US20010011120A1 - Process for the production of cyclic siloxane - Google Patents
Process for the production of cyclic siloxane Download PDFInfo
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- US20010011120A1 US20010011120A1 US09/765,047 US76504701A US2001011120A1 US 20010011120 A1 US20010011120 A1 US 20010011120A1 US 76504701 A US76504701 A US 76504701A US 2001011120 A1 US2001011120 A1 US 2001011120A1
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- United States
- Prior art keywords
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- sio
- siloxane
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- general formula
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- -1 cyclic siloxane Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 34
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000006043 5-hexenyl group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000010533 azeotropic distillation Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 125000005372 silanol group Chemical group 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 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 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BQRXDWAQRKZDIO-UHFFFAOYSA-N hex-1-enyl-dimethoxy-methylsilane Chemical compound CCCCC=C[Si](C)(OC)OC BQRXDWAQRKZDIO-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- KOIZGANULZZTMH-UHFFFAOYSA-N (acetyloxy-hex-1-enyl-methylsilyl) acetate Chemical compound CCCCC=C[Si](C)(OC(C)=O)OC(C)=O KOIZGANULZZTMH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- DBFRRVRADQVMID-UHFFFAOYSA-N dibromo-hex-1-enyl-methylsilane Chemical compound CCCCC=C[Si](C)(Br)Br DBFRRVRADQVMID-UHFFFAOYSA-N 0.000 description 1
- CHSOOADWBVJAOF-VOTSOKGWSA-N dichloro-[(E)-hex-1-enyl]-methylsilane Chemical compound CCCC\C=C\[Si](C)(Cl)Cl CHSOOADWBVJAOF-VOTSOKGWSA-N 0.000 description 1
- LNHPNZQMQXHNRD-UHFFFAOYSA-N dichloro-hept-1-enyl-methylsilane Chemical compound CCCCCC=C[Si](C)(Cl)Cl LNHPNZQMQXHNRD-UHFFFAOYSA-N 0.000 description 1
- XQOLMPJRVURWFY-UHFFFAOYSA-N dichloro-hex-5-enyl-methylsilane Chemical compound C[Si](Cl)(Cl)CCCCC=C XQOLMPJRVURWFY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- SSPMTNRPJDLEEB-UHFFFAOYSA-N hex-1-enyl-diiodo-methylsilane Chemical compound CCCCC=C[Si](C)(I)I SSPMTNRPJDLEEB-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LCOBJRDVAAUIFK-UHFFFAOYSA-N n-(dimethylamino-hex-1-enyl-methylsilyl)-n-methylmethanamine Chemical compound CCCCC=C[Si](C)(N(C)C)N(C)C LCOBJRDVAAUIFK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LBKJNHPKYFYCLL-UHFFFAOYSA-N potassium;trimethyl(oxido)silane Chemical compound [K+].C[Si](C)(C)[O-] LBKJNHPKYFYCLL-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HSNUIYJWTSJUMS-UHFFFAOYSA-N sodium;trimethyl(oxido)silane Chemical compound [Na+].C[Si](C)(C)[O-] HSNUIYJWTSJUMS-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
Definitions
- the present invention is a process for producing high-purity cyclic siloxane. More specifically, it is a process for producing high-purity cyclic siloxane by reducing the amount of silanol-containing linear siloxane contained as an impurity in cyclic siloxane.
- Cyclic siloxane can be prepared by the hydrolysis and condensation of diorganodichlorosilane or diorganocyclosilazane, and organopolysiloxane can be obtained by polymerizing such cyclic siloxane.
- linear siloxanes or silanes containing silanol groups are contained in the cyclic siloxane as impurities, and it is known that such silanes or linear siloxanes inhibit an increase in the molecular weight of the organopolysiloxane.
- the present invention is a process for the production of a cyclic siloxane described by formula
- R 1 is an alkenyl group having 6 to 14 carbon atoms
- b is an integer of one or greater
- c is an integer of 3 or greater
- d is an integer of 3 or greater.
- the present invention is a process for the production of a cyclic siloxane described by formula
- R 1 is an alkenyl group having 6 to 14 carbon atoms
- b is an integer of one or greater
- c is an integer of 3 or greater
- d is an integer of 3 or greater.
- siloxane mixture which serves as the starting material is made up of a silane or a linear siloxane described by general formula
- R 1 is an alkenyl group having 6 to 14 carbon atoms and b is an integer of 1 or greater and a cyclic siloxane described by general formula
- R 1 is as described above and c is an integer of 3 or greater.
- R 1 is an alkenyl group having 6 to 14 carbon atoms, exemplified by 5-hexenyl, 6-heptenyl, and 7-octenyl, with alkenyl groups having 6 to 10 carbon atoms, in particular, 5-hexenyl, being especially preferable from the standpoint of the ease of access to starting materials and the ease of synthesis.
- b in the above formulas is an integer of 1 or greater, preferably, an integer of 1 to 50, and especially preferably, an integer of 1 to 20.
- c in the above formulas is an integer of 3 or greater, preferably, an integer of 3 to 20.
- This type of siloxane mixture can be represented by the average formula
- R 1 is an alkenyl group having 6 to 14 carbon atoms, exemplified by the same groups as those mentioned above and e is a number greater than 1, preferably, a number between 1 and 30 (exclusive of 1).
- a siloxane mixture preferably has, for instance, at least 100 ppm of silanol groups, and, especially preferably, at least 1000 ppm of silanol groups.
- silanol mixture be prepared by reacting a silane described by general formula
- R 1 is an alkenyl group having 6 to 14 carbon atoms and X is a hydrolyzable group or a cyclic silazane described by general formula
- R 1 is the same as described above
- R 2 is a hydrogen atom or a monovalent hydrocarbon group
- a is an integer of 3 or greater with an equivalent or greater quantity of water.
- R 1 is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above.
- X in the formula above is a hydrolyzable group, exemplified by chlorine, bromine, iodine, and other halogen atoms; acetoxy, acryloxy, methacryloxy, and other acyloxy groups; methoxy, ethoxy, propoxy, and other alkoxy groups; amino groups; methylamino, ethylamino, dimethylamino, diethylamino, and other substituted amino groups.
- Such silane is exemplified by hexenylmethyldichlorosilane, heptenylmethyldichlorosilane, octenylmethyldichlorosilane, hexenylmethyldibromosilane, hexenylmethyldiiodosilane, hexenylmethyldiacetoxysilane, hexenylmethyldimethoxysilane, hexenylmethyldimethoxysilane, and hexenylmethylbis(dimethylamino)silane.
- R 1 is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above.
- R 2 in the above formula is a hydrogen atom or a monovalent hydrocarbon group, with the monovalent hydrocarbon group of R 2 exemplified by methyl, ethyl, propyl, and other alkyl groups; vinyl, allyl, butenyl, and other alkenyl groups; phenyl, tolyl, and other aryl groups; and benzyl, phenethyl, and other aralkyl groups.
- a in the formula above is an integer of 3 or greater, preferably an integer of 3 to 10.
- Such cyclic silazane is exemplified by the following compounds.
- the present process is characterized by causing the above-mentioned siloxane mixture to react using an alkali catalyst.
- the reaction consists in the cleavage of siloxane bonds followed by a rearrangement reaction (rearrangement) leading to recombination, or a condensation reaction among silanol groups.
- the alkali catalyst is exemplified by potassium hydroxide, sodium hydroxide, lithium hydroxide, cerium hydroxide, and other alkali metal hydroxides; sodium trimethylsilanolate, potassium trimethylsilanolate, potassium dimethylpolysiloxanolate, and other alkali metal silanolates.
- an amount such that the quantity of the alkali metal in the catalyst is 0.001-0.05 parts by weight is preferable from the standpoint of the higher rate of reaction as well as the ease of neutralizing the alkali catalyst after the reaction.
- the above-mentioned reaction can be carried out in the absence of a solvent, but it is preferable to conduct it in the presence of an aprotic organic solvent in order to selectively produce cyclic siloxane from a siloxane mixture consisting of a silane or a linear siloxane and a cyclic siloxane. Furthermore, it is preferable to conduct the above-mentioned reaction at the reflux temperature of the aprotic organic solvent in order to subject the by-produced water to azeotropic distillation.
- Hexane, heptane, octane, and other aliphatic hydrocarbons, as well as benzene, toluene, xylene, and other aromatic hydrocarbons are suggested as examples of such aprotic organic solvents.
- the amount of addition of the aprotic organic solvent it is preferable to add an amount sufficient to at least efficiently remove the by-produced water from the reaction system.
- the purity of the cyclic siloxane can be further enhanced by using a larger quantity of aprotic organic solvent, it is preferable to use the aprotic organic solvent in a quantity equivalent or greater than that of the siloxane mixture.
- a polar aprotic organic solvent it is preferable to use a polar aprotic organic solvent, because this can promote the above-mentioned reaction.
- Tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethylformamide, dimethylsulfoxide, and hexamethylphosphortriamide are suggested as examples of such polar aprotic organic solvents.
- It is preferable to use a necessary minimum amount of solvent because if a large amount of the polar aprotic organic solvent is used the by-produced water ends up dissolved therein which makes the removal of the water from the reaction system difficult.
- the amount of the polar aprotic organic solvent is preferably such that it constitutes not more than 10 wt %, and especially preferably not more than 5 wt % relative to the siloxane mixture.
- reaction temperature can be made considerably lower. Although there are no limitations concerning the temperature of the reaction in the present process, generally it is preferable for the temperature to be in the range of from 100° C. to 160° C.
- the progress of the reaction can be monitored using gas chromatography (GLC) and gel permeation chromatography (GPC).
- the reaction end point can be determined as the point in time at which all changes as measured by GLC and GPC end.
- the above-mentioned reaction can be terminated by neutralizing the alkali catalyst by adding acid.
- Phosphoric acid, moist carbon dioxide, and other inorganic acids; acetic acid, propionic acid, and other organic acids; trimethylchlorosilane, dimethyldichlorosilane, and other chlorosilanes are suggested as examples of the acids used as neutralizing agents.
- the target cyclic siloxane described by general formula (R 1 (CH 3 )SiO) c can be obtained by separating the byproduct salts by filtration, washing, or other means, removing the solvent and other low-boiling substances by heating under reduced pressure, and if necessary refining the product by means of distillation or other methods.
- R 1 in the formula above is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above.
- c in the above formula is an integer of 3 or greater, preferably an integer of 3 to 20.
- the present process permits preparation of cyclic siloxane with a silanol group content of 50 ppm or less and high molecular weight organopolysiloxanes can be obtained from such cyclic siloxane.
- silanol group content of 1.8 wt % and consisting of 5-hexenylmethylcyclosiloxane and a 5-hexenylmethylsiloxane oligomer having both terminal ends of the molecular chain blocked by silanol groups.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
A process for the production of a cyclic siloxane described by formula
(R1(CH3)SiO)d
comprising reacting in the presence of an alkali catalyst a siloxane mixture comprising a silane or a linear siloxane described by general formula
HO(R1(CH3)SiO)bH
and a cyclic siloxane described by general formula
(R1(CH3)SiO)c,
where R1 is an alkenyl group having 6 to 14 carbon atoms, b is an integer of one or greater, c is an integer of 3 or greater, and d is an integer of 3 or greater.
Description
- The present invention is a process for producing high-purity cyclic siloxane. More specifically, it is a process for producing high-purity cyclic siloxane by reducing the amount of silanol-containing linear siloxane contained as an impurity in cyclic siloxane. Cyclic siloxane can be prepared by the hydrolysis and condensation of diorganodichlorosilane or diorganocyclosilazane, and organopolysiloxane can be obtained by polymerizing such cyclic siloxane. However, linear siloxanes or silanes containing silanol groups are contained in the cyclic siloxane as impurities, and it is known that such silanes or linear siloxanes inhibit an increase in the molecular weight of the organopolysiloxane.
- The authors of the present invention have attempted to use distillation in order to separate the silanol-containing linear siloxane contained in cyclic siloxane in the process of forming high molecular weight organopolysiloxane by polymerizing a cyclic siloxane having methyl groups and alkenyl groups having 6 to 14 carbon atoms. However due to the high boiling point of cyclic siloxane it has proved difficult to obtain high-purity cyclic siloxane.
- It is an object of the present invention to provide a process for the production of high-purity cyclic siloxane by reducing the amount of silanol-containing linear siloxane contained as an impurity in cyclic siloxane having alkyl groups and alkenyl groups 6 to 14 carbon atoms.
- The present invention is a process for the production of a cyclic siloxane described by formula
- (R1(CH3)SiO)d
- comprising reacting in the presence of an alkali catalyst a siloxane mixture comprising a silane or a linear siloxane described by general formula
- HO(R1(CH3)SiO)bH
- and a cyclic siloxane described by general formula
- (R1(CH3)SiO)c,
- where R 1 is an alkenyl group having 6 to 14 carbon atoms, b is an integer of one or greater, c is an integer of 3 or greater, and d is an integer of 3 or greater.
- The present invention is a process for the production of a cyclic siloxane described by formula
- (R1(CH3)SiO)d
- comprising reacting in the presence of an alkali catalyst a siloxane mixture comprising a silane or a linear siloxane described by general formula
- HO(R1(CH3)SiO)bH
- and a cyclic siloxane described by general formula
- (R1(CH3)SiO)c,
- where R 1 is an alkenyl group having 6 to 14 carbon atoms, b is an integer of one or greater, c is an integer of 3 or greater, and d is an integer of 3 or greater.
- The cyclic siloxane production process of the present invention is explained in detail hereinbelow. In the present process the siloxane mixture which serves as the starting material is made up of a silane or a linear siloxane described by general formula
- HO(R1(CH3)SiO)bH
- where R 1 is an alkenyl group having 6 to 14 carbon atoms and b is an integer of 1 or greater and a cyclic siloxane described by general formula
- (R1(CH3)SiO)c
- where R 1 is as described above and c is an integer of 3 or greater. In the above formulas, R1 is an alkenyl group having 6 to 14 carbon atoms, exemplified by 5-hexenyl, 6-heptenyl, and 7-octenyl, with alkenyl groups having 6 to 10 carbon atoms, in particular, 5-hexenyl, being especially preferable from the standpoint of the ease of access to starting materials and the ease of synthesis. Also, b in the above formulas is an integer of 1 or greater, preferably, an integer of 1 to 50, and especially preferably, an integer of 1 to 20. Additionally, c in the above formulas is an integer of 3 or greater, preferably, an integer of 3 to 20. There are no limitations concerning the ratio of the silane or linear siloxane to the cyclic siloxane in such a siloxane mixture. This type of siloxane mixture can be represented by the average formula
- HO(R1 (CH3)SiO)eH
- where R 1 is an alkenyl group having 6 to 14 carbon atoms, exemplified by the same groups as those mentioned above and e is a number greater than 1, preferably, a number between 1 and 30 (exclusive of 1). Such a siloxane mixture preferably has, for instance, at least 100 ppm of silanol groups, and, especially preferably, at least 1000 ppm of silanol groups.
- It is preferable that such a silanol mixture be prepared by reacting a silane described by general formula
- R1(CH3)SiX2
- where R 1 is an alkenyl group having 6 to 14 carbon atoms and X is a hydrolyzable group or a cyclic silazane described by general formula
- (R1(CH3)SiNR2)a
- where R 1 is the same as described above, R2 is a hydrogen atom or a monovalent hydrocarbon group, and a is an integer of 3 or greater with an equivalent or greater quantity of water. The reaction consists in a hydrolysis of the above-mentioned silane or cyclic silazane and a subsequently occurring condensation reaction.
- In the silane described by general formula
- R1(CH3)SiX2,
- R 1 is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above. Also, X in the formula above is a hydrolyzable group, exemplified by chlorine, bromine, iodine, and other halogen atoms; acetoxy, acryloxy, methacryloxy, and other acyloxy groups; methoxy, ethoxy, propoxy, and other alkoxy groups; amino groups; methylamino, ethylamino, dimethylamino, diethylamino, and other substituted amino groups. Such silane is exemplified by hexenylmethyldichlorosilane, heptenylmethyldichlorosilane, octenylmethyldichlorosilane, hexenylmethyldibromosilane, hexenylmethyldiiodosilane, hexenylmethyldiacetoxysilane, hexenylmethyldimethoxysilane, hexenylmethyldimethoxysilane, and hexenylmethylbis(dimethylamino)silane.
- In the cyclic silazane described by general formula
- (R1(CH3)SiNR2)a,
- R 1 is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above. Also, R2 in the above formula is a hydrogen atom or a monovalent hydrocarbon group, with the monovalent hydrocarbon group of R2 exemplified by methyl, ethyl, propyl, and other alkyl groups; vinyl, allyl, butenyl, and other alkenyl groups; phenyl, tolyl, and other aryl groups; and benzyl, phenethyl, and other aralkyl groups. Also, a in the formula above is an integer of 3 or greater, preferably an integer of 3 to 10. Such cyclic silazane is exemplified by the following compounds.
- (CH2═CHCH2CH2CH2CH2(CH3)SiNH)3,
- (CH2═CHCH2CH2CH2CH2(CH3)SiNH)4,
- (CH2═CHCH2CH2CH2CH2(CH3)SiN(CH3))4.
- The present process is characterized by causing the above-mentioned siloxane mixture to react using an alkali catalyst. The reaction consists in the cleavage of siloxane bonds followed by a rearrangement reaction (rearrangement) leading to recombination, or a condensation reaction among silanol groups. In the present process the alkali catalyst is exemplified by potassium hydroxide, sodium hydroxide, lithium hydroxide, cerium hydroxide, and other alkali metal hydroxides; sodium trimethylsilanolate, potassium trimethylsilanolate, potassium dimethylpolysiloxanolate, and other alkali metal silanolates. There are no limitations concerning the amount of addition of the alkali catalyst, however, an amount such that the quantity of the alkali metal in the catalyst is 0.001-0.05 parts by weight is preferable from the standpoint of the higher rate of reaction as well as the ease of neutralizing the alkali catalyst after the reaction.
- In the present process the above-mentioned reaction can be carried out in the absence of a solvent, but it is preferable to conduct it in the presence of an aprotic organic solvent in order to selectively produce cyclic siloxane from a siloxane mixture consisting of a silane or a linear siloxane and a cyclic siloxane. Furthermore, it is preferable to conduct the above-mentioned reaction at the reflux temperature of the aprotic organic solvent in order to subject the by-produced water to azeotropic distillation. Hexane, heptane, octane, and other aliphatic hydrocarbons, as well as benzene, toluene, xylene, and other aromatic hydrocarbons are suggested as examples of such aprotic organic solvents. Although there are no limitations concerning the amount of addition of the aprotic organic solvent, it is preferable to add an amount sufficient to at least efficiently remove the by-produced water from the reaction system. In addition, because the purity of the cyclic siloxane can be further enhanced by using a larger quantity of aprotic organic solvent, it is preferable to use the aprotic organic solvent in a quantity equivalent or greater than that of the siloxane mixture.
- In addition, it is preferable to use a polar aprotic organic solvent, because this can promote the above-mentioned reaction. Tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethylformamide, dimethylsulfoxide, and hexamethylphosphortriamide are suggested as examples of such polar aprotic organic solvents. It is preferable to use a necessary minimum amount of solvent, because if a large amount of the polar aprotic organic solvent is used the by-produced water ends up dissolved therein which makes the removal of the water from the reaction system difficult. The amount of the polar aprotic organic solvent is preferably such that it constitutes not more than 10 wt %, and especially preferably not more than 5 wt % relative to the siloxane mixture.
- In the present process when an aprotic organic solvent is used the reaction temperature can be made considerably lower. Although there are no limitations concerning the temperature of the reaction in the present process, generally it is preferable for the temperature to be in the range of from 100° C. to 160° C.
- In the present process, the progress of the reaction can be monitored using gas chromatography (GLC) and gel permeation chromatography (GPC). In addition, the reaction end point can be determined as the point in time at which all changes as measured by GLC and GPC end. The above-mentioned reaction can be terminated by neutralizing the alkali catalyst by adding acid. Phosphoric acid, moist carbon dioxide, and other inorganic acids; acetic acid, propionic acid, and other organic acids; trimethylchlorosilane, dimethyldichlorosilane, and other chlorosilanes are suggested as examples of the acids used as neutralizing agents. The target cyclic siloxane described by general formula (R 1(CH3)SiO)c can be obtained by separating the byproduct salts by filtration, washing, or other means, removing the solvent and other low-boiling substances by heating under reduced pressure, and if necessary refining the product by means of distillation or other methods. R1 in the formula above is an alkenyl group having 6 to 14 carbon atoms exemplified by the same groups as those mentioned above. Also, c in the above formula is an integer of 3 or greater, preferably an integer of 3 to 20. The present process permits preparation of cyclic siloxane with a silanol group content of 50 ppm or less and high molecular weight organopolysiloxanes can be obtained from such cyclic siloxane.
- The present process for the production of cyclic siloxane is explained in further detail by referring to the below provided application examples. In the examples all percentages (%) are based upon weight.
- 40 g Of toluene and 371 g of water were placed in a 1-L flask equipped with a stirrer, a thermometer, and a cooling tube. After that, 252 g of 5-hexenylmethyldichlorosilane were added thereto in a dropwise manner while stirring the toluene and water. Upon termination of the dropwise addition the mixture was allowed to stand to cause it to undergo phase separation and the water layer was removed and the organic layer was washed three times. 1.3 g Of sodium hydrogencarbonate was added to the organic layer after thoroughly stirring the mixture it was filtered. Toluene was removed by heating the filtrate under reduced pressure thereby obtaining 164 g of a colorless transparent liquid. When the liquid was subjected to 29Si-Nuclear Magnetic Resonance (29Si-NMR) analysis it was found to be a siloxane mixture described by average formula
- HO(CH2═CHCH2CH2CH2CH2(CH3)SiO)13.1H
- having a silanol group content of 1.8 wt % and consisting of 5-hexenylmethylcyclosiloxane and a 5-hexenylmethylsiloxane oligomer having both terminal ends of the molecular chain blocked by silanol groups.
- 675 g Of xylene, 756 g of the siloxane mixture prepared in Reference Example 1, and 0.14 g potassium hydroxide in powder form were placed in a 2-L flask equipped with a stirrer, a thermometer, and a cooling tube. The mixture was refluxed under heating to cause it to react while removing the by-produced water by means of azeotropic distillation. As soon as water elution stopped, 28 g of dimethylformamide were added to the mixture and refluxing under heating was continued in order to elute water and then the mixture was cooled down. After neutralizing the potassium hydroxide using a sufficient quantity of carbon dioxide gas, the mixture was subjected to filtration and xylene was removed from the filtrate by heating it under reduced pressure thereby obtaining 695 g of a pale yellow transparent liquid. When the liquid was subjected to 29Si-NMR analysis, it was found to be a mixture consisting of 2.8% 5-hexenylmethylcyclosiloxane described by formula
- (CH2═CHCH2CH2CH2CH2(CH3)SiO)3,
- 72.9% 5-hexenylmethylcyclosiloxane described by formula
- (CH2═CHCH2CH2CH2CH2(CH3)SiO)4,
- 18.4% 5-hexenylmethylcyclosiloxane described by formula
- (CH2═CHCH2CH2CH2CH2(CH3)SiO)5,
- and 5.9% 5-hexenylmethylcyclosiloxane described by formula
- (CH2═CHCH2CH2CH2CH2(CH3)SiO)6,
- and when the mixture was analyzed using an infrared spectrophotometer (IR), it was found that the content of silanol groups in the mixture was 47 ppm.
- 1.58 kg Of the 5-hexenylmethylcyclosiloxane mixture prepared in Application Example 1, 38.28 kg of octamethylcyclotetrasiloxane, 80 g of a dimethylpolysiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups, described by average formula
- (CH3)3SiO((CH3)2SiO)8Si(CH3)3,
- and 72 g potassium polysiloxanolate described by average formula
- KO((CH3)2SiO)37K
- were placed in a 50-L vessel equipped with a high-torque stirrer, a thermometer, and a cooling pipe. The mixture was heated to 150° C. under atmospheric pressure and the reaction was conducted for 6 hours. After that, a neutralization reaction was carried out by bubbling carbon dioxide gas from the bottom of the reaction vessel for 1 hour at a rate of 500 L/hr. Subsequently, to remove octamethylcyclotetrasiloxane and other low-boiling components, treatment was conducted for 2 hours under a reduced pressure at 10 Torr and 150° C. After cooling, 36 kg of a gummy colorless transparent liquid was obtained. When the liquid was analyzed using a Fourier transform infrared spectrophotometer (FTIR), it was found that it was a copolymer of 5-hexenylmethylsiloxane and a dimethylsiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups with a content of silanol groups of 50 ppm and a content of 5-hexenyl groups of 2.32%. In addition, when the copolymer was analyzed using gel permeation chromatography (GPC, it was found to have a weight average molecular weight of 279,000 and a number average molecular weight of 164,000.
- 1.58 kg Of the 5-hexenylmethylcyclosiloxane mixture prepared in Application Example 1, 38.28 kg of octamethylcyclotetrasiloxane, 80 g of a dimethylpolysiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups described by average formula
- (CH3)3SiO((CH3)2SiO)8Si(CH3)3,
- and 400 g of tetramethylammonium siloxanolate described by average formula
- (CH3)4NO((CH3)2SiO)100N(CH3)4
- were placed in a 50-L vessel equipped with a high-torque stirrer, a thermometer, and a cooling pipe. The mixture was heated to 90° C. under atmospheric pressure and the reaction was conducted for 3 hours. Subsequently, after increasing the temperature to 150° C., treatment was conducted for 2 hours under a reduced pressure of 10 Torr and 150° C. to remove octamethylcyclotetrasiloxane and other low-boiling components. After cooling, 36.2 kg of a gummy colorless transparent liquid was obtained. When the liquid was analyzed using a FTIR spectrophotometer it was found that it was a copolymer of 5-hexenylmethylsiloxane and a dimethylsiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups, with a content of silanol groups of 53 ppm and a content of 5-hexenyl groups of 2.32%. In addition when the copolymer was analyzed using GPC, it was found to have a weight average molecular weight of 298,000 and a number average molecular weight of 175,000.
- The 5-hexenylmethylcyclosiloxane mixture prepared in Application Example 1 at a rate of 0.206 kg/hr, octamethylcyclotetrasiloxane at a rate of 5 kg/hr, dimethylpolysiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups described by average formula
- (CH3)3SiO((CH3)2SiO)8Si(CH3)3
- at a rate of 10.4 g/hr, and potassium polysiloxanolate described by average formula
- KO((CH3)2SiO)37K
- at a rate of 9.4 g/hr, were continuously supplied to a 10-L hermetically sealed vessel heated to 165° C. A neutralization reaction was carried out using a sufficient quantity of carbon dioxide gas at the outlet of the reaction vessel. Subsequently, the solution was fed to a reduced-pressure pot at 10 Torr and 165° C. to remove octamethylcyclotetrasiloxane and other low-boiling components. After cooling, a gummy colorless transparent liquid was obtained. When the liquid was analyzed using a FTIR spectrophotometer it was found that it was a copolymer of 5-hexenylmethylsiloxane and dimethylsiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups, with a content of silanol groups of 48 ppm and a content of 5-hexenyl groups of 2.32%. When the copolymer was analyzed using GPC it was found to have a weight average molecular weight of 285,000 and a number average molecular weight of 168,000.
- 1.58 kg Of the siloxane mixture prepared in Reference Example 1, 38.28 kg of octamethylcyclotetrasiloxane, 80 g of a dimethylpolysiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups described by average formula
- (CH3)3SiO((CH3)2SiO)8Si(CH3)3,
- and 72 g of potassium polysiloxanolate described by average formula
- KO((CH3)2SiO)37K
- were placed in a 50-L vessel equipped with a high-torque stirrer, a thermometer, and a cooling pipe. The mixture was heated to 150° C. under atmospheric pressure and the reaction was conducted for 6 hours. After that, a neutralization reaction was carried out by bubbling carbon dioxide gas from the bottom of the reaction vessel for 1 hour at a rate of 500 L/hr. Subsequently, to remove octamethylcyclotetrasiloxane and other low-boiling components, treatment was conducted for 2 hours under reduced pressure state at 10 Torr and 150° C. After cooling, 36 kg of a colorless transparent liquid was obtained. When the liquid was analyzed using a FTIR spectrophotometer it was found that it was a copolymer of 5-hexenylmethylsiloxane and dimethylsiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups, with a content of silanol groups of 167 ppm and a content of 5-hexenyl groups of 2.31%. In addition when the copolymer was analyzed using GPC it was found to have a weight average molecular weight of 204,000 and a number average molecular weight of 118,000.
- 1.58 kg Of the siloxane mixture prepared in Reference Example 1, 38.28 kg of octamethylcyclotetrasiloxane, 80 g of a dimethylpolysiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups described by average formula
- (CH3)3SiO((CH3)2SiO)8Si(CH3)3,
- and 400 g of tetramethylammonium siloxanolate described by average formula
- (CH3)4NO((CH3)2SiO)100N(CH3)4
- were placed in a 50-L vessel equipped with a high-torque stirrer, a thermometer, and a cooling pipe. The mixture was heated to 90° C. under atmospheric pressure and the reaction was conducted for 3 hours. However, although the start of the polymerization reaction was detected it stopped halfway and it was impossible to obtain a copolymer with a high degree of polymerization consisting of 5-hexenylmethylsiloxane and a dimethylsiloxane having both terminal ends of the molecular chain blocked by trimethylsiloxy groups.
Claims (11)
1. A process for the production of a cyclic siloxane described by formula
(R1(CH3)SiO)d
comprising reacting in the presence of an alkali catalyst a siloxane mixture comprising a silane or a linear siloxane described by general formula
HO(R1(CH3)SiO)bH
and a cyclic siloxane described by general formula
(R1(CH3)SiO)c
where R1 is an alkenyl group having 6 to 14 carbon atoms, b is an integer of one or greater, c is an integer of 3 or greater, and d is an integer of 3 or greater.
2. The process of , where R1 is an alkenyl group having 6 to 10 carbon atoms.
claim 1
3. The process of , where R1 is a 5-hexenyl group.
claim 1
4. The process of , where the reacting is carried out using an alkali catalyst in the presence of an aprotic organic solvent.
claim 1
5. The process of , where by-produced water is subjected to azeotropic distillation using an aprotic organic solvent.
claim 4
6. The process of , where the siloxane mixture is obtained by reacting a silane described by general formula
claim 1
R1(CH3)SiX2
or a cyclic silazane described by general formula
(R1(CH3)SiNR2)a,
where R1 is an alkenyl group having 6 to 14 carbon atoms, X is a hydrolyzable group, R2 is a hydrogen atom or a monovalent hydrocarbon group, and a is an integer of 3 or greater with an equivalent or greater quantity of water.
7. The process of , where b is an integer of 1 to 50.
claim 1
8. The process of , where b is an integer of 1 to 20.
claim 1
9. The process of , where c is an integer of 3 to 20.
claim 1
10. The process of , where the alkali catalyst is selected from the group consisting of alkali metal hydroxides and alkali metal silanolates.
claim 1
11. The process of , where the aprotic organic solvent is polar.
claim 4
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000019696A JP4663838B2 (en) | 2000-01-28 | 2000-01-28 | Method for producing cyclic siloxane |
| JP2000-019696 | 2000-01-28 | ||
| JPJP2000-019696 | 2000-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20010011120A1 true US20010011120A1 (en) | 2001-08-02 |
| US6448360B2 US6448360B2 (en) | 2002-09-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/765,047 Expired - Lifetime US6448360B2 (en) | 2000-01-28 | 2001-01-19 | Process for the production of cyclic siloxane |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6448360B2 (en) |
| EP (1) | EP1125939B1 (en) |
| JP (1) | JP4663838B2 (en) |
| DE (1) | DE60112486T2 (en) |
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| US20070203263A1 (en) * | 2004-04-15 | 2007-08-30 | Wacker Chemie Ag | Process For The Continuous Preparation Of Silicone Emulsions |
| US20140107309A1 (en) * | 2012-10-15 | 2014-04-17 | Shin-Etsu Chemical Co., Ltd. | Method for preparing a polyorganosiloxane |
| US20150175749A1 (en) * | 2012-07-11 | 2015-06-25 | Wacker Chemie Ag | Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacycles |
| US9284340B2 (en) | 2012-07-11 | 2016-03-15 | Wacker Chemie Ag | Oxasilacycles and method for the production thereof |
| CN112552334A (en) * | 2020-12-08 | 2021-03-26 | 江西贝特利新材料有限公司 | Preparation method of hexamethylcyclotrisilazane |
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|---|---|---|---|---|
| CN103333338B (en) * | 2013-07-11 | 2016-05-11 | 江苏天辰新材料股份有限公司 | A kind of vinyl silicone oil and synthetic method thereof |
| FR3153615A1 (en) | 2023-09-28 | 2025-04-04 | Elkemsilicones France Sas | Depolymerization of organopolysiloxane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070203263A1 (en) * | 2004-04-15 | 2007-08-30 | Wacker Chemie Ag | Process For The Continuous Preparation Of Silicone Emulsions |
| US20150175749A1 (en) * | 2012-07-11 | 2015-06-25 | Wacker Chemie Ag | Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacycles |
| US9284340B2 (en) | 2012-07-11 | 2016-03-15 | Wacker Chemie Ag | Oxasilacycles and method for the production thereof |
| US9309358B2 (en) * | 2012-07-11 | 2016-04-12 | Wacker Chemie Ag | Crosslinkable siloxanes by acid-catalyzed polymerization of oxasilacycles |
| US20140107309A1 (en) * | 2012-10-15 | 2014-04-17 | Shin-Etsu Chemical Co., Ltd. | Method for preparing a polyorganosiloxane |
| US9139700B2 (en) * | 2012-10-15 | 2015-09-22 | Shin-Etsu Chemical Co., Ltd. | Method for preparing a polyorganosiloxane |
| CN112552334A (en) * | 2020-12-08 | 2021-03-26 | 江西贝特利新材料有限公司 | Preparation method of hexamethylcyclotrisilazane |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1125939B1 (en) | 2005-08-10 |
| JP2001206949A (en) | 2001-07-31 |
| EP1125939A1 (en) | 2001-08-22 |
| DE60112486T2 (en) | 2006-04-20 |
| DE60112486D1 (en) | 2005-09-15 |
| US6448360B2 (en) | 2002-09-10 |
| JP4663838B2 (en) | 2011-04-06 |
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