JPH0259156B2 - - Google Patents
Info
- Publication number
- JPH0259156B2 JPH0259156B2 JP58017409A JP1740983A JPH0259156B2 JP H0259156 B2 JPH0259156 B2 JP H0259156B2 JP 58017409 A JP58017409 A JP 58017409A JP 1740983 A JP1740983 A JP 1740983A JP H0259156 B2 JPH0259156 B2 JP H0259156B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- bis
- general formula
- silylpropyl
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- GMCSUHLZHZOPDY-UHFFFAOYSA-N bis(3-silylpropyl) carbonate Chemical compound C(OCCC[SiH3])(OCCC[SiH3])=O GMCSUHLZHZOPDY-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- -1 silane compound Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 125000003545 alkoxy group Chemical group 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ANXMAYDZRZNTQM-UHFFFAOYSA-N C(C)OC(OCC)[SiH2]CCCOC(OCCC[SiH2]C(OCC)OCC)=O Chemical compound C(C)OC(OCC)[SiH2]CCCOC(OCCC[SiH2]C(OCC)OCC)=O ANXMAYDZRZNTQM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OLBGECWYBGXCNV-UHFFFAOYSA-N 3-trichlorosilylpropanenitrile Chemical compound Cl[Si](Cl)(Cl)CCC#N OLBGECWYBGXCNV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- XJLTZAGUXSAJCZ-UHFFFAOYSA-N methyl 3-trimethoxysilylpropanoate Chemical compound COC(=O)CC[Si](OC)(OC)OC XJLTZAGUXSAJCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Surface Treatment Of Glass (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Description
本発明は一般式
（但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。）で示されるビス
（シリルプロピル）カーボネート及びその製造方
法を提供するものである。
従来、Ａ―Ｂ―SiX3（Ｘはハロゲン原子または
アルコキシ基、Ａは官能基、Ｂは直鎖または分枝
状のアルキレン基などを表わす）で示される官能
性アルキルシラン化合物、例えば３―アミノプロ
ピルトリエトキシシラン、２―シアノエチルトリ
クロロシラン、２―メトキシカルボニルエチルト
リメトキシシランなどは公知な化合物で繊維表面
などへの撥水処理剤、潤滑剤、防錆剤等に使用さ
れることが知られている。
本発明者は長年有用な種々の官能性有機珪素化
合物の合成研究を読けて来たが、新規な化合物で
ある。一般式
（但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。）
で示されるビス（シリルプロピル）カーボネート
を合成し、その構造及び用途を確認して、本発明
を完成し提供するに至つた。
即ち、本発明の新規化合物であるビス（シリル
プロピル）カーボネートは一般式、
（但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。）で示される。
上記式中、Ｒで示されるアルキル基は、メチル
基、エチル基、ｎ―プロピル基などの炭素数１〜
６のアルキル基であり、また、R′Oで示されるア
ルコキシ基はメトキシ基、エトキシ基、ｎ―プロ
ポキシ基、など炭素数が１〜６のアルコキシ基で
ある。
本発明のビス（シリルプロピル）カーボネー
ト、即ち、
は、常温常圧下では無色透明液体状で存在する。
また本発明のビス（シリルプロピル）カーボネー
トは一般に次の(イ)〜(ニ)のような手段で一般式の各
化合物であることを確認することが出来る。
(イ) 赤外線吸収スペクトル（IR）を測定するこ
とにより、1740〜1750cm-1付近にカーボネート
化合物に特有なカルボニル基にもとずく強い吸
収が現われる。なお、単離精製した無色透明液
体である生成物を高温、例えば200℃以上に加
熱した場合、連続的に泡を発生して分解するこ
と、即ち脱炭酸反応を起こすことからも生成物
がカーボネート類に属していることを知ること
ができる。
(ロ) 13炭素核磁気共鳴スペクトル（ 13C−
NMR）を測定することによつて分子中に存在
するメチレン基ならびにカーボネート基、珪素
原子上のアルキル基の種類、さらにアルコキシ
基の種類を知ることが出来る。
即ち、 13C−NMR（テトラメチルシラン基
準）に於いて156ppm付近にカーボネート化合
物に特有なカルボニル基の炭素原子に基づくピ
ーク、70ppm付近にカーボネートの酸素原子に
隣接するメチレン基の炭素原子に基づくピー
ク、23ppm付近にトリメチレン基の中央に位置
するメチレン基の炭素原子に基づくピーク、８
〜15ppm付近に珪素原子に隣接したメチレン基
の炭素原子に基づくピークを示す。なお、それ
ぞれのピーク強度を相対的に比較することによ
り、それぞれの結合基の個数を知ることが出来
る。
(ハ) 質量スペクトル（MS）を測定し、観察され
る各ピーク（一般にはイオンの分子量を電子の
荷電数ｅで割つたｍ／ｅで表わされる質量数）
に相当する組成式を算出することにより、測定
に供した試料の結合様式さらに終局的にはその
分子量を推定することが出来る。さらに極めて
注意深く測定を行なうと、強度的には弱いが対
応する分子量に相当する分子イオンピーク
（M）を観察することができる。
さらに前記一般式においてR′Oがエトキシ
基、Ｒがメチル基である場合、ｍ／e133に極め
て強い
The present invention is based on the general formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) The present invention provides a bis(silylpropyl) carbonate represented by the following formula and a method for producing the same. Conventionally, functional alkylsilane compounds represented by AB-SiX 3 (X is a halogen atom or an alkoxy group, A is a functional group, B is a linear or branched alkylene group, etc.), such as 3-amino Propyltriethoxysilane, 2-cyanoethyltrichlorosilane, 2-methoxycarbonylethyltrimethoxysilane, etc. are well-known compounds that are known to be used as water repellent treatment agents for fiber surfaces, lubricants, rust preventive agents, etc. ing. Although the present inventor has been studying the synthesis of various useful functional organosilicon compounds for many years, this is a new compound. general formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) The present invention was completed by synthesizing bis(silylpropyl) carbonate and confirming its structure and uses. We have come to offer this service. That is, the novel compound of the present invention, bis(silylpropyl) carbonate, has the general formula: (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) In the above formula, the alkyl group represented by R has 1 to 1 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group.
6, and the alkoxy group represented by R'O is an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, or an n-propoxy group. The bis(silylpropyl)carbonate of the present invention, namely: exists as a colorless and transparent liquid at room temperature and pressure.
Further, the bis(silylpropyl) carbonate of the present invention can generally be confirmed to be each compound of the general formula by the following methods (a) to (d). (b) By measuring the infrared absorption spectrum (IR), a strong absorption based on the carbonyl group characteristic of carbonate compounds appears around 1740 to 1750 cm -1 . In addition, when the product, which is an isolated and purified colorless transparent liquid, is heated to a high temperature, for example, 200°C or higher, it continuously generates bubbles and decomposes, that is, a decarboxylation reaction occurs, so the product becomes carbonate. You can know that it belongs to a class. (b) 13 carbon nuclear magnetic resonance spectrum ( 13 C−
By measuring NMR), it is possible to know the types of methylene groups, carbonate groups, alkyl groups on silicon atoms, and alkoxy groups present in the molecule. That is, in 13 C-NMR (tetramethylsilane standard), there is a peak at around 156 ppm based on the carbon atom of the carbonyl group specific to carbonate compounds, and a peak at around 70 ppm based on the carbon atom of the methylene group adjacent to the oxygen atom of the carbonate. , a peak based on the carbon atom of the methylene group located in the center of the trimethylene group around 23 ppm, 8
A peak based on the carbon atom of the methylene group adjacent to the silicon atom is shown around ~15 ppm. Note that the number of each bonding group can be determined by relatively comparing the respective peak intensities. (c) Measure the mass spectrum (MS) and each peak observed (generally the mass number expressed as m/e, which is the molecular weight of the ion divided by the number of electron charges e)
By calculating the compositional formula corresponding to , it is possible to estimate the binding mode and ultimately the molecular weight of the sample subjected to measurement. Furthermore, if measurements are carried out extremely carefully, a molecular ion peak (M) corresponding to the corresponding molecular weight can be observed, although the intensity is weak. Furthermore, when R'O is an ethoxy group and R is a methyl group in the above general formula, it is extremely strong against m/e133.
【式】に相当するピーク、 ｍ／e175にA peak corresponding to [formula], m/e175
【式】に相
当するピークの他に対応する分子量に相当する
ピーク（M）からエタノールが脱離したと考
えられるピーク、即ち、M―46のピークが観
察される。同様にR′Oがメトキシ基でＲがメチ
ル基の場合、ｍ／e105に極めて強い
In addition to the peak corresponding to [Formula], a peak that is considered to be the result of desorption of ethanol from the peak (M) corresponding to the corresponding molecular weight, ie, a peak of M-46, is observed. Similarly, if R′O is a methoxy group and R is a methyl group, it is extremely strong against m/e105.
【式】に相当するピーク、ｍ／e147 にPeak corresponding to [formula], m/e147 to
【式】に相当するピ
ークの他に対応する分子量に相当するピーク
（M）からメタノールが脱離したと考えられ
るピーク、即ち、M―32のピークが観察され
る。同様にＲ，R′が他の組合わせの場合も特
有のピークを観察することが出来る。
(ニ) 元素分析によつて炭素、水素、珪素の各重量
％を求め、さらに認知された各元素の重量％の
和を100から減じることにより、酸素の重量％
を算出することが出来、従つて、該生成物の組
成式を決定することが出来る。
本発明のビス（シリルプロピル）カーボネート
は高沸点を有する無色無臭の透明液体であり、具
体的には後述する実施例に示すが、一般の有機化
合物と同じように分子量が大きくなる程沸点が高
くなる傾向がある。本発明のビス（シリルプロピ
ル）カーボネートはベンゼン、エーテル、ヘキサ
ン、クロロホルム、四塩化炭素、アセトニトリ
ル、Ｎ，Ｎ―ジメチルホルムアミドなど一般の有
機溶媒に良く溶ける。本発明の化合物は、R′Oで
示されるアルコキシ基に対応するアルコールと異
種のアルコールに溶かすと、徐々にではあるが溶
媒となるアルコールの量に応じてアルコキシ基の
一部あるいは条件によつてはアルコキシ基の全て
が溶媒として用いられた異種のアルコキシ基に変
化するのが一般的である。また、前記一般式で示
されるカーボネートを含水溶媒に添加すると発熱
を伴う加水分解反応が起こり、対応するポリシル
セスキオキサン化合物に変化する。この際前記一
般式に於けるR′Oに相当する部分がハロゲン原子
である化合物は、R′Oがアルコキシ基である本発
明の化合物に比べ、加水分解反応の速度が大きい
傾向にある。また、該加水分解は溶媒に水酸化ナ
トリウム、水酸化カリウム、アンモニア等の塩基
類あるいは塩酸、硫酸、酢酸等の酸類を添加する
ことにより大いに促進される。本発明のビス（シ
リルプロピル）カーボネートは無溶媒あるいは不
活性溶媒中で200℃以上に加熱した場合、連続的
に脱炭酸反応を起こす。該脱炭酸反応は加熱温度
が高くなる程、激しくなる傾向にある。なお脱炭
酸反応後の分解物も一般に無色透明の液体であ
る。
本発明のビス（シリルプロピル）カーボネート
の製造方法は特に限定されず如何なる方法によつ
て得てもよい。一般に好適に採用される代表的な
製造方法を以下に説明する。即ち、下記式で示さ
れるジアリルカーボネートと一般式
（但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。）で示されるアル
キルジアルコキシシランとを触媒存在下に反応さ
せることによつて好収率で目的とするビス（シリ
ルプロピル）カーボネートを得ることが出来る。
上記式で示されるジアリルカーボネートは、そ
の製法に限定されず、例えば、公知の製法で得ら
れるものが特に制限されずに使用出来る。またア
ルキルジアルコキシシランは一般式
（但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。）で示される化合
物で、その製法に限定されず使用出来る。また該
反応に用いられる触媒は、いわゆるヒドロシリル
化反応に一般的に用いられる触媒であれば特に限
定されず使用することが出来るが、例えば、塩化
白金酸、塩化白金酸カリウム、白金黒、Pt／Ｃ、
Pt／アルミナ、pt／シリカ、PtCl2（PPh3）2等の
白金化合物；PdCl2、PdCl2（PPh3）2、PdCl2
（C6H5CN）2等のパラジウム化合物；RhCl3、
RhCl（PPh3）3等のロジウム化合物などが好適であ
る。
本発明に於けるジアリルカーボネートとアルキ
ルジアルコキシシランとの反応の代表例は後述す
る実施例で詳述する。上記の反応は一般に無溶媒
に於いても実施することが出来るが、通常、溶媒
の存在下に実施するのが一般的である。溶媒とし
ては、原料或いは触媒と反応しない極性非水溶媒
ならば特に限定されず用いることが出来、一般に
はベンゼン、トルエン、ヘキサン等の炭化水素系
溶媒；クロロホルム、四塩化炭素等のハロゲン化
炭化水素系溶媒；ジメチルエーテル、ジエチルエ
ーテル等のエーテル系溶媒等が好適に使用され
る。
また前記反応条件は特に限定されるものではな
いが、原料の種類、触媒の種類、溶媒の有無又は
種類等によつて異なる場合があるので予め好適な
条件を選定して実施するのが好ましい。一般には
−20〜160℃の温度下に、数10分〜40時間の範囲
で選べば十分である。また反応圧力は大気圧下に
十分に進行するので通常は常圧で実施すればよ
く、必要に応じて加圧下或いは減圧下で実施する
ことも出来る。
また、本発明の化合物は、前記反応式に従いジ
アリルカーボネートとアルコキシシランとを反応
させることによつて得られる他に、次のような方
法によつて得ることも出来る。即ち、一般式
（但し、Ｙはハロゲン原子で、Ｒは炭素数１〜６
のアルキル基である。）で示されるビス（ハロシ
リルプロピル）カーボネートと一般式R′OH（但
し、R′はＲと同種もしくは異種の炭素数１〜６
のアルキル基である。）で示されるアルコールと
を触媒の存在下又は不存在下に反応させることに
よつて得ることが出来る。この場合、一般に上記
一般式中のアルキル基は炭素原子数１〜６の範囲
であれば直状又は分枝状のいずれであつても良
い。また前記反応に於ける触媒は一般に塩基であ
れば特に限定されず使用出来、特にアンモニア、
ジエチルアミン、ｎ―プロピルアミン、イソプロ
ピルアミン、ｎ―ブチルアミン、sec―ブチルア
ミン、イソブチルアミン、ｎ―アミルアミン、イ
ソアミルアミン、トリエチルアミン、ジ―７―ブ
チルアミン等の１〜３級の低級アルキルアミン；
アニリン、ピリジン、Ｎ，Ｎ―ジメチルアニリ
ン、Ｏ―トルイジン、ｍ―トルイジン、ｐ―トル
イジン、ベンジルアミン、α―フエニルエチルア
ミン、β―フエニルエチルアミン等の芳香族アミ
ンなどの含窒素化合物が好適に使用される。
更にまた、前記したように本発明の化合物は、
アルコキシ基が低級になる程高級アルコキシ基に
置換され易い性質を有するので、このような性状
を利用すれば、低級アルコキシ基を含む本発明の
ビス（シリルプロピル）カーボネートを該アルコ
キシ基よりも高級なアルコールと接触させ、置換
反応により生成する低級アルコールを連続的に分
別蒸留等の手段で分離することによつて、目的の
アルコキシ基を含むビス（シリルプロピル）カー
ボネートとすることが出来る。
本発明のビス（シリルプロピル）カーボネート
は、前記一般式から或いは前記性状の説明からも
明らかなように、カーボネート基と両端に珪素を
含む化合物である。該カーボネート基は前記した
ように加熱することによつて炭酸ガスとして離脱
するので、この性状を利用した発泡剤としての用
途がある。また前記した含有珪素に基因し撥水性
の強いものであるので撥水剤としての用途も有す
る。
また、本発明のビス（シリルプロピル）カーボ
ネートは部分的に又は完全に加水分解させること
によつて高密度に架橋した強固な透明被膜とする
ことが出来る。例えば、ガラス、セメント、モル
タル等の無機材料；紙、木材、セルロース、プラ
スチツク等の有機材料について種々の形態の加工
物の表面に塗布した後、加水分解することにより
該加工物表面に透明で強固な被膜を形成すること
ができる。
本発明を更に具体的に説明するために以下実施
例を挙げて説明するが、本発明はこれらの実施例
に限定されるものではない。
実施例 １
ビス（３―ジクロロメチルシリルプロピル）カ
ーボネート（37.2ｇ、0.1モル）、無水ベンゼン
（50ml）の混合物を食塩／氷を用いた寒剤浴で冷
却し、撹拌しながら無水エタノール（70ml）と無
水ベンゼン（70ml）の混合物をゆつくり滴下し
た。滴下終了後も冷却を続けながら２時間撹拌し
た。さらに撹拌下、該冷却溶液に乾燥窒素ガスを
通気して大部分の塩化水素を追い出した後、乾燥
アンモニアガスを、もはや塩化アンモニウムの白
色沈殿が生成しなくなるまで通気した。再び乾燥
窒素ガスを該冷却溶液に通気することにより、過
剰のアンモニアガスを追い出した。生成した塩化
アンモニウムを加圧ろ過により除去し、さらにろ
液中に含まれる低沸点成分を蒸留によつて除いた
後、残渣を真空蒸留することにより沸点154℃／
２mmHgの無色透明液体（35.1ｇ）を得た。赤外
線吸収スペクトルを測定したところ1745cm-1にカ
ーボネート基のカルボニル結合に由来する強い吸
収が認められた。その元素分析値はC48.97％、
H9.57％であつてC17H38O7Si2（410.65）に対する
計算値であるC49.72％、H9.33％に一致した。ま
た質量スペクトルを測定したところｍ／e364に分
子量に相当する分子イオンピーク（Ｍ
）からエ
タノールが脱離したと考えられるピーク、即ちＭ
―46のピークが観察された。またｍ／e175に
（C2H5O）2CH3SiCH2CH2CH2
に対応するピー
ク、ｍ／e133に（C2H5O）2CH3Si
に対応するピ
ークが観察された。さらに 13C−nmrを測定し、
観察された各ピークの化学シフト値を解析した結
果は次の通りであつた。
以上の結果から単離生成物がビス（３―ジエト
キシメチルシリルプロピル）カーボネートである
ことが明らかとなつた。
収率は用いたビス（３―ジクロロメチルシリル
プロピル）カーボネートに対して85.5％であつ
た。
実施例 ２
無水エタノールのかわりに無水メタノールを用
いた以外は実施例１と同様に行なつたところ沸点
128〜131℃／２mmHgの無色透明な液体（31.6ｇ）
を得た。
赤外線吸収スペクトルを測定したところ1745cm
-1にカーボネート基のカルボニル結合に基づく吸
収が認められた。その元素分析値はC44.31％、
H8.54％であつてC13H30O7Si2（354.55）に対する
計算値であるC44.04％、H8.53％によく一致し
た。また質量スペクトルを測定したところ、ｍ／
e322に分子量に相当する分子イオンピーク（Ｍ
）からメタノールが脱離したと考えられるピー
ク、即ちＭ
―32のピークが観察された。また、
ｍ／e147に（CH3O）2CH3SiCH2CH2CH2M
に
対応する強いピーク、ｍ／e105に
（CH3O）2CH3SiM
に対応する強いピークが観察
された。さらに 13C―nmrを測定し観測された各
ピークの化学シフト値を解析した結果は次の通り
であつた。
上記の結果から単離生成物がビス（３―ジメト
キシメチルシリルプロピル）カーボネートである
ことが明らかとなつた。収率は用いたビス（３―
ジクロロメチルシリルプロピル）カーボネートに
対して89.1％であつた。
実施例 ３
ジアリルカーボネート（29.6ｇ、0.2モル）、無
水ベンゼン（120ml）、白金黒（18mg）の混合物に
ジエトキシメチルシラン（33.5ｇ）を滴下しなが
ら、磁気撹拌下に２時間加熱還流した。反応混合
物を加圧ろ過した後、水浴上30〜50℃で低沸点成
分を真空（約２mmHg）留去した後、残渣を２回
真空蒸留することにより沸点154℃／２mmHgの無
色透明な液体（61.5ｇ）を得た。
このものについて種々のスペクトル測定を行な
い、実施例１で別途合成法を記載して得られたビ
ス（３―ジエトキシメチルシリルプロピル）カー
ボネートと同一であることを確認した。収率はジ
アルキルカーボネートに対して81.6％であつた。
実施例 ４
ジエトキシメチルシラン（69.2ｇ）のかわりに
ジメトキシメチルシラン（53.1ｇ）を用いた以外
は実施例３と同様に行なつたところ、沸点129〜
131℃／２mmHgの無色透明な液体（28.4ｇ）を得
た。
このものについて種々のスペクトル測定を行な
い、実施例２で別途合成法を記載して得られたビ
ス（３―ジメトキシメチルシリルプロピル）カー
ボネートと同一であることを確認した。収率はジ
アリルカーボネートに対して80.1％であつた。
参考例
本発明のビス（シリルプロピル）カーボネート
及び公知の各種の珪素含有カーボネート化合物を
それぞれ被膜形成剤として用い、該被膜形成剤の
保存安定性及び得られた被膜の耐擦傷性を評価し
た。
被膜を形成させるプラスチツク成形品として、
市販のポリメチルメタクリレート板状体を用い
た。まず、前処理としてポリメチルメタクリレー
ト板状体をメタノールで洗浄して充分に風乾し、
表面を清浄な状態とした。その後、本発明のビス
（シリルプロピル）カーボネート及び公知の各種
の珪素含有カーボネート合物を用いた下記組成の
被膜形成剤中に上記のポリメチルメタクリレート
板状体を浸漬し、室温で充分風乾した後、80℃で
３時間加熱硬化させて被膜を形成させた。
被膜形成剤は、各成分の合計濃度が加水分解及
び縮合反応後の反応生成物の濃度に換算して30重
量％になるように溶媒のイソプロピルアルコール
に溶解及び分散させ、次いで、アルコキシ基又は
ハロゲン原子の加水分解に必要な量の0.05規定塩
酸を室温で添加して１日放置熱成した後、硬化触
媒として酢酸ナトリウム／酢酸（１／10重量比）
を反応生成物の換算量に対して２重量％加えて調
製した。In addition to the peak corresponding to [Formula], a peak considered to be due to methanol being desorbed from the peak (M) corresponding to the corresponding molecular weight, ie, a peak M-32, is observed. Similarly, unique peaks can be observed when R and R' are used in other combinations. (d) Determine the weight percent of each of carbon, hydrogen, and silicon by elemental analysis, and then subtract the sum of the weight percent of each recognized element from 100 to determine the weight percent of oxygen.
can be calculated, and therefore the compositional formula of the product can be determined. The bis(silylpropyl) carbonate of the present invention is a colorless, odorless, transparent liquid with a high boiling point, and will be specifically shown in the examples below, but as with general organic compounds, the larger the molecular weight, the higher the boiling point. There is a tendency to The bis(silylpropyl) carbonate of the present invention is well soluble in common organic solvents such as benzene, ether, hexane, chloroform, carbon tetrachloride, acetonitrile, and N,N-dimethylformamide. When the compound of the present invention is dissolved in an alcohol different from the alcohol corresponding to the alkoxy group represented by R′O, the alkoxy group gradually dissolves depending on the amount of alcohol serving as a solvent or depending on the conditions. It is common for all of the alkoxy groups to be converted to a different type of alkoxy group used as a solvent. Furthermore, when the carbonate represented by the above general formula is added to a water-containing solvent, an exothermic hydrolysis reaction occurs and the carbonate is converted into the corresponding polysilsesquioxane compound. In this case, compounds in which the moiety corresponding to R'O in the above general formula is a halogen atom tend to have a higher rate of hydrolysis reaction than the compounds of the present invention in which R'O is an alkoxy group. Further, the hydrolysis is greatly promoted by adding bases such as sodium hydroxide, potassium hydroxide, and ammonia, or acids such as hydrochloric acid, sulfuric acid, and acetic acid to the solvent. When the bis(silylpropyl) carbonate of the present invention is heated to 200°C or higher without a solvent or in an inert solvent, a decarboxylation reaction occurs continuously. The decarboxylation reaction tends to become more intense as the heating temperature becomes higher. Note that the decomposed product after the decarboxylation reaction is also generally a colorless and transparent liquid. The method for producing bis(silylpropyl) carbonate of the present invention is not particularly limited and may be obtained by any method. A typical manufacturing method that is generally suitably employed will be described below. That is, diallyl carbonate represented by the following formula and the general formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) By reacting with an alkyldialkoxysilane represented by the following in the presence of a catalyst, the desired target can be obtained in good yield. Bis(silylpropyl) carbonate can be obtained. The diallyl carbonate represented by the above formula is not limited to its production method, and for example, those obtained by known production methods can be used without particular limitation. Also, alkyldialkoxysilane has the general formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) The compound can be used without being limited to its manufacturing method. The catalyst used in the reaction is not particularly limited as long as it is a catalyst commonly used in so-called hydrosilylation reactions, but examples include chloroplatinic acid, potassium chloroplatinate, platinum black, Pt/ C,
Platinum compounds such as Pt/alumina, pt/silica, PtCl 2 (PPh 3 ) 2 ; PdCl 2 , PdCl 2 (PPh 3 ) 2 , PdCl 2
Palladium compounds such as (C 6 H 5 CN) 2 ; RhCl 3 ,
Rhodium compounds such as RhCl(PPh 3 ) 3 are suitable. Representative examples of the reaction between diallyl carbonate and alkyldialkoxysilane in the present invention will be described in detail in the Examples below. Although the above reaction can generally be carried out without a solvent, it is generally carried out in the presence of a solvent. As the solvent, any polar nonaqueous solvent that does not react with the raw materials or the catalyst can be used without particular limitation, and generally hydrocarbon solvents such as benzene, toluene, hexane, etc.; halogenated hydrocarbons such as chloroform, carbon tetrachloride, etc. Ether solvents such as dimethyl ether and diethyl ether are preferably used. Further, the reaction conditions are not particularly limited, but may vary depending on the type of raw material, the type of catalyst, the presence or absence of a solvent, etc., so it is preferable to select suitable conditions in advance and carry out the reaction. Generally, it is sufficient to select a temperature of -20 to 160°C for several tens of minutes to 40 hours. Further, since the reaction pressure proceeds sufficiently under atmospheric pressure, it is usually sufficient to carry out the reaction at normal pressure, but it is also possible to carry out the reaction under increased pressure or reduced pressure if necessary. In addition to being obtained by reacting diallyl carbonate and alkoxysilane according to the above reaction formula, the compound of the present invention can also be obtained by the following method. That is, the general formula (However, Y is a halogen atom, and R has 1 to 6 carbon atoms.
is an alkyl group. ) and the general formula R′OH (where R′ is the same or different type of carbon number 1 to 6)
is an alkyl group. ) in the presence or absence of a catalyst. In this case, generally the alkyl group in the above general formula may be either straight or branched as long as it has 1 to 6 carbon atoms. In addition, the catalyst in the above reaction is generally a base and can be used without particular limitation, especially ammonia,
1-3 lower alkylamines such as diethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, n-amylamine, isoamylamine, triethylamine, di-7-butylamine;
Nitrogen-containing compounds such as aromatic amines such as aniline, pyridine, N,N-dimethylaniline, O-toluidine, m-toluidine, p-toluidine, benzylamine, α-phenylethylamine, and β-phenylethylamine are preferably used. used. Furthermore, as mentioned above, the compound of the present invention is
The lower the alkoxy group is, the more likely it is to be substituted with a higher alkoxy group. Therefore, by utilizing this property, the bis(silylpropyl) carbonate of the present invention containing a lower alkoxy group can be substituted with a higher alkoxy group. The desired bis(silylpropyl) carbonate containing an alkoxy group can be obtained by contacting it with an alcohol and continuously separating the lower alcohol produced by the substitution reaction by means such as fractional distillation. The bis(silylpropyl) carbonate of the present invention is a compound containing a carbonate group and silicon at both ends, as is clear from the general formula or from the description of the properties. Since the carbonate group is released as carbon dioxide gas by heating as described above, this property can be used as a blowing agent. Furthermore, since it has strong water repellency due to the silicon content mentioned above, it can also be used as a water repellent. Further, the bis(silylpropyl) carbonate of the present invention can be partially or completely hydrolyzed to form a strong transparent coating that is highly crosslinked. For example, inorganic materials such as glass, cement, and mortar; and organic materials such as paper, wood, cellulose, and plastics are applied to the surface of various types of workpieces and then hydrolyzed to make them transparent and strong. A coating can be formed. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 A mixture of bis(3-dichloromethylsilylpropyl) carbonate (37.2 g, 0.1 mol) and anhydrous benzene (50 ml) was cooled in a salt/ice cryogen bath and mixed with anhydrous ethanol (70 ml) with stirring. A mixture of anhydrous benzene (70ml) was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred for 2 hours while continuing to cool. With further stirring, dry nitrogen gas was bubbled through the cooled solution to drive out most of the hydrogen chloride, and then dry ammonia gas was bubbled through until no more white precipitate of ammonium chloride formed. Excess ammonia gas was driven off by again bubbling dry nitrogen gas through the cooled solution. After removing the generated ammonium chloride by pressure filtration and further removing low-boiling components contained in the filtrate by distillation, the residue was vacuum distilled to a boiling point of 154℃/
A colorless transparent liquid (35.1 g) with a pressure of 2 mmHg was obtained. When the infrared absorption spectrum was measured, a strong absorption derived from the carbonyl bond of the carbonate group was observed at 1745 cm -1 . Its elemental analysis value is C48.97%,
The H content was 9.57%, which matched the calculated values of C 49.72% and H 9.33% for C 17 H 38 O 7 Si 2 (410.65). In addition, when the mass spectrum was measured, there was a peak at m/e364 that is considered to be the desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, that is, M
-46 peaks were observed. Further, a peak corresponding to (C 2 H 5 O) 2 CH 3 SiCH 2 CH 2 CH 2 was observed at m/e175, and a peak corresponding to (C 2 H 5 O) 2 CH 3 Si was observed at m/e133. Furthermore, 13 C−nmr was measured,
The results of analyzing the chemical shift values of each observed peak were as follows. The above results revealed that the isolated product was bis(3-diethoxymethylsilylpropyl) carbonate. The yield was 85.5% based on the bis(3-dichloromethylsilylpropyl) carbonate used. Example 2 The same procedure as Example 1 was carried out except that anhydrous methanol was used instead of anhydrous ethanol, and the boiling point was
Colorless and transparent liquid (31.6g) at 128-131℃/2mmHg
I got it. The infrared absorption spectrum was measured and it was 1745 cm.
Absorption based on the carbonyl bond of the carbonate group was observed in -1 . Its elemental analysis value is C44.31%,
The H8.54% was in good agreement with the calculated values of C44.04 % and H8.53% for C13H30O7Si2 ( 354.55 ). Also, when we measured the mass spectrum, we found that m/
The molecular ion peak corresponding to the molecular weight (M
), a peak considered to be due to the desorption of methanol, ie, a peak of M-32, was observed. Also,
A strong peak corresponding to (CH 3 O) 2 CH 3 SiCH 2 CH 2 CH 2 M was observed at m/e147, and a strong peak corresponding to (CH 3 O) 2 CH 3 SiM was observed at m/e105. Furthermore, the results of 13 C-nmr measurement and analysis of the chemical shift values of each observed peak were as follows. The above results revealed that the isolated product was bis(3-dimethoxymethylsilylpropyl) carbonate. The yield is the bis(3-
It was 89.1% based on dichloromethylsilylpropyl) carbonate. Example 3 Diethoxymethylsilane (33.5 g) was added dropwise to a mixture of diallyl carbonate (29.6 g, 0.2 mol), anhydrous benzene (120 ml), and platinum black (18 mg) while heating under reflux for 2 hours under magnetic stirring. After filtering the reaction mixture under pressure, low-boiling components were distilled off under vacuum (approximately 2 mmHg) on a water bath at 30-50°C, and the residue was vacuum distilled twice to obtain a colorless transparent liquid with a boiling point of 154°C/2 mmHg ( 61.5g) was obtained. Various spectral measurements were performed on this product, and it was confirmed that it was the same as bis(3-diethoxymethylsilylpropyl) carbonate obtained by separately describing the synthesis method in Example 1. The yield was 81.6% based on dialkyl carbonate. Example 4 The same procedure as Example 3 was performed except that dimethoxymethylsilane (53.1g) was used instead of diethoxymethylsilane (69.2g), and the boiling point was 129~
A colorless and transparent liquid (28.4 g) was obtained at 131° C./2 mmHg. Various spectral measurements were performed on this product, and it was confirmed that it was the same as bis(3-dimethoxymethylsilylpropyl) carbonate obtained by separately describing the synthesis method in Example 2. The yield was 80.1% based on diallyl carbonate. Reference Example The bis(silylpropyl) carbonate of the present invention and various known silicon-containing carbonate compounds were used as film-forming agents, and the storage stability of the film-forming agents and the scratch resistance of the resulting films were evaluated. As a plastic molded product that forms a film,
A commercially available polymethyl methacrylate plate was used. First, as a pretreatment, the polymethyl methacrylate plate was washed with methanol and thoroughly air-dried.
The surface was kept clean. Thereafter, the above-mentioned polymethyl methacrylate plate was immersed in a film forming agent having the following composition using the bis(silylpropyl) carbonate of the present invention and various known silicon-containing carbonate compounds, and was thoroughly air-dried at room temperature. A film was formed by heating and curing at 80°C for 3 hours. The film forming agent is dissolved and dispersed in isopropyl alcohol as a solvent so that the total concentration of each component is 30% by weight in terms of the concentration of the reaction product after hydrolysis and condensation reaction, and then the alkoxy group or halogen Add the amount of 0.05N hydrochloric acid necessary for atomic hydrolysis at room temperature, heat it for one day, and then add sodium acetate/acetic acid (1/10 weight ratio) as a curing catalyst.
was added in an amount of 2% by weight based on the equivalent amount of the reaction product.
【表】
得られた被膜の厚さは、いずれも５〜10μｍで
あつた。
各被膜形成剤から得た被膜の評価結果を第１表
に示した。
尚、被膜の性能評価は下記の方法により実施し
た。
(1) 耐擦傷性試験
福田機械工業(株)製耐擦傷性試験器に、＃0000
のスチールウールを取り付け、１Kg荷重下試験
片表面を10回往復させた後の表面の傷つき程度
を目視により観察し、全く傷つかなかつた状態
をＡ、そしてポリメチルメタリレート生地の非
常に傷つき易い状態をＥとして、Ａ〜Ｅの５段
階にて評価した。
(2) 保存安定性試験
各被膜形成剤を40℃に保つた温水槽に放置
し、下記の基準で評価した。
20日以上粘度変化のないものをＡ、１週間で
ゲル化したものをＢ、３日以内でゲル化したも
のをＣとして３段階にて表示した。[Table] The thickness of the obtained coatings was 5 to 10 μm in all cases. Table 1 shows the evaluation results of the films obtained from each film forming agent. The performance of the coating was evaluated by the following method. (1) Scratch resistance test #0000 in a scratch resistance tester manufactured by Fukuda Machinery Co., Ltd.
After attaching steel wool and reciprocating the surface of the specimen 10 times under a load of 1 kg, the degree of damage to the surface was visually observed. was evaluated in five stages from A to E. (2) Storage stability test Each film-forming agent was left in a hot water tank kept at 40°C and evaluated according to the following criteria. The results were classified into three levels: A for those with no change in viscosity for 20 days or more, B for those that gelled in one week, and C for those that gelled within 3 days.
【表】
但し、No.１〜４は比較参考例である。
[Table] However, Nos. 1 to 4 are comparative reference examples.
Claims (1)
数１〜６のアルキル基である。） で示されるビス（シリルプロピル）カーボネー
ト。 ２ ジアリルカーボネートと一般式 （但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。） で示されるシラン化合物とを触媒の存在下に反応
させることを特徴とする一般式 （但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。） で示されるビス（シリルプロピル）カーボネート
の製造方法。 ３ 一般式 （但し、Ｙはハロゲン原子で、Ｒは炭素数１〜６
のアルキル基である。） で示されるビス（ハロシリルプロピル）カーボネ
ートと一般式 R′OH （但し、R′はＲと同種もしくは異種の炭素数１
〜６のアルキル基である。） で示されるアルコールとを触媒の存在下又は不存
在下に反応させることを特徴とする一般式 （但し、ＲおよびR′は同種もしくは異種の炭素
数１〜６のアルキル基である。） で示されるビス（シリルプロピル）カーボネート
の製造方法。[Claims] 1. General formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) Bis(silylpropyl) carbonate represented by: 2 Diallyl carbonate and general formula (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) A general formula characterized by reacting a silane compound represented by the following in the presence of a catalyst: (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) A method for producing bis(silylpropyl) carbonate represented by: 3 General formula (However, Y is a halogen atom, and R has 1 to 6 carbon atoms.
is an alkyl group. ) Bis(halosilylpropyl) carbonate with the general formula R′OH (where R′ is the same or different type of carbon number 1)
~6 alkyl group. ) is reacted with the alcohol represented by the following in the presence or absence of a catalyst: (However, R and R' are the same or different alkyl groups having 1 to 6 carbon atoms.) A method for producing bis(silylpropyl) carbonate represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58017409A JPS59144791A (en) | 1983-02-07 | 1983-02-07 | Bis(silylpropyl) carbonate and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58017409A JPS59144791A (en) | 1983-02-07 | 1983-02-07 | Bis(silylpropyl) carbonate and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59144791A JPS59144791A (en) | 1984-08-18 |
| JPH0259156B2 true JPH0259156B2 (en) | 1990-12-11 |
Family
ID=11943199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58017409A Granted JPS59144791A (en) | 1983-02-07 | 1983-02-07 | Bis(silylpropyl) carbonate and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59144791A (en) |
-
1983
- 1983-02-07 JP JP58017409A patent/JPS59144791A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| ZH. OBSHCH. KHIM.=1973 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59144791A (en) | 1984-08-18 |
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