CN112080098A - 一种高强度弹性发泡材料及其制备工艺 - Google Patents
一种高强度弹性发泡材料及其制备工艺 Download PDFInfo
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- CN112080098A CN112080098A CN202011004824.8A CN202011004824A CN112080098A CN 112080098 A CN112080098 A CN 112080098A CN 202011004824 A CN202011004824 A CN 202011004824A CN 112080098 A CN112080098 A CN 112080098A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000005187 foaming Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 34
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 28
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 6
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 239000000178 monomer Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 36
- 229920001971 elastomer Polymers 0.000 claims description 34
- -1 unsaturated silicon nitrile Chemical class 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 15
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 12
- 229920000715 Mucilage Polymers 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003623 enhancer Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
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- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 8
- 229960001553 phloroglucinol Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
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- 239000007788 liquid Substances 0.000 claims description 3
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- 239000012265 solid product Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- XBICPFKOMKSLJI-UHFFFAOYSA-N trimethyl (3-propyloxiran-2-yl)methyl silicate Chemical compound C(CC)C1C(CO[Si](OC)(OC)OC)O1 XBICPFKOMKSLJI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011414 polymer cement Substances 0.000 claims 1
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000032683 aging Effects 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- DRUNROHLGBEQMK-UHFFFAOYSA-N 1,3,3,4,4-pentamethylpiperidin-2-one Chemical compound CN1CCC(C)(C)C(C)(C)C1=O DRUNROHLGBEQMK-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical group O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002190 fatty acyls Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VJPIFPYWTTUINA-UHFFFAOYSA-N trimethyl 3-(oxiran-2-ylmethoxy)propyl silicate Chemical compound CO[Si](OC)(OC)OCCCOCC1CO1 VJPIFPYWTTUINA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种高强度弹性发泡材料,包括如下重量份的各组分:超支化硅腈基橡胶100份、氧化锌4‑5份、硬脂酸锌0.5‑1份、炭黑9‑10份、硫黄2‑2.3份、促进剂1.3‑1.7份、偶氮二甲酰胺10‑12份。本发明超支化硅腈基橡胶在制备过程中通过抗氧化增强剂进行交联,进而提高了制备的聚合物的聚合程度,进一步提高了聚合物的强度,进而使得制备的超支化聚合物具有较高的强度,同时由于超支化结构使得聚合物具有大量的支链结构,使得其韧性增强,进而使得制备的超支化聚合物具有较高的韧性和强度。
Description
技术领域
本发明属于橡胶材料制备领域,涉及一种高强度弹性发泡材料及其制备工艺。
背景技术
丁腈橡胶由于具有较高的耐油性能被广泛应用于制造各种耐油像胶制品,由于其耐油性能,其发泡材料由于具有较高的回弹性能被应用于油料的密封,而丁腈橡胶发泡材料本身的耐老化性能和强度较低,现有技术中通常通过将丁腈橡胶与聚氯乙烯材料进行复合,实现高强度、高回弹和耐老化性,但是由于其他聚合物材料(聚氯乙烯材料)的加入,使得制备的聚合物是通过丁腈橡胶和聚氯乙烯混合的,其整体的耐油性能会有影响,并且虽然聚氯乙烯具有一定的耐老化性能,但是其中掺杂有大量的丁腈橡胶,使得材料仍会部分老化,因此现有技术中通常在材料中添加抗老化剂,但是抗老化剂在聚合物中容易分散不均匀,甚至出现抽离现象,进而造成其耐老化性能降低。
发明内容
本发明的目的在于提供一种高强度弹性发泡材料及其制备工艺,制备的超支化硅腈基橡胶在制备过程中使用的支化不饱和硅腈单体是以苯环为中心的支化结构,使得每个交联单元中心都是以苯环为中心,并且超支化硅腈基橡胶在制备过程中通过抗氧化增强剂进行交联,进而提高了制备的聚合物的聚合程度,进一步提高了聚合物的强度,进而使得制备的超支化聚合物具有较高的强度,同时由于超支化结构使得聚合物具有大量的支链结构,使得其韧性增强,进而使得制备的超支化聚合物具有较高的韧性和强度,无需另外添加聚合物增强其强度,进而也就不会造成其耐油性能降低。
本发明的目的可以通过以下技术方案实现:
一种高强度弹性发泡材料,包括如下重量份的各组分:
超支化硅腈基橡胶100份、氧化锌4-5份、硬脂酸锌0.5-1份、炭黑9-10份、硫黄2-2.3份、促进剂1.3-1.7份、偶氮二甲酰胺10-12份;
一种高强度弹性发泡材料的具体制备过程如下:
将超支化硅腈基橡胶、氧化锌、硬脂酸锌、炭黑、促进剂加入160℃的密炼机中混炼8-9min,然后降温至80℃加入硫磺和偶氮二甲酰胺,混炼均匀后调节辊距下片,然后将胶料在180℃下静止发泡,得到高强度弹性发泡材料,由于超支化硅腈基橡胶为超支化结构,提高了其分散性能,进而使得添加的炭黑和偶氮二甲酰胺能够均匀分散,由于炭黑的加入能够对紫外线和臭氧有一定的屏蔽作用,提高抗氧化性能,在炭黑均匀分散后,使得聚合物橡胶的抗氧化性能均匀,并且偶氮二甲酰胺的均匀分散使得聚合物材料的发泡性能更均匀,制备的发泡材料泡孔更均匀。
其中超支化硅腈基橡胶的具体制备过程如下:
第一步,将支化不饱和硅腈单体加入乙醇溶液中搅拌溶解,配成质量浓度为45%的支化不饱和硅腈单体溶液,然后将支化不饱和硅腈单体溶液、乳化剂、电解质溶液、活化剂溶液和水同时加入反应釜中,向反应釜中不断的通氮气30-40min,再降温至-5℃,再有质量流量计计量加入定量的丁二烯单体,然后升温至5-10℃后加入引发剂和叔十二硫醇,接着控制反应釜的压力为0.2-0.3MPa,反应7h后升温至30-35℃,当单体转化率为70%-80%时,向其中加入甲基二硫代氨基甲酸钠,继续搅拌20-30min,然后将得到的胶浆在脱气釜中进行抽真空除去未反应的单体,得到聚合物胶浆;由于支化不饱和硅腈单体是以苯环为中心的支化结构,并且支化链上含有氧基硅烷键,通过单体与丁二烯之间的聚合作用制备超支化的橡胶聚合物,使得聚合物链上均匀的引入大量的氧基硅烷键,并且每个交联单元中心都是以苯环为中心,进而使得制备的超支化聚合物具有较高的强度,同时由于超支化结构使得聚合物的韧性增强,进而使得制备的超支化聚合物具有较高的韧性和强度,同时由于聚合物链上均匀的引入大量的氧基硅烷键,使得制备的聚合物具有均匀的耐热性能;
其中各组分原料的重量份如下:支化不饱和硅腈单体溶液73-82份、丁二烯62-68份、乳化剂3-5份、电解质0.6-0.8份、活化剂0.05-0.07份、引发剂0.14-0.18份、叔十二硫醇0.19-0.21份、甲基二硫代氨基甲酸钠0.2-0.3份、水175-180份;
乳化剂为电解阴离子表面活性剂,电解质为磷酸钠或硫酸钠中的一种或者多种,活化剂为乙二胺四乙酸四钠盐,引发剂为异丙苯过氧化氢或叔丁基过氧化氢中的一种;
第二步,将得到的聚合物胶浆、乙酸乙酯和醋酸钠同时加入反应釜中,搅拌冷却,在5-10℃下反应6h,反应过程中不断滴加质量浓度为40%的过氧乙酸溶液,加完后再反应7-8h,冷却条件下加液碱至pH=10,然后升温至70-80℃向其中加入抗氧增强剂,搅拌反应4-5h后冷却,然后进行过滤洗涤烘干,得到高强度抗氧橡胶聚合物;其中每千克聚合物胶浆中加入乙酸乙酯3.5-3.8L,加入醋酸钠420-430g,加入质量浓度为40%的过氧乙酸溶液3.2-3.3kg,加入抗氧增强剂101-104g;由于制备的超支化聚合物具有较高的韧性和强度,同时生成的支化聚合物链上含有大量的双键,在过氧乙酸的氧化作用下生成环氧基团,而抗氧化增强剂中引入有两个烷基胺,能够与其中的环氧基团进行开环反应,进而使得支化聚合物的丁二烯单元之间通过抗氧化增强剂进行交联,进而提高了制备的聚合物的聚合程度,进一步提高了聚合物的强度,同时由于制备的超支化聚合物链上均匀的引入大量的氧基硅烷键,使得制备的聚合物具有均匀的耐热性能,抗氧增强剂中引入有氧基硅烷键,进而使得丁二烯交联单元之间通过含有氧基硅烷键的抗氧增强剂交联后,聚合物丁二烯单元之间也引入氧基硅烷键,而支化不饱和硅腈单体本身就引入有氧基硅烷键,进而使得制备的橡胶聚合物各部分单体均能够连接氧基硅烷键,使得氧基硅烷键均匀的分布在制备的橡胶聚合物中,进而使得制备的橡胶聚合物具有均匀且较高的耐热老化性能;同时由于其中炭黑的加入能够对紫外线和臭氧有一定的屏蔽作用,而部分直接作用在聚合物上的紫外线则直接通过交联后网状结构上的五甲基哌啶酮实现对自由基的捕获,并且大量硅氧烷键的引入,提高了聚合物的耐高温性能,使得制备的聚合物具有较高的耐老化性能;
其中支化不饱和硅腈单体的制备方法如下:
步骤1:在反应釜上设置有冷凝管,同时冷凝管连接副产物HCl吸收装置,将间苯三酚和乙醚同时加入反应釜中,搅拌溶解,然后控制在10℃下向反应釜中滴加二甲基二氯硅烷,控制2h内滴加完全,然后搅拌反应8-10h,接着向其中滴加乙二醇,控制1h内滴加完全,然后升温至95-100℃回流反应10-12h,减压蒸馏除去过量的反应物和溶剂后得到产物A;其中间苯三酚、二甲基二氯硅烷和乙二醇按照物质的量之比为1:3:3.2-3.3的比例加入;
步骤2:将氯铬酸吡啶盐和二氯甲烷加入反应釜中搅拌,在氮气保护下加入产物A,室温下搅拌反应3-4h,然后加入无水乙醚,搅拌均匀后进行抽滤,蒸除滤液中的溶剂,将得到的固体产物用水洗涤烘干,得到产物B;其中每克产物A中加入氯铬酸吡啶盐2.6-2.7g,加入二氯甲烷18-20mL;
步骤3:将产物B和苯同时加入反应釜中搅拌溶解,升温至140-145℃加入乙酸酐和醋酸钠,保温反应15-16h,冷却,加入水和乙酸乙酯,搅拌10min后用盐酸调节Ph=1-2,然后静置分层,分取乙酸乙酯层,水层用乙酸乙酯提取3次后合并乙酸乙酯层,水洗两次后用无水硫酸钠脱水,过滤,滤液减压回收溶剂,得到产物C;其中每千克产物B中加入乙酸酐1.45-1.48kg,加入醋酸钠320-340g,加入苯7-7.5kg;
步骤4:将产物C加入丙酮溶液中搅拌溶解,然后向其中加入浓氨水和三氯化磷,升温至80-90℃保温反应6-7h,然后蒸去溶剂、未反应的浓氨水和三氯化磷,在残留物中加入二氯乙烷和三氯氧磷,搅拌加热至回流,持续回流反应9-10h,然后进行旋蒸除去其中溶剂和未反应的物质,得到支化不饱和硅腈单体;其中每千克产物C中加入浓氨水820-830g,三氯化磷310-320g,丙酮3.6-3.8L,二氯乙烷4.3-4.7L,三氯氧磷520-530g;产物C中含有羧基,在浓氨水和三氯化磷的作用下形成酰胺,酰胺在三氯氧磷的作用下进行脱水反应,形成腈基;
其中抗氧化增强剂的具体制备过程如下:
(1)将2,2,6,6-四甲基-4-哌啶酮加入乙醚溶液中搅拌溶解,然后向其中加入(3-环氧丙基丙氧基)三甲氧基硅烷,升温至70-75℃回流反应4-5h,减压蒸发回收溶剂,然后将得到的产物加入苯中,搅拌混合5-10min后过滤,然后依次用水和丙酮洗涤烘干,得到氧基硅烷化哌啶酮,其中n(2,2,6,6-四甲基-4-哌啶酮):n((3-环氧丙基丙氧基)三甲氧基硅烷)=1:1.2-1.3
(2)将氧基硅烷化哌啶酮加入乙醇中搅拌溶解,然后向其中加入丙烯酰胺和乙醇钠,升温至80-85℃回流反应2h,然后再向其中补加乙醇钠,升温至100-105℃回流反应5-6h,将产物用去离子水洗涤4-5次后用无水硫酸钠进行干燥过滤,滤液旋蒸除去溶剂和未反应物质,得到双酰胺基氧基硅烷化哌啶酮;其中n(氧基硅烷化哌啶酮):n(丙烯酰胺)=1:2.3-2.4,每摩尔氧基硅烷化哌啶酮中加入乙醇钠86-92g,第一次加入乙醇钠的质量为第二次加入乙醇钠质量的2.3-2.4倍,由于氧基硅烷化哌啶酮羰基两侧的甲基碳上的活泼氢被乙醇钠夺取,生成的碳负离子与丙烯酰胺进行共轭加成,进而使得丙烯酰胺接枝在哌啶酮羰基两侧的甲基上;
(3)将质量浓度为10%的氢氧化钠溶液加入反应釜中,然后向其中加入双酰胺基氧基硅烷化哌啶酮,冰水浴降温至0-5℃滴加质量浓度为10%的次氯酸钠溶液,控制30min内滴加完,然后缓慢升温至70-75℃并保温反应50-60min,冷却至室温后加入氯化钠的饱和溶液,然后在连续萃取器中用乙醚萃取15-20h,接着用氢氧化钠干燥,蒸除乙醚后得到抗氧化增强剂;其中每千克双酰胺基氧基硅烷化哌啶酮中加入质量浓度为10%的氢氧化钠溶液5L,加入次氯酸钠溶液2.3-2.4kg;由于酰胺容易水解,使得反应过程中氨基含量降低,通过将酰胺基团进行氨化反应制备成氨基,能够稳定存在,制备的抗氧化增强剂中含有受阻胺基团,同时位于受阻胺基团的两侧引入有烷氨基链,提供两个氨基进行交联,同时受阻胺的一侧通过氨基接枝有硅氧烷键,进而使得制备的抗氧增强剂能够通过氨基进行交联反应,同时通过受阻胺基团实现抗氧化性能,通过硅氧烷键的作用提高其热稳定性。
本发明的有益效果:
1、本发明制备的超支化硅腈基橡胶在制备过程中使用的支化不饱和硅腈单体是以苯环为中心的支化结构,使得每个交联单元中心都是以苯环为中心,并且超支化硅腈基橡胶在制备过程中通过抗氧化增强剂进行交联,进而提高了制备的聚合物的聚合程度,进一步提高了聚合物的强度,进而使得制备的超支化聚合物具有较高的强度,同时由于超支化结构使得聚合物具有大量的支链结构,使得其韧性增强,进而使得制备的超支化聚合物具有较高的韧性和强度,无需另外添加聚合物增强其强度,进而也就不会造成其耐油性能降低。
2、本发明制备的聚合物材料具有超支化结构,其中支化链上均接枝有氧基硅烷键,使得硅氧烷键位点增多,制备的聚合物具有均匀的耐热性能,同时抗氧增强剂中引入有氧基硅烷键,进而使得丁二烯交联单元之间通过含有氧基硅烷键的抗氧增强剂交联后,聚合物丁二烯单元之间也引入氧基硅烷键,而支化不饱和硅腈单体本身就引入有氧基硅烷键,进而使得制备的橡胶聚合物各部分单体均能够连接氧基硅烷键,使得氧基硅烷键均匀的分布在制备的橡胶聚合物中,进而使得制备的橡胶聚合物具有均匀且较高的耐热老化性能,同时由于聚合物之间通过抗氧增强剂连接,使得抗氧增强剂均匀的在聚合物链上,而抗氧增强剂中含有受阻胺基团,使得制备的橡胶材料中均匀分布有受阻胺基团,能够实现较高的抗臭氧性能,避免了直接在聚合物中添加耐老化剂,容易分散不均匀或者抽离造成其耐老化性能降低。
3、本发明制备的橡胶材料具有超支化结构,进而使得加入的发泡剂和炭黑材料能够均匀分散,发泡剂的均匀分散使得发泡均匀稳定,进而使得材料的回弹性能稳定,同时炭黑能够均匀屏蔽紫外线,炭黑均匀分散后使得其抗紫外线性能均匀。
具体实施方式
实施例1:
支化不饱和硅腈单体的制备方法如下:
步骤1:在反应釜上设置有冷凝管,同时冷凝管连接副产物HCl吸收装置,将1mol间苯三酚和1kg乙醚同时加入反应釜中,搅拌溶解,然后控制在10℃下向反应釜中滴加3mol二甲基二氯硅烷,控制2h内滴加完全,然后搅拌反应8h,接着向其中滴加3.3mol乙二醇,控制1h内滴加完全,然后升温至95℃回流反应12h,减压蒸馏除去过量的反应物和溶剂后得到产物A;对产物A进行红外分析,在在3420cm-1和1063cm-1处出现了醇羟基红外吸收峰,同时在1100cm-1处出现了硅氧键的红外吸收峰;
步骤2:将260g氯铬酸吡啶盐和1.8L二氯甲烷加入反应釜中搅拌,在氮气保护下加入100g产物A,室温下搅拌反应3-4h,然后加入无水乙醚,搅拌均匀后进行抽滤,蒸除滤液中的溶剂,将得到的固体产物用水洗涤烘干,得到产物B;对产物B进行红外分析,在1727cm-1处出现了醛基的红外吸收峰,同时1063cm-1处的吸收峰消失;
步骤3:将100g产物B和720g苯同时加入反应釜中搅拌溶解,升温至140℃加入147g乙酸酐和33g醋酸钠,保温反应16h,冷却,加入水和乙酸乙酯,搅拌10min后用盐酸调节Ph=1-2,然后静置分层,分取乙酸乙酯层,水层用乙酸乙酯提取3次后合并乙酸乙酯层,水洗两次后用无水硫酸钠脱水,过滤,滤液减压回收溶剂,得到产物C,反应结构式如下所示,同时对产物C进行红外分析,1727cm-1处的红外吸收峰消失,1702cm-1处出现了烯酸中羧基的吸收峰;
步骤4:将1kg产物C加入3.7L丙酮溶液中搅拌溶解,然后向其中加入825g浓氨水和525g三氯化磷,升温至90℃保温反应6h,然后蒸去溶剂、未反应的浓氨水和三氯化磷,在残留物中加入二氯乙烷和三氯氧磷,搅拌加热至回流,持续回流反应10h,然后进行旋蒸除去其中溶剂和未反应的物质,得到支化不饱和硅腈单体;对产物进行红外分析,1702cm-1处的红外吸收峰消失,同时在2230cm-1处出现了腈基的红外吸收峰;
实施例2:
支化不饱和硅腈单体的制备方法与实施例1相同,将实施例1步骤1中使用的间苯三酚替换为丙三醇。
实施例3:
不饱和硅腈单体的制备方法与实施例1相同,将实施例1步骤1中使用的间苯三酚替换为对苯二酚。
实施例4:
不饱和硅腈单体的制备方法与实施例1相同,将实施例1步骤1中使用的间苯三酚替换为苯酚。
实施例5:
不饱和腈单体的制备方法与实施例1相同,删除步骤1和步骤2,同时将步骤3中使用的产物B替换为苯乙醛。
实施例6:
抗氧化增强剂的具体制备过程如下:
(1)将1mol2,2,6,6-四甲基-4-哌啶酮加入800mL乙醚溶液中搅拌溶解,然后向其中加入1.25mol(3-环氧丙基丙氧基)三甲氧基硅烷,升温至75℃回流反应5h,减压蒸发回收溶剂,然后将得到的产物加入苯中,搅拌混合5min后过滤,然后依次用水和丙酮洗涤烘干,得到氧基硅烷化哌啶酮;对产物进行红外分析,在1100cm-1处出现了硅氧键的红外吸收峰;
(2)将1mol氧基硅烷化哌啶酮加入1L乙醇中搅拌溶解,然后向其中加入2.35mol丙烯酰胺和63g乙醇钠,升温至85℃回流反应2h,然后再向其中补加26.8g乙醇钠,升温至100℃回流反应6h,将产物用去离子水洗涤5次后用无水硫酸钠进行干燥过滤,滤液旋蒸除去溶剂和未反应物质,得到双酰胺基氧基硅烷化哌啶酮;对产物进行红外分析,在3183cm-1和3360cm-1处出现了酰胺中氨基的的红外吸收双峰,1620cm-1处出现了烯烃基团的红外吸收峰;
(3)将500mL质量浓度为10%的氢氧化钠溶液加入反应釜中,然后向其中加入100g双酰胺基氧基硅烷化哌啶酮,冰水浴降温至5℃滴加235g质量浓度为10%的次氯酸钠溶液,控制30min内滴加完,然后缓慢升温至75℃并保温反应50min,冷却至室温后加入氯化钠的饱和溶液,然后在连续萃取器中用乙醚萃取20h,接着用氢氧化钠干燥,蒸除乙醚后得到抗氧化增强剂;对产物进行红外分析可知,1620cm-1处的红外吸收峰消失。
实施例7:
抗氧化增强剂的具体制备过程如下:
(1)将1mol2,2,6,6-四甲基-4-哌啶酮加入1L乙醇中搅拌溶解,然后向其中加入2.35mol丙烯酰胺和63g乙醇钠,升温至85℃回流反应2h,然后再向其中补加26.8g乙醇钠,升温至100℃回流反应6h,将产物用去离子水洗涤5次后用无水硫酸钠进行干燥过滤,滤液旋蒸除去溶剂和未反应物质,得到双酰胺基哌啶酮;
(2)将500mL质量浓度为10%的氢氧化钠溶液加入反应釜中,然后向其中加入100g双酰胺基哌啶酮,冰水浴降温至5℃滴加235g质量浓度为10%的次氯酸钠溶液,控制30min内滴加完,然后缓慢升温至75℃并保温反应50min,冷却至室温后加入氯化钠的饱和溶液,然后在连续萃取器中用乙醚萃取20h,接着用氢氧化钠干燥,蒸除乙醚后得到抗氧化增强剂。
实施例8:
一种高强度弹性发泡材料的具体制备过程如下:
第一步,将实施例1制备的支化不饱和硅腈单体加入乙醇溶液中搅拌溶解,配成质量浓度为45%的支化不饱和硅腈单体溶液,然后将800g支化不饱和硅腈单体溶液、35g脂肪醇酰硫酸钠、7g磷酸钠、0.6g乙二胺四乙酸四钠盐和1.75kg水同时加入反应釜中,向反应釜中不断的通氮气30-40min,再降温至-5℃,再有质量流量计计量加入650g丁二烯单体,然后升温至5℃后加入1.6g异丙苯过氧化氢和2g叔十二硫醇,接着控制反应釜的压力为0.2-0.3MPa,反应7h后升温至30-35℃,当单体转化率为73%时,向其中加入2.3g甲基二硫代氨基甲酸钠,继续搅拌20min,然后将得到的胶浆在脱气釜中进行抽真空除去未反应的单体,得到聚合物胶浆;
第二步,将1kg得到的聚合物胶浆、3.7L乙酸乙酯和425g醋酸钠同时加入反应釜中,搅拌冷却,在10℃下反应6h,反应过程中不断滴加3.25kg质量浓度为40%的过氧乙酸溶液,加完后再反应8h,冷却条件下加液碱至pH=10,然后升温至70℃向其中加入103g实施例5制备的抗氧增强剂,搅拌反应5h后冷却,然后进行过滤洗涤烘干,得到高强度抗氧橡胶聚合物;
第三步:将1kg超支化硅腈基橡胶、45g氧化锌、8g硬脂酸锌、95g炭黑、14g促进剂加入160℃的密炼机中混炼9min,然后降温至80℃加入22g硫磺和110g偶氮二甲酰胺,混炼均匀后调节辊距下片,然后将胶料在180℃下静止发泡,得到高强度弹性发泡材料,该橡胶材料在120℃的1号油中浸泡72h后,该材料的拉伸强度变化率只有5.4%,由此可知,该材料具有较高的耐油性能。
实施例9:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例1制备的支化不饱和硅腈单体替换为实施例2制备的支化不饱和硅腈单体。
实施例10:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例1制备的支化不饱和硅腈单体替换为实施例3制备的不饱和硅腈单体。
实施例11:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例1制备的支化不饱和硅腈单体替换为实施例4制备的不饱和硅腈单体。
实施例12:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例1制备的支化不饱和硅腈单体替换为实施例5制备的不饱和腈单体,同时在第一步中添加113g硅烷偶联剂KH560。
实施例13:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例6制备的抗氧增强剂替换为实施例7制备的抗氧增强剂。
实施例14:
一种高强度弹性发泡材料的具体制备过程与实施例7相同,将实施例7中使用的实施例6制备的抗氧增强剂替换为实施例6中步骤(2)中制备的双酰胺基氧基硅烷化哌啶酮。
试验例:
(1)参照ASTM D471标准对制备的发泡材料进行力学性能测定,具体测定结果如表1所示:
表1实施例8-13制备的发泡材料的力学性能测定结果
由表1可知,实施例8中制备的发泡材料聚合物同时具有较高的拉伸强度和断裂伸长率,由于制备的支化不饱和硅腈单体是以苯环为中心的支化结构,并且支化链上含有氧基硅烷键,通过单体与丁二烯之间的聚合作用制备超支化的橡胶聚合物,使得聚合物链上均匀的引入大量的氧基硅烷键,并且每个交联单元中心都是以苯环为中心,进而使得制备的超支化聚合物具有较高的强度,同时由于超支化结构使得聚合物的韧性增强,进而使得制备的超支化聚合物具有较高的韧性和强度,超支化聚合物通过抗氧化增强剂交联后使得制备的橡胶材料的交联程度增大,进而使得制备的产物强度进一步增大;实施例9中由于制备的支化不饱和单体中不是以苯环为中心,进而使得产物的刚性降低,强度降低,实施例10、实施例11和实施例12中由于聚合物制备过程中使用的单体不具有不同方向的支化链,进而使得制备的聚合物的支化程度降低,进而使得材料的断裂强度大大降低,而强度稍微增加,同时实施例12中由于单体中没有引入氧基硅烷键,因此与实施例11相比,其韧性稍有降低,实施例13中由于在抗氧增强剂中没有引入支链-长链氧基硅烷,进而使得其韧性进一步降低,实施例14中由于在反应过程中抗氧增强剂两端直接连接酰胺基团,由于酰胺基团在水中容易水解,进而影响抗氧增强剂的交联性能,进而使得制备的聚合物强度降低。
(2)将实施例8-14中的发泡材料都均匀的分切成三块,通过金相显微镜观察实施例8-14发泡材料的形貌,然后读取金相图片的泡孔,测定每块发泡材料中平均泡孔直径,然后计算泡孔直径的最大差值=三块发泡材料泡孔平均直径中最大值-三块发泡材料泡孔平均直径中最小值,计算结果可知,实施例8中泡孔直径的最大差值2μm、实施例9中泡孔直径的最大差值3μm、实施例13泡孔直径的最大差值2μm,实施例14中泡孔直径的最大差值4μm,实施例10中泡孔直径的最大差值12μm,实施例11中泡孔直径的最大差值16μm,实施例12中泡孔直径的最大差值16μm;综上可知,实施例8、9、13和14中制备的发泡材料泡孔均匀,直径相差较小,由于其中使用的橡胶材料具有超支化结构,进而使得加入的发泡剂能够均匀分散,使得发泡均匀稳定,而实施例10-12中橡胶材料发泡不均匀,泡孔直径相差较大,由于使用的橡胶材料不是超支化结构,造成发泡材料不能完全均匀分散,使得发泡性能不均匀。
(3)对实施例8-14中制备的橡胶材料进行老化试验,具体实验过程如下:
①臭氧老化过程:按照ASTM D1171标准测定橡胶材料的耐臭氧性能,测定结果可知,实施例8-14中制备的橡胶材料老化后均无龟裂情况产生。
②热老化过程中:在140℃的热老化试验箱中老化72h,然后测定老化前后材料的拉伸强度,计算老化前后橡胶材料的拉伸强度保留率,实施例8中保留率为96.3%,实施例9中保留率为96.1%,实施例14中保留率为95.7%,由于实施例8、9和14中聚合物材料均匀超支化结构,其中支化链上均接枝有氧基硅烷键,使得硅氧烷键位点增多,制备的聚合物具有均匀的耐热性能,同时抗氧增强剂中引入有氧基硅烷键,进而使得丁二烯交联单元之间通过含有氧基硅烷键的抗氧增强剂交联后,聚合物丁二烯单元之间也引入氧基硅烷键,而支化不饱和硅腈单体本身就引入有氧基硅烷键,进而使得制备的橡胶聚合物各部分单体均能够连接氧基硅烷键,使得氧基硅烷键均匀的分布在制备的橡胶聚合物中,进而使得制备的橡胶聚合物具有均匀且较高的耐热老化性能;而实施例10保留率为93.4%,实施例11中保留率为93.1%,由于制备的聚合物非超支化结构,进而使得其中氧基硅烷键的作用位点降低,造成其耐热性能降低,同时实施例12中保留率为88.2%,不仅由于非超支化结构造成的氧基硅烷键的作用位点减少,同时由于单体中没有引入硅氧烷键,而是直接在聚合物过程中添加KH560,而KH560不能均匀接枝在聚合物中,容易从聚合物中抽离,进而使得耐热性能降低,同时实施例13中保留率为90.6%,由于抗氧增强剂中没有引入氧基硅烷键,进而使得聚合物中不能实现单体间均通过连接有氧基硅烷键,使得其耐热性能降低。
同时由于其中炭黑的加入能够对紫外线和臭氧有一定的屏蔽作用,而部分直接作用在聚合物上的紫外线则直接通过交联后网状结构上的五甲基哌啶酮实现对自由基的捕获,并且大量硅氧烷键的引入,提高了聚合物的耐高温性能,使得制备的聚合物具有较高的耐老化性能;
③紫外光老化过程:在紫外光老化实验箱中,其中紫外光照强度为1100μm/cm2,照射时间为1000h,然后测定老化前后材料的拉伸强度,计算老化前后橡胶材料的拉伸强度保留率,实施例8、实施例9、实施例13、实施例14保留率都在94%以上,而实施例10保留率为91.6%,实施例11保留率为90.9%,实施例12保留率为90.5%,由于实施例8、实施例9、实施例13、实施例14制备的橡胶材料为超支化结构,其中加入的炭黑能够均匀分散,炭黑能够均匀屏蔽紫外线,进而使得其抗紫外线性能均匀,而实施例10-12中制备的橡胶聚合物由于非超支化结构,进而使得其中炭黑材料容易分散不均,造成光屏蔽作用减弱。
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。显然,根据本说明书的内容,可作很多的修改和变化。本说明书选取并具体描述这些实施例,是为了更好地解释本发明的原理和实际应用,从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (10)
1.一种高强度弹性发泡材料,其特征在于,包括如下重量份的各组分:
超支化硅腈基橡胶100份、氧化锌4-5份、硬脂酸锌0.5-1份、炭黑9-10份、硫黄2-2.3份、促进剂1.3-1.7份、偶氮二甲酰胺10-12份;
其中超支化硅腈基橡胶的具体制备过程如下:
第一步,在反应釜上设置有冷凝管,同时冷凝管连接副产物HCl吸收装置,将间苯三酚和乙醚同时加入反应釜中,搅拌溶解,然后控制在10℃下向反应釜中滴加二甲基二氯硅烷,然后搅拌反应8-10h,接着向其中滴加乙二醇,然后升温至95-100℃回流反应10-12h,减压蒸馏,得到产物A;
第二步,将氯铬酸吡啶盐和二氯甲烷加入反应釜中搅拌,在氮气保护下加入产物A,室温下搅拌反应3-4h,然后加入无水乙醚,搅拌均匀后进行抽滤,蒸除滤液中的溶剂,将得到的固体产物用水洗涤烘干,得到产物B;
第三步,将产物B和苯同时加入反应釜中搅拌溶解,升温至140-145℃加入乙酸酐和醋酸钠,保温反应15-16h,冷却,加入水和乙酸乙酯,搅拌10min后用盐酸调节pH=1-2,然后分层提取后水洗干燥过滤,接着减压蒸馏得到产物C;
第四步,将产物C加入丙酮溶液中搅拌溶解,然后向其中加入浓氨水和三氯化磷,升温至80-90℃保温反应6-7h,然后蒸去溶剂、未反应的浓氨水和三氯化磷,在残留物中加入二氯乙烷和三氯氧磷,搅拌加热至回流,持续回流反应9-10h,然后进行旋蒸除去其中溶剂和未反应的物质,得到支化不饱和硅腈单体;
第五步,将支化不饱和硅腈单体加入乙醇溶液中搅拌溶解,配成质量浓度为45%的支化不饱和硅腈单体溶液,然后将支化不饱和硅腈单体溶液、乳化剂、电解质溶液、活化剂溶液和水同时加入反应釜中,向反应釜中不断的通氮气30-40min,再降温至-5℃,再有质量流量计计量加入定量的丁二烯单体,然后升温至5-10℃后加入引发剂和叔十二硫醇,接着控制反应釜的压力为0.2-0.3MPa,反应7h后升温至30-35℃,当单体转化率为70%-80%时,向其中加入甲基二硫代氨基甲酸钠,继续搅拌20-30min,然后将得到的胶浆在脱气釜中进行抽真空除去未反应的单体,得到聚合物胶浆;
第六步,将得到的聚合物胶浆、乙酸乙酯和醋酸钠同时加入反应釜中,搅拌冷却,在5-10℃下反应6h,反应过程中不断滴加质量浓度为40%的过氧乙酸溶液,加完后再反应7-8h,冷却条件下加液碱至pH=10,然后升温至70-80℃向其中加入抗氧增强剂,搅拌反应4-5h后冷却,然后进行过滤洗涤烘干,得到高强度抗氧橡胶聚合物。
2.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第一步中间苯三酚、二甲基二氯硅烷和乙二醇按照物质的量之比为1:3:3.2-3.3的比例加入。
3.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第二步中每克产物A中加入氯铬酸吡啶盐2.6-2.7g,加入二氯甲烷18-20mL。
4.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第三步中每千克产物B中加入乙酸酐1.45-1.48kg,加入醋酸钠320-340g,加入苯7-7.5kg。
5.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第四步中每千克产物C中加入浓氨水820-830g,三氯化磷310-320g,丙酮3.6-3.8L,二氯乙烷4.3-4.7L,三氯氧磷520-530g。
6.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第五步中各组分原料的重量份如下:支化不饱和硅腈单体溶液73-82份、丁二烯62-68份、乳化剂3-5份、电解质0.6-0.8份、活化剂0.05-0.07份、引发剂0.14-0.18份、叔十二硫醇0.19-0.21份、甲基二硫代氨基甲酸钠0.2-0.3份、水175-180份。
7.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,第六步中每千克聚合物胶浆中加入乙酸乙酯3.5-3.8L,加入醋酸钠420-430g,加入质量浓度为40%的过氧乙酸溶液3.2-3.3kg,加入抗氧增强剂101-104g。
8.根据权利要求1所述的一种高强度弹性发泡材料,其特征在于,抗氧化增强剂的具体制备过程如下:
(1)将2,2,6,6-四甲基-4-哌啶酮加入乙醚溶液中搅拌溶解,然后向其中加入(3-环氧丙基丙氧基)三甲氧基硅烷,升温至70-75℃回流反应4-5h,减压蒸发回收溶剂,然后将得到的产物加入苯中,搅拌混合5-10min后过滤,然后依次用水和丙酮洗涤烘干,得到氧基硅烷化哌啶酮;
(2)将氧基硅烷化哌啶酮加入乙醇中搅拌溶解,然后向其中加入丙烯酰胺和乙醇钠,升温至80-85℃回流反应2h,然后再向其中补加乙醇钠,升温至100-105℃回流反应5-6h,将产物水洗后干燥过滤,接着进行减压蒸馏得到双酰胺基氧基硅烷化哌啶酮;
(3)将质量浓度为10%的氢氧化钠溶液加入反应釜中,然后向其中加入双酰胺基氧基硅烷化哌啶酮,冰水浴降温至0-5℃滴加质量浓度为10%的次氯酸钠溶液,控制30min内滴加完,然后缓慢升温至70-75℃并保温反应50-60min,冷却至室温后加入氯化钠的饱和溶液,接着用乙醚萃取并用氢氧化钠干燥,蒸除乙醚后得到抗氧化增强剂。
9.根据权利要求8所述的一种高强度弹性发泡材料,其特征在于,步骤(2)中n(氧基硅烷化哌啶酮):n(丙烯酰胺)=1:2.3-2.4,每摩尔氧基硅烷化哌啶酮中加入乙醇钠86-92g,第一次加入乙醇钠的质量为第二次加入乙醇钠质量的2.3-2.4倍。
10.一种根据权利要求1所述的高强度弹性发泡材料的制备方法,其特征在于,具体制备过程如下:
将超支化硅腈基橡胶、氧化锌、硬脂酸锌、炭黑、促进剂加入160℃的密炼机中混炼8-9min,然后降温至80℃加入硫磺和偶氮二甲酰胺,混炼均匀后调节辊距下片,然后将胶料在180℃下静止发泡,得到高强度弹性发泡材料。
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