JP7203197B2 - 架橋性オルガノシロキサン組成物 - Google Patents
架橋性オルガノシロキサン組成物 Download PDFInfo
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- JP7203197B2 JP7203197B2 JP2021507970A JP2021507970A JP7203197B2 JP 7203197 B2 JP7203197 B2 JP 7203197B2 JP 2021507970 A JP2021507970 A JP 2021507970A JP 2021507970 A JP2021507970 A JP 2021507970A JP 7203197 B2 JP7203197 B2 JP 7203197B2
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- 239000000203 mixture Substances 0.000 title claims description 69
- 125000005375 organosiloxane group Chemical group 0.000 title description 3
- -1 n-octyl Chemical group 0.000 claims description 59
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 24
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- 238000000034 method Methods 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
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- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
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- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 7
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical group C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
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- 239000000463 material Substances 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 238000007259 addition reaction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- CGNBXJVIEZZNMG-UHFFFAOYSA-N bis(4-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=C(C=C1)[Si](C)(C)C1=CC=C(C=C1)[SiH](C)C CGNBXJVIEZZNMG-UHFFFAOYSA-N 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- RMZSTOAGUSEJFY-UHFFFAOYSA-N methyl-[methyl(phenyl)silyl]oxy-phenylsilane Chemical compound C=1C=CC=CC=1[SiH](C)O[SiH](C)C1=CC=CC=C1 RMZSTOAGUSEJFY-UHFFFAOYSA-N 0.000 description 3
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- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- QRLBICHXRCOJDU-UHFFFAOYSA-N methyl(phenyl)silane Chemical compound C[SiH2]C1=CC=CC=C1 QRLBICHXRCOJDU-UHFFFAOYSA-N 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- UFVCOEBIYOCJCG-UHFFFAOYSA-N methyl-[4-[4-[methyl(phenyl)silyl]phenyl]phenyl]-phenylsilane Chemical group C[SiH](C1=CC=C(C=C1)C1=CC=C(C=C1)[SiH](C1=CC=CC=C1)C)C1=CC=CC=C1 UFVCOEBIYOCJCG-UHFFFAOYSA-N 0.000 description 1
- FSCVJWOCZOPLET-UHFFFAOYSA-N methyl-[4-[methyl(phenyl)silyl]phenyl]-phenylsilane Chemical compound C=1C=C([SiH](C)C=2C=CC=CC=2)C=CC=1[SiH](C)C1=CC=CC=C1 FSCVJWOCZOPLET-UHFFFAOYSA-N 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical class [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- PTUUTGJMRQWABQ-UHFFFAOYSA-N triphenyl(phenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[SiH2]C1=CC=CC=C1 PTUUTGJMRQWABQ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Description
(A)式:[RaR1 bR2 cSiO2/2]m (I)
のシクロシロキサンと、
(B)2個のSi結合水素原子、および少なくとも1個の芳香族基を有する有機ケイ素化合物と、
(C)脂肪族多重結合へのSi結合水素の付加を促進する触媒と
を含むヒドロシリル架橋性組成物を提供する。
R1は、ビニル、ビシクロヘプテニル、3a,4,5,6,7,7a-ヘキサヒドロ-4,7-メタノ-1H-インデニルまたは2-プロペニルを表し、
R2は、フェニル、o-,m-もしくはp-トリルまたはベンジルを表し、
aは、0または1であり、
bは、0または1であり、
cは、0、1または2であり、
mは、3、4または5、好ましくは3または4、特に好ましくは3であり、
ただし、a+b+cは2であり、シロキサン分子(A)当たり少なくとも3個の基R1が存在し、シロキサン分子(A)当たり少なくとも(m-3)個の基R2が存在する。
基R1は、好ましくはビニルである。
基R2は、好ましくはフェニルである。
式:R4 eHfR5 gSiO(4-e-f-g)/2 (II)
の単位を含む有機ケイ素化合物である。
R5は、同一であっても異なっていてもよく、一価または二価の、SiC結合した、必要に応じて置換された脂肪族飽和芳香族炭化水素基を表し、
eは、0、1、2または3、好ましくは0、1または2、特に好ましくは1または2であり、fは、0、1または2、好ましくは1または2であり、gは、0、1または2、好ましくは1または2であり、ただし、e+f+gは4以下であり、分子当たり2個のSi結合水素原子と少なくとも1個の芳香族基とが存在する。
そのような白金触媒(C)の例は、金属状および微細化白金(これらは、二酸化ケイ素、酸化アルミニウムまたは活性炭などの担体上に配置されていてもよい)、白金の化合物または錯体であり、例えば、ハロゲン化白金(例えば、PtCl4、H2PtCl6・6H2O、Na2PtCl4・4H2O)、白金-オレフィン錯体、白金-アルコール錯体、白金-アルコキシド錯体、白金-エーテル錯体、白金-アルデヒド錯体、白金-ケトン錯体(例えばH2PtCl6・6H2Oとシクロヘキサノンとの反応生成物)、白金-ビニルシロキサン錯体(特に、検出可能な量の無機結合ハロゲンを含むかまたは含まない白金-ジビニルテトラメチルジシロキサン錯体)、ビス(γ-ピコリン)白金二塩化物、トリメチレンジピリジン白金二塩化物、ジシクロペンタジエン白金二塩化物、ジメチルスルホキシドエチレン白金(II)二塩化物、ならびに四塩化白金とオレフィンおよび第一級アミンもしくは第二級アミンまたは第一級および第二級アミンとの反応生成物(例えば1-オクテンに溶解した四塩化白金とsec-ブチルアミンとの反応生成物)、または欧州特許第110370号明細書によるアンモニウム-白金錯体、ならびにN-ヘテロ環状カルベン(NHC)との白金錯体、例えば、[1,3-ビス(2,6-ジイソプロピルフェニル)イミダゾール-2-イリデン][1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン]白金(0)(CAS 849830-54-2)、[1,3-ビス(2,6-ジイソプロピルフェニル)イミダゾリジニリデン][1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン]白金(0)(CAS 873311-51-4)、[1,3-ビス(シクロヘキシル)イミダゾール-2-イリデン][1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン]白金(0)(CAS 400758-55-6)、1,3-ビス(2,4,6-トリメチルフェニル)-3,4,5,6-テトラヒドロピリミジン-1-イウム白金(ジビニルテトラメチルジシロキサン)、1,3-ビス(2,6-ジメチルフェニル)-3,4,5,6-テトラヒドロピリミジン-1-イウム白金(ジビニルテトラメチルジシロキサン)および1,3-ビス(2-メチルフェニル)-3,4,5,6-テトラヒドロピリミジン-1-イウム白金(ジビニルテトラメチルジシロキサン)である。
成分(A)、(B)および(C)に加えて、本発明の組成物は、成分(A)、(B)および(C)とは異なるさらなる物質、例えば、抑制剤(D)、添加剤(E)および溶媒(F)、を含んでいてもよい。
(A1)シクロトリシロキサン、
(B)結合剤、
(C)触媒、
必要に応じて(D)抑制剤、
必要に応じて(E)添加剤、および
必要に応じて(F)溶媒
を含む組成物である。
(A1)シクロトリシロキサン、
(B)二価の、SiC結合した、必要に応じて置換された、式(II)の2つの単位を互いに連結する脂肪族飽和芳香族炭化水素基である基R5を少なくとも1個有する結合剤、
(C)触媒、
(D)抑制剤、
必要に応じて(E)添加剤、および
必要に応じて(F)溶媒
を含む組成物である。
(A2)芳香族シクロシロキサン、
(B)結合剤、
(C)触媒、
必要に応じて(D)抑制剤、
必要に応じて(E)さらなる構成要素、および
必要に応じて(F)溶媒
を含む組成物である。
(A2)芳香族シクロシロキサン、
(B)二価の、SiC結合した、必要に応じて置換された、式(II)の2つの単位を互いに連結する脂肪族飽和芳香族炭化水素基である基R5を少なくとも1個有する結合剤、
(C)触媒、
(D)抑制剤、
必要に応じて(E)さらなる構成要素、および
必要に応じて(F)溶媒
を含む組成物である。
本発明の成形品の、23℃で測定される弾性率は、0.70GPaを超えることが望ましく、好ましくは0.80GPaを超え、特に好ましくは1.00GPaを超え、とりわけ好ましくは1.40GPaを超える。
本発明の文脈において、DIN 53019に準拠した動的粘度は、特に明記しない限り、23℃の温度および1013hPaの気圧で測定される。測定は、Anton Paar “Physica MCR 300”回転レオメーターを使用して行う。ここでは、1~200mPa・sの粘度については、1.13mmのリング測定スロットを備える同軸シリンダー測定システム(CC 27)を使用する。一方、200mPa・sを超える粘度については、コーンプレート測定システム(CP 50-1測定コーンを備えるSearle-System)を使用する。せん断速度は、ポリマーの粘度(100s-1で1~99mPa・s;200s-1で100~999mPa・s;120s-1で1000~2999mPa・s;80s-1で3000~4999mPa・s;62s-1で5000~9999mPa・s;50s-1で10,000~12,499mPa・s;38.5s-1で12,500~15,999mPa・s;33s-1で16,000~19,999mPa・s;25s-1で20,000~24,999mPa・s;20s-1で25,000~29,999mPa・s;17s-1で30,000~39,999mPa・s;10s-1で40,000~59,999mPa・s;5s-1で60,000~149,999;3.3s-1で150,000~199,999mPa・s;2.5s-1で200,000~299,999mPa・s;1.5s-1で300,000~1,000,000mPa・s)に合わせて設定している。
DMA、曲げ強度測定および圧縮試験測定を実施するために、シリンダー状加硫物から試験片を作製した。シリンダー状加硫物は、長さ×内径=150mm×10mmの寸法を有するステンレス鋼管(ステンレス鋼製のスクリュートップキャップで一方を密閉した)中で製造した。シクロシロキサン組成物の付着を防ぐために、ポリテトラフルオロエチレン製の底部シールをスクリュートップの内側に配置し;ステンレス鋼管の内面を、シロキサン組成物を充填する前に、適切なサイズの試験管ブラシを使用してWACKER(登録商標)SILICONE PASTE Pでわずかに濡らし、続いて、上記管を180℃で2時間保管した。次に、上記管にシクロシロキサン組成物を充填し、窒素雰囲気中の再循環空気オーブン内で180℃で72時間、次に、250℃でさらに2時間硬化させた。ステンレス鋼管を、開口側が上を向くように直立させた。次に、試験片を脱型する前に、試験片を管内で23℃に冷却した。硬化中に覆われなかった側の試験片の最上部20mmは、それ以上使用せずに廃棄した。
測定パラメータ:
・機器:ARESレオメーター(TA-機器)
・温度範囲:-100℃~300℃
・加熱速度:窒素パージで4K/min
・周波数:1Hz
・ひずみ:最初は0.03%、測定信号がしきい値を下回ると自動的に増加
本発明の文脈において、圧縮特性(降伏応力)は、標準DIN EN ISO 604:2003-12に準拠して実施した。
・機器:Instron 3369 試験システム
・ロードセル:50kN
・圧縮ピストン:50mm
・試験速度:1mm/min
・温度:25℃、28%RH
・初期荷重:40N
・潤滑剤:なし
本発明において、曲げ強度および曲げ弾性率は、ISO 178:2011-04 方法Aに準拠して、60mmの支持距離L、5mm/minの試験速度で測定した。測定は、23℃および相対湿度50%で行った。好ましい手順は次のとおりである:長さ×直径=100mm×9.5mmの寸法を有するシリンダー状試験片を使用した。測定は、それぞれの場合において5つの試験片で実施した。曲げ強度σfM(試験中に試験片が受ける最大曲げ応力(ISO 178:2011-04、6ページ、第3.4章を参照))は、式
本発明の文脈において、数平均分子量Mnおよび重量平均分子量Mwは、それぞれの場合において、g/molの単位であり、DIN 1333:1992-02 セクション4に準拠して最も近い10の位に丸められて、固定相としてポリスチレン-co-ジビニルベンゼンをベースとし、10,000Å、500Åおよび100Åの順序で、排除サイズが450,000g/molを超える、異なる細孔サイズ分布を有する3つのカラムにより構成されるカラムアセンブリのポリスチレン標準に対する較正による、DIN 55672-1/ISO 160414-1およびISO 160414-3に準拠したサイズ排除クロマトグラフィー(SEC/GPC)によって測定される。フェニル含有成分はTHF溶離液で測定され、非フェニル含有成分はトルエン溶離液で測定される。分析は、屈折率検出器を使用して、45±1℃のカラム温度で実施される。
環状混合物1
250mlの乾燥アセトン(≦0.01%水;VWR International GmbH、D-ダルムシュタットから市販)中、52.92g(630mmol)の無水炭酸水素ナトリウム(Sigma-Aldrich Chemie GmbH、D-シュタインハイムから市販)および49.84g(630mmol)の無水ピリジン(Sigma-Aldrich Chemie GmbH、D-シュタインハイムから市販)を、窒素雰囲気下で最初に装入した。次に、190mlの乾燥アセトンに溶解した128.00g(630mmol)のビニルフェニルジクロロシラン(Gelest,Inc.,11 East Steel Rd.,Morrisville,PA 19067から市販)を1時間かけて滴下し、次に混合物を室温で3時間撹拌した。続いて混合物を濾過し、固形残留物を180mlの乾燥アセトンで洗浄した。合わせた濾液から溶媒および揮発性成分を80℃および1mbarで除去し、油性残留物を再度濾過した。29Si NMR分析によれば、(PhViSiO2/2)3 55mol%と(PhViSiO2/2)4 26mol%とを含み、さらに平均組成(PhViSiO2/2)7.5(PhVi(OH)SiO1/2)2を有する線状シロキサン 19mol%を含む無色の油(環状混合物1)88.6gが得られた。
例1に記載の手順を、環状混合物1の代わりに50.0gの1,3,5-トリメチル-1,3,5-トリビニルシクロトリシロキサン(CAS 3901-77-7;abcr GmbH、D-カールスルーエから市販)および59.23gの1,4-ビス(ジメチルシリル)ベンゼンを使用するという変更を加えて繰り返した。測定結果を表1に示す。
例1に記載の手順を、34.4gの1,4-ビス(ジメチルシリル)ベンゼンの代わりに47.76gの4,4’-ビス(ジメチルシリル)ビフェニルを使用するという変更を加えて繰り返した。測定結果を表1に示す。
例1に記載の手順を、環状混合物1の代わりに50.0gの1,3,5,7-トリメチル-1,3,5,7-テトラビニルシクロテトラシロキサン(CAS 2554-06-5;abcr GmbH、D-カールスルーエから市販)および59.23gの1,4-ビス(ジメチルシリル)ベンゼンを使用するという変更を加えて繰り返した。測定結果は表1に示す。
Claims (11)
- (A)式:[RaR1 bR2 cSiO2/2]m (I)
のシクロシロキサンと、
(B)2個のSi結合水素原子、および少なくとも1個の芳香族基を有する有機ケイ素化合物と、
(C)脂肪族多重結合へのSi結合水素の付加を促進する触媒
を含む、ヒドロシリル架橋性組成物。
[上記式中、
Rは、メチル、n-ブチル、tert-ブチル、シクロヘキシル、n-オクチル、2-エチルヘキシル、2,2,4-トリメチルペンチルまたは2,4,4-トリメチルペンチルを表し、
R1は、ビニル、ビシクロヘプテニル、3a,4,5,6,7,7a-ヘキサヒドロ-4,7-メタノ-1H-インデニルまたは2-プロペニルを表し、
R2は、フェニル、o-,m-もしくはp-トリルまたはベンジルを表し、
aは、0または1であり、
bは、0または1であり、
cは、0、1または2であり、
mは、3、4または5であり、
ただし、a+b+cは2であり、シロキサン分子(A)当たり少なくとも3個の基R1が存在し、シロキサン分子(A)当たり少なくとも(m-3)個の基R2が存在する。] - 成分(A)が、mが3であり、a=b=1であり、c=0である式(I)のシクロトリシロキサン(A1)であることを特徴とする、請求項1に記載の組成物。
- 成分(A)が、mが3、4または5である式(I)の芳香族シクロシロキサン(A2)であり、シクロシロキサン分子(A2)当たり、少なくとも3個の基R1が存在し、a=0およびb=c=1である少なくとも1個の単位が存在することを特徴とする、請求項1に記載の組成物。
- 成分(A)が、(Ph(Bch)SiO2/2)4、(Ph(Dcp)SiO2/2)4、(Ph(Bch)SiO2/2)3、(Ph(Dcp)SiO2/2)3、(PhViSiO2/2)3、(PhViSiO2/2)4または(PhViSiO2/2)5であり、前記式中、Meはメチルであり、Viはビニルであり、Bchはビシクロヘプテニルであり、Dcpは3a,4,5,6,7,7a-ヘキサヒドロ-4,7-メタノ-1H-インデニルであり、Phはフェニルあることを特徴とする、請求項3に記載の組成物。
- 結合剤(B)が、
式:R4 eHfR5 gSiO(4-e-f-g)/2 (II)
の単位を含む有機ケイ素化合物であることを特徴とする、請求項1~4の一項以上に記載の組成物。
[上記式中、R4は、同一であっても異なっていてもよく、一価または二価の、SiC結合した、必要に応じて置換された脂肪族飽和炭化水素基を表し、
R5は、同一であっても異なっていてもよく、一価または二価の、SiC結合した、必要に応じて置換された脂肪族飽和芳香族炭化水素基を表し、
eは、0、1、2または3であり、
fは、0、1または2であり、
gは、0、1または2であり、
ただし、e+f+gは4以下であり、分子当たり2個のSi結合水素原子と少なくとも1個の芳香族基とが存在する。] - 触媒(C)が、白金、ならびにその化合物および錯体であることを特徴とする、請求項1~5の一項以上に記載の組成物。
- (A1)シクロトリシロキサン、
(B)結合剤、
(C)触媒、
必要に応じて(E)添加剤、および
必要に応じて(F)溶媒
を含む組成物であることを特徴とする、請求項1または2に記載の組成物。 - (A2)芳香族シクロシロキサン、
(B)結合剤、
(C)触媒、
必要に応じて(E)添加剤、および
必要に応じて(F)溶媒
を含む組成物であることを特徴とする、請求項1または3に記載の組成物。 - 前記個々の成分を混合することにより、請求項1~8の一項以上に記載の組成物を製造する方法。
- 請求項1~8の一項以上に記載の組成物を架橋することによって製造される成形品。
- 23℃で測定される弾性率が0.70GPaを超えることを特徴とする、請求項10に記載の成形品。
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