CN102002174B - Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof - Google Patents
Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof Download PDFInfo
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- CN102002174B CN102002174B CN2010105488920A CN201010548892A CN102002174B CN 102002174 B CN102002174 B CN 102002174B CN 2010105488920 A CN2010105488920 A CN 2010105488920A CN 201010548892 A CN201010548892 A CN 201010548892A CN 102002174 B CN102002174 B CN 102002174B
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- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 title abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000005060 rubber Substances 0.000 claims abstract description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 229920001897 terpolymer Polymers 0.000 claims abstract description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 235000010216 calcium carbonate Nutrition 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 abstract description 18
- 229920002943 EPDM rubber Polymers 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 4
- 235000021355 Stearic acid Nutrition 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 239000008117 stearic acid Substances 0.000 abstract 1
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- -1 glycol ethers Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940074869 marquis Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a styrene butadiene rubber (SBR) sponge composite material and a preparation method thereof and relates to the preparation method of the SBR sponge composite material. SBR rubber 1502 is prepared by the following steps of: sequentially adding 30 to 50 mass parts of ethylene propylene terpolymer, 170 to 180 mass parts of light calcium carbonate serving as a filler, 28 to 30 mass parts of argil, 23 to 25 mass parts of black smoke serving as a reinforcing agent N330, 67 to 70 mass parts of naphthenic oil serving as a softener, 2.7 to 3 mass parts of dispersant AFLUX-42, 2 to 2.3 mass parts of antioxidant, 2.5 to 2.8 mass parts of protective wax, 2.7 to 2.8 mass parts of stearic acid, 9 to 9.5 mass parts of zinc oxide, 5 to 6 mass parts of vulcanizing agent and vulcanizing agent aid, 19 to 21 mass parts of activated charcoal (AC) foaming agent, 70 to 73.5 mass parts of flame retardant and 2.5 to 2.8 mass parts of processing aid into an internal mixer for mixing, performing thin passing, cooling and extruding; performing primary vulcanization and secondary vulcanization; and foaming. The composite material has the advantages that: an ethylene-propylene-diene monomer (EPDM) has high ageing resistance, saturation non-polarity and non-self-reinforcing property and can absorb a large amount of oil and a large number of fillers; simultaneously, the flame retardant is added, so that the product has high flame retardance and high antistatic property.
Description
Technical field:
The present invention relates to the preparation method of SBR sponge matrix material.
Background technology:
SBR sponge matrix material is widely used in fields such as physical fitness, footwear material, bag material, medical protector, aquatic sports.Domestic existing SBR sponge matrix material main raw material is that styrene-butadiene rubber(SBR) and other raw material ratio mix through processing, forms sponge through the foaming of vulcanizing press HTHP post vulcanization again.The common shortcomings such as anti-aging is indifferent, easy firing, heat-shrinkable is big, tensile strength is low, compression deformation rate is big that exist of domestic existing SBR sponge matrix material.Usually its prescription is a radix with the SBR100 mass parts, allocates weighting agent 151～157 mass parts into by mass parts, tenderizer 53～55 mass parts; Strengthening agent 26～26.3 mass parts; Processing aid 15～16 mass parts, vulcanizing agent and auxiliary agent 2～2.5 mass parts, promoting agent 8～9 mass parts; Dispersion agent 3～4 mass parts, whipping agent 13～18 mass parts.
SBR sponge matrix material master glue is with styrene-butadiene rubber(SBR) 1502, and weighting agent is with light calcium carbonate and carclazyte, and tenderizer is a RUBBER PROCESS OIL with oil generally; Strengthening agent is generally used carbon black, and processing aid is used white factice, and vulcanizing agent is generally used Sulfur; Vulcanization aid is generally used thiazole accelerator; Promoting agent is generally used Triple Pressed Stearic Acid and zinc oxide, and dispersion agent is generally used AFLUX-42, and whipping agent is generally with DPT or AC.
With following example existing general making method is described: with 100 parts in 1502 glue, carclazyte 82.6,73.3 parts of fine particle calcium carbonates; 2.2 parts of Sulfur and auxiliary agents, 54.4 parts of treated oils, 26.1 parts of carbon blacks; 15.2 parts of white factices, 2 parts of Triple Pressed Stearic Acid, 6.5 parts in zinc oxide; 3 parts of AFLUX-42 dispersion agents drop into internal mixer sequentially and mix and expect that the machine of beginning to pratise to the broad logical postcooling 12hr of 10min under 15min to 120 ℃, use the forcing machine slice with the machine preheating 6min that begins to pratise again, the first 1800T oil press of using; Vapor pressure is about 3 kilograms, carries out one step cure about time 30min; The oil press vapor pressure that uses 300T at last is about 6 kilograms, carries out the post vulcanization foaming about time 20min.Goods are through detecting: tensile strength is 2 kilograms of f/cm
2, elongation is 210%, 1.33 kilograms of f/cm of tear strength
2, density is 0.219g/cm
3, percent thermal shrinkage (70 ℃ 24hr) are MD:4%; CD:5%, compression deformation rate are that (23 ℃ is 30% 22hr), and goods were parked after 7 days has obvious aging characteristics, and naked light leaves and can not extinguish and burning always after lighting with naked light.
In sum, domestic existing SBR sponge matrix material exists anti-aging indifferent, easy firing, shortcoming such as heat-shrinkable is big, and tensile strength is low, and compression deformation rate is big.
Summary of the invention:
The objective of the invention is to overcome above-mentioned defective, a kind of New type of S BR sponge matrix material and preparation method thereof is provided.
SBR sponge composite-material formula of the present invention is: with SBR rubber 1502100 mass parts is radix, and allocating terpolymer EP rubber (EPDM) into by mass parts is 30～50 parts, 170～180 parts of weighting agent light calcium carbonates; 28～30 parts of carclazytes, 23～25 parts of strengthening agent N330 black smokes, 67～70 parts of tenderizer NOs; Dispersant A FLUX-42 is 2.7～3 parts, 2～2.3 parts in oxidation inhibitor, 2.5～2.8 parts of protection waxes; 2.7～2.8 parts of Triple Pressed Stearic Acid, 9 parts～9.5 parts in zinc oxide, 5～6 parts of vulcanizing agent and auxiliary agents thereof; 19～21 parts of AC whipping agents, 70～73.5 parts of fire retardants (wherein 36～39 parts of clorafins, 34～34.5 parts of Antimony Trioxide: 99.5Mins), 2.5～2.8 parts of alcohols processing aids.
Preparing method of the present invention is: with SBR rubber 1,502 100 mass parts is radix, and allocating terpolymer EP rubber (EPDM) into by mass parts is 30～50 parts, 170～180 parts of weighting agent light calcium carbonates; 28～30 parts of carclazytes, 23～25 parts of strengthening agent N330 black smokes, 67～70 parts of tenderizer NOs; Dispersant A FLUX-42 is 2.7～3 parts, 2～2.3 parts in oxidation inhibitor, 2.5～2.8 parts of protection waxes; 2.7～2.8 parts of Triple Pressed Stearic Acid, 9 parts～9.5 parts in zinc oxide, 5～6 parts of vulcanizing agent and auxiliary agents thereof; 19～21 parts of AC whipping agents, 70～73.5 parts of fire retardants (wherein 36～39 parts of clorafins, 34～34.5 parts of Antimony Trioxide: 99.5Mins), 2.5～2.8 parts of alcohols processing aids drop into internal mixer sequentially and mix and expect that the machine of beginning to pratise to the broad logical postcooling 12hr of 10min under 15min to 120 ℃; Use the forcing machine slice with the machine preheating 6min that begins to pratise again; Earlier using 1800T oil press, vapor pressure is about 3 kilograms, carries out one step cure about time 30min; The oil press vapor pressure that uses 300T at last is about 6 kilograms, carries out the post vulcanization foaming about time 20min.
The invention has the advantages that: present method is developed the defective on its performance of maximum range reduction under the prerequisite that guarantees its property to the more above-mentioned performance deficiencies of domestic SBR sponge matrix material.For obtaining this effect; We find that EPDM has outstanding ageing resistance (ozone resistance, thermally-stabilised, heat-resistant aging, anti-day marquis's property, chemical-resistant resistance, oil resistance); EPDM is that saturated nonpolar is not from reinforcement property simultaneously; Can absorb a large amount of oil and fillers and make its properties influence little, therefore in the traditional sponge composite-material formula of SBR, add the fine above-mentioned defective of improving SBR sponge matrix material of EPDM ability, allocate fire retardant simultaneously into and make goods possess strong flame retardant resistance and static resistance; Make the SBR sponge can not cause that the incendiary probability is extremely low because of static sparking at compounding machine (rigging machine) compound tense.
Embodiment:
Embodiment 1: with SBR1502 glue 100 mass parts, and EPDM30 part, 170 parts of fine particle calcium carbonates, 29 parts of carclazytes; 23 parts of N330 black smokes, 67 parts of NOs, AFLUX-42 are 2.7 parts, 2.7 parts of Triple Pressed Stearic Acid; 9 parts in zinc oxide, 2.1 parts in oxidation inhibitor, 2.5 parts of protection waxes; 5 parts of vulcanizing agent and auxiliary agents, 19 parts of AC whipping agents, fire retardant chlorinated paraffin-70 are 36 parts; 34 parts of fire retardant Antimony Trioxide: 99.5Mins, 2.6 parts of processing aid glycol ethers drop into internal mixer sequentially and mix and expect that the machine of beginning to pratise to the broad logical postcooling 12hr of 10min under 15min to 120 ℃, use the forcing machine slice with the machine preheating 6min that begins to pratise again; Earlier using 1800T oil press, vapor pressure is about 3 kilograms, carries out one step cure about time 30min; The oil press vapor pressure that uses 300T at last is about 6 kilograms, carries out the post vulcanization foaming about time 20min.
Embodiment 2: with SBR1502 glue 100 mass parts, and EPDM50 part, 180 parts of fine particle calcium carbonates, 30 parts of carclazytes; 25 parts of N330 black smokes, 70 parts of NOs, AFLUX-42 are 3 parts, 2.8 parts of Triple Pressed Stearic Acid; 9.5 parts in zinc oxide, 2.3 parts in oxidation inhibitor, 2.8 parts of protection waxes; 6 parts of vulcanizing agent and auxiliary agents, 21 parts of AC whipping agents, fire retardant chlorinated paraffin-70 are 39 parts; 34.5 parts of fire retardant Antimony Trioxide: 99.5Mins, 2.8 parts of processing aid glycol ethers drop into internal mixer sequentially and mix and expect that the machine of beginning to pratise to the broad logical postcooling 12hr of 10min under 15min to 120 ℃, use the forcing machine slice with the machine preheating 6min that begins to pratise again; Earlier using 1800T oil press, vapor pressure is about 3 kilograms, carries out one step cure about time 30min; The oil press vapor pressure that uses 300T at last is about 6 kilograms, carries out the post vulcanization foaming about time 20min.
Last instance 2 goods are through detecting: tensile strength is 5 kilograms of f/cm
2, elongation is 250%, 1.5 kilograms of f/cm of tear strength
2, density is 0.190g/cm
3, percent thermal shrinkage (70 ℃, 24hr) be MD:3% ↓; CD:3%, compression deformation rate are that (23 ℃ is 25% 22hr); Goods were parked after 15 days does not have aging characteristics; Light the back naked light with naked light and leave promptly and extinguish (oxygen index＞34), and the fire retardant chlorinated paraffin-70 has antistatic property simultaneously, the goods recombination energy reduces static sparking.
By we can find out in the SBR sponge composite-material formula and to add that tensile strength, tear strength, elongation, percent thermal shrinkage, compression deformation rate, anti ageing property, the flame retardant resistance of product improves significantly behind EPDM and the fire retardant in the data of above-mentioned instance.Draw in the practice in 100 parts of SBR and add 30～50 parts, its performance and cost are the most moderate in 70～73 parts of scopes of fire retardant.Product is through client's reflection on probation superior performance, and from putting out, cutting composite safe and corrosion resistance are strong from fire.
Claims (2)
1. SBR sponge matrix material, it is characterized in that: SBR sponge composite-material formula is: with SBR rubber 1,502 100 mass parts is radix, allocating terpolymer EP rubber into by mass parts is 30～50 parts; 170～180 parts of weighting agent light calcium carbonates; 28～30 parts of carclazytes; 23～25 parts of strengthening agent N330 black smokes; 67～70 parts of tenderizer NOs; Dispersant A FLUX-42 is 2.7～3 parts; 2～2.3 parts in oxidation inhibitor; 2.5～2.8 parts of protection waxes; 2.7～2.8 parts of Triple Pressed Stearic Acid; 9 parts～9.5 parts in zinc oxide; 5～6 parts of vulcanizing agent and auxiliary agents thereof; 19～21 parts of AC whipping agents; 70～73.5 parts of fire retardants, wherein 36～39 parts of clorafins, 34～34.5 parts of Antimony Trioxide: 99.5Mins; 2.5～2.8 parts of alcohols processing aids.
2. the preparation method of a SBR sponge matrix material, it is characterized in that: the preparation method is: with SBR rubber 1,502 100 mass parts is radix, allocating terpolymer EP rubber into by mass parts is 30～50 parts; 170～180 parts of weighting agent light calcium carbonates; 28～30 parts of carclazytes; 23～25 parts of strengthening agent N330 black smokes; 67～70 parts of tenderizer NOs; Dispersant A FLUX-42 is 2.7～3 parts; 2～2.3 parts in oxidation inhibitor; 2.5～2.8 parts of protection waxes; 2.7～2.8 parts of Triple Pressed Stearic Acid; 9 parts～9.5 parts in zinc oxide; 5～6 parts of vulcanizing agent and auxiliary agents thereof; 19～21 parts of AC whipping agents; 70～73.5 parts of fire retardants, wherein 36～39 parts of clorafins, 34～34.5 parts of Antimony Trioxide: 99.5Mins; 2.5～2.8 parts of alcohols processing aids; Drop into sequentially and expect under 15min to 120 ℃ of the mixer mixing that mill is opened and refine thin logical postcooling 12hr to 10min; Use the forcing machine slice with mill preheating 6min again; Earlier using 1800T oil press, vapor pressure is 3 kilograms, and time 30min carries out one step cure; The oil press vapor pressure that uses 300T at last is 6 kilograms, and time 20min carries out the post vulcanization foaming.
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| CN2010105488920A CN102002174B (en) | 2010-11-17 | 2010-11-17 | Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof |
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| CN2010105488920A CN102002174B (en) | 2010-11-17 | 2010-11-17 | Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof |
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| CN102504415B (en) * | 2011-10-10 | 2014-07-02 | 沈阳化工大学 | Light-colored microporous EPDM sponge rubber and preparation method thereof |
| CN105885138A (en) * | 2016-04-20 | 2016-08-24 | 苏州蔻美新材料有限公司 | Composite for producing rehabilitation equipment and preparation method of composite |
| CN108017813A (en) * | 2016-10-31 | 2018-05-11 | 天步（上海）体育运动用品有限公司 | A kind of new type rubber sponge composite and its forming method |
| CN106589500A (en) * | 2016-12-05 | 2017-04-26 | 钦州市钦南区生产力促进中心 | Sponge composite material and preparation method thereof |
| CN111533965A (en) * | 2020-06-03 | 2020-08-14 | 厦门正新橡胶工业有限公司 | Anti-blooming environment-friendly rubber formula for tires |
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| CN1008143B (en) * | 1988-09-21 | 1990-05-30 | 辽宁省铁岭市橡胶厂 | Lasting process of raw foam-rubber inner-sole of bonded rubber shoes |
| EP2039553B1 (en) * | 2007-09-20 | 2010-06-02 | Toyoda Gosei Co., Ltd. | Automobile weather strip |
| CN101280076A (en) * | 2008-06-04 | 2008-10-08 | 泉州至和织造有限公司 | SBR diving material and preparation thereof |
| CN101608037B (en) * | 2008-06-21 | 2011-11-16 | 比亚迪股份有限公司 | Sponge rubber composition and preparation method thereof |
| CN101724172B (en) * | 2009-12-04 | 2012-07-04 | 江苏工业学院 | Industrial production method for ethylene propylene diene rubber molded sealed cell sponge rubber |
| CN101781415A (en) * | 2010-03-15 | 2010-07-21 | 尚盟运动用品(惠阳)有限公司 | Styrene butadiene rubber sponge |
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Denomination of invention: Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof Effective date of registration: 20130912 Granted publication date: 20120111 Pledgee: China Merchants Bank, Limited by Share Ltd, Quanzhou Jiangnan sub branch Pledgor: Zhihe (Fujian) Technologies Co., Ltd. Registration number: 2013350000027 |
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Denomination of invention: Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof Effective date of registration: 20141022 Granted publication date: 20120111 Pledgee: China Merchants Bank, Limited by Share Ltd, Quanzhou Jiangnan sub branch Pledgor: Zhihe (Fujian) Technologies Co., Ltd. Registration number: 2014990000879 |
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Denomination of invention: Styrene butadiene rubber (SBR) sponge composite material and preparation method thereof Effective date of registration: 20160316 Granted publication date: 20120111 Pledgee: China Merchants Bank, Limited by Share Ltd, Quanzhou Jiangnan sub branch Pledgor: Zhihe (Fujian) Technologies Co., Ltd. Registration number: 2016990000218 |
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