rubber are 0.05 μ m～0.2 μ m.
6. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1 is characterized in that described oil-resisting type powdered rubber comprises at least a of following material: powder nbr rubber, carboxyl butyronitrile powdered rubber, esters of acrylic acid powdered rubber.
7. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 6 is characterized in that described oil-resisting type powdered rubber comprises at least a of following material: vulcanize powder nbr rubber entirely, vulcanize carboxyl butyronitrile powdered rubber, full propylene sulfide esters of gallic acid powdered rubber entirely.
8. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1 is characterized in that the polyolefine in the described polyolefin plastics component comprises: polypropylene, polyethylene, modified polyolefin comprises: modified polypropene, modified poly ethylene.
9. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1 is characterized in that described polarity graft component comprises maleic anhydride, glycidyl methacrylate, and percentage of grafting is 0.1～10%.
10. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 9, the percentage of grafting that it is characterized in that described polarity graft component is 0.1～5%.
11. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1, the weight ratio that it is characterized in that described oil-resisting type powdered rubber and polyolefin plastics component is 40: 60～75: 25.
12. oil-resistant fully-vulcanized thermoplastic elastomer according to claim 1 is characterized in that described polyolefine is a polypropylene; Described modified polyolefin is a modified polypropene, and modified polypropene is selected from maleic anhydride inoculated polypropylene or glycidyl methacrylate graft polypropylene; Described oil-resisting type powdered rubber is full sulfuration carboxyl butyronitrile powdered rubber.
13. preparation method according to each described oil-resistant fully-vulcanized thermoplastic elastomer of claim 1～12, it is characterized in that above-mentioned oil-resisting type powdered rubber and the blend of polyolefin plastics component melts, and make oil-resistant fully-vulcanized thermoplastic elastomer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671451B (en) * | 2008-09-11 | 2012-05-30 | 中国石油化工股份有限公司 | Soft level oil-resistant fully-vulcanized thermoplastic elastomer and preparation method thereof |
| CN101671459B (en) * | 2008-09-11 | 2013-05-01 | 中国石油化工股份有限公司 | Fully-vulcanized polypropylene/acrylate rubber thermoplastic elastomer and preparation method thereof |
| CN104592631A (en) * | 2015-01-09 | 2015-05-06 | 安徽中意胶带有限责任公司 | Environment-friendly flame-retardant thermoplastic elastomer and preparation method thereof |
| CN105255088A (en) * | 2015-10-08 | 2016-01-20 | 湖北福尔家家高新科技有限公司 | Heat-resistant, oil-resistant and acid-and-alkali-resistant modified polypropylene and preparation method |
| CN106883512A (en) * | 2017-03-16 | 2017-06-23 | 鑫同吸塑（深圳）有限公司 | A kind of PP composite material that lotus leaf effect is formed to greasy dirt and preparation method thereof |
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2001
- 2001-12-28 CN CNB011434570A patent/CN1180012C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671451B (en) * | 2008-09-11 | 2012-05-30 | 中国石油化工股份有限公司 | Soft level oil-resistant fully-vulcanized thermoplastic elastomer and preparation method thereof |
| CN101671459B (en) * | 2008-09-11 | 2013-05-01 | 中国石油化工股份有限公司 | Fully-vulcanized polypropylene/acrylate rubber thermoplastic elastomer and preparation method thereof |
| CN104592631A (en) * | 2015-01-09 | 2015-05-06 | 安徽中意胶带有限责任公司 | Environment-friendly flame-retardant thermoplastic elastomer and preparation method thereof |
| CN105255088A (en) * | 2015-10-08 | 2016-01-20 | 湖北福尔家家高新科技有限公司 | Heat-resistant, oil-resistant and acid-and-alkali-resistant modified polypropylene and preparation method |
| CN105255088B (en) * | 2015-10-08 | 2017-09-19 | 湖北福尔家家高新科技有限公司 | A kind of heat-resisting acid/alkali-resistant modified polypropene and preparation method |
| CN106883512A (en) * | 2017-03-16 | 2017-06-23 | 鑫同吸塑（深圳）有限公司 | A kind of PP composite material that lotus leaf effect is formed to greasy dirt and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1180012C (en) | 2004-12-15 |
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