CN117964951A - Foaming rubber formula - Google Patents
Foaming rubber formula Download PDFInfo
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- CN117964951A CN117964951A CN202410037139.7A CN202410037139A CN117964951A CN 117964951 A CN117964951 A CN 117964951A CN 202410037139 A CN202410037139 A CN 202410037139A CN 117964951 A CN117964951 A CN 117964951A
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- foaming
- accelerator
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 140
- 239000005060 rubber Substances 0.000 title claims abstract description 140
- 238000005187 foaming Methods 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 93
- 239000004088 foaming agent Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 31
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 31
- 229920001194 natural rubber Polymers 0.000 claims abstract description 31
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims abstract description 17
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 11
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 5
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 5
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000011593 sulfur Substances 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 18
- 239000006229 carbon black Substances 0.000 claims description 18
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- 229920001821 foam rubber Polymers 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010058 rubber compounding Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- 235000019492 Cashew oil Nutrition 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229940059459 cashew oil Drugs 0.000 claims description 3
- 239000010467 cashew oil Substances 0.000 claims description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000003784 tall oil Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- -1 t-butylperoxy Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 239000010692 aromatic oil Substances 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000007906 compression Methods 0.000 description 101
- 230000006835 compression Effects 0.000 description 101
- 239000011148 porous material Substances 0.000 description 61
- 230000032683 aging Effects 0.000 description 44
- 238000010438 heat treatment Methods 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000008859 change Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 14
- 235000019832 sodium triphosphate Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 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 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a foaming rubber formula, and relates to the technical field of high polymer materials. The foaming rubber formula provided by the invention comprises the following components in parts by weight: 100 parts of natural rubber, 5-30 parts of liquid rubber, 5-30 parts of reinforcing filler, 1-2 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator, 2-15 parts of active agent, 2-5 parts of anti-aging agent, 3-5 parts of dispersing agent and 5-10 parts of foaming agent; the liquid rubber is one or more of polyisoprene rubber, polybutadiene rubber and butadiene-isoprene rubber. According to the invention, the aromatic oil in the foaming rubber is replaced by the liquid rubber, after vulcanization, the liquid rubber is crosslinked with the main natural rubber, and compared with the foaming rubber using the aromatic oil as a softener, the tensile strength and the tearing strength of the foaming rubber can be increased.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a foaming rubber formula.
Background
The foaming rubber based on natural rubber (foam rubber for short) is a very important polymer material, has the characteristics of good heat preservation, shock absorption, sound absorption, corrosion resistance and the like, and is widely applied to the fields of industry, agriculture, national defense, transportation, machinery manufacturing, medicine and health, daily life and the like.
In the prior art, in order to smoothly foam rubber, a softener is often required to be added into a formula, and the hardness of the rubber is reduced, so that the rubber can be smoothly foamed. The commonly used softener is an aromatic oil. However, the tensile strength of the foamed rubber obtained by using aromatic oil as a softener is low.
Disclosure of Invention
The invention aims to provide a foaming rubber formula, and the foaming rubber obtained by adopting the formula has high tensile strength.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a foaming rubber formula which comprises the following components in parts by weight: 100 parts of natural rubber, 5-30 parts of liquid rubber, 5-30 parts of reinforcing filler, 1-2 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator, 2-15 parts of active agent, 2-5 parts of anti-aging agent, 3-5 parts of dispersing agent and 5-10 parts of foaming agent; the liquid rubber is one or more of polyisoprene rubber, polybutadiene rubber and butadiene-isoprene rubber.
Preferably, the preparation method of the liquid rubber comprises the following steps: mixing Ni complex, organic solvent, methylaluminoxane and olefin, and carrying out polymerization reaction to obtain liquid rubber;
the olefin is isoprene and/or butadiene;
the Ni complex has a structure represented by any one of Ni1 to Ni 8:
Preferably, the molar ratio of the Ni complex to the methylaluminoxane is 1: (50-2000).
Preferably, the molar ratio of the Ni complex to the olefin is 1: (200-100000).
Preferably, the temperature of the polymerization reaction is 30-70 ℃ and the time is 12-48 h.
Preferably, the vulcanizing agent IS one or more of ordinary sulfur, insoluble sulfur IS-60, insoluble sulfur IS-90, insoluble sulfur HDOT-70, vulcanizing agent DCP, dicumyl peroxide, di (tert-butylperoxydiisopropyl) benzene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 1-bis (tert-butylperoxy) 3, 5-trimethylcyclohexane and bis (2, 4-dichlorobenzoyl) peroxide.
Preferably, the foaming agent comprises one or more of foaming agent H, foaming agent FA, naHCO 3, foaming agent AC, foaming agent AIBN, foaming agent OBSH, foaming agent TSH and foaming agent BSH.
Preferably, the vulcanization accelerator comprises one or more of accelerator D, accelerator DM, accelerator DTDM and accelerator TMTD.
Preferably, the active agent comprises zinc oxide and/or stearic acid.
Preferably, the reinforcing filler comprises one or more of carbon black, white carbon black, tall oil modified resin, high styrene resin, cashew oil modified resin, calcium carbonate, clay, and talc.
The invention provides a foaming rubber formula which comprises the following components in parts by weight: 100 parts of natural rubber, 5-30 parts of liquid rubber, 5-30 parts of reinforcing filler, 1-2 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator, 2-15 parts of active agent, 2-5 parts of anti-aging agent, 3-5 parts of dispersing agent and 5-10 parts of foaming agent; the liquid rubber is one or more of polyisoprene rubber, polybutadiene rubber and butadiene-isoprene rubber. According to the invention, the aromatic oil in the foaming rubber is replaced by the liquid rubber, after vulcanization, the liquid rubber and the main natural rubber are crosslinked together, and compared with the foaming rubber using the aromatic oil as a softener, the tensile strength of the foaming rubber can be increased.
Detailed Description
The invention provides a foaming rubber formula which comprises the following components in parts by weight: 100 parts of natural rubber, 5-30 parts of liquid rubber, 5-30 parts of reinforcing filler, 1-2 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator, 2-15 parts of active agent, 2-5 parts of anti-aging agent, 3-5 parts of dispersing agent and 5-10 parts of foaming agent; the liquid rubber is one or more of polyisoprene rubber, polybutadiene rubber and butadiene-isoprene rubber.
In the present invention, unless specifically stated, all raw materials used are commercially available products well known in the art.
The liquid rubber will be described first.
In the present invention, the liquid rubber is preferably self-prepared, and the preparation method of the liquid rubber preferably comprises the following steps:
Mixing Ni complex, organic solvent, methylaluminoxane and olefin, and carrying out polymerization reaction to obtain liquid rubber;
the olefin is isoprene and/or butadiene;
the Ni complex has a structure represented by any one of Ni1 to Ni 8:
In the present invention, the Ni complex is preferably prepared by the preparation of the Ni complex preferably including: taking a baked clean schlenk tube, and replacing internal gas with argon three times; sequentially adding NiBr 2, toluene and diimine ligand, and reacting for 12-24 hours at room temperature to obtain Ni complex. In the present invention, the ratio of the amount of NiBr 2, toluene and diimine ligand is preferably 1 mmol/10 mL: (1-1.2) mmol. In the present invention, the diimine ligand has a structure represented by any one of formulas 1 to 8:
in the present invention, the Ni complex serves as a main catalyst.
In the present invention, the organic solvent is preferably toluene, n-hexane, n-octane or xylene; the toluene is preferably anhydrous toluene. In the present invention, the ratio of the Ni complex to the organic solvent is 1mg:1mL.
In the invention, the Methyl Aluminoxane (MAO) has the structural general formulaWherein n is a natural number of 4 to 40; in the present invention, the methylaluminoxane is purchased from aledine. In the present invention, the methylaluminoxane is used as a cocatalyst. In the present invention, the molar ratio of the Ni complex to methylaluminoxane is preferably 1: (50 to 2000), more preferably 1: (200 to 1500), more preferably 1: (500-1000).
In the invention, the olefin is isoprene and/or butadiene, and when the olefin is isoprene and butadiene, the invention has no special requirement on the proportion of the isoprene and butadiene, and the proportion can be any. In the present invention, the olefin is used as a reaction monomer. In the present invention, the molar ratio of the Ni complex to olefin is 1: (200 to 100000), more preferably 1: (2000 to 98000), more preferably 1: (10000 to 90000), more preferably 1: (20000 to 80000).
In the present invention, the mixing of the Ni complex, the organic solvent, the methylaluminoxane and the olefin preferably includes: the Ni complex is mixed with an organic solvent in an anhydrous and anaerobic environment, and the mixture is heated to 50 ℃ and then is kept for 0.5h, and then methylaluminoxane and olefin are sequentially added.
In the present invention, the polymerization reaction temperature is preferably 30 to 70 ℃, more preferably 40 to 60 ℃, still more preferably 50 ℃, and the holding time is preferably 12 to 48 hours, more preferably 20 to 40 hours, still more preferably 24 hours.
After the polymerization reaction is finished, the invention preferably adds acid methanol solution into the obtained polymerization product system to quench the reaction, washes the polymer by ethanol and dries to obtain the liquid rubber.
In the invention, the acidic methanol solution is preferably obtained by mixing hydrochloric acid and methanol, and the mass fraction of the hydrochloric acid is preferably 36-38%; the concentration of the acidic methanol solution is 1% mol/L.
The following is a description of the foam rubber formulation of the present invention.
The foaming rubber formula provided by the invention comprises 100 parts of natural rubber in parts by weight.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 5-30 parts of liquid rubber, preferably 10-25 parts, and more preferably 15-20 parts. In the present invention, the liquid rubber is used as a softener, and after vulcanization, the liquid rubber is crosslinked with the main natural rubber, and the tensile strength and tear strength of the foamed rubber can be increased as compared with those of the foamed rubber using aromatic oil as a softener.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 5-30 parts of reinforcing filler, preferably 10-25 parts, and more preferably 15-20 parts. In the present invention, the reinforcing filler is preferably one or more of carbon black, white carbon black, tall oil modified resin, high styrene resin, cashew oil modified resin, calcium carbonate, clay and talc; among them, the carbon black is preferably carbon black N660. In the present invention, the reinforcing filler functions to enhance the abrasion resistance and strength of rubber.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 1-2 parts of vulcanizing agent, preferably 1.2-1.8 parts, and more preferably 1.4-1.6 parts. In the present invention, the vulcanizing agent IS preferably one or more of ordinary sulfur, insoluble sulfur IS-60, insoluble sulfur IS-90, insoluble sulfur HDOT-70, vulcanizing agent DCP, dicumyl peroxide, di (t-butylperoxy-diisopropyl) benzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1-bis (t-butylperoxy) 3, 5-trimethylcyclohexane and bis (2, 4-dichlorobenzoyl) peroxide.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 1-5 parts of vulcanization accelerator, preferably 2-4 parts, and more preferably 2.5-3.5 parts. In the present invention, the vulcanization accelerator preferably includes one or more of accelerator D, accelerator DM, accelerator DTDM, and accelerator TMTD.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 2-15 parts of an active agent, preferably 4-13 parts, and more preferably 6-10 parts. In the present invention, the active agent preferably includes zinc oxide and/or stearic acid.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 2-5 parts of an anti-aging agent, preferably 2.5-4.5 parts, and more preferably 3-4 parts. In the present invention, the antioxidant preferably includes one or more of an antioxidant 4010, an antioxidant RD, an antioxidant 4020, and an antioxidant 4010 NA.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 3-5 parts of dispersing agent, preferably 3.5-4.5 parts, and more preferably 4 parts. In the present invention, the dispersant preferably includes one or more of sodium tripolyphosphate, guar gum, sodium dodecyl sulfate, polyacrylamide, and sodium pyrophosphate.
Based on the weight parts of the natural rubber, the foaming rubber formula provided by the invention comprises 5-10 parts of foaming agent, preferably 6-9 parts, and more preferably 7-8 parts. In the present invention, the foaming agent preferably includes one or more of foaming agent H, foaming agent FA, naHCO 3, foaming agent AC, foaming agent AIBN, foaming agent OBSH, foaming agent TSH and foaming agent BSH.
The preparation process of the foaming rubber is not particularly required, and the preparation process well known in the art can be adopted. In the embodiment of the invention, the method specifically comprises the following steps: adding natural rubber, an active agent, an anti-aging agent, a dispersing agent, a foaming agent and a reinforcing filler into an internal mixer, and mixing for 3 minutes; adding the liquid rubber into an internal mixer, and mixing for 2 minutes; adding a vulcanizing agent and a vulcanization accelerator into an internal mixer, mixing for 2 minutes, and vulcanizing the obtained mixed rubber to obtain the foaming rubber.
The following examples are provided to illustrate the foam rubber formulations provided in accordance with the present invention in detail, but they should not be construed as limiting the scope of the invention.
The liquid rubbers used in the following examples were prepared as follows:
preparation of Ni 1-liquid rubber:
ni1 complex (1 eq.) was added to the reaction flask under anhydrous and anaerobic conditions, then anhydrous toluene (10 mL) was added and stirring was started; then heating the reaction bottle to 50 ℃, and preserving heat for half an hour to increase the dissolution amount of the Ni complex in the solvent; then, methylaluminoxane (200 eq.) and isoprene/butadiene (each 1000eq., total 2000 eq.) were added in sequence, and the polymerization was carried out for 24 hours, after the reaction was completed, the reaction was quenched by adding an acidic methanol solution, and the obtained polymer was washed twice with ethanol and dried, to obtain Ni 1-liquid rubber.
Preparation of Ni 2-liquid rubber-Ni 8-liquid rubber:
Referring to the preparation process of Ni 1-liquid rubber, only Ni1 complex is replaced with Ni 2-Ni 8 complex to obtain Ni 2-liquid rubber-Ni 8-liquid rubber.
GPC test results showed that Ni 1-liquid rubber Mn=6260 g/mol, PDI=2.5; ni 2-liquid rubber mn=6140 g/mol, pdi=2.2; ni 3-liquid rubber mn=6700 g/mol, pdi=2.5; ni 4-liquid rubber mn=5510 g/mol, pdi=2.6; ni 5-liquid rubber mn=6680 g/mol, pdi=2.8; ni 6-liquid rubber mn=5560 g/mol, pdi=3.3; ni 7-liquid rubber mn=6390 g/mol, pdi=2.4; ni 8-liquid rubber mn=6830 g/mol, pdi=2.5.
Preparation of Ni 9-liquid rubber:
Ni complex (1 eq.) was added to the reaction flask under anhydrous and anaerobic conditions, then anhydrous toluene (10 mL) was added and stirring was started; then heating the reaction bottle to 50 ℃, and preserving heat for half an hour; after that, methylaluminoxane (10 eq.) and isoprene/butadiene (1000 eq. Each, 2000eq. Total) were added in sequence and reacted for 24h. After the reaction was completed, an acidic methanol solution was added, the reaction was quenched, and the obtained polymer was washed twice with ethanol and dried to obtain Ni 9-liquid rubber, mn=13560 g/mol, pdi=2.2.
Preparation of Ni 10-liquid rubber and Ni 11-liquid rubber:
Changing the amount of methylaluminoxane to 50eq. And 100eq. Based on the preparation of Ni 9-liquid rubber, resulting in Ni 10-liquid rubber (mn=11082 g/mol, pdi=2.4) and Ni 11-liquid rubber (mn=8420 g/mol, pdi=2.5);
preparation of Ni 12-liquid rubber:
Ni complex (1 eq.) was added to the reaction flask under anhydrous and anaerobic conditions, then anhydrous toluene (10 mL) was added and stirring was started; then heating the reaction bottle to 50 ℃, and preserving heat for half an hour; then, methylaluminoxane (200 eq.) and butadiene (2000 eq.) were added in this order and reacted for 24h. After the reaction was completed, an acidic methanol solution was added, the reaction was quenched, and the obtained polymer was washed twice with ethanol and dried to obtain Ni 12-liquid rubber, mn=7130 g/mol, pdi=2.4.
Preparation of Ni 13-liquid rubber:
Ni complex (1 eq.) was added to the reaction flask under anhydrous and anaerobic conditions, then anhydrous toluene (10 mL) was added and stirring was started; then heating the reaction bottle to 50 ℃, and preserving heat for half an hour; then, methylaluminoxane (200 eq.) and isoprene (2000 eq.) were added in this order and reacted for 24h. After the reaction is finished, adding an acidic methanol solution, quenching the reaction, washing the obtained polymer twice with ethanol, and drying to obtain Ni 13-liquid rubber, wherein Mn=6560 g/mol and PDI=2.3.
The following examples performance test reference criteria are as follows:
Tensile strength, elongation at break, permanent set at break, see GB/T528-2009; constant compression set is described in GB 5602-1985; ageing performance test is referred to GB 3512-2014; rebound refers to GB/T10807; brittle temperature is referred to GB 1682-2014.
The preparation process of the foaming rubber comprises the following steps: adding natural rubber, an active agent, an anti-aging agent, a dispersing agent, a foaming agent and a reinforcing filler into an internal mixer, and mixing for 3 minutes; adding the liquid rubber into an internal mixer, and mixing for 2 minutes; adding a vulcanizing agent and a vulcanization accelerator into an internal mixer, mixing for 2 minutes, vulcanizing the obtained mixed rubber, wherein the vulcanization temperature is 143 ℃, and the vulcanization time is 45 minutes, so as to obtain the foaming rubber.
Example 1
100 Parts of natural rubber, 20 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 5 parts of Ni 1-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming agent FA.
Tensile strength is 5.8MPa; elongation at break is 380%; 32% of permanent deformation after tearing; constant compression deformation of 2.9%, and heating the compressed sample to 26 ℃; constant compression deformation is 6.7% after aging (70 ℃ C. Multiplied by 24 h), and the temperature of a sample is raised by 27 ℃ after aging compression; the brittle temperature is not cracked and sticky at minus 55 ℃; the mass change rate before and after aging is 1.1%; the rebound after 30 ten thousand constant compressions was 12%. The micro-pore structure of the obtained sample is mainly a closed pore structure and has a small number of micropores with an open pore structure. The thickness of the hole wall is 260-530 mu m.
Note that: the smaller the temperature rise after compression, the higher the thermal stability of the sample, and the stronger the aging resistance; the smaller the mass change rate is, the more stable the sample structure is; the higher the rebound, the more stable the structure; the brittle temperature is not cracked or sticky at the temperature of minus 55 ℃, which indicates that the sample has good low temperature resistance performance; tensile strength is 5.8MPa; the elongation at break is 380%, and the larger the data is, the better the sample performance is; the higher the thickness of the pore wall, the more stable the structure is, and the structure is not easily damaged. From the above data, the foamed rubber obtained in example 1 has stable structure, good thermal stability, strong aging resistance and high tensile strength.
Example 2
The difference from example 1 is that the amount of Ni 1-liquid rubber was changed from 5 parts to 10 parts.
Tensile strength is 4.3MPa; elongation at break is 550%; 36% of permanent deformation after breaking; constant compression deformation of 2.0%, and heating to 24 ℃ after compression; constant compression deformation 6.1% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before aging is 1.0%; rebound after 30 ten thousand constant compressions was 18%. The micro-pore structure of the obtained sample is mainly a closed pore structure and has a small number of micropores with an open pore structure. The thickness of the hole wall is 220-500 mu m.
Example 3
The difference from example 1 is that the amount of Ni 1-liquid rubber was changed from 5 parts to 20 parts.
Tensile strength is 3.6MPa; elongation at break is 550%; 30% of permanent deformation after breaking; constant compression deformation of 3.2%, and heating to 25 ℃ after compression; constant compression deformation 5.9% after aging (70 ℃ x 24 h), and heating to 25 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; the rebound after 30 ten thousand constant compressions was 23%. The micro-pore structure of the obtained sample is mainly a closed pore structure, and part of the micro-pore structure is micropores with an open pore structure. The thickness of the hole wall is between 230 and 600 mu m.
Example 4
100 Parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 30 parts of Ni 1-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming agent FA.
The tensile strength is 2.3MPa; elongation at break of 475%; 25% of permanent deformation after tearing; constant compression deformation of 3.3%, and heating to 28 ℃ after compression; constant compression deformation 6.4% after aging (70 ℃ x 24 h), and heating to 29 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; the rebound after 30 ten thousand constant compressions was 16%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 180-660 mu m.
Example 5
100 Parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 2-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming agent FA.
Tensile strength is 4.0MPa; elongation at break is 490%; 25% of permanent deformation after tearing; constant compression deformation of 3.3%, and heating to 28 ℃ after compression; constant compression deformation 6.4% after aging (70 ℃ x 24 h), and heating to 29 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 26%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 280-660 mu m.
Example 6
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 3-liquid rubber.
100 Parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 3-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming aid FA.
Tensile strength is 4.9MPa; elongation at break of 350%; permanent set at break 26%; constant compression deformation is 3.4%, and the temperature is raised by 26 ℃ after compression; constant compression deformation 5.9% after aging (70 ℃ x 24 h), and heating to 28 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.1%; rebound after 30 ten thousand constant compressions was 22%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 250 and 600 mu m.
Example 7
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 4-liquid rubber.
Tensile strength is 4.7MPa; elongation at break of 375%; 25% of permanent deformation after tearing; constant compression deformation is 3.4%, and the temperature is raised by 26 ℃ after compression; constant compression deformation 5.7% after aging (70 ℃ x 24 h), and heating to 27 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.1%; the rebound after 30 ten thousand constant compressions was 20%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 220-615 mu m.
Example 8
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 5-liquid rubber.
100 Parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 5-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming aid FA.
Tensile strength is 4.8MPa; elongation at break of 365%; permanent set at break 26%; constant compression deformation of 3.3%, and heating to 25 ℃ after compression; constant compression deformation 5.9% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.2%; rebound after 30 ten thousand constant compressions was 21%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 220-610 mu m.
Example 9
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 6-liquid rubber.
Tensile strength is 5.4MPa; elongation at break of 282%; permanent set at break 26%; constant compression deformation of 2.9%, and heating to 25 ℃ after compression; constant compression deformation 5.1% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 24%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 230 and 590 mu m.
Example 10
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 7-liquid rubber.
Tensile strength is 2.6MPa; elongation at break is 390%; 18% of permanent deformation after tearing; constant compression deformation of 4.2%, and heating to 26 ℃ after compression; constant compression deformation 7.3% after aging (70 ℃ x 24 h), and heating to 28 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.2%; the rebound after 30 ten thousand constant compressions was 17%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 210 and 635 mu m.
Example 11
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 8-liquid rubber.
Tensile strength is 3.6MPa; elongation at break of 362%; breaking permanent deformation 22%; constant compression deformation of 3.7%, and heating to 25 ℃ after compression; constant compression deformation 5.4% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.1%; the rebound after 30 ten thousand constant compressions was 20%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 230 and 600 mu m.
Example 12
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 9-liquid rubber.
Tensile strength is 6.2MPa; elongation at break of 254%; 16% of permanent deformation after breaking; constant compression deformation of 2.4%, and heating to 25 ℃ after compression; constant compression deformation after aging (70 ℃ for 24 hours) is 3.7%, and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 25%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 250 and 520 mu m.
Example 13
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 10-liquid rubber.
Tensile strength is 5.7MPa; elongation at break is 279%; 19% of permanent deformation after tearing; constant compression deformation of 2.9%, and heating to 25 ℃ after compression; constant compression deformation 4.3% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 21%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 220-540 mu m.
Example 14
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 11-liquid rubber.
Tensile strength is 5.5MPa; elongation at break is 290%; 25% of permanent deformation after tearing; constant compression deformation of 2.9%, and heating to 25 ℃ after compression; constant compression deformation 5.0% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 0.9%; rebound after 30 ten thousand constant compressions was 22%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 200-575 μm.
Example 15
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 12-liquid rubber.
Tensile strength is 3.0MPa; elongation at break of 370%; 19% of permanent deformation after tearing; constant compression deformation of 2.8%, and heating to 26 ℃ after compression; constant compression deformation 5.6% after aging (70 ℃ x 24 h), and heating to 27 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 21%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 225-565 μm.
Example 16
100 Parts of natural rubber, 30 parts of carbon black (N660), 5 parts of sulfur IS-601, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 1-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming agent FA.
Tensile strength is 3.5MPa; elongation at break of 420%; 21% of permanent deformation after tearing; constant compression deformation of 2.5%, and heating to 25 ℃ after compression; constant compression deformation 5.1% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; the rebound after 30 ten thousand constant compressions was 23%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 220-530 mu m.
Example 17
100 Parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 1-liquid rubber and 5 parts of a foaming agent OBSH.
Tensile strength is 2.7MPa; elongation at break of 440%; 20% of permanent deformation after breaking; constant compression deformation of 2.8%, and heating to 25 ℃ after compression; constant compression deformation 4.8% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 26%. The vast majority of the microscopic pores of the resulting sample were closed cell structures. The thickness of the hole wall is 220-480 mu m.
Example 18
The only difference from example 5 is that the Ni 2-liquid rubber was replaced with Ni 12-liquid rubber:
100 parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 12-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming aid FA.
Tensile strength is 2.8MPa; elongation at break of 430%; 23% of permanent deformation after tearing; constant compression deformation is 2.4%, and the temperature is raised by 26 ℃ after compression; constant compression deformation 4.5% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 25%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is between 250 and 490 mu m.
Example 19
The only difference from example 6 is that the Ni 3-liquid rubber was replaced with Ni 13-liquid rubber:
100 parts of natural rubber, 30 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of Ni 13-liquid rubber, 5 parts of a foaming agent H and 5 parts of a foaming aid FA.
Tensile strength is 2.5MPa; elongation at break 510%; 27% of permanent deformation after tearing; constant compression deformation of 2.6%, and heating to 26 ℃ after compression; constant compression deformation 4.4% after aging (70 ℃ x 24 h), and heating to 26 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.0%; rebound after 30 ten thousand constant compressions was 26%. The microscopic pores of the obtained sample have both closed pore structures and open pore structures. The thickness of the hole wall is 245-505 mu m.
Comparative example 1
The only difference from example 3 is that the Ni 1-liquid rubber was replaced with an equal amount of aromatic oil.
100 Parts of natural rubber, 20 parts of carbon black (N660), 1 part of ordinary sulfur, 5 parts of stearic acid, 5 parts of zinc oxide, 2 parts of an anti-aging agent (RD), 3 parts of a dispersing agent (sodium tripolyphosphate), 1 part of an accelerator (DM), 1 part of an accelerator (TMTD), 1 part of an accelerator (DTDM), 20 parts of aromatic oil, 5 parts of each of a foaming agent H and a foaming agent FA
Tensile strength is 0.8MPa; elongation at break 340%; 30% of permanent deformation after breaking; constant compression deformation of 4.4%, and heating to 26 ℃ after compression; constant compression deformation 5.9% after aging (70 ℃ x 24 h), and heating to 28 ℃ after compression; the brittle temperature is not cracked and sticky at minus 55 ℃; mass change rate before and after aging is 1.3%; the rebound after 30 ten thousand constant compressions was 20%. The micro-pore structure of the obtained sample is mainly a closed pore structure, and part of the micro-pore structure is micropores with an open pore structure. The thickness of the hole wall is 220-630 mu m.
From the above examples and comparative examples, the present invention replaces aromatic oil in the foamed rubber with liquid rubber, and after vulcanization, the liquid rubber is crosslinked with the main natural rubber, and the tensile strength of the foamed rubber can be increased as compared with the foamed rubber using aromatic oil as a softener, while maintaining the structural stability of the foamed rubber.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The foaming rubber formula is characterized by comprising the following components in parts by weight: 100 parts of natural rubber, 5-30 parts of liquid rubber, 5-30 parts of reinforcing filler, 1-2 parts of vulcanizing agent, 1-5 parts of vulcanization accelerator, 2-15 parts of active agent, 2-5 parts of anti-aging agent, 3-5 parts of dispersing agent and 5-10 parts of foaming agent; the liquid rubber is one or more of polyisoprene rubber, polybutadiene rubber and butadiene-isoprene rubber.
2. The foam rubber formulation according to claim 1, wherein the method of preparing the liquid rubber comprises the steps of: mixing Ni complex, organic solvent, methylaluminoxane and olefin, and carrying out polymerization reaction to obtain liquid rubber;
the olefin is isoprene and/or butadiene;
the Ni complex has a structure represented by any one of Ni1 to Ni 8:
3. the foam rubber formulation according to claim 2, wherein the molar ratio of Ni complex to methylaluminoxane is 1: (50-2000).
4. A foam rubber formulation according to claim 2 or 3, wherein the molar ratio of Ni complex to olefin is 1: (200-100000).
5. The foam rubber formulation according to claim 2, wherein the polymerization reaction is carried out at a temperature of 30 to 70 ℃ for a period of 12 to 48 hours.
6. The foam rubber formulation of claim 1, wherein the vulcanizing agent IS one or more of ordinary sulfur, insoluble sulfur IS-60, insoluble sulfur IS-90, insoluble sulfur HDOT-70, vulcanizing agent DCP, dicumyl peroxide, di (t-butyldiisopropyl peroxide) benzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1-bis (t-butylperoxy) 3, 5-trimethylcyclohexane, and bis (2, 4-dichlorobenzoyl) peroxide.
7. The foam rubber formulation of claim 1, wherein said foaming agent comprises one or more of foaming agent H, foaming agent FA, naHCO 3, foaming agent AC, foaming agent AIBN, foaming agent OBSH, foaming agent TSH and foaming agent BSH.
8. The foam rubber formulation of claim 1, wherein said vulcanization accelerator comprises one or more of accelerator D, accelerator DM, accelerator DTDM, and accelerator TMTD.
9. The foam rubber formulation of claim 1, wherein the active agent comprises zinc oxide and/or stearic acid.
10. The foam rubber formulation of claim 1, wherein said reinforcing filler comprises one or more of carbon black, white carbon black, tall oil modified resins, high styrene resins, cashew oil modified resins, calcium carbonate, china clay and talc.
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