CN101503422B - Method for preparing methyl phenyl ring siloxane mixture - Google Patents
Method for preparing methyl phenyl ring siloxane mixture Download PDFInfo
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- CN101503422B CN101503422B CN2009100968045A CN200910096804A CN101503422B CN 101503422 B CN101503422 B CN 101503422B CN 2009100968045 A CN2009100968045 A CN 2009100968045A CN 200910096804 A CN200910096804 A CN 200910096804A CN 101503422 B CN101503422 B CN 101503422B
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- aminomethyl phenyl
- cracking
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- reaction
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- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 125000003944 tolyl group Chemical group 0.000 title claims abstract description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title description 39
- 238000005336 cracking Methods 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract 5
- -1 aminomethyl phenyl Chemical group 0.000 claims description 90
- 230000003301 hydrolyzing effect Effects 0.000 claims description 21
- 235000019198 oils Nutrition 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 6
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- XCCRWOHQJUPENA-UHFFFAOYSA-N NC[Si](OCCCC)(OCCCC)C1=CC=CC=C1 Chemical compound NC[Si](OCCCC)(OCCCC)C1=CC=CC=C1 XCCRWOHQJUPENA-UHFFFAOYSA-N 0.000 claims description 2
- NAOMQJFTEHUHRO-UHFFFAOYSA-N [phenyl(dipropoxy)silyl]methanamine Chemical compound NC[Si](OCCC)(OCCC)C1=CC=CC=C1 NAOMQJFTEHUHRO-UHFFFAOYSA-N 0.000 claims description 2
- RPJIJHUHHYFHRB-UHFFFAOYSA-N [phenyl-di(propan-2-yloxy)silyl]methanamine Chemical compound NC[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 RPJIJHUHHYFHRB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000019476 oil-water mixture Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003921 oil Substances 0.000 abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 10
- 239000003292 glue Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003566 sealing material Substances 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 21
- 238000009835 boiling Methods 0.000 description 16
- 229920001971 elastomer Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000005046 Chlorosilane Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical group Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000005052 trichlorosilane Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 241000237502 Ostreidae Species 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 235000020636 oyster Nutrition 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 3
- UEKPZMHIAMUMGG-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O[SiH2]O1)(C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12)C)(C)C)C Chemical compound C[Si]1(O[Si](O[Si](O[SiH2]O1)(C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12)C)(C)C)C UEKPZMHIAMUMGG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000001367 organochlorosilanes Chemical class 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JAQGRBKAAWYOKD-UHFFFAOYSA-N NC[Si]1(O[SiH2]O[SiH2]O1)C1=CC=CC=C1 Chemical compound NC[Si]1(O[SiH2]O[SiH2]O1)C1=CC=CC=C1 JAQGRBKAAWYOKD-UHFFFAOYSA-N 0.000 description 2
- NIBADJGLXVMKLY-UHFFFAOYSA-N NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 Chemical compound NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 NIBADJGLXVMKLY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- CFMVOYREGHZAQA-UHFFFAOYSA-N chlorosilane trichloro(methyl)silane Chemical compound C[Si](Cl)(Cl)Cl.Cl[SiH3] CFMVOYREGHZAQA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- CUKLZXPWGNJWBW-UHFFFAOYSA-N dichloro-(2-methylphenyl)-phenylsilane Chemical compound CC1=CC=CC=C1[Si](Cl)(Cl)C1=CC=CC=C1 CUKLZXPWGNJWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of a methyl phenyl cyclosiloxane mixture, in particular a preparation method of a methyl phenyl cyclosiloxane mixture which does not contain trifunctional impurity. In the invention, methyl phenyl dialkoxy silane and a catalyst react; when a refraction index nD<25> of a received alcohol-water mixture generated by the reaction is close to 1.3325, the reaction is stopped; standing and layering are carried out; and then, cracking reaction is carried out on an oil layer and the catalyst so as to obtain the target product. The invention has the advantages of simple production process, washing water saving, low cracking temperature and energy saving. A mixed ring body can be used as a basic polymer for a methyl phenyl high-temperature glue which has high phenyl content, high viscosity, high molecular weight, no cross binding and flat gravitational flow. The methyl phenyl mixed ring body can also be used for preparing high-temperature resistant and radiation resistant materials needed by high-temperature organosilicone heat-conducting silicon oil and a nuclear power facility and also be used for preparing power-type LED organosilicone sealing materials.
Description
Technical field
The present invention relates to a kind of preparation method of methyl phenyl ring siloxane mixture, specifically be meant a kind of preparation method who does not contain the methyl phenyl ring siloxane mixture of trifunctional impurity.
Background technology
The mixture that methyl phenyl ring siloxane mixture is made up of homologues such as aminomethyl phenyl cyclotrisiloxane, aminomethyl phenyl cyclotetrasiloxane, aminomethyl phenyl D5 and isomer thereof; For example; The aminomethyl phenyl cyclotrisiloxane exists cis and trans two kinds of geometrical isomers; The aminomethyl phenyl cyclotetrasiloxane exists a kind of cis and three kinds of trans geometrical isomers, and also there are four kinds of geometrical isomers in the aminomethyl phenyl D5.
Methyl phenyl ring siloxane mixture (is called for short the aminomethyl phenyl mixed methylcyclosiloxane; As follows) in organosilicon industry a kind of important material; Be widely used in synthesis of methyl phenyl silicone oil, methyl phenyl silicone resin and methyl phenyl silicone rubber rubber; Have performances such as excellent radiation hardness, high-low temperature resistant, high refractive index thereby give material, have important application in fields such as all trades and professions especially space flight and aviation, ocean salt spray resistance coating, defence and militaries.
The traditional preparation process technology of aminomethyl phenyl mixed methylcyclosiloxane is the hydrolytic rupture technology of dichloromethyl phenylsilane; Be about to the hydrolysing oil that dichloromethyl phenylsilane elder generation hydrolysis generation aminomethyl phenyl mixed methylcyclosiloxane and methylphenyl siloxane linear body are formed; And then in the presence of catalyst for cracking; Under the high temperature high vacuum condition cracking of methylphenyl siloxane linear body is generated the aminomethyl phenyl mixed methylcyclosiloxane, and from reaction system, separate.Because cracking process remains a balanced reaction process; Both existed linear methylphenyl siloxane to be cracked into the reaction of low molecular methyl phenyl ring siloxane; Also exist the methyl phenyl ring siloxane ring-opening polymerization to generate the reaction of methylphenyl siloxane linear body simultaneously; Therefore; The traditional preparation process technology of aminomethyl phenyl mixed methylcyclosiloxane also is attended by a large amount of scission reaction residues, the high boiling substance that it mainly is made up of the methylphenyl siloxane linear body when obtaining methyl phenyl ring siloxane.
In addition; In the various preparation technologies of dichloromethyl phenylsilane, all generated the phenyl-trichloro-silicane by product inevitably; Because the atmospheric boiling point of dichloromethyl phenylsilane is 205.5 ℃; The atmospheric boiling point of phenyl-trichloro-silicane is 201 ℃, and both all belong to high boiler material and boiling-point difference has only 4.5 ℃, thereby is difficult to obtain not contain the high-purity methyl diphenyl dichlorosilane of three-functionality-degree phenyl-trichloro-silicane.Owing in dichloromethyl phenylsilane, contain the phenyl-trichloro-silicane of three-functionality-degree inevitably; So prepare in the aminomethyl phenyl mixed methylcyclosiloxane process by the dichloromethyl phenylsilane hydrolytic rupture, also contain the impurity of three-functionality-degree in the aminomethyl phenyl mixed methylcyclosiloxane of gained.
Owing to there is three-functionality-degree impurity, when the aminomethyl phenyl mixed methylcyclosiloxane that adopts above-mentioned prepared as polymerization single polymerization monomer, (, be called for short D through homopolymerization or with the dimethyl-ring body like octamethylcyclotetrasiloxane
4) wait monomer to prepare the high-molecular weight organosilicon material through the copolymerization mode, when especially preparing the high-temp glue base polymer, it is crosslinked to cause base polymer to occur, and has a strong impact on the preparation and the application of polymer organosilicon material.
For improving the quality of aminomethyl phenyl ring body, reduce the content of three-functionality-degree impurity, researcher adopts the whole bag of tricks to attempt both at home and abroad, and chemical process also is used to this sepn process.Proposed methane amide or N are joined in the mixture of organochlorosilane among the FRP FR1141735 (its equating patent US2738359), made itself and trichlorosilane form solid complex, and then separate dichlorosilane through distillating method; But this method need be used a large amount of methane amides, is unfavorable for being applied in the mixture that contains the high concentration organic trichlorosilane.Moreover even the complex compound of generation does not decompose under the boiling point of N yet, this has seriously hindered the recovery and reuse of methane amide.
Equally; In FRP FR1466546 (its equating patent US3441584), also proposed in the organochlorosilane mixture, to add three-(alkylamino) phosphine oxide and trichlorosilane and formed solid complex, thereby made and become possibility through the rectifying separation dichlorosilane; And trichlorosilane can be able to regeneration through decomposing complex compound subsequently.Yet this method needs the molal quantity of operation at low temperatures and use phosphorus oxide to be far longer than the molal quantity of trichlorosilane.
Moreover, reported among the FRP FR1240180 (its equating patent US3002988) through adding phosphoric acid removes trichlorine or tetrachloro verivate from the organochlorosilane mixture method.Can obtain pure dichlorosilane through rectifying subsequently.This process need uses the phosphoric acid that is several times as much as trichlorosilane or tetrachloro silicane molar weight.Thereby when reaction finished, dichlorosilane also can react with phosphoric acid, and this will reduce the recovery of dichlorosilane.
U.S. Pat 3637781 has been reported H
3PO
4, (SiMe
3)
3PO
4, aprotic solvent such as HPT joins in the dichloromethyl phenylsilane that contains phenyl-trichloro-silicane; Make the phenyl-trichloro-silicane and the aprotic solvent of three-functionality-degree form a kind of unsettled intermediate complex; Add alcohols such as propyl carbinol then; Make aprotic solvent regeneration; And then reaction mixture carried out rectifying separation, finally obtain purity and be 99.8% dichloromethyl phenylsilane, but dichloromethyl phenylsilane purity does not still reach the requirement of the required dichloromethyl phenylsilane purity of high-temp glue＞99.95%.
U.S. Pat 4402796 has been reported with tetramethylene sulfone and alkyl compound and has been made cosolvent; Take the liquid extraction technology from mixture, to separate the method for close boiling point chlorosilane; But the document does not provide technical parameters such as concrete sepn process and separating obtained product gas purity; Just, proved the feasibility of liquid-liquid extraction technical point from dichloromethyl phenylsilane and phenyl-trichloro-silicane mixture through the selectivity coefficient β value of various chlorosilanes in tetramethylene sulfone and alkyl compound.
The mixture that people such as MILLER (WO2007067723) form the substituted organic cpds of single cyanic acid, the substituted organic cpds of nitro, the substituted organosilicon mixture of single cyanic acid, nitro substituted organosilicon compound or they joins in the chlorosilane mixture that contains than lower boiling chlorosilane and higher chlorosilane as the distillation auxiliary agent; Utilize the distillation auxiliary agent can increase the relative volatility of approaching three-functionality-degree chlorosilane (METHYL TRICHLORO SILANE) of boiling point and dichlorosilane (dimethyldichlorosilane(DMCS)), help the separation of mixed chlorosilane.But, then do not report for dichloromethyl phenylsilane and phenyl-trichloro-silicane.
Li Meijiang etc. (CN200810059117.1) mix the mixture of dialkyldichlorosilan,s with the dichloromethyl phenylsilane of being produced by the pyrocondensation method; Slowly add to be equipped with in water and the water-fast non-polar organic solvent and carry out abundant hydrolysis reaction, isolate organic layer again, washing is to neutral; Remove organic solvent; Obtain hydrolyzation material, hydrolyzation material and catalyzer are added in the reactor drum again, vacuum tightness is not less than under the condition of 20mmHg and is warming up to 250～300 ℃ gradually; Cracking obtains methyl phenyl ring siloxane mixture, but products therefrom still contains the trifunctional impurity of considerable part.
Face great challenge owing to from dichloromethyl phenylsilane-phenyl-trichloro-silicane mixture, separate the dichloromethyl phenylsilane that does not contain phenyl-trichloro-silicane of purifying; In order to obtain the aminomethyl phenyl ring body of the required quality of high-temp glue rubber; People have developed the operational path that catalystic pyrolysis prepares the aminomethyl phenyl ring body again; This is a way of doing something against one's will; This operational path be with the dichloromethyl phenylsilane that contains phenyl-trichloro-silicane through the catalytic hydrolysis polycondensation, generate the mixture (hydrolysing oil) of PSI linear body and aminomethyl phenyl mixed methylcyclosiloxane, hydrolysing oil is carried out Pintsch process under catalyst action; The aminomethyl phenyl mixed methylcyclosiloxane (being called for short " ring body ") that is still contained three-functionality-degree impurity; Again a ring body is carried out ring-opening polymerization, and then add catalyst for cracking and carry out cracking, the secondary ring body of gained can satisfy the specification of quality of high-temp glue rubber basically.For example; (J.Am.Chem.Soc.1948 such as R.N.Lewis; 70:1115-1117) with (J.Am.Chem.Soc.1948 such as C.W.Young; 70:3758-3764.) all having reported with the PSI to be that raw material directly carries out the method that thermo-cracking prepares methyl phenyl ring siloxane, Guinet and Puthet adopt alkaline carbonate as catalyzer thermo-cracking PSI in U.S. Pat 3484469, have prepared methyl phenyl ring siloxane.
Kuznetsova etc. adopt Lithium Hydroxide MonoHydrate or lithium silicon alkoxide in U.S. Pat 3558681 be catalyzer, and PSI has been carried out thermo-cracking, the preparation methyl phenyl ring siloxane.Li Meijiang etc. (CN200710069405.0) are then to contain phenyl silica trifunctional chain link (SiPhO
1.5) be T
PMethyl phenyl silicone be raw material method through thermo-cracking under base catalysis, also prepared methyl phenyl ring siloxane.Visible from above-mentioned operational path, need in the pyrolysis method technology prepare qualified cyclosiloxane through operations such as catalytic pyrolysis, rectifying, this arts demand is at high temperature operated, and is easy to generate high boiling material, complex process in addition, cost is high, and yield is low.
In sum; Because dichloromethyl phenylsilane and phenyl-trichloro-silicane boiling point are approaching and boiling point is higher; Cause dichloromethyl phenylsilane to separate very difficulty of purification; Further influenced the quality of aminomethyl phenyl ring body, can't satisfy of the requirement of high performance organo-silicon developing material for aminomethyl phenyl ring body quality.Though with the dichloromethyl phenylsilane is raw material; The ring body quality that makes through the second pyrolysis method meets the demands basically; But this technological process route is long, the raw material effective rate of utilization is low, process energy consumption and facility investment is big, production efficiency is low; Therefore, less energy-consumption, high-level efficiency, environmental protection, high purity and the research and development that do not contain the aminomethyl phenyl ring body preparation technology of trifunctional impurity are very important.
Be to remove the trifunctional impurity of trace in the aminomethyl phenyl mixed methylcyclosiloxane, improve aminomethyl phenyl mixed methylcyclosiloxane quality, avoid containing and occur crosslinkedly in the macromolecular compound preparation of aminomethyl phenyl silica chain link, guarantee that prepared base polymer number-average molecular weight is greater than 5 * 10
5G/mol satisfies high temperature silicon rubber for the base polymer performance demands, and it is raw material that the present invention proposes with high-purity methyl phenyl dialkoxy silicane, does not contain the method for the aminomethyl phenyl mixed methylcyclosiloxane of trifunctional impurity through hydrolytic condensation and cracking technology preparation.
The aminomethyl phenyl dialkoxy silicane can adopt contract method and alcoholysis method of sodium to prepare; Replacing dichloromethyl phenylsilane with the aminomethyl phenyl dialkoxy silicane is the aminomethyl phenyl mixed methylcyclosiloxane that feedstock production does not contain trifunctional impurity, and advantage is to be easy to obtain high purity, do not contain the aminomethyl phenyl dialkoxy silicane of trifunctional impurity through known stripping technique.For example; Aminomethyl phenyl diethoxy silane boiling point is 92.4 ℃/1.13KPa; The phenyl triethoxysilane boiling point is 112 ~ 113 ℃/1.33KPa, and both boiling points differ bigger, can not contained the high-purity methyl diethylamino phenyl TMOS of phenyl triethoxysilane through rectifying.
Wu Guanli etc. (China Synthetic Rubber Industry, 1981,4:299-300.) with NaOH be catalyzer, the aminomethyl phenyl diethoxy silane is hydrolyzed, then with hydrolysate and octamethylcyclotetrasiloxane (D
4) under the catalysis of TMAH silicon alkoxide, be aggregated in earlier and carry out cracking, both contained (CH
3)
2The SiO chain link also contains CH
3(C
6H
5) mixture of SiO chain link, this mixture can be used as the raw material of high phenyl content Zylox.Li Qiang, gold-tinted speed and river fine jade rosy clouds (China Synthetic Rubber Industry, 2004,27 (1): 10-12) with aminomethyl phenyl diethoxy silane and octamethylcyclotetrasiloxane (D
4) be raw material, hydrolyzing methyl phenyl diethoxy silane under acidic conditions, hydrolysate are under base catalysis and D
4Ring-opening copolymerization has prepared the hydroxy-end capped PSI oligopolymer of high phenyl content.
Above-mentioned bibliographical information can prepare the organosilicon macromolecule material that contains aminomethyl phenyl silica chain link from the aminomethyl phenyl diethoxy silane, but the preparation method of aminomethyl phenyl mixed methylcyclosiloxane is not provided.The aminomethyl phenyl diethoxy silane belongs to hazardous substance, and transportation is restricted, simultaneously also be difficult to directly be used for the exploitation of organosilicon derived product as raw material, and do not contain three-functionality-degree impurity the aminomethyl phenyl mixed methylcyclosiloxane can with D
4Making HMW and the not crosslinked organosilicon macromolecule material that contains aminomethyl phenyl silica chain link Deng the organosilicon ring body through ring opening copolymer, is the important source material of organosilicon industry; On the other hand; Widely-used cyclosiloxane of organosilicon middle and lower reaches industry rather than chlorosilane or organoalkoxysilane prepare silicone oil, Zylox and silicone resin as raw material; Therefore; Methyl phenyl ring siloxane is the hydrolysis condensation product of dichloromethyl phenylsilane and aminomethyl phenyl dialkoxy silicane, also is the main products form that dichloromethyl phenylsilane and aminomethyl phenyl dialkoxy silicane are able to use in organosilicon industry.
This patent has reported that the high-purity methyl diethylamino phenyl TMOS not contain three-functionality-degree impurity is a raw material, in the presence of basic catalyst or an acidic catalyst, is hydrolyzed, and the oil reservoir (hydrolysing oil) that hydrolysis generates is handled through layering with water layer.When using an acidic catalyst; Hydrolysing oil needs to be neutral through operations such as neutralization, washings until hydrolysing oil; And then the adding catalyst for cracking, when using basic catalyst, oil reservoir can directly mix with catalyst for cracking to neutral without washing; Thereafter under certain temperature and pressure, do not contain the method for the aminomethyl phenyl mixed methylcyclosiloxane of trifunctional impurity through the flash distillation acquisition.Aminomethyl phenyl mixed methylcyclosiloxane preparation method of the present invention have production technique simple, save bath water, hydrolysing oil cracking temperature low, save characteristics such as not producing in trifunctional impurity and hydrolytic condensation and the cracking process Siliciumatom utilization ratio height in the energy, the cracking process; Gained aminomethyl phenyl ring body be specially adapted to the required high phenyl content of high-temp glue, HV, HMW, not crosslinked, from the preparation of the aminomethyl phenyl rubber of levelling, also can be used as the required high temperature resistant radiation hardness material of power-type LED packaged material, high temperature organosilicon heat conduction silicone oil and nuclear power facility of high transmission rate, high refractive index.
Summary of the invention
The object of the present invention is to provide a kind of do not appear in the newspapers; The aminomethyl phenyl mixed methylcyclosiloxane preparation method who does not contain three-functionality-degree impurity, the aminomethyl phenyl mixed methylcyclosiloxane of acquisition can be used for preparing need not in organic silicon high-temperature glue rubber and this method implementation process organic dialkoxy silicane hydrolyzate washed to neutrality and can directly carry out cracking to prepare organic ring siloxane mixture.
Another object of the present invention is to provide a kind of aminomethyl phenyl mixed methylcyclosiloxane that does not contain three-functionality-degree impurity; This mixed methylcyclosiloxane can be used as high phenyl content, HV, HMW, not crosslinked, from the base polymer of the aminomethyl phenyl high-temp glue of levelling; This aminomethyl phenyl mixed methylcyclosiloxane also can be used for preparing high temperature organosilicon heat conduction silicone oil and the required high temperature resistant radiation hardness material of nuclear power facility, also can be used for preparing the power-type LED organosilicon encapsulating material.
The present invention is achieved through following technical scheme:
A kind of preparation method who does not contain the aminomethyl phenyl mixed methylcyclosiloxane of three-functionality-degree impurity, its key step comprises:
(1) will not contain in the reactor drum that mixing liquid that the aqueous solution of aminomethyl phenyl dialkoxy silicane and an acidic catalyst or the alkali metal hydroxide catalyzer of trifunctional impurity forms by a certain percentage joins separator column that filler is housed and cat head still head; Reaction is hydrolyzed under normal pressure and 70 ~ 125 ℃; Utilize still head reverse flow valve control reflux ratio; Receive alcohol-water mixture that reaction generates, measure the refractive index n of overhead distillate
D 25, when its numerical value near 1.3325 the time, stopped reaction, after the reaction mixture cooling, standing demix.
(2) when using an acidic catalyst aqueous solution, reaction mixture temperature reduced to room temperature after, be neutralized to neutrality with alkaline neutraliser after, with deionized water wash for several times, the reaction mixture sat after the washing is separated water layer after for some time again with oil reservoir.
(3) when using the aqueous solution of alkali metal hydroxide catalyzer; Utilize simple operationss such as decant, separatory that the oil-water mixture of standing demix is separated; The upper strata alkaline aqueous solution of collecting can partially or completely replace required moisture of aminomethyl phenyl dialkoxy silicane hydrolytic condensation process and base metal catalysts, realizes the recycle of waste water; Lower floor's oil reservoir of collecting does not need further to adopt water or other any solvent washs, can carry out cracking.
(4) oil reservoir with catalyst for cracking and collection joins in the cracking reactor, under certain temperature, certain pressure intensity, carries out cracking, and the split product of collection is aminomethyl phenyl mixed methylcyclosiloxane of the present invention.
As preferably, the aminomethyl phenyl dialkoxy silicane described in the above-mentioned preparation method is the mixture of one or more compositions in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dipropoxy silane, aminomethyl phenyl diisopropoxy silane, the aminomethyl phenyl dibutoxy silane; As better selection, the aminomethyl phenyl dialkoxy silicane described in the above-mentioned preparation method is the mixture of a kind of or both compositions in aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane.
As preferably, an acidic catalyst described in the step among the above-mentioned preparation method (1) is a sulfuric acid, and as better selection, an acidic catalyst described in the above-mentioned preparation method is the 5wt% vitriolic aqueous solution.
As preferably; Alkali metal hydroxide catalyzer described in the step among the above-mentioned preparation method (1) is one or more among LiOH and hydrate thereof, NaOH, KOH, RbOH, the CsOH; As better selection, the base metal catalysts described in the above-mentioned preparation method is LiOH or its hydrate.
As preferably; The mass ratio of catalyzer described in the above-mentioned preparation method and aminomethyl phenyl dialkoxy silicane is 0.01 ~ 20: 100; As better selection, the mass ratio of catalyzer described in the above-mentioned preparation method and aminomethyl phenyl dialkoxy silicane is 0.1 ~ 5: 100.
As preferably; The mass ratio of aminomethyl phenyl dialkoxy silicane described in the above-mentioned preparation method and deionized water is 1: 0.1 ~ 100; As better selection, the mass ratio of aminomethyl phenyl dialkoxy silicane described in the above-mentioned preparation method and deionized water is 1: 0.2 ~ 5.
As preferably, the catalyst for cracking described in the above-mentioned preparation method is one or more among LiOH and hydrate thereof, NaOH, KOH, RbOH, the CsOH, and as better selection, the catalyst for cracking described in the above-mentioned preparation method is Li0H or its hydrate.
As preferably, the consumption of the catalyst for cracking described in the above-mentioned preparation method is 0.01 ~ 50wt% of hydrolysing oil quality, and as better selection, the consumption of catalyst for cracking is 0.1 ~ 10.0wt% of hydrolysing oil quality.
Hydrolyst described in the above-mentioned preparation method and catalyst for cracking both can be selected different types of catalyzer; Also can select same kind of catalyzer; As preferably; Hydrolyst described in the above-mentioned preparation method and catalyst for cracking are chosen as with a kind of catalyzer, and as better selection, hydrolyst described in the above-mentioned preparation method and catalyst for cracking are LiOH or its hydrate.
Beneficial effect: advantage of the present invention be production technique simple, save use bath water, cracking temperature low, save characteristics such as not producing in trifunctional impurity and hydrolytic condensation and the cracking process Siliciumatom utilization ratio height in the energy, the cracking process; Gained aminomethyl phenyl ring body be specially adapted to the required high phenyl content of high-temp glue, HV, HMW, not crosslinked, from the preparation of the aminomethyl phenyl rubber of levelling, also can be used as the required high temperature resistant radiation hardness material of power-type LED packaged material, high temperature organosilicon heat conduction silicone oil and nuclear power facility of high transmission rate, high refractive index.
Embodiment
The present invention can further specify through following embodiment, but embodiment is not the restriction to protection domain of the present invention.
Embodiment 1
With 521.8g purity greater than 99.8wt% and do not contain aminomethyl phenyl diethoxy silane, the 5.2144gLiOHH of three-functionality-degree impurity
2O and 684g deionized water join in three mouthfuls of round-bottomed flasks of the 2000mL that has mechanical stirring, temperaturecontrol sensor and filler separator column; Filler separator column port is connected with still head; Through valve place on the adjustment still head discharging pipeline, the reflux ratio that can regulate the cat head material.Above-mentioned reaction mixture is heated up through the electrically heated chuck, between 80 ~ 100 ℃, make the condensation reaction that is hydrolyzed of aminomethyl phenyl diethoxy silane, valve place on the adjustment still head discharging pipeline slowly receives the ethanol-water mixture that reaction generates.Behind the reaction 6h, receive and obtain the 633.5g ethanol-water mixture, the refractive index that records overhead distillate is near 1.3325, and stopped reaction is reduced to room temperature with reaction mixture, leaves standstill.Bottoms is transferred to separating funnel, collects 353.4g oyster white oily matter and 208.6g alkaline aqueous solution.Above-mentioned oyster white oily matter is poured in three mouthfuls of round-bottomed flasks of 500mL, added 1.5748g LiOHH simultaneously
2O; Under reduced pressure heat up and carry out cracking; Collecting boiling range is the overhead fraction of 230 ~ 246 ℃/0.1kPa; Finally obtain the 337.93g cut, in hydrolytic condensation and the cracking process, the overall utilization of Si (in the product in the quality of Si and the raw material aminomethyl phenyl dialkoxy silicane ratio of Si quality) is 92.95%.Analyze through GC-MS, contain trimethyl triphenyl cyclotrisiloxane 37.91wt% in the aminomethyl phenyl mixed methylcyclosiloxane of gained, tetramethyl tetraphenyl cyclotetrasiloxane 56.02wt%, pentamethyl-pentapheneyl cyclotetrasiloxane 6.07wt% does not contain trifunctional impurity.
Bubbling pipe is housed, temperature is taken into account in the there-necked flask of vacuum system, adds the above-mentioned aminomethyl phenyl mixed methylcyclosiloxane of 45.93g, 100g octamethylcyclotetrasiloxane and 0.29g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, under decompression (720mmHg) and nitrogen bubble; At 48 ~ 50 ℃ of dehydration 30min, add the TMAH silicon alkoxide then as catalyzer, its consumption is counted the 0.01wt% of all cyclosiloxane total masses with pure TMAH; Under 600mmHg pressure, be warming up to 100 ℃ then, polymerization 1.5h, fast decompression is to 740mmHg again; Make its further polymerization 2.5h; After removing vacuum, be warming up to more than 150 ℃, keep 1h with decomposition catalyst.Under 750mmHg pressure, be warming up to 180 ℃ and keep 5h then, obtain the phenyl mole fraction after the cooling and be 20% methyl phenyl vinyl rubber to remove low-boiling-point substance.Through gpc analysis, with respect to PS, its molecular weight is 6.78 * 10
5G/mol; Get 2g methyl phenyl vinyl rubber sample, be placed in the 25mL toluene solution, stir under the room temperature, behind the 1h, sample is dissolving fully in toluene.
Embodiment 2
With 500g purity greater than 99.8wt% and do not contain 208.6g alkaline aqueous solution and the 420g deionized water collected in the aminomethyl phenyl diethoxy silane, embodiment 1 hydrolysate oil water separation process of three-functionality-degree impurity and join in three mouthfuls of round-bottomed flasks of the 2000mL that has mechanical stirring, temperaturecontrol sensor and filler separator column; Filler separator column port is connected with still head; Through valve place on the adjustment still head discharging pipeline, the reflux ratio that can regulate the cat head material.Above-mentioned reaction mixture is heated up through the electrically heated chuck, between 80 ~ 100 ℃, make the condensation reaction that is hydrolyzed of aminomethyl phenyl diethoxy silane, valve place on the adjustment still head discharging pipeline slowly receives the ethanol-water mixture that reaction generates.Behind the reaction 8h, the refractive index that records overhead distillate is near 1.3325, and stopped reaction is reduced to room temperature with reaction mixture, leaves standstill.Bottoms is transferred to separating funnel, collects 327.8g oyster white oily matter.Above-mentioned oyster white oily matter is poured in three mouthfuls of round-bottomed flasks of 500mL, added 1.0g LiOHH simultaneously
2O under reduced pressure heats up and carries out cracking, and collecting boiling range is the overhead fraction of 230 ~ 246 ℃/0.1kPa, finally obtains the 308.76g cut, and in hydrolytic condensation and the cracking process, the overall utilization of Si is 95.35%.Analyze through GC-MS, contain trimethyl triphenyl cyclotrisiloxane 38.06wt% in the aminomethyl phenyl mixed methylcyclosiloxane of gained, tetramethyl tetraphenyl cyclotetrasiloxane 56.16wt%, pentamethyl-pentapheneyl cyclotetrasiloxane 5.79wt% does not contain trifunctional impurity.
Press the identical method of embodiment 1; Aminomethyl phenyl mixed methylcyclosiloxane with embodiment 2 preparations replaces the aminomethyl phenyl mixed methylcyclosiloxane among the embodiment 1, and preparation phenyl mole fraction is 20% methyl phenyl vinyl rubber, through gpc analysis; With respect to PS, its molecular weight is 6.63 * 10
5G/mol; Get 2g methyl phenyl vinyl rubber sample, be placed in the 25mL toluene solution, stir under the room temperature, behind the 1h, sample is dissolving fully in toluene.
Embodiment 3 and embodiment 4
Except that the kind that changes hydrolytic condensation catalyzer, catalyst for cracking and consumption, temperature of reaction and the reaction times, all the other conditions are with embodiment 1, and according to experimentizing with embodiment 1 same program, the gained result is as shown in the table.
Following table is embodiment 3 and 4 proportioning raw materials, reaction conditions and reaction result
Press the identical method of embodiment 1; Aminomethyl phenyl mixed methylcyclosiloxane with embodiment 4 preparations replaces the aminomethyl phenyl mixed methylcyclosiloxane among the embodiment 1, and preparation phenyl mole fraction is 20% methyl phenyl vinyl rubber, through gpc analysis; With respect to PS, its molecular weight is 5.79 * 10
5G/mol; Get 2g methyl phenyl vinyl rubber sample, it as in the 25mL toluene solution, is stirred under the room temperature, behind the 1h, sample is dissolving fully in toluene.
Embodiment 5
With 500g purity greater than 99.8wt% and do not contain the aminomethyl phenyl diethoxy silane of three-functionality-degree impurity, dilute sulphuric acid and the 800g deionized water that 200g concentration is 5wt% joins in three mouthfuls of round-bottomed flasks of the 2000mL that has mechanical stirring, temperaturecontrol sensor and filler separator column; Filler separator column port is connected with still head; Through valve place on the adjustment still head discharging pipeline, the reflux ratio that can regulate the cat head material.Above-mentioned reaction mixture is heated up through the electrically heated chuck, between 80 ~ 101 ℃, make the condensation reaction that is hydrolyzed of aminomethyl phenyl diethoxy silane, valve place on the adjustment still head discharging pipeline slowly receives the ethanol-water mixture that reaction generates.Behind the reaction 10h, record the refractive index n of overhead distillate
D 25Near 1.3325, stopped reaction is reduced to room temperature with reaction mixture.Add powdered sodium carbonate, reaction mixture is neutralized to neutrality, adopt deionized water wash again 3 times, standing demix separates water layer with separating funnel with oil reservoir, obtain the light yellow oily liquid of 293g.
It is in 500mL and the three mouthfuls of round-bottomed flasks that have division box that oil reservoir is transferred to a volume, adds 110g toluene, under normal pressure and refluxing toluene temperature, carries out branch water, and normal pressure is warming up to 180 ℃ of steamings and removes toluene then, obtains the shallow khaki color oily liquids of 277.0g.
The above-mentioned shallow khaki color oily liquids of 100g is poured in three mouthfuls of round-bottomed flasks of 250mL, do not added catalyst for cracking, under 0.1kPa pressure, heat up gradually; Directly carry out cracking; During still temperature rise to 320 ℃, cat head does not have cut and refluxes, behind the 10min; The trim the top of column liquid temp is 120 ℃, the gelation of tower still material.
Embodiment 6
The shallow khaki color oily liquids of 150g that obtains among the embodiment 5 is joined in the cracker that volume is 250mL, add 1.5g LiOHH simultaneously
2O under reduced pressure heats up and carries out cracking, and collecting boiling range is the overhead fraction of 225 ~ 244 ℃/0.1kPa, finally obtains the 129.87g cut.Analyze through GC-MS, contain trimethyl triphenyl cyclotrisiloxane 38.30wt% in the aminomethyl phenyl mixed methylcyclosiloxane of gained, tetramethyl tetraphenyl cyclotetrasiloxane 57.65wt%, pentamethyl-pentapheneyl cyclotetrasiloxane 4.05wt% does not contain trifunctional impurity.
Press the identical method of embodiment 1; Aminomethyl phenyl mixed methylcyclosiloxane with embodiment 6 preparations replaces the aminomethyl phenyl mixed methylcyclosiloxane among the embodiment 1, and preparation phenyl mole fraction is 20% methyl phenyl vinyl rubber, through gpc analysis; With respect to PS, its molecular weight is 6.09 * 10
5G/mol; Get 2g methyl phenyl vinyl rubber sample, be placed in the 25mL toluene solution, stir under the room temperature, behind the 1h, sample is dissolving fully in toluene.
Claims (5)
1. the preparation method of a methyl phenyl ring siloxane mixture, its step comprises:
(1) will not contain in the reactor drum that mixing liquid that the aqueous solution of aminomethyl phenyl dialkoxy silicane and the alkali metal hydroxide catalyzer of trifunctional impurity forms by a certain percentage joins separator column that filler is housed and cat head still head; Reaction is hydrolyzed under normal pressure and 70～125 ℃; Receive alcohol-water mixture that reaction generates; Measure the refractive index
of overhead distillate; When its numerical value near 1.3325 the time; Stopped reaction, after the reaction mixture cooling, standing demix;
(2) separate the oil-water mixture of standing demix, following oil reservoir is continued to employ and is carried out cracking;
(3) with among LiOH and hydrate thereof, NaOH, KOH, RbOH, the CsOH one or more as catalyst for cracking; Join in the cracking reactor with the oil reservoir of collecting; Under certain temperature, certain pressure intensity, carry out cracking, the split product of collection is a methyl phenyl ring siloxane mixture;
Wherein, the alkali metal hydroxide catalyzer is LiOH or its hydrate;
The aminomethyl phenyl dialkoxy silicane is the mixture of one or more compositions in aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dipropoxy silane, aminomethyl phenyl diisopropoxy silane, the aminomethyl phenyl dibutoxy silane.
2. preparation method according to claim 1 is characterized in that: described aminomethyl phenyl dialkoxy silicane is the mixture of a kind of or both compositions in aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane.
3. preparation method according to claim 1 is characterized in that: the mass ratio of hydrolyst described in the step (1) and aminomethyl phenyl dialkoxy silicane is 0.1～20: 100.
4. preparation method according to claim 1 is characterized in that: the catalyst for cracking described in the step (3) is LiOH or its hydrate, and the consumption of catalyst for cracking is 0.01～50wt% of hydrolysing oil quality.
5. preparation method according to claim 4 is characterized in that: the consumption of the catalyst for cracking described in the step (3) is 0.1～10.0wt% of hydrolysing oil quality.
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| CN103626798B (en) * | 2013-12-12 | 2016-01-20 | 中蓝晨光化工研究设计院有限公司 | A kind of not containing the preparation method of polyfunctionality impurity methyl phenyl ring siloxane |
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| CN111518132B (en) * | 2020-06-01 | 2023-09-26 | 上海树脂厂有限公司 | Preparation method of methylphenyl mixed ring body and preparation method of methylphenyl silicon rubber |
| CN117510856B (en) * | 2023-12-04 | 2024-04-30 | 四川启科新材料有限责任公司 | Method for preparing phenyl mixed ring body through chemical degradation |
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| CN101343285A (en) * | 2008-08-28 | 2009-01-14 | 杭州师范大学 | Methyl-phenyl hybrid ring siloxane preparing method |
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| US3558681A (en) * | 1968-12-18 | 1971-01-26 | Alexandra Grigorievna Kuznetso | Method for the production of methylphenylcyclotri-and tetrasiloxanes |
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