CN101845195A - Wear-resistant thermoplastic elastomer and preparation method thereof - Google Patents
Wear-resistant thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a wear-resistant thermoplastic elastomer, which is prepared from the following raw materials in percentage by weight: 10 to 80 percent of matrix resin, 10 to 60 percent of master batch, 0 to 42 percent of extending oil, 0 to 20 percent of thermoplastic resin, 0 to 30 percent of mineral filler, 0 to 1.5 percent of coupling agent, 0.1 to 2 percent of processing aid and 0.1 to 2 percent of stabilizing agent. The invention also discloses a method for preparing the wear-resistant thermoplastic elastomer. SBS, SEBS and the like are adopted as the matrix resin, and the problem of poor wear resistance of SBC thermoplastic elastomers is solved through improvement of a mixing formular and a process; the prepared thermoplastic elastomer has good wear resistance; compared with the TPU products with good wear resistance, the thermoplastic elastomer has low cost; in the whole process of modifying and producing the material, chemical solvents are not used, the influence on the environment is small, the halogen is free and the environment is protected; and the leftover material of the thermoplastic elastomer can be repeatedly used.
Description
Technical field.
The present invention relates to polymeric material field, particularly a kind of wear-resistant thermoplastic elastomer and preparation method thereof.
Background technology
Thermoplastic elastomer (Thermoplastic Elastomer, abbreviation TPE) also claims thermoplastic elastomer (Thermoplastic Rubber, be called for short TPR), be a kind of rubber and thermoplastics characteristic of having concurrently, show as under the normal temperature under rubber elastomeric state, the high temperature again can plasticizing forming macromolecular material.Thermoplastic elastomer has multiple possible structure, the most basic one is to need at least two mutual dispersive polymer phases, under normal use temperature, one is fluid (its glass transition temperature Tg is lower than normal use temperature) mutually, another is solid (its Tg is higher than normal use temperature) mutually, and has interaction between the two-phase.This structure is given mechanical property and the use properties that it is similar to rubber, and the processing characteristics of thermoplastics, thereby can erect a bridge block between plastics and rubber.With regard to processing, it is a kind of plastics; With regard to character, it is again a kind of rubber.
Present domestic styrene-butadiene-styrene class elastomerics of inciting somebody to action wherein is referred to as SBS (styrene-butadiene-styrene block copolymer), be the thermoplasticity styrene-butadiene-styrene block copolymer, custom is called thermoplastic styrene butadiene rubber.SBS appropriate directed hydrogenation in the presence of catalyzer then makes polybutadiene segments be hydrogenated to polyethylene (E) and polybutene (B) segment, obtains hydrogenated styrene-butadiene-styrene block copolymers (SEBS).The two all belongs to the category of styrene analog thermoplastic elastomer (SBC class elastomerics).
SBC class elastomerics and traditional hot solidity rubber phase ratio have and can recycle repeatedly, meet consumption concepts such as nontoxic, environmental protection, and goods machine-shaping is convenient, and goods profile, size etc. are accurately control easily, intensity height, the advantage that utilization property is strong.Therefore, in fields such as automobile, building, medicine equipment, packing, household electrical appliance and the consumer's goods, but the thermoplastic elastomer of injection moulding just progressively replaces traditional rubber, and obtains to use widely.
But simultaneously because SBC class elastomeric seal wear resistance is not enough, deformation for a long time is big, and reasons such as heat-resisting and oil resistance difference can only partly replace thermoset rubber, has restricted seriously that the SBC class is elastomeric to be further developed and use.Therefore, will expand its Application Areas greatly if can invent a kind of attrition resistant SBC analog thermoplastic elastomer.
Application number is to disclose a kind of wear resistant thermoplastic elastomer material composition in 01126902.2 the Chinese patent, it comprises following component and content (weight part): elastomerics 500-1000, thermoplastics 50-500, oxidation inhibitor 1-10, the steady agent 1-10 of light, anti-wear agent A 20-80, anti-wear agent B 10-60, linking agent 0-10 and other auxiliary agents 0-30.It is a matrix resin with ethylene-octene copolymer, terpolymer EP rubber, ethylene vinyl acetate elastomerics, by polytetrafluoroethylene (PTFE) and silicone reasonable composite having been made a kind of TPE material with excellent wear-resisting property.
At present, also not at the research report that improves SBC analog thermoplastic elastomer wear resisting property.
Summary of the invention
The invention provides that a kind of wear resistance is good, the wear-resistant thermoplastic elastomer of asepsis environment-protecting.
A kind of wear-resistant thermoplastic elastomer comprises following raw materials by weight percent:
Matrix resin 10%～80%
Extending oil 0～42%
Masterbatch 10%～60%
Thermoplastic resin 0～20%
Mineral filler 0～30%
Coupling agent 0～1.5%
Processing aid 0.1%～2%
Stablizer 0.1%～2%;
Wherein, described masterbatch is made by following raw materials by weight percent:
Vector resin 50%～80%
Compatilizer 0～30%
Anti-wear agent 5%～20%
Inorganic nano-particle 4%～25%.
As preferably:
Described matrix resin is selected from one or both in styrene-butadiene-styrene block copolymer (SBS), the hydrogenated styrene-butadiene-styrene block copolymers (SEBS).For example, can the section of selecting for use rise (KRATON): D-1102, D-1153; Korea S LG chemistry: SBS LG-501, LG-411; Platform rubber (TAIPOL): SBS 4202, SEBS6151; Ba Ling petrochemical industry: one or more in the commercially available prod of the trades mark such as SBS YH-788, YH-792, SEBS YH-503.
Described vector resin is selected from a kind of in thermoplastic polyurethane (TPU), terpolymer EP rubber (EPDM), Thermoplastic Vulcanizate (TPV), the thermoplastic polyester elastomer (TPEE) or at least two kinds.
Described compatilizer is selected from least a in hydrogenated styrene-butadiene-styrene block copolymers-maleic anhydride grafts (SEBS-g-MAH), terpolymer EP rubber-maleic anhydride grafts (EPDM-g-MAH), polyolefin elastomer-maleic anhydride grafts (POE-g-MAH), ethane-acetic acid ethyenyl ester graft copolymer (EVA-g-MAH), the acrylic acid esters co-polymer.For example, optional liter: 9801 with Shanghai day; Company is risen by U.S. section: FG1901; E.I.Du Pont Company: EMA (ethylene-methyl acrylate copolymer) 1125,1330, one or more in the commercially available prod of EEA (ethylene-ethyl acrylate copolymer) 2112 trades mark such as grade.
Described anti-wear agent be selected from described anti-wear agent be selected from urethane (PU) class anti-wear agent, silicone powder, silicone master batch, ultrahigh molecular weight polyethylene(UHMWPE) (ultrahigh molecular weight polyethylene(UHMWPE) be meant glutinous all relatively molecular weight more than 1,500,000, the weight average relative molecular weight is at the linear polyethylene more than 3,000,000) in a kind of or at least two kinds.All can directly adopt the commercially available prod, for example, can select the FYTE-68 of Dongguan City Fiat static science and technology for use; The MB50-001 of Dow corning commercially available prod such as (trades mark).
Described inorganic nano-particle is selected from one or both in the white carbon black of nano active, the nano organic montmorillonite.For example, can select the DK4 commercially available prod such as (trades mark) of Zhejiang Feng Hong company for use.
Described thermoplastic resin is selected from a kind of in polypropylene, polyethylene, the polystyrene or at least two kinds.
Described extending oil be selected from flash-point greater than 200 ℃ saturated straight chain alkane oil, flash-point greater than in 200 ℃ the naphthenic oil one or both.For example, can select U.S.'s sun-stone (SUNPAR) for use: 150, the two dragons of Korea S: 150SN, Japanese bright dipping (Idemitsu): PW-90, Kelamayi: KN4020, one or more in the 32# wet goods commercially available prod.
Described mineral filler is selected from a kind of in talcum powder, lime carbonate, kaolin, mica powder, the wollastonite or at least two kinds.For example, can select the product of domestic production producer for use as many companies such as: Guilin Tian Cheng, Jiangsu Rieter, the inferior Thailands in Dalian.
Described coupling agent is as the compatilizer of matrix resin and inorganic mineral weighting agent, can select a kind of in titanate coupling agent, the silane coupling agent or at least two kinds for use.For example, can select NDZ-101, NDZ-201, KH-550, the KH-570 of NanJing Shuguang Chemical Group Co., Ltd. for use, one or more in the commercially available prod such as KR-TTS, KR-238 of U.S. Kenrich petroleum chemistry company.
Described processing aid is selected from a kind of in lipid acid, soap, fatty acid amide, polyethylene wax, the silicone material or at least two kinds.For example, can select at least a in the commercially available prod such as hard ester acid, calcium stearate, Zinc Stearate, silicone powder, silicone master batch, erucicamide for use.
Described stablizer is selected from and contains a kind of in benzophenone functional compounds stablizer (being the benzophenone stablizer), Hinered phenols stablizer, phosphorous acid esters stablizer, the hindered amines stablizer or at least two kinds.For example, can select at least a in UV-531,1010,168,1076, (Ciba company product) trade mark commercially available prod such as 1024 for use.
The present invention also provides a kind of preparation method of wear-resistant thermoplastic elastomer, has advantage simple to operate, as to be suitable for suitability for industrialized production.
The preparation method of described wear-resistant thermoplastic elastomer comprises step:
(1) sending into rotating speed after vector resin, compatilizer, anti-wear agent and inorganic nano-particle are mixed is extruding pelletization in 300 rev/mins～400 rev/mins the twin screw extruder, obtains masterbatch;
(2) matrix resin and even, the to be filled oil of extending oil thorough mixing are blotted back adding mineral filler fully by resin, in whipping process, add coupling agent treatment, add processing aid, stablizer, masterbatch and thermoplastic resin then, send into rotating speed after mixing and be extruding pelletization in 300 rev/mins～400 rev/mins the twin screw extruder, make wear-resistant thermoplastic elastomer;
Wherein, each section extruder temperature is 160 ℃～220 ℃ in the twin screw extruder, and the temperature of each section screw rod can be the same or different.
Described twin screw extruder can be selected this area equipment commonly used for use.
Beneficial effect of the present invention is embodied in:
The present invention adopts SBC analog thermoplastic elastomers such as SBS, SEBS as matrix resin, with urethane (PU) class abrasion-resistant powder, ultrahigh molecular weight polyethylene(UHMWPE), silicone etc. is anti-wear agent, and nanoparticle such as compound organo montmorillonite, solved the problem that the SBC analog thermoplastic elastomer wears no resistance by improvement to the blending prescription.
The present invention is by preparation methods such as mother materials, further guarantee the dispersion effect of nanoparticle and ultrahigh molecular weight polyethylene(UHMWPE) etc., optimize product performance, further solved the problem that the SBC analog thermoplastic elastomer wears no resistance, obtain a kind of attrition resistant thermoplastic elastic material.
The prepared thermoplastic elastomer wear resistance of the present invention is good, compares with the TPU product that wear resistance is good, and is cheap, and do not relate to the use of chemical solvents in the whole material modification production process, little to environmental influence, halogen-free environmental, the scrap stock of thermoplastic elastomer are also reusable simultaneously.
Wear-resistant thermoplastic elastomer of the present invention can replace traditional rubber, is applied in related productss such as industrial castor, high-grade sole and sports belt more widely.
Embodiment
Embodiment 1
With 200 weight part TPU vector resins (Yantai ten thousand China), 20 weight part FG1901 (composition SEBS-g-MAH, company is risen by U.S. section), 20 weight part anti-wear agent FYTE-68 (composition PU), 10 weight part silicone master batch (Dow corning) and 20 weight part nano organic montmorillonite DK4 (Zhejiang Feng Hong) stirred in the pot premix 3 minutes in height, send into rotating speed after mixing and be in 300 rev/mins the twin screw extruder, each extruder temperature of twin screw extruder is set in 160 ℃, shear through twin screw, mixing, extrude by head, tie rod, air-cooled, pelletizing, obtain 270 weight part masterbatch after the drying, stand-by.
By following parts by weight that SEBS and extending oil thorough mixing is even, oil to be filled is blotted the back fully by resin and adds mineral filler, in whipping process, add coupling agent treatment, follow-up adding processing aid, stablizer and masterbatch mix in mixer, material behind the mixing is sent into shearing, mixing in the twin screw extruder by feeder, each extruder temperature of twin screw extruder is set in 180 ℃, 20 hertz of feeding frequencies, 300 rev/mins of engine speeds.Through head extrude, tie rod, air-cooled, pelletizing, drying and packing, make the wear-resistant thermoplastic elastomer finished product.
SEBS (platform rubber) 6151:100 part
Paraffin oil 150SN:100 part
Masterbatch: 200 parts
Talcum powder: 25 parts
Silane coupling agent KH550 (Nanjing dawn chemical industry
Group Co.,Ltd) 0.5 part
Erucicamide (processing aid, Ciba company): 3 parts
Antioxidant 1010 (A.O.1010, Hinered phenols stablizer): 1 part
Oxidation inhibitor 168 (A.O.168, phosphorous acid esters stablizer): 1 part
UV531 (benzophenone stablizer): 1 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??78 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??13.6 |
| ?DIN53516 | ??mm 3 | ??ASTM?D-412 | ??133 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??12.5 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??464.5 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??43.8 |
| Proportion | ??- | ??ASTM?D-792 | ??1.051 |
In conjunction with above data as can be known: compound by above technology and component, the wear resistance of gained material is good.Simultaneously, also kept elastomerics to have good elasticity.
Embodiment 2
Except adopting the raw material of following weight part, each extruder temperature of twin screw extruder is set in outside 200 ℃, and the preparation of masterbatch, wear-resistant thermoplastic elastomer makes wear-resistant thermoplastic elastomer with embodiment 1.
SEBS (Ba Ling petrochemical industry) YH 503:100 part
Paraffin oil 150SN:100 part
Masterbatch: 200 parts
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
Embodiment 3
Except the raw material that adopts following weight part, the preparation of masterbatch, wear-resistant thermoplastic elastomer makes wear-resistant thermoplastic elastomer with embodiment 1.
SEBS (platform rubber) 6151:100 part
Paraffin oil PW-90:100 part
Masterbatch: 200 parts
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
The sample that embodiment 2 and embodiment 3 are made carries out performance test, result such as following table:
| Performance | Unit | Testing method | Embodiment 2 test values | Embodiment 3 test values |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??80 | ??82 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??16.3 | ??11.3 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??165 | ??124 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??10.2 | ??14.2 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??503.2 | ??443.2 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??40.8 | ??45.6 |
| Proportion | ??- | ??ASTM?D-792 | ??1.049 | ??1.053 |
Embodiment 4
Except the raw material that adopts following weight part, the preparation of masterbatch, wear-resistant thermoplastic elastomer makes wear-resistant thermoplastic elastomer with embodiment 1.
SEBS (platform rubber) 6151:100 part
Paraffin oil 150SN:100 part
Masterbatch: 150 parts
Erucicamide: 2.5 parts
A.O.1010:0.7 part
A.O.168:0.7 part
UV531:0.7 part.
Embodiment 5
Except the raw material that adopts following weight part, the preparation of masterbatch, wear-resistant thermoplastic elastomer is with embodiment 1, and wherein polypropylene adds mixer with masterbatch, makes wear-resistant thermoplastic elastomer.
SEBS (platform rubber) 6151:100 part
Paraffin oil 150SN:100 part
Masterbatch: 150 parts
Polypropylene: 15 parts
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
The sample that embodiment 4 and embodiment 5 are made carries out performance test, result such as following table:
| Performance | Unit | Testing method | Embodiment 4 test values | Embodiment 5 test values |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??73 | ??84 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??10.3 | ??12.3 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??224 | ??213 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??8.9 | ??9.6 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??463.2 | ??482.4 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??36.6 | ??35.6 |
| Proportion | ??- | ??ASTM?D-792 | ??1.043 | ??1.037 |
Embodiment 6
Except the raw material that adopts following weight part, the preparation of masterbatch, wear-resistant thermoplastic elastomer makes wear-resistant thermoplastic elastomer with embodiment 1.
SBS (Ba Ling petrochemical industry) YH 792:100 part
Paraffin oil 150SN:50 part
Masterbatch: 150 parts
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
Embodiment 7
Except adopting the raw material of following weight part, each extruder temperature of twin screw extruder is set in outside 180 ℃, and the preparation of masterbatch, wear-resistant thermoplastic elastomer makes wear-resistant thermoplastic elastomer with embodiment 1.
792 100 parts of SBS (Ba Ling petrochemical industry) YH
6,151 50 parts of SEBS (platform rubber)
Paraffin oil 150SN:150 part
Masterbatch: 250 parts
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
The sample that embodiment 6 and embodiment 7 are made carries out performance test, result such as following table:
| Performance | Unit | Testing method | Embodiment 6 test values | Embodiment 7 test values |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??81 | ??80 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??19.3 | ??16.6 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??264 | ??203 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??7.5 | ??9.8 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??560.9 | ??502.4 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??37.4 | ??42.1 |
| Proportion | ??- | ??ASTM?D-792 | ??1.056 | ??1.053 |
Embodiment 8
With 200 weight part EPDM vector resins (LG-DOW), 40 weight parts glutinous all relatively molecular weight 1,500,000 or more and the weight average relative molecular weight in the linear polyethylene more than 3,000,000 (Zhenjiang treasured Riamb), 40 weight part nano organic montmorillonite DK4 (Zhejiang Feng Hong) and the white carbon black of 40 weight part nano actives (Shandong hundred million persons of outstanding talent) stirred in the pot premix 5 minutes in height, send into rotating speed after mixing and be in 400 rev/mins the twin screw extruder, each extruder temperature of twin screw extruder is set in 220 ℃, shear through twin screw, mixing, extrude by head, tie rod, air-cooled, pelletizing, obtain 320 weight part masterbatch after the drying, stand-by.
Press following parts by weight with SEBS and extending oil 32# white oil (Kelamayi, Xinjiang, white oil (be flash-point greater than 200 ℃ saturated straight chain alkane oil)) thorough mixing is even, oil to be filled is blotted the back fully by resin and adds mineral filler, in whipping process, add coupling agent treatment, follow-up adding processing aid, stablizer, masterbatch and thermoplastic resin mix in mixer, material behind the mixing is sent in the twin screw extruder by feeder and is sheared, mixing, each extruder temperature of twin screw extruder is set in 200 ℃, 20 hertz of feeding frequencies, 400 rev/mins of engine speeds.Through head extrude, tie rod, air-cooled, pelletizing, drying and packing, make the wear-resistant thermoplastic elastomer finished product.
SEBS (platform rubber) 6151:40 part
32# white oil: 120 parts
Masterbatch: 80 parts
Polyethylene (Iranian petrochemical industry): 20 parts
Lime carbonate (Jiangsu Rieter): 30 parts
Titanate coupling agent NDZ-101 (Nanjing dawn chemical industry
Group Co.,Ltd): 1 part
Polyethylene wax (processing aid, Linan Hua Yang): 0.5 part
Antioxidant 1010 (A.O.1010, Hinered phenols stablizer): 2 parts
Oxidation inhibitor 168 (A.O.168, phosphorous acid esters stablizer): 1.5 parts
UV531:1.5 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??90 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??12.8 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??293 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??8.4 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??386 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??34.2 |
| Proportion | ??- | ??ASTM?D-792 | ??1.124 |
Embodiment 9
With 320 weight part TPV vector resins (all put down on the mountain), 10 weight part silicone master batch (DOW CORNING), 10 weight parts glutinous all relatively molecular weight 1,500,000 or more and the weight average relative molecular weight stirred in the pot premix 6 minutes at the linear polyethylene more than 3,000,000 (Zhenjiang treasured Riamb) and the white carbon black of 20 weight part nano actives (Shandong hundred million persons of outstanding talent) in height, send into rotating speed after mixing and be in 350 rev/mins the twin screw extruder, each extruder temperature of twin screw extruder is set in 190 ℃, shear through twin screw, mixing, extrude by head, tie rod, air-cooled, pelletizing, obtain 360 weight part masterbatch after the drying, stand-by.
Press following parts by weight with SEBS, SBS and extending oil 4010 (Kelamayi, Xinjiang, flash-point is greater than 200 ℃ naphthenic oil) thorough mixing is even, oil to be filled is blotted the back fully by resin and adds mineral filler, adds coupling agent treatment in whipping process, follow-up adding processing aid, stablizer, masterbatch and thermoplastic resin mix in mixer, material behind the mixing is sent into shearing, mixing in the twin screw extruder by feeder, each extruder temperature of twin screw extruder is set in 180 ℃, 20 hertz of feeding frequencies, 350 rev/mins of engine speeds.Through head extrude, tie rod, air-cooled, pelletizing, drying and packing, make the wear-resistant thermoplastic elastomer finished product.
SEBS (platform rubber) 6151:56 part
SBS (English is chemistry entirely) 685:80 part
4010:56 part
Masterbatch: 41.2 parts
Polypropylene: (Shanghai petrochemical industry) 10 parts
Wollastonite (Xinyu, Jiangxi): 102 parts
2 parts of silane coupling agent KH-556 (Nanjing dawn)
Zinc Stearate (processing aid, the grand chemical industry of space): 0.4 part
Antioxidant 1076 (A.O.1076, Hinered phenols stablizer): 0.2 part
Oxidation inhibitor 168 (A.O.168, phosphorous acid esters stablizer): 0.1 part
UV531:1.5 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??85 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??6.2 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??283 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??16.7 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??402 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??53 |
| Performance | Unit | Testing method | Test value |
| Proportion | ??- | ??ASTM?D-792 | ??1.213 |
Embodiment 10
232 weight part TPEE vector resins (Dupont), 120 weight part EMA1125 (E.I.Du Pont Company), 32 weight part silicone powder (loose inferior chemical industry) and the 16 weight parts nano imvite DK4 (Zhejiang Feng Hong) that organises was stirred in the pot premix 4 minutes in height, send into rotating speed after mixing and be in 380 rev/mins the twin screw extruder, each extruder temperature of twin screw extruder is set in 220 ℃, through twin screw shearing, mixing, extrude, obtain 400 weight part masterbatch behind the tie rod, air-cooled, pelletizing, drying by head, stand-by.
Press following parts by weight with SBS and extending oil 150SN (the two dragons of Korea S, flash-point is greater than 200 ℃ saturated straight chain alkane oil) thorough mixing is even, oil to be filled is blotted the back fully by resin and adds mineral filler, adds coupling agent treatment in whipping process, follow-up adding processing aid, stablizer, masterbatch and thermoplastic resin mix in mixer, material behind the mixing is sent into shearing, mixing in the twin screw extruder by feeder, each extruder temperature of twin screw extruder is set in 200 ℃, 20 hertz of feeding frequencies, 400 rev/mins of engine speeds.Through head extrude, tie rod, air-cooled, pelletizing, drying and packing, make the wear-resistant thermoplastic elastomer finished product.
SBS (high mountainization) 815:288.8 part
150SN:20 part
Masterbatch: 40 parts
Polyethylene (Fushun): 20 parts
Kaolin (Ninghai good and): 20 parts
Silane coupling agent KH-556:3 part
Silicone powder (processing aid): 4 parts
Antioxidant 1076 (A.O.1076, Hinered phenols stablizer): 2 parts
Oxidation inhibitor 168 (A.O.168, phosphorous acid esters stablizer): 1 part
UV531:1 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??83 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??9.3 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??296 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??17.8 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??587 |
| Performance | Unit | Testing method | Test value |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??38.6 |
| Proportion | ??- | ??ASTM?D-792 | ??1.042 |
Comparative Examples 1
Except the raw material that adopts following weight part, the preparation of wear-resistant thermoplastic elastomer makes thermoplastic elastomer with embodiment 1.
SEBS (platform rubber) 6151:100 part
Paraffin oil 150SN:100 part
Talcum powder: 25 parts
0.5 part of silane coupling agent KH550
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??25 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??1.6 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??350 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??8.6 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??772.7 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??8.2 |
| Proportion | ??- | ??ASTM?D-792 | ??0.89 |
In conjunction with above data as can be known: by wearing no resistance of the compound gained material of above component.
Comparative Examples 2
Except the raw material that adopts following weight part, the preparation of wear-resistant thermoplastic elastomer is with embodiment 1, and wherein polypropylene adds mixer with masterbatch, makes thermoplastic elastomer.
SEBS (platform rubber) 6151:100 part
Paraffin oil 150SN:100 part
Polypropylene: 54 parts
Talcum powder: 25 parts
0.5 part of silane coupling agent KH550
Erucicamide: 3 parts
A.O.1010:1 part
A.O.168:1 part
UV531:1 part.
The above-mentioned thermoplastic elastomer that makes is carried out performance test, result such as following table:
| Performance | Unit | Testing method | Test value |
| Shore hardness | ??ShoreA | ??ASTM?D-2240 | ??78 |
| Melting index (MFI) | ??g/10min | ??ASTM?D-1238 | ??10.6 |
| ??DIN53516 | ??mm 3 | ??ASTM?D-412 | ??350 |
| Tensile break strength | ??Mpa | ??ASTM?D-412 | ??11.6 |
| Tension fracture elongation rate | ??％ | ??ASTM?D-412 | ??772.7 |
| Tear strength | ??KN/m | ??ASTM?D-1922 | ??40.1 |
| Proportion | ??- | ??ASTM?D-792 | ??0.923 |
Analyze as can be known: after reaching same rigidity with routine interpolation polypropylene process, by wearing no resistance of the compound gained material of above component.
Claims (10)
1. wear-resistant thermoplastic elastomer comprises following raw materials by weight percent:
Matrix resin 10%～80%
Extending oil 0～42%
Masterbatch 10%～60%
Thermoplastic resin 0～20%
Mineral filler 0～30%
Coupling agent 0～1.5%
Processing aid 0.1%～2%
Stablizer 0.1%～2%;
Wherein, described masterbatch is made by following raw materials by weight percent:
Vector resin 50%～80%
Compatilizer 0～30%
Anti-wear agent 5%～20%
Inorganic nano-particle 4%～25%.
2. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described matrix resin is selected from one or both in styrene-butadiene-styrene block copolymer, the hydrogenated styrene-butadiene-styrene block copolymers.
3. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described vector resin is selected from a kind of in thermoplastic polyurethane, terpolymer EP rubber, Thermoplastic Vulcanizate, the thermoplastic polyester elastomer or at least two kinds.
4. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described compatilizer is selected from a kind of in hydrogenated styrene-butadiene-styrene block copolymers-maleic anhydride grafts, terpolymer EP rubber-maleic anhydride grafts, polyolefin elastomer-maleic anhydride grafts, ethane-acetic acid ethyenyl ester graft copolymer, the acrylate copolymer or at least two kinds;
Perhaps, described anti-wear agent be selected from urethane, silicone powder, silicone master batch, glutinous all relatively molecular weight more than 1,500,000 and a kind of in the linear polyethylene more than 3,000,000 of weight average relative molecular weight or at least two kinds;
Perhaps, described inorganic nano-particle is selected from one or both in the white carbon black of nano active, the nano organic montmorillonite.
5. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described extending oil be selected from flash-point greater than 200 ℃ saturated straight chain alkane oil, flash-point greater than in 200 ℃ the naphthenic oil one or both.
6. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described thermoplastic resin is selected from a kind of in polypropylene, polyethylene, the polystyrene or at least two kinds.
7. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described mineral filler is selected from a kind of in talcum powder, lime carbonate, kaolin, mica powder, the wollastonite or at least two kinds.
8. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described coupling agent is selected from a kind of in titanate coupling agent, the silane coupling agent or at least two kinds.
9. wear-resistant thermoplastic elastomer as claimed in claim 1 is characterized in that: described processing aid is selected from a kind of in lipid acid, soap, fatty acid amide, silicone, the polyethylene wax or at least two kinds.
Perhaps, described stablizer is selected from and contains a kind of in benzophenone functional compounds photostabilizer, hindered phenol stabilizer, phosphite ester stabilizer, the hindered amine as light stabilizer or at least two kinds.
10. as the preparation method of each described wear-resistant thermoplastic elastomer of claim 1～9, comprise step:
(1) sending into rotating speed after vector resin, compatilizer, anti-wear agent, inorganic nano-particle are mixed is extruding pelletization in 300 rev/mins～400 rev/mins the twin screw extruder, obtains masterbatch;
(2) matrix resin and extending oil thorough mixing is even, oil to be filled is blotted the back fully by resin and adds mineral filler, in whipping process, add coupling agent treatment, add processing aid, stablizer, masterbatch and thermoplastic resin then, send into rotating speed after mixing and be extruding pelletization in 300 rev/mins～400 rev/mins the twin screw extruder, make wear-resistant thermoplastic elastomer;
Wherein, each section extruder temperature is 160 ℃～220 ℃.
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