CN102311588A - Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof - Google Patents
Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof Download PDFInfo
- Publication number
- CN102311588A CN102311588A CN201110203118A CN201110203118A CN102311588A CN 102311588 A CN102311588 A CN 102311588A CN 201110203118 A CN201110203118 A CN 201110203118A CN 201110203118 A CN201110203118 A CN 201110203118A CN 102311588 A CN102311588 A CN 102311588A
- Authority
- CN
- China
- Prior art keywords
- agent
- parts
- retardant
- rubber
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000005060 rubber Substances 0.000 title claims abstract description 57
- 238000005187 foaming Methods 0.000 title claims abstract description 22
- 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 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- 229920002681 hypalon Polymers 0.000 claims abstract description 9
- 238000005728 strengthening Methods 0.000 claims abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 238000000748 compression moulding Methods 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 230000001737 promoting effect Effects 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- WGKLIJDVPACLGG-UHFFFAOYSA-N trizinc diborate hydrate Chemical compound O.[Zn++].[Zn++].[Zn++].[O-]B([O-])[O-].[O-]B([O-])[O-] WGKLIJDVPACLGG-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims 2
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 41
- 239000003963 antioxidant agent Substances 0.000 abstract description 13
- 230000003078 antioxidant effect Effects 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 11
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 239000005062 Polybutadiene Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000005484 gravity Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 244000043261 Hevea brasiliensis Species 0.000 abstract 2
- 239000012190 activator Substances 0.000 abstract 2
- 229920003052 natural elastomer Polymers 0.000 abstract 2
- 229920001194 natural rubber Polymers 0.000 abstract 2
- 229920002857 polybutadiene Polymers 0.000 abstract 2
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 abstract 1
- 150000004826 dibenzofurans Chemical class 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000002341 toxic gas Substances 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 10
- 239000004808 2-ethylhexylester Substances 0.000 description 9
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 9
- 239000004200 microcrystalline wax Substances 0.000 description 9
- 235000019808 microcrystalline wax Nutrition 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 6
- 125000001246 bromo group Chemical class Br* 0.000 description 4
- 150000004768 bromobenzenes Chemical class 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000000176 photostabilization Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- JBZRLVKMCLOFLG-UHFFFAOYSA-N O=S=Cl Chemical compound O=S=Cl JBZRLVKMCLOFLG-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Abstract
The invention relates to a rubber foaming sole material and a manufacturing method thereof, and especially relates to a manufacturing method of the sole footwear products which has high requirements on lightweighting, the flame retardation performance and the wear resistance. The material comprises the following compositions: a chlorosulfonated polyethylene rubber (CSM), a butadiene rubber (BR), a natural rubber (NR), a plasticizer, a strengthening agent, an activator, a coupling agent, a vulcanizing agent, an accelerating agent, and an antioxidant. In the invention, a series of sole materials are prepared through screening coupling agents, accelerating agents, activators, foaming agents, and fire retardants and reasonably controlling a technology on the basis of rubbers, softening oil and the strengthening agent, the lightweight and flame retardation footwear outsole material which has a density of 0.8-1.0g/cm<3> and has a maximum heat release rate of equal to or less than 110KW/m<2> and a DIN abrasion of equal to or less than 120mm<3> in tests with a tapered calorimeter is obtained through optimizing the formula and the technology. The material has the following advantages: 1, the specific gravity is light, and the flame retardation and the wear resistance are excellent; 2, the heat resistance and the light resistance are good, and the fire retardant is not easy to migrate from the surface; and 3, toxic gases of polybrominated dibenzo-p-dioxin (PBDD) and polybrominated dibenzo-furan (PBDF) are not released in combustion when a sole is discarded.
Description
(1) technical field
The present invention relates to a kind of light flame-retardant rubber foaming sole material material and method of manufacture thereof.This material is applicable to the sole to lightweight, fire-retardant, footwear that the wear resisting property requirement is all higher.
(2) background technology
At present, the sole of the brogan that heatproof is had relatively high expectations is a main raw material(s) with X 050 (CR) mainly, is fire retardant with decabromodiphynly oxide and Antimony Trioxide: 99.5Min, makes the sole with anti-flaming function.Yet the X 050 rubber is prone to crystallization, sclerosis when low temperature, and package stability is poor.What shelf lives of X 050 rubber was long is 1 year, and short then only have half a year, and the staging life of rubber is too short, is unfavorable for preserving.And above-mentioned material for sole of shoe exists following not enough: (1) proportion is bigger, and density is at 1.2-1.4g/cm
3Between, sole is heavy, hard, poor, has influenced to wear comfortableness, and foot is easy to generate fatigue, and performance and completion that staff's operating technology of executing the task is moved have produced certain disadvantageous effect; (2) thermotolerance at the bottom of the flame retardant shoes, photostabilization are poor, and fire retardant comes out from surface transport easily, thereby loses flame-retarding characteristic; (3) after shoes were discarded, because the existence of polybrominated diphenyl ether retardant in the sole discharges deleterious many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF) when burning, serious environment pollution threatened human health.For this reason, the research of the light flame-retardant rubber soles novel material of environment-friendly type receives much attention.
Chlorosulfonated polyethylene rubber (CSM) is a kind ofly to make the saturation type elastomerics of main chain with Vilaterm, and photoaging, anti-ozone and chemical resistance were excellent in anti-day, and physicals and processing characteristics are good.The introducing of chlorine makes it possess difficult combustion and oil resistance, makes cross-linking set owing to introduce sulphinyl chlorine simultaneously, makes it as conventional rubber, to be easy to sulfuration.The rerum natura of CSM, price are similar with X 050, and the shelf lives of rubber, than the long 1-2 of the storage period of X 050 doubly, and process industrial art performance was also good than the latter more than 2 years.
Research report about fire-retardant CSM has: Liu Minghui has prepared a kind of flame retardant rubber sheet material in CN 1746211 patents; The flame retardant rubber material of main part that relates to is any in CR, viton, the chlorosulfonated polyethylene rubber; Synergist S-421 95 comprises vulcanizing agent, promoting agent, strengthening agent, promotor, tenderizer, anti-aging agent, weighting agent and fire retardant; Its Shao Er A type hardness tester scope is the 70-90 degree, and it is nonflammable to leave naked light, and flame retardant effect is excellent.
The money Huanghai Sea etc. are at technology, the vulcanization system of 2006 " world rubber industry " the 33rd volume the 2nd phase 14-17 page or leaf to chlorosulfonated polyethylene rubber, and sufficient research and discussion have been carried out in aspects such as low-temperature performance; The rubber compounding of design, not only use characteristics is outstanding, and sulfuration is able to solve, and resistance to low temperature is greatly improved, and flame retardant properties more meets environmental protection standard.
It is the fire-retardant core conveyer belt prescription of material of main part that Zhang Baowei has designed with chlorosuphonated-polyethylene (CSM)/chlorinatedpolyethylene (CPE)/epichlorohydrin rubber (CO) at 2002 " rubber industry " the 49th volume 225-228 page or leaf.Concrete prescription is: CSM/CPE/CO 50/25/25, lead sulfate tribasic 5, dibasic lead phosphite 4, vulcanizing agent DCP 3.5, co-cure agent TAIC 1.5, co-cure agent HVA-21.5, antioxidant MB 1.5, antioxidant NBC 1.0, anti-aging agent RD 1.0, fire retardant TBC 8.0, Antimony Trioxide: 99.5Min 10, white lake 25, fire retardant TCEP 15, pottery scholar 20, talcum powder 30, static inhibitor 3, high wear-resistant carbon black 12.
Wu Daohu etc. coat the development and the exploitation of glue at the detailed antiseptic fire-retardation CSM travelling belt of having inquired into 105 ℃ of temperature resistant grades of 1997 " specialty elastomer goods " the 18th volume 10-16 page or leaf; It cooperates as follows basically: CSM-40/CSM-20 70-80/30-20, tribasic span come lead plumbate 40-44, washing potter's clay and LEE whiten powder 70-80, white lake 45-60; The rubber item resistance to elevated temperatures and the physical and mechanical properties of development are good; And has good oil resistant, anti-extraction, the acidproof antiseptic property that waits.
Li Jingwu etc. at the rational formula (material and mass parts) that " electric wire " the 4th phase in 1997 25-29 page or leaf has designed used for rolling stock flame retardant cable CSM sheath material are: CSM 100; Vulcanization system (PbO+MgO+HVA-2+DPTT) 18.5-19.5; Softening system (TOTM+WB350+ paraffin) 23-26; Fire retardant (white lake+Antimony Trioxide: 99.5Min+molybdic oxide) 70-80; Filler reinforcement system (calcinated argil+LEE whiten powder ten light calcium carbonates+WHITE CARBON BLACK) 75-85; Antioxidant NBC 2-3; Surface-treated agent 1.2-1.4; Other 10-15.
Strict spring sun-light etc. are used prescription at the chlorosuphonated-polyethylene of " electric wire " the 3rd phase in 1993 21-23 page or leaf design and the fire retardant jacket flexible cable of natural minor official glue and usefulness; Used fire retardant has clorafin; Decabromodiphynly oxide; Antimony Trioxide: 99.5Min and white lake, and enumerated the combustion test situation of six kinds of prescriptions, and the use properties of fire-retardant rubber cover finished product flexible cable.
More than have following problem about the research of fire-retardant CSM report: about the vulcanization system of CSM, as adopting plumbous oxide, though the cross-linked rubber quality is good, its black in color, and toxicity is bigger, unfavorable to environmental protection; About the flame-retardant system of CSM, as adopting PBDE, deleterious many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF) are emitted in then material waste gas afterfire, and serious environment pollution threatens human health.More than the research majority is to be used for aspects such as electric wire, travelling belt coating glue, fire retarding conveying band, spread goods.
About fire-retardant chlorosulfonated polyethylene rubber, the research that particularly flame-retardant expanded chlorosulfonated polyethylene rubber is used for sole does not appear in the newspapers.The present invention will be main raw material with CSM, adopt vulcanization system, flame-retardant system, the foaming system of environment-friendly type, preparation lightweight, fire-retardant, attrition resistant comfortable environment-protection type flame retardant shoes bottom material.
(3) summary of the invention
The present invention aims to provide a kind of light flame-retardant rubber foaming sole material material and method of manufacture thereof.
The said a kind of light flame-retardant rubber foaming sole material material of the present invention, its component and mass ratio are:
The strengthening agent that the present invention adopted is a precipitator method hydrated SiO 2, claims WHITE CARBON BLACK again.Softening agent described here is at least a in the hot fat (TOTM) of dioctyl sebacate (DOS), tri trimellitate, the Tritolyl Phosphate (TCP).
Described fire retardant is ammonium polyphosphate, anhydrous zinc borate, contain at least a in hydrate zinc borate, brominated polystyrene, the TDE.
Described whipping agent is 4,4 '-compsn of OBSH (OBSH), Cellmic C 121 (AC) or AC and sodium hydrogencarbonate.
Described promoting agent is at least a in glycol ether (DEG), polyoxyethylene glycol (PEG), tetramethylolmethane (PER), TriMethylolPropane(TMP), the trimethylolethane.
Described coupling agent is at least a in tetra-sulfurized pair (triethoxy propyl group) silane (Si-69), two-(3-triethoxyl silane propyl group)-disulphide (Si-75), 3-aminopropyl triethoxysilane (KH550), the 3-mercaptopropyltriethoxysilane (KH580).
Described vulcanizing agent is at least a in sulphur (S), Natural manganese dioxide (MgO), zinc oxide (ZnO), cyanacrylate (TAIC), the epoxy resin.
Described promotor is 2,2 '-at least a in the dibenzothiazole disulfide (DM, MBTS), tetramethylthiuram monosulfide (TMTM, TS), 2-thiol benzothiazole (M, MBT), tetramethyl-thiuram disulfide (TMTD, TT), tetraethylthiuram disulfide (TETD), bis-pentamethylenethiuram tetrasulfide (DPTT, TRA).
Anti-aging agent described here comprises chemical antiager and physical antioxidant; Wherein said chemical antiager is N, N-nickel dibutyl dithiocarbamate (NBC), N-sec.-propyl-N '-diphenyl-para-phenylene diamine (4010NA), 2 mercapto benzimidazole (MB), 2,2; 4-trimethylammonium-1; 2-dihyaroquinoline polymer (RD, TMQ), N-(1 (4020, at least a in 6PPD); Described physical antioxidant is at least a in paraffin wax, Microcrystalline Wax, the antifog wax.
The present invention can also add this area other processing aids commonly used, like pigment, white dyes, photostabilizer etc.
A kind of light weight flame retardant rubber foaming sole material of the present invention and method of manufacture thereof is characterized in that method of manufacture described here comprises order of addition(of ingredients) and two aspects of preparation technology:
(1) order of addition(of ingredients): 1. add cis-butadiene cement, tree elastomer, chlorosulfonated polyethylene rubber; 2. add strengthening agent; 3. add Zinic stearas, coupling agent and softening oil; 4. add anti-aging agent, promoting agent; 5. add fire retardant, whipping agent; 6. add promotor; 7. add vulcanizing agent; (2) preparation technology: the tree elastomer in the above-mentioned weight proportion is plasticated with mill in 45～55 ℃ of scopes, and the roll spacing of mill is adjusted into 3～4mm, makes it reach certain plasticity number and takes off for use; The roll spacing of mill is adjusted to 1mm; Again cis-1,4-polybutadiene rubber, chlorosuphonated-polyethylene being crossed roller takes off for 1～2 time; And then the tree elastomer that will plasticate carries out mixing with cis-1,4-polybutadiene rubber, the chlorosuphonated-polyethylene of crossing roller with mill; Mixing roller temperature control in 55～65 ℃ of scopes, mixing time 5～8 minutes; Roll spacing with mill is adjusted into 3～4mm then, adds various auxiliary agents by said sequence, and mixing roller temperature still is controlled in 55～65 ℃ of scopes; Treat that at last the roller temperature drops to below 60 ℃, add vulcanizing agent and approach logical 3 times that roll spacing is set at 1mm, thick logical 2 slices require cut-parts with slitter according to setting then, and at room temperature park the above compression molding of 24h, the flame-retardant expanded rubber-sole of preparation light weight.
The present invention has prepared a series of material for sole of shoe through the screening of coupling agent, promotor, promoting agent, whipping agent, fire retardant and the reasonable control of technology on rubber, softening oil and strengthening agent basis, see embodiment 1～8 for details.The advantage of this kind light weight flame retardant rubber foaming sole material is following: (1) proportion is lighter, and specific density is at 0.8～1.0g/cm
3Between; (2) thermotolerance at the bottom of the flame retardant shoes, photostabilization are good, and fire retardant is difficult for coming out from surface transport; (3) after shoes are discarded, when burning, do not discharge deleterious many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF), meet Germany simultaneously yet about the regulations of dioxin and the regulation of EPA.
The present invention can adopt mill, Banbury mixer to carry out blend, slice.Adopt method processing such as injection moulding, mold pressing, notes pressure, its Application Areas relates to sole, rubber pad and all kinds of rubber items thereof etc.
(4) embodiment
Embodiment 1:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 3.0 parts of PEG, TOTM5.0 part, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 418s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 58 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.25g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 79mm
3Press GB1040 standard testing tensile strength 20.2MPa, elongation at break 653%; Press GB/T 3903.12-2005 standard testing angle tear strength 37N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 392kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 2:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 10 parts of brominated polystyrenes, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 406s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 63 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.29g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 86mm
3Press GB1040 standard testing tensile strength 12.3MPa, elongation at break 573%; Press GB/T 3903.12-2005 standard testing angle tear strength 35N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 132kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 3:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 20 parts of brominated polystyrenes, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 400s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 64 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.32g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 99mm
3Press GB1040 standard testing tensile strength 11.4MPa, elongation at break 583%; Press GB/T 3903.12-2005 standard testing angle tear strength 36N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 118kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 4:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 30 parts of brominated polystyrenes, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 393s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 67 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.35g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 124mm
3Press GB1040 standard testing tensile strength 9.6MPa, elongation at break 530%; Press GB/T 3903.12-2005 standard testing angle tear strength 39N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 92kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 5:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 40 parts of brominated polystyrenes, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 388s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 68 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.38g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 144mm
3Press GB1040 standard testing tensile strength 8.0MPa, elongation at break 531%; Press GB/T 3903.12-2005 standard testing angle tear strength 36N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 105kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 6:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 20 parts of brominated polystyrenes, 1.0 parts of OBSH, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 479s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 51 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 0.9g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 117mm
3Press GB1040 standard testing tensile strength 9.0MPa, elongation at break 607%; Press GB/T 3903.12-2005 standard testing angle tear strength 29N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 101kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 7:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 30 parts of brominated polystyrenes, 1.0 parts of OBSH, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 457s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 47 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 1.0g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 140mm
3Press GB1040 standard testing tensile strength 5.7MPa, elongation at break 545%; Press GB/T 3903.12-2005 standard testing angle tear strength 23N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 109kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 8:
Forming (mass ratio) is: 85 parts of CSM, 15 parts of BR, 30 parts of WHITE CARBON BLACKs, 20 parts of brominated polystyrenes, 1.5 parts of OBSH, 3.0 parts of PEG, 5.0 parts of TOTM, 5.0 parts in Natural manganese dioxide, 3.0 parts of DPTT, 0.5 part of TAIC, 2.0 parts of tetramethylolmethanes, 1.0 parts of Zinic stearass, 1.0 parts of antioxidant NBCs, 0.5 part of Microcrystalline Wax.
By said ratio weighing, mixing, t when no rotor rheometer records 150 ℃ of the engineering sulfurizing times of rubber unvulcanizate by above-mentioned technology
90Be 476s, then compression molding under 150 ℃ of conditions.Sample is tested its hardness (Shore A) 48 more than 22.0 ℃ of condition held of room temperature 24h, specific density is 0.8g/cm
3Press QB/T2884-2007 standard testing DIN abrasion and be 119mm
3Press GB1040 standard testing tensile strength 6.7MPa, elongation at break 551%; Press GB/T 3903.12-2005 standard testing angle tear strength 27N/mm.Learn that through the test of taper calorimeter the maximum heat rate of release during this material combustion is 109kW/m by ASTM E 1354/ISO5660 standard
2
Embodiment 1-5 can know that relatively along with the fire retardant consumption strengthens, the maximum heat rate of release is by 392kW/m
2Progressively be reduced to 132kW/m
2, 118kW/m
2, 92kW/m
2, 105kW/m
2This shows that the add-on of fire retardant brominated polystyrene is less than 30 parts the time in this system, the maximum heat rate of release reduces gradually, yet, further strengthening the fire retardant consumption, the maximum heat rate of release increases on the contrary, and flame retardant effect descends on the contrary.Tensile strength progressively descend, yet fire retardant has 20 parts to be increased to 30 parts along with fire retardant increases, and tensile strength changes very little.Exceed most is that along with the fire retardant consumption increases, angle tear strength is influenced hardly, even when fire retardant added 30 parts, it is best that tear strength reaches unexpectedly.The density of material is along with the adding of fire retardant, and density progressively increases.Along with the fire retardant consumption increases, DIN wears and tears progressively by 99mm
3Rise to 144mm
3, visible, along with the fire retardant consumption increases, its wear resistance descends.By above analysis, take all factors into consideration the balance between flame retardant properties, wear resisting property and the mechanical property, add 20～30 parts of researchs of carrying out flame-retardant foam material with fire retardant.
Embodiment 3 and embodiment 6, embodiment 8 can know that relatively in this system, add the fire retardant of equal parts (promptly 20 parts), after foaming, specific density is by 1.32g/cm
3Reduce to 0.9g/cm
3, even reduce to 0.8g/cm
3, see that from taper calorimeter test result the maximum heat rate of release changes little, this shows that before and after this fire retardant material foaming, flame retardant properties does not have considerable change; Tensile strength, tear strength descend to some extent; Wear resisting property is worn and torn by 99mm by DIN
3Reduce to 117mm
3, 119mm
3, but as the footwear outer bottom, its wear resisting property is still very excellent.
Embodiment 4 and embodiment 7 relatively can know, in this system, add 30 parts of fire retardants, and after foaming, specific density is by 1.35g/cm
3Reduce to 1.0g/cm
3See that from taper calorimeter test result the maximum heat rate of release is by 92kW/m
2Increase to 109kW/m
2, before and after the foaming, flame retardant properties slightly descends; Tensile strength, tear strength descend more obvious; The DIN abrasion are by 124mm
3Reduce to 140mm
3
Can know by above analysis, in system involved in the present invention, when adding 20 parts of fire retardants, can obtain a well balanced between flame retardant properties, specific density, the mechanical property.
Embodiment 6 and 8 prepared rubber soles materials among the present invention have light specific gravity, flame retardant properties is good, and good abrasion resistance and mechanical property are arranged again simultaneously.The advantage of this light weight flame retardant shoes bottom material is following: proportion is lighter, and specific density is at 0.8～1.0g/cm
3Between; Wear resisting property is excellent; Thermotolerance, photostabilization at the bottom of the flame retardant shoes are good, and fire retardant is difficult for coming out from surface transport; After sole is discarded, when burning, do not discharge deleterious many bromobenzenes Dui Wei dioxin (PBDD) and many bromines dibenzofuran (PBDF), meet Germany about the regulations of dioxin and the regulation of EPA.
In sum, the rubber soles with light weight, anti-flaming function that the present invention is prepared can promote the competitiveness of product in market, and good economic benefit and social benefit are arranged, and bright development prospect is arranged.
The used starting material of the present invention are commercial prod.Used chlorosulfonated polyethylene rubber (CSM) is Du Pont (Dupont) product among the present invention, and the trade mark is H40.Cis-butadiene cement is that petrochemical complex limited-liability company Beijing, Beijing Yanshan Mountain branch office produces, and the trade mark is BR9000.Tree elastomer (NR) adopts safe home-made STR-5L.
Taper calorimeter test condition that the present invention carried out and testing tool title, model details are following:
(1) sample size: 10mm * 10mm * 6mm;
(2) instrument title: taper calorimeter, model: FTT Standard Cone Calorimeter, manufacturer: Fire Testing Technology, Limited, U.K..
(3) test condition: each sample is 35kW/m in radiation power all
2Test under (heat flow rate per unit area of typical small-sized fire) condition, the actual emanations area of sample is 0.01m
2, exhaust gas flow is 24L/s.
Claims (9)
1. light flame-retardant rubber foaming sole material material is characterized in that its component and mass ratio are:
Wherein, said whipping agent be 4,4 '-compsn of OBSH, Cellmic C 121 or Cellmic C 121 and sodium hydrogencarbonate.
2. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that strengthening agent is a precipitator method hydrated SiO 2, claims WHITE CARBON BLACK again.
3. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that softening agent is at least a in the hot fat of dioctyl sebacate, tri trimellitate, the Tritolyl Phosphate.
4. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that fire retardant is ammonium polyphosphate, anhydrous zinc borate, contains at least a in hydrate zinc borate, brominated polystyrene, the TDE.
5. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that promoting agent is at least a in glycol ether, polyoxyethylene glycol, tetramethylolmethane, TriMethylolPropane(TMP), the trimethylolethane.
6. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that coupling agent is at least a in tetra-sulfurized pair (triethoxy propyl group) silane, two-(3-triethoxyl silane propyl group)-disulphide, 3-aminopropyl triethoxysilane, the 3-mercaptopropyltriethoxysilane.
7. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that vulcanizing agent is at least a in sulphur, Natural manganese dioxide, zinc oxide, cyanacrylate, the epoxy resin.
8. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1; It is characterized in that promotor be 2,2 '-at least a in the dibenzothiazole disulfide, tetramethylthiuram monosulfide, 2-thiol benzothiazole, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, bis-pentamethylenethiuram tetrasulfide.
9. a kind of light flame-retardant rubber foaming sole material material as claimed in claim 1 is characterized in that its preparation method is following: (1) order of addition(of ingredients): 1. add cis-butadiene cement, tree elastomer, chlorosulfonated polyethylene rubber; 2. add strengthening agent; 3. add Zinic stearas, coupling agent and softening agent; 4. add anti-aging agent, promoting agent; 5. add fire retardant, whipping agent; 6. add promotor; 7. add vulcanizing agent; (2) preparation technology: the tree elastomer in the above-mentioned weight proportion is plasticated with mill in 45～55 ℃ of scopes, and the roll spacing of mill is adjusted into 3～4mm, makes it reach certain plasticity number and takes off for use; The roll spacing of mill is adjusted to 1mm; Again cis-1,4-polybutadiene rubber, chlorosuphonated-polyethylene being crossed roller takes off for 1～2 time; And then the tree elastomer that will plasticate carries out mixing with cis-1,4-polybutadiene rubber, the chlorosuphonated-polyethylene of crossing roller with mill; Mixing roller temperature control in 55～65 ℃ of scopes, mixing time 5～8 minutes; Roll spacing with mill is adjusted into 3～4mm then, adds various auxiliary agents by said sequence, and mixing roller temperature still is controlled in 55～65 ℃ of scopes; Treat that at last the roller temperature drops to below 60 ℃, add vulcanizing agent and approach logical 3 times that roll spacing is set at 1mm, thick logical 2 slices require cut-parts with slitter according to setting then, and at room temperature park the above compression molding of 24h, the flame-retardant expanded rubber-sole of preparation light weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102031180A CN102311588B (en) | 2011-07-20 | 2011-07-20 | Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102031180A CN102311588B (en) | 2011-07-20 | 2011-07-20 | Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102311588A true CN102311588A (en) | 2012-01-11 |
| CN102311588B CN102311588B (en) | 2012-12-12 |
Family
ID=45425177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102031180A Expired - Fee Related CN102311588B (en) | 2011-07-20 | 2011-07-20 | Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102311588B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604171A (en) * | 2012-03-16 | 2012-07-25 | 中国皮革和制鞋工业研究院 | Production process for rubber foam material by means of compression molding |
| CN102816351A (en) * | 2012-08-27 | 2012-12-12 | 苏州伟伦运动休闲用品有限公司 | Low-specific-gravity rubber foam sole and production method thereof |
| CN103102605A (en) * | 2013-03-07 | 2013-05-15 | 中国皮革和制鞋工业研究院 | Environmentally-friendly ultralight flame-retardant rubber sole material and manufacturing method thereof |
| CN103627161A (en) * | 2013-11-20 | 2014-03-12 | 济南开发区星火科学技术研究院 | Environment-friendly corrosion-resistant epichlorohydrin rubber |
| CN103724695A (en) * | 2013-12-13 | 2014-04-16 | 芜湖佳诚电子科技有限公司 | High-strength uvioresistant rectangular ring |
| CN103865109A (en) * | 2012-12-14 | 2014-06-18 | 中国人民解放军总后勤部军需装备研究所 | Compact/foamed rubber sole and its special foaming rubber |
| CN103960816A (en) * | 2014-05-22 | 2014-08-06 | 浙江润阳新材料科技有限公司 | Shoe sole used for diabetic patient and slipper made of shoe sole |
| CN104356441A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Wear-resistant antistatic rubber shoe sole and preparation method thereof |
| CN106117655A (en) * | 2016-07-29 | 2016-11-16 | 王莹 | A kind of anti-slippery butadiene rubber material |
| CN107200946A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of chlorosulfonated polyethylene microcellular foam material and preparation method thereof |
| CN107236164A (en) * | 2017-07-28 | 2017-10-10 | 扬州多力鞋服有限公司 | A kind of high-temperature insulation is anti-to pierce through anti-skid multifunctional safety shoe |
| CN108102235A (en) * | 2017-12-20 | 2018-06-01 | 青岛科技大学 | The crawler belt rubber material and preparation method used under a kind of particular surroundings |
| CN108329609A (en) * | 2018-02-27 | 2018-07-27 | 合肥择浚电气设备有限公司 | A kind of high-strength Antistatic insulating material of heat-proof combustion-resistant and preparation method thereof |
| CN108570169A (en) * | 2017-03-08 | 2018-09-25 | 阿乐斯企业有限两合公司 | Flexible foam with improved isolation performance |
| CN109181131A (en) * | 2018-09-20 | 2019-01-11 | 安徽江淮汽车集团股份有限公司 | A kind of CSM foamed material and preparation method thereof |
| CN110041633A (en) * | 2019-05-09 | 2019-07-23 | 广州市欧橡隔热材料有限公司 | Natural rubber and preparation method thereof |
| CN111234400A (en) * | 2020-03-31 | 2020-06-05 | 界首市通达塑业有限公司 | Light-weight flame-retardant rubber sole material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154296A (en) * | 1995-10-25 | 1997-07-16 | 株式会社东星化学 | Method for manufacturing outsoles of shoes |
| CN1746211A (en) * | 2004-09-06 | 2006-03-15 | 刘明辉 | Fire-retardant rubber plate |
| CN101255243A (en) * | 2008-04-02 | 2008-09-03 | 际华三五一四制革制鞋有限公司 | Double-density shoe leather fast curing rubber size suitable for injection technique and production method thereof |
| CN101759939A (en) * | 2008-12-25 | 2010-06-30 | 李宁体育(上海)有限公司 | High wear-resistant foaming rubber and shoe outsole produced from same |
| CN101885865A (en) * | 2010-08-09 | 2010-11-17 | 中国皮革和制鞋工业研究院 | High shock-resistant, wear-resistant sport shoe sole material and manufacturing method thereof |
-
2011
- 2011-07-20 CN CN2011102031180A patent/CN102311588B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154296A (en) * | 1995-10-25 | 1997-07-16 | 株式会社东星化学 | Method for manufacturing outsoles of shoes |
| CN1746211A (en) * | 2004-09-06 | 2006-03-15 | 刘明辉 | Fire-retardant rubber plate |
| CN101255243A (en) * | 2008-04-02 | 2008-09-03 | 际华三五一四制革制鞋有限公司 | Double-density shoe leather fast curing rubber size suitable for injection technique and production method thereof |
| CN101759939A (en) * | 2008-12-25 | 2010-06-30 | 李宁体育(上海)有限公司 | High wear-resistant foaming rubber and shoe outsole produced from same |
| CN101885865A (en) * | 2010-08-09 | 2010-11-17 | 中国皮革和制鞋工业研究院 | High shock-resistant, wear-resistant sport shoe sole material and manufacturing method thereof |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604171B (en) * | 2012-03-16 | 2014-01-29 | 中国皮革和制鞋工业研究院 | Production process for rubber foam material by means of compression molding |
| CN102604171A (en) * | 2012-03-16 | 2012-07-25 | 中国皮革和制鞋工业研究院 | Production process for rubber foam material by means of compression molding |
| CN102816351A (en) * | 2012-08-27 | 2012-12-12 | 苏州伟伦运动休闲用品有限公司 | Low-specific-gravity rubber foam sole and production method thereof |
| CN103865109A (en) * | 2012-12-14 | 2014-06-18 | 中国人民解放军总后勤部军需装备研究所 | Compact/foamed rubber sole and its special foaming rubber |
| CN103865109B (en) * | 2012-12-14 | 2016-01-27 | 中国人民解放军总后勤部军需装备研究所 | A kind of closely knit/Foamed rubber shoe sole and special-purpose foaming rubber thereof |
| CN103102605A (en) * | 2013-03-07 | 2013-05-15 | 中国皮革和制鞋工业研究院 | Environmentally-friendly ultralight flame-retardant rubber sole material and manufacturing method thereof |
| CN103627161A (en) * | 2013-11-20 | 2014-03-12 | 济南开发区星火科学技术研究院 | Environment-friendly corrosion-resistant epichlorohydrin rubber |
| CN103724695A (en) * | 2013-12-13 | 2014-04-16 | 芜湖佳诚电子科技有限公司 | High-strength uvioresistant rectangular ring |
| CN103960816A (en) * | 2014-05-22 | 2014-08-06 | 浙江润阳新材料科技有限公司 | Shoe sole used for diabetic patient and slipper made of shoe sole |
| CN104356441A (en) * | 2014-11-13 | 2015-02-18 | 茂泰(福建)鞋材有限公司 | Wear-resistant antistatic rubber shoe sole and preparation method thereof |
| CN107200946B (en) * | 2016-03-16 | 2022-08-12 | 青岛科技大学 | Chlorosulfonated polyethylene microporous foam material and preparation method thereof |
| CN107200946A (en) * | 2016-03-16 | 2017-09-26 | 青岛科技大学 | A kind of chlorosulfonated polyethylene microcellular foam material and preparation method thereof |
| CN106117655A (en) * | 2016-07-29 | 2016-11-16 | 王莹 | A kind of anti-slippery butadiene rubber material |
| CN108570169A (en) * | 2017-03-08 | 2018-09-25 | 阿乐斯企业有限两合公司 | Flexible foam with improved isolation performance |
| CN108570169B (en) * | 2017-03-08 | 2021-11-12 | 阿乐斯企业有限两合公司 | Flexible foam with improved insulating properties |
| CN107236164B (en) * | 2017-07-28 | 2018-12-18 | 扬州多力鞋服有限公司 | A kind of anti-puncture anti-skid multifunctional safety shoe of high-temperature insulation |
| CN107236164A (en) * | 2017-07-28 | 2017-10-10 | 扬州多力鞋服有限公司 | A kind of high-temperature insulation is anti-to pierce through anti-skid multifunctional safety shoe |
| CN108102235A (en) * | 2017-12-20 | 2018-06-01 | 青岛科技大学 | The crawler belt rubber material and preparation method used under a kind of particular surroundings |
| CN108102235B (en) * | 2017-12-20 | 2020-03-10 | 青岛科技大学 | Rubber material for crawler belt used in special environment and preparation method thereof |
| CN108329609A (en) * | 2018-02-27 | 2018-07-27 | 合肥择浚电气设备有限公司 | A kind of high-strength Antistatic insulating material of heat-proof combustion-resistant and preparation method thereof |
| CN109181131A (en) * | 2018-09-20 | 2019-01-11 | 安徽江淮汽车集团股份有限公司 | A kind of CSM foamed material and preparation method thereof |
| CN110041633A (en) * | 2019-05-09 | 2019-07-23 | 广州市欧橡隔热材料有限公司 | Natural rubber and preparation method thereof |
| CN111234400A (en) * | 2020-03-31 | 2020-06-05 | 界首市通达塑业有限公司 | Light-weight flame-retardant rubber sole material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102311588B (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311588B (en) | Lightweight, flame retardant and rubber foaming sole material and manufacturing method thereof | |
| CN103637462B (en) | A kind of industrial and mining enterprises protection rubber overshoes | |
| CN103642097B (en) | A kind of preparation method of the nitrile rubber for preparing high abrasion float grease seal sealing ring | |
| CN102276884B (en) | High-strength high-elongation wear-resistant environmentally-friendly rubber sole rubber and preparation method thereof | |
| CN106459498B (en) | Coating rubber composition used for conveyer belt | |
| CN103102605A (en) | Environmentally-friendly ultralight flame-retardant rubber sole material and manufacturing method thereof | |
| CN102417668A (en) | Cable sheath material for wind power generation and production method thereof | |
| CN105331000A (en) | Cover rubber for high-abrasion-resistance flame-retardant steel wire rope core conveying belt and preparation method thereof | |
| CN103965524A (en) | Low-temperature-resistant sole material and preparation method thereof | |
| CN103131067A (en) | Shipboard cable CR and CPE blending type sheath rubber | |
| CN104961929A (en) | Low-smoke flame-retardant rubber cable material and preparation method thereof | |
| CN102501481A (en) | Composite fluororubber adhesive plaster and preparation method thereof | |
| CN103113640A (en) | High-performance freezing-resistant and flame-retardant chloroprene rubber covering material | |
| CN104072824A (en) | Special cable material for styrene-butadiene rubber sleeved field detection cable and preparation method of special cable material | |
| CN107189145A (en) | A kind of rubber composition and preparation method thereof | |
| TWI706982B (en) | Rubber composition for hose and hose | |
| CN103333373A (en) | Acid and alkali resistant rubber boot vamp rubber compound and preparation method thereof | |
| CN102070800B (en) | Nitrile rubber protective sleeve | |
| KR101661515B1 (en) | Method for cork-synthetic rubber vulcanized product | |
| CN107216560B (en) | A kind of kevlar fabric unitary-core flame-resistant conveying belt and its manufacturing method | |
| CN104705871A (en) | Blended rubber special protective fabric | |
| US6874165B2 (en) | Modified NBR gloves | |
| CN106084510B (en) | A kind of haloflex colour oil resistant fire retarding conveying band and manufacturing method | |
| CN103483643A (en) | Rubber composition for firefighting shoes | |
| CN105860298B (en) | A kind of footwear environmental-protection flame-retardant fire proofing material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121212 Termination date: 20200720 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| DD01 | Delivery of document by public notice |
Addressee: Wang Yunmajingwen Document name: Notice of termination of patent right |
|
| DD01 | Delivery of document by public notice |