JPS6129611B2 - - Google Patents
Info
- Publication number
- JPS6129611B2 JPS6129611B2 JP58066892A JP6689283A JPS6129611B2 JP S6129611 B2 JPS6129611 B2 JP S6129611B2 JP 58066892 A JP58066892 A JP 58066892A JP 6689283 A JP6689283 A JP 6689283A JP S6129611 B2 JPS6129611 B2 JP S6129611B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- phenyl group
- molecular weight
- represent
- containing polysiloxane
- 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
Links
- -1 polysiloxane Polymers 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000007265 chloromethylation reaction Methods 0.000 description 5
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JZMYRQHKOYJYQO-UHFFFAOYSA-N methanol;1,2-xylene Chemical group OC.CC1=CC=CC=C1C JZMYRQHKOYJYQO-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Description
〔産業上の利用分野〕
本発明は、電子線、軟Ｘ線等の高エネルギ線用
レジスト材料、電気絶縁材料、保護材等の電子部
品材料として、また撥水剤等の表面処理剤とし
て、あるいは、イオン交換膜等の機能膜の基材と
して使用可能な高分子量のベンゼン環含有ポリシ
ロキサン及びその製造方法に関する。
〔従来技術〕
ポリシロキサンは有機ポリマーに比べ、優れた
耐熱性、耐寒性を示し、電気特性が広い温度範囲
で安定であること、等から機能膜材料、電気・電
子材料として多くの用途が開けつつある。特に、
フエニル基含有ポリシロキサンはガラス転移温度
が高いため強く固い膜が得られることが考えら
れ、その使用範囲が大幅に伸びることが期待され
る。しかしながら、フエニル基含有ポリシロキサ
ンの高分子量のものを得ることは従来の製造法で
は困難である。すなわち、従来のポリシロキサン
の製造法は、クロロシランを加水分解して環状シ
リコーンオリゴマーをを作り、更に酸又はアルカ
リ触媒の存在下で重合するものである。ポリジメ
チルシロキサンでは50万以上の分子量のものも得
られているがフエニル基含有シロキサン、特にジ
フエニルシロキサンでは1000〜1400程度の低分子
量ポリマーしか得られず、またオリゴマーとの分
離も困難である。そのため、均一で使用可能な高
分子膜を得ることができないなどポリマーとして
の特徴を充分に生かせない欠点があつた。
また、従来のポリシロキサンでは適当な反応基
を分子内にもつていないので、高機能性を発現さ
せるための官能基の導入はほとんどなされていな
かつた。
〔発明の目的〕
本発明は、これらの欠点を解決するためになさ
れたものであつて、その目的は高分子量でかつ反
応性が高く、多様な誘導体の合成が可能なクロロ
メチル基をもつベンゼン環含有ポリシロキサン及
びその製造方法を提供することにある。
〔発明の構成〕
すなわち、本発明を概説すれば、本発明の第１
の発明はベンゼン環含有ポリシロキサンの発明で
あつて、下記一般式：
（式中Ｒ，R′及びR″は、同一又は異なり、水
素、アルキル基及びフエニル基よりなる群から選
択した１種の基を示し、ｌ，ｍ及びｎは、０又は
正の整数を示し、ｌとｍが同時に０になることは
ない）で表わされる繰返し単位を含有することを
特徴とする。
そして、本発明の第２の発明は、上記一般式
で表わされる繰返し単位を含有するベンゼン環含
有ポリシロキサンの製造方法の発明であつて、フ
エニル基含有シロキサンオリゴマーあるいは低分
子量のフエニル基含有ポリシロキサンに、フリー
デルクラフツ型触媒の存在下、クロロメチル低級
アルキルエーテルを反応させることを特徴とす
る。
上記製造方法において原料として使われるの
は、フエニル基含有環状シリコーンオリゴマー、
例えばヘキサフエニルシクロトリンシロキサン、
オクタフエニルシクロテトラシロキサンを、酸又
はアルカリで重合した低分子量ポリフエニル基含
有シロキサンが挙げられる。その他、ポリジフエ
ニルシロキサン、ポリジメチルジフエニルシロキ
サン等のフエニル基含有シロキサンオリゴマーも
使用可能である。また、触媒のフリーデルクラフ
ツ型触媒としては、塩化アルミニウム、塩化第二
鉄、三フツ化ホウ素、塩化亜鉛、塩化第二スズ、
四塩化チタン等の一般のフリーデルクラフツ反応
の触媒として用いられているものが挙げられる。
また、クロロメチル低級アルキルエーテルとして
はクロロメチルメチルエーテル、クロロメチルエ
チルエーテル等が挙げられる。
製造は原料のフエニル基含有シロキサンオリゴ
マーあるいは低分子量フエニル基含有ポリシロキ
サンを、クロロメチル低級アルキルエーテルに溶
解し、フリーデルクラフツ型触媒を加えて、反応
温度−10℃〜室温で反応させることにより行う。
前記反応は四塩化炭素、トリクロロエタン等の溶
媒中で行うこともできる。
反応は、30分から30時間で終了し、メタノール
で沈殿させ、ケトンーアルコール系で再沈殿を繰
返すことにより精製する。本発明で得られるベン
ゼン環含有ポリシロキサンの分子量は、一万〜
100万であり、原料濃度、触媒濃度、反応濃度、
反応時間によつて制御することができる。
高分子量化の原因は次のＡの４点が考えられ
る。すなわち、(1)クロロメチル化の進行により、
クロロメチル基が未置換のフエニル核と、分子間
的な反応で架橋が起る。(2)末端に残つているOH
基とクロロメチル基の反応によつて分子間架橋が
起る。(3)末端にあるOH基同士のフリーデルクラ
フツ触媒による脱水縮合、(4)末端にあるOH基と
フエニル基との間のフリーデルクラフツ触媒によ
る架橋である。
本発明のベンゼン環含有ポリシロキサンは高い
ガラス転移温度をもち均一なフイルムを形成する
ことができる。また、電子線等の高エネルギ線に
対して高い感応性を示すクロロメチル基を含み四
塩化炭素、四フツ化炭素のガスプラズマに対して
耐性のあるベンゼン環をもちまた、酸素ガスプラ
ズマに対して高い耐性をもつシロキサン構造とな
つているため高エネルギ線用レジスト材料として
使用できる。また、高分子量ベンゼン環含有シロ
キサンは水に全く不溶性でありガラスや陶磁器な
どの基材にシリコーン処理して基材に撥水性を付
与することができる。
また、本発明において製造される高分子量ベン
ゼン環含有ポリシロキサンはクロロメチル基を含
むため、多様な誘導体の合成が可能であり、例え
ばアミノ化処理により陰イオン交換膜が得られ
る。また種類の官能基を導入することにより高機
能性膜として使用可能である。
〔実施例〕
次に本発明を実施例により説明するが、本発明
はこれらに限定されるものではない。
実施例 １
オクタフエニルシクロテトラシロキサン50ｇと
テトラヒドロフラン100ml、水酸化カリウム250mg
をガラス管に入れ、脱気封管し、重合温度70℃で
24時間反応させた。内容物を水―メタノール
（１：４）溶液に注ぎこみ白色の重合体を得た。
重合体は数回メタノール―キシレン系で再沈殿す
ることにより精製した。得られたポリジフエニル
シロキサンは重量平均分子量＝1.3×103、分
散度／＝2.6、ガラス転移温度150℃であつ
た。
次に、上記で得たポリジフエニルシロキサン20
ｇをクロロメチルメチルエーテル500mlに溶か
し、塩化第二スズ20mlを触媒として、−50℃で10
時間反応させた。反応液をメタノール中に注ぎこ
み白色固体のポリマーを得た。第１図はこのポリ
マーの赤外線吸収スペクトルのグラフである。第
１図において、横軸は波数（cm-1）又は波長（μ
ｍ）を縦軸は透過度を表わす。第１図にみられる
ように800cm-1にジ置換フエニルに帰属される吸
収が、また2200cm-1にクロロメチル基のメチレン
基に帰属される吸収がみられクロロメチル化され
たことが確認できた。元素分析からこのポリマー
のクロロメチル化率は20％またゲルパーミエーシ
ヨンクロマトグラフイーから計算した重量平均分
子量＝1.2×104、分散度／＝1.8であり
約10倍の分子量増加がみられた。
実施例 ２
実施例１で得たポリジフエニルシロキサン25ｇ
をクロロメチルメチルエーテル500mlに溶かし塩
化第二スズ25mlを触媒として−50℃で12時間反応
させた。反応液をメタノール中に注ぎこみ白色固
体のポリマーを得た。元素分析からこのポリマー
のクロロメチル化率は17％またゲルパーミエーシ
ヨンクロマトグラフイーから計算した重量平均分
子量＝4.7×104、／＝3.5であり約40倍
の分子量増加がみられた。
実施例 ３
実施例１において、オクタフエニルシクロテト
ラシロキサンの代りに、テトラフエニルテトラメ
チルシクロテトラシロキサンとオクタフエニルシ
クロテトラシロキサンの混合物を混合比をかえて
ポリマーを合成し、また実施例２の条件でクロロ
メチル化を行つた。表１にフエニル基含有量とガ
ラス転移温度、分子量を示す。
[Industrial Field of Application] The present invention can be used as a resist material for high-energy rays such as electron beams and soft X-rays, as an electronic component material such as an electrical insulating material and a protective material, and as a surface treatment agent such as a water repellent. Alternatively, the present invention relates to a high molecular weight benzene ring-containing polysiloxane that can be used as a base material for functional membranes such as ion exchange membranes, and a method for producing the same. [Prior art] Compared to organic polymers, polysiloxane has excellent heat resistance and cold resistance, and its electrical properties are stable over a wide temperature range, so it has many applications as a functional film material and an electrical/electronic material. It's coming. especially,
Since phenyl group-containing polysiloxane has a high glass transition temperature, it is thought that strong and hard films can be obtained, and the range of its use is expected to expand significantly. However, it is difficult to obtain a high molecular weight phenyl group-containing polysiloxane using conventional production methods. That is, the conventional method for producing polysiloxane is to hydrolyze chlorosilane to produce a cyclic silicone oligomer, which is then polymerized in the presence of an acid or alkali catalyst. Polydimethylsiloxanes with molecular weights of 500,000 or more have been obtained, but phenyl group-containing siloxanes, especially diphenylsiloxanes, can only yield low molecular weight polymers of about 1,000 to 1,400, and separation from oligomers is also difficult. As a result, there were drawbacks such as the inability to obtain a uniform and usable polymer membrane, which prevented the polymer from taking full advantage of its characteristics. Furthermore, since conventional polysiloxanes do not have suitable reactive groups in their molecules, there has been little introduction of functional groups to develop high functionality. [Object of the Invention] The present invention was made to solve these drawbacks, and its purpose is to develop benzene with a chloromethyl group that has a high molecular weight, high reactivity, and allows synthesis of various derivatives. An object of the present invention is to provide a ring-containing polysiloxane and a method for producing the same. [Structure of the Invention] That is, if the present invention is summarized, the first aspect of the present invention is as follows.
The invention is an invention of a benzene ring-containing polysiloxane, which has the following general formula: (In the formula, R, R' and R'' are the same or different and represent one type of group selected from the group consisting of hydrogen, an alkyl group and a phenyl group, and l, m and n represent 0 or a positive integer. , l and m are never 0 at the same time).The second invention of the present invention is a benzene containing a repeating unit represented by the above general formula. An invention of a method for producing a ring-containing polysiloxane, characterized in that a phenyl group-containing siloxane oligomer or a low molecular weight phenyl group-containing polysiloxane is reacted with chloromethyl lower alkyl ether in the presence of a Friedel-Crafts type catalyst. In the above manufacturing method, the raw materials used are phenyl group-containing cyclic silicone oligomers,
For example, hexaphenylcyclothrine siloxane,
Examples include low molecular weight polyphenyl group-containing siloxanes obtained by polymerizing octaphenylcyclotetrasiloxane with acid or alkali. In addition, phenyl group-containing siloxane oligomers such as polydiphenylsiloxane and polydimethyldiphenylsiloxane can also be used. In addition, Friedel-Crafts type catalysts include aluminum chloride, ferric chloride, boron trifluoride, zinc chloride, tin chloride,
Examples include those commonly used as catalysts for Friedel-Crafts reactions, such as titanium tetrachloride.
Further, examples of the chloromethyl lower alkyl ether include chloromethyl methyl ether and chloromethyl ethyl ether. Production is performed by dissolving the raw material phenyl group-containing siloxane oligomer or low molecular weight phenyl group-containing polysiloxane in chloromethyl lower alkyl ether, adding a Friedel-Crafts type catalyst, and reacting at a reaction temperature of -10°C to room temperature. .
The reaction can also be carried out in a solvent such as carbon tetrachloride or trichloroethane. The reaction is completed in 30 minutes to 30 hours, and the product is purified by repeating precipitation with methanol and reprecipitation with a ketone-alcohol system. The molecular weight of the benzene ring-containing polysiloxane obtained in the present invention is from 10,000 to
1 million, and the raw material concentration, catalyst concentration, reaction concentration,
It can be controlled by the reaction time. The following four points A are considered to be the cause of the increase in molecular weight. That is, (1) due to the progress of chloromethylation,
Crosslinking occurs through an intermolecular reaction between the chloromethyl group and the unsubstituted phenyl nucleus. (2) OH remaining at the end
Intermolecular crosslinking occurs due to the reaction between the group and the chloromethyl group. (3) Dehydration condensation between the OH groups at the ends using a Friedel-Crafts catalyst, and (4) crosslinking between the OH groups at the ends and the phenyl group using a Friedel-Crafts catalyst. The benzene ring-containing polysiloxane of the present invention has a high glass transition temperature and can form a uniform film. In addition, it contains a chloromethyl group that is highly sensitive to high-energy beams such as electron beams, and has a benzene ring that is resistant to carbon tetrachloride and carbon tetrafluoride gas plasmas. Because it has a siloxane structure with high resistance, it can be used as a resist material for high-energy beams. Further, high molecular weight benzene ring-containing siloxane is completely insoluble in water, and can be applied to base materials such as glass and ceramics by silicone treatment to impart water repellency to the base materials. Further, since the high molecular weight benzene ring-containing polysiloxane produced in the present invention contains a chloromethyl group, it is possible to synthesize various derivatives, and for example, an anion exchange membrane can be obtained by amination treatment. Furthermore, by introducing various types of functional groups, it can be used as a highly functional membrane. [Example] Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Example 1 50g of octaphenylcyclotetrasiloxane, 100ml of tetrahydrofuran, 250mg of potassium hydroxide
was placed in a glass tube, degassed and sealed, and polymerized at a polymerization temperature of 70℃.
The reaction was allowed to proceed for 24 hours. The contents were poured into a water-methanol (1:4) solution to obtain a white polymer.
The polymer was purified by reprecipitation several times with a methanol-xylene system. The obtained polydiphenylsiloxane had a weight average molecular weight of 1.3×10 3 , a degree of dispersion of 2.6, and a glass transition temperature of 150°C. Next, the polydiphenylsiloxane 20 obtained above
Dissolve g in 500 ml of chloromethyl methyl ether, use 20 ml of stannic chloride as a catalyst, and heat at -50°C for 10 min.
Allowed time to react. The reaction solution was poured into methanol to obtain a white solid polymer. FIG. 1 is a graph of the infrared absorption spectrum of this polymer. In Figure 1, the horizontal axis is the wave number (cm -1 ) or the wavelength (μ
m), the vertical axis represents the transmittance. As seen in Figure 1, an absorption attributed to di-substituted phenyl was observed at 800 cm -1 and an absorption attributed to the methylene group of the chloromethyl group was observed at 2200 cm -1 , confirming that chloromethylation occurred. Ta. Elemental analysis showed that the chloromethylation rate of this polymer was 20%, and weight average molecular weight calculated from gel permeation chromatography was 1.2×10 4 and dispersity/=1.8, indicating an approximately 10-fold increase in molecular weight. . Example 2 25g of polydiphenylsiloxane obtained in Example 1
was dissolved in 500 ml of chloromethyl methyl ether and reacted for 12 hours at -50°C using 25 ml of stannic chloride as a catalyst. The reaction solution was poured into methanol to obtain a white solid polymer. Elemental analysis showed that the chloromethylation rate of this polymer was 17%, and weight average molecular weight calculated from gel permeation chromatography was 4.7×10 4 , /=3.5, indicating an approximately 40-fold increase in molecular weight. Example 3 In Example 1, a mixture of tetraphenyltetramethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane was used instead of octaphenylcyclotetrasiloxane in a different mixing ratio to synthesize a polymer. Chloromethylation was performed under the following conditions. Table 1 shows the phenyl group content, glass transition temperature, and molecular weight.
【表】
応用例 １〜２
実施例１，２で得たクロロメチル化ポリジフエ
ニルシロキサンをメチルイソブチルケトンに溶解
し、シリコンウエハに約0.5μｍの厚さに塗布し
100℃で20分間窒素気流中プリベークした。プリ
ベーク後、加速電圧20KVの電子線照射を行つ
た。照射後ウエハをメチルエチルケトン：イソプ
ロピルアルコール＝４：１の混合溶媒で現象し、
イソプロピルアルコールでリンスした。この時初
期膜厚の50％が残る電子線照射量を表２に示し
た。それぞれ実用上十分利用な感度でありまた１
μｍ以下の高い解像性を示した。[Table] Application examples 1 to 2 The chloromethylated polydiphenylsiloxane obtained in Examples 1 and 2 was dissolved in methyl isobutyl ketone and coated on a silicon wafer to a thickness of about 0.5 μm.
Prebaking was performed at 100°C for 20 minutes in a nitrogen stream. After prebaking, electron beam irradiation was performed at an accelerating voltage of 20 KV. After irradiation, the wafer was treated with a mixed solvent of methyl ethyl ketone: isopropyl alcohol = 4:1,
Rinse with isopropyl alcohol. Table 2 shows the electron beam irradiation amount at which 50% of the initial film thickness remained. Each has a sensitivity that is sufficient for practical use, and 1
It showed high resolution of less than μm.
【表】
また表３にクロロメチル化ポリジフエニルシロ
キサンのO2，CF4，CCl4，CCl2F2を用いた反応
性イオンエツチングした際のエツチング速度を示
す。シロキサン構造、フエニル基をもつため高い
耐性をもつことが理解される。[Table] Table 3 also shows the etching rate of chloromethylated polydiphenylsiloxane when reactive ion etching was performed using O 2 , CF 4 , CCl 4 , and CCl 2 F 2 . It is understood that it has high resistance due to its siloxane structure and phenyl group.
以上説明したように、本発明の高分子量ベンゼ
ン環含有ポリシロキサンを使用することにより、
耐熱性、耐候性に優れた均一なフイルムを得るこ
とができる。また本発明の製造法では高分子量化
と同時に高い反応性をもち多様な誘導体の合成が
可能なクロロメチル基の導入がなされるので、高
エネルギ線用レジスト材料、あるいはイオン交換
膜等の機能膜の基材として使用できる利点があ
る。
As explained above, by using the high molecular weight benzene ring-containing polysiloxane of the present invention,
A uniform film with excellent heat resistance and weather resistance can be obtained. In addition, in the production method of the present invention, a chloromethyl group that has high reactivity and can be synthesized into various derivatives is introduced at the same time as high molecular weight, so it can be used as a resist material for high energy beams or as a functional membrane such as an ion exchange membrane. It has the advantage that it can be used as a base material.
第１図は本発明の実施例１で得られた化合物の
赤外線吸収スペクトルのグラフである。
FIG. 1 is a graph of the infrared absorption spectrum of the compound obtained in Example 1 of the present invention.
Claims (1)
素、アルキル基及びフエニル基よりなる群から選
択した１種の基を示し、ｌ，ｍ及びｎは、０又は
正の整数を示し、ｌとｍが同時に０になることは
ない）で表わされる繰返し単位を含有することを
特徴とするベンゼン環含有ポリシロキサン。 ２ 下記一般式： （式中Ｒ，R′及びR″は、同一又は異なり、水
素、アルキル基及びフエニル基よりなる群から選
択した１種の基を示し、ｌ，ｍ及びｎは、０又は
正の整数を示し、ｌとｍが同時に０になることは
ない）で表わされる繰返し単位を含有するベンゼ
ン環含有ポリシロキサンを製造する方法におい
て、フエニル基含有シロキサンオリゴマーあるい
は低分子量のフエニル基含有ポリシロキサンに、
フリーデルクラフツ型触媒の存在下、クロロメチ
ル低級アルキルエーテルを反応させることを特徴
とする上記ベンゼン環含有ポリシロキサンの製造
方法。[Claims] 1. The following general formula: (In the formula, R, R' and R'' are the same or different and represent one type of group selected from the group consisting of hydrogen, an alkyl group and a phenyl group, and l, m and n represent 0 or a positive integer. A benzene ring-containing polysiloxane characterized by containing a repeating unit represented by the following formula (1 and m are not 0 at the same time). 2 The following general formula: (In the formula, R, R' and R'' are the same or different and represent one type of group selected from the group consisting of hydrogen, an alkyl group and a phenyl group, and l, m and n represent 0 or a positive integer. , l and m are never 0 at the same time), in which a phenyl group-containing siloxane oligomer or a low molecular weight phenyl group-containing polysiloxane,
The method for producing the benzene ring-containing polysiloxane described above, which comprises reacting chloromethyl lower alkyl ether in the presence of a Friedel-Crafts type catalyst.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066892A JPS59193925A (en) | 1983-04-18 | 1983-04-18 | Polysiloxane containing benzene ring and its preparation |
| US06/580,468 US4507384A (en) | 1983-04-18 | 1984-02-15 | Pattern forming material and method for forming pattern therewith |
| EP84101686A EP0122398B1 (en) | 1983-04-18 | 1984-02-17 | Pattern forming material and method for forming pattern therewith |
| DE8484101686T DE3480735D1 (en) | 1983-04-18 | 1984-02-17 | IMAGE GENERATING MATERIAL AND METHOD FOR PRODUCING IMAGES. |
| US06/680,739 US4564579A (en) | 1983-04-18 | 1984-12-12 | Pattern forming material of a siloxane polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066892A JPS59193925A (en) | 1983-04-18 | 1983-04-18 | Polysiloxane containing benzene ring and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193925A JPS59193925A (en) | 1984-11-02 |
| JPS6129611B2 true JPS6129611B2 (en) | 1986-07-08 |
Family
ID=13329016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58066892A Granted JPS59193925A (en) | 1983-04-18 | 1983-04-18 | Polysiloxane containing benzene ring and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59193925A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6222853A (en) * | 1985-07-22 | 1987-01-31 | Osaka Soda Co Ltd | Rubber composition having excellent ultra-low-temperature properties and oil resistance |
| JP6367635B2 (en) * | 2014-07-24 | 2018-08-01 | 国立研究開発法人物質・材料研究機構 | Anion exchange membrane material and anion exchange membrane |
-
1983
- 1983-04-18 JP JP58066892A patent/JPS59193925A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59193925A (en) | 1984-11-02 |
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