CN1233746C - Peel-off nanometer composite material of grafted silicone rubber and clay and its prepn. - Google Patents
Peel-off nanometer composite material of grafted silicone rubber and clay and its prepn. Download PDFInfo
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- CN1233746C CN1233746C CN01127115.9A CN01127115A CN1233746C CN 1233746 C CN1233746 C CN 1233746C CN 01127115 A CN01127115 A CN 01127115A CN 1233746 C CN1233746 C CN 1233746C
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- clay
- silicone rubber
- grafted silicone
- composite material
- nanometer composite
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 74
- 239000004927 clay Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000004945 silicone rubber Substances 0.000 title claims description 49
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000005060 rubber Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims description 26
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005341 cation exchange Methods 0.000 claims description 15
- 241000628997 Flos Species 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000009775 high-speed stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- -1 polydimethylsiloxane Polymers 0.000 claims description 13
- 241000282326 Felis catus Species 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 16
- 239000010410 layer Substances 0.000 abstract description 14
- 239000004094 surface-active agent Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000843 powder Substances 0.000 description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 12
- 229910001961 silver nitrate Inorganic materials 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 241000370738 Chlorion Species 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 230000004044 response Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002114 nanocomposite Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000260 silastic Polymers 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Polymers 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XJENSLNYTFOSKA-UHFFFAOYSA-M [Cl-].C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.[Cl-].[NH4+] Chemical compound [Cl-].C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.[Cl-].[NH4+] XJENSLNYTFOSKA-UHFFFAOYSA-M 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a novel stripping grafting silicon rubber / clay nanometer composite material and a preparation method thereof. The method comprises: layered silicate modified by a cationic surface active agent and an unsaturated organic monomer, namely polydimethyl siloxane, which is in end capping by a hydroxyl group react by modified silicon-rubber raw rubber obtained by a grafting copolymerization method, and then, the reaction product is solidified and shaped; because the grafting silicon rubber has a special molecular structure, a disperse phase can be easily stripped into a nanometer-stage single-layer clay sheet layer no matter by physical or chemical intercalation driving force. The mechanical performance and the oil resistance of the solidified grafting silicon rubber / clay nanometer composite material can be obviously improved.
Description
The invention provides a kind of peel-off nanometer composite material of grafted silicone rubber and clay and preparation method thereof, the grafted silicone rubber rubber and the cats product modified layered silicate that specially refer to the reaction of a kind of polysiloxane and unsaturated organic monomers are filled into a kind of high strength that forms in the grafted silicone rubber and the exfoliated nano-composite with oil-proofness.
In general, nano composite polymer/laminated silicate material can be divided into three types in macroscopical matrix material, intercal type hybrid material, exfoliated nano-composite; Under first kind of situation, layered silicate generally keeps original state of aggregation, and polymkeric substance does not have intercalation in silicate layer, and promptly inorganics and polymkeric substance just mechanically mix, and at this moment, layered silicate plays conventional fillers.Under second kind of situation, be that polymkeric substance is inserted in the silicate layer, but silicate still keeps original crystalline structure, silicate content at the content of intercal type hybrid material than higher, general silicate content must be increased to higher degree, and mechanical property just can be significantly improved.Under the third situation, silicate layer (1nm is thick) is dispersed in the successive polymeric matrix.Compare with intercal type hybrid material mesosilicic acid salts contg, silicate content generally is very low in exfoliated nano-composite, but mechanical property can increase substantially, and the character of exfoliated nano-composite depends on the character of original polymer consumingly.
The used raw-silastic continuously of Chinese patent CN1163288A is a polydimethylsiloxane, rather than the polysiloxane in this patent and unsaturated organic monomers be by the resulting grafted silicone rubber rubber of graft copolymerization, and do not use the organic silicon surfactant that this patent is mentioned; Because the polynite/silicon rubber system of the resultant modification of CN1163288A is the intercal type hybrid material, disperse phase is the body of combining closely of multilayer clay crystal layer, phase farmland size is bigger, thereby influenced the mechanical property of matrix material, this system must be added 10～20% modified Portland, silicon rubber just can have use value, and has increased the cost of matrix material so greatly, and the hybrid material of gained is unsuitable for doing the oil resistant seal gum.
Polysiloxane and unsaturated organic monomers are to improve the effective ways of the physical and mechanical properties of polysiloxane by the method for graft copolymerization, though the modify and graft silicon rubber that obtains has higher mechanical property and certain oil resistant, solvent resistance, but its mechanical property, oil resistant, solvent resistance all do not reach the ideal effect, also must further improve.If can be by the method for modifying of nano composite polymer/laminated silicate material, have nano composite material very high-intensity, the oil-resisting type that can work thereby form under bigger load, wide temperature range, elevated pressures, then this technology will have more wide application prospect.
The purpose of this invention is to provide a kind of novel peel-off nanometer composite material of grafted silicone rubber and clay and preparation method thereof.Grafted silicone rubber is because its specific molecule structure, no matter be that the intercalation motivating force of physics or chemistry all can make disperse phase be easy to peel off to be nano level individual layer clay layer, phase farmland size is little, thereby the mechanical property of matrix material significantly improves.The present invention need only add modified Portland seldom, just can make the intensity of grafted silicone rubber and extension at break improve very big degree, and the oil-proofness of matrix material is improved.
Peel-off nanometer composite material of grafted silicone rubber and clay of the present invention is characterized in that the feed composition of described matrix material and content are as follows: (weight part)
Grafted silicone rubber rubber 100
Clay 0.5～2
Cats product 0.4～2
Dispersion medium 20～100
Linking agent 1～10
Promotor 0.1～1
The grafted silicone rubber rubber that the present invention was suitable for is hydroxy-end capped polydimethylsiloxane and unsaturated organic monomers (as methyl methacrylate, butyl methacrylate, ethyl propenoate, vinyl cyanide, vinylbenzene, vinyl acetate etc.) the method synthetic one class modified silicon rubber rubber by monobasic, binary, three-component grafted copolymerization.
The clay that the present invention was suitable for is a kind of layered silicate that belongs to 2: 1 types, each unit cell is by carrying the layer of aluminum oxygen octahedra in the middle of two silicon-oxy tetrahedrons secretly, connect by public Sauerstoffatom between the two, this tetrahedron and octahedral close-packed structure make its crystal arrangement with high-sequential, and the about 1nm of every layer thickness, length * wide is 100 * 100nm
2Lamella, interfloor distance is approximately about 1nm, clay alumina octahedral top trivalent aluminium is made a layer internal surface have negative charge by divalence magnesium isomorphous substitution, superfluous negative charge compensates by the positively charged ion of interlayer absorption, as Na
+, K
+, Ca
2+, Mg
2+Deng, after response type or organic cation effect, can make polysiloxane macromonomer be inserted into interlayer at an easy rate.The modified clay raw material particle size is 30～40 μ m in the matrix material, and its cationic exchange total volume is 70～120 milligramequivalents/100g.
The used cats product of the present invention is the tensio-active agent of the siliceous or non-silicon of a class.Siliceous tensio-active agent is (RO)
3SiR
1NR
2R
3R
4, wherein R is CH
3Or C
2H
5, R
1For-CH
3-or-C
2H
5R
2-, R
2Be CH
3-or C
2H
5R
2-, R
3Be CH
3-or C
2H
5R
2-, R
4Be chain alkyl or aliphatics vinylformic acid and ester derivative thereof, X is Cl.Chain alkyl is dodecyl, hexadecyl, octadecyl, and aliphatics vinylformic acid and ester derivative thereof are CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-.
The tensio-active agent of the non-silicon that the present invention is used is a hexadecyl trimethyl ammonium bromide.
The used dispersion medium of the present invention is water, alcohols, dimethyl formamide etc., and this class dispersion medium can make clay particles disperse and cation exchange reaction carry out.
The used linking agent of the present invention can be the alkyl silane of multiple functional radical, the organoalkoxysilane of multiple functional radical etc., as tetraethoxy, silane coupling agent etc.
The used promotor of the present invention can be dibutyl tin laurate.
A kind of peel-off nanometer composite material of grafted silicone rubber and clay is characterized in that following these steps to carrying out:
With cation exchange capacity is 0.5～20 part of the clay of 70～120 milligramequivalents/100g, and high-speed stirring in the presence of 20～100 parts dispersion medium forms steady suspension.0.4～2 part of cats product is added in the dispersion medium, 20～75 ℃ of reactions 2～96 hours, the floss of gained after filtration, washing, dry, be organoclay composites after pulverizing.
Above-mentioned organoclay composites through the cats product modification is scattered in 100 parts of grafted silicone rubber rubbers for 0.5～2 part, stir after 5～10 hours, add 1～10 part of linking agent, promotor dibutyl tin laurate 0.1～1 weight part, pour in the mould, place for 20～40 ℃ and promptly got product in 14～24 hours.
The present invention has the following advantages than prior art:
The used raw-silastic continuously of the present invention is a grafted silicone rubber.It is the method synthetic one class modified silicon rubber rubber that is passed through monobasic, binary, three-component grafted copolymerization by hydroxy-end capped polydimethylsiloxane and unsaturated organic monomers (as methyl methacrylate, butyl methacrylate, ethyl propenoate, vinyl cyanide, vinylbenzene, vinyl acetate etc.).Grafted silicone rubber is because its specific molecule structure, no matter be that the intercalation motivating force of physics or chemistry all can make disperse phase be easy to peel off to be nano level individual layer clay layer, phase farmland size is little, thereby the mechanical property of matrix material significantly improves.The present invention need only add modified Portland seldom, just can make the intensity of grafted silicone rubber improve 20～25%, and extension at break improves 10～20%, and the oil-proofness of matrix material has obtained further improvement.
The purpose of this invention is to provide a kind of novel peel-off nanometer composite material of grafted silicone rubber and clay and preparation method thereof.The present invention has adopted the cats product of siliceous or non-silicon, behind this two classes tensio-active agent and the laminar silicic acid reactant salt, make grafted silicone rubber molecular chain intercalation enter the lamella of silicate again, the particulate that layered silicate is easy to peel off into nanometer scale is dispersed in the grafted silicone rubber matrix.
The present invention has reduced the cost of resistance oil silicone rubber.The prior art for preparing resistance oil silicone rubber is owing to will use expensive fluorine monomer, and this monomer needs from external import.The present invention adopts low-cost layered silicate to strengthen the purpose that grafted silicone rubber reaches the raising oil-proofness simultaneously; Because silicone rubber based glue is the silicon rubber of graft type, the price of unsaturated organic monomers is significantly less than the price of raw-silastic continuously in addition.The factor of this two aspect has all reduced the price of resistance oil silicone rubber.
The present invention has well solved the nanoparticle scattering problem.Modified layered silicate is easy to be dispersed in the grafted silicone rubber rubber and forms nano level individual layer clay layer because the particle of modified clay is bigger and amount of filler seldom, so there is not the problem of reunion.
Embodiment 1
With cation exchange capacity is clay 05 gram of 100 milligramequivalents/100g, adds water 20ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 0.4 gram is added in the suspension, 20 ℃ of reactions 96 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 18 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 2
With cation exchange capacity is clay 1 gram of 100 milligramequivalents/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 0.8 gram is added in the suspension, 40 ℃ of reactions 24 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 3
With cation exchange capacity is clay 2 grams of 100 milligramequivalents/100g, adds water 80ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 1.6 grams are added in the suspension, 35 ℃ of reactions 80 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 18 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 4
With cation exchange capacity is clay 0.5 gram of 100 milligramequivalents/100g, adds water 20ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Tensio-active agent hexadecyl trimethyl ammonium bromide 0.4 gram is dissolved in the hot water of 10ml, is added drop-wise to then in the above-mentioned suspension, 70～75 ℃ of reactions 2 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20 ℃ 24 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 5
With cation exchange capacity is clay 1 gram of 100 milligramequivalents/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Cats product hexadecyl trimethyl ammonium bromide 0.8 gram is dissolved in the hot water of 16ml, is added drop-wise to then in the above-mentioned suspension, 70～75 ℃ of reactions 2 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing) in, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20 ℃ 24 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 6
With cation exchange capacity is clay 2 grams of 100 milligramequivalents/100g, adds water 80ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Tensio-active agent hexadecyl trimethyl ammonium bromide 1.6 grams are dissolved in the hot water of 32ml, are added drop-wise to then in the above-mentioned suspension, 70～75 ℃ of reactions 2 hours.The floss of gained after filtration, washing with water to filtrate does not have bromide anion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 32 ℃ 20 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 1.
Embodiment 7 (Comparative Examples 1)
100 gram grafted silicone rubbers (PDMS-MMA)) add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate in, stir, pour in the polytetrafluoroethyldisk disk, placed at least 22 hours under 35 ℃, promptly get Comparative Examples 1.Its performance sees Table 1.
Embodiment 8 (Comparative Examples 2)
Add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate in the hydroxy-end capped polydimethylsiloxane of 100 grams, stir, pour in the polytetrafluoroethyldisk disk, placed at least 20 hours under 36 ℃, promptly get Comparative Examples 2.Its performance sees Table 1.
Embodiment 9 (Comparative Examples 3)
(filler is gas phase SiO to commercially available room temperature vulcanized silicone rubber
2), its performance sees Table 1.
Embodiment 10
With cation exchange capacity is clay 0.5 gram of 120 milligramequivalents/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type surfactant active [3-(trimethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 0.8 gram is added in the suspension, 40 ℃ of reactions 24 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA-BA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20 ℃ 24 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 2.
Embodiment 11
With cation exchange capacity is clay 1 gram of 100 milligramequivalents/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type surfactant active [3-(trimethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 0.8 gram is added in the suspension, 35 ℃ of reactions 72 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA-BA) with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.Its performance sees Table 2.
Embodiment 12 (Comparative Examples 1)
100 gram grafted silicone rubbers (PDMS-MMA-BA)) add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate in, stir, pour in the polytetrafluoroethyldisk disk, placed at least 14 hours under 40 ℃, promptly get Comparative Examples 1.Its performance sees Table 2.
Embodiment 13
With cation exchange capacity is clay 2 grams of 70 milligramequivalents/100g, adds water 100ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(trimethoxy is silica-based) propyl group] dodecyl dimethyl ammonium chloride 1.8 grams are added in the suspension, 30 ℃ of reactions 76 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-St-VAc) with machine,massing, stirred 8 hours, add 1 gram tetraethoxy and 1 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.
Embodiment 14
With cation exchange capacity is clay 1 gram of 70 milligramequivalents/100g, adds water 50ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(trimethoxy is silica-based) propyl group] hexadecyldimethyl benzyl ammonium ammonium chloride 0.8 gram is added in the suspension, 30 ℃ of reactions 76 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-St-VAc) with machine,massing, stirred 8 hours, add 8 gram tetraethoxys and 0.4 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 36 ℃ 34 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.
Embodiment 15
With cation exchange capacity is clay 1 gram of 100 milligramequivalents/100g, adds water 50ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.With response type organic silicon surfactant 2-[(methacryloxy) ethyl] dimethyl [3-(trimethoxy is silica-based) methyl] ammonium chloride 0.5 gram adds in the suspension, 20 ℃ of reactions 96 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA-BA) with machine,massing, stirred 10 hours, add 5 gram tetraethoxys and 0.6 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.
Embodiment 16
With cation exchange capacity is clay 2 grams of 120 milligramequivalents/100g, adds water 100ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.With response type organic silicon surfactant 2-[(acryloxy) ethyl] dimethyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride 2 gram adds in the suspension, 40 ℃ of reactions 76 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder art is scattered in the 100 gram grafted silicone rubbers (PDMS-MMA-EA-AN) with machine,massing, stirred 5 hours, add 10 gram tetraethoxys and 0.1 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 32 hours, and promptly got nanometer composite material of grafted silicone rubber and clay.
Table 1
Table 2
Claims (7)
1. peel-off nanometer composite material of grafted silicone rubber and clay is characterized in that the feed composition of described matrix material and weight part content are as follows:
Grafted silicone rubber rubber 100
Clay 0.5～20
Cats product 0.4～2
Dispersion medium 20～100
Linking agent 1～10
Promotor 0.1～1.
2. a kind of peel-off nanometer composite material of grafted silicone rubber and clay according to claim 1 is characterized in that described grafted silicone rubber rubber is hydroxy-end capped polydimethylsiloxane and the unsaturated organic monomers method synthetic one class modified silicon rubber rubber by monobasic or binary or three-component grafted copolymerization.
3. a kind of peel-off nanometer composite material of grafted silicone rubber and clay according to claim 2 is characterized in that described unsaturated organic monomers is methyl methacrylate or butyl methacrylate or ethyl propenoate or vinyl cyanide or vinylbenzene or vinyl acetate.
4. a kind of peel-off nanometer composite material of grafted silicone rubber and clay according to claim 1 is characterized in that described cats product structure is (RO)
3SiR
1N
+R
2R
3R
4X
-, wherein R is CH
3-or C
2H
5-, R
1For-CH
2-or-C
3H
6-, R
2, R
3Be CH
3-, R
4Be chain alkyl or aliphatics vinylformic acid and ester derivative thereof, X is Cl.
5. a kind of peel-off nanometer composite material of grafted silicone rubber and clay according to claim 4 is characterized in that described chain alkyl is dodecyl or hexadecyl or octadecyl; Aliphatics vinylformic acid and aliphatic acrylate derivative are CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-.
6. a kind of peel-off nanometer composite material of grafted silicone rubber and clay according to claim 1 is characterized in that cats product is a hexadecyl trimethyl ammonium bromide.
7. peel-off nanometer composite material of grafted silicone rubber and clay is characterized in that following these steps to carrying out:
With cation exchange capacity is 0.5～20 part of the clay of 70～120 milligramequivalents/100g, and high-speed stirring in the presence of 20～100 parts dispersion medium forms steady suspension; 0.4～2 part of cats product is added in the dispersion medium, 20～75 ℃ of reactions 2～96 hours, the floss of gained after filtration, washing, dry, be organoclay composites after pulverizing;
Above-mentioned organoclay composites through the cats product modification is scattered in 100 parts of grafted silicone rubber rubbers for 0.5～2 part, stir after 5～10 hours, add 1～10 part of linking agent, 0.1～1 part of promotor dibutyl tin laurate, pour in the mould, place for 20～40 ℃ and promptly got product in 14～24 hours.
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