CN1724589A - Thermoplastic elastomer and its production method - Google Patents
Thermoplastic elastomer and its production method Download PDFInfo
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- CN1724589A CN1724589A CNA2005100126091A CN200510012609A CN1724589A CN 1724589 A CN1724589 A CN 1724589A CN A2005100126091 A CNA2005100126091 A CN A2005100126091A CN 200510012609 A CN200510012609 A CN 200510012609A CN 1724589 A CN1724589 A CN 1724589A
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Abstract
The invention provides a high elasticity thermal plasticity elastic body and the method to make. The weight proportion of the elastic body includes: plasticity ingredient styrene-butadiene-styrene block copolymer 100, filling naphthenic oil or white oil 40-60, modification agent 0-110, stabilizing agent 2-10, lubricant 2-65, and other bulk agent 10-300. The invention has advantages of low compression deformation, strong flexing resistance and good resilience.
Description
Technical field
The present invention relates to a kind of high-elasticity thermoplastic elastomerics of exempting to vulcanize, be particularly useful for the insulation and the sheath material of line, cable; Snappiness environment-friendly type sebific duct, glue rope, glue rod in the body-building apparatus; Elastic sole; Automobile and motor vehicle, Aluminum plastics door and window sealed strip and sealing member belong to plastics or elastomeric material technical field.
Background technology
At present, insulation of China's line, cable industry and sheath material, automobile and motor vehicle, Aluminum plastics door and window sealed strip and sealing member consumption are maximum is vulcanized elastomers such as igelite and natural rubber, butadiene-styrene rubber, neoprene latex, second third glue.Contain CL in the polyvinyl chloride
-1, in the used stablizer Sn is arranged
+ 2, Pb
+ 2, Cd
+ 2, Cr
+ 6Deng harmful ion, products such as the line of being produced, cable product or sealed strip in use can deferred reaction, discharges the HCL obnoxious flavour, contaminate environment.The vulcanization aid of rubber has toxic materials such as sulphur, thiazole, thiuram, carbaminate, thiocarbamide, the also most residual poisonous and harmful substances of byproduct that reaction generates; Adopt vapor sulfurizing process in production line, the cable process, the boiler oil burning produces stack gas and waste sludge discharge, environment is caused severe contamination, and be high temperature, high top pressure operation, and operation sequence is complicated and dangerous.Another defective of sulfuration process is because of sulphur makes copper conductor send out dirt, blackening to the erosion action of copper conductor, influences quality, reduces work-ing life.The applicant discloses 03109074.5 and 03109075.3 two kind of thermoplastic elastomer and production method in 2003, their basic combination is respectively " polyurethane termoplastic elastomer and styrene butadiene-Sipacril 2739OF ", " styrene-butadiene block copolymer (SBS); styrene butadiene-Sipacril 2739OF (MBS); ethylene-propylene rubber(EPR) ", development along with society, people's Environmental awareness strengthens gradually, sulfuration is exempted from exploitation, free of contamination thermoplastic elastomer environmental type material is a cable industry, sealed strip, the sealing member industry, snappiness sebific duct in footwear material and the body-building apparatus, the glue rope, the task of top priority of glue rod industry.
Summary of the invention
Technical problem to be solved by this invention is compatible according to some molecular material similar performances, the character complementation, the mechanism of mutual modification, a kind of high-elasticity thermoplastic elastomerics and production method are provided, as cable industry, sealed strip, sealing member industry, the environment-friendly type substituted product of snappiness sebific duct, glue rope, glue rod industry in footwear material and the body-building apparatus.
Technical scheme of the present invention is achieved in that a kind of thermoplastic elastomer, it is characterized in that described elastomerics comprises following weight part application percentage: plasticity composition styrene-butadiene-styrene block copolymer 100, fill naphthenic oil or white oil 40-60, properties-correcting agent 0-110, stablizer 2-10, other weighting agent of lubricant 2-65 10-300.
Described thermoplastic elastomer comprises that also the part of the styrene-butadiene-styrene block copolymer of following weight part application percentage substitutes composition: styrene isoprene styrene block copolymer (SIS), hydrogenated styrene-butadiene block copolymer is or/and styrene butadiene-acrylonitrile copolymer 20-40, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
Described thermoplastic elastomer also comprises the shared rubber constituent of following weight part application percentage: ethylene-propylene diene copolymer and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, ethylene-propylene diene copolymer and polyethylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polyethylene; Dynamic Vulcanized Thermoplastic Elastomer; ethylene propylene rubber is or/and terpolymer EP rubber 20-80, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
The properties-correcting agent of described thermoplastic elastomer comprises following weight part application percentage: polystyrene, high-phenylethylene, a-Methylstyrene Low-Polymer and vinylformic acid styrene esters multipolymer, a-Methylstyrene Low-Polymer, new LDPE (film grade), high density polyethylene(HDPE) is or/and ethene-vinyl acetate 0-100, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
The weighting agent of described thermoplastic elastomer also comprises following weight part application percentage: light magnesium oxide, aluminium hydroxide, ultra-fine mica powder, the calcining kaolin, transparent white carbon black, Magnesium Carbonate Light 41-45 is or/and light calcium carbonate 0-300, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
The stablizer of described thermoplastic elastomer comprises following weight part application percentage: barium stearate is or/and calcium-zinc composite stabilizer 1-5, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
The lubricant of described thermoplastic elastomer comprises following weight part application percentage: stearic acid 1-3, paraffin 1-2, naphthenic oil are or/and white oil 0-58, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
Described method of producing thermoplastic elastomer, adopt following steps to finish:
A, quantitative styrene-butadiene-styrene block copolymer (SBS) and naphthenic oil or white oil be placed in the blender stir, emit, in container, left standstill 4-8 hour, make it oil-filled standby;
B, with oil-filled styrene-butadiene-styrene block copolymer (SBS) and all fill material add in the blender in fully stir under the 70-100 ℃ of temperature 15-20 minute evenly after, plasticate under 120-180 ℃ of temperature with single screw rod or twin screw plastics extruder, utilize earnestly or cold cut equipment is cut into the cylinder shape particle that volume is equivalent to 4mm * 4mm * 3mm or 3mm * 3mm * 3mm volume, cooling back packing is finished product.
Step B also can realize like this in the described method of producing thermoplastic elastomer: whole materials are added in the Banbury mixer plasticate under 140 ℃ of-160 ℃ of temperature; to plasticate material on opening rubber mixing machine in 110-150 ℃ of thin-pass three times; make thin-pass sheet thickness less than 1mm; roll into the film of 3mm or 4mm thickness then; be cut into the micelle of 4mm * 4mm * 3mm or 3mm * 3mm * 3mm after the cooling with slicing machine and dicing machine, packing is finished product.
Step B also can realize like this in the described method of producing thermoplastic elastomer: the material that will plasticate with plastics extruder, blended rubber and the weighting agent of plasticating without plastics extruder on the open mill in mix once more under the 130-160 ℃ of temperature plasticate evenly after; thin-pass three times; make thin-pass film thickness less than 1mm; roll into the film of 3mm or 4mm thickness then; be cut into the micelle of 4mm * 4mm * 3mm or 3mm * 3mm * 3mm after the cooling with slicing machine and dicing machine, packing is finished product.
It is low that products such as the cable of thermoplastic elastomer material production of the present invention, sealed strip, sealing member, footwear material, snappiness pipe, snappiness glue rope not only compress modification, and anti-flexibility is strong, and ageing-resistant, and screen resilience is strong.Not only can produce various electric wires, cable, also can produce automobile and motor vehicle, the Aluminum plastics door and window sealed strip, in various, high, low-pressure hose, by injection moulding, various processes such as blowing or extrusion molding, make the mechanical part of multiple mechanical different performance requirement, injection moulded shoes and sole, used snappiness sebific duct in the body-building apparatus, the glue rope, multiple products such as rope rod, when producing the said products with production material of the present invention, remove sulfidation from, equipment is simple, technology is easy, but with common plastics forcing machine or rubber vulcanizing machine of changing slightly or all extrusion mouldings of the special-purpose forcing machine of thermoplastic elastomer, tailing can utilize repeatedly again, saves material and productive expense, does not produce the three wastes and environmental pollution in the production process; Product in use can not produce the discharging of any obnoxious flavour and toxic substance yet, causes environmental pollution.
Embodiment
Embodiment 1
Component:
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
Fill 40 parts of naphthenic oils;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
Production method: quantitative styrene-butadiene-styrene block copolymer (SBS) and naphthenic oil be placed in the blender stir, emit.In container, left standstill 4-8 hour, and made it oil-filled standby.Then oil-filled styrene-butadiene-styrene block copolymer (SBS) and auxiliary agent are added in the blender after fully stirring 15-20 under the 70-100 ℃ of temperature and dividing evenly, plasticate under 120 ℃ of-140 ℃ of temperature with single screw rod or twin screw plastics extruder, utilize earnestly or cold cut equipment is cut into the cylinder shape particle that volume is equivalent to 4mm * 4mm * 3mm or 3mm * 3mm * 3mm volume, cooling back packing is finished product;
Embodiments of the invention 1 provide-kind of the simplest embodiment, promptly styrene-butadiene-styrene block copolymer (SBS) fill naphthenic oil can be directly as the thermoplastic elastomer product.
Embodiment 2
Component:
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
Fill 40 parts of naphthenic oils;
40 parts of polystyrene (PS666D);
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
Production method: with embodiment 1
Embodiment 3
Component:
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
Fill 40 parts of naphthenic oils;
40 parts of polystyrene (PS666D);
100 parts of light calcium carbonates;
35 parts of tenderizer-white oils;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
Production method: with embodiment 1, in the above-described embodiments, filler loading is big more, needs adding tenderizer naphthenic oil or white oil many more.
Embodiment 4
Component:
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
Fill 40 parts of naphthenic oils;
40 parts of polystyrene (PS666D);
1 part of barium stearate;
30 parts of ethene-vinyl acetates (EVA14-);
20 parts of transparent white carbon blacks (active silica);
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
Production method: with embodiment 1
Embodiment 5
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
40 parts of naphthenic oils;
20 parts of styrene butadiene-acrylonitrile copolymers (ABS);
20 parts of polymethyl acrylates (PMMA);
30 parts of ethene-vinyl acetates (EVA14-2);
20 parts of calcining kaolins;
130 parts of light calcium carbonates;
55 parts of tenderizer-No. 15 white oils;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
Production method: with embodiment 1
Embodiment 6
Component:
100 parts of styrene-butadiene-styrene block copolymers (SBS YH-815);
Fill 40 parts of naphthenic oils;
40 parts of polystyrene (PS666D);
20 parts of high-phenylethylenes (HS-860);
30 parts of ethene-vinyl acetates (EVA 14-2);
70 parts in binary second third glue (glue sheet);
30 parts of ethylene-propylene diene copolymers (3745P glue sheet);
2.5 parts of a-Methylstyrene Low-Polymer (M80);
150 parts of light calcium carbonates;
55 parts of tenderizer-naphthenic oils;
2 parts of pigment or carbon blacks;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
2 parts of pigment;
Added in the foregoing description elastomeric component and also used rubber, can be used as in the practical application and a lot of with the material of rubber, as ethylene-propylene diene copolymer and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, ethylene-propylene diene copolymer and polyethylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polyethylene; Dynamic Vulcanized Thermoplastic Elastomer; ethylene propylene rubber, terpolymer EP rubber etc.
Production method:
Quantitative styrene-butadiene-styrene block copolymer (SBS) and naphthenic oil or white oil (account for SBS total amount 40%) be placed in the blender stir, emit, in container, left standstill 4-8 hour, make it oil-filled standby.To under 130 ℃ of-180 ℃ of temperature, plasticate in whole materials adding Banbury mixeies; to plasticate material on opening rubber mixing machine in 110-150 ℃ of thin-pass three times; make thin-pass sheet thickness less than 1mm; roll into the film of 3mm or 4mm thickness then; be cut into the micelle of 4mm * 4mm * 3mm or 3mm * 3mm * 3mm after the cooling with slicing machine and dicing machine, packing is finished product.
Embodiment 7
Component:
60 parts of styrene-butadiene-styrene block copolymers (SBS YH-801,802,803);
20 parts of styrene isoprene styrene block copolymer (SIS) (SIS);
20 parts of hydrogenated styrene-butadiene-styrene block copolymers (SEBS);
Fill 60 parts of naphthenic oils;
40 parts of polystyrene (PS666D);
20 parts of high-phenylethylenes (HS-860);
30 parts of ethene-vinyl acetates (EVA 14-2);
50 parts of ethylene-propylene diene copolymer/polypropylene (EPTM/PP) Dynamic Vulcanized Thermoplastic Elastomer (ATR);
30 parts in binary second third glue (particulate state);
20 parts of ethylene-propylene diene copolymers (3745P particulate state);
2.5 parts of a-Methylstyrene Low-Polymer (M80);
3 parts of a-Methylstyrene Low-Polymer and vinylformic acid styrene esters multipolymers (MS290);
10 parts of light magnesium oxides;
40 parts in aluminium hydroxide;
30 parts of ultra-fine mica powders;
30 parts in lightweight carbonic acid;
50 parts of light calcium carbonates;
58 parts of tenderizer-white oils;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
2 parts of pigment;
Styrene isoprene styrene block copolymer (SIS) and hydrogenated styrene-butadiene-styrene block copolymers substitute component as the part of styrene-butadiene-styrene block copolymer in the foregoing description.
Production method: with embodiment 1,
Embodiment 8
Component:
100 parts of styrene-butadiene-styrene block copolymer segmented copolymers;
Fill 60 parts of naphthenic oils;
50 parts of polystyrene (PS666D);
20 parts of new LDPE (film grade)s (LDPE);
10 parts of high density polyethylene(HDPE)s (HDPE);
30 parts of ethene-vinyl acetates (EVA 28-25);
50 parts of ethylene-propylene diene copolymer/polypropylene (EPTM/PP) Dynamic Vulcanized Thermoplastic Elastomer (ATR);
20 parts of butadiene-styrene rubber/polypropylene (SBR/PP) Dynamic Vulcanized Thermoplastic Elastomer;
30 parts of natural gum/polypropylene (NR/PP) Dynamic Vulcanized Thermoplastic Elastomer;
10 parts of light magnesium oxides;
40 parts in aluminium hydroxide;
30 parts of ultra-fine mica powders;
30 parts of Magnesium Carbonate Light 41-45s;
50 parts of light calcium carbonates;
55 parts of tenderizer-naphthenic oils;
1 part of barium stearate;
2 parts of calcium-zinc composite stabilizers;
2 parts of stearic acid;
3 parts in paraffin;
2 parts of pigment;
Production method: with embodiment 7, properties-correcting agent is selected polystyrene in the foregoing description, new LDPE (film grade), high density polyethylene(HDPE), ethene-vinyl acetate is as properties-correcting agent, high-phenylethylene in actual applications, a-Methylstyrene Low-Polymer and vinylformic acid styrene esters multipolymer, a-Methylstyrene Low-Polymer etc. all can be used as properties-correcting agent, as changing softening temperature etc.
Listed examples of the present invention is intended to further illustrate the combination formula and the production method of this thermoplastic elastomer, and scope of the present invention is not constituted any restriction, the product that obtains with the embodiment of the invention and all can obtain the thermoplastic elastomer product via claims of the present invention are described.
Claims (10)
1, a kind of thermoplastic elastomer, it is characterized in that described elastomerics comprises following weight part application percentage: plasticity composition styrene-butadiene-styrene block copolymer 100, fill naphthenic oil or white oil 40-60, properties-correcting agent 0-100, stablizer 2-10, lubricant 2-65, other weighting agent 10-300.
2, thermoplastic elastomer according to claim 1, it is characterized in that described elastomerics comprises that also the part of the styrene-butadiene-styrene block copolymer of following weight part application percentage substitutes composition: styrene isoprene styrene block copolymer (SIS), hydrogenated styrene-butadiene block copolymer is or/and styrene butadiene-acrylonitrile copolymer 20-40, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
3, thermoplastic elastomer according to claim 1 and 2, it is characterized in that described elastomerics also comprises the shared rubber constituent of following weight part application percentage: ethylene-propylene diene copolymer and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, ethylene-propylene diene copolymer and polyethylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polypropylene Dynamic Vulcanized Thermoplastic Elastomer, natural gum and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; butadiene-styrene rubber and polyethylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polypropylene Dynamic Vulcanized Thermoplastic Elastomer; cis-butadiene cement and polyethylene; Dynamic Vulcanized Thermoplastic Elastomer; ethylene propylene rubber is or/and terpolymer EP rubber 20-80, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
4, thermoplastic elastomer according to claim 1, it is characterized in that described elastomer modification agent comprises following weight part application percentage: polystyrene, high-phenylethylene, a-Methylstyrene Low-Polymer and vinylformic acid styrene esters multipolymer, a-Methylstyrene Low-Polymer, new LDPE (film grade), high density polyethylene(HDPE) are or/and ethene-vinyl acetate 0-110, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
5, thermoplastic elastomer according to claim 1, it is characterized in that described elastomeric weighting agent also comprises following weight part application percentage: light magnesium oxide, aluminium hydroxide, ultra-fine mica powder, the calcining kaolin, transparent white carbon black, Magnesium Carbonate Light 41-45 are or/and light calcium carbonate 0-300, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
6, thermoplastic elastomer according to claim 1, it is characterized in that described elastomeric stablizer comprises following weight part application percentage: barium stearate is or/and calcium-zinc composite stabilizer 1-5, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
7, thermoplastic elastomer according to claim 1, it is characterized in that described elastomeric lubricant comprises following weight part application percentage: stearic acid 1-3, paraffin 1-2, naphthenic oil is or/and white oil 0-58, based on the styrene-butadiene-styrene block copolymer of 100 weight parts.
8, method of producing thermoplastic elastomer according to claim 1, its feature comprise and adopt following steps to finish:
A, quantitative styrene-butadiene-styrene block copolymer (SBS) and naphthenic oil or white oil be placed in the blender stir, emit, in container, left standstill 4-8 hour, make it oil-filled standby;
B, with oil-filled styrene-butadiene-styrene block copolymer (SBS) and all fill material add in the blender in fully stir under the 70-100 ℃ of temperature 15-20 minute evenly after, plasticate under 120-180 ℃ of temperature with single screw rod or twin screw plastics extruder, utilize earnestly or cold cut equipment is cut into the cylinder shape particle that volume is equivalent to 4mm * 4mm * 3mm or 3mm * 3mm * 3mm volume, cooling back packing is finished product.
9, method of producing thermoplastic elastomer according to claim 8; it is characterized in that step B: whole materials are added in the Banbury mixer under 140 ℃ of-160 ℃ of temperature, plasticate; to plasticate material on opening rubber mixing machine in 110-150 ℃ of thin-pass three times; make thin-pass sheet thickness less than 1mm; roll into the film of 3mm or 4mm thickness then; be cut into the micelle of 4mm * 4mm * 3mm or 3mm * 3mm * 3mm after the cooling with slicing machine and dicing machine, packing is finished product.
10, method of producing thermoplastic elastomer according to claim 8; it is characterized in that step B: the material that will plasticate with plastics extruder, blended rubber and the weighting agent of plasticating without plastics extruder on the open mill in mix once more under the 130-160 ℃ of temperature plasticate evenly after; thin-pass three times; make thin-pass film thickness less than 1mm; roll into the film of 3mm or 4mm thickness then; be cut into the micelle of 4mm * 4mm * 3mm or 3mm * 3mm * 3mm after the cooling with slicing machine and dicing machine, packing is finished product.
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2005
- 2005-06-17 CN CNB2005100126091A patent/CN100467529C/en not_active Expired - Fee Related
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Assignee: CANGZHOU HUIYOU WIRE & CABLE CO., LTD. Assignor: Yan Junlong Contract fulfillment period: 2009.6.1 to 2014.6.1 contract change Contract record no.: 2009130000100 Denomination of invention: Thermoplastic elastomer and its production process Granted publication date: 20090311 License type: Exclusive license Record date: 2009.8.6 |
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