CN102070865A - Modified TPI/PP dynamically vulcanized thermoplastic elastomer - Google Patents
Modified TPI/PP dynamically vulcanized thermoplastic elastomer Download PDFInfo
- Publication number
- CN102070865A CN102070865A CN200910230427XA CN200910230427A CN102070865A CN 102070865 A CN102070865 A CN 102070865A CN 200910230427X A CN200910230427X A CN 200910230427XA CN 200910230427 A CN200910230427 A CN 200910230427A CN 102070865 A CN102070865 A CN 102070865A
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- CN
- China
- Prior art keywords
- tpi
- thermoplastic elastomer
- dcp
- mah
- nanometer sio
- 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.)
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Links
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 19
- 229920001155 polypropylene Polymers 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 5
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 229920006342 thermoplastic vulcanizate Polymers 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000899 Gutta-Percha Substances 0.000 description 2
- 240000000342 Palaquium gutta Species 0.000 description 2
- -1 Polypropylene Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920000588 gutta-percha Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a nanomaterial-filled modified trans-1,4-polyisoprene rubber/polypropylene (TPI/PP) dynamically vulcanized thermoplastic elastomer. On the basis of dynamically vulcanizing for preparing a TPI/PP blended thermoplastic elastomer, the mechanical property, the thermostability and the heat-resistant deformation performance of the thermoplastic vulcanizate (TPV) are improved by a method of filling with nano-SiO2, grafting, cross-linking and modifying by using maleic anhydride/styrene/dicumyl peroxide (MAH/St/DCP). For example, various mechanical properties of the TPV adopting the TPI/PP which is prepared by dynamically vulcanizing are all greatly improved compared with those of a TPI/PP simple blend. When filling by adopting the nano-SiO2, the hardness and the tearing strength of the TPV are both increased, and the tensile strength and the elongation at break show a trend of increasing first and then decreasing.
Description
(1) technical field
The present invention relates to the preparation of the improved modification TPI/PP of a kind of mechanical property dynamic vulcanization thermoplastic elastomer.Prepare at dynamic vulcanization on the basis of TPI/PP blending thermoplastic elastomer, use nanometer SiO
2Fill, the grafting of many molten monomers of maleic anhydride/vinylbenzene/dicumyl peroxide (MAH/St/DCP), cross-linking method carry out modification.Belong to the composite modified field of macromolecular material.
(2) background technology
" on the spot " formation that cures under linking agent effect when dynamic vulcanization thermoplastic elastomer (TPV) is elastomerics and rigid thermoplastic's melt blending.Polypropylene (PP) becomes the first-selected plastics of preparation TPV owing to have abundant raw material, cheap, good combination property.
High trans-1,4-polyisoprene rubber (TPI) claim synthetic gutta-percha or gutta-percha, Ba Lata glue again, can be used as the substitute of the rare expensive Ba Lata glue in source.The monomer whose chain link is regular anti-form-1, and 4-arranges, and has the molecular chain order of height, is easy to crystallization, under the normal temperature for hard solid is the plastics attitude, crystalline melt point T
m=60～65 ℃.Because of containing a large amount of two keys in the molecular chain, can carry out vulcanization crosslinking again with the vulcanization process of common unsaturated rubber.When reaching certain cross-linking density, constraint makes it change elastomerics into to the segment crystalline by cross-linking set.
Nano material is meant the general name of the solid material of median size in 1nm～100nm scope, and its character both had been different from single atom, molecule, is different from the common solid material again, can demonstrate characteristics such as unique small-size effect, surface effects.Nano material under the situation of conventional weighting material, just can obviously be improved intensity, the toughness of polymkeric substance at content.
Adopt how monomer-grafted molten polymer to report to some extent in recent years as the research of blend solubilizing agent.Different with common single-component molten monomer graftomer, the percentage of grafting of polycomponent molten monomer graftomer is higher, and because the degraded of polymkeric substance is suppressed in the grafting process, the mechanical property of graftomer is able to good maintenance, thereby can produce significant effect aspect the blend mechanical property improving the blend morphology structure and improve.
(3) summary of the invention
The objective of the invention is to by the molecular designing means,, adopt the grafting of many molten monomers, crosslinked method of modifying to improve nanometer SiO from the angle of rubber plastic blend
2Bonding strength between dispersing uniformity in blend and TPI and PP two-phase interface, thereby the mechanical property of raising dynamic vulcanization TPI/PP thermoplastic elastomer.Wherein used high trans-1,4-polyisoprene are that the mass polymerization of load titanium catalysis isoprene forms, and unvulcanized TPI has following character:
This high trans-1, the fusing point of 4-polyisoprene are about 60 ℃, have better machining property and tubing properties under 70～80 ℃ processing temperature.Its roller behavior is near natural rubber, and processing environment is good.
(4) embodiment
1. starting material
High trans-1,4-polyisoprene (TPI)
Adopt supported titanium catalyst catalysis isoprene polymerization to form anti-form-1,4-structural content 〉=97%.
Polypropylene (PP), nanometer SiO
2, material such as maleic anhydride, vinylbenzene, dicumyl peroxide is common commercially available product.
2. blended rubber preparation technology
In mill TPI is plasticated earlier, the back adds MAH, St, DCP, nanometer SiO to treat to plasticate fully by TPI
2Mixing even, add stearic acid, zinc oxide, anti-aging agent, promotor, sulphur again, 4-6 back of thin-pass sheet down makes master batch, and again with the PP blend, dynamic vulcanization makes the TPI/PP thermoplastic elastomer.
Under tabulate 1 for 5 Example formulations of the present invention, table 2 is 5 fundamental propertys that the embodiment sizing material is obtained.
The basic recipe of table 1 embodiment material
The fundamental property of table 2 embodiment
As can be seen from Table 2, adopt MAH/St/DCP grafting, cross-linking modified TPI/PP/ nanometer SiO
2Behind the co-mixing system, the rebound degree of thermoplastic elastomer is constant substantially; Increase along with the MAH/St/DCP massfraction, the hardness of thermoplastic elastomer slightly improves, fracture tensile strength, tear strength and tensile yield present the back downward trend that rises earlier, but its tensile strength and tear strength are better than not adopting MAH/St/DCP grafting, crosslinked TPI/PP/ nanometer SiO all the time
2Thermoplastic elastomer; When MAH/St/DCP massfraction=3.75/1.875/0.375, comprehensive mechanical property the best.
Above-mentioned experimental result shows, adopts the grafting of many molten monomers, crosslinked method modification TPI/PP/ nanometer SiO
2Thermoplastic elastomer has significantly improved its comprehensive mechanical property.
Claims (3)
1. one kind is adopted nanometer SiO
2Fill the grafting of many molten monomers of maleic anhydride/vinylbenzene/dicumyl peroxide (MAH/St/DCP), cross-linking modified TPI/PP dynamic vulcanization thermoplastic elastomer.It is characterized in that with dicumyl peroxide (DCP) be initiator, maleic anhydride (MAH) and vinylbenzene (St) are grafted monomer, to TPI/PP/ nanometer SiO
2Thermoplastic elastomer carries out modification, has improved nanometer SiO
2Dispersed uniform, improve the bonding strength of TPI and PP two-phase interface, made the mechanical property of TPV obtain large increase.
2. the high trans used-1 according to claim 1,4-polyisoprene (TPI) is synthetic for supported titanium catalyst mass polymerization preparation, and the TPI feature of uncured is as follows:
3. nanometer SiO according to claim 1
2Fill, the grafting of many molten monomers of maleic anhydride/vinylbenzene/dicumyl peroxide (MAH/St/DCP), cross-linking modified TPI/PP dynamic vulcanization thermoplastic elastomer, its basic recipe consists of:
(1) TPI/PP/ nanometer SiO
2/ MAH/St/DCP=60/40/3/ variable
(2) adopt unified prescription to add auxiliary material, and process with same process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910230427XA CN102070865A (en) | 2009-11-19 | 2009-11-19 | Modified TPI/PP dynamically vulcanized thermoplastic elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910230427XA CN102070865A (en) | 2009-11-19 | 2009-11-19 | Modified TPI/PP dynamically vulcanized thermoplastic elastomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102070865A true CN102070865A (en) | 2011-05-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910230427XA Pending CN102070865A (en) | 2009-11-19 | 2009-11-19 | Modified TPI/PP dynamically vulcanized thermoplastic elastomer |
Country Status (1)
| Country | Link |
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| CN (1) | CN102070865A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018035320A (en) * | 2016-09-02 | 2018-03-08 | 日立造船株式会社 | Polyolefin resin composition and method for producing the same |
| CN112662109A (en) * | 2020-12-10 | 2021-04-16 | 广东圆融新材料有限公司 | TPV composite material and preparation method thereof |
| CN114541043A (en) * | 2022-02-25 | 2022-05-27 | 青岛科技大学 | Preparation method of real-time vulcanized elastomer fiber membrane |
-
2009
- 2009-11-19 CN CN200910230427XA patent/CN102070865A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018035320A (en) * | 2016-09-02 | 2018-03-08 | 日立造船株式会社 | Polyolefin resin composition and method for producing the same |
| CN112662109A (en) * | 2020-12-10 | 2021-04-16 | 广东圆融新材料有限公司 | TPV composite material and preparation method thereof |
| CN114541043A (en) * | 2022-02-25 | 2022-05-27 | 青岛科技大学 | Preparation method of real-time vulcanized elastomer fiber membrane |
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Application publication date: 20110525 |