TW200916507A - New silicone compound, and raw material thereof and method for producing the silicone compound - Google Patents
New silicone compound, and raw material thereof and method for producing the silicone compound Download PDFInfo
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- TW200916507A TW200916507A TW097109529A TW97109529A TW200916507A TW 200916507 A TW200916507 A TW 200916507A TW 097109529 A TW097109529 A TW 097109529A TW 97109529 A TW97109529 A TW 97109529A TW 200916507 A TW200916507 A TW 200916507A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002994 raw material Substances 0.000 title description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- -1 sesquiterpene compound Chemical class 0.000 claims description 74
- 229930004725 sesquiterpene Natural products 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 10
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012454 non-polar solvent Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 42
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 23
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 239000012044 organic layer Substances 0.000 description 18
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- HRWIFYPHGUZPKB-UHFFFAOYSA-N 1,1,2-trimethoxydodec-1-ene Chemical compound COC(=C(OC)OC)CCCCCCCCCC HRWIFYPHGUZPKB-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229920002675 Polyoxyl Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920002098 polyfluorene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
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- 238000010992 reflux Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZCRHCHOHWXDDGH-UHFFFAOYSA-N CCCCCCCCCCC(OC)(OC)OC Chemical compound CCCCCCCCCCC(OC)(OC)OC ZCRHCHOHWXDDGH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CWZQYRJRRHYJOI-UHFFFAOYSA-N 1,1,1-trimethoxydecane Chemical compound CCCCCCCCCC(OC)(OC)OC CWZQYRJRRHYJOI-UHFFFAOYSA-N 0.000 description 1
- KWISWUFGPUHDRY-UHFFFAOYSA-N 1-Chloro-2-methylpropene Chemical compound CC(C)=CCl KWISWUFGPUHDRY-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KFTIUWSUHUGYDT-UHFFFAOYSA-N 10-chloro-9,10-dimethylicosane Chemical compound CC(C(CCCCCCCCCC)(C)Cl)CCCCCCCC KFTIUWSUHUGYDT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- CJEAKKMNOSJYMY-UHFFFAOYSA-N 2-chloro-2-methylundecane Chemical compound CCCCCCCCCC(C)(C)Cl CJEAKKMNOSJYMY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KTVOSHSUBQTBDU-UHFFFAOYSA-N 3-chlorododecane Chemical compound CCCCCCCCCC(Cl)CC KTVOSHSUBQTBDU-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- IOGOPQACKPVLRU-UHFFFAOYSA-N CC(=CC(CCCCCCCCC)Cl)C Chemical compound CC(=CC(CCCCCCCCC)Cl)C IOGOPQACKPVLRU-UHFFFAOYSA-N 0.000 description 1
- MCCBWOQJCTZMIY-UHFFFAOYSA-N CC(C(CC)(C)Cl)CCCCCCCC Chemical compound CC(C(CC)(C)Cl)CCCCCCCC MCCBWOQJCTZMIY-UHFFFAOYSA-N 0.000 description 1
- QPUYRBYFXRATSK-UHFFFAOYSA-N CC(C(Cl)(C(C)(C)C)C)CCCCCCCC Chemical compound CC(C(Cl)(C(C)(C)C)C)CCCCCCCC QPUYRBYFXRATSK-UHFFFAOYSA-N 0.000 description 1
- ULVYVDQSYNHPJX-UHFFFAOYSA-N CC(C(Cl)(C1=CC=CC=C1)C)CCCCCCCC Chemical compound CC(C(Cl)(C1=CC=CC=C1)C)CCCCCCCC ULVYVDQSYNHPJX-UHFFFAOYSA-N 0.000 description 1
- SGQLZDVACHGXHQ-UHFFFAOYSA-N CC(C(Cl)(C1CCCCC1)C)CCCCCCCC Chemical compound CC(C(Cl)(C1CCCCC1)C)CCCCCCCC SGQLZDVACHGXHQ-UHFFFAOYSA-N 0.000 description 1
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- SPGRUQJKCMJQAZ-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(C(C)C)Cl Chemical compound CCCCCCCCC(C)C(C)(C(C)C)Cl SPGRUQJKCMJQAZ-UHFFFAOYSA-N 0.000 description 1
- MQZBWGWETRPDNJ-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(C1CCCC1)Cl Chemical compound CCCCCCCCC(C)C(C)(C1CCCC1)Cl MQZBWGWETRPDNJ-UHFFFAOYSA-N 0.000 description 1
- WQQUHDYGEFXTNA-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(CCCC)Cl Chemical compound CCCCCCCCC(C)C(C)(CCCC)Cl WQQUHDYGEFXTNA-UHFFFAOYSA-N 0.000 description 1
- UXOLIGUKXFUBMI-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(CCCCC)Cl Chemical compound CCCCCCCCC(C)C(C)(CCCCC)Cl UXOLIGUKXFUBMI-UHFFFAOYSA-N 0.000 description 1
- FELXMOPVYCANND-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(CCCCCC)Cl Chemical compound CCCCCCCCC(C)C(C)(CCCCCC)Cl FELXMOPVYCANND-UHFFFAOYSA-N 0.000 description 1
- FSLCODQJATVYDU-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(CCCCCCC)Cl Chemical compound CCCCCCCCC(C)C(C)(CCCCCCC)Cl FSLCODQJATVYDU-UHFFFAOYSA-N 0.000 description 1
- OCLLYFSDSGMSDX-UHFFFAOYSA-N CCCCCCCCC(C)C(C)(CCCCCCCC)Cl Chemical compound CCCCCCCCC(C)C(C)(CCCCCCCC)Cl OCLLYFSDSGMSDX-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ANUMBTODEQDFNN-UHFFFAOYSA-N trichloromethylcyclohexane Chemical compound ClC(Cl)(Cl)C1CCCCC1 ANUMBTODEQDFNN-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
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- 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
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- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
Description
200916507 九、發明說明 【發明所屬之技術領域】 本發明係關於新穎之硬化性聚矽氧化合物及其原料、 與硬化性聚矽氧化合物之製造方法’具體而言，係關於適 合利用作爲具有多數硬化性官能基之電子材料、光學材料 、電子光學材料等’且，亦可利用作爲對高分子材料賦予 難燃性、耐熱性、電性絕緣性、表面特性、硬度、力學強 度、耐藥品性、透明性等之添加劑之新穎硬化性聚矽氧化 合物及其原料、與取得此聚砂氧化合物之製造方法。 【先前技術】 關於一般式〔RSi〇3/2〕n所示之矽倍半噚烷，直到目 前已進行許多硏究。於Chem· Rev_ 1995，95，1409中記載 B aney等人關於矽倍半噚烷的總說，除了梯型構造、完全 縮合型構造及不完全縮合構造的矽倍半噚烷以外’報導未 示出一定構造之具有非晶質構造的矽倍半噚院等。又’若 根據 Organometallics，1991，10，2556 ’ 將 戊基 一氣砂院 或環己基三氯矽烷於丙酮中水解’則可取得不完全縮合構 造的矽倍半噚烷。此處，所謂完全縮合型構造之砂倍半鳴 烷爲意指由多數的環狀構造所形成’且形成封閉空間者（ 所謂籠型砍氧院樹脂）’所謂不完全縮合構13之砂丨π + & 烷，係意指無法塞入至少一個以上完全縮合構造，無法封 閉空間者。 關於具有此類完全縮合型或不完全縮合型構造之砂倍 -6 - 200916507 半Df烷，例如可利用作爲熱可塑性樹脂之改質劑、高分子 材料之難燃劑、提高耐熱性、耐候性、電性絕緣性、表面 特性、硬度、力學強度、耐藥品性等之添加劑。最近，爲 了使用作爲聚合物的結構單元，乃檢討導入各種官能基以 賦予與其他樹脂之相溶性及聚合性的方法。一般而言，已 熟知終端具有矽烷醇基（S i - OH基）的矽倍半噚烷，利用 矽烷醇之反應性進行衍生出新的矽倍半噚烷。又，已提案 令具有三官能水解性基之矽烷化合物於一價鹼金屬氫氧化 物存在下，於有機溶劑中水解，合成具有Si-ONa作爲反 應性活性基的不完全縮合型構造矽倍半噚烷，並且以具有 依據目的之官能基的氯矽烷反應之矽倍半噚烷的衍生物（ 參照專利文獻1及2 )。 但是，一般而言，矽倍半噚烷的衍生物與其他樹脂的 相溶性差，無法均勻混合，又，於使用至塗膜時發生白化 ’並且由塗膜中滲出令添加量具有限制等之問題。更且， 先前的矽倍半鸣烷衍生物使用作爲電子材料和光學材料時 ’爲了利用作爲聚合物的結構單位，期望衍生物本身具有 硬化性’但就本發明者等所知，充分具備此類特性者並無 報告例。 〔專利文獻1〕 W02002/094839公報 〔專利文獻2〕 W02003/024870公報 【發明內容】 〔發明所欲解決之課題〕 -7- 200916507 於是，本發明者等人爲了解決先前矽倍半鸣烷衍生物 關於與其他樹脂之相溶性和硬化性等所具有的問題，結果 成功合成分子量分佈被控制，且具有多數指定之硬化性官 能基之含羥基的矽倍半噚烷，且以此含羥基的矽倍半噚烷 作爲原料所得的硬化性聚矽氧化合物，發現可解決此等全 部問題’並且完成本發明。 因此，本發明之目的爲在於提供與其他樹脂之相溶性 優良，並且硬化性亦優良之新穎的硬化性聚矽氧化合物。 又，本發明之其他目的爲在於提供可作爲取得上述硬 化性聚矽氧化合物之原料之含羥基的矽倍半鸣烷化合物。 更且，本發明之其他目的爲在於提供可短時間’且低 費用取得上述硬化性聚矽氧化合物之硬化性聚砂氧化合物 的製造方法。 (解決課題之手段） 即，本發明爲下述一般式（1 )所示之硬化性聚较氧 化合物。 (RSi〇3/2) n ( R1 ( CH3) 2Si〇l/2] m (1) 〔但，R及…爲氫原子、碳數6~10之芳基含有基、碳數 1〜10之直鏈狀或分支狀之烷基、碳數4~10之環烷基、碳 數2~3之烯基、或由下述式（2)〜（4) 200916507200916507 IX. INSTRUCTIONS OF THE INVENTION [Technical Fields of the Invention] The present invention relates to a novel curable polydecene oxide compound and a raw material thereof, and a method for producing a curable polydecane oxide compound. An electronic material, an optical material, an electro-optical material, or the like of a curable functional group can also be used as a polymer material to impart flame retardancy, heat resistance, electrical insulating properties, surface properties, hardness, mechanical strength, and chemical resistance. A novel curable polyxanthene compound, an additive such as transparency, a raw material thereof, and a method for producing the polysiloxane compound. [Prior Art] With regard to the sesquiterpene oxide shown by the general formula [RSi〇3/2]n, many studies have been conducted until now. In the case of Chemet Rev. 1995, 95, 1409, the general description of a sesquioxanes by Baney et al., except for the ladder structure, the fully condensed structure and the incompletely condensed structure of sesquiterpenes, is not reported. A 构造 噚 噚 噚 等 等 等 等 等 。 。 。 。 。 。 Further, if it is hydrolyzed by a group of Organometallics, 1991, 10, 2556', or a cyclohexyltrichloromethane in acetone, an incompletely condensed structure of sesquiterpene can be obtained. Here, the so-called fully condensed structure of sesquiterpene is a sand 丨 which is formed by a plurality of annular structures and forms a closed space (so-called cage-type chopper resin). π + & alkane means a substance that cannot be inserted into at least one complete condensed structure and cannot be closed. Regarding the sand -6 - 200916507 semi-Df alkane having such a completely condensed or incompletely condensed structure, for example, a modifier for a thermoplastic resin, a flame retardant for a polymer material, heat resistance, weather resistance, and the like can be used. Additives such as electrical insulation, surface properties, hardness, mechanical strength, and chemical resistance. Recently, in order to use a structural unit as a polymer, a method of introducing various functional groups to impart compatibility with other resins and polymerizability has been examined. In general, it is well known that the terminal has a decyl alcohol group (S i - OH group), and a novel sesquiterpene is derived by utilizing the reactivity of a stanol. Further, it has been proposed to hydrolyze a decane compound having a trifunctional hydrolyzable group in an organic solvent in the presence of a monovalent alkali metal hydroxide to synthesize an incompletely condensed structure having Si-ONa as a reactive active group. Derivative of decane and a sesquiterpene which is reacted with chlorodecane having a functional group according to purpose (refer to Patent Documents 1 and 2). However, in general, a derivative of sesquiterpene is inferior in compatibility with other resins, and it is not uniformly mixed, and whitening occurs when it is applied to a coating film, and bleed out from the coating film limits the amount of addition. problem. In addition, when the conventional sesquiterpene derivative is used as an electronic material and an optical material, it is desirable that the derivative itself has curability in order to utilize a structural unit as a polymer, but it is well known to the inventors of the present invention. There are no report cases for class features. [Patent Document 1] WO02/094839 (Patent Document 2) WO2003/024870A SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] -7- 200916507 Thus, the inventors of the present invention have succeeded in order to solve the previous sesquiterpene-halfane derivative. With regard to the problems associated with compatibility with other resins, and the like, as a result, it was successfully synthesized to have a hydroxyl group-containing sesquiterpene having a majority of the specified curable functional groups, and having a hydroxyl group-containing The curable polyfluorene oxide obtained by using sesquiterpene as a raw material has been found to solve all of the problems' and the present invention has been completed. Accordingly, an object of the present invention is to provide a novel curable polyxanthene compound which is excellent in compatibility with other resins and which is excellent in hardenability. Further, another object of the present invention is to provide a hydroxyl group-containing oxime hemane compound which can be used as a raw material for obtaining the above-mentioned hard polyoxygen compound. Furthermore, another object of the present invention is to provide a method for producing a curable polyoxyn compound which can obtain the above-mentioned curable polyphosphonium compound in a short time and at a low cost. (Means for Solving the Problem) The present invention is a curable polyoxo compound represented by the following general formula (1). (RSi〇3/2) n ( R1 ( CH3) 2Si〇l/2] m (1) [However, R and ... are a hydrogen atom, an aryl group having a carbon number of 6 to 10, and a carbon number of 1 to 10; a linear or branched alkyl group, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a formula (2) to (4) 200916507
(但，式中之1爲1〜3之整數，R2爲表示氫原子或甲基） 中選出，R及R1中，各取代基可相互爲相同或相異者亦 可，但至少於一般式（1 )所示之1分子中，具有2個以 上碳數2〜3之烯基、及式（2 )〜（4 )所組成群中選出任 一者的硬化性官能基，且R中至少一者爲上述硬化性官能 基。又，η爲表示6〜20之整數，m爲1〜6之整數，n/m爲 1〜10之範圍。更且，Mw = 500〜5000，Mw/Mn=1.0〜1.5之範 圍〕 又，本發明爲下述一般式（5 )所示之含羥基的矽倍 半噚烷化合物 [RSi〇3/2 ] n C H01/2 ] m ( 5 ) 〔但，R爲氫原子、碳數6〜10之芳基含有基、碳數1〜10 之直鍵狀或分支狀之院基、碳數4〜10之環完基、碳數 2〜3之烯基、或由下述式（2)〜（4) 200916507 〔化2〕 R2(However, in the formula, 1 is an integer of 1 to 3, R2 is a hydrogen atom or a methyl group), and in R and R1, each substituent may be the same or different from each other, but at least in the general formula. (1) one of the molecules shown, having two or more alkenyl groups having 2 to 3 carbon atoms and a curable functional group selected from the group consisting of formulas (2) to (4), and at least R One is the above-mentioned curable functional group. Further, η is an integer representing 6 to 20, m is an integer of 1 to 6, and n/m is in the range of 1 to 10. Further, Mw = 500 to 5000, and Mw/Mn = a range of 1.0 to 1.5. Further, the present invention is a hydroxyl group-containing sesquiterpene compound [RSi〇3/2] represented by the following general formula (5). n C H01/2 ] m ( 5 ) [However, R is a hydrogen atom, an aryl group having a carbon number of 6 to 10, a straight bond or a branch having a carbon number of 1 to 10, and a carbon number of 4 to 10 Ring-based, alkenyl group having 2 to 3 carbon atoms, or by the following formula (2) to (4) 200916507 [Chemical 2] R2
(但，式中之1爲1〜3之整數，R2爲表示氫原子或甲基） 中選出’ R可相互爲相同或相異者亦可，但一般式（5) 所示之1分子中之R的至少一者爲碳數2~3之烯基、及由 式（2 )〜（4 )所組成群中選出任一者之硬化性官能基。 又，η爲表示6〜20之整數，m爲1〜6之整數，n/m爲 1 〜10 之範圍。更且，Mw = 500〜5000，Mw/Mn=1.0~1.5 之範 圍〕 更且，本發明爲上述之硬化性聚矽氧化合物之製造方 法，其爲令下述一般式（6)(However, in the formula, 1 is an integer of 1 to 3, R2 is a hydrogen atom or a methyl group), and 'R may be the same or different from each other, but one molecule represented by the general formula (5) At least one of R is an alkenyl group having 2 to 3 carbon atoms and a curable functional group selected from the group consisting of formulas (2) to (4). Further, η is an integer representing 6 to 20, m is an integer of 1 to 6, and n/m is a range of 1 to 10. Further, Mw = 500 to 5,000, and Mw/Mn = a range of 1.0 to 1.5. Further, the present invention is a method for producing the above-mentioned curable polyxanthene compound, which is to give the following general formula (6)
RSiX 〔但，R爲氫原子、碳數6〜10之芳基含有基、碳數1〜1〇 之直鏈狀或分支狀之院基、碳數4〜10之環院基、碳數 2〜3之烯基、或由下述式（2)〜（4) -10- 200916507 〔化3〕RSiX [However, R is a hydrogen atom, an aryl group having a carbon number of 6 to 10, a linear or branched carbon group having a carbon number of 1 to 1 Å, a ring group having a carbon number of 4 to 10, and a carbon number of 2 Alkenyl group of ~3, or by the following formula (2)~(4)-10-200916507 [Chemical 3]
(但’式中之！爲i〜3之整數’ R2爲表示氫原子或甲基） 中選出’ X爲表示水解性基〕所示之1種以上的矽化合物 ’且’至少1種之矽化合物的R爲碳數2~3之烯基，及由 上述式（2 )〜（4 )所組成群中選出任一者之硬化性官能 基之1種以上之矽化合物，於RsiX3 :鹼性觸媒〇莫 耳：1莫耳範圍之鹼性觸媒存在下，於極性溶劑及非極性 溶劑之混合溶劑中水解，生成下述一般式（5 ) 〔RSi〇3/2〕n〔 HO 丨/2〕m ( 5 ) (但’ R舄同上述。η爲表示6〜2 0之整數、m爲1〜6之整 ’ n/m爲1〜1 〇之範圍）所示之含羥基的矽倍半噚烷化 € % 胃單氯矽烷反應爲其特徵之硬化性聚矽氧化合物 的製造方法。 本1S月之硬化性聚矽氧化合物的製造方法中，首先， β ± 5® - @式（6 )所示之矽化合物於指定溶劑及鹼性觸 媒存在下水解’取得上述一般式（5 )所示之含羥基的矽 ί咅# Df @ ft合物’令此含羥基之矽倍半噚烷化合物與單氯 -11 - 200916507 砂院類反應，取得上述一般式（1)之硬化性聚砍氧化合 物。 此處，關於一般式（6)及後述一般式（7)中之矽化 合物的各個R ’若列舉氫原子以外之取代基的具體例’則 碳數2〜3之烯基可列舉乙烯基、烯丙基等^ 1〜10之直鏈 狀或分支狀之烷基可列舉甲基、乙基、丙基、1-甲基乙基 、丁基、2 -甲基丙基、1，1-二甲基乙基、戊基、己基、 1，1，2-三甲基丙基、庚基、辛基、2,2,4-三甲基戊基、壬基 、癸基等。碳數4〜10之環烷基可列舉環戊基、環己基。 碳數6〜10之芳基含有基可列舉苯基、4_甲基苯基、4_甲 氧基苯基、6·乙烯基苯基、4-(1-甲基乙烯基）苯基、4· (3 -丁烯基）苯基、萘基等。上述式（2)之例可列舉甲 烯丙烯氧甲基、3·甲基丙烯氧丙基、3 -丙烯氧丙基等。上 述式（3 )之例可列舉3 -縮水甘油氧丙基等。上述式（4 ) 之例可列舉2- ( 3,4-環氧環己基）乙酯等。另外’此些官 能基爲一般之官能基，並無限定。一般式（1 )之硬化性 聚矽氧化合物爲具有至少二個以上之硬化性官能基。即’ 一般式（1 )之硬化性聚矽氧化合物若例如由16個@所構 成，則至少全部R之1 2.5莫耳％以上爲如上述硬化性官 能基般調整一般式（6 )及（7 )之矽化合物的添加量。 又，一般式（6 )中之X爲水解基’其例可列舉氯原 子、或碳數1〜4之烷氧基（烷氧基）。其中’院氧基可列 舉甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異 丁氧基、第三丁氧基、其中亦以反應性高的甲氧基爲佳。 -12- 200916507 關於一般式（6 )所示之矽化合物，至少一種矽化合 物的R爲使用碳數2〜3之烯基、及由下述式（2)〜（4) 所組成群中選出任一種硬化性官能基之一種以上的矽化合 物0(In the formula, 'an integer of i to 3', R2 is a hydrogen atom or a methyl group, and one or more kinds of anthracene compound 'expressed as a hydrolyzable group', and 'at least one type' R of the compound is an alkenyl group having 2 to 3 carbon atoms, and one or more kinds of sulfonium compounds selected from the group consisting of the above formulas (2) to (4), and RsiX3: basic Catalyst: In the presence of a basic catalyst in the range of 1 molar, it is hydrolyzed in a mixed solvent of a polar solvent and a non-polar solvent to form the following general formula (5) [RSi〇3/2]n[ HO 丨/2]m ( 5 ) (but 'R 舄 is the same as above. η is an integer representing 6 to 20, m is a total of 1 to 6 'n/m is a range of 1 to 1 〇). A method for producing a sclerosing polyxanthene characterized by a reaction of sesquiterpene alkylation. In the method for producing a sclerosing polyoxo compound of the present invention, first, the hydrazine compound represented by β ± 5® - @ (6) is hydrolyzed in the presence of a specified solvent and an alkaline catalyst to obtain the above general formula (5). The hydroxyl group-containing 矽ί咅# Df @ ft compound is shown to react the hydroxy-containing sesquiterpene compound with the monochloro-11 - 200916507 sand chamber to obtain the sclerosing property of the above general formula (1) Polyoxygenated compounds. Here, the specific examples of the substituents other than the hydrogen atom of each R ' of the oxime compound in the general formula (6) and the general formula (7) to be described later may be a vinyl group, and the alkenyl group having 2 to 3 carbon atoms may be a vinyl group. The linear or branched alkyl group of the allyl group and the like may be exemplified by methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1- Dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl, octyl, 2,2,4-trimethylpentyl, decyl, decyl and the like. Examples of the cycloalkyl group having 4 to 10 carbon atoms include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 6-vinylphenyl group, and a 4-(1-methylvinyl)phenyl group. 4 (3-butenyl)phenyl, naphthyl and the like. Examples of the above formula (2) include a methacryloxymethyl group, a 3-methacryloxypropyl group, a 3-propyleneoxypropyl group and the like. Examples of the above formula (3) include 3-glycidoxypropyl group and the like. Examples of the above formula (4) include 2-(3,4-epoxycyclohexyl)ethyl ester. In addition, these functional groups are general functional groups and are not limited. The curable polyxanthene compound of the general formula (1) has at least two or more hardening functional groups. In other words, if the curable polyoxyxene compound of the general formula (1) is composed of, for example, 16 @, at least 2.5 mol% or more of all R is adjusted as in the above-mentioned curable functional group, and the general formula (6) and 7) The amount of the compound added. Further, in the general formula (6), X is a hydrolyzable group, and examples thereof include a chlorine atom or an alkoxy group (alkoxy group) having 1 to 4 carbon atoms. The 'oxyl group' can be exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy, among which methoxy is also highly reactive. The base is good. -12- 200916507 With respect to the anthracene compound represented by the general formula (6), R of at least one anthracene compound is selected from the group consisting of an alkenyl group having 2 to 3 carbon atoms and a group consisting of the following formulas (2) to (4); Any one or more bismuth compounds of a hardening functional group
(4) 又，關於一般式（6 )所示之砂化合物的水解反應所 使用之鹼性觸媒的使用量，係令矽化合物（R S i X 3 )與鹼 性觸媒的比例爲RSiX3 :鹼性觸媒=4〜10莫耳：1莫耳。 鹼性觸媒之使用量若爲此範圍，則可防止高分子量之矽倍 半_烷化合物的生成，並且取得如下說明之不完全縮合型 之含有羥基的矽倍半鸣烷化合物。鹼性觸媒之使用量若少 於上述範圍，則縮合反應加速並且成爲膠化的原因，相反 地，使用量若變多，則抑制縮合反應，且未反應的矽烷醇 基依舊殘存許多，令反應未完成。 關於將一般式（6 )所不之砂化合物水解時所用的鹼 性觸媒，可列舉例如，氫氧化四甲基銨、氫氧化四乙基銨 、氫氧化四丁基錢、氫氧化节基三甲基錢、氣氧化千基三 乙基銨等之氫氧化銨鹽。其中，氫氧化四甲基銨因觸媒活 -13- 200916507 性高故較佳使用。另外，鹼性觸媒通常使用水溶液型式。 又，關於水解時所用的有機溶劑，由控制反應速度之 觀點而言，使用極性溶劑與非極性溶劑之二相系進行爲佳 。其中，關於極性溶劑若示出具體例，則可列舉甲酚、乙 醇、2-丙醇等之醇類。關於非極性溶劑若示出具體例，則 可列舉甲苯、二甲苯、苯等。其中亦以2_丙醇與甲苯爲佳 。關於極性溶劑與非極性溶劑之體積比，極性溶劑/非極 性溶劑=1/5〜5/1爲佳，且以1/2爲更佳。 關於水解反應之反應條件，反應溫度爲0〜60°c爲佳， 且以20〜40°C爲更佳。反應溫度若低於0°C，則反應速度 變慢且水解基以未反應之狀態殘存令反應時間變多之結果 ，另一方面，若高於60°C則反應速度過快，進行複雜的縮 合反應，結果促進水解產物的高分子量化。又，反應時間 爲2小時以上爲佳。若反應時間未滿2小時，則水解反應 無法充分進行’且水解性基以未反應之狀態殘存的狀態。 上述水解反應中必須存在水，但其由鹼性觸媒之水溶 液中亦可供給’未另外加水亦可。水量以足於將水解性基 予以水解的份量以上，較佳爲理論量之1.0〜1 . 5倍量爲佳 。若少於此範圍則水解性基爲以未反應之狀態殘存，若相 反變多，則反應的進行快速，成爲膠化的原因。 水解反應終了後，例如，使用弱酸性水溶液予以中和 ，並將此溶液以食鹽水洗淨，將系中的鹼性觸媒、水分及 其他雜質充分除去後，再以無水硫酸鎂等之乾燥劑予以乾 燥，使用減壓濃縮等之手段則可回收含羥基之矽倍半鸣烷 -14- 200916507 化合物。此時，爲了完全中和加入過量弱酸性水溶液爲佳 ，具體而言，弱酸性水溶液相對於鹼性觸媒的莫耳比爲 1.0〜1.5倍量爲佳，且以1.25倍量爲更佳。即使若殘存少 量的鹼性觸媒，亦令殘存的矽烷醇基反應且高分子量化。 弱酸性水溶液可使用硫酸稀釋水溶液、鹽酸稀釋水溶 '液' 檸檬酸水溶液、醋酸水溶液、氯化銨水溶液、蘋果酸水溶 液、磷酸水溶液、草酸水溶液等。 上述所得之含羥基的矽倍半噚烷化合物可以下列一般 式（5 )表示。 [R S ΐ Ο 3 /2 ] η [ Η Ο 1 /2 ] m ( 5 ) 〔但，R爲氫原子、碳數6〜ίο之芳基含有基、碳數1〜10 之直鏈狀或分支狀之烷基、碳數4〜10之環烷基、碳數 2~3之烯基、或由下述式（2) ~(4)(4) The amount of the alkaline catalyst used in the hydrolysis reaction of the sand compound represented by the general formula (6) is such that the ratio of the ruthenium compound (RS i X 3 ) to the basic catalyst is RSiX3: Alkaline catalyst = 4 to 10 moles: 1 mole. When the amount of the basic catalyst used is in this range, the formation of a high molecular weight sesulane compound can be prevented, and a hydroxy-containing sesquiazine compound having an incomplete condensation type as described below can be obtained. When the amount of the basic catalyst used is less than the above range, the condensation reaction accelerates and becomes a cause of gelation. Conversely, if the amount used is increased, the condensation reaction is suppressed, and the unreacted stanol group remains a lot. The reaction was not completed. The basic catalyst used for the hydrolysis of the sand compound which is not represented by the general formula (6) may, for example, be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or a hydroxide base. Ammonium hydroxide salt of trimethyl ketone, gas oxidized benzyltriethylammonium or the like. Among them, tetramethylammonium hydroxide is preferably used because of its high activity of 13-200916507. In addition, alkaline catalysts usually use an aqueous solution type. Further, the organic solvent used in the hydrolysis is preferably a two-phase system of a polar solvent and a non-polar solvent from the viewpoint of controlling the reaction rate. Here, examples of the polar solvent include alcohols such as cresol, ethanol, and 2-propanol. Specific examples of the nonpolar solvent include toluene, xylene, benzene, and the like. Among them, 2-propanol and toluene are preferred. Regarding the volume ratio of the polar solvent to the nonpolar solvent, the polar solvent/nonpolar solvent = 1/5 to 5/1 is more preferable, and 1/2 is more preferable. With respect to the reaction conditions of the hydrolysis reaction, the reaction temperature is preferably from 0 to 60 ° C, more preferably from 20 to 40 ° C. When the reaction temperature is lower than 0 ° C, the reaction rate becomes slow, and the hydrolysis group remains in an unreacted state to increase the reaction time. On the other hand, when the temperature is higher than 60 ° C, the reaction rate is too fast, and the reaction is complicated. The condensation reaction results in a high molecular weight of the hydrolyzed product. Further, the reaction time is preferably 2 hours or longer. When the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently, and the hydrolyzable group remains in an unreacted state. Water must be present in the above hydrolysis reaction, but it may be supplied from an aqueous solution of an alkaline catalyst. The amount of water is more than the amount of the hydrolyzable group to be hydrolyzed, preferably from 1.0 to 1. The amount of the theoretical amount is preferably 5. If it is less than this range, the hydrolyzable group remains in an unreacted state, and if it is relatively large, the reaction progresses rapidly and becomes a cause of gelation. After the completion of the hydrolysis reaction, for example, it is neutralized with a weakly acidic aqueous solution, and the solution is washed with saline, and the alkaline catalyst, water, and other impurities in the system are sufficiently removed, and then dried with anhydrous magnesium sulfate or the like. The agent is dried, and the hydroxy-containing sesquiterpene-14-200916507 compound can be recovered by means of concentration under reduced pressure or the like. In this case, it is preferred to completely neutralize the excessively weakly acidic aqueous solution. Specifically, the molar ratio of the weakly acidic aqueous solution to the basic catalyst is preferably 1.0 to 1.5 times, more preferably 1.25 times. Even if a small amount of alkaline catalyst remains, the remaining stanol groups are reacted and polymerized. The weakly acidic aqueous solution may be diluted with an aqueous solution of sulfuric acid, diluted with water, a 'liquid' aqueous solution of citric acid, an aqueous solution of acetic acid, an aqueous solution of ammonium chloride, an aqueous solution of malic acid, an aqueous solution of phosphoric acid, an aqueous solution of oxalic acid or the like. The hydroxyl group-containing sesquiterpene compound obtained above can be represented by the following general formula (5). [RS ΐ Ο 3 /2 ] η [ Η Ο 1 /2 ] m ( 5 ) [However, R is a hydrogen atom, an aryl group having a carbon number of 6 to ί, a linear group or a branch having a carbon number of 1 to 10; An alkyl group, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a formula (2) to (4)
(但，式中之1爲1~3之整數，R2爲表示氫原子或甲基） 中選出，R可相互爲相同或相異者亦可，但—般式（” -15- 200916507 所示之1分子中之R的至少一者爲碳數2〜3之烯基、及由 式（2 ) ~ ( 4 )所組成群中選出任一者之硬化性官能基， 又，η爲表示6〜2 0之整數，m爲1〜6之整數，n / m爲 1~1〇 之範圍。更且 ’ Mw = 500~5000，Mw/Mn=l.0-1.5 之範 圍〕。 一般式（5)所示之含羥基的矽倍半噚烷化合物，由 於認爲於終端具有一部分矽烷醇基且無法形成完全封閉的 空間，故爲不完全縮合型的矽倍半噚烷。 其次，令一般式（5 )所示之含羥基的矽倍半噚烷化 合物以單氯矽烷反應。此時所用之單氯矽烷較佳爲下述一 般式（7 )表示。 6 化 cl R1 H3I H3 cIsi-Ic 但，R]爲碳數6〜10之芳基含有基、碳數〗〜10之直鏈狀或 分支狀之烷基碳數4〜10之環烷基、碳數2〜3之烯基、或 由下述式（2) 、 （3) 、 （4)屮選出 -16- 200916507 〔化7〕(However, 1 in the formula is an integer from 1 to 3, R2 is a hydrogen atom or a methyl group), and R may be the same or different from each other, but the general formula (" -15-200916507 shows At least one of R in one molecule is an alkenyl group having 2 to 3 carbon atoms, and a hardening functional group selected from any one of the groups consisting of formulas (2) to (4), and η is 6 An integer of ~20, m is an integer from 1 to 6, and n / m is in the range of 1 to 1 。. Further, 'Mw = 500 to 5000, the range of Mw/Mn = 1.0-1.5. 5) The hydroxyl group-containing sesquiterpene oxide compound shown is an incompletely condensed sesquiterpene gas because it is considered to have a part of a stanol group at the terminal and cannot form a completely closed space. The hydroxyl group-containing sesquiterpene compound represented by the formula (5) is reacted with monochlorodecane. The monochlorosilane used at this time is preferably represented by the following general formula (7): 6 c1 R3 H3I H3 cIsi-Ic However, R] is an aryl group having a carbon number of 6 to 10, a linear or branched alkyl group having 4 to 10 carbon atoms, and an alkenyl group having 2 to 3 carbon atoms; Or by the following formula (2), ( 3), (4) Selected -16- 200916507 [Chem. 7]
(但’式中之1爲1〜3之整數，R2爲表示氫原子或甲基） 〇 若列舉一般式（7)所示之單氯矽烷，則可例示二甲 基乙烯基氯矽烷、二甲基烯丙基氯矽烷、三甲基氯矽烷、 二甲基乙基氯矽烷、二甲基丙基氯矽烷、二甲基-1-甲基乙 基氯矽烷、二甲基丁基氯矽烷、二甲基-2-甲基丙基氯矽烷 、二甲基-1，1-二甲基乙基氯矽烷、二甲基戊基氯矽烷、二 甲基己基氯矽烷、二甲基-1，1,2 -三甲基丙基氯矽烷、二甲 基庚基氯矽烷、二甲基辛基氯矽烷、二甲基-2,2,4-三甲基 戊基氯矽烷、二甲基壬基氯矽烷、二甲基癸基氯矽烷、二 甲基環戊基氯矽烷、二甲基環己基氯矽烷、二甲基苯基氯 矽烷、二甲基-4 -甲基苯基氯矽烷、二甲基-4 -甲氧苯基氯 矽烷、二甲基_4_乙烯基苯基氯矽烷、二甲基_4- ( 1-甲基 乙烯基）苯基氯矽烷、二甲基_4- ( 3-丁烯基）苯基氯矽烷 、二甲基萘基氯矽烷、二甲基甲基丙烯氧甲基氯矽烷、二 甲基-3-甲基丙烯氧丙基氯矽烷、二甲基-3·丙烯氧丙基氯 矽烷、二甲基-3-縮水甘油氧丙基氯矽烷、二甲基-2-(3,4-環氧環己基）乙基氯矽烷、二甲基- 2-( 3，4-環氧環己基） -17- 200916507 乙基氯矽烷、二甲基氯矽烷等。此處，一般式（1)之硬 化性聚矽氧化合物爲具有至少二個以上之硬化性官能基。 例如，若一般式（1 )之硬化性聚矽氧化合物爲由16個矽 所構成，則至少全部之R及R1之12·5旲耳％以上爲碳數 2〜3之烯基、及由式（2)〜（4)所組成群中選出任一者 之硬化性官能基般調整一般式（6 )及（7 )之矽化合物的 裝入量。即，於一般式（6 )及（7 )之矽化合物中’視需 要若使用各個取代基R及R 1爲不同二種以上的混合物即 可 ° 又，一般式（5 )之含羥基的矽倍半噚烷化合物與單 氯矽烷的反應，較佳於鹼性條件下進行。關於鹼性條件並 無特別限制，可利用公知的反應方法，例如，使用四氫呋 喃作爲有機溶劑，且於鹼之三乙胺存在下令一般式（5) 之含羥基的矽倍半鸣烷化合物與單氯矽烷反應即可，或者 ’使用吡啶兼作爲溶劑和鹼，並且令含羥基之矽倍半_院 化合物與單氯矽烷反應亦可。 關於上述含羥基之矽倍半噚烷化合物與單氯砂院的反 應條件’例如令含經基之砂倍半吗院化合物溶解於 0.1〜2.0M之四氫呋喃，並且相對於羥基使用1當量以上之 三乙胺’或者將兼作爲溶劑和鹼之含羥基的矽倍半曙院， 相對於含羥基之矽倍半鸣烷溶解於0. 1〜2.0M之啦α定的混 合液，於氮等之惰性氣體氛圍氣下，於室溫歷1小時滴下 單氯矽烷’其後，於室溫下進行攪拌2小時以上。此時， 若反應時間短’則有時反應未完成。反應終了後，加入甲 18- 200916507 苯和水，令一般式（1 )之硬化性聚矽氧化合物溶解於甲 苯，並將反應生成之鹽於水層中溶解除去。有機層使用硫 酸鎂等之乾燥劑予以乾燥，所使用之鹼及溶劑經由減壓濃 縮除去，則可取得一般式（1 )之硬化性聚矽氧化合物。 關於單氯矽烷之使用量，例如一般式（7 )所示之單 氯矽烷時，以足於捕捉一般式（5 )所示之含羥基的矽倍 半鸣烷化合物之矽烷醇基之份量以上，較佳爲理論量之 1.0〜1.5倍量爲佳。雖然即使過量加入亦無問題，但在後 處理時，若殘存未反應的單氯矽烷，則生成二矽氧烷故精 製困難。另外，後處理時所產生的二矽氧烷若爲沸點低者 ’則可經由減壓濃縮予以除去。沸點高者爲以理論量進行 反應’若不會殘存未反應單氯矽烷且不會生成二矽氧烷即 可。 其次’經由上述含羥基之矽倍半噚烷化合物與單氯矽 烷的反應，則可取得下述一般式（1 )所示之硬化性聚矽 氧化合物。 [RSi〇3/2 ] n ( R1 ( CH3 ) 2Si01/2 ] m ( 1 ) 〔但，R及R1爲氫原子、碳數6〜10之芳基含有基、碳數 1〜10之直鏈狀或分支狀之烷基、碳數4〜10之環烷基、碳 數2〜3之烯基、或由上述式（2)〜（4)(但，式中之1 爲1〜3之整數，R2爲表示氫原子或甲基）中選出，r及 R 1中’各取代基可相互爲相同或相異者亦可，但至少於一 -19- 200916507 般式（1)所示之1分子中，具有2個以上碳數2-基、及式（2)〜（4)所組成群中選出任一者的硬 能基，且，R中至少一者爲上述硬化性官能基。又 表示6〜2 0之整數，m爲1〜6之整數，n/m爲1〜10 。更且，Mw = 5 00〜5 000，Mw/Mn=l _0〜1 .5 之範圍〕 分子中不含有2個以上之硬化性官能基，則使用作 物之結構單位時，無法經由交聯充分擴展網路，故 〇 一般式（1)所示之聚矽氧化合物爲由一般式（ 示之不完全縮合型的矽倍半噚烷所衍生，故與籠型 爲類似之構造。即’ 一般式（1 )所示之聚砂氧化 保持籠型矽氧烷的特性，且’與其他樹脂的相溶性1 又，一般式（1 )之硬化性聚矽氧化合物，爲 一般式（5 )之含羥基的矽倍半噚烷化合物作爲原 成，故分子量分佈被控制’所得聚矽氧化合物的 500〜5000，較佳爲500~2000’表示分子量分佈之 爲1.0~1·5之範圍內（Mw:重量平均分子量、Μη 均分子量）。 (發明之效果） 若根據本發明’則可在高產率下取得含有二個 化性官能基的硬化性聚砂氧化合物。更且’此硬化 氧化合物爲與聚矽氧系硬化性樹脂和有機硬化性樹 相溶性，可廣泛使用作爲經基化’自由基聚合性樹 j之嫌 化性官 ’ η爲 之範圍 ，若1 爲聚合 爲不佳 :5 )所 矽氧烷 合物爲 憂良。 由上述 料所合 M w爲 M w/Mn :數平 以上硬 性聚矽 脂具有 脂組成 -20- 200916507 物的原料’又，亦可利用作爲用以提高高分子材料之 性、耐熱性、電性絕緣性、表面特性、硬度、力學強 耐藥品性等之添加劑。 又’本發明中之含羥基的矽倍半噚烷化合物爲具 應性高的羥基’故可衍生具有如上述特性之有用的新 化性聚矽氧化合物，且，可利用作爲產率佳之合成手. 【實施方式】 以下’根據實施例及比較例更加詳細說明本發明 ’本發明並非根據此些實施例等限定其範圍。 〔實施例1〕 於具備攪拌機及滴下漏斗的反應容器中，加入作 劑的2 -丙醇（IPA) 205毫升及甲苯411毫升，並裝 爲鹼性觸媒的26 %氫氧化四甲基銨（TMAH水溶液） 克（156毫莫耳）。又’於滴下漏斗中加入IPA 136 、三甲氧基甲基矽烷（東麗 Dowconing · Silicone 股 公司製SZ-6070 ) 46.6克（ 3 42毫莫耳）及三甲氧基 基矽烷（信越化學工業股份有限公司製K B Μ - 1 0 0 3 ) 克（342毫莫耳）’一邊攪拌反應容器，一邊於室溫 小時滴下。滴下終了後，於室溫攪拌5小時。5小時 後，加入1 〇%檸檬酸水溶液並攪拌2小時予以中和。 以甲苯萃取’有機層以飽和食鹽水洗淨2次，有機層 酸鎂予以乾燥。濾除無水硫酸鎂，並濃縮取得4 6 · 1 難燃 度、 有反 穎硬 另外 爲}谷 入作 54.9 毫升 份有 乙烯 5 0.7 歷 3 攪拌 水層 以硫 克（ -21 - 200916507 回收率86%)水解產物（含羥基之矽倍半噚烷化合物）。 lit t @ S 5：砂倍半鸣烷化合物於各種有機溶劑中爲可溶的 無色黏性液體。 '測$上述所得之含羥基之矽倍半噚烷化合物〔 CH3Si〇3/2〕k〔 CH2 = CHSi〇3/2〕j〔 h〇1/2〕m 的 GPC 結果 示於圖 1。由圖 1，Mw=1188，Mw/Mn=1.326。 $ 測定此含羥基之矽倍半噚烷化合物(However, 1 in the formula is an integer of 1 to 3, and R2 represents a hydrogen atom or a methyl group.) If a monochlorodecane represented by the general formula (7) is exemplified, dimethylvinyl chlorodecane, Methylallylchlorodecane, trimethylchlorodecane, dimethylethylchlorodecane, dimethylpropyl chlorodecane, dimethyl-1-methylethylchlorodecane, dimethylbutylchlorodecane , dimethyl-2-methylpropyl chlorodecane, dimethyl-1,1-dimethylethyl chlorodecane, dimethyl amyl chlorodecane, dimethylhexyl chlorodecane, dimethyl-1 1,1,2-Trimethylpropyl chlorodecane, dimethylheptylchlorodecane, dimethyloctylchlorodecane, dimethyl-2,2,4-trimethylpentylchlorodecane, dimethyl Nonyl chlorodecane, dimethyl decyl chlorodecane, dimethyl cyclopentyl chlorodecane, dimethyl cyclohexyl chlorodecane, dimethylphenyl chlorodecane, dimethyl-4-methylphenyl chlorodecane , dimethyl-4-methoxyphenylchlorodecane, dimethyl-4-methylphenyl chlorodecane, dimethyl-4-(1-methylvinyl)phenyl chlorodecane, dimethyl _ 4-(3-butenyl)phenylchlorodecane, dimethylnaphthylchlorodecane, Dimethyl methacryloxymethyl chlorodecane, dimethyl-3-methylpropoxypropyl chlorodecane, dimethyl-3 propylene oxypropyl chlorodecane, dimethyl-3-glycidoxy propyl Chlorodecane, dimethyl-2-(3,4-epoxycyclohexyl)ethylchlorodecane, dimethyl-2-(3,4-epoxycyclohexyl)-17- 200916507 ethyl chlorodecane, Dimethylchlorodecane, etc. Here, the hard polyoxygen compound of the general formula (1) has at least two or more hardening functional groups. For example, when the curable polyoxyxene compound of the general formula (1) is composed of 16 fluorenes, at least all of R and R1 are 12·5 旲% or more and are carbon 2 to 3 alkenyl groups, and The amount of the ruthenium compound of the general formulae (6) and (7) is adjusted in the same manner as the curable functional group selected from the group consisting of the formulas (2) to (4). That is, in the quinone compound of the general formulae (6) and (7), if necessary, if each of the substituents R and R 1 is used as a mixture of two or more kinds, the hydroxy group-containing oxime of the general formula (5) The reaction of the sesquiterpene compound with monochlorodecane is preferably carried out under basic conditions. The basic conditions are not particularly limited, and a known reaction method can be used, for example, using tetrahydrofuran as an organic solvent, and a hydroxyl group-containing fluorenyl-halfane compound of the general formula (5) in the presence of a base of triethylamine The chlorodecane may be reacted, or 'the pyridine may be used as a solvent and a base, and the hydroxy group-containing compound may be reacted with monochlorodecane. The reaction conditions of the above-mentioned hydroxyl group-containing sesquiterpene compound and the monochlorosilane compound are as follows, for example, the siliceous compound containing the warp group is dissolved in tetrahydrofuran of 0.1 to 2.0 M, and 1 equivalent or more is used with respect to the hydroxyl group. The mixture of triethylamine or a hydroxyl group-containing sesquiterpene broth, which is also used as a solvent and a base, is dissolved in a mixture of 0. 1~2.0M in a nitrogen solution. Under the inert gas atmosphere, monochloromethane was dropped at room temperature for 1 hour, and then stirred at room temperature for 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed. After the completion of the reaction, -18-200916507 benzene and water were added to dissolve the hardening polysiloxane of the general formula (1) in toluene, and the salt formed by the reaction was dissolved and removed in the aqueous layer. The organic layer is dried with a desiccant such as magnesium sulfate, and the base and solvent to be used are removed by concentration under reduced pressure to obtain a curable polyoxo compound of the general formula (1). The amount of the monochloromethane to be used, for example, in the case of the monochloromethane represented by the general formula (7), is sufficient to capture the amount of the stanol group of the hydroxyl group-containing fluorenose compound which is represented by the general formula (5). Preferably, it is preferably 1.0 to 1.5 times the theoretical amount. Although it is not problematic even if it is added in excess, if unreacted monochloromethane remains in the post-treatment, dioxane is formed, which makes it difficult to prepare. Further, if the dioxane which is produced during the post-treatment has a low boiling point, it can be removed by concentration under reduced pressure. If the boiling point is high, the reaction is carried out in a theoretical amount. If unreacted monochloromethane is not left and dioxane is not formed. Then, by the reaction of the above-mentioned hydroxyl group-containing sesquiterpene compound and monochlorosilane, the curable polysiloxane compound represented by the following general formula (1) can be obtained. [RSi〇3/2 ] n ( R1 ( CH3 ) 2Si01/2 ] m ( 1 ) [However, R and R1 are a hydrogen atom, an aryl group having a carbon number of 6 to 10, and a linear chain having a carbon number of 1 to 10. a linear or branched alkyl group, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a formula (2) to (4) (however, 1 in the formula is 1 to 3) An integer, R2 is a hydrogen atom or a methyl group, and the substituents in r and R 1 may be the same or different from each other, but at least one of the formulas (1) is represented by the formula (1). In one molecule, a hard energy group having two or more carbon number 2-groups and a group consisting of the formulas (2) to (4) is selected, and at least one of R is the above-mentioned curable functional group. Further, an integer of 6 to 20 is shown, m is an integer of 1 to 6, and n/m is 1 to 10. Further, Mw = 5 00 to 5 000, and Mw/Mn = l _0 to 1.5. When two or more hardening functional groups are not contained, when the structural unit of the crop is used, the network cannot be sufficiently expanded by crosslinking, so that the polyoxane compound represented by the general formula (1) is of a general formula (shown Incompletely condensed type of sesquiterpene is derived from a cage That is, the polycrystalline oxide shown in the general formula (1) retains the characteristics of the cage-type oxirane, and the compatibility with other resins is 1 and the curable polyxanthene compound of the general formula (1) is a general formula. (5) The hydroxyl group-containing sesquiterpene compound is used as a raw material, so the molecular weight distribution is controlled to be '500 to 5000, preferably 500 to 2000' of the obtained polyoxo compound, and the molecular weight distribution is 1.0 to 1.5. Within the range (Mw: weight average molecular weight, Μη average molecular weight). (Effect of the invention) According to the present invention, a curable polyoxyn compound containing two functional functional groups can be obtained at a high yield. The hardening oxygen compound is compatible with the polyoxygen curable resin and the organic curable tree, and can be widely used as a range of the radicalized radical polymerizable tree η, if 1 is an aggregation. Poor: 5) The oxyalkylene compound is sorrowful. The Mw of the above material is M w/Mn: the number of the above-mentioned hard poly-resin has a fat composition of -20-200916507. Can be used as a property to improve the properties and resistance of polymer materials Additives such as heat, electrical insulation, surface properties, hardness, mechanical strength, chemical resistance, etc. Further, the hydroxyl group-containing sesquiterpene compound in the present invention is a highly hydroxyl group, and thus can be derived as described above. A useful new-type polyoxo compound having characteristics, and can be utilized as a synthetic hand having a good yield. [Embodiment] Hereinafter, the present invention will be described in more detail based on examples and comparative examples, and the present invention is not based on such embodiments and the like. [Example 1] In a reaction vessel equipped with a stirrer and a dropping funnel, 205 ml of 2-propanol (IPA) and 411 ml of toluene were added as a catalyst, and 26% hydroxide of a basic catalyst was added. Tetramethylammonium (TMAH aqueous solution) g (156 mmol). In addition, IPA 136 and trimethoxymethyl decane (SZ-6070, manufactured by Towon Co., Ltd.) were added to the dropping funnel. 46.6 g (3 42 mmol) and trimethoxy decane (Shin-Etsu Chemical Co., Ltd.) The company made KB Μ - 1 0 0 3 ) g (342 mmol) while stirring the reaction vessel while dropping at room temperature. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After 5 hours, 1 〇% aqueous citric acid solution was added and stirred for 2 hours to be neutralized. The organic layer was washed twice with saturated brine, and the organic layer was dried. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 4 6 · 1 flame retardancy, which was reversed and hardened by another addition. 54.9 ml of ethylene was added to the mixture. 5 liters of the mixture was stirred with water to sulfur (-21 - 200916507 recovery rate 86 %) Hydrolyzate (hydroxyl-containing sesquiterpene compound). Lt t @ S 5: A sand-free half-halfane compound is a colorless viscous liquid which is soluble in various organic solvents. The GPC results of the above-mentioned hydroxyl group-containing sesquiterpene compound [CH3Si〇3/2]k[CH2 = CHSi〇3/2]j[h〇1/2]m obtained are shown in Fig. 1. From Figure 1, Mw = 1188, Mw / Mn = 1.326. Measure the hydroxyl group-containing sesquiterpene compound
〔CH3Si03/2〕k〔 cH2 = CHSi03/2〕』〔HO!。〕m 的 W-NMR 結果示於圖2。由圖2，確認乙烯基、甲基及矽烷醇基的 波峰。比較〔CH3Si〇3/2〕k : 〔 CH2 = CHSi03/2〕』：〔 HOi/2〕m的積分比時，爲2.989: 3.000: 1.067，其官能 基比率爲0.966: l.ooo: 1.〇67。因此，由於η爲k與j的 和’故 n/m=1.843。又，計算由 Mw=1188 及 n/m=1.84 所 導出的 k:j: m 之比爲 7.479: 7.753: 8.226，且 Si 爲 15 的縮合體’確認含有8個羥基、8個硬化性官能基。 其次於具備攪拌機及滴下漏斗的反應容器中，稱量上 述所得之含羥基的矽倍半噚烷化合物3 6 · 3克（3 1毫莫耳 )和吡啶207毫升並且進行氮氣更換。於滴下漏斗中加入 三甲基氯砂院（東麗Dowconing· Silicone股份有限公司 製PRX-24 ) 36.0克（331毫莫耳），並於室溫歷1小時滴 下。滴下終了後於室溫攪拌2小時。2小時攪拌後，加入 甲苯207毫升和純水207毫升，將有機層和水層分離。有 機層以飽和食鹽水洗淨後，有機層以無水硫酸鎂予以乾燥 。濾除無水硫酸鎂，並濃縮，取得45 · 7克（回收率97% -22- 200916507 )硬化性聚矽氧化合物。此硬化性聚矽氧化合物於各種有 機溶劑中爲可溶的無色液體。 測定此硬化性聚矽氧化合物〔CH3Si03/2〕k〔 CH2 = CHSi03/2 ) j ( ( CH3 ) 3Si01/2〕GPC 結果示於圖 3 。由 GPC 之測定結果（圖 3 ) ，Mw= 1 520、 M w/M n= 1 2 7 0 〇 測定此硬化性聚矽氧化合物〔CH3Si03/2〕k〔 CH2 = CHSi03/2〕』〔(CH3 ) 3Si01/2〕m 的 h-NMR 結果示 於圖 4。由圖 4 比較〔CH2 = CHSi03/2〕j: ( CH3Si03/2 J k + 〔(CH3 ) 3Si01/2〕m 的積分比時，爲 3.000 : 8.699，k ·· j :m的積分比爲2.989: 3.000: 5.801，k: j : m的比率爲 0.966 ： 1.000: 0.645。因此，由於n爲k與j的和，故 n/m = 3.0 5。另外，含羥基之矽倍半噚烷化合物的羥基與其 硬化性聚矽氧化合物之三甲基甲矽烷基數爲不同，認爲係 因在吡啶存在下，矽烷醇基彼此間爲一部分縮合。 又，計算由Mw=1 520及n/m = 3.05所導出的k : j : m 之比爲7.469: 7_743: 5.020’且Si爲20的縮合體，確認 含有8個硬化性官能基。 〔實施例2〕 於具備攪拌機及滴下漏斗的反應容器中，加入作爲溶 劑的2-丙醇（IPA) 60毫升及甲苯12〇毫升，並裝入作爲 鹼性觸媒的26%氫氧化四甲基銨（TMAH水溶液）1 6 _ 1克 (45.9毫莫耳）。又，於滴下漏斗中加入IPA 40毫升和 -23- 200916507 二甲氧基乙烯基砂院（信越化學工業股份有限公 KBM-1003) 29_6克（ 200毫莫耳），—邊攪拌反應容 一邊於室溫歷3小時滴下。滴下終了後，於室溫攪拌 時。5小時攪拌後，加入1 0 °/。檸檬酸水溶液並擾拌2 予以中和。水層以甲苯萃取’有機層以飽和食鹽水洗 次’有機層以硫酸鎂予以乾燥。濾除無水硫酸鎂，並 取得1 4 _ 3克（回收率9 2 % )水解產物（含羥基之矽 D萼烷化合物）。此含羥基之矽倍半噚烷於各種有機溶 爲可溶的無色黏性液體。 測定此含羥基之矽倍半噚院化合物〔C Η 2 = C H S i Ο η〔 Η Ο 3 / 2〕m的G P C結果示於圖5。由G P C之測定結 圖 5) ，Mw = 850、Mw/Mn=l,162。 其次於具備攪拌機及滴下漏斗的反應容器中，稱 羥基的矽倍半噚烷化合物1 〇 · 8克（1 2 _ 7毫莫耳）和 82.5毫升並且進行氮氣更換。於滴下漏斗中加入三甲 烯基氯矽烷（東麗Dowconing · Silicone股份有限公 )20.7克（172毫莫耳），並於室溫歷1小時滴下。 終了後於室溫攪拌2小時。2小時攪拌後，加入甲苯 毫升和純水8 2.5毫升，將有機層和水層分離。有機 飽和食鹽水洗淨後，有機層以無水硫酸鎂予以乾燥。 無水硫酸鎂，並濃縮，取得14.1克（回收率90% ) 性聚矽氧化合物。此硬化性聚矽氧化合物於各種有機 中爲可溶的無色液體。 測定此硬化性聚矽氧化合物〔CH2 = CHSi03/2〕 司製 器， 5小 小時 淨2 濃縮 倍半 劑中 3/2〕 果（ 量含 吡啶 基乙 司製 滴下 82.5 層以 濾除 硬化 溶劑 η [ -24- 200916507 CH2 = CH(CH3) 2〇1/2〕m 的 GPC 結果示於圖 6。由 GPC 之 測定結果（圖 6) ，Mw=1 226、Mw/Mn=1.133。 測定此硬化性聚砂氧化合物〔C Η 2 = C H S i Ο 3 / 2〕η〔 CH2 = CH ( CH3 ) 2〇1/2 ] m ^ W-NMR 結果示於圖 7。由圖 7 比較〔CH2 = CHSi03/2〕„ ： 〔 CH2 = CH ( CH3 ) 201/2〕m 的 積分比時，爲11.375: 6.000。因此，n: m的比率爲 1.000 ： 0.3 5 8，n/m = 2_79。 又，計算由Mw=1226及n/m = 2.79所導出的n: m之 比爲7.114: 2.547’且Si爲9的縮合體，確認含有9個 硬化性官能基。 〔實施例3〕 於具備攪拌機及滴下漏斗的反應容器中，加入作爲溶 劑的2_丙醇（IP A ) 48毫升及甲苯194毫升，並裝入作爲 鹼性觸媒的2 6 %氫氧化四甲基錢（τ M A Η水溶液）9 · 6克 (27毫莫耳）。又，於滴下漏斗中加入ΙρΑ 32毫升 '三 甲氧基乙燦基矽烷（信越化學工業股份有限公司製 ΚΒΜ1 003 ) 1 1.9克（80毫莫耳），及3_縮水甘油氧丙基 二甲氧基砂院（fg越化學工棊股份有限製LS-2940) 20.0 克（80毫莫耳），一邊攪拌反應容器，一邊於室溫歷3小 時滴F。滴下終了後，於室溫攪拌5小時。5小時攪拌後 ，加入1 0%檸檬酸水溶液並攪拌2小時予以中和。水層以 甲本卒取，有機層以飽和食鹽水洗淨2次，有機層以硫酸 鎂予以乾鉍。濾除無水硫酸鎂，並濃縮取得1 7 _ 8克（回 -25- 200916507 收率89% )水解產物（含羥基之矽倍半噚烷化合物）。此 含經基之矽倍半噚烷化合物於各種有機溶劑中爲可溶的無 色黏性液體。 測定此含羥基之矽倍半噚烷化合物〔CH2 ( 〇 ) CHCH2〇 ( CH2 ) 3S1O3/2 ] 1c〔 CH2 = CHSi〇2/3〕J〔 H01/2〕m 的GPC結果示於圖8。由GPC之測定結果（圖8 )， M w = 1 3 7 9 ' Mw/Mn=1.282。 其次於具備攪拌機及滴下漏斗的反應容器中，稱量含 羥基的矽倍半鸣烷化合物1 〇 · 8克（8毫莫耳）和吡啶8 2 毫升並且進行氮氣更換。於滴下漏斗中加入二甲基乙烯基 氯砂院（東麗 Dowconing· Silicone股份有限公司製） 20_7克（171毫莫耳），並於室溫歷1小時滴下。滴下終 了後於室溫攪拌2小時。2小時攪拌後，加入甲苯8 2毫升 和純水8 2毫升，將有機層和水層分離。有機層以飽和食 鹽水洗淨後，有機層以無水硫酸鎂予以乾燥。濾除無水硫 酸鎂，並濃縮，取得1 1 . 7克、回收率9 1 %之硬化性聚矽 氧化合物。此硬化性聚矽氧化合物於各種有機溶劑中爲可 溶的無色液體。 測定此硬化性聚矽氧化合物 〔CH2 ( 0) CHCH20 ( CH2) 3S1O3/2] k [ CH2 = CHSi〇2/3 ) j 〔CH2 = CH(CH3) 2〇1/2〕出的 GPC 結果示於圖 9。由 GPC 之測疋結果（圖 9) ，Mw=1624、Μ\ν/Μη=1·293。 測定此硬化性聚矽氧化合物 〔CH2 ( 0 ) CHCH2OSi〇3/2〕k〔 C Η 2 = C H S i Ο 3/2〕j〔 -26- 200916507 CH2 = CH(CH3) 2〇w2〕m 的1H-NMR 結果示於圖 10。由圖 10 比較〔CH2 ( Ο) CHCH2CH2CH2Si03/2〕k : 〔CH2 = CHSi03/2〕： 〔 CH2 = CH ( CH3 ) 201/2〕m 的積分比 時，爲2.000: 3.000: 1.496。因此，由於n爲k與j的和 ，故 k: j: m 之比率爲 1: 1 : 0.249，n/m = 8.032。 又，計算由Mw=1136及n/m=8.03所導出的n: m之 比爲6.02 8 : 6.02 8 : 1.5 0 1 ’且Si爲14的縮合體，確認含 有1 4個硬化性官能基。 〔實施例4〕 於具備攪拌機及滴下漏斗的反應容器中，加入作爲溶 劑的2-丙醇（IPA) 182毫升及甲苯363毫升，並裝入作 爲鹼性觸媒的26%氫氧化四甲基銨（TMAH水溶液）35_9 克（102鼋莫耳）。又，於滴下漏斗中加入ΙρΑ ι21毫升 、二甲氧基乙烯基矽烷（信越化學工業股份有限公司製 KBM1003) 44.8克（303毫莫耳）、及三甲氧基苯基矽烷 60_0克（303毫莫耳），一邊攪拌反應容器，一邊於室溫 歷3小時滴下。滴下終了後’於室溫攪拌5小時。5小時 攪拌後’加入1 0 %檸檬酸水溶液並攪拌2小時予以中和。 水層以甲本卒取，有機層以飽和食鹽水洗淨2次，有機層 以硫酸鎂予以乾燥。濾除無水硫酸鎂，並濃縮取得5 6.8 克（回收率8 8 % )水解產物（含羥基之矽倍半噚烷化合物 )°此a經基之砂倍半噚烷化合物於各種有機溶劑中爲可 溶的無色黏性液體。 -27- 200916507 測定此含羥基之矽倍半噚烷化合物 〔CH2 = CHSi〇3/2〕k〔 PhSi〇3/山〔H〇1/2〕m 的 GPC 結果 示於圖11 。由GPC之測定結果，Mw= 1 492 、 M w/Mn= 1.4 3 6。 其次於具備攪拌機及滴下漏斗的反應容器中，稱量含 羥基的矽倍半鸣烷化合物53.0克（36毫莫耳）和啦陡 304毫升並且進行氮氣更換。於滴下漏斗中加入三甲基乙 烯基氯矽烷（東麗Dowconing. Silicone股份有限公司製 )44.1克（366毫莫耳）’並於室溫歷1小時滴下。滴下 終了後於室溫攪拌2小時。2小時攪拌後，加入甲苯3 〇 5 毫升和純水3 〇 5毫升，將有機層和水層分離。有機層以飽 和食鹽水洗淨後，有機層以無水硫酸鎂予以乾燥。濾除無 水硫酸鎂，並濃縮，取得5 5.2克（回收率91 % )硬化性 聚矽氧化合物。此硬化性聚矽氧化合物於各種有機溶劑中 爲可溶的無色液體。 測定此硬化性聚矽氧化合物〔CH2 = CHSi03/2〕k〔 PhSi03/2〕J〔 CH2 = CH ( CH3 ) 201/2〕m 的 GPC 結果示於圖 12 。由 GPC 之測定結果（圖 12 ) ， Mw= 1 6 8 5 、 M w/Mn= 1 · 4 2 6 〇 測定此硬化性聚矽氧化合物〔CH2 = CHSi03/2〕k〔 PhSi03/2〕j〔 CH2 = CH ( CH3 ) 201/2〕m 的】H-NMR 結果示 於圖 13。圖 13 比較〔CH2 = CHSi03/2〕k: 〔PhSi03/2〕j: 〔CH2 = CH ( CH3 ) 201/2〕m 的積分比時，爲 13.831 : 20.004 ： 6.000。因此，k: j: m 的比率爲 4.610:4.001: -28- 200916507 1.000，由於η爲k與j的和，故n/m = 7.22。 又，計算由Mw= 1 68 5及k + j/m = 7.22所導出的k : j : m之比爲7.198: 7.198: 1.994，且Si爲17的縮合體，確 認含有8個硬化性官能基。 〔比較例1〕 於具備攪拌機、滴下漏斗之反應容器中，加入作爲溶 劑的甲苯200毫升，並裝入作爲鹼性觸媒的5%氫氧化四 甲基銨（TMAH水溶液）39.0克（21毫莫耳）。於滴下漏 斗中加入甲苯 60毫升。三甲氧基甲基矽烷（東麗 Dowconing. Silicone 股份有限公司製 SZ-6070) 24.5 克（ 179毫莫耳）、及三甲氧基乙烯基矽烷（信越化學股份有 限公司製KBM1003) 26.7克（179毫莫耳），一邊攪拌反 應容器，一邊於室溫歷2小時滴下三甲氧基乙烯基矽烷的 甲苯溶液。三甲氧基乙烯基矽烷滴下終了後，未加熱攪拌 2小時，將此反應溶液靜置1日，其後，進行後再縮合。 取出滴下漏斗並於反應谷益中裝備迪安-斯達克（Dean and Starlc)裝置、冷卻管’且將液溫加熱至75t並除去副產 物之甲醇後’以液溫1 〇 5 °C迴流加熱甲苯。攪拌迴流3小 時後’恢復至室溫令反應終了。反應溶液以1 0 %檸檬酸水 溶液23 · 0克中和後，以飽和食鹽水洗淨並以無水硫酸鎂 脫水。濾除無水硫酸鎂’並濃縮取得3 3 _ 7克、產率7 2 % 之下述再縮合物（8 )。此再縮合物於各種有機溶劑中爲 難丨谷的白色固體。所得之下述再縮合物（8)的ope圖示 -29- 200916507 於圖1 4。另外，此處所謂之再縮合，係指將三烷氧基矽烷 於有機極性溶劑及鹼性觸媒存在下，水解、縮聚，並將所 得之水解產物再度於非極性溶劑及鹼性觸媒存在下縮合， 爲完全縮合型之矽倍半噚烷（籠型矽倍半噚烷樹脂）的製 造方法（特開2004- 1 43449號公報）。 C CH3S1O3/2 ] ,〔 CH2 = CHSi03/2〕h ( 8) 〔比較例2〕 於具備攪拌機、滴下漏斗之反應容器中，加入作爲溶 劑的甲苯200毫升，並裝入作爲鹼性觸媒的5 %氫氧化四 甲基銨水溶液（T M A Η水溶液）3 9.0克（2 1毫莫耳）。於 滴下漏斗中加入甲苯6〇毫升和三甲氧基乙烯基矽烷（信 越化學股份有限公司製ΚΒΜ1003) 53·0 ( 358莫耳），一 邊攪拌反應容器，一邊於室溫歴2小時滴下三甲氧基乙烯 基矽烷的甲苯溶液。三甲氧基乙烯矽烷滴下終了後，未加 熱攪拌2小時，將此反應溶液靜置1日，其後，進行再縮 合。取出滴下漏斗並於反應容器中裝備迪安-斯達克裝置 、冷卻管，且將液溫加熱至7 5 °C並除去副產物之甲醇後， 以液溫1 0 5 °C迴流加熱甲苯。攪拌迴流3小時後，恢復至 室溫令反應終了。反應溶液以10%檸檬酸水溶液23.0克 中和後’以飽和食鹽水洗淨並以無水鎂脫水。濾除無水硫 酸鎂’並濃縮取得30.03克、產率83 %之下述再縮合物（ 9 )。此再縮合物於各種有機溶劑中爲難溶的白色固體。 -30- 200916507 所得之下述再縮合物（9 )的GPC圖示於圖1 5。 [CH2 = CHSi03/2 ] g ( 9 ) 〔相溶性試驗〕 將上述實施例1〜4所得之硬化性聚矽氧化合物與下述 (1 0 )〜（1 4 )所示之聚矽氧系硬化性樹脂以重量比1 : 1 混合並評價相溶性。又，關於上述比較例1及2所得者亦 同樣評價。結果示於表1。另外，評價爲以目視進行，於 透明之情形以◦表示，察見白濁之情形以X表示。 -31 - 200916507 8 化 h3,l .lc—s—o-s-H I _-0-0H-si-o-si-c I - H3Ch H· c -3 .3c 1H3H-s-c —_—.o 3 3 H L Hc-s-c a _3c H3I—H3c-s-c H3 1 1 /l\ 5 3 ? 4 2[CH3Si03/2]k[ cH2 = CHSi03/2]』[HO!. The W-NMR results of m] are shown in Fig. 2. From Fig. 2, the peaks of the vinyl group, the methyl group and the stanol group were confirmed. When the integral ratio of [CH3Si〇3/2]k: [CH2 = CHSi03/2]": [HOi/2]m is 2.989: 3.000: 1.067, the functional group ratio is 0.966: l.ooo: 1. 〇67. Therefore, since η is the sum of k and j ', n/m = 1.843. Further, the ratio of k:j: m derived from Mw=1188 and n/m=1.84 was 7.479: 7.753: 8.226, and the condensate of Si of 15 was confirmed to contain 8 hydroxyl groups and 8 hardening functional groups. . Next, in the reaction vessel equipped with a stirrer and a dropping funnel, the obtained hydroxyl group-containing sesquiterpene compound 33.6 g (3 1 mmol) and pyridine 207 ml were weighed and replaced with nitrogen. To the dropping funnel, 36.0 g (331 mmol) of trimethyl chloride sand (PRX-24 manufactured by Toray Co., Ltd.) was added and dropped at room temperature for 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 207 ml of toluene and 207 ml of pure water were added, and the organic layer and the aqueous layer were separated. After the organic layer was washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 45·7 g (recovery rate 97% -22-200916507) of a hardening polysiloxane. The curable polyxanthene compound is a soluble colorless liquid in various organic solvents. The result of measuring the curable polydecane oxy-compound [CH3Si03/2]k[CH2=CHSi03/2)j((CH3)3Si01/2] GPC is shown in Fig. 3. The measurement result by GPC (Fig. 3), Mw = 1 520, M w / M n = 1 2 7 0 〇 The h-NMR results of the hardening polyoxyl compound [CH3Si03/2]k[CH2 = CHSi03/2]"[(CH3)3Si01/2]m are shown In Fig. 4, when the integral ratio of [CH2 = CHSi03/2]j: (CH3Si03/2 J k + [(CH3 ) 3Si01/2] m is compared by Fig. 4, it is 3.000: 8.699, k ·· j : m The integral ratio is 2.989: 3.000: 5.801, k: j: The ratio of m is 0.966 : 1.000: 0.645. Therefore, since n is the sum of k and j, n/m = 3.0 5. In addition, the hydroxy group is halved. The hydroxyl group of the decane compound is different from the trimethylmethanone number of the curable polyoxyxene, and it is considered that the stanol groups are partially condensed with each other in the presence of pyridine. Further, the calculation is made by Mw=1 520 and n. / m = 3.05 The derived k: j : m ratio is 7.469: 7_743: 5.020' and Si is a condensate of 20, and it is confirmed that it contains eight hardening functional groups. [Example 2] It is equipped with a stirrer and a dropping funnel. reaction Into the vessel, 60 ml of 2-propanol (IPA) and 12 ml of toluene were added as a solvent, and charged with 26% tetramethylammonium hydroxide (TMAH aqueous solution) as an alkaline catalyst 1 6 _ 1 g (45.9) In addition, add IPA 40 ml and -23- 200916507 dimethoxy vinyl sand yard (Shin-Etsu Chemical Industry Co., Ltd. KBM-1003) 29_6 g (200 mmol), - edge The reaction mixture was stirred at room temperature for 3 hours. After the completion of the dropwise addition, the mixture was stirred at room temperature. After stirring for 5 hours, 10 ° / citric acid aqueous solution was added and the mixture was disturbed with 2 to neutralize. The aqueous layer was extracted with toluene. The organic layer was washed with a saturated aqueous solution of sodium chloride. The organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was removed by filtration, and a hydrolyzed product (hydroxyl-containing D-decane compound) of 1 4 _ 3 g (recovery rate 92%) was obtained. The hydroxy-containing sesquiterpene is soluble in various organic soluble soluble colorless viscous liquids. The hydroxy-containing sesquiterpenoid compound [C Η 2 = CHS i Ο η [ Η Ο 3 / 2] m is determined. The GPC results are shown in Figure 5. Figure 5) was determined by GPC, Mw = 850, Mw / Mn = 1,162. Next, in a reaction vessel equipped with a stirrer and a dropping funnel, a hydroxy sesquisesquioxane compound 1 〇 · 8 g (1 2 -7 μm) and 82.5 ml were weighed and replaced with nitrogen. To the dropping funnel, 20.7 g (172 mmol) of trimethylenyl chlorodecane (Dongli Dowconing, Silicone Co., Ltd.) was added, and the mixture was dropped at room temperature for 1 hour. After the end, it was stirred at room temperature for 2 hours. After stirring for 2 hours, toluene ml and 82.5 ml of pure water were added, and the organic layer and the aqueous layer were separated. After washing with organic saturated brine, the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was added and concentrated to obtain 14.1 g (recovery rate: 90%) of a polyoxymethylene compound. This hardenable polyoxynitride is a soluble colorless liquid in various organic compounds. Determination of the curable polyfluorene oxide compound [CH2 = CHSi03/2], 5 hours, 2 hours in the net 2 concentration sesquid, 3/2] Fruit (82.5 layers of pyridyl ethane to remove the hardening solvent) The GPC results of η [ -24- 200916507 CH2 = CH(CH3) 2〇1/2]m are shown in Fig. 6. The results of GPC measurement (Fig. 6), Mw = 1 226, Mw/Mn = 1.133. The results of the sclerosing polyoxalate [C Η 2 = CHS i Ο 3 / 2] η [ CH2 = CH ( CH3 ) 2 〇 1/2 ] m ^ W-NMR are shown in Fig. 7. Compare with Fig. 7 [CH2 = CHSi03/2]„ : The integral ratio of [CH2 = CH(CH3) 201/2]m is 11.375: 6.000. Therefore, the ratio of n: m is 1.000 : 0.3 5 8,n/m = 2_79. The condensate of n: m derived from Mw=1226 and n/m = 2.79 was 7.114: 2.547' and Si was 9 and it was confirmed that it contained 9 hardening functional groups. [Example 3] To the reaction vessel in which the funnel was dropped, 48 ml of 2-propanol (IP A ) and 194 ml of toluene as a solvent were added, and charged with 2 6 % of tetramethylammonium hydroxide (aqueous solution of τ MA 作为) as an alkaline catalyst. 9 · 6 grams (27 mmol). In addition, ΙρΑ 32 ml of 'trimethoxyethyl decyl decane (manufactured by Shin-Etsu Chemical Co., Ltd. ΚΒΜ1 003) 1 1.9 g (80 mmol), and 3_shrinkage were added to the dropping funnel. Glyceroxypropyl dimethoxy sand court (fg Yue Chemical Industry Co., Ltd. has limited LS-2940) 20.0 g (80 mmol), while stirring the reaction vessel, dripping F at room temperature for 3 hours. After the end of the drip Stir at room temperature for 5 hours. After stirring for 5 hours, add 10% aqueous citric acid solution and stir for 2 hours to neutralize. The water layer was taken as a nail, and the organic layer was washed twice with saturated brine. The magnesium sulfate was dried. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 1 7 -8 g (return -25 - 200916507 yield 89%) of a hydrolyzed product (hydroxyl-containing sesquiterpene compound). The sesquiterpene compound is a soluble colorless viscous liquid in various organic solvents. The hydroxy-containing sesquiterpene compound [CH2(〇)CHCH2〇(CH2)3S1O3/2] 1c[CH2 = CHSi was determined. The GPC results of 〇2/3]J[H01/2]m are shown in Fig. 8. The results of measurement by GPC (Fig. 8) M w = 1 3 7 9 'Mw / Mn = 1.282. Next, in a reaction vessel equipped with a stirrer and a dropping funnel, a hydroxyl group-containing oxime hemane compound 1 〇 · 8 g (8 mmol) and pyridine 8 2 ml were weighed and replaced with nitrogen. To the dropping funnel, dimethyl vinyl chloride sand (manufactured by Toray Dowconing Silicone Co., Ltd.) 20-7 g (171 mmol) was added, and the mixture was dropped at room temperature for 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 8 2 ml of toluene and 82 ml of pure water were added, and the organic layer and the aqueous layer were separated. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 11.77 g of a sclerosing polyoxyl compound having a recovery rate of 91%. The curable polydecene oxide is a soluble colorless liquid in various organic solvents. The GPC results of the hardening polyfluorene compound [CH2(0)CHCH20(CH2)3S1O3/2] k [CH2 = CHSi〇2/3) j [CH2 = CH(CH3) 2〇1/2] were measured. In Figure 9. The measured result by GPC (Fig. 9), Mw=1624, Μ\ν/Μη=1·293. The hardening polyoxo[CH2(0)CHCH2OSi〇3/2]k[C Η 2 = CHS i Ο 3/2]j[ -26- 200916507 CH2 = CH(CH3) 2〇w2]m was determined. The results of 1H-NMR are shown in Fig. 10. From Fig. 10, the integral ratio of [CH2 ( Ο) CHCH2CH2CH2Si03/2]k : [CH2 = CHSi03/2]: [CH2 = CH (CH3) 201/2] m is 2.000: 3.000: 1.496. Therefore, since n is the sum of k and j, the ratio of k: j: m is 1: 1 : 0.249, n/m = 8.032. Further, a condensate having a ratio of n:m derived from Mw = 1136 and n/m = 8.03 of 6.02 8 : 6.02 8 : 1.5 0 1 ' and Si of 14 was calculated, and it was confirmed that 14 kinds of curable functional groups were contained. [Example 4] 182 ml of 2-propanol (IPA) and 363 ml of toluene as a solvent were placed in a reaction vessel equipped with a stirrer and a dropping funnel, and charged with 26% tetramethylammonium hydroxide as an alkaline catalyst. Ammonium (TMAH aqueous solution) 35_9 g (102 鼋 Mo). Further, 滴ρΑ ι 21 ml, dimethoxyvinyl decane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 44.8 g (303 mmol), and trimethoxyphenyl decane 60-_0 g (303 mmol) were added to the dropping funnel. The ear was stirred while being stirred at room temperature for 3 hours while stirring the reaction vessel. After the end of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, '10% aqueous citric acid solution was added and stirred for 2 hours to neutralize. The aqueous layer was taken up in the form of a base, and the organic layer was washed twice with saturated brine, and the organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 5 6.8 g (recovery rate of 8 8 %) of a hydrolyzed product (hydroxyl-containing sesquiterpene compound). The a-sodium sesquiterpene compound was used in various organic solvents. Soluble colorless viscous liquid. -27- 200916507 The GPC results of the hydroxyl group-containing sesquiterpene compound [CH2 = CHSi〇3/2]k [ PhSi〇3/Mountain [H〇1/2]m are shown in Fig. 11. As a result of measurement by GPC, Mw = 1 492 and M w / Mn = 1.4 3 6. Next, in a reaction vessel equipped with a stirrer and a dropping funnel, 53.0 g (36 mmol) of a hydrazine-containing hemi-halfane compound and 304 ml of a hydroxyl group were weighed and replaced with nitrogen. To the dropping funnel, 44.1 g (366 mmol) of trimethylvinyl chlorodecane (manufactured by Toray Dowconing. Silicone Co., Ltd.) was added and dropped at room temperature for 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 3 ml of toluene and 5 ml of pure water were added, and the organic layer and the aqueous layer were separated. After the organic layer was washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 55.2 g (yield: 91%) of a sclerosing polyoxyl compound. The curable polydecene oxide is a soluble colorless liquid in various organic solvents. The GPC results of the measurement of the curable polyfluorene compound [CH2 = CHSi03/2]k[ PhSi03/2]J[CH2 = CH(CH3) 201/2]m are shown in Fig. 12. From the measurement results of GPC (Fig. 12), Mw = 1 6 8 5 , M w / Mn = 1 · 4 2 6 〇 The hardening polysiloxane (CH2 = CHSi03/2) k [ PhSi03/2]j was measured. The H-NMR results of [CH2 = CH(CH3)201/2]m are shown in Fig. 13. Figure 13 Comparison of [CH2 = CHSi03/2]k: [PhSi03/2]j: [CH2 = CH (CH3) 201/2] m The integral ratio is 13.831 : 20.004 : 6.000. Therefore, the ratio of k: j: m is 4.610:4.001: -28- 200916507 1.000, since η is the sum of k and j, so n/m = 7.22. Further, a condensate having a ratio of k:j:m derived from Mw = 1 68 5 and k + j/m = 7.22 of 7.198: 7.198: 1.994 and Si of 17 was calculated, and it was confirmed that it contained 8 hardening functional groups. . [Comparative Example 1] To a reaction vessel equipped with a stirrer and a dropping funnel, 200 ml of toluene as a solvent was added, and 39.0 g of a 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst was charged (21 m. Moore). Add 60 ml of toluene to the dropping funnel. Trimethoxymethyl decane (SZ-6070, manufactured by Toray Dowconing. Silicone Co., Ltd.) 24.5 g (179 mmol), and trimethoxyvinyl decane (KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) 26.7 g (179 m Moore), while stirring the reaction vessel, a toluene solution of trimethoxyvinyl decane was dropped at room temperature for 2 hours. After the dropwise addition of trimethoxyvinyl decane, the mixture was stirred without heating for 2 hours, and the reaction solution was allowed to stand for 1 day, after which it was recondensed. The dropping funnel was taken out and equipped with a Dean and Starlc apparatus, a cooling tube ', and the liquid temperature was heated to 75 t and the by-product methanol was removed in the reaction, and the toluene was refluxed at a liquid temperature of 1 〇 5 ° C. . After stirring at reflux for 3 hours, the reaction was returned to room temperature to complete the reaction. The reaction solution was neutralized with a 10% citric acid aqueous solution of 23.0 g, washed with saturated brine and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 3 3 - 7 g of a yield of 72% of the following recondensate (8). This recondensate is a white solid which is difficult to store in various organic solvents. The ope diagram of the obtained recondensate (8) described below is shown in Fig. 14 of -29-200916507. In addition, the term "recondensation" as used herein refers to hydrolysis, polycondensation of a trialkoxysilane in the presence of an organic polar solvent and a basic catalyst, and the resulting hydrolyzate is again present in a non-polar solvent and an alkaline catalyst. The lower condensation is a method for producing a completely condensed type of sesquiterpene (cage type sesquiterpene resin) (JP-A-2004-143749). C CH3S1O3/2 ] , [CH2 = CHSi03/2]h (8) [Comparative Example 2] 200 ml of toluene as a solvent was placed in a reaction vessel equipped with a stirrer and a dropping funnel, and charged as an alkaline catalyst. 5 mM tetramethylammonium hydroxide aqueous solution (TMA hydrazine aqueous solution) 3 9.0 g (2 1 mmol). To the dropping funnel, 6 ml of toluene and trimethoxyvinyl decane (ΚΒΜ1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 53·0 (358 mol) were added, and the reaction vessel was stirred while dropping trimethoxy at room temperature for 2 hours. A solution of vinyl decane in toluene. After the dropwise addition of trimethoxyvinyl decane, the mixture was stirred without heating for 2 hours, and the reaction solution was allowed to stand for 1 day, and then re-condensed. The dropping funnel was taken out and equipped with a Dean-Stark apparatus and a cooling tube in a reaction vessel, and the liquid temperature was heated to 75 ° C to remove methanol as a by-product, and then toluene was heated under reflux at a liquid temperature of 1 0 5 °C. After stirring under reflux for 3 hours, it was returned to room temperature to complete the reaction. The reaction solution was neutralized with 23.0 g of a 10% aqueous citric acid solution, and then washed with saturated brine and dehydrated with anhydrous magnesium. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 30.03 g of a yield of 83% of the following recondensate (9). This recondensate is a poorly soluble white solid in various organic solvents. -30- 200916507 The GPC chart of the following recondensate (9) obtained is shown in Fig. 15. [CH2 = CHSi03/2] g (9) [Compatibilization test] The curable polyxanthene compounds obtained in the above Examples 1 to 4 and the polyoxynoxy group represented by the following (1 0 ) to (1 4 ) are The curable resin was mixed at a weight ratio of 1:1 and the compatibility was evaluated. Further, the same as those of the above Comparative Examples 1 and 2 were also evaluated. The results are shown in Table 1. In addition, the evaluation was performed by visual observation, and the case of transparency was indicated by ◦, and the case where white turbidity was observed was indicated by X. -31 - 200916507 8 H3,l .lc—s—osH I _-0-0H-si-o-si-c I - H3Ch H· c -3 .3c 1H3H-sc —_—.o 3 3 HL Hc-sc a _3c H3I-H3c-sc H3 1 1 /l\ 5 3 ? 4 2
-02 H31H3__c-s-c b - H H 3 3 H 1 H )c-s-c 2 —_—^(1 o 3 3 H _L H 9 7 CH3 -Si—〇- I ch3 c-s-c CH3 -Si——Ο Ι CH,-02 31 H , , ,
CH3 I -Si I CH c 2〜7 8 (14)CH3 I -Si I CH c 2~7 8 (14)
3 1 /IV 32- 200916507 〔表1〕 (1〇) (11) (12) (13 ) (14) 實施例1 〇 〇 〇 〇 〇 實施例2 〇 〇 〇 〇 〇 實施例3 〇 〇 〇 〇 〇 實施例4 〇 〇 〇 〇 〇 比較例1之再 縮合物（8 ) X X X X X 比較例2之再 縮合物（9 ) X X X X X [CH3Si〇3/2 ] , ( CH2 = CHSi〇3/2 3 h (9 ) ： [ CH2 = CHSi03/2 3 g 【圖式簡單說明】 圖1爲含羥基之矽倍半噚烷化合物〔CH3Si03/2〕k〔 CH2 = CHSi03/2〕j〔 H01/2〕⑴的 GPC 圖。 圖2爲含羥基之矽倍半噚烷化合物〔CH3Si03/2〕k〔 CH2 = CHSi03/2 ] j C H01/2 ] m 的1H-NMR 圖。 圖 3爲硬化性聚矽氧化合物〔CH3Si03/2〕k〔 CH2 = CHSi〇3/2 ] J C ( CH3 ) 3Si01/2〕GPC 圖。 圖 4爲硬化性聚矽氧化合物〔CH3Si〇3/2〕k〔 CH2 = CHSi03/2 ] j ( ( CH3 ) 3Si01/2〕m 的'H-NMR 圖。 圖5爲含羥基之矽倍半噚烷化合物〔C H 2 = C H S i O n〔 H〇i/2〕m 的 GPC 圖》 圖6爲硬化性聚矽氧化合物〔CH2 = CHSi03/2〕n〔 CH2 = CH(CH3) 2〇i/2 ]⑺的 GPC 圖。 圖 7爲硬化性聚矽氧化合物〔CH2 = CHSi03/2〕n〔 -33- 200916507 CH2 = CH(CH3) 2〇1/2〕rn 的 iH-NMR 圖。 圖 8爲含羥基之矽倍半噚烷化合物〔CH2 ( Ο ) CHCH20Si03/2 ] k〔 CH2 = CHSi03/2〕j〔 H01/2〕„的 GPC 圖 o3 1 /IV 32- 200916507 [Table 1] (1〇) (11) (12) (13) (14) Example 1 〇〇〇〇〇 Example 2 〇〇〇〇〇 Example 3 〇〇〇〇 〇 Example 4 再 Recondensate of Comparative Example 1 (8) XXXXX Recondensate of Comparative Example 2 (9) XXXXX [CH3Si〇3/2 ] , ( CH2 = CHSi〇3/2 3 h ( 9) : [ CH2 = CHSi03/2 3 g [Simple description of the diagram] Figure 1 shows the hydroxy-containing sesquiterpene compound [CH3Si03/2]k[CH2 = CHSi03/2]j[ H01/2](1) Figure 2 is a 1H-NMR chart of a hydroxy-containing sesquiterpene compound [CH3Si03/2]k[CH2 = CHSi03/2] j C H01/2 ] m. Figure 3 is a hardenable polyoxyxene compound. [CH3Si03/2]k[CH2 = CHSi〇3/2] JC (CH3) 3Si01/2] GPC Figure 4. Figure 4 is a hardening polyoxo compound [CH3Si〇3/2]k[CH2 = CHSi03/2] 'H-NMR chart of j ((CH3) 3Si01/2]m. Figure 5 is a GPC chart of a hydroxy-containing sesquiterpene compound [CH 2 = CHS i O n[ H〇i/2]m 6 is a hardening polyoxo compound [CH2 = CHSi03/2]n[CH2 = CH(CH3) 2〇i/2 ] Fig. 7 is an iH-NMR chart of a sclerosing polyoxo compound [CH2 = CHSi03/2]n [ -33- 200916507 CH2 = CH(CH3) 2〇1/2] rn. Figure 8 is a hydroxyl group. GPC chart of sesquiterpene compound [CH2 ( Ο ) CHCH20Si03/2 ] k[ CH2 = CHSi03/2]j[ H01/2] „
圖9爲硬化性聚矽氧化合物〔CH2 ( O) CHCH20Si03/2 〕k [ CH2 = CHSi03/2 ] j C CH2 = CH ( CH3) 2〇i/2 ] m 的 GPC 圖。 圖 10 爲硬化性聚矽氧化合物〔ch2 ( o ) CHCH20Si03/2 ) k〔 CH2 = CHSi03/2〕j〔 CH2 = CH ( CH3 ) 20W2 〕m 的 1 H - N M R 圖。 圖11爲含羥基之矽倍半噚烷化合物〔CH2 = CHSi03/2 〕k [ PhSiOs/2 ] j C H01/2 ] :^的 GPC 圖。 圖12爲硬化性聚矽氧化合物〔CH2 = CHSi03/2〕k〔 PhSi〇3/2) j [ CH2 = CH ( CH3) 2〇u2]爪的 GPC 圖。 圖13爲硬化性聚矽氧化合物〔CH2 = CHSi03/2〕k〔 PhSi03/2〕j〔CH2 = CH(CH3) 20 丨/2〕„!的 W-NMR 圖。 圖 14 爲比較例 1〔 CH3Si03/2〕』〔CH2 = CHSi03/2〕h 的G P C圖。 圖 15 爲比較例 2〔CH2 = CHSi03/2〕g 的 GPC 圖。 -34-Figure 9 is a GPC chart of the curable polyoxynium compound [CH2(O)CHCH20Si03/2]k [CH2 = CHSi03/2] j C CH2 = CH(CH3) 2〇i/2 ] m. Figure 10 is a 1 H - N M R diagram of a hardening polyoxyl compound [ch2 ( o ) CHCH20Si03/2 ) k [ CH2 = CHSi03/2]j [ CH2 = CH ( CH3 ) 20W2 ] m . Figure 11 is a GPC chart of a hydroxy-containing sesquiterpene compound [CH2 = CHSi03/2]k [ PhSiOs/2 ] j C H01/2 ] :^. Figure 12 is a GPC chart of the hardening polyoxo compound [CH2 = CHSi03/2]k[ PhSi〇3/2) j [ CH2 = CH (CH3) 2〇u2]. Figure 13 is a W-NMR chart of a hardening polyfluorinated compound [CH2 = CHSi03/2]k[ PhSi03/2]j[CH2 = CH(CH3) 20 丨/2] „! Figure 14 is a comparative example 1 GPC chart of CH3Si03/2]』[CH2 = CHSi03/2]h Fig. 15 is a GPC chart of Comparative Example 2 [CH2 = CHSi03/2]g. -34-
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