JPH0531891B2 - - Google Patents
Info
- Publication number
- JPH0531891B2 JPH0531891B2 JP1123446A JP12344689A JPH0531891B2 JP H0531891 B2 JPH0531891 B2 JP H0531891B2 JP 1123446 A JP1123446 A JP 1123446A JP 12344689 A JP12344689 A JP 12344689A JP H0531891 B2 JPH0531891 B2 JP H0531891B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polyorganosilsesquioxane
- solvent
- temperature
- pressure
- 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
- 229920000642 polymer Polymers 0.000 claims description 51
- 239000012530 fluid Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000001569 carbon dioxide Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012691 depolymerization reaction Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- -1 3-cyanopropyl group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Silicon Polymers (AREA)
Description
〔産業上の利用分野〕
本発明は、臨界超過流体又は温度もしくは圧力
のいずれか一方が物質固有の臨界値を超える亜臨
界状態の不活性流体を利用したポリオルガノシル
セスキオキサン重合体の精製方法に関する。
〔従来の技術〕
平均組成式RSiO3/2
（但し、式中Ｒは１価の有機基であり、けい素原
子の数は10〜1000である。）
で示されるポリオルガノシルセスキオキサン重合
体は、一般に耐熱塗料、コーテイング材及びバイ
ンダーフイルム等に使用されているが、近年エレ
クトロニクス用としても注目を集めている。エレ
クトロニクス用としてのポリオルガノシルセスキ
オキサン重合体は、多くの有機溶媒や無機溶媒を
使用して製造され、その製造工程では多くの溶媒
除去工程がある。
従来、かかる溶媒除去方法としては、例えば材
料静置型による熱風加熱方式、材料移送型による
通気バンド乾燥方法並びに真空乾燥及び減圧蒸留
方法等が採用されている。
〔発明が解決しようとする課題〕
しかしながら、ポリオルガノシルセスキオキサ
ン重合体の種類によつては熱安定性が乏しい場合
があり、かかる重合体を上記乾燥・蒸留工程に供
すると、乾燥・蒸留工程時の加熱により解重合反
応が発生し、ポリオルガノシルセスキオキサン重
合体の品質が低下するという問題があつた。
このため、解重合反応の発生を抑制する目的で
製造工程中に含有された溶媒沸点近傍の比較的低
温の条件下における乾燥処理も行なわれている
が、この方法は乾燥時間が非常に長くなるため、
ポリオルガノシルセスキオキサン重合体の量産化
及び製造工程の短縮化の面で大きな障害となつて
いる。
それ故、ポリオルガノシルセスキオキサン重合
体をその構造を壊さず、品質劣化を生じさせずに
短時間で精製し得る方法の開発が望まれる。
本発明は上記事情に鑑みなされたもので、ポリ
オルガノシルセスキオキサン重合体の溶媒除去操
作において、解重合反応を可及的に防止し得ると
共に、短時間で溶媒を除去し得るポリオルガノシ
ルセスキオキサン重合体の精製方法を提供するこ
とを目的とする。
〔課題を解決するための手段及び作用〕
本発明者は上記目的を達成するため鋭意検討を
重ねた結果、平均組成式RSiO3/2（但し、式中Ｒ及
びけい素原子の数は前記に同じ。）で示されるポ
リオルガノシルセスキオキサン重合体、好ましく
は下記一般式(1)
（但し、式中R1とR2は互いに同一又は異種の１
価の有機基であり、ｎは８〜200の整数である。）
で示されるポリオルガノシルセスキオキサン重合
体と無機溶媒及び／又は有機溶媒とが混在する系
に、臨界超過状態又は温度もしくは圧力のいずれ
か一方の物質固有の臨界値を超える亜臨界状態の
担持流体、例えば60℃、200気圧の（臨界超過状
態）の二酸化炭素を接触させ、この担持流体で上
記溶媒を抽出してポリオルガノシルセスキオキサ
ン重合体から分離することにより、常温に近い温
度で溶媒除去操作を行なつても極めて短時間に溶
媒を除去し得、従つて平均組成式RSiO3/2で示さ
れるポリオルガノシルセスキオキサン重合体、特
に上記(1)式で示されるポリオルガノシルセスキオ
キサン重合体が熱安定性に乏しくとも、加熱によ
る解重合反応を可及的に防止できることを知見
し、本発明をなすに至つた。
従つて、本発明は平均組成式RSiO3/2で示され
るポリオルガノシルセスキオキサン重合体及び溶
媒を含有する系に、臨界超過状態又は温度もしく
は圧力のいずれか一方が物質固有の臨界値を超え
る亜臨界状態の担持流体を接触させ、該担持流体
で上記溶媒をポリオルガノシルセスキオキサン重
合体から分離することを特徴とするポリオルガノ
シルセスキオキサン重合体の精製方法を提供す
る。
なお、本発明の精製方法の原理及び理論は公知
であるが（例えば特公昭54−10539号公報）、ポリ
オルガノシルセスキオキサン重合体、特に上記(1)
式で示されるポリオルガノシルセスキオキサンに
応用した場合、上述した効果が得られることは本
発明者による新知見である。
以下、本発明について更に詳しく説明する。
本発明は、上述したようにポリオルガノシルセ
スキオキサン重合体と溶媒とを含む系から臨界超
過状態又は亜臨界状態の担持流体を使用して溶媒
を除去し、ポリオルガノシルセスキオキサン重合
体を精製するものである。
ここで、本発明の方法で精製するポリオルガノ
シルセスキオキサン重合体は平均組成式RSiO3/2
で示される、けい素原子の数が10〜1000であるポ
リオルガノシルセスキオキサン重合体、好ましく
は下記一般式(1)
で示されるポリオルガノシルセスキオキサン重合
体である。上記平均組成式におけるＲ、上記(1)式
におけるR1とR2は１価の有機基であり、このよ
うな基としては例えばメチル基、エチル基、プロ
ピル基、ブチル基、２−エチルブチル基、オクチ
ル基、ラウリル基、ステアリル基などのアルキル
基、ビニル基、アリル基、ヘキセニル基などのア
ルケニル基、フエニル基、ヒドロキシフエニル
基、トリル基、キシリル基、ナフチル基、ジフエ
ニル基などのアリール基、ベンジル基、２−フエ
ニルエチル基などのアラルキル基、シクロペンチ
ル基、シクロヘキシル基などのシクロアルキル基
またはこれらの基の炭素原子に結合した水素原子
の一部又は全部をハロゲン原子、ヒドロキシ基、
シアノ基などで置換したクロロメチル基、トリフ
ルオロプロピル基、２−シアノエチル基、３−シ
アノプロピル基、３−メチル−４−ヒドロキシベ
ンジル基などから選択される基、あるいは、エポ
キシ基、アミノ基、メタクリロキシ基、カルボキ
シル基、ポリオキシアルキレン基、メルカプト
基、ヒドロキシ基などを有する１価の基などが挙
げられる。なお、上記式(1)におけるｎは重合度を
示し、これは８〜200の整数である。
また、上記ポリオルガノシルセスキオキサン重
合体を含み、該重合体から除去する溶媒は、ポリ
オルガノシルセスキオキサン重合体の製造工程で
使用した溶媒あるいは副生した溶媒であり、これ
は無機及び／又は有機溶媒である。なお、ポリオ
ルガノシルセスキオキサン重合体の溶媒中での濃
度は特に制限されないが、効率上ポリオルガノシ
ルセスキオキサン重合体の濃度が60重量％以上の
ものが好ましい。
本発明で使用する担持流体としては、臨界温度
が常温近傍に有することが好ましく、このような
物質としては、例えば二酸化炭素（CO2）（臨界
圧力73気圧、臨界温度31.3℃）、亜酸化窒素
（N2O）（臨界圧力71.7気圧、臨界温度36.5℃）、
エタン（C2H6）（臨界圧力48.3気圧、臨界温度
32.4℃）やエチレン（CH2＝CH2）（臨界圧力50
気圧、臨界温度9.2℃）等の低級炭化水素などが
挙げられる。
本発明では上記流体を温度及び圧力の両方を臨
界値以上にした臨界超過状態、又は温度もしくは
圧力のいずれか一方を物質固有の臨界値を超える
亜臨界状態に調整するが、上記物質のパラメータ
ーは広く知られており、加熱、加圧等により調整
することができる。
本発明は、上記臨界超過状態又は亜臨界状態と
した担持流体を上記ポリオルガノシルセスキオキ
サン重合体及び溶媒を含有する系に接触させて、
該担持流体で該溶媒を分離除去するものである
が、この分離（抽出）操作は、例えば、予め一つ
の抽出槽に担持流体とポリオルガノシルセスキオ
キサン重合体溶液を仕込み、攪拌下で接触させる
方法、ポリオルガノシルセスキオキサン重合体溶
液を仕込んだ抽出槽の下方より担持流体をバブリ
ング方式により供給する方法、ポリオルガノシル
セスキオキサン重合体溶液を抽出槽上方より連続
的に流し込みつつ、下方より担持流体を連続的に
供給する方法等を採用できる。ここで担持流体を
連続的に供給する場合は、予め担持流体を臨界超
過状態又は温度あるいは圧力のどちらか一方が物
質固有の臨界値を超える亜臨界状態に調整するこ
とが好ましい。
抽出条件は担持流体の種類によつても異なる
が、圧力は約50〜約500気圧、より好ましくは約
50〜約300気圧の範囲が通常である。圧力を高く
すると単位時間当りの抽出量は増加するものの、
ポリオルガノシルセスキオキサン重合体の一部も
担持流体に伴つて抽出され、収率が低下するの
で、約300気圧より低い圧力とすることが好まし
い。また、温度は約０℃〜約100℃の範囲で行な
うことができるが、温度を高くすると単位時間当
りの抽出量が低下する。従つて、抽出量の低下を
防止し、かつポリオルガノシルセスキオキサン重
合体の解重合反応を抑制するため、担持流体の臨
界温度近傍、例えば50℃以下とすることが好まし
い。上記条件で抽出する場合、担持流体の圧力、
温度を選定したり、担持流体の供給量を選定する
ことにより抽出速度を制御することができる。
なお、抽出操作後、溶媒を含んだ担持流体を抽
出槽と連結した少なくとも一つの分離槽に移し、
担持流体から溶媒を分離回収することができる。
この場合、圧力を低下させるか又は温度を上昇
させることにより、あるいはこれら両操作を行な
うことにより、担持流体の溶解度を低下させて溶
媒を分離回収することができる。分離回収した溶
媒は、再びポリオルガノシルセスキオキサン重合
体の製造工程で使用することが可能であり、従つ
て高価な溶媒を多量に使用するポリオルガノシル
セスキオキサン重合体の製造において、本発明の
精製方法は極めて経済的に有利である。一方、担
持流体も再びガス又は液体状で回収できるため、
多量の担持流体を循環使用することができる。
発明の効果
以上説明したように、本発明は、上記(1)式で示
されるポリオルガノシルセスキオキサン重合体及
び溶媒を含有する系に、臨界超過状態又は温度も
しくは圧力のどちらか一方が物質固有の臨界値を
超える亜臨界状態の担持流体を接触させ、該担持
流体で上記溶媒をポリオルガノシルセスキオキサ
ン重合体から分離するようにしたので、精製操作
を常温近傍で行なうことができ、ポリオルガノシ
ルセスキオキサン重合体の解重合反応を可及的に
防止して、ポリオルガノシルセスキオキサン重合
体の品質低下を防止できると共に、精製時間も従
来より大幅に短縮でき、ポリオルガノシルセスキ
オキサン重合体の量産化及び製造工程を短縮化す
ることができるものである。
以下、実施例と比較例を示し、本発明を具体的
に説明するが、本発明は下記実施例に制限される
ものではない。なお、以下の例で％は重量％を示
す。
実施例 １
上記(1)式においてR1及びR2がメチル基で分子
量3100のポリオルガノシルセスキオキサン重合体
を含む溶液（溶媒：テトラヒドロフラン（THF）
約18％、水約18％；合計36〜40％）500ｇを容積
４の高圧槽容器に仕込み、温度45℃とした後、
圧力200気圧、温度60℃の臨界超過状態の二酸化
炭素を高圧槽下部からバブリング方式により連続
的に流し込み、45℃の一定温度で抽出を行なうと
共に、高圧層上方の流体出口からTHFと水を含
む二酸化炭素を抜き出して低圧分離槽（圧力60気
圧、温度60℃）に導き、該槽内でTHFと水を二
酸化炭素から分離し、二酸化炭素を再び高圧槽下
部に戻して循環使用した。
この抽出操作を設定圧力の二酸化炭素が高圧槽
に入り、溶媒を抽出した後、低圧分離槽に入つた
時点から５時間（抽出時間）行なつた。
次に、上記抽出後のポリオルガノシルセスキオ
キサン重合体中に残存するTHFと水の量を分析
した。
結果を第１表に示す。
実施例 ２〜４
二酸化炭素の圧力を250気圧、300気圧及び350
気圧にした以外は同一抽出温度で実施例１と同様
に抽出を行ない、ポリオルガノシルセスキオキサ
ン重合体中に残存するTHFと水の量を分析した。
その結果を第１表に併記する。
実施例 ５、６
二酸化炭素の圧力を300気圧にし、抽出温度を
60℃及び35℃にした以外は実施例１と同様に抽出
を行ない、ポリオルガノシルセスキオキサン重合
体中に残存するTHFと水の量を分析した。その
結果を第２表に示す。
[Industrial Application Field] The present invention relates to the purification of polyorganosilsesquioxane polymers using a supercritical fluid or an inert fluid in a subcritical state in which either the temperature or the pressure exceeds the critical value inherent to the substance. Regarding the method. [Prior art] Polyorganosilsesquioxane polymers having the average compositional formula RSiO 3/2 (wherein R is a monovalent organic group and the number of silicon atoms is 10 to 1000) Coalescence is generally used in heat-resistant paints, coating materials, binder films, etc., but in recent years it has also attracted attention for use in electronics. Polyorganosilsesquioxane polymers for electronics are manufactured using many organic and inorganic solvents, and the manufacturing process involves many solvent removal steps. Conventionally, such solvent removal methods include, for example, a hot air heating method using a material-stationary type, an aeration band drying method using a material-transfer type, and vacuum drying and reduced-pressure distillation methods. [Problems to be Solved by the Invention] However, depending on the type of polyorganosilsesquioxane polymer, thermal stability may be poor, and when such a polymer is subjected to the above drying/distillation process, the drying/distillation process There was a problem in that a depolymerization reaction occurred due to heating during the process and the quality of the polyorganosilsesquioxane polymer deteriorated. For this reason, in order to suppress the occurrence of depolymerization reactions, drying treatment is carried out under relatively low temperature conditions near the boiling point of the solvent contained in the manufacturing process, but this method requires a very long drying time. For,
This is a major obstacle in the mass production of polyorganosilsesquioxane polymers and in shortening the manufacturing process. Therefore, it is desired to develop a method that can purify a polyorganosilsesquioxane polymer in a short time without destroying its structure or causing quality deterioration. The present invention has been made in view of the above circumstances, and is a polyorganosil sesquioxane polymer that can prevent the depolymerization reaction as much as possible and remove the solvent in a short time in the solvent removal operation of polyorganosilsesquioxane polymers. An object of the present invention is to provide a method for purifying sesquioxane polymers. [Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the present inventor found that the average composition formula RSiO 3/2 (wherein R and the number of silicon atoms in the formula are as described above) ), preferably a polyorganosilsesquioxane polymer represented by the following general formula (1) (However, in the formula, R 1 and R 2 are the same or different ones.
It is a valent organic group, and n is an integer of 8 to 200. ) In a system in which the polyorganosilsesquioxane polymer shown in By contacting a carrier fluid, e.g. carbon dioxide at 60°C and 200 atmospheres (supercritical state), and extracting the solvent with this carrier fluid to separate it from the polyorganosilsesquioxane polymer, the temperature near room temperature can be achieved. The solvent can be removed in a very short time even if the solvent is removed using The present inventors have discovered that even though organosilsesquioxane polymers have poor thermal stability, depolymerization reactions caused by heating can be prevented as much as possible, leading to the present invention. Therefore, the present invention provides a system containing a polyorganosilsesquioxane polymer having the average composition formula RSiO 3/2 and a solvent in which either the supercritical state or the temperature or pressure has a critical value inherent to the substance. A method for purifying a polyorganosilsesquioxane polymer is provided, which comprises bringing into contact a carrier fluid in a super-subcritical state and separating the solvent from the polyorganosilsesquioxane polymer with the carrier fluid. Although the principle and theory of the purification method of the present invention are known (for example, Japanese Patent Publication No. 10539/1983), it is important to note that the principles and theories of the purification method of the present invention are well known (for example, Japanese Patent Publication No. 10539/1983).
It is a new finding by the present inventors that when applied to the polyorganosilsesquioxane represented by the formula, the above-mentioned effects can be obtained. The present invention will be explained in more detail below. As described above, the present invention removes the solvent from a system containing a polyorganosilsesquioxane polymer and a solvent using a carrier fluid in a supercritical state or a subcritical state, and produces a polyorganosilsesquioxane polymer. It purifies. Here, the polyorganosilsesquioxane polymer purified by the method of the present invention has an average compositional formula of RSiO 3/2
A polyorganosilsesquioxane polymer having 10 to 1000 silicon atoms, preferably represented by the following general formula (1) It is a polyorganosilsesquioxane polymer shown by R in the above average compositional formula and R 1 and R 2 in the above formula (1) are monovalent organic groups, such as methyl group, ethyl group, propyl group, butyl group, 2-ethylbutyl group. , alkyl groups such as octyl, lauryl, and stearyl; alkenyl groups such as vinyl, allyl, and hexenyl; aryl groups such as phenyl, hydroxyphenyl, tolyl, xylyl, naphthyl, and diphenyl; , benzyl group, aralkyl group such as 2-phenylethyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, or some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atom, hydroxy group,
A group selected from a chloromethyl group, trifluoropropyl group, 2-cyanoethyl group, 3-cyanopropyl group, 3-methyl-4-hydroxybenzyl group substituted with a cyano group, or an epoxy group, an amino group, Examples include monovalent groups having a methacryloxy group, a carboxyl group, a polyoxyalkylene group, a mercapto group, a hydroxy group, and the like. Note that n in the above formula (1) indicates the degree of polymerization, which is an integer from 8 to 200. In addition, the solvent that contains the above-mentioned polyorganosilsesquioxane polymer and is removed from the polymer is a solvent used in the manufacturing process of the polyorganosilsesquioxane polymer or a by-produced solvent, which is an inorganic and /or an organic solvent. The concentration of the polyorganosilsesquioxane polymer in the solvent is not particularly limited, but in terms of efficiency, it is preferable that the concentration of the polyorganosilsesquioxane polymer is 60% by weight or more. The carrier fluid used in the present invention preferably has a critical temperature near normal temperature, and examples of such substances include carbon dioxide (CO 2 ) (critical pressure 73 atm, critical temperature 31.3°C), nitrous oxide, etc. (N 2 O) (critical pressure 71.7 atm, critical temperature 36.5°C),
Ethane (C 2 H 6 ) (critical pressure 48.3 atm, critical temperature
32.4℃) and ethylene (CH 2 = CH 2 ) (critical pressure 50
Examples include lower hydrocarbons such as atmospheric pressure and critical temperature of 9.2℃). In the present invention, the above-mentioned fluid is adjusted to a supercritical state in which both the temperature and pressure are above a critical value, or to a subcritical state in which either the temperature or the pressure exceeds the critical value inherent to the substance, but the parameters of the above-mentioned substance are It is widely known and can be adjusted by heating, pressurizing, etc. The present invention provides a method of contacting the carrier fluid in a supercritical or subcritical state with a system containing the polyorganosilsesquioxane polymer and a solvent,
The solvent is separated and removed using the carrier fluid, and in this separation (extraction) operation, for example, the carrier fluid and the polyorganosilsesquioxane polymer solution are charged in advance into one extraction tank, and brought into contact with each other under stirring. A method in which a supporting fluid is supplied from below an extraction tank containing a polyorganosilsesquioxane polymer solution by a bubbling method, a method in which a polyorganosilsesquioxane polymer solution is continuously poured from above an extraction tank, A method of continuously supplying the carrier fluid from below can be adopted. When the carrier fluid is continuously supplied here, it is preferable to adjust the carrier fluid in advance to a supercritical state or a subcritical state in which either the temperature or the pressure exceeds a critical value specific to the substance. Extraction conditions vary depending on the type of carrier fluid, but the pressure is about 50 to about 500 atmospheres, more preferably about
A range of 50 to about 300 atmospheres is normal. Although increasing the pressure increases the extraction amount per unit time,
Pressures below about 300 atmospheres are preferred because some of the polyorganosilsesquioxane polymer is also extracted with the carrier fluid, reducing yield. Further, the temperature can be in the range of about 0°C to about 100°C, but if the temperature is increased, the amount of extraction per unit time will decrease. Therefore, in order to prevent a decrease in the extraction amount and to suppress the depolymerization reaction of the polyorganosilsesquioxane polymer, it is preferable to maintain the temperature near the critical temperature of the supporting fluid, for example, 50° C. or lower. When extracting under the above conditions, the pressure of the supporting fluid,
The rate of extraction can be controlled by selecting the temperature and the amount of support fluid supplied. After the extraction operation, the carrier fluid containing the solvent is transferred to at least one separation tank connected to the extraction tank,
The solvent can be separated and recovered from the carrier fluid. In this case, the solubility of the carrier fluid can be lowered and the solvent can be separated and recovered by lowering the pressure or increasing the temperature, or by performing both of these operations. The separated and recovered solvent can be used again in the production process of polyorganosilsesquioxane polymers. The purification method of the invention is extremely economically advantageous. On the other hand, since the supported fluid can be recovered in gas or liquid form,
Large amounts of carrier fluid can be recycled. Effects of the Invention As explained above, the present invention provides a system containing a polyorganosilsesquioxane polymer represented by the above formula (1) and a solvent in a supercritical state or in a state where either the temperature or the pressure is Since the solvent is separated from the polyorganosilsesquioxane polymer by contacting with a carrier fluid in a subcritical state exceeding the inherent critical value, the purification operation can be performed at around room temperature, By preventing the depolymerization reaction of the polyorganosilsesquioxane polymer as much as possible, it is possible to prevent the deterioration of the quality of the polyorganosilsesquioxane polymer, and the purification time can be significantly shortened compared to conventional methods. This makes it possible to mass produce sesquioxane polymers and shorten the manufacturing process. EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples, % indicates weight %. Example 1 A solution containing a polyorganosilsesquioxane polymer with a molecular weight of 3100 in which R 1 and R 2 are methyl groups in the above formula (1) (solvent: tetrahydrofuran (THF))
(approximately 18%, water approximately 18%; total 36-40%) was placed in a high-pressure tank with a volume of 4, and the temperature was set to 45℃.
Carbon dioxide in a supercritical state at a pressure of 200 atm and a temperature of 60°C is continuously flowed from the bottom of the high-pressure tank using a bubbling method, and extraction is performed at a constant temperature of 45°C, while THF and water are added from the fluid outlet above the high-pressure layer. Carbon dioxide was extracted and led to a low-pressure separation tank (pressure: 60 atm, temperature: 60°C), where THF and water were separated from the carbon dioxide, and the carbon dioxide was returned to the lower part of the high-pressure tank for circulation. This extraction operation was carried out for 5 hours (extraction time) from the time when carbon dioxide at a set pressure entered the high-pressure tank, extracted the solvent, and then entered the low-pressure separation tank. Next, the amounts of THF and water remaining in the polyorganosilsesquioxane polymer after the above extraction were analyzed. The results are shown in Table 1. Examples 2 to 4 The pressure of carbon dioxide was set to 250 atm, 300 atm, and 350 atm.
Extraction was carried out in the same manner as in Example 1 at the same extraction temperature except that the atmospheric pressure was used, and the amounts of THF and water remaining in the polyorganosilsesquioxane polymer were analyzed.
The results are also listed in Table 1. Examples 5 and 6 The pressure of carbon dioxide was set to 300 atm, and the extraction temperature was set to 300 atm.
Extraction was carried out in the same manner as in Example 1 except that the temperature was 60°C and 35°C, and the amounts of THF and water remaining in the polyorganosilsesquioxane polymer were analyzed. The results are shown in Table 2.
【表】【table】
【表】
実施例 ７〜９
実施例１と同じポリオルガノシルセスキオキサ
ン重合体を含む溶液（溶媒：THF約40％、水約
35％；合計75〜80％）を用い、二酸化炭素の圧力
を120気圧、200気圧、250気圧とした以外は実施
例１と同一抽出温度で同様に抽出を行ない、ポリ
オルガノシルセスキオキサン重合体中に残存する
THFと水の量を分析した。その結果を第３表に
示す。[Table] Examples 7 to 9 A solution containing the same polyorganosilsesquioxane polymer as in Example 1 (solvent: about 40% THF, about 40% water)
Extraction was carried out in the same manner as in Example 1 at the same extraction temperature except that the carbon dioxide pressure was changed to 120 atm, 200 atm, and 250 atm. remain during merging
The amounts of THF and water were analyzed. The results are shown in Table 3.
【表】
比較例 １、２
実施例１と同じポリオルガノシルセスキオキサ
ン重合体を含む溶液（溶媒：テトラヒドロフラン
約18％、水約18％；合計約40％）1000ｇを0.125
m3の恒温槽に仕込み、10mmHg（0.013気圧）で120
℃及び180℃の温度において真空乾燥処理を行な
い、上記圧力、温度に達した時点から５時間〜50
時間の上記溶液の重量減少を測定した。その結果
を第４表に示す。なお、上記実施例３、４の操作
について行なつた重量減少の結果を第４表に併記
する。[Table] Comparative Examples 1 and 2 A solution containing the same polyorganosilsesquioxane polymer as in Example 1 (solvent: about 18% tetrahydrofuran, about 18% water; total about 40%) 1000g was mixed with 0.125%
Pour into a constant temperature bath of 120 m3 at 10 mmHg (0.013 atm).
℃ and 180℃ for 5 hours to 50 minutes after reaching the above pressure and temperature.
The weight loss of the above solution over time was measured. The results are shown in Table 4. The results of the weight reduction performed in the operations of Examples 3 and 4 are also listed in Table 4.
【表】
第１表〜第４表の結果から、本発明の精製方法
は常温に近い温度で行なつているにもかかわら
ず、抽出速度が高いことが認められる。[Table] From the results in Tables 1 to 4, it can be seen that the extraction rate is high even though the purification method of the present invention is carried out at a temperature close to room temperature.
Claims (1)
子の数は10〜1000である。） で示されるポリオルガノシルセスキオキサン重合
体及び溶媒を含有する系に、臨界超過状態又は温
度もしくは圧力のいずれか一方が物質固有の臨界
値を超える亜臨界状態の担持流体を接触させ、該
担持流体で上記溶媒をポリオルガノシルセスキオ
キサン重合体から分離することを特徴とするポリ
オルガノシルセスキオキサン重合体の精製方法。 ２ ポリオルガノシルセスキオキサン重合体が下
記一般式(1) （但し、式中R1とR2は互いに同一又は異種の１
価の有機基であり、ｎは８〜200の整数である。） で示される請求項１記載のポリオルガノシルセス
キオキサン重合体の精製方法。[Claims] 1. A polyorganosilsesquioxide represented by the average composition formula RSiO 3/2 (wherein R is a monovalent organic group and the number of silicon atoms is 10 to 1000) A system containing a Sun polymer and a solvent is brought into contact with a carrier fluid in a supercritical state or in a subcritical state in which either the temperature or the pressure exceeds the critical value inherent to the substance, and the solvent is transferred to the polyorganosil by using the carrier fluid. A method for purifying a polyorganosilsesquioxane polymer, the method comprising separating it from a sesquioxane polymer. 2 The polyorganosilsesquioxane polymer has the following general formula (1) (However, in the formula, R 1 and R 2 are the same or different ones.
It is a valent organic group, and n is an integer of 8 to 200. ) A method for purifying a polyorganosilsesquioxane polymer according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1123446A JPH02302437A (en) | 1989-05-17 | 1989-05-17 | Method for purifying polyorganosilsesquioxane polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1123446A JPH02302437A (en) | 1989-05-17 | 1989-05-17 | Method for purifying polyorganosilsesquioxane polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02302437A JPH02302437A (en) | 1990-12-14 |
| JPH0531891B2 true JPH0531891B2 (en) | 1993-05-13 |
Family
ID=14860810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1123446A Granted JPH02302437A (en) | 1989-05-17 | 1989-05-17 | Method for purifying polyorganosilsesquioxane polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02302437A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051682A (en) * | 1996-12-23 | 2000-04-18 | E. I. Du Pont De Nemours And Company | Polymerization of fluoropolymers in carbon dioxide |
| US20030181749A1 (en) * | 2002-03-21 | 2003-09-25 | Kunzler Jay F. | Supercritical fluid extraction of vitreoretinal silicone tamponades |
| KR101501015B1 (en) * | 2012-12-13 | 2015-03-10 | 한국생산기술연구원 | A fabrication method of polysilsequioxane using carbon dioxide as solvent and polysilsequioxane prepared by the same. |
-
1989
- 1989-05-17 JP JP1123446A patent/JPH02302437A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02302437A (en) | 1990-12-14 |
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