CN101671451B - Soft level oil-resistant fully-vulcanized thermoplastic elastomer and preparation method thereof - Google Patents
Soft level oil-resistant fully-vulcanized thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN101671451B CN101671451B CN2008102221874A CN200810222187A CN101671451B CN 101671451 B CN101671451 B CN 101671451B CN 2008102221874 A CN2008102221874 A CN 2008102221874A CN 200810222187 A CN200810222187 A CN 200810222187A CN 101671451 B CN101671451 B CN 101671451B
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Abstract
The invention provides a soft level oil-resistant fully-vulcanized polyolefine thermoplastic elastomer and a preparation method thereof, which relate to the technical field of thermoplastic elastomer. The fully-vulcanized polyolefine thermoplastic elastomer is formed by melting and mixing the components which include polyolefine plastics and a rubber component, wherein the weight ratio of the rubber component to the polyolefine plastics is 30:70-75:25. The rubber component is a mixture of rubber particles with a cross-linked structure and a softener, wherein the content of the softener is 30-120% of the rubber particles by weight; and the rubber particles comprise fully-vulcanized powdered nitrile rubber and/or fully-vulcanized powdered carboxy nitrile rubber, the mean particle diameter is 0.02mum-1mum, and the gel content is 60% by weight or higher. The softener is selected from at least one of a phthalic acid ester compound, dioctyl terephthalate, a trimellitate compound and a pyromellitic ester compound. The thermoplastic elastomer of the invention has good comprehensive properties of oil resistance, low hardness, high elongation at break and the like.
Description
Technical field
The present invention relates to thermoplastic elastomer, further say, the present invention relates to the preparation method of a kind of soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer and this full vulcanizing polyolefine thermoplastic elastomer.
Background technology
The applicant's patent " a kind of oil-resistant fully-vulcanized thermoplastic elastomer and preparation method thereof " discloses a kind of oil-resistant fully-vulcanized thermoplastic elastomer in (ZL01143457.0), and it is got by the component blend of oil-resisting type powdered rubber with crosslinking structure that comprises median size 0.02 μ m-0.5 μ m and polyolefine.Wherein the polyolefin plastics component is made up of polyolefine and modified polyolefin.The contained rubber phase particle diameter of the oil-resistant fully-vulcanized thermoplastic elastomer of this patent is little, and tensile strength and elongation at break are higher, and outward appearance is good and have a good processing forming.This patent provides a kind of comparatively easy method for preparing said full vulcanizing polyolefine thermoplastic elastomer simultaneously; This method is different from dynamic vulcanization process; It uses general rubber plastic blend equipment and does not need special blending equipment; 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.But the thermoplastic elastomer hardness of this prior art for preparing is bigger, and elongation at break can't reach enough height, can't prepare other oil resistant thermoplastic elastomer of the soft level of good comprehensive properties; In this prior art, because powdered rubber content is bigger, particle diameter is very little, so in elastomeric preparation process, the powdered rubber flowability is lower, can not long-time continuous prepare thermoplastic elastomer in addition.
Summary of the invention
Technical problem to be solved by this invention provides a kind of soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer, and it has good comprehensive performances such as oil resistant, soft, high elongation at tear.
Another technical problem to be solved by this invention provides a kind of comparatively easy method for preparing said soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer; This method has been simplified preparation technology; Reduced production cost, in the preparation process of soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer, the ultra-fine fully vulcanized powder rubber of one of raw material is mobile to be improved; Processing condition are easy to control, realize long continuous production.
For realizing the foregoing invention purpose; The present invention has added tenderizer in order to reduce its hardness on existing oil-resisting type full vulcanizing polyolefine thermoplastic elastomer basis; The contriver finds pleasantly surprisedly in test; Owing to have the existence of the rubber particles of crosslinking structure in the full vulcanizing polyolefine thermoplastic elastomer of the present invention, improved polar tenderizer and nonpolar polyolefinic consistency greatly, and the existence of tenderizer also improved the flowability of rubber particles.When reducing hardness, unexpectedly improved the elongation at break of oil-resisting type full vulcanizing polyolefine thermoplastic elastomer.
Soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer of the present invention comprises the polyolefin plastics and the rubber components of blend, and said rubber components is 30:70-75:25 with polyolefin plastics weight ratio mutually, and it is preferably 50:50-75:25.Said rubber components is to have the rubber particles of crosslinking structure and the mixture of tenderizer, and wherein the content of tenderizer is 100 weight parts in rubber particles, and 30 to 120 weight parts are preferably 50 to 100 weight parts.
In full vulcanizing polyolefine thermoplastic elastomer of the present invention, polyolefin plastics is selected from the blend etc. of homopolymer, multipolymer and the polyolefin plastics of polyolefin plastics.Be preferably at least a in the following material: alfon, propylene copolymer, Alathon or ethylene copolymer etc.
In the rubber components in full vulcanizing polyolefine thermoplastic elastomer of the present invention, said rubber particles with crosslinking structure is preferably the rubber particles of equal phase structure, and its gel content is in 60% weight or higher, preferred 80% weight or higher.Said rubber particles median size is 0.02 μ m-1 μ m, is preferably 0.05 μ m-0.5 μ m, and more excellent is 0.05 μ m-0.3 μ m.
The rubber particles with crosslinking structure among the present invention is to adopt the prepared fully vulcanized powder rubber of Chinese patent ZL00816450.9 (its preference application is the one Chinese patent application of submitting on December 3rd, 1,999 99125530.5).In the preparation process, preferentially select the fully vulcanized powder rubber of oil-resisting type for use, it can comprise at least a in the following fully vulcanized powder rubber: form of finely divided powder, mehtod paracril, form of finely divided powder, mehtod carboxy nitrile rubber.This kind fully vulcanized powder rubber is meant that gel content reaches 60% weight or higher, and more excellent is 75% weight or higher, and need not with separant after the drying is free flowable rubber micro mist.The particle diameter of this powdered rubber is 0.02 μ m-2 μ m, is preferably 0.03 μ m-1.5 μ m, and more excellent is 0.05 μ m-0.5 μ m.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and under the observation of existing microtechnique, does not find layering in the particulate, divides the phenomenon that equates uneven phase.This powdered rubber is through with corresponding rubber latex cross-linking radiation and with rubber particles particle diameter fixed.
In the rubber components in full vulcanizing polyolefine thermoplastic elastomer of the present invention, said tenderizer is selected from least a in phthalate compound, dioctyl terephthalate, trimellitic acid ester compound and the PMA ester compound.Wherein, phthalate compound is selected from but is not limited only at least a in dimethyl phthalate, diethyl phthalate, Witcizer 300, dihexyl phthalate, phthalic acid two (2-ethyl oneself) ester, dinoctyl phthalate, dimixo-octyl phthalate, DINP, Di Iso Decyl Phthalate, phthalic acid two isotridecyl esters, DCHP, phthalic acid dimethyl-cyclohexanol, phthalic acid two (methoxyl group second) ester, phthalic acid two (butoxy) ester, butyl benzyl phthalate, diphenyl phthalate, phthalic acid C7-C9 alkyl ester, phthalic acid C9-C11 alkyl ester and the positive alkyl ester of phthalic acid C6-C10; The trimellitic acid ester compound is selected from but is not limited only at least a in tri trimellitate (2-ethyl oneself) ester, triisodecyl trimellitate, tri trimellitate isotridecyl ester, tri trimellitate ester in positive hot positive last of the ten Heavenly stems and the triisooctyl trimellitate; The PMA ester compound is selected from but is not limited only to 1,2,4,5-PMA four (2-ethylhexyl).
The preparation method of soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer of the present invention may further comprise the steps:
At first; With the rubber particles as the full vulcanizing polyolefine thermoplastic elastomer disperse phase of the present invention with crosslinking structure according to said consumption and tenderizer thorough mixing after; Form rubber components; Utilize common melt-blending process in the rubber and plastic processing then, rubber components and polyolefin plastics are made full vulcanizing polyolefine thermoplastic elastomer by said consumption through the granulation of rubber plastic blend equipment melt blending.The said gel content that adopts when the gel content of rubber phase is blend in the full vulcanizing polyolefine thermoplastic elastomer of preparation thus with rubber particles itself of crosslinking structure.
In the preparation process, the blending temperature of material is the common processing temperature of polyolefin plastics, should select not only guaranteeing the complete fusion of polyolefin plastics 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 and the expanding material of plastic working in right amount.In the blend process, can said rubber phase and the disposable blend of polyolefin plastics be extruded, also can a part of rubber phase and polyolefin plastics blend be processed master batch, and then carry out the secondary blend with remaining rubber particles and extrude.
Employed rubber plastic blend equipment can be mill among the preparation method of the present invention, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
Because the present invention adopts a kind of comparatively simple preparation technology; Prepare soft other oil-resisting type full vulcanizing polyolefine thermoplastic elastomer of level, and can realize long continuous production, reduced production cost; Be applicable to requirement of industrialized batch production, make product have very strong competitiveness.And soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer of the present invention has unexpectedly obtained high elongation at tear, thereby has had good comprehensive performances when reducing hardness.The present invention has enlarged the durometer level of oil-resisting type thermoplastic elastomer thus, has enlarged its Application Areas, so thermoplastic elastomer of the present invention has fabulous application prospect.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention does not receive the restriction of these embodiment, and scope of the present invention proposes in the appended claims book.
Embodiment 1
Median size is about the full sulfuration powder nbr rubber of 0.1 μ m, and (Sinopec Beijing Research Institute of Chemical Industry's northization is ground chemical industry New Tech S. R. L. and is produced; The trade mark is VP-401) and tri trimellitate (2-ethyl oneself) ester (LG Corp of South Korea production) with 100/60 ratio thorough mixing after; And Vestolen PP 7052 (Yanshan Petrochemical; Trade mark PPR) with 50/50 mixed; Add 0.5% antioxidant 1010 (Switzerland vapour Ba Jiaji production) again, with the ZSK-25 type twin screw extruder extruding pelletization of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃ and 195 ℃ (head temperature).Pellet is processed the standard batten with injection moulding, carry out each item performance test, the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer result who records lists in the table 1.
Comparative Examples 1
Except that not adding tri trimellitate (the 2-ethyl is own) ester, other is with embodiment 1, and the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer result who records lists in the table 1.
Embodiment 2
Median size is about the full sulfuration powder nbr rubber of 0.1 μ m, and (Sinopec Beijing Research Institute of Chemical Industry's northization is ground chemical industry New Tech S. R. L. and is produced; The trade mark is VP-401) and tri trimellitate (2-ethyl oneself) ester (LG Corp of South Korea production) with 100/60 ratio thorough mixing after; And Vestolen PP 7052 (Yanshan Petrochemical; Trade mark PPR) with 70/30 mixed; Add 0.5% antioxidant 1010 (Switzerland vapour Ba Jiaji production) again, with the ZSK-25 type twin screw extruder extruding pelletization of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃ and 195 ℃ (head temperature).Pellet is processed the standard batten with injection moulding, carry out each item performance test, the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer result who records lists in the table 1.
Embodiment 3
Except that sulfuration powder nbr rubber and tri trimellitate (the 2-ethyl is own) ester is by 100/80 the mixed entirely, all the other are all identical with embodiment 2, and the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer result who records lists in the table 1.
Comparative Examples 2
Except that not adding tri trimellitate (the 2-ethyl is own) ester, other is with embodiment 2, and the thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer result who records lists in the table 1.
Embodiment 4
Median size is about the full sulfuration carboxyl butyronitrile powdered rubber of 0.05 μ m, and (Sinopec Beijing Research Institute of Chemical Industry's northization is ground chemical industry New Tech S. R. L. and is produced; The trade mark is VP-501) and tri trimellitate (2-ethyl oneself) ester (LG Corp of South Korea production) with 100/50 ratio thorough mixing after; And Vestolen PP 7052 (Yanshan Petrochemical; Trade mark PPR) with 50/50 mixed; Add 0.5% antioxidant 1010 (Switzerland vapour Ba Jiaji production) again, with the ZSK-25 type twin screw extruder extruding pelletization of German WP company, each section of forcing machine temperature is respectively: 170 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃ and 195 ℃ (head temperature).Pellet is processed the standard batten with injection moulding, carry out each item performance test, the full sulfuration carboxy nitrile rubber/polypropylene thermoplastic elastomer result who records lists in the table 1.
Comparative Examples 3
Except that not adding tri trimellitate (the 2-ethyl is own) ester, other is with embodiment 4, and the full sulfuration carboxy nitrile rubber/polypropylene thermoplastic elastomer result who records lists in the table 1.
Table 1
The soft level oil-resistant type thermoplastic elastomer of the embodiment of the invention has soft, high elongation at tear and good excellent comprehensive performances such as oil-proofness.
Claims (9)
1. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer comprises the polyolefin plastics and the rubber components of blend, and the weight ratio of said rubber components and polyolefin plastics is 30: 70-75: 25; Said polyolefin plastics is at least a in the following material: alfon, propylene copolymer, Alathon or ethylene copolymer; Said rubber components is to have the rubber particles of crosslinking structure and the mixture of tenderizer, and wherein the content of tenderizer is 100 weight parts in rubber particles, 30 to 120 weight parts; Said rubber particles with crosslinking structure comprises the form of finely divided powder, mehtod paracril or/and the form of finely divided powder, mehtod carboxy nitrile rubber, and its median size is 0.02 μ m-1 μ m, and its gel content is in 60% weight or higher; Said tenderizer is selected from the trimellitic acid ester compound.
2. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: said rubber components is 50 with polyolefin plastics weight ratio mutually: 50-75: 25.
3. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: said rubber particles with crosslinking structure is equal phase structure.
4. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: said median size with crosslinking structure rubber particles is 0.05 μ m-0.5 μ m.
5. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 4 is characterized in that: said median size with crosslinking structure rubber particles is 0.05 μ m-0.3 μ m.
6. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: said gel content with crosslinking structure rubber particles is in 80% weight or higher.
7. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: the content of said tenderizer is 100 weight parts in rubber particles, 50 to 100 weight parts.
8. soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer as claimed in claim 1 is characterized in that: said trimellitic acid ester compound is selected from least a in tri trimellitate (2-ethyl oneself) ester, triisodecyl trimellitate, tri trimellitate isotridecyl ester and the tri trimellitate ester in positive hot positive last of the ten Heavenly stems.
9. like the preparation method of each described soft level oil-resistant type full vulcanizing polyolefine thermoplastic elastomer among the claim 1-8; May further comprise the steps: at first; With said rubber particles with crosslinking structure according to said ratio and said tenderizer thorough mixing after; Form rubber components, utilize common melt-blending process in the rubber and plastic processing then, rubber components and polyolefin plastics are made full vulcanizing polyolefine thermoplastic elastomer by said consumption through the granulation of rubber plastic blend equipment melt blending.
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| EP0202782A2 (en) * | 1985-04-24 | 1986-11-26 | The British Petroleum Company p.l.c. | Process for the production of a thermoplastic elastomer composition |
| US4822834A (en) * | 1988-04-19 | 1989-04-18 | The United States Of America As Represented By The Secretary Of The Air Force | Vibration damping composition suitable for outer space temperature variations |
| CN1252419A (en) * | 1998-10-23 | 2000-05-10 | 中国石油兰州化学工业公司 | Intermingled material of polypropyene and thermoplastic nitrile rubber elastomer |
| CN1381520A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process |
| CN1428367A (en) * | 2001-12-28 | 2003-07-09 | 中国石油化工股份有限公司 | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0202782A2 (en) * | 1985-04-24 | 1986-11-26 | The British Petroleum Company p.l.c. | Process for the production of a thermoplastic elastomer composition |
| US4822834A (en) * | 1988-04-19 | 1989-04-18 | The United States Of America As Represented By The Secretary Of The Air Force | Vibration damping composition suitable for outer space temperature variations |
| CN1252419A (en) * | 1998-10-23 | 2000-05-10 | 中国石油兰州化学工业公司 | Intermingled material of polypropyene and thermoplastic nitrile rubber elastomer |
| CN1381520A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process |
| CN1428367A (en) * | 2001-12-28 | 2003-07-09 | 中国石油化工股份有限公司 | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method |
Non-Patent Citations (1)
| Title |
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| 徐晓冬等."新型CNBR/PP全交联型热塑性弹性体的制备与形态、结构及性能研究".《高等学校化学学报》.2003,第24卷(第11期),第2107-2112页. |
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