JPH01132606A - Production of silyl vinyl ether polymer - Google Patents
Production of silyl vinyl ether polymerInfo
- Publication number
- JPH01132606A JPH01132606A JP28928787A JP28928787A JPH01132606A JP H01132606 A JPH01132606 A JP H01132606A JP 28928787 A JP28928787 A JP 28928787A JP 28928787 A JP28928787 A JP 28928787A JP H01132606 A JPH01132606 A JP H01132606A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl ether
- polymerization
- polymer
- catalyst
- silyl
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- PPJTVWKLYZPWAI-UHFFFAOYSA-N ethenoxysilicon Chemical compound [Si]OC=C PPJTVWKLYZPWAI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- 239000002734 clay mineral Substances 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 239000002904 solvent Substances 0.000 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 7
- 229910052901 montmorillonite Inorganic materials 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 aluminum halides Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229940102001 zinc bromide Drugs 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ALXDDWGEZDTXOE-UHFFFAOYSA-N 1-(dimethoxymethyl)-3-nitrobenzene Chemical compound COC(OC)C1=CC=CC([N+]([O-])=O)=C1 ALXDDWGEZDTXOE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GSZKLTJTSQMAOD-UHFFFAOYSA-N 3-(dimethylamino)propanal Chemical compound CN(C)CCC=O GSZKLTJTSQMAOD-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- ZHBDKVWQJKYIFF-UHFFFAOYSA-M hydron;tetrabutylazanium;difluoride Chemical compound F.[F-].CCCC[N+](CCCC)(CCCC)CCCC ZHBDKVWQJKYIFF-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- BPWYCYDQDGCUEG-UHFFFAOYSA-N tert-butyl-ethenoxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OC=C BPWYCYDQDGCUEG-UHFFFAOYSA-N 0.000 description 1
- IARSSOVWSJAVSZ-UHFFFAOYSA-N tris(dimethylamino)sulfanium Chemical compound CN(C)[S+](N(C)C)N(C)C IARSSOVWSJAVSZ-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、アルデヒドを開始剤とするシリルビニルエー
テル重合体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a silyl vinyl ether polymer using an aldehyde as an initiator.
（従来技術）
従来、アルデヒドを開始剤とするシリルビニルエーテル
重合体の製造方法ついては、米国特許箱４．５４４，７
２４号明ｗＡ書において公知である。(Prior Art) Conventionally, a method for producing a silyl vinyl ether polymer using an aldehyde as an initiator is disclosed in U.S. Pat. No. 4,544,7.
It is publicly known in No. 24 Meiwa book.
この米国特許によれば、触媒としてはビフルオライドイ
オン源となる化合物、例えばカリウムビフルオライド、
テトラブチルアンモニウムビフルオライドもしくはトリ
ス（ジメチルアミノ）スルホニウムビフルオライド、ま
たはルイス酸、例えばヨウ化亜鉛、臭化亜鉛、塩化亜鉛
、三フッ化ホウ素のエーテル付加体もしくはジアルキル
アルミニウムハライドが示され、好ましい触媒としてビ
フルオライドイオン、臭化亜鉛、塩化亜鉛およびヨウ化
亜鉛、特に臭化亜鉛が最も好適であると示されている。According to this US patent, the catalyst may be a compound that serves as a source of bifluoride ions, such as potassium bifluoride,
Tetrabutylammonium bifluoride or tris(dimethylamino)sulfonium bifluoride or Lewis acids such as zinc iodide, zinc bromide, zinc chloride, ether adducts of boron trifluoride or dialkyl aluminum halides are indicated and preferred. Bifluoride ions, zinc bromide, zinc chloride and zinc iodide, especially zinc bromide, have been shown to be most suitable as catalysts.
また、溶媒としてはモノマー、開始剤または開始剤前駆
体及び触媒を十分に分散または溶解させる非プロトン性
の溶媒が好適であることが示され、例えば亜鉛化合物を
触媒として使用するときはトルエン、キシレン等の芳香
族炭化水素、脂肪族炭化水素または塩素化された炭化水
素に限定され、好適な溶媒としてトルエン、ジクロルメ
タン、１．２−ジクロルエタンが挙げられている。In addition, it has been shown that an aprotic solvent that can sufficiently disperse or dissolve the monomer, initiator or initiator precursor, and catalyst is suitable as a solvent. For example, when using a zinc compound as a catalyst, toluene, xylene, etc. It is limited to aromatic hydrocarbons, aliphatic hydrocarbons, or chlorinated hydrocarbons such as, and toluene, dichloromethane, and 1,2-dichloroethane are mentioned as suitable solvents.
さらに、シリルビニルエーテルとしては次式（Ｉ）で示
されるモノマーにおいて、特に各々のＲ基がアルキルで
あり、そして全部のＲ基中の炭素原子の総数が少なくと
も６個であること、および少なくとも１個のＲ基が分枝
鎖状アルキルであることがより好適であると示されてい
る。Furthermore, as a silyl vinyl ether, each R group is an alkyl in a monomer of the following formula (I), and the total number of carbon atoms in all R groups is at least 6, and at least 1 It has been shown that it is more preferred that the R group is a branched alkyl.
ＣＨ２＝ＣＨ−０５ｊ（Ｒ）３ （１）（発明
が解決しようとする問題点）
しかしながら、上記した従来のシリルビニルエーテル重
合体の製造方法においては、触媒としてビフルオライド
イオンまたはルイス酸を用いるため、重合終了後、溶解
している触媒を除去する水洗あるいは再沈殿の操作が必
要である。また、従来法では一般式（１）で示されるモ
ノマーの中で、工業的に量産され安価に入手できるモノ
マーはトリメチルシリルビニルエーテルであるが、この
モノマーでは重合収率が低く且つ分子量の低いポリマー
しか生成しないために、ｔ−ブチルジメチルシリルビニ
ルエーテルの様に分岐アルキル基をもつモノマーを使用
する必要があった。CH2=CH-05j(R)3 (1) (Problems to be Solved by the Invention) However, in the above-described conventional method for producing a silyl vinyl ether polymer, bifluoride ions or Lewis acids are used as catalysts. After completion of polymerization, water washing or reprecipitation operations are required to remove the dissolved catalyst. In addition, among the monomers represented by general formula (1) in the conventional method, trimethylsilyl vinyl ether is an industrially mass-produced and inexpensively available monomer, but this monomer has a low polymerization yield and produces only a low molecular weight polymer. In order to prevent this, it was necessary to use a monomer having a branched alkyl group such as t-butyldimethylsilyl vinyl ether.
（問題点を解決するための手段）
本発明者は、シリルビニルエーテルの重合について鋭意
研究を重ねた結果、触媒として固体酸を用いることによ
り前述の問題点が解決されることを見い出し、本発明を
完成するに至フた。(Means for Solving the Problems) As a result of extensive research into the polymerization of silyl vinyl ether, the present inventor discovered that the above-mentioned problems could be solved by using a solid acid as a catalyst, and developed the present invention. I almost finished it.
即ち、本発明は、アルデヒドを開始剤とするシリルビニ
ルエーテルの重合に際して、触媒として固体酸を用いる
ことを特徴とするシリルビニルエーテルの重合体の製造
方法である。That is, the present invention is a method for producing a silyl vinyl ether polymer, which is characterized in that a solid acid is used as a catalyst during the polymerization of silyl vinyl ether using an aldehyde as an initiator.
本発明において用いられる触媒は、固体酸の機能を有す
るものであれば、公知の触媒が特に限定されない、かか
る固体酸触媒としては粘土鉱物、シリカアルミナ、陽イ
オン交換樹脂、硫酸、リン酸、マロン酸など通常の酸を
シリカゲル、アルミナなどの担体に付着させた固型化酸
、酸化亜鉛、酸化アルミニウム、酸化バナジウム、Ｚｒ
リン酸塩、タングステン酸、ヘテロポリ酸等が挙げられ
る。好適には粘土鉱物が用いられ、例えばモンモリロナ
イト、酸性白土雲母、フッ素四ケイ素雲母、タルク、ゼ
オライト、カオリナイト等が含まれていることが好まし
い。The catalyst used in the present invention is not particularly limited to any known catalyst as long as it has the function of a solid acid.Such solid acid catalysts include clay minerals, silica alumina, cation exchange resins, sulfuric acid, phosphoric acid, and malon. Solidified acids made by adhering ordinary acids such as acids to carriers such as silica gel and alumina, zinc oxide, aluminum oxide, vanadium oxide, and Zr.
Examples include phosphates, tungstic acid, heteropolyacids, and the like. Preferably, clay minerals are used, including montmorillonite, acid white mica, fluorotetrasilicon mica, talc, zeolite, kaolinite, and the like.
本発明において用いられるシリルビニルエーテルは、−
船底（２）
％式％（２）
で示されるモノマーであり、ここでＲ，Ｒ’およびＲ”
は炭素原子数が１〜１０個のアルキル基、アーリル基、
アルカリル基およびアラルキル基からなる群よりそれぞ
れ別個に選ばれる基である。The silyl vinyl ether used in the present invention is -
Bottom (2) is a monomer with the formula % (2) where R, R' and R''
is an alkyl group having 1 to 10 carbon atoms, an aryl group,
They are each independently selected from the group consisting of an alkaryl group and an aralkyl group.
本発明においては、シリルビニルエーテルとして工業的
に量産され安価に入手できるトリメチルシリルビニルエ
ーテルが好適に用いられ、重合収率が高く且つ分子量の
高い重合体を得ることが出来る。In the present invention, trimethylsilyl vinyl ether, which is industrially mass-produced and available at low cost, is preferably used as silyl vinyl ether, and a polymer with a high polymerization yield and high molecular weight can be obtained.
本発明において開始剤として用いられるアルデヒドは、
アルデヒド基を有するものであれば特に限定されず、例
えば脂肪族アルデヒド、芳香族アルデヒド、ポリマーア
ルデヒド等であり、具体的にはアセトアルデヒド、イソ
ブチルアルデヒド、３−（ジメチルアミノ）プロピオン
アルデヒド、３．３’ 、３”−（１，３，５−ベンゼ
ントリイル）トリス（プロピオンアルデヒド）、ベンズ
アルデヒド、テレフタールアルデヒド、又これらの前駆
体（例えばアルデヒドアセタール、オルトエステル等）
、ならびにアクロレインのホモポリマー、コポリマー等
である。The aldehyde used as an initiator in the present invention is
It is not particularly limited as long as it has an aldehyde group, such as aliphatic aldehydes, aromatic aldehydes, polymeric aldehydes, etc. Specifically, acetaldehyde, isobutyraldehyde, 3-(dimethylamino)propionaldehyde, 3.3' , 3”-(1,3,5-benzentriyl)tris(propionaldehyde), benzaldehyde, terephthalaldehyde, and their precursors (e.g. aldehyde acetal, orthoester, etc.)
, as well as homopolymers and copolymers of acrolein.
本発明において用いられる重合方法は、常法の重合方法
が用いられ、無溶媒重合でもよく、溶媒重合であっても
よいが、発熱的である重合中の温度を制御する際には溶
媒重合が有利である。溶媒としては、ジエチルエーテル
、１．２ジメトキシエタン、ニトロアルカン等の非プロ
トン性極性溶媒、トルエン等の芳香族炭化水素、ジクロ
ルメタン等のハロゲン系炭化水素、ヘプタン等の脂肪族
炭化水素が用いられる０重合温度は一１００〜１２０℃
である。開始剤はモノマー／開始剤のモル比が１より大
になる濃度で用いる。開始剤の量は公知の重合方法に従
って、生成物の分子量を制御するために変えることがで
きる。The polymerization method used in the present invention is a conventional polymerization method, and may be non-solvent polymerization or solvent polymerization. However, when controlling the temperature during exothermic polymerization, solvent polymerization is preferred. It's advantageous. As the solvent, aprotic polar solvents such as diethyl ether, 1.2 dimethoxyethane, and nitroalkanes, aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as dichloromethane, and aliphatic hydrocarbons such as heptane are used. Polymerization temperature is -100~120℃
It is. The initiator is used at a concentration such that the monomer/initiator molar ratio is greater than 1. The amount of initiator can be varied according to known polymerization methods to control the molecular weight of the product.
（効果）
以上の説明により理解されるように、アルデヒドを開始
剤とするシリルビニルエーテルの重合に際して、触媒と
して固体酸を用いることを特徴とする本発明によれば、
重合終了後、濾過により簡単に触媒を系外に除去または
回収出来、非常に簡単な操作でポリマーを効率よく得る
ことが出来る。(Effects) As understood from the above explanation, according to the present invention, which is characterized in that a solid acid is used as a catalyst in the polymerization of silyl vinyl ether using an aldehyde as an initiator.
After the polymerization is completed, the catalyst can be easily removed or recovered from the system by filtration, and the polymer can be efficiently obtained with a very simple operation.
また、従来技術では十分に高重合しなかったり、収率の
低かったトリメチルシリルビニルエーテルの重合におい
ても、本発明により高収率で高重合度のポリマーを得る
ことが出来る。また、本発明では、重合終了後、触媒を
除去するための化学的処理を必要としないため、重合生
成物は次式（３）に示すようなポリビニルアルコールの
シリルエーテル体として得られる。Further, even in the case of polymerization of trimethylsilyl vinyl ether, which was not sufficiently polymerized or had a low yield using conventional techniques, the present invention makes it possible to obtain a polymer with a high yield and a high degree of polymerization. Further, in the present invention, since no chemical treatment for removing the catalyst is required after the completion of polymerization, the polymerization product is obtained as a silyl ether of polyvinyl alcohol as shown in the following formula (3).
（ここでＡｒはアリル基、Ｒ，Ｒ’およびＲ”は前記と
同じ）
さらに、本発明の生成したポリマーについて、高分子反
応、加水分解反応等の修飾は、従来公知の方法を限定な
く使用出来る。(Here, Ar is an allyl group, and R, R', and R'' are the same as above.) Furthermore, the polymer produced by the present invention can be modified by polymer reaction, hydrolysis reaction, etc. using conventionally known methods without limitation. I can do it.
（実施例）
以下、具体的に本発明の実施例を示すが、本発明はこれ
らの実施例に限定されるものではない。(Examples) Examples of the present invention will be specifically shown below, but the present invention is not limited to these Examples.
実施例１
アルゴン導入管、撹拌装置および温度計付きの反応容器
に、溶媒としてジクロルメタン３ ｍ 党。Example 1 3 m of dichloromethane was added as a solvent to a reaction vessel equipped with an argon inlet, a stirrer and a thermometer.
開始剤としてベンズアルデヒド０．０２１ ｇ （０゜
２ミリモル）および触媒としてアルミニウム交換モンモ
リロナイト（平均粒径０．４μｍ）５０ｍｇを添加し、
５℃に冷却した０次に、モノマーとしてトリメチルシリ
ルビニルエーテル０．７３ｇ （６゜３ミ１ＪｔＪｌ）
を３分間添加し、５℃で３０分間重合させた。Adding 0.021 g (0.2 mmol) of benzaldehyde as an initiator and 50 mg of aluminum-exchanged montmorillonite (average particle size 0.4 μm) as a catalyst,
After cooling to 5°C, add 0.73 g of trimethylsilyl vinyl ether (6°3 mm 1 JtJl) as a monomer.
was added for 3 minutes and polymerized at 5°C for 30 minutes.
重合終了後、濾過により触媒を除去したのち、溶媒、未
反応モノマーを減圧乾燥により留去し、無色透明の重合
物０．６５ｇ （収率８６％）を得た。このポリマーゲ
ルパーミェーションクロマトグラフィー（以下、ＧＰＣ
と略称する）のより求めた重量平均分子量Ｍｗ＝３２６
２．数平均分子量Ｍｎ＝１７０２、および分子量分布Ｍ
ｎ ／ Ｍ ｎ＝１．９８であった。After the polymerization was completed, the catalyst was removed by filtration, and the solvent and unreacted monomers were distilled off by drying under reduced pressure to obtain 0.65 g (yield: 86%) of a colorless and transparent polymer. This polymer gel permeation chromatography (hereinafter referred to as GPC)
Weight average molecular weight Mw = 326 determined from
2. Number average molecular weight Mn=1702, and molecular weight distribution M
n/M n=1.98.
比較例１
実施例１において、触媒としてアルミニウム交換モンモ
リロナイトのかわりに、臭化亜鉛５６ｍｇ （０，２５
ミリｔｐｋ）を用い、５℃で５時間重合させた。重合終
了後、触媒を除去するために、重曹水を加えて中和後、
ポリマーをエーテルで抽出し、抽出液を２回水洗した後
、乾燥し濃縮することにより、無色透明のポリマ、７０
．１７ｇ（収率２１％））ｉ！得た。このポリマーはＧ
ＰＣより、Ｍｗ＝９９０、Ｍｎ＝７７０．Ｍｗ／Ｍｎ＝
１．２９であった。Comparative Example 1 In Example 1, 56 mg of zinc bromide (0,25
Polymerization was carried out at 5° C. for 5 hours. After the polymerization is completed, in order to remove the catalyst, add sodium bicarbonate solution to neutralize it.
The polymer was extracted with ether, the extract was washed twice with water, dried and concentrated to obtain a colorless and transparent polymer, 70%
．． 17g (21% yield))i! Obtained. This polymer is G
From PC, Mw=990, Mn=770. Mw/Mn=
It was 1.29.
以上の結果より、触媒として固体酸を用いると、トリメ
チルシリルビニルエーテルの重合活性が高いのみならず
、重合物の後工程が簡単であり、本発明の効果が明白で
ある。From the above results, when a solid acid is used as a catalyst, not only the polymerization activity of trimethylsilyl vinyl ether is high, but also the post-process of the polymerization is simple, and the effects of the present invention are obvious.
実施例２
実施例１において、触媒としてアルミニウム交換モンモ
リロナイトのかわりに鉄交換モンモリロナイトを用い、
３０℃で１５分間重合させた。Example 2 In Example 1, iron-exchanged montmorillonite was used instead of aluminum-exchanged montmorillonite as the catalyst,
Polymerization was carried out at 30°C for 15 minutes.
無色透明の重合物０．６２ｇ （収率８３％）を得た。0.62 g (yield: 83%) of a colorless and transparent polymer was obtained.
Ｍｎ＝１０１９．Ｍｗ＝１４９７．Ｍｗ／Ｍｎ＝１．４
７であった。Mn=1019. Mw=1497. Mw/Mn=1.4
It was 7.
実施例３
実施１９１１において触媒としてアルミニウム交換モン
モリロナイトのかわりに、アルミニム交換フッ素四ケイ
素雲母を５０＋ｍｇを用い、開始剤としてＰ−シアノベ
ンズアルデヒド０．０２６ｇ （０゜２ミリモル）を用
い、３０℃で１０分間重合させた。Example 3 In Run 1911, 50+ mg of aluminum-exchanged fluorotetrasilicon mica was used instead of aluminum-exchanged montmorillonite as a catalyst, 0.026 g (0° 2 mmol) of P-cyanobenzaldehyde was used as an initiator, and the reaction was carried out at 30°C for 10 minutes. Polymerized.
無色透明の重合物０．８７ｇ （収率８８％）を得た。0.87 g (yield: 88%) of a colorless and transparent polymer was obtained.
Ｍｎ＝１２２８．Ｍｗ＝１７２１．Ｍｗ／Ｍｎ＝１．４
０であった。Mn=1228. Mw=1721. Mw/Mn=1.4
It was 0.
実施例４
実施例１において触媒としてアルミニウム交換モンモリ
ロナイトのかわりに、アルミニウム交換フッ素四ケイ素
雲母を５０＋＋＋ｇ用い、開始剤としてｍ−ニトロベン
ズアルデヒドジメチルアセタール０．０３４ｇ （０，
２ミリモＩＳ）、触媒としてニトロエタン３ ｍ Ｑを
用い３０℃で１０分間重合させた。Example 4 In Example 1, 50+++ g of aluminum-exchanged fluorotetrasilicon mica was used instead of aluminum-exchanged montmorillonite as a catalyst, and 0.034 g of m-nitrobenzaldehyde dimethyl acetal was used as an initiator.
Polymerization was carried out at 30°C for 10 minutes using 3 mQ of nitroethane as a catalyst.
無色透明の重合物０．５９ｇ （収率７７％）を得た。0.59 g (yield 77%) of a colorless and transparent polymer was obtained.
訂＝１０６７、Ｍ居＝１３７６、ｒｗ／Ｍｎ＝１．２９
であった。Correction=1067, M=1376, rw/Mn=1.29
Met.
実施例５
実施例１において触媒としてアルミニウム交換モンモリ
ロナイトのかわりにカルシウム交換Ｙ型ゼオライトを用
い３０℃で５０時間重合させた。Example 5 In Example 1, calcium-exchanged Y-type zeolite was used instead of aluminum-exchanged montmorillonite as a catalyst, and polymerization was carried out at 30° C. for 50 hours.
無色透明の重合物０．４６ｇ （収率６０％）を得たｅ
Ｍｎ＝７６８．Ｍｗ＝ １１５５．韮／Ｍπ＝１．５
０であった。0.46 g (yield 60%) of a colorless and transparent polymer was obtained.
Mn=768. Mw=1155. Dwarf/Mπ=1.5
It was 0.
実施例６
実施例１において触媒としてアルミニウム交換モンモリ
ロナイトのかわりにシリカ担持ノスーモリブドリン酸（
担持量１０重量％）を用い３０℃で２時間重合させた。Example 6 In Example 1, silica-supported nosomolybdophosphoric acid (
Polymerization was carried out at 30° C. for 2 hours.
無色透明の重合物０．４４ｇ （収率５７％）を得た＠
Ｍｎ＝ １３２５．Ｍｗ＝２４９６．Ｍｗ／Ｍｎ＝１
．８８であった。Obtained 0.44 g (yield 57%) of a colorless and transparent polymer @
Mn=1325. Mw=2496. Mw/Mn=1
．． It was 88.
Claims (1)
重合に際して、触媒として固体酸を用いることを特徴と
するシリルビニルエーテル重合体の製造方法。 ２）固体酸として、粘土鉱物を用いることを特徴とする
特許請求の範囲第１項記載の製造方法。[Claims] 1) A method for producing a silyl vinyl ether polymer, which comprises using a solid acid as a catalyst in the polymerization of silyl vinyl ether using an aldehyde as an initiator. 2) The manufacturing method according to claim 1, characterized in that a clay mineral is used as the solid acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62289287A JPH0733405B2 (en) | 1987-11-18 | 1987-11-18 | Method for producing silyl vinyl ether polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62289287A JPH0733405B2 (en) | 1987-11-18 | 1987-11-18 | Method for producing silyl vinyl ether polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01132606A true JPH01132606A (en) | 1989-05-25 |
| JPH0733405B2 JPH0733405B2 (en) | 1995-04-12 |
Family
ID=17741223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62289287A Expired - Lifetime JPH0733405B2 (en) | 1987-11-18 | 1987-11-18 | Method for producing silyl vinyl ether polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733405B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962470A1 (en) * | 1998-06-01 | 1999-12-08 | Nippon Shokubai Co., Ltd. | Production process for polyvinyl ether and catalyst used for the process |
| EP1593697A1 (en) * | 2003-02-10 | 2005-11-09 | Japan Science and Technology Agency | Polyvinyl ethers having silicon-containing functional groups or atomic groups at the end and process for production thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6123609A (en) * | 1984-06-19 | 1986-02-01 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Silylated vinyl alcohol polymer |
-
1987
- 1987-11-18 JP JP62289287A patent/JPH0733405B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6123609A (en) * | 1984-06-19 | 1986-02-01 | イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− | Silylated vinyl alcohol polymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962470A1 (en) * | 1998-06-01 | 1999-12-08 | Nippon Shokubai Co., Ltd. | Production process for polyvinyl ether and catalyst used for the process |
| US6235859B1 (en) | 1998-06-01 | 2001-05-22 | Nippon Shokubah Co Ltd | Production process for polyvinyl ether and catalyst used for the process |
| EP1593697A1 (en) * | 2003-02-10 | 2005-11-09 | Japan Science and Technology Agency | Polyvinyl ethers having silicon-containing functional groups or atomic groups at the end and process for production thereof |
| EP1593697A4 (en) * | 2003-02-10 | 2006-04-05 | Japan Science & Tech Agency | Polyvinyl ethers having silicon-containing functional groups or atomic groups at the end and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0733405B2 (en) | 1995-04-12 |
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