CN105238009B - A kind of high-strength abrasion-proof oil resistant polyurethane elastomer - Google Patents
A kind of high-strength abrasion-proof oil resistant polyurethane elastomer Download PDFInfo
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- CN105238009B CN105238009B CN201510654521.3A CN201510654521A CN105238009B CN 105238009 B CN105238009 B CN 105238009B CN 201510654521 A CN201510654521 A CN 201510654521A CN 105238009 B CN105238009 B CN 105238009B
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- polyurethane elastomer
- resistant polyurethane
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- strength abrasion
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 24
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 20
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960000892 attapulgite Drugs 0.000 claims abstract description 11
- 239000004330 calcium propionate Substances 0.000 claims abstract description 11
- 235000010331 calcium propionate Nutrition 0.000 claims abstract description 11
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- -1 Alkene ester Chemical class 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 9
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- 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 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical group C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 claims 1
- FIBARIGPBPUBHC-UHFFFAOYSA-N octyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCCC1OC1CCCCCCCC FIBARIGPBPUBHC-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229940117958 vinyl acetate Drugs 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 24
- 239000002131 composite material Substances 0.000 abstract description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 10
- 239000003831 antifriction material Substances 0.000 abstract description 10
- 150000002009 diols Chemical class 0.000 abstract description 10
- 239000004417 polycarbonate Substances 0.000 abstract description 10
- 229920000515 polycarbonate Polymers 0.000 abstract description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 10
- 229910021485 fumed silica Inorganic materials 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 6
- 229940057995 liquid paraffin Drugs 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 description 3
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical class NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM80‑120份、聚碳酸酯二元醇60‑90份、壬二酸二辛酯10‑30份、乙氧基化烷基酚硫酸铵5‑15份、甲苯二异氰酸酯2‑8份、丙酸钙3‑6份、气相白炭黑1‑5份、凹凸棒土2‑8份、氧化钙3‑9份、双酚a二缩水甘油醚2‑5份、环氧硬脂酸辛酯1‑6份、复合填料3‑5份、减磨剂2‑4份、硫化剂1‑4份、抗氧化剂2‑6份、交联助剂1‑8份、促进剂2‑6份、扩链剂3‑7份。本发明所述的高强度耐磨耐油聚氨酯弹性体强度高，耐磨和耐油性能优异。The invention discloses a high-strength wear-resistant and oil-resistant polyurethane elastomer. The raw materials include: 80-120 parts of ethylene vinyl acetate EVM, 60-90 parts of polycarbonate diol, and 10-10 parts of dioctyl azelate 30 parts, 5-15 parts of ethoxylated alkylphenol ammonium sulfate, 2-8 parts of toluene diisocyanate, 3-6 parts of calcium propionate, 1-5 parts of fumed silica, 2-8 parts of attapulgite, 3-9 parts of calcium oxide, 2-5 parts of bisphenol A diglycidyl ether, 1-6 parts of epoxy octyl stearate, 3-5 parts of composite filler, 2-4 parts of anti-friction agent, 1-4 parts of vulcanizing agent 2-6 parts of antioxidant, 1-8 parts of cross-linking auxiliary agent, 2-6 parts of accelerator, 3-7 parts of chain extender. The high-strength wear-resistant and oil-resistant polyurethane elastomer of the invention has high strength and excellent wear-resistant and oil-resistant properties.
Description
技术领域technical field
本发明涉及聚氨酯材料领域，尤其涉及一种高强度耐磨耐油聚氨酯弹性体。The invention relates to the field of polyurethane materials, in particular to a high-strength wear-resistant and oil-resistant polyurethane elastomer.
背景技术Background technique
聚氨酯是一种性能优良的高分子合成材料，既具有橡胶的弹性又有塑料的硬度，而且还具有良好的机械性能、耐磨性能和回弹性能，利用它的这些优点可用来制作滑轮鞋的轮子。聚四氢呋喃体系的高回弹轮料虽然弹性和耐磨性好，但生产成本高而不便于全民推广。而价格低廉的普通的聚醚型聚氨酯弹性体冲击回弹都在50％以下，耐磨性和耐油性差，强度低。Polyurethane is a polymer synthetic material with excellent performance. It has both the elasticity of rubber and the hardness of plastic, and it also has good mechanical properties, wear resistance and resilience. Using its advantages, it can be used to make pulley shoes. wheel. Although the high-resilience wheel material of the polytetrahydrofuran system has good elasticity and wear resistance, the production cost is high and it is not convenient for the general public. However, common polyether polyurethane elastomers with low price have an impact rebound of less than 50%, poor wear resistance and oil resistance, and low strength.
发明内容Contents of the invention
为解决背景技术中存在的技术问题，本发明提出一种高强度耐磨耐油聚氨酯弹性体，强度高，耐磨和耐油性能优异。In order to solve the technical problems in the background technology, the present invention proposes a high-strength wear-resistant and oil-resistant polyurethane elastomer, which has high strength and excellent wear-resistant and oil-resistant properties.
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM80-120份、聚碳酸酯二元醇60-90份、壬二酸二辛酯10-30份、乙氧基化烷基酚硫酸铵5-15份、甲苯二异氰酸酯2-8份、丙酸钙3-6份、气相白炭黑1-5份、凹凸棒土2-8份、氧化钙3-9份、双酚a二缩水甘油醚2-5份、环氧硬脂酸辛酯1-6份、复合填料3-5份、减磨剂2-4份、硫化剂1-4份、抗氧化剂2-6份、交联助剂1-8份、促进剂2-6份、扩链剂3-7份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 80-120 parts of ethylene vinyl acetate EVM, 60-90 parts of polycarbonate diol, 10-10 parts of dioctyl azelate 30 parts, 5-15 parts of ethoxylated alkylphenol ammonium sulfate, 2-8 parts of toluene diisocyanate, 3-6 parts of calcium propionate, 1-5 parts of fumed white carbon black, 2-8 parts of attapulgite, 3-9 parts of calcium oxide, 2-5 parts of bisphenol A diglycidyl ether, 1-6 parts of epoxy octyl stearate, 3-5 parts of composite filler, 2-4 parts of friction reducing agent, 1-4 parts of vulcanizing agent 2-6 parts of antioxidant, 1-8 parts of cross-linking auxiliary agent, 2-6 parts of accelerator, 3-7 parts of chain extender.
优选地，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为80-90％。Preferably, the mass content of vinyl acetate in the ethylene vinyl acetate EVM is 80-90%.
优选地，复合填料按如下工艺进行制备：将聚丙烯和蒙脱土混合均匀，加热至450-500℃，保温10-20min，冷却至常温，然后加入聚四氟乙烯球磨8-16min，得物料a；将轻质碳酸钙和磷酸二氢铝混合均匀，加热至70-90℃，保温5-15min，然后加入季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。Preferably, the composite filler is prepared according to the following process: uniformly mix polypropylene and montmorillonite, heat to 450-500°C, keep warm for 10-20min, cool to room temperature, and then add polytetrafluoroethylene ball mill for 8-16min to obtain the material a; Mix light calcium carbonate and aluminum dihydrogen phosphate evenly, heat to 70-90°C, keep warm for 5-15min, then add pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b evenly, Dried, ground, and cooled to room temperature to obtain a composite filler.
优选地，复合填料的制备工艺中，聚丙烯、蒙脱土、聚四氟乙烯、轻质碳酸钙、磷酸二氢铝和季戊四醇三丙烯酸酯的重量比为2-9：1-5：3-8：4-9：3-4：2-5。Preferably, in the preparation process of the composite filler, the weight ratio of polypropylene, montmorillonite, polytetrafluoroethylene, light calcium carbonate, aluminum dihydrogen phosphate and pentaerythritol triacrylate is 2-9:1-5:3- 8:4-9:3-4:2-5.
优选地，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比2-6：1-3：3-5混合而成。Preferably, the antifriction agent is formed by mixing methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 2-6:1-3:3-5.
优选地，硫化剂为硫磺、过氧化物硫化剂、含氢硅烷硫化剂、树脂类硫化剂中的一种。Preferably, the vulcanizing agent is one of sulfur, peroxide vulcanizing agent, hydrosilane vulcanizing agent and resin vulcanizing agent.
优选地，抗氧化剂为抗氧剂1010、抗氧剂4010、抗氧剂4020中的一种或两种以上组合物。Preferably, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 4010, and antioxidant 4020.
优选地，交联助剂为三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、对醌二肟、二硫化四甲基秋兰姆、烷基化三亚乙基四胺二硫化秋兰姆中的一种或两种以上组合物。Preferably, the crosslinking aid is triallyl cyanurate, triallyl isocyanurate, p-quinone dioxime, tetramethylthiuram disulfide, alkylated triethylenetetramine di A combination of one or more than two kinds of thiuram sulfide.
优选地，促进剂为过氧化二异丙苯或1,3-二特丁基过氧化二异丙苯。Preferably, the accelerator is dicumyl peroxide or 1,3-di-tert-butyl dicumyl peroxide.
优选地，扩链剂为4，4’-二氨基-3，3’-二氯二苯基甲烷、3，5-二甲硫基甲苯二胺和二乙基甲苯二胺中一种或两种以上组合物。Preferably, the chain extender is one or both of 4,4'-diamino-3,3'-dichlorodiphenylmethane, 3,5-dimethylthiotoluenediamine and diethyltoluenediamine the above compositions.
本发明所述的一种高强度耐磨耐油聚氨酯弹性体，其原料包括乙烯醋酸乙烯酯EVM、聚碳酸酯二元醇、壬二酸二辛酯、乙氧基化烷基酚硫酸铵、甲苯二异氰酸酯、丙酸钙、气相白炭黑、凹凸棒土、氧化钙、双酚a二缩水甘油醚、环氧硬脂酸辛酯、复合填料、减磨剂、硫化剂、抗氧化剂、交联助剂、促进剂和扩链剂，其中以乙烯醋酸乙烯酯EVM为主料，辅助添加聚碳酸酯二元醇、壬二酸二辛酯、乙氧基化烷基酚硫酸铵和甲苯二异氰酸酯为乙烯醋酸乙烯酯EVM的辅助添加料，通过合理控制配比，有效提高了乙烯醋酸乙烯酯EVM的强度、耐磨性和耐油性；添加的丙酸钙、气相白炭黑、凹凸棒土和氧化钙作为填料，有效提高了本发明所述高强度耐磨耐油聚氨酯弹性体的强度，添加的双酚a二缩水甘油醚、环氧硬脂酸辛酯、复合填料、减磨剂、硫化剂、抗氧化剂、交联助剂、促进剂和扩链剂作为助剂，有效提高了本发明所述高强度耐磨耐油聚氨酯弹性体的耐油性能和耐磨性能。A high-strength wear-resistant and oil-resistant polyurethane elastomer according to the present invention, its raw materials include ethylene vinyl acetate EVM, polycarbonate diol, dioctyl azelate, ethoxylated alkylphenol ammonium sulfate, toluene Diisocyanate, calcium propionate, fumed silica, attapulgite, calcium oxide, bisphenol a diglycidyl ether, epoxy octyl stearate, composite filler, friction reducing agent, vulcanizing agent, antioxidant, crosslinking assistant Agents, accelerators and chain extenders, in which ethylene vinyl acetate EVM is used as the main material, and polycarbonate diol, dioctyl azelate, ethoxylated alkylphenol ammonium sulfate and toluene diisocyanate are added as auxiliary materials. Auxiliary additives for ethylene vinyl acetate EVM, through reasonable control of the ratio, effectively improve the strength, wear resistance and oil resistance of ethylene vinyl acetate EVM; added calcium propionate, fumed silica, attapulgite and oxidation Calcium is used as a filler to effectively improve the strength of the high-strength wear-resistant and oil-resistant polyurethane elastomer of the present invention. The added bisphenol A diglycidyl ether, epoxy octyl stearate, composite fillers, antifriction The oxidizing agent, cross-linking auxiliary agent, accelerator and chain extender are used as auxiliary agents to effectively improve the oil resistance and wear resistance of the high-strength wear-resistant and oil-resistant polyurethane elastomer of the present invention.
具体实施方式detailed description
下面结合具体实施例对本发明做出详细说明，应当了解，实施例只用于说明本发明，而不是用于对本发明进行限定，任何在本发明基础上所做的修改、等同替换等均在本发明的保护范围内。The present invention will be described in detail below in conjunction with specific embodiments. It should be understood that the embodiments are only used to illustrate the present invention, rather than to limit the present invention. within the scope of protection of the invention.
具体实施方式中，乙烯醋酸乙烯酯EVM的重量份可以为80份、85份、90份、95份、100份、105份、110份、115份、120份；聚碳酸酯二元醇的重量份可以为60份、65份、70份、75份、80份、85份、90份；壬二酸二辛酯的重量份可以为10份、12份、15份、18份、20份、22份、25份、28份、30份；乙氧基化烷基酚硫酸铵的重量份可以为5-15份；甲苯二异氰酸酯的重量份可以为2份、3份、4份、5份、6份、7份、8份；丙酸钙的重量份可以为3份、3.5份、4份、4.5份、5份、5.5份、6份、6.5份、6份；气相白炭黑的重量份可以为1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份；凹凸棒土的重量份可以为2份、3份、4份、5份、6份、7份、8份；氧化钙的重量份可以为3份、4份、5份、6份、7份、8份、9份；双酚a二缩水甘油醚的重量份可以为2份、2.5份、3份、3.5份、4份、4.5份、5份；环氧硬脂酸辛酯的重量份可以为1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份；复合填料的重量份可以为3份、3.5份、4份、4.5份、5份；减磨剂的重量份可以为2份、2.5份、3份、3.5份、4份；硫化剂的重量份可以为1份、1.5份、2份、2.5份、3份、3.5份、4份；抗氧化剂的重量份可以为2份、3份、4份、5份、6份；交联助剂的重量份可以为1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份、6.5份、7份、7.5份、8份；促进剂的重量份可以为2份、3份、4份、5份、6份；扩链剂的重量份可以为3份、4份、5份、6份、7份。In the specific embodiment, the parts by weight of ethylene vinyl acetate EVM can be 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts; The weight of polycarbonate diol Part can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts; The weight part of dioctyl azelate can be 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts; the weight part of ethoxylated alkylphenol ammonium sulfate can be 5-15 parts; the weight part of toluene diisocyanate can be 2 parts, 3 parts, 4 parts, 5 parts , 6 parts, 7 parts, 8 parts; the parts by weight of calcium propionate can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 6 parts; The parts by weight can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts; the parts by weight of attapulgite can be 2 parts, 3 parts, 4 parts, 5 parts , 6 parts, 7 parts, 8 parts; The parts by weight of calcium oxide can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts; The parts by weight of bisphenol a diglycidyl ether can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts; The parts by weight of epoxy octyl stearate can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts; the weight parts of composite filler can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts; the weight parts of friction reducer can be 2 parts, 2.5 parts , 3 parts, 3.5 parts, 4 parts; the parts by weight of vulcanizing agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts; the parts by weight of antioxidant can be 2 parts, 3 parts , 4 parts, 5 parts, 6 parts; the parts by weight of the cross-linking auxiliary agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts; the weight parts of accelerator can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts; the weight parts of chain extender can be 3 parts, 4 parts, 5 copies, 6 copies, 7 copies.
实施例1Example 1
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM100份、聚碳酸酯二元醇75份、壬二酸二辛酯20份、乙氧基化烷基酚硫酸铵10份、甲苯二异氰酸酯5份、丙酸钙4.5份、气相白炭黑3份、凹凸棒土5份、氧化钙6份、双酚a二缩水甘油醚3.5份、环氧硬脂酸辛酯3.5份、复合填料4份、减磨剂3份、硫磺2.5份、抗氧剂10104份、三烯丙基氰脲酸酯4.5份、过氧化二异丙苯4份、4，4’-二氨基-3，3’-二氯二苯基甲烷5份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 100 parts of ethylene vinyl acetate EVM, 75 parts of polycarbonate diol, 20 parts of dioctyl azelate, ethoxylate 10 parts of alkylphenol ammonium sulfate, 5 parts of toluene diisocyanate, 4.5 parts of calcium propionate, 3 parts of fumed silica, 5 parts of attapulgite, 6 parts of calcium oxide, 3.5 parts of bisphenol a diglycidyl ether, cyclic 3.5 parts of octyl oxystearate, 4 parts of composite filler, 3 parts of friction reducing agent, 2.5 parts of sulfur, 10104 parts of antioxidant, 4.5 parts of triallyl cyanurate, 4 parts of dicumyl peroxide, 4 parts , 5 parts of 4'-diamino-3,3'-dichlorodiphenylmethane.
其中，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为85％。Wherein, the mass content of vinyl acetate in ethylene vinyl acetate EVM is 85%.
复合填料按如下工艺进行制备：按重量份将5.5份聚丙烯和3份蒙脱土混合均匀，加热至475℃，保温15min，冷却至常温，然后加入5.5份聚四氟乙烯球磨12min，得物料a；将6.5份轻质碳酸钙和3.5份磷酸二氢铝混合均匀，加热至80℃，保温10min，然后加入3.5份季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。The composite filler is prepared according to the following process: mix 5.5 parts of polypropylene and 3 parts of montmorillonite uniformly by weight, heat to 475 ° C, keep warm for 15 minutes, cool to room temperature, and then add 5.5 parts of polytetrafluoroethylene and ball mill for 12 minutes to obtain the material a; Mix 6.5 parts of light calcium carbonate and 3.5 parts of aluminum dihydrogen phosphate evenly, heat to 80°C, keep warm for 10 minutes, then add 3.5 parts of pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b Homogenize, dry, grind, and cool to room temperature to obtain a composite filler.
其中，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比4：2：4混合而成。Among them, the antifriction agent is a mixture of methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 4:2:4.
实施例2Example 2
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM80份、聚碳酸酯二元醇90份、壬二酸二辛酯10份、乙氧基化烷基酚硫酸铵15份、甲苯二异氰酸酯2份、丙酸钙6份、气相白炭黑1份、凹凸棒土8份、氧化钙3份、双酚a二缩水甘油醚5份、环氧硬脂酸辛酯1份、复合填料5份、减磨剂2份、过氧化物硫化剂4份、抗氧剂40102份、三烯丙基异氰脲酸酯8份、1,3-二特丁基过氧化二异丙苯2份、3，5-二甲硫基甲苯二胺7份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 80 parts of ethylene vinyl acetate EVM, 90 parts of polycarbonate diol, 10 parts of dioctyl azelate, ethoxylate 15 parts of alkylphenol ammonium sulfate, 2 parts of toluene diisocyanate, 6 parts of calcium propionate, 1 part of fumed silica, 8 parts of attapulgite, 3 parts of calcium oxide, 5 parts of bisphenol a diglycidyl ether, cyclic 1 part of octyl oxystearate, 5 parts of composite filler, 2 parts of antifriction agent, 4 parts of peroxide curing agent, 40102 parts of antioxidant, 8 parts of triallyl isocyanurate, 1,3-di 2 parts of dicumyl peroxide and 7 parts of 3,5-dimethylthiotoluenediamine.
其中，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为80％。Wherein, the mass content of vinyl acetate in ethylene vinyl acetate EVM is 80%.
复合填料按如下工艺进行制备：按重量份将2份聚丙烯和5份蒙脱土混合均匀，加热至450℃，保温20min，冷却至常温，然后加入3份聚四氟乙烯球磨16min，得物料a；将4份轻质碳酸钙和4份磷酸二氢铝混合均匀，加热至70℃，保温15min，然后加入2份季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。The composite filler is prepared according to the following process: mix 2 parts of polypropylene and 5 parts of montmorillonite uniformly by weight, heat to 450 ° C, keep warm for 20 minutes, cool to room temperature, and then add 3 parts of polytetrafluoroethylene and ball mill for 16 minutes to obtain the material a; Mix 4 parts of light calcium carbonate and 4 parts of aluminum dihydrogen phosphate evenly, heat to 70°C, keep warm for 15 minutes, then add 2 parts of pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b Homogenize, dry, grind, and cool to room temperature to obtain a composite filler.
其中，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比2：3：3混合而成。Among them, the antifriction agent is a mixture of methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 2:3:3.
实施例3Example 3
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM120份、聚碳酸酯二元醇60份、壬二酸二辛酯30份、乙氧基化烷基酚硫酸铵5份、甲苯二异氰酸酯8份、丙酸钙3份、气相白炭黑5份、凹凸棒土2份、氧化钙9份、双酚a二缩水甘油醚2份、环氧硬脂酸辛酯6份、复合填料3份、减磨剂4份、含氢硅烷硫化剂1份、抗氧剂40206份、对醌二肟1份、过氧化二异丙苯6份、4，4’-二氨基-3，3’-二氯二苯基甲烷3份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 120 parts of ethylene vinyl acetate EVM, 60 parts of polycarbonate diol, 30 parts of dioctyl azelate, ethoxylate 5 parts of alkylphenol ammonium sulfate, 8 parts of toluene diisocyanate, 3 parts of calcium propionate, 5 parts of fumed silica, 2 parts of attapulgite, 9 parts of calcium oxide, 2 parts of bisphenol a diglycidyl ether, cyclic 6 parts of octyl oxystearate, 3 parts of composite filler, 4 parts of antifriction agent, 1 part of hydrosilane vulcanizing agent, 40206 parts of antioxidant, 1 part of p-quinonedioxime, 6 parts of dicumyl peroxide, 4 parts , 3 parts of 4'-diamino-3,3'-dichlorodiphenylmethane.
其中，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为90％。Wherein, the mass content of vinyl acetate in ethylene vinyl acetate EVM is 90%.
复合填料按如下工艺进行制备：按重量份将9份聚丙烯和1份蒙脱土混合均匀，加热至500℃，保温10min，冷却至常温，然后加入8份聚四氟乙烯球磨8min，得物料a；将9份轻质碳酸钙和3份磷酸二氢铝混合均匀，加热至90℃，保温5min，然后加入5份季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。The composite filler is prepared according to the following process: mix 9 parts of polypropylene and 1 part of montmorillonite uniformly by weight, heat to 500 ° C, keep warm for 10 minutes, cool to room temperature, and then add 8 parts of polytetrafluoroethylene and ball mill for 8 minutes to obtain the material a; Mix 9 parts of light calcium carbonate and 3 parts of aluminum dihydrogen phosphate evenly, heat to 90°C, keep warm for 5 minutes, then add 5 parts of pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b Homogenize, dry, grind, and cool to room temperature to obtain a composite filler.
其中，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比6：1：5混合而成。Among them, the antifriction agent is a mixture of methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 6:1:5.
实施例4Example 4
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM85份、聚碳酸酯二元醇85份、壬二酸二辛酯15份、乙氧基化烷基酚硫酸铵12份、甲苯二异氰酸酯3份、丙酸钙5份、气相白炭黑2份、凹凸棒土7份、氧化钙4份、双酚a二缩水甘油醚4份、环氧硬脂酸辛酯2份、复合填料4.5份、减磨剂2.5份、含氢硅烷硫化剂3份、抗氧剂40203份、二硫化四甲基秋兰姆7份、过氧化二异丙苯3份、3，5-二甲硫基甲苯二胺6份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 85 parts of ethylene vinyl acetate EVM, 85 parts of polycarbonate diol, 15 parts of dioctyl azelate, ethoxylate 12 parts of alkylphenol ammonium sulfate, 3 parts of toluene diisocyanate, 5 parts of calcium propionate, 2 parts of fumed silica, 7 parts of attapulgite, 4 parts of calcium oxide, 4 parts of bisphenol a diglycidyl ether, cyclic 2 parts of octyl oxystearate, 4.5 parts of composite filler, 2.5 parts of antifriction agent, 3 parts of hydrosilane vulcanizing agent, 40203 parts of antioxidant, 7 parts of tetramethylthiuram disulfide, dicumyl peroxide 3 parts, 6 parts of 3,5-dimethylthiotoluenediamine.
其中，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为82％。Wherein, the mass content of vinyl acetate in ethylene vinyl acetate EVM is 82%.
复合填料按如下工艺进行制备：按重量份将3份聚丙烯和4份蒙脱土混合均匀，加热至460℃，保温18min，冷却至常温，然后加入4份聚四氟乙烯球磨14min，得物料a；将5份轻质碳酸钙和3.8份磷酸二氢铝混合均匀，加热至75℃，保温12min，然后加入3份季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。The composite filler is prepared according to the following process: mix 3 parts of polypropylene and 4 parts of montmorillonite uniformly by weight, heat to 460 ° C, keep warm for 18 minutes, cool to room temperature, and then add 4 parts of polytetrafluoroethylene and ball mill for 14 minutes to obtain the material a; Mix 5 parts of light calcium carbonate and 3.8 parts of aluminum dihydrogen phosphate evenly, heat to 75°C, keep warm for 12 minutes, then add 3 parts of pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b Homogenize, dry, grind, and cool to room temperature to obtain a composite filler.
其中，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比3：2.5：3.5混合而成。Among them, the antifriction agent is a mixture of methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 3:2.5:3.5.
实施例5Example 5
本发明提出的一种高强度耐磨耐油聚氨酯弹性体，其原料按重量份包括：乙烯醋酸乙烯酯EVM115份、聚碳酸酯二元醇65份、壬二酸二辛酯25份、乙氧基化烷基酚硫酸铵8份、甲苯二异氰酸酯7份、丙酸钙4份、气相白炭黑4份、凹凸棒土3份、氧化钙8份、双酚a二缩水甘油醚3份、环氧硬脂酸辛酯5份、复合填料3.5份、减磨剂3.5份、树脂类硫化剂2份、抗氧剂10105份、烷基化三亚乙基四胺二硫化秋兰姆2份、1,3-二特丁基过氧化二异丙苯5份、二乙基甲苯二胺4份。A high-strength wear-resistant and oil-resistant polyurethane elastomer proposed by the present invention, its raw materials include by weight: 115 parts of ethylene vinyl acetate EVM, 65 parts of polycarbonate diol, 25 parts of dioctyl azelate, ethoxylate 8 parts of alkylphenol ammonium sulfate, 7 parts of toluene diisocyanate, 4 parts of calcium propionate, 4 parts of fumed silica, 3 parts of attapulgite, 8 parts of calcium oxide, 3 parts of bisphenol a diglycidyl ether, cyclic 5 parts of octyl oxystearate, 3.5 parts of composite filler, 3.5 parts of friction reducing agent, 2 parts of resin vulcanizing agent, 10105 parts of antioxidant, 2 parts of alkylated triethylenetetramine thiuram disulfide, 1, 5 parts of 3-di-t-butyl dicumyl peroxide and 4 parts of diethyltoluenediamine.
其中，乙烯醋酸乙烯酯EVM中醋酸乙烯酯的质量含量为88％。Wherein, the mass content of vinyl acetate in ethylene vinyl acetate EVM is 88%.
复合填料按如下工艺进行制备：按重量份将8份聚丙烯和2份蒙脱土混合均匀，加热至490℃，保温12min，冷却至常温，然后加入7份聚四氟乙烯球磨10min，得物料a；将8份轻质碳酸钙和3.2份磷酸二氢铝混合均匀，加热至85℃，保温8min，然后加入4份季戊四醇三丙烯酸酯搅拌至常温得到物料b，然后将物料a和物料b混合均匀，烘干，研磨，冷却至室温得到复合填料。The composite filler is prepared according to the following process: mix 8 parts of polypropylene and 2 parts of montmorillonite uniformly by weight, heat to 490 ° C, keep warm for 12 minutes, cool to room temperature, and then add 7 parts of polytetrafluoroethylene for ball milling for 10 minutes to obtain the material a; Mix 8 parts of light calcium carbonate and 3.2 parts of aluminum dihydrogen phosphate evenly, heat to 85°C, keep warm for 8 minutes, then add 4 parts of pentaerythritol triacrylate and stir to normal temperature to obtain material b, then mix material a and material b Homogenize, dry, grind, and cool to room temperature to obtain a composite filler.
其中，减磨剂为甲基硅油、氟碳乳液和液体石蜡按重量比5：1.5：4.5混合而成。Among them, the antifriction agent is a mixture of methyl silicone oil, fluorocarbon emulsion and liquid paraffin in a weight ratio of 5:1.5:4.5.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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Address after: No. 36 Tashan West Road, Lai'an County, Chuzhou City, Anhui Province, China 239200 Patentee after: Chuzhou Global Polyurethane Technology Co.,Ltd. Country or region after: China Address before: No. 36 Tashan West Road, Lai'an County, Chuzhou City, Anhui Province, China 239200 Patentee before: CHUZHOU HUANQIU POLYURETHANE TECHNOLOGY Co.,Ltd. Country or region before: China |