CN107200938A - A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene - Google Patents
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene Download PDFInfo
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- CN107200938A CN107200938A CN201610151000.0A CN201610151000A CN107200938A CN 107200938 A CN107200938 A CN 107200938A CN 201610151000 A CN201610151000 A CN 201610151000A CN 107200938 A CN107200938 A CN 107200938A
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- methylstyrene
- foamed material
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 229920001577 copolymer Polymers 0.000 title claims abstract description 27
- JBAUPCNQUQGXJT-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene;2-methylprop-1-ene Chemical class CC(C)=C.CC1=CC=C(C=C)C=C1 JBAUPCNQUQGXJT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000004014 plasticizer Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- -1 4,4'- oxybis-benzenesulfonyl Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 229960002447 thiram Drugs 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 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 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000013016 damping Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 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 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000007493 shaping process Methods 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 claims 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 239000012567 medical material Substances 0.000 abstract description 3
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 239000008393 encapsulating agent Substances 0.000 abstract description 2
- 239000012774 insulation material Substances 0.000 abstract description 2
- 125000006850 spacer group Chemical group 0.000 abstract description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- OYUMYJKDVNCXAX-UHFFFAOYSA-N 2-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O OYUMYJKDVNCXAX-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
- 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
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2323/22—Copolymers of isobutene; butyl rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of co-polymer foamed material of brominated isobutylene p-methylstyrene and preparation method thereof, its formula includes BIMSM100 parts, 0 100 parts of filler, 0 30 parts of plasticizer, 2 15 parts of foaming agent, 05 parts of activating agent, 05 parts of vulcanizing agent；05 parts of accelerator；05 parts of antioxidant, and preparation method is provided with above-mentioned formula.It the method can be widely used in the fields such as heat-barrier material, encapsulant, insulation material, buffering spacer, sound absorbing plate, medical material utensil, Aero-Space.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of brominated isobutylene-p-methylstyrene is co-polymer foamed
Material and preparation method thereof.
Background technology
According to《Chinese high molecular foam material industry production need to be predicted looks forward to the prospect with Development-Pattern Transformation analysis report》Data display,
During 2008 second half year to 2009 first half of the year, influenceed by global financial crisis, certain downslide occurs in domestic economy,
Associated outlet trade is a greater impact, and flexible foamed materials industry development speed slows down.Market scale in 2008 is 54.83
Hundred million yuan, increase by 11.58% on a year-on-year basis, market scale is 61.19 hundred million yuan within 2009, and year-on-year growth rate is 11.60%, is compared
The first two years, there is different degrees of decline.Since the second half year in 2009, global economy started recovery, domestic family
The development of the relevant industries such as electricity, electronic product and Leisure Sport starts slowly to recover the development speed before financial crisis.In advance
Meter is after 2010, and the flexible foamed materials industry of China will have lasting fast development, it is contemplated that annual growth will exceed
15%, it is up to 10,000,000,000 yuan to market scale in 2012.
Brominated isobutylene-p-methylstyrene copolymer has disordered structure, this be due to monomer reactivity ratio it is basic
It is identical.After aggregated and subsequent bromination, some of p-methylstyrene groups are converted into active brominating methyl styrene
Group.In the polymer of these main chain saturations containing isobutene, the p-methylstyrene of 1%-5% mol ratios and
The brominated p-methylstyrene of 0.5%-1.3% mol ratios.Its glass transition temperature or second order transition temperature are with to methylbenzene
The increase of ethylene contents and raise, typically about -57 DEG C.
It was found from from the structure of BIMSM elastomers, carbon-to-carbon double bond is free of in its main chain, C-C crosslinkings can be formed and be good for,
And main chain is saturation, so its heat resistance and ozone resistance are greatly enhanced.This glue does not contain age resistor, oligomeric
The material such as thing and epoxidized soybean oil, high purity.BIMSM air-tightness, heat endurance, ozone resistance, oxidation are steady
It is qualitative to be better than halogenated butyl rubber.
The content of the invention
It is an object of the invention to provide a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene and its preparation side
Method, the method can be widely used in heat-barrier material, encapsulant, insulation material, buffering spacer, sound absorbing plate, medical material
The fields such as glassware tool, Aero-Space.
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, its formula is as follows：BIMSM100 parts, fill out
0-100 parts of material, 0-30 parts of plasticizer, 0-15 parts of foaming agent, 0-5 parts of activating agent, 0-5 parts of vulcanizing agent；Accelerator
0-5 parts；0-5 parts of antioxidant.
Filler is the one or more in carbon black, white carbon, calcium carbonate, kaolin, talcum powder.
Plasticizer is the one or more in aromatic naphtha, paraffin oil, n-butene isobutylene copolymers (PB).
Foaming agent is any of azodicarbonamide (AC), 4,4'- oxybis-benzenesulfonyl hydrazides (OBSH).
Activating agent is the one or more in zinc oxide (ZnO) stearic acid (SA), zinc stearate (ZnSt).
Vulcanizing agent is that magnesia (MgO), Sulfur (S), alkylphenol formaldehyde resin (SP-1045), peroxidating two are different
One or more in propyl benzene (DCP).
Vulcanization accelerator is benzothiazole disulfide (DM), tetramethylthiuram disulfide (TMTD), dimethyl two
Thiocarbamates (ZDMC), tetra-sulfurized pair pentamethylene thiuram (DPTT), Triallyl isocyanurate (TAIC)
In one or more.
Antioxidant is β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 2,6-
One or more in di-tert-butyl-4-methy phenol (BHT).
A kind of preparation method of the co-polymer foamed material of brominated isobutylene-p-methylstyrene, its step is as follows：
1) mixed refining process
In BIMSM input banburies, banbury temperature is 80-120 DEG C, sequentially adds filler, plasticizer, age resistor
And fire retardant etc., 5-10min is kneaded, vulcanizing agent, foaming agent is added, 3-5min is kneaded, roll spacing 2mm is finally adjusted,
Bottom sheet discharges, and obtains elastomeric compound；
2) sulfur foam
1. free foaming technique：Elastomeric compound is put into Rubber Extruder, extruder extrusion predetermined shape sheet material, and passed through
Guide wheel is transported in foaming furnace, and foaming furnace is that electric heating air blast is uniformly heated, and leading portion is crosslinked or microwave radiation equipped with infra-red radiation
Crosslinking, the temperature that temperature imports foaming furnace from extruder to foaming furnace terminal temperature is respectively set as 130-180 DEG C, this plate
Time of the material in foaming furnace is 15-30 minutes, is cooled down after foaming through water cooling tank, is cut, and Novel high-damping is made and inhales
Sound expanded material.
2. moulded from foam technique, mould, pressure 10-20MPa, 160-180 DEG C of temperature, time are inserted by elastomeric compound
Load weighted film, using mode hopping foaming, i.e., is encased in mould by 5-15min, the defined time, pressure and
At a temperature of after saturation, open mould and obtain foaming plate, cool down at room temperature, Novel high-damping sound absorption expanded material is made.
The preparation method of another co-polymer foamed material of brominated isobutylene-p-methylstyrene, its step is as follows：
1) prepared by elastomeric compound
(1) parts by weights also known as takes required rubber, filler and plasticizer；(2) banbury temperature setting is 60-100 DEG C,
Rotating speed is 40-60rpm, rubber, filler, plasticizer is put into banbury, mixing is uniform, control dump temperature is low
In 120 DEG C；(3) 12h is parked in elastomeric compound dumping, tabletting, cooling；(4) sizing material after parking is added on a mill
Vulcanizing system.
2) extrusion/compression molding
Elastomeric compound is put into extruder, extrusion board, tubing or required shape.
3) presulfurization
The drying tunnel that the batch mixing glue of shaping is put into 100-160 DEG C carries out presulfurization, and prevulcanisation time is 3min-40min, sulphur
Change mode is hot-air cure, microwave radiation crosslinking or infra-red radiation crosslinking etc..
4) supercritical foaming
The good sample of presulfurization is put into autoclave, is passed through physical blowing agent and is warming up to 40-150 DEG C, is forced into
After 5-60Mpa, saturation 0.5-72h, poromerics is made in pressure release.Wherein ultra physical foaming agent is CO2, N2, fourth
One or more in alkane, pentane.
5) post-cure, sizing；
Presulfurization micro-foaming material is put into post-cure in another drying tunnel, sizing, wherein drying tunnel temperature is 100-180 DEG C,
Cure time is 10-60min, and vulcanization is hot-air cure, microwave radiation crosslinking or infra-red radiation crosslinking etc..
Compared with prior art, the invention has the advantages that：
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene is a kind of high performance elastomer material, is not only had
There are hypotonicity and high damping property, the sound absorption soundproof effect of rubber excellent, and with certain intensity, hardness and heat surely
Qualitative, weatherability, ozone resistance are excellent；And the expanded material of wherein supercritical foaming method preparation is more clean, can use
In the product that medical material etc. requires higher.
Brief description of the drawings
In Fig. 1 preparation methods of the present invention, the scanning electron microscope (SEM) photograph of embodiment 1；
In Fig. 2 preparation methods of the present invention, the scanning electron microscope (SEM) photograph of embodiment 2；
In Fig. 3 preparation methods of the present invention, the scanning electron microscope (SEM) photograph of embodiment 3；
In Fig. 4 preparation methods of the present invention, the scanning electron microscope (SEM) photograph of embodiment 4.
Embodiment
The present invention is described further with reference to embodiment：
Embodiment 1
100 parts of BIMSM, 15 parts of filler, 0 part of plasticizer, 2 parts of foaming agent, 1 part of activating agent, 1 part of vulcanizing agent；
1 part of accelerator；1 part of antioxidant.
Filler is carbon black.
Plasticizer is aromatic naphtha.
Foaming agent is azodicarbonamide (AC).
Activating agent is zinc oxide (ZnO).
Vulcanizing agent is magnesia (MgO).
Vulcanization accelerator is benzothiazole disulfide (DM).
Antioxidant is β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid.
In BIMSM input banburies, banbury temperature is 80 DEG C, sequentially adds filler, plasticizer, age resistor etc.,
5-10min is kneaded, vulcanizing agent, foaming agent is added, 3-5min is kneaded, roll spacing 2mm is finally adjusted, bottom sheet discharges,
Obtain elastomeric compound.Elastomeric compound is inserted into mould, pressure 10MPa, 160 DEG C of temperature, time 15min is sent out using mode hopping
Load weighted film, i.e., be encased in mould by bubble method, under defined time, pressure and temperature after saturation, opens mould
Tool obtains foaming plate, and its scanning electron microscope (SEM) photograph is shown in Fig. 1.
Embodiment 2
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, its formula is as follows：BIMSM100 parts, fill out
50 parts of material, 10 parts of plasticizer, 6 parts of foaming agent, 5 parts of activating agent, 2.5 parts of vulcanizing agent；4 parts of accelerator；Antioxygen
0.5 part of agent.
Filler is kaolin.
Plasticizer is paraffin oil.
Foaming agent is 4,4'- oxybis-benzenesulfonyl hydrazides (OBSH).
Activating agent is stearic acid (SA.
Vulcanizing agent is Sulfur (S).
Vulcanization accelerator is tetramethylthiuram disulfide (TMTD)
Antioxidant is 2,6- di-tert-butyl-4-methy phenols (BHT).
In BIMSM input banburies, banbury temperature is 100 DEG C, sequentially adds filler, plasticizer, age resistor etc.,
5-10min is kneaded, vulcanizing agent, foaming agent is added, 3-5min is kneaded, roll spacing 2mm is finally adjusted, bottom sheet discharges,
Obtain elastomeric compound.Elastomeric compound is inserted into mould, pressure 10MPa, 180 DEG C of temperature, time 6min is sent out using mode hopping
Load weighted film, i.e., be encased in mould by bubble method, under defined time, pressure and temperature after saturation, opens mould
Tool obtains foaming plate, and its scanning electron microscope (SEM) photograph is shown in Fig. 2.
Embodiment 3
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, its formula is as follows：BIMSM100 parts, fill out
30 parts of material, 5 parts of plasticizer, 3 parts of activating agent, 2 parts of vulcanizing agent；3 parts of accelerator；2 parts of antioxidant.
Filler is white carbon.
Plasticizer is n-butene isobutylene copolymers (PB).
Activating agent is zinc stearate (ZnSt).
Vulcanizing agent is alkylphenol formaldehyde resin (SP-1045).
Vulcanization accelerator is tetra-sulfurized pair pentamethylene thiuram (DPTT).
Antioxidant is β-positive octadecanol ester (antioxidant 1076) of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 2,6-
The mixture of di-tert-butyl-4-methy phenol (BHT).
Banbury temperature setting is 120 DEG C, and rotating speed is 60rpm, and rubber, filler, plasticizer are put into banbury,
Mixing is uniform, and 12h is parked in elastomeric compound dumping, tabletting, cooling；Sizing material after parking is added into vulcanizing system on a mill.
Elastomeric compound is put into extruder, extrusion board.The drying tunnel that the elastomeric compound of shaping is put into 160 DEG C carries out presulfurization, pre- sulphur
The change time is 15min.The good sample of presulfurization is put into autoclave, is passed through N2And be warming up to 40 DEG C, be forced into
After 16Mpa, saturation 24h, pressure release；Then presulfurization micro-foaming material is put into post-cure in another drying tunnel, sizing,
Wherein drying tunnel temperature is 180 DEG C, and cure time is 3min, and microcellular foam material is obtained after being taken out from drying tunnel, and it scans electricity
Mirror figure is shown in Fig. 3.
Embodiment 4
A kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, its formula is as follows：BIMSM100 parts, fill out
60 parts of material, 10 parts of plasticizer, 1 part of activating agent, 2 parts of vulcanizing agent；3 parts of accelerator；1 part of antioxidant.
Filler is kaolin.
Plasticizer is aromatic naphtha, paraffin oil, the mixture of n-butene isobutylene copolymers (PB).
Foaming agent is azodicarbonamide (AC).
Activating agent is zinc stearate (ZnSt).
Vulcanizing agent is cumyl peroxide (DCP).
Vulcanization accelerator is Triallyl isocyanurate (TAIC).
Antioxidant is 2,6- di-tert-butyl-4-methy phenols (BHT).
Banbury temperature setting is 100 DEG C, and rotating speed is 60rpm, and rubber, filler, plasticizer are put into banbury,
3min is kneaded, vulcanizing agent, accelerator is then added, 2min is kneaded, 12h is parked in dumping, tabletting, cooling.Will be mixed
Refining is placed in mould, and compression molding presulfurization, wherein vulcanizing agent temperature are 140 DEG C, prevulcanisation time 10min.Pre- sulphur
The sample changed is put into autoclave, is passed through CO2And be warming up to 130 DEG C, be forced into 20Mpa, after saturation 2h,
Pressure release, takes out sample, and cooling obtains microcellular foam material, its scanning electron microscope (SEM) photograph is shown in Fig. 4.
The property indices of the expanded material obtained by above-described embodiment are detected according to a conventional method, it is real
Apply a 1-4 testing result and be shown in Table 1
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Shore C hardness | 14 | 27 | 19 | 25 |
| Density g/cm3 | 0.209 | 0.395 | 0.286 | 0.435 |
| Resilience | 63 | 68 | 67 | 66 |
| Tensile strength/MPa | 0.33 | 0.39 | 0.51 | 0.92 |
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail previous embodiment, and one of ordinary skill in the art still can be to foregoing each implementation
The technical scheme of example is modified, or carries out equivalent substitution to which part technical characteristic；And these modifications or replacement,
The essence of appropriate technical solution is not set to depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, it is characterised in that its formula is as follows：BIMSM100 parts, 0-100 parts of filler, 0-30 parts of plasticizer, 0-15 parts of foaming agent, 0-5 parts of activating agent, 0-5 parts of vulcanizing agent；0-5 parts of accelerator；0-5 parts of antioxidant.
2. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, it is characterised in that filler is the one or more in carbon black, white carbon, calcium carbonate, kaolin, talcum powder.
3. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, it is characterised in that plasticizer is the one or more in aromatic naphtha, paraffin oil, n-butene isobutylene copolymers (PB).
4. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, it is characterized in that, foaming agent is any of azodicarbonamide (AC), 4,4'- oxybis-benzenesulfonyl hydrazides (OBSH), microballoon foaming agent.
5. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, characterized in that, activating agent is the one or more in zinc oxide (ZnO) stearic acid (SA), zinc stearate (ZnSt).
6. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, characterized in that, vulcanizing agent is the one or more in magnesia (MgO), Sulfur (S), alkylphenol formaldehyde resin (SP-1045), cumyl peroxide (DCP).
7. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, characterized in that, vulcanization accelerator is the one or more in benzothiazole disulfide (DM), tetramethylthiuram disulfide (TMTD), DMDS carbaminate (ZDMC), tetra-sulfurized pair pentamethylene thiuram (DPTT), Triallyl isocyanurate (TAIC).
8. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene according to claims 1, it is characterized in that, antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyls) the positive octadecanol ester (antioxidant 1076) of propionic acid, the one or more in 2,6- di-tert-butyl-4-methy phenols (BHT).
9. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, it is characterised in that its preparation process is as follows：
1) mixed refining process
In BIMSM input banburies, banbury temperature is 80-120 DEG C, sequentially adds filler, plasticizer, and age resistor and fire retardant etc. knead 5-10min, add vulcanizing agent, foaming agent, knead 3-5min, finally adjusts roll spacing 2mm, and bottom sheet discharging obtains elastomeric compound；
2) sulfur foam
1. free foaming technique：Elastomeric compound is put into Rubber Extruder, extruder extrudes predetermined shape sheet material, and be transported to by guide wheel in foaming furnace, foaming furnace is that electric heating air blast is uniformly heated, and leading portion is crosslinked or microwave radiation crosslinking equipped with infra-red radiation, and the temperature that temperature imports foaming furnace from extruder to foaming furnace terminal temperature is respectively set as 130-180 DEG C, time of this sheet material in foaming furnace is 15-30 minutes, cool down, cut through water cooling tank after foaming, Novel high-damping sound absorption expanded material is made.
2. moulded from foam technique, elastomeric compound is inserted into mould, pressure 10-20MPa, 160-180 DEG C of temperature, time 5-15min, using mode hopping foaming, load weighted film is encased in mould, under defined time, pressure and temperature after saturation, mould is opened and obtains foaming plate, cool down at room temperature, Novel high-damping sound absorption expanded material is made.
10. a kind of co-polymer foamed material of brominated isobutylene-p-methylstyrene, it is characterised in that its preparation process is as follows：
1) prepared by elastomeric compound
(1) parts by weights also known as takes required rubber, filler and plasticizer；(2) banbury temperature setting is 60-100 DEG C, and rotating speed is 40-60rpm, rubber, filler, plasticizer is put into banbury, mixing is uniform, and control dump temperature is less than 120 DEG C；(3) 12h is parked in elastomeric compound dumping, tabletting, cooling；(4) sizing material after parking is added into vulcanizing system on a mill.
2) extrusion/compression molding
Elastomeric compound is put into extruder, extrusion board, tubing or required shape.
3) presulfurization
The drying tunnel that the batch mixing glue of shaping is put into 100-160 DEG C carries out presulfurization, and prevulcanisation time is 2min-40min, and vulcanization is hot-air cure, microwave radiation crosslinking or infra-red radiation crosslinking.
4) physical blowing
The good sample of presulfurization is put into autoclave, is passed through physical blowing agent and is warming up to 40-150 DEG C, is forced into 5-60Mpa, after saturation 0.5-72h, pressure release, and poromerics is made.Wherein physical blowing agent is CO2, N2, butane, the one or more in pentane.
5) post-cure, sizing；
Micro-foaming material is put into post-cure in another drying tunnel, sizing, wherein drying tunnel temperature is 100-180 DEG C, cure time is 10-60min, vulcanization is hot-air cure, microwave radiation crosslinking or infra-red radiation crosslinking.
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| US11702525B2 (en) | 2018-12-04 | 2023-07-18 | Exxonmobil Chemical Patents Inc. | Cationomeric polyolefin compositions and methods for production and use thereof |
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