CN103834075A - Dynamic vulcanization thermoplastic elastomer composition with high wear resistance - Google Patents
Dynamic vulcanization thermoplastic elastomer composition with high wear resistance Download PDFInfo
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- CN103834075A CN103834075A CN201410085291.9A CN201410085291A CN103834075A CN 103834075 A CN103834075 A CN 103834075A CN 201410085291 A CN201410085291 A CN 201410085291A CN 103834075 A CN103834075 A CN 103834075A
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- Prior art keywords
- thermoplastic elastomer
- dynamic vulcanization
- elastomer composition
- wearing feature
- vulcanization thermoplastic
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 36
- 238000004073 vulcanization Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 15
- -1 polyoxymethylene Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910018557 Si O Inorganic materials 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 239000005060 rubber Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920002943 EPDM rubber Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920006602 NBR/PVC Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of thermoplastic elastomers, and particularly relates to a dynamic vulcanization thermoplastic elastomer composition with good wear resistance and oil resistance. The thermoplastic elastomer provided by the invention consists of polyformaldehyde, hydrogenated butadiene-acrylonitrile rubber, wear-resistant filler, a vulcanizing agent and a plasticizer. The thermoplastic elastomer is prepared by dynamic vulcanization processing through a twin-screw extruder, and has good physical and mechanical properties and remarkable wear resistance.
Description
Technical field
The present invention relates to thermoplastic elastomer technical field, particularly relate to a kind of dynamic vulcanization thermoplastic elastomer composition with high-wear resistance.
Background technology
Dynamic vulcanization thermoplastic elastomer be a class by dynamic vulcanization technology by the high-performance thermoplastic elastomerics of existing plastics and rubber combined preparation, have snappiness and the plastic hot plasticity of rubber concurrently, can use and recycle by reprocessabilty.From U.S. Mengshan since all (Monsanto) company obtains dynamic vulcanization thermoplastic ethylene-propylene rubber/polyolefine elastomer patent (U.S. Pat 4130535 and US4311628) the earliest, the dynamic vulcanization thermoplastic elastomer of multiple rubber/plastic blend system is successfully prepared, and comprises the systems such as EPDM/PP, EPDM/PBT, EPDM/PA, EPDM/PE, NR/PP, NR/PE, IIR/PP, ACM/PP, NBR/PP, NBR/PA, NBR/PVC, ACM/PET.Dynamic vulcanization thermoplastic elastomer selects the principle of rubber and plastics except having good elasticity, processing characteristics and consistency, also expect that it has original performance of rubber used and plastic fraction, such as EPDM/PP dynamic vulcanization thermoplastic elastomer has weathering resistance and the water tolerance that EPDM is good, NBR/PA dynamic vulcanization thermoplastic elastomer has the oil-proofness of NBR and the thermotolerance of PA.
In existing patented technology and bibliographical information, still not about the report of dynamic vulcanization thermoplastic elastomer with high-wearing feature.Polyoxymethylene is a kind of engineering plastics with good self lubricity and high-wearing feature, be widely used in bearing, the gear uniform wearability mechanicals of having relatively high expectations, and hydrogenated nitrile-butadiene rubber is except oil-proofness and Good Heat-resistance, its wear resistance is one of kind best in rubber.In addition, graphite and molybdenumdisulphide are highly effective packing materials in wear-resistant macromolecule material, and silicone oil can reduce its frictional coefficient in macromolecular material.The present invention utilizes to have the composition for thermoplastic elastomer that the polyoxymethylene of excellent abrasive resistance and hydrogenated nitrile-butadiene rubber and high-wearing feature filler are prepared by dynamic vulcanization technology simultaneously, and the dynamic vulcanization thermoplastic elastomer of this high-wearing feature can be for fields such as elastic bearing, instrument sheaths.
Summary of the invention
The present invention aims to provide a kind of dynamic vulcanization thermoplastic elastomer composition with high-wearing feature, and this composition, except having good elasticity and processing characteristics, also has good oil-proofness, thermotolerance, and especially wear resistance is outstanding.
The particular content of invention is as follows:
A dynamic vulcanization thermoplastic elastomer composition with high-wearing feature, is characterized in that, component and the content of described thermoplastic elastomer are as follows:
Described polyoxymethylene is copolymerized methanal, and it is about melt flow rate (MFR) under the test condition of 2.16kg and is about 1-30g/10min at 190 ℃ of pressure.
Described hydrogenated nitrile-butadiene rubber is the hydrogenated nitrile-butadiene rubber that saturation ratio is greater than 90%.
Described wear resistant filler is one or both compositions in graphite, molybdenumdisulphide.
Described vulcanizing agent is dicumyl peroxide, 2, one or both compositions in 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane.
Described silicone oil is the linear polysiloxanes of liquid state under a class room temperature, a class take repeat Si-O key as main chain, on Siliciumatom directly connection organic group polymkeric substance.
Described coupling agent is for being the low molecule silicoorganic compound of a class, and its general formula is RSiX3, and in formula, R representative and polymer molecule have the active function groups of avidity or response capacity, comprise oxygen base, sulfydryl, vinyl, epoxy group(ing), amide group, aminopropyl etc.; X represents the alkoxyl group that can be hydrolyzed, and comprises halogen, alkoxyl group, acyloxy etc.
The tensile strength 10-20MPa of described thermoplastic elastomer, elongation at break is 190-270%, and tear strength is 40-55KN/m, and Akron abrasion is 0.05-1.11cm
3/ 1.61km.
Beneficial effect:
Beneficial effect of the present invention is, the high-wearing feature dynamic vulcanization thermoplastic elastomer of invention not only has the good physical and mechanical properties such as thermotolerance, oil-proofness, and has outstanding wear resistance.Compared with simple hydrogenated nitrile-butadiene rubber, material of the present invention is that thermoplastic elastic material can reprocessabilty utilization, and moulding is convenient, and compared with pure polyoxymethylene, material of the present invention has good elasticity.The present composition can be for fields such as elastic bearing, instrument sheaths.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Kematal is selected from the Delrin100T type of E.I.Du Pont Company, and melt flow index is 2g/10min(190 ℃, 2.16kg)
Hydrogenated nitrile-butadiene rubber is selected from the TherbanA3406 of Lanxess Corporation, and mooney viscosity is 100 ℃ 63 of ML (1+4), and saturation ratio is 99.1%.
Graphite, granularity is 500 orders; Molybdenumdisulphide particle diameter is 1.5 microns.
Vulcanizing agent is 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane (i.e. two 2,5 vulcanizing agents).
Silicone oil is commercially available dimethyl silicone oil.
Coupling agent be goldschmidt chemical corporation two-(the silica-based propyl group of γ-triethoxy) tetrasulfide (being Si-69).
Following table is the concrete proportioning raw materials (data unit is weight part) of several embodiments of the present invention:
Embodiment working method
Take various raw materials by the various embodiments described above proportioning respectively, by Si-69 and graphite or (with) molybdenumdisulphide mixes and carries out surface treatment.Use equipment for length-to-diameter ratio be 56:1, the dynamic vulcanization response type forcing machine that screw diameter is 33mm.The graphite processed by kematal, hydrogenated nitrile-butadiene rubber, with Si-69 (with) or molybdenumdisulphide, two 2,5 vulcanizing agents utilize weight-loss type feeding to claim to join in forcing machine, dimethyl silicone oil is injected in machine barrel stage casing by liquor pump.Set the processing temperature of suitable twin screw extruder, raw material through twin screw high speed shear, mixing, then dynamic vulcanization is extruded, tie rod, the dynamic vulcanization thermoplastic elastomer composition that cooling, pelletizing can obtain high-wearing feature.
Embodiment the performance test results
For the technical indicator advantage of polyoxymethylene/hydrogenated nitrile-butadiene rubber dynamic vulcanization thermoplastic elastomer material of the present invention is described, we utilize current widely used Pp/epdm dynamic vulcanization thermoplastic elastomer as a comparison.
Following table is the concrete proportioning raw materials (data unit is weight part) of comparative example of the present invention:
| Raw material | Embodiment 1 | Embodiment 2 |
| Co-polypropylene (PP) | 30 | 40 |
| Terpolymer EP rubber (EPDM) | 70 | 60 |
| Graphite | 7.5 | 7.5 |
| Molybdenumdisulphide | 7.5 | 7.5 |
| Resol | 3 | 3 |
| Naphthenic oil | 4 | 4 |
| Si-69 | 3 | 3 |
The working method of comparative example
With embodiment working method, vulcanizing agent two 2,5 is replaced by resol, dimethyl silicone oil is replaced by naphthenic oil.
Comparative example performance index
| Performance index | Embodiment 1 | Embodiment 2 |
| Hardness (Shao Shi), degree | 67A | 74A |
| Tensile strength, MPa | 6.5 | 8.1 |
| Elongation at break, % | 270 | 220 |
| Tear strength, KN/m | 32 | 38 |
| Akron abrasion, cm3/1.61km | 0.56 | 0.42 |
| Compression set, Type B sample | 41 | 48 |
| Oil-proofness (IRM903,150 ℃ × 336h), volume change, % | 32 | 31 |
From embodiment and comparative example, compared with the Pp/epdm dynamic vulcanization thermoplastic elastomer of polyoxymethylene/hydrogenated nitrile-butadiene rubber dynamic vulcanization thermoplastic elastomer of the present invention and current widespread use, its wear resistance significantly improves, and No. 903, high temperature resistant polarity oily aspect, the volume change of material of the present invention is very little, all do not exceed 10%, illustrate and there is satisfactory stability, there is serious variation in the volume of comparative example, volume change exceedes 30%, substantially loses using value.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (8)
1. a dynamic vulcanization thermoplastic elastomer composition with high-wearing feature, is characterized in that, component and the content of described thermoplastic elastomer are as follows:
2. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, is characterized in that, described polyoxymethylene is copolymerized methanal, and it is about melt flow rate (MFR) under the test condition of 2.16kg and is about 1-30g/10min at 190 ℃ of pressure.
3. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, is characterized in that, described hydrogenated nitrile-butadiene rubber is the hydrogenated nitrile-butadiene rubber that saturation ratio is greater than 90%.
4. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, is characterized in that, described wear resistant filler is one or both compositions in graphite, molybdenumdisulphide.
5. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, is characterized in that, described vulcanizing agent is dicumyl peroxide, 2, one or both compositions in 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane.
6. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, it is characterized in that, described silicone oil is the linear polysiloxanes of liquid state under a class room temperature, a class take repeat Si-O key as main chain, on Siliciumatom directly connection organic group polymkeric substance.
7. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, it is characterized in that, described coupling agent is for being the low molecule silicoorganic compound of a class, its general formula is RSiX3, in formula, R representative and polymer molecule have the active function groups of avidity or response capacity, comprise oxygen base, sulfydryl, vinyl, epoxy group(ing), amide group, aminopropyl etc.; X represents the alkoxyl group that can be hydrolyzed, and comprises halogen, alkoxyl group, acyloxy etc.
8. high-wearing feature dynamic vulcanization thermoplastic elastomer composition according to claim 1, it is characterized in that, the tensile strength 10-20MPa of described thermoplastic elastomer, splitting elongation is 190-270%, tear strength is 40-55KN/m, and Akron abrasion is 0.05-1.11cm
3/ 1.61km.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410085291.9A CN103834075A (en) | 2014-03-10 | 2014-03-10 | Dynamic vulcanization thermoplastic elastomer composition with high wear resistance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410085291.9A CN103834075A (en) | 2014-03-10 | 2014-03-10 | Dynamic vulcanization thermoplastic elastomer composition with high wear resistance |
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| Publication Number | Publication Date |
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| CN103834075A true CN103834075A (en) | 2014-06-04 |
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| CN201410085291.9A Pending CN103834075A (en) | 2014-03-10 | 2014-03-10 | Dynamic vulcanization thermoplastic elastomer composition with high wear resistance |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262728A (en) * | 2014-09-24 | 2015-01-07 | 湖北华强科技有限责任公司 | Rubber with low Mooney viscosity and high oil resistance as well as preparation method and application thereof in screw pump stator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225416B1 (en) * | 1994-11-07 | 2001-05-01 | Hoechst Aktiengesellschaft | Polyacetal moldings with directly molded-on function elements |
| CN1464899A (en) * | 2001-05-30 | 2003-12-31 | 大赛璐－德固萨株式会社 | Composite dispersion and process for production thereof |
| CN101921453A (en) * | 2010-09-14 | 2010-12-22 | 中蓝晨光化工研究院有限公司 | Toughened polyoxymethylene blended modifier and preparation method thereof |
-
2014
- 2014-03-10 CN CN201410085291.9A patent/CN103834075A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225416B1 (en) * | 1994-11-07 | 2001-05-01 | Hoechst Aktiengesellschaft | Polyacetal moldings with directly molded-on function elements |
| CN1464899A (en) * | 2001-05-30 | 2003-12-31 | 大赛璐－德固萨株式会社 | Composite dispersion and process for production thereof |
| CN101921453A (en) * | 2010-09-14 | 2010-12-22 | 中蓝晨光化工研究院有限公司 | Toughened polyoxymethylene blended modifier and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262728A (en) * | 2014-09-24 | 2015-01-07 | 湖北华强科技有限责任公司 | Rubber with low Mooney viscosity and high oil resistance as well as preparation method and application thereof in screw pump stator |
| CN104262728B (en) * | 2014-09-24 | 2016-06-29 | 湖北华强科技有限责任公司 | A kind of low Mooney high oil resistivity rubber, preparation method and the application on screw pump stator |
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Application publication date: 20140604 |