CN116802186A - Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane, and method for producing polysiloxane - Google Patents
Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane, and method for producing polysiloxane Download PDFInfo
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- CN116802186A CN116802186A CN202280011656.6A CN202280011656A CN116802186A CN 116802186 A CN116802186 A CN 116802186A CN 202280011656 A CN202280011656 A CN 202280011656A CN 116802186 A CN116802186 A CN 116802186A
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- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 92
- -1 polysiloxane Polymers 0.000 title claims abstract description 82
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims description 64
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 31
- 238000004817 gas chromatography Methods 0.000 description 26
- 238000005259 measurement Methods 0.000 description 24
- 229910052736 halogen Inorganic materials 0.000 description 21
- 150000002367 halogens Chemical class 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 18
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 17
- 239000012535 impurity Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000005046 Chlorosilane Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000004879 turbidimetry Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000000998 batch distillation Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001944 continuous distillation Methods 0.000 description 3
- RLWXXXHAQBWSPA-UHFFFAOYSA-N fluoromethanol Chemical compound OCF RLWXXXHAQBWSPA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- 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
- C07F7/20—Purification, separation
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
Provided are a silicon compound containing an HFIP group (an aromatic alkoxysilane containing an HFIP group) having a reduced content of a specific halosilane compound, a method for producing the same, a polysiloxane obtained by polymerizing a silicon compound containing an HFIP group, and a method for producing the same. Provided is a silicon compound comprising a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2), wherein the content of the halosilane compound represented by the formula (2) is more than 0 mass ppm and not more than 1000 mass ppm.
Description
Technical Field
One embodiment of the present application relates to a silicon compound containing hexafluoroisopropanol group and a method for producing the same. Alternatively, one embodiment of the present application relates to a polysiloxane obtained by polymerizing the silicon compound and a method for producing the same.
Background
A polymer compound containing a siloxane bond (hereinafter, sometimes referred to as a polysiloxane polymer compound or simply referred to as a polysiloxane) is used in the field of semiconductors as a coating material or a sealing material, by utilizing its high heat resistance, transparency, and the like. In addition, the material has high oxygen plasma resistance and is used as a material for a resist layer.
In order to use a polysiloxane polymer compound as a resist, it is required to be soluble in an alkali such as an alkali developer. As means for making it soluble in an alkali developer, introduction of an acidic group into a polysiloxane polymer compound is exemplified. Examples of such acidic groups include phenol groups, carboxyl groups, and fluoromethanol (fluoroarbinol) groups. But are known as: when a polysiloxane polymer compound containing a phenol group or a carboxyl group is used at a high temperature, there are cases where deterioration in transparency, coloring, and the like occur or heat resistance is poor.
Patent documents 1 and 2 disclose that a fluoromethanol group, for example, hexafluoroisopropanol group { 2-hydroxy-1, 3-fluoroisopropyl [ -C (CF), as an acidic group, is introduced into a polysiloxane polymer compound 3 ) 2 OH]A polysiloxane polymer compound obtained by the following process, which may be referred to as HFIP group.
Patent document 1 discloses an organosilicon compound having an HFIP group (R 3 Si-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 OH) is produced by a method (R represents an alkoxy group having 1 to 3 carbon atoms). The organosilicon compound is prepared by reacting CH 2 ＝CH-CH 2 -C(CF 3 ) 2 The compound having an HFIP group represented by OH is obtained by hydrosilylation with a trialkoxysilane containing an alkoxy group having 1 to 3 carbon atoms.
Patent document 2 discloses a polymer compound in which a fluoromethanol group is bonded to a main chain composed only of siloxane via a divalent hydrocarbon group having 1 to 20 carbon atoms and being linear, branched, cyclic or bridged.
The organosilicon compound described in patent document 1 contains an ethylene bond (-CH) between an HFIP group and a silicon atom 2 -CH 2 In the polymer compound described in patent document 2, an aliphatic hydrocarbon group is sandwiched between an HFIP group and a silicon atom of a siloxane main chain.
Further, patent documents 3 and 4 disclose a method for producing an HFIP group-containing silicon compound (1) in which an HFIP group is directly bonded to a silicon atom, and a polysiloxane-containing polymer compound containing an HFIP group obtained by polymerizing (1), and show that: the polysiloxane polymer compound exhibits higher heat resistance than the polymer compound described in the aforementioned patent document 1. Also disclosed is: the polysiloxane polymer compound containing HFIP group has both transparency and alkali solubility.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2004-256503
Patent document 2: japanese patent laid-open No. 2002-55456
Patent document 3: japanese patent laid-open publication No. 2014-156461
Patent document 4: international publication No. 2019/167770
Disclosure of Invention
Problems to be solved by the application
For example, in the production process of the HFIP group-containing silicon compound (1) described in patent document 3 and patent document 4, a compound containing halogen other than fluorine is used, and therefore, it is possible to obtain the HFIP group-containing silicon compound (1) containing impurities including halogen other than fluorine. In general, in order to use an alkoxysilane for electronic material applications, a low content of halogen-containing impurities is sometimes required.
The inventors found that: in the production methods of the HFIP group-containing silicon compound (1) described in patent documents 3 and 4, it was found that a specific halosilane compound was contained as one of halogen-containing impurities, and: by reducing the content of the halosilane compound, there is room for improvement in reducing the content of halogen-containing impurities.
Accordingly, an object of the present application is to provide a silicon compound containing an HFIP group (hereinafter also referred to as an aromatic alkoxysilane containing an HFIP group) having a reduced content of a specific halosilane compound, a process for producing the same, a polysiloxane obtained by polymerizing a silicon compound containing an HFIP group, and a process for producing the same.
Solution for solving the problem
The present inventors have conducted intensive studies on a novel method for removing halogen-containing impurities remaining in HFIP-group-containing alkoxysilane. The result shows that: by performing the distillation operation again after removing the high boiling point component by the distillation operation, the halogen-containing impurities remaining in the HFIP group-containing alkoxysilane can be removed.
An embodiment of the present application provides a silicon compound including a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2), wherein the content of the halosilane compound represented by the formula (2) is more than 0 mass ppm and not more than 1000 mass ppm.
(in the formula (1), R 1 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkyl group having 1 to 10 carbon atomsFluoroalkyl of R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, and a+b+c=4. )
(in the formula (2), R 1a Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2a Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is an integer of 1 to 3, bb is an integer of 0 to 2, cc is an integer of 0 to 2, dd is an integer of 1 to 3, aa+bb+cc+dd=4. )
The upper limit of the content of the halosilane compound may be 100 mass ppm or less.
The group represented by the following chemical formula in the formula (1) and the formula (2) may be 1 or more selected from the group consisting of the groups represented by the following formulas (2A) to (2D).
(line segment crossing wavy line represents a connecting key.)
(the line segments intersecting the wavy lines represent the connection keys respectively.)
aa may be 1.
dd may be 1.
R 2 a may be methyl or ethyl.
The halosilane compound may be aa 1, bb 0, dd 1 or 2, cc 1 or 2, R 2a A compound represented by the formula (2) which is methyl or ethyl.
When the content of the silicon compound (meta) represented by the formula (1) composed of the group represented by the formula (2A) is taken as Xa mol and the content of the silicon compound (para) represented by the formula (1) composed of the group represented by the formula (2B) is taken as Ya mol, the relation Ya/(ya+xa) <0.10 can be satisfied.
The halide ion concentration may be 100 mass ppm or less.
An embodiment of the present application provides a method for producing a silicon compound, comprising at least the steps of:
a first distillation step of distilling a mixture containing at least a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2) to recover a first mixture containing the silicon compound represented by the formula (1) and a low boiling point component having a boiling point lower than that of the silicon compound represented by the formula (1); and
a second distillation step of distilling the first mixture obtained in the first step, which contains the silicon compound represented by the formula (1) and a low boiling point component having a boiling point lower than that of the silicon compound represented by the formula (1), to recover the silicon compound represented by the formula (1),
the content of the halosilane compound represented by the formula (2) is 1000 mass ppm or less.
(in the formula (1), R 1 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, and a+b+c=4. )
(in the above formula (2), R 1a Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2a Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is an integer of 1 to 3, bb is an integer of 0 to 2, cc is an integer of 0 to 2, dd is an integer of 1 to 3, aa+bb+cc+dd=4. )
An embodiment of the present application provides a polysiloxane obtained by polymerizing any of the above silicon compounds.
The halide ion concentration may be 1000 mass ppm or less.
An embodiment of the present application provides a method for producing a polysiloxane, wherein any of the silicon compounds described above is polymerized.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present application, there can be provided a silicon compound containing an HFIP group (an aromatic alkoxysilane containing an HFIP group) having a reduced content of a specific halosilane compound, a method for producing the same, a polysiloxane obtained by polymerizing a silicon compound containing an HFIP group, and a method for producing the same.
Detailed Description
Hereinafter, a silicon compound (HFIP group-containing aromatic alkoxysilane), a method for producing the same, a polysiloxane, and a method for producing the same according to embodiments of the present application will be described. The embodiments of the present application are not limited to the descriptions of the embodiments and examples shown below. In the present specification, unless otherwise specified, the expression "X to Y" in the description of the numerical range indicates X or more and Y or less.
In the expression of the group (atomic group) in the present specification, the expression of whether substituted or unsubstituted includes both of the non-substituted group and the substituted group. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "cyclic alkyl group" includes not only a monocyclic structure but also a polycyclic structure. "cycloalkyl" is also the same.
In the present specification, the term-C (CF) 3 ) 2 The hexafluoroisopropanol group shown by OH is expressed as "HFIP group".
The silicon compound according to one embodiment of the present application contains an HFIP group-containing aromatic alkoxysilane and a halosilane compound described below.
< HFIP group-containing aromatic alkoxysilane >
The HFIP group-containing aromatic alkoxysilane (silicon compound) used in the present application is represented by the following general formula (1), and has a structure in which an HFIP group and a silicon atom are directly bonded to an aromatic ring.
In the formula (1), R 1 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms. R is R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 5. a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, and a+b+c=4.
Among these, regarding the group represented by the following chemical formula in the HFIP group-containing aromatic alkoxysilane represented by the formula (1), n is preferably 1 or 2, and particularly preferably 1 or more selected from the group consisting of the groups represented by the following formulas (2A) to (2D).
In addition, a is preferably 1. In the above formulae (2A) to (2D), a line segment intersecting the wavy line represents a connecting bond.
As R 1 An alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is particularly preferable.
As R 2 Preferably a straight-chain alkyl group having 1 to 4 carbon atoms or a branched-chain alkyl group having 3 to 4 carbon atoms, and all or a part of hydrogen atoms in the alkyl group is optionally substituted with fluorine atoms. Specifically, as R 2 Methyl, ethyl, 1-propyl, 2-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-fluoroethyl, 2-trifluoroethyl 3-fluoropropyl, 3-difluoropropyl, 3-trifluoropropyl, 2, 3-tetrafluoropropyl 2, 3-pentafluoropropyl, 1, 3-hexafluoroisopropyl, and the like, methyl or ethyl is particularly preferred.
< halosilane Compound >
The halosilane compound contained in the silicon compound of the present application is represented by the following formula (2). As will be described later, the halogenated silane compound represented by the following formula (2) is preferably not contained in the silicon compound of the present application, but in the production process of the HFIP group-containing aromatic alkoxysilane (1), halogen and/or a halogen compound may be contained as a raw material or as a by-product, and therefore, it is difficult to set the content of the halogenated silane compound in the silicon compound of the present application to 0 mass ppm. The silicon compound of the present application is characterized in that the content of the halosilane compound represented by the following formula (2) is reduced to a level which has not been conventionally found.
In the formula (2), R 1a Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2a Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X is a chlorine atom, a bromine atom or an iodine atom, n isAn integer of 1 to 5, aa is an integer of 1 to 3, bb is an integer of 0 to 2, cc is an integer of 0 to 2, dd is an integer of 1 to 3, aa+bb+cc+dd=4.
Among these, n may be 1 or 2, particularly 1 or more selected from the group consisting of groups represented by the following formulas (2A) to (2D), in the halosilane compound represented by the formula (2).
In addition, aa may be 1. In the above formulae (2A) to (2D), a line segment intersecting the wavy line represents a connecting bond.
In one embodiment, dd may be 1.
R 1a Can be an alkyl group having 1 to 5 carbon atoms, in particular a methyl group.
As R 2a The alkyl group may be a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and all or a part of hydrogen atoms in the alkyl group may be optionally substituted with fluorine atoms. Specifically, as R 2a Examples thereof include methyl, ethyl, 1-propyl, 2-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-fluoroethyl, 2-trifluoroethyl 3-fluoropropyl, 3-difluoropropyl, 3-trifluoropropyl, 2, 3-tetrafluoropropyl 2, 3-pentafluoropropyl, 1, 3-hexafluoroisopropyl, and the like, in particular, it may be methyl or ethyl.
The silicon compound of the present application mainly contains an HFIP group-containing aromatic alkoxysilane represented by the formula (1), and in one embodiment, the content of the halosilane compound represented by the formula (2) is more than 0 mass ppm and not more than 1000 mass ppm. The upper limit of the content of the halosilane compound represented by the formula (2) is preferably 100 mass ppm or less. The content of the halosilane compound represented by the formula (2) in the silicon compound of the present application is preferably 0 mass ppm as the content thereof is smaller, but in the production process of the HFIP group-containing aromatic alkoxysilane (1), halogen and/or a halogen compound may be contained as a raw material or as a by-product, and therefore, it is difficult to set the content of the halosilane compound in the silicon compound of the present application to 0 mass ppm. In addition, from the technical viewpoint of detecting the halosilane compound, the detection limit may be set to a lower limit. For example, 10 mass ppm may be set as the lower limit. In the present specification, the content of the halosilane compound represented by the formula (2) is measured by gas chromatography.
In one embodiment, the concentration of halide ions in the silicon compound of the present application is preferably 100 mass ppm or less. In the present specification, the halide ions to be measured are evaluated as halide ions including halogen contained in the halosilane compound represented by the formula (2). The halide ion to be measured is chloride ion, bromide ion or iodide ion.
In the silicon compound of the present application, the halide ion concentration may be 0 mass ppm, and as described above, in the production process using the halogen compound, it is difficult to set the halide ion concentration to 0, and the detection limit may be set to the lower limit from the viewpoint of the technique for detecting the halide ion concentration. For example, 0.1 mass ppm may be set as the lower limit. In the present specification, the halide ion concentration can be selected by selecting an optimum measurement method according to the sample to be measured. The silicon compound of the present application is a solid measurement sample, and the measurement sample containing the silicon compound of the present application and a water-insoluble organic solvent is measured by ion chromatography. Alternatively, a measurement sample containing the silicon compound or polysiloxane of the present application and containing a water-soluble organic solvent, or a measurement sample containing a reaction solvent used in a method for producing polysiloxane described later, for example, is measured by silver chloride turbidimetry.
In one embodiment, when the halide ion concentration is measured in a solution containing a silicon compound, the halide ion concentration of the silicon compound of the present application can be calculated from the halide ion concentration of a measurement sample containing an organic solvent. For example, the halide ion concentration (ppm) of the organic solvent and the weight (g) of the organic solvent-containing measurement sample can be subtracted from the halide ion concentration (ppm) of the organic solvent-containing measurement sample to obtain the halide ion amount (g) of the measurement sample excluding the halide ions derived from the organic solvent (hereinafter referred to as the halide ion amount (1)). Further, the mass (g) of the silicon compound in the measurement sample containing the organic solvent can be obtained from the concentration (mass%) of the measurement sample containing the organic solvent and the weight (g) of the measurement sample containing the organic solvent. The halide ion amount (1) obtained above is considered to be derived from a silicon compound, and therefore, the halide ion concentration (ppm) of the silicon compound can be calculated from the halide ion amount (1) and the mass (g) of the silicon compound in the measurement sample.
In one embodiment, when the content of the silicon compound (meta) represented by the formula (1) composed of the group represented by the formula (2A) is taken as Xa mol and the content of the silicon compound (para) represented by the formula (1) composed of the group represented by the formula (2B) is taken as Ya mol, the relationship of Ya/(ya+xa) <0.10 can be satisfied.
The silicon compound according to the embodiment of the present application is solid at room temperature (for example, 20 ℃) and can improve the fluidity of the solid by satisfying the above-described relation. In particular, the smaller the value of the above-mentioned relational expression is, the more fluidity tends to be improved, and is preferable from the viewpoint of the handling properties of the solid.
It is known that the meta-position and para-position differ in polymerization reactivity, and that the variation in polymerization reactivity can be suppressed by satisfying the above-described relationship. In particular, the smaller the value of the above-mentioned relational expression is, the more the deviation in polymerization reactivity tends to be suppressed, and is preferable from the viewpoints of the quality of the polymer and the stability of production.
[ method for producing silicon Compound ]
The method for producing the silicon compound according to the present application is not particularly limited, and a method for producing an aromatic alkoxysilane (1) containing an HFIP group can be used. A typical manufacturing method is described below.
The compounds represented by the general formula (1) are known and can be synthesized by, for example, the methods described in patent documents 3 and 4.
[ refining method ]
The synthesized HFIP group-containing aromatic alkoxysilane (1) contains halogen and/or a halogen compound generated by a raw material or a side reaction. That is, since the halogen and/or the halogen compound as described above are contained in the silicon compound in a state before purification, the halosilane compound represented by the formula (2) is easily produced when the conventional purification operation is performed. Accordingly, in the method for producing a silicon compound according to the present application, in one embodiment, the following purification method is used.
The purification method of the present application is characterized in that the halogen-containing impurity is reduced by performing a first step in which an HFIP group-containing aromatic alkoxysilane represented by the formula (1) is fed to a distillation step to recover a mixture containing the HFIP group-containing aromatic alkoxysilane and a low boiling point component having a boiling point lower than that of the HFIP group-containing aromatic alkoxysilane, and a subsequent second step in which the mixture containing the HFIP group-containing aromatic alkoxysilane and the low boiling point component obtained in the first step is fed to the distillation step again to recover the HFIP group-containing aromatic alkoxysilane. Hereinafter, the operation will be described in detail.
[ Pre-distillation (first distillation step) ]
In the present application, as the first distillation step, an aromatic alkoxysilane containing an HFIP group is distilled (pre-distilled) for the purpose of removing a high boiling point component. In the case where the precise distillation (main distillation) is directly performed without performing the preliminary distillation (in the case of the conventional purification operation), the halosilane compound represented by the formula (2) is produced as a by-product. It can be speculated that it is generated as follows: the high boiling halogen-containing impurities remaining in the HFIP group-containing aromatic alkoxysilane are decomposed by heat during distillation, and hydrogen halide and alkoxy groups (Si-OR) 2 ) And the exchange reaction occurs. The above-mentioned thermal decomposition reaction continues to occur during distillation although the decomposition rate is low, and therefore it is difficult to completely separate the halogen-containing impurity, i.e., the halosilane compound, from the HFIP group-containing aromatic alkoxysilane.
On the other hand, by performing the preliminary distillation, it is possible to recover a mixture containing the HFIP group-containing aromatic alkoxysilane and a low boiling point component having a boiling point lower than that of the HFIP group-containing aromatic alkoxysilane, and remove the halogen-containing impurities having a high boiling point, which are thermally decomposed, as a residue in the form of a pot. By subjecting the distillation fraction obtained in this operation to distillation refining again, the halosilane compound is separated from the HFIP group-containing aromatic alkoxysilane, whereby the halogen-containing impurities can be reduced.
The method of the preliminary distillation is not particularly limited, and a multistage distillation, a batch distillation having a rectifying column, a continuous distillation, or a thin film distillation or the like in which the operation is repeated may be used in addition to the single distillation. The optimum distillation temperature in the distillation is significantly different depending on the type of the HFIP group-containing aromatic alkoxysilane (1) to be purified, and is preferably in the range of 100℃to 200 ℃. If the temperature is too high, the thermal decomposition may cause a decrease in yield. More preferably, the preliminary distillation is carried out at a temperature in the range of 100℃to 180 ℃. The pressure at the time of the preliminary distillation is not particularly limited, and is preferably adjusted according to the boiling point of the HFIP group-containing aromatic alkoxysilane, and specifically, the preliminary distillation is preferably carried out at 0.01 to 101kPa (atmospheric pressure).
In the present application, after the above-described pre-distillation is performed, the obtained distillation fraction is distilled again, whereby the halogen-containing impurities are reduced. In this case, the main halogen-containing impurity contained in the distillation fraction of the preliminary distillation is the halosilane compound (2) by-produced during the preliminary distillation. Therefore, the removal of the halosilane compound (2) can be performed before the main distillation. Examples of such a removal step include using OR in the formula (1) 2 Equivalent alcohols (so-called HOR 2 ) And performing retreatment, water washing and the like.
[ Main distillation (second distillation Process) ]
Next, as a second distillation step, main distillation is performed for the purpose of recovering the HFIP group-containing aromatic alkoxysilane (1) and removing the halosilane compound (2). The method of the main distillation is not particularly limited, and a multistage distillation, a batch distillation/continuous distillation including a rectifying column, or a thin film distillation or the like may be used in which the operation is repeated, in addition to the single distillation. Among them, from the viewpoint of separation from the halosilane compound (2), batch distillation/continuous distillation with a rectifying column is preferable. The optimum distillation temperature in the main distillation is significantly different depending on the type of the HFIP group-containing aromatic alkoxysilane (1) to be purified, as in the case of the preliminary distillation, and is preferably in the range of 100 to 200 ℃, more preferably in the range of 100 to 180 ℃. The pressure during the main distillation is not particularly limited as in the case of the preliminary distillation, and is preferably adjusted according to the boiling point of the aromatic alkoxysilane containing an HFIP group, and specifically, the main distillation is preferably performed at 0.01 to 101kPa (atmospheric pressure).
Polysiloxane ]
The polysiloxane according to the present embodiment is a polysiloxane obtained by polymerizing the silicon compound according to the present application, and has at least 1 siloxane bond. Methods for producing polysiloxanes are known and can be synthesized, for example, by the methods described in patent documents 3 and 4.
Specifically, the above-mentioned silicon compound of the present application is taken into a reaction vessel, then, water for hydrolyzing the silicon compound of the present application, an acid catalyst for allowing the polycondensation reaction to proceed, and a reaction solvent are added to the reactor, and then, the reaction solution is stirred at room temperature or while heating, and the hydrolysis and polycondensation reaction are allowed to proceed, thereby obtaining the HFIP group-containing polysiloxane polymer compound of the present application.
The reaction solvent may be any solvent that dissolves the raw material compound, and the solvent may be a water-soluble or water-insoluble organic solvent, and examples thereof include an alcohol-based solvent and an ether-based solvent. The water-soluble organic solvent in the present application means an organic solvent having a solubility in water of more than 50g/L, and the water-insoluble organic solvent means an organic solvent having a solubility in water of 50g/L or less. Examples of the water-soluble organic solvent include lower alcohols, lower ethers, lower ketones, and lower esters, and specifically include methanol (solubility in water: arbitrary mixture), ethanol (solubility in water: arbitrary mixture), 1-propanol (solubility in water: arbitrary mixture), isopropanol (solubility in water: 1000 g/L), 1-butanol (solubility in water: 77 g/L), diethyl ether (solubility in water: 60 g/L), acetonitrile (solubility in water: 1000 g/L), tetrahydrofuran (solubility in water: arbitrary mixture), N-dimethylformamide (solubility in water: arbitrary mixture), and N-methyl-2-pyrrolidone (solubility in water: arbitrary mixture). Examples of the water-insoluble solvent include hydrocarbons, higher ethers, and higher ketones, and specifically toluene (solubility in water: 0.526 g/L), diisopropyl ether (solubility in water: 11 g/L), and methyl tert-butyl ether (solubility in water: 42 g/L) and the like.
In the present application, since the content of the halosilane represented by the formula (2) contained in the HFIP group-containing aromatic alkoxysilane represented by the formula (1) is reduced, a polysiloxane having a low halogen content can be obtained by polymerizing these. In one embodiment, the halide ion concentration in the polysiloxane is 1000 mass ppm or less.
Examples
Hereinafter, the present application will be specifically described with reference to examples, but the present application is not limited to these examples.
The various analyses in this example were performed by the methods shown below.
[ Gas Chromatography (GC) ]
The purity of the silicon compound and the content of the chlorosilane compound corresponding to the formula (2) were measured by using a gas chromatograph manufactured by Shimadzu corporation under the trade name Shimadzu GC-2010 and a column using a capillary column DB1 (60 mm. Times.0.25 mm. Phi. Times.1 μm).
[ chloride ion measurement ]
In this example, chloride ions were measured as halogens.
[ ion chromatography ]
The measurement sample of the silicon compound of the present application in a solid state and the measurement sample containing the silicon compound of the present application and a water-insoluble organic solvent are measured by ion chromatography. For the measurement of chloride ions by ion chromatography, methyl t-butyl ether and ultrapure water were added to the measurement sample and stirred, and then the aqueous layer was poured into an ion chromatograph (DIONEX (registered trademark) aquon manufactured by Thermo Fisher Scientific company to measure. The column uses Dionex (registered trademark) Ion Pac AS22.
[ silver chloride turbidimetry ]
The sample containing the silicon compound or polysiloxane of the present application and containing the water-soluble organic solvent is measured by a silver chloride turbidimetry method using silver nitrate. The silver chloride turbidimetry was performed according to JISB 8224:2016. The nitric acid was 60% by mass nitric acid prescribed in JIS K8541, the silver nitrate aqueous solution was 1.2mol/L silver nitrate aqueous solution, methanol was added to the measurement sample, and the mixture was adjusted to a uniform sample, and then the measurement was performed at a measurement wavelength of 335 nm.
[ molecular weight measurement ]
The molecular weight of the polymer was measured by gel permeation chromatography (HLC-8320 GPC, manufactured by Tosoh corporation) to determine GPC, and the weight average molecular weight (Mw) was calculated as polystyrene.
Synthesis example 1
To a 1L autoclave equipped with a stirrer, 360g (1.70 mol) of phenyltrichlorosilane and 5.70g (0.0425 mol) of aluminum chloride were added. Then, 271g (1.63 mol) of hexafluoroacetone was added thereto for 5 hours while maintaining the internal temperature at 5 to 15 ℃ after the nitrogen substitution, and stirring was continued for 12 hours. After the completion of the reaction, the reaction solution was transferred to a 3L glass reaction apparatus having a thermometer, a mechanical stirrer, a serpentine return tube and a capacity of being replaced under a dry nitrogen atmosphere, and the flask contents were heated to 60℃while stirring. Thereafter, while bubbling nitrogen gas, 376g (8.16 mol) of absolute ethanol was added dropwise over 3 hours using a dropping pump, and the alkoxylation reaction was performed while removing hydrogen chloride. Thereafter, excess ethanol was distilled off using a decompression pump. The resultant mixture was subjected to a water washing operation, whereby 611g (GC area%: 1-3 substituent (meta) =86.7%, 1-4 substituent (para) =3.7%, triethoxyphenylsilane=5.3%, and others: 4.3%) of a mixture containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene was obtained. In the obtained mixture, 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chlorodiethoxysilylbenzene (i.e., less than 10 mass ppm as the lower limit of detection) as a chlorosilane compound represented by formula (2) was not detected in GC, and the chloride ion concentration was 1.4ppm.
Example 1
200g of the mixture containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene obtained in Synthesis example 1, single distillation was carried out at a distillation temperature of 125 to 135℃and a reduced pressure of 1.2kPa to give 190g of a catalyst containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: GC purity 88.2%), 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para: GC purity of 3.9%), 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chlorodiethoxysilylbenzene (20 mass ppm was detected in GC). The obtained fraction was subjected to precise distillation at a distillation temperature of 143 to 146℃and a reduced pressure of 0.2kPa using a distillation apparatus having a distillation stage number of 15, whereby 144g of 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: GC purity 99.4%), 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para: GC purity 0.5%) (yield 72%). 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chlorodiethoxysilylbenzene (i.e., less than 10 mass ppm as the lower limit of detection) as a chlorosilane compound represented by formula (2) was not detected in GC, and the chloride ion concentration was 0.3ppm.
Comparative example 1
200g of the mixture containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene obtained in Synthesis example 1 was subjected to a distillation apparatus having a distillation stage number of 15, the fine distillation was carried out at a distillation temperature of 143 to 146℃and a reduced pressure of 0.1kPa, whereby 146g of 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: GC purity 99.2%), 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para: GC purity 0.4%) (yield 73%). 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chlorodiethoxysilylbenzene, which is a chlorosilane compound represented by formula (2), was detected in GC at 1700 mass ppm and at a chloride ion concentration of 140ppm.
When example 1 was compared with comparative example 1, the GC purity and yield of 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta) represented by formula (1) were approximately equivalent (the GC purity of example 1 was 99.4% and the yield was 72%, and the GC purity of comparative example 1 was 99.2% and the yield was 73%), but with respect to the chlorosilane compound and chloride ion concentration represented by formula (2), example 1 gave significantly lower values than comparative example 1.
It is also clear from this that the starting materials obtained in synthesis example 1 were used in the same manner as in example 1 and comparative example 1: example 1 falling within the scope of the present application is more effective as a method for reducing chlorine-containing impurities.
Synthesis example 2
To a 1L autoclave equipped with a stirrer, 325g (1.70 mol) of dichloro (methyl) phenylsilane and 5.70g (0.0425 mol) of aluminum chloride were added. Then, 271g (1.63 mol) of hexafluoroacetone was added thereto for 5 hours while maintaining the internal temperature at 5 to 15 ℃ after the nitrogen substitution, and stirring was continued for 12 hours. After the completion of the reaction, the reaction solution was transferred to a 3L glass reaction apparatus having a thermometer, a mechanical stirrer, a serpentine return tube and a capacity of being replaced under a dry nitrogen atmosphere, and the flask contents were heated to 60℃while stirring. Thereafter, while bubbling nitrogen gas, 251g (5.44 mol) of absolute ethanol was added dropwise using a dropping pump over 3 hours, and the alkoxylation reaction was performed while removing hydrogen chloride. Thereafter, excess ethanol was distilled off using a decompression pump. The resultant mixture was subjected to a water washing operation, thereby obtaining 514g (GC area%: 1-3 substituent (meta) =79.9%, 1-4 substituent (para) =6.2%, diethoxy (methyl) phenylsilane=4.4%, and others: 9.5%) of a mixture containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) diethoxy (methyl) silylbenzene. In the obtained mixture, 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chloro (diethoxy) methylsilylbenzene (i.e., less than 10 mass ppm as the lower limit of detection) as a chlorosilane compound represented by the formula (2) was not detected in GC, and the chloride ion concentration was 6.8ppm.
Example 2
200g of the mixture containing 3- (2-hydroxy-1, 3-hexafluoroisopropyl) diethoxy (methyl) silyl benzene obtained in Synthesis example 2 was subjected to single distillation at a distillation temperature of 97 to 107℃and a reduced pressure of 0.5kPa, and a distillation apparatus having a distillation stage number of 15 was used again, the resulting fraction was subjected to precise distillation at a distillation temperature of 103 to 106℃and a reduced pressure of 0.5kPa to obtain 110g of 3- (2-hydroxy-1, 3-hexafluoroisopropyl) diethoxy (methyl) silylbenzene (meta-form: GC purity 99.9%), 4- (2-hydroxy-1, 3-hexafluoroisopropyl) diethoxy (methyl) silylbenzene (para: GC purity 0.1%) (yield 55%). 3- (2-hydroxy-1, 3-hexafluoroisopropyl) chloro (ethoxy) methylsilylbenzene (i.e., less than 10 mass ppm as the lower limit of detection) as a chlorosilane compound represented by formula (2) was not detected in GC, and the chloride ion concentration was 9.3ppm.
Example 3
3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: GC purity of 99.4%), a mixture (chloride ion concentration=2.5 ppm) of 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para-isomer: GC purity of 0.5%) 30g (74 mmol), water, 4.2g (233 mmol), acetic acid, 0.2g (3 mmol) and stirring at 75℃for 24 hours, thereby obtaining a polysiloxane polymer compound containing an HFIP group. As a result of measurement of GPC, mw=1970, and chloride ion concentration was 3.9ppm.
Example 4
In order to obtain the polysiloxane polymer compound, a reaction solvent may be used for the purpose of performing the polycondensation reaction as described above. To 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: 28g of a mixture (chloride ion concentration=2.5 ppm) of 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para-isomer: GC purity: 0.5%) was added with 12g of ethanol as a reaction solvent to prepare a 70 mass% ethanol solution (chloride ion concentration: 1.7 ppm), and it was confirmed that a polysiloxane polymer was obtained by the same procedure as in example 3. As a result of measurement of GPC after the reaction, mw=1850, chloride ion concentration was 2.7ppm.
Example 5
Similarly, 3- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (meta form: 28g of a mixture (chloride ion concentration=2.5 ppm) of 4- (2-hydroxy-1, 3-hexafluoroisopropyl) triethoxysilylbenzene (para-isomer: GC purity: 0.5%) was added with 12g of toluene as a reaction solvent to prepare a 70 mass% toluene solution (chloride ion concentration: 1.0 ppm), and it was confirmed that a polysiloxane polymer was obtained by the same procedure as in example 3. As a result of measurement of GPC after the reaction, mw=1620, and chloride ion concentration were 1.6ppm.
Claims (13)
1. A silicon compound comprising a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2), wherein the content of the halosilane compound represented by the formula (2) is more than 0 mass ppm and not more than 1000 mass ppm,
in the formula (1)，R 1 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2 Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, a+b+c=4,
in the formula (2), R 1a Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2a Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is an integer of 1 to 3, bb is an integer of 0 to 2, cc is an integer of 0 to 2, dd is an integer of 1 to 3, aa+bb+cc+dd=4.
2. The silicon compound according to claim 1, wherein the upper limit of the content of the halosilane compound is 100 mass ppm or less.
3. The silicon compound according to claim 1 or 2, wherein the group represented by the following chemical formula in the formula (1) and the formula (2) is 1 or more selected from the group consisting of the groups represented by the following formulas (2A) to (2D),
the line segment intersecting the wavy line represents a connecting key,
the segments intersecting the wavy lines represent the connection keys, respectively.
4. The silicon compound according to any one of claims 1 to 3, wherein aa is 1.
5. The silicon compound according to any one of claims 1 to 4, wherein dd is 1.
6. The silicon compound according to any one of claims 1 to 5, wherein the R 2a Is methyl or ethyl.
7. The silicon compound according to any one of claims 1 to 3, wherein the halosilane compound is aa is 1, bb is 0, dd is 1 or 2, cc is 1 or 2, R 2a A compound represented by the formula (2) which is methyl or ethyl.
8. The silicon compound according to claim 3, wherein when the content of the silicon compound (meta) represented by the formula (1) composed of the group represented by the formula (2A) is Xa mol and the content of the silicon compound (para) represented by the formula (1) composed of the group represented by the formula (2B) is Ya mol,
satisfies the relationship Ya/(ya+Xa) < 0.10.
9. The silicon compound according to any one of claims 1 to 8, wherein a halide ion concentration is 100 mass ppm or less.
10. A method for producing a silicon compound, characterized by comprising the steps of:
a first distillation step of distilling a mixture containing at least a silicon compound represented by the following formula (1) and a halosilane compound represented by the following formula (2) to recover a first mixture containing the silicon compound represented by the formula (1) and a low boiling point component having a boiling point lower than that of the silicon compound represented by the formula (1); and
a second distillation step of distilling the first mixture obtained in the first step to recover the silicon compound represented by the formula (1),
the content of the halosilane compound represented by the formula (2) is 1000 mass ppm or less,
in the formula (1), R 1 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2 Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 5, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, a+b+c=4,
in the formula (2), R 1a Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a fluoroalkyl group having 1 to 10 carbon atoms, R 2a Each independently is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a chlorine atom, a bromine atom or an iodine atom, n is an integer of 1 to 5, aa is an integer of 1 to 3, bb is an integer of 0 to 2, cc is an integer of 0 to 2, dd is an integer of 1 to 3, aa+bb+cc+dd=4.
11. A polysiloxane obtained by polymerizing the silicon compound according to any one of claims 1 to 9.
12. The polysiloxane according to claim 11, wherein the halide ion concentration is 1000 mass ppm or less.
13. A method for producing a polysiloxane, wherein the silicon compound according to any one of claims 1 to 9 is polymerized.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021-017792 | 2021-02-05 | ||
| JP2021017792 | 2021-02-05 | ||
| PCT/JP2022/003177 WO2022168735A1 (en) | 2021-02-05 | 2022-01-27 | Silicon compound containing hexafluoroisopropanol group, method for producing silicon compound, polysiloxane, and method for producing polysiloxane |
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| CN116802186A true CN116802186A (en) | 2023-09-22 |
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| KR (1) | KR20230142534A (en) |
| CN (1) | CN116802186A (en) |
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| JP4019247B2 (en) | 2000-06-02 | 2007-12-12 | 信越化学工業株式会社 | Polymer compound, resist material, and pattern forming method |
| JP4172291B2 (en) | 2003-02-27 | 2008-10-29 | 東亞合成株式会社 | Method for producing organosilicon compound |
| JP6281288B2 (en) * | 2013-01-21 | 2018-02-21 | セントラル硝子株式会社 | Silicon compound containing hexafluoroisopropanol group, method for producing the same, and polymer compound obtained by polymerization thereof |
| JP6323225B2 (en) * | 2013-11-01 | 2018-05-16 | セントラル硝子株式会社 | Positive photosensitive resin composition, film production method using the same, and electronic component |
| US20210061827A1 (en) * | 2018-02-28 | 2021-03-04 | Central Glass Company, Limited | Silicon Compound Containing Hexafluoroisopropanol Group, and Method for Producing Same |
| CN113166548A (en) * | 2018-10-30 | 2021-07-23 | 中央硝子株式会社 | Resin composition, photosensitive resin composition, cured film, method for producing cured film, patterned cured film, and method for producing patterned cured film |
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| JPWO2022168735A1 (en) | 2022-08-11 |
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