JPH0356535A - Production of oxazoline polymer/silica composite molded article - Google Patents
Production of oxazoline polymer/silica composite molded articleInfo
- Publication number
- JPH0356535A JPH0356535A JP19044689A JP19044689A JPH0356535A JP H0356535 A JPH0356535 A JP H0356535A JP 19044689 A JP19044689 A JP 19044689A JP 19044689 A JP19044689 A JP 19044689A JP H0356535 A JPH0356535 A JP H0356535A
- Authority
- JP
- Japan
- Prior art keywords
- oxazoline polymer
- silica
- polymer
- oxazoline
- molded article
- 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 58
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 101
- 239000000377 silicon dioxide Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 10
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims abstract description 3
- 238000001879 gelation Methods 0.000 claims description 11
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 29
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 6
- -1 triethoxysilyl group Chemical group 0.000 description 24
- 239000002994 raw material Substances 0.000 description 22
- 229920000765 poly(2-oxazolines) Polymers 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 8
- 239000012456 homogeneous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VERUITIRUQLVOC-UHFFFAOYSA-N 2-butyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCC1=NCCO1 VERUITIRUQLVOC-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、オキサゾリンポリマー／シリカ複合成形体の
製造方法に関し、さらに詳しくは、繊維状，膜状の如き
各種形態のシリカ成形体を円滑有利に製造することがで
きる特定のゾルーゲル法を用いた新規な方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing an oxazoline polymer/silica composite molded product, and more specifically, it relates to a method for producing a silica molded product in various forms such as fibrous and film shapes. This invention relates to a novel method using a specific sol-gel method, which can be produced in the following manner.
［従来の技術］
従来より、多孔質シリカの製造方法としては種々の方法
が提案されている。その一つは、シリカ粉体を仮焼し熱
分解せしめて粒子または粒子間に気孔を形成させた後、
焼結する方法である。この方法では、孔径の揃った多孔
質シリカを製造することが困難であり、また繊維状，膜
状の如き各種用途に応じた形態に成形することが難しい
。他の方法として、アルコキシシランを原料としたゾル
ーゲル法が多孔質シリカの製造方法として提案されてい
る．このゾルーゲル法による場合には、得られる多孔質
シリカの細孔径は通常極めて小さく、またこの細孔径を
大きくしようとすると、細孔径分布が広くなるという難
点が認められる。[Prior Art] Conventionally, various methods have been proposed as methods for producing porous silica. One method is to calcinate and thermally decompose silica powder to form particles or pores between the particles.
This is a method of sintering. With this method, it is difficult to produce porous silica with uniform pore diameters, and it is also difficult to form it into forms suitable for various uses, such as fibrous or membrane forms. As another method, a sol-gel method using alkoxysilane as a raw material has been proposed as a method for producing porous silica. When this sol-gel method is used, the pore size of the porous silica obtained is usually extremely small, and if the pore size is increased, the pore size distribution becomes wider.
［発明が解決しようとする課題］
本発明の目的は、上記従来技術の難点を解消し、細孔径
及びその分布のコントロールが容易にできるとともに、
各種用途に応じた適宜の形態にすることができる多孔質
シリカの製造技術を新規に提供することにある．
（課題を解決するための手段】
本発明者の研究によれば、ゾルーゲル法の場合には、例
えば有機ボリマーを用いて上記の目的が達成されるが、
用いる有機ボリマーによっては特に均一分散性不良に基
く次のような難点が残ってしまう。例えば、有機ボリマ
ー溶液中でアルコキシシランの加水分解重合反応を行な
い、反応溶液系をゲル化せしめた後、生成した多孔質ゲ
ル中の有機ボリマーを除去し、その後に焼成するなどの
方法により、細孔径及びその分布を容易にコントロール
し得るのであるが、ゲル化工程で相分離を伴うため、均
一分散性が損なわれるとともに、適宜形態への賦形性に
も難点が残る。[Problems to be Solved by the Invention] The purpose of the present invention is to solve the problems of the above-mentioned conventional techniques, to easily control the pore diameter and its distribution, and to
The purpose of this project is to provide a new manufacturing technology for porous silica that can be formed into appropriate forms for various uses. (Means for Solving the Problems) According to the research of the present inventors, in the case of the sol-gel method, the above object is achieved using, for example, an organic polymer;
Depending on the organic polymer used, the following drawbacks may remain due to poor uniform dispersibility. For example, after performing a hydrolytic polymerization reaction of alkoxysilane in an organic polymer solution and gelling the reaction solution system, the organic polymer in the generated porous gel is removed, and then baking is performed. Although the pore size and its distribution can be easily controlled, the gelation process involves phase separation, which impairs uniform dispersibility and leaves problems in shaping into an appropriate shape.
上記の如き問題点の認識に基いて更に研究を重ねた結果
、次のような興味深い知見を得るに至ったものである．
すなわち、ポリオキサゾリン末端へトリエトキシシリル
基などを導入することにより、これとアルコキシシラン
との共加水分解重合が可能となり、生成ゲルはシリカと
ポリオキサゾリンとが化学結合によって強固に連結され
ているので、ゲル化工程での相分離が解消される。また
、ポリオキサゾリン自体はシランあるいはシリカと極め
て親和性が良いので、ゲル化の前でも後でも両者が均一
に分散されており、これらいずれの段階においても適宜
形態への賦形性が優れている。従って、上記特定のポリ
オキサゾリンとアルコキシシランを用いたゾルーゲル法
によれば、各種用途に応じた適宜形態のボリマー／シリ
カ複合成形体が均一分散状態を保持して円滑有利に製造
され得る。而して、本発明により製造される成形体を高
温で熱処理すれば、ゲル体中のポリオキサゾリン部分が
消失することによって、各種形態で且つ細孔径及びその
分布がコントロールされた多孔質シリカを得ることがで
きる。As a result of further research based on the recognition of the above problems, we have obtained the following interesting findings.
In other words, by introducing a triethoxysilyl group or the like to the end of polyoxazoline, co-hydrolysis polymerization of this and alkoxysilane becomes possible, and the resulting gel has silica and polyoxazoline firmly connected by chemical bonds. , phase separation in the gelation process is eliminated. In addition, since polyoxazoline itself has extremely good affinity with silane or silica, both are uniformly dispersed both before and after gelation, and it has excellent shaping properties into the appropriate form at any of these stages. . Therefore, according to the sol-gel method using the above-mentioned specific polyoxazoline and alkoxysilane, polymer/silica composite molded bodies of appropriate shapes for various uses can be smoothly and advantageously produced while maintaining a uniformly dispersed state. When the molded body produced according to the present invention is heat-treated at a high temperature, the polyoxazoline portion in the gel body disappears, thereby producing porous silica in various forms with controlled pore diameters and distribution. be able to.
かくして本発明は、上記知見に基いて完或されたもので
あり、加水分解重合性シリル基含有オキサゾリンポリマ
ーと加水分解重合性シランとを共加水分解重合反応させ
てゲル化せしめ、該ゲル化の前乃至後に賦形を行なうこ
とを特徴とするオキサゾリンポリマー／シリカ複合成形
体の製造方法を新規に提供するものである。Thus, the present invention has been completed based on the above findings, and involves co-hydrolytically polymerizing a hydrolytically polymerizable silyl group-containing oxazoline polymer and a hydrolytically polymerizable silane to form a gel. The present invention provides a novel method for producing an oxazoline polymer/silica composite molded article, which is characterized by performing shaping before or after the process.
本発明によれば、シリカの三次元ネットワーク中にオキ
サゾリンポリマーが化学結合により組み込まれた複合成
形体が円滑有利に製造され得る。According to the present invention, a composite molded article in which an oxazoline polymer is incorporated into a three-dimensional network of silica through chemical bonding can be smoothly and advantageously produced.
また、本発明によれば、繊維状，膜状の如き各種用途に
応じた形態のボリマー／シリカ複合或形体が自由に製造
され得る．，シかも、本発明の複合成形体は、特定シラ
ンと特定ボリマーとの親和性及び共加水分解重合による
化学結合の両者が相俟って、相分離のない非常に均一な
ものとなり、賦形性が良好なだけでなく、透明性に優れ
たものである．更に、本発明の複合或形体は、これを高
温熱処理することにより、その形態を保持した状態で細
孔径及びその分布がコントロールされた多孔質シリカ体
に容易に変換することができる．本発明において、加水
分解重合性シリル基含有オキサゾリンポリマーとしては
、種々のものが広範囲にわたって例示され得る。まず、
加水分解重合性シリル基としては、通常はトリメトキシ
シリル基，トリエトキシシリル基の如きトリアルコキシ
シリル基が好適なものとして例示されるが、その他のト
リクロロシリル基，ヒドロキシシリル基なども採用され
得る。また、該加水分解重合性シリル基は、オキサゾリ
ンポリマーの片末端に導入されていても良く、両末端に
導入されていても良い。オキサゾリンポリマーへの加水
分解重合性シリル基の導入方法についても特に限定はな
く、例えばオキサゾリンの開環重合における生長末端の
オキサゾリニウム塩の反応性を利用する方法などが挙げ
られる．求核剤としてのアミノブロビルトリエトキシシ
ランを上記の生長末端オキサゾリニウム塩に反応させて
アンモニウム塩の形とし、これを塩基性イオン交換樹脂
で処理することにより、末端にトリエトキシシリル基を
有するポリオキサゾリンを得ることができる．また、末
端に二重結合を有するオキサゾリンポリマーとトリアル
コキシシランとのヒドロシリル化反応などによっても、
末端にトリエトキシシリル基を有するポリオキサゾリン
を得ることができる．
次に、オキサゾリンボリマ一部分についても、その種類
，分子量など種々の変更が可能である。Furthermore, according to the present invention, polymer/silica composite bodies having various shapes such as fibrous and membrane shapes can be produced according to various uses. However, the composite molded article of the present invention is extremely uniform without phase separation due to the affinity between the specific silane and the specific polymer and the chemical bonding caused by co-hydrolytic polymerization. It not only has good properties but also excellent transparency. Furthermore, by subjecting the composite shaped body of the present invention to high-temperature heat treatment, it can be easily converted into a porous silica body with controlled pore size and distribution while maintaining its morphology. In the present invention, a wide variety of hydrolytically polymerizable silyl group-containing oxazoline polymers can be exemplified. first,
As the hydrolytically polymerizable silyl group, trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group are usually exemplified as preferred, but other trichlorosilyl groups, hydroxysilyl groups, etc. may also be employed. . Further, the hydrolytically polymerizable silyl group may be introduced at one end or both ends of the oxazoline polymer. There are no particular limitations on the method for introducing hydrolytically polymerizable silyl groups into the oxazoline polymer, and examples include methods that utilize the reactivity of the oxazolinium salt at the growing end in ring-opening polymerization of oxazoline. Aminobrobyltriethoxysilane as a nucleophile is reacted with the above propagating terminal oxazolinium salt to form an ammonium salt, which is then treated with a basic ion exchange resin to form a polyester having a triethoxysilyl group at the terminal. Oxazoline can be obtained. In addition, by a hydrosilylation reaction between an oxazoline polymer having a double bond at the end and a trialkoxysilane, etc.
A polyoxazoline with a triethoxysilyl group at the end can be obtained. Next, the oxazoline borimer portion can also be changed in various ways, such as its type and molecular weight.
例えば、種類についてはオキサゾリン，メチルオキサゾ
リン，エチルオキサゾリン，プチルオキサゾリン，オク
チルオキサゾリンなどのボリマーが例示され、分子量に
ついても重合度１〜２００程度のものなどが特に限定さ
れることなく例示され得る。これらの分子量，種類、あ
るいは上記片末端か両末端か、さらには後述の特定オキ
サゾリンポリマーの仕込比などによって、目的成形体の
吸水性，親水性，溶媒親和性などを変えることができる
とともに、本発明成形体からの多孔質シリカの細孔径や
細孔分布をコントロールすることもできる。For example, as for the type, polymers such as oxazoline, methyloxazoline, ethyloxazoline, butyloxazoline, and octyloxazoline are exemplified, and as for the molecular weight, those with a degree of polymerization of about 1 to 200 can be exemplified without particular limitation. The water absorbency, hydrophilicity, solvent affinity, etc. of the target molded article can be changed by changing the molecular weight, type, whether the above-mentioned one or both ends, and the ratio of the specific oxazoline polymer described later. It is also possible to control the pore diameter and pore distribution of the porous silica produced from the inventive molded article.
本発明における加水分解重合性シランについても、特に
限定されることなく、広範囲にわたって種々のものが例
示され得る。例えば、テトラメトキシシラン，テトラエ
トキシシランの如きテトラアルコキシシランなどが好適
なものとして例示され、その他ゾルーゲル法において通
常用いられる各種シラン類あるいは部分的に重合させた
シラン類なども挙げられる。The hydrolytically polymerizable silane in the present invention is not particularly limited, and a wide variety of silanes can be exemplified. For example, preferred examples include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, as well as various silanes commonly used in the sol-gel method and partially polymerized silanes.
本発明において、特定オキサゾリンポリマーと特定シラ
ンの反応割合（仕込比）は、目的とする成形体の用途，
性能など、あるいはその先の多孔質シリカの用途，性能
などに応じて適宜選定され得る．更に、該反応割合は、
使用する特定オキサゾリンポリマーの種類，分子量など
に応じても、その好適な範囲を適宜変更することが可能
である．例えば、特定オキサゾリンポリマー／特定シラ
ンの重量比で１／０．０１〜ｌ７１００程度の広い範囲
から選定され得るものであり、通常は１／Ｏ．１〜１／
１０程度が好ましく採用され得る。In the present invention, the reaction ratio (feeding ratio) between the specific oxazoline polymer and the specific silane is determined depending on the intended use of the molded product.
It can be selected as appropriate depending on the performance, etc., or the future use and performance of porous silica. Furthermore, the reaction rate is
The preferred range can be changed as appropriate depending on the type, molecular weight, etc. of the specific oxazoline polymer used. For example, the specific oxazoline polymer/specific silane weight ratio can be selected from a wide range of about 1/0.01 to 7,100, and usually 1/O. 1~1/
A value of about 10 can be preferably adopted.
本発明における共加水分解重合反応は、従来のゾルーゲ
ル法におけると同様の操作，条件のもとに適宜実施可能
であり、特に限定される理由はないが、具体的に説明す
れば次の通りである。例えば、特定オキサゾリンポリマ
ーと特定シランをアルコール溶媒に溶かして均一溶液と
し、そこへ塩酸などを滴下して撹拌することにより反応
を行なう。反応は通常溶媒中で行なうのが望ましく、こ
の場合の溶媒としては、メタノール，エタノールの如き
アルコール類、エーテル類などが採用され得る。反応温
度は室温でも良く、Ｏ〜５０℃程度？範囲から適宜選定
され得る。また、反応時間についても特に限定はなく、
例えば２４時間程度でも反応させることができ、反応温
度などに応じて更に長時間や短時間を適宜採用すること
もできる。その他、窒素気流下での反応や０．５〜１気
圧程度の減圧下での反応などが適宜採用可能である。The cohydrolysis polymerization reaction in the present invention can be carried out as appropriate under the same operations and conditions as in the conventional sol-gel method, and there is no particular reason to limit it, but a specific explanation is as follows. be. For example, a specific oxazoline polymer and a specific silane are dissolved in an alcohol solvent to form a homogeneous solution, and hydrochloric acid or the like is added dropwise to the solution and stirred to carry out the reaction. It is usually desirable to carry out the reaction in a solvent, and in this case, alcohols such as methanol and ethanol, ethers, etc. can be used as the solvent. The reaction temperature may be room temperature, or about 0~50℃? It can be selected as appropriate from the range. There is also no particular limitation on the reaction time;
For example, the reaction can be carried out for about 24 hours, and a longer or shorter time can be adopted as appropriate depending on the reaction temperature. In addition, reaction under a nitrogen stream, reaction under reduced pressure of about 0.5 to 1 atm, etc. can be appropriately employed.
本発明においては、特定オキサゾリンポリマーが特定シ
ランと相溶性良好であり、また上記加水分解重合反応に
よる生成ゲルはシリカとオキサゾリンポリマーとが化学
結合で強固に■連結されて一体ネットワークを形成して
いるので、ゲル化の前でも後で−も相分離は生起せず、
均一透明状態を保持している。而して、本発明において
は、上記ゲル化の前乃至後に繊維状，膜秋なと適宜形態
に賦形されるが、得られる成形体は均一透明のものとし
て得られる．ゲル化反応において溶媒が用いられた場合
には、この溶媒を適宜の段階で除去することができる。In the present invention, the specific oxazoline polymer has good compatibility with the specific silane, and the gel produced by the above hydrolytic polymerization reaction has silica and oxazoline polymer firmly connected by chemical bonds to form an integral network. Therefore, no phase separation occurs before or after gelation.
Maintains uniform transparency. Therefore, in the present invention, the molded product is shaped into an appropriate shape such as fibrous or membrane-like before or after the above-mentioned gelation, but the molded product obtained is uniformly transparent. If a solvent is used in the gelation reaction, this solvent can be removed at an appropriate stage.
例えば、賦形後に溶媒の除去が可能であり、あるいはゲ
ル化反応過程で溶媒の除去を行なうこともできる。さら
には、ゲル化後に溶媒の除去を行なって、その後に賦形
を行なうこともできる．賦形態様がコーティングなどの
場合には、ゲル化前に基材へのコーティングを行ない、
基材上でゲル化反応せしめてシリカ／ボリマー複合体被
膜を形成するなどが有利である。For example, the solvent can be removed after shaping, or the solvent can be removed during the gelation reaction process. Furthermore, it is also possible to remove the solvent after gelation and then perform shaping. If the form of imposition is coating, etc., the base material is coated before gelation,
It is advantageous to carry out a gelation reaction on the substrate to form a silica/polymer composite coating.
また、本発明における賦形態様は、広範囲にわたって採
用可能であり、例えば上記コーティングを初めとして繊
維状，球状，管状，膜状，板状，棒状などが挙げられる
。これらの成形体は、その形態を保持したままで多孔質
シリカ体への変換が可能である。勿論、シリカ／ボリマ
ー複合成形体のままでも、該複合成形体の親水性．親和
性，透明性などの各種性能を生かした用途に適用するこ
とができる。賦形方法としても、目的とする成形体の形
態に応じて好適な方法が適宜選択され得るものであり、
溶液を用いた流延法や塗布法，繊維状や管状などへの押
出成形法，膜状や板状などへのプレス成形法，管状や複
雑形状などへの遠心成形法，その他各種形状への注型或
形法などが採用され得る。In addition, a wide range of shapes can be employed in the present invention, and examples include the above-mentioned coating, as well as fibrous, spherical, tubular, membrane, plate, and rod shapes. These molded bodies can be converted into porous silica bodies while maintaining their shape. Of course, the hydrophilicity of the silica/polymer composite molded product can be improved even if it is left as is. It can be applied to applications that take advantage of various properties such as affinity and transparency. As for the shaping method, a suitable method can be selected as appropriate depending on the form of the intended molded product,
Casting and coating methods using solutions, extrusion molding into fibers and tubes, press molding into membranes and plates, centrifugal molding into tubes and complex shapes, and other various shapes. Casting or molding methods may be employed.
本発明のシリカ／ボリマー複合成形体を多孔質シリカ体
へ変換する場合、通常はオキサゾリンポリマーの分解温
度以上の高温で熱処理すれば良いが、例えば３００〜８
００℃程度の温度で３〜２４時間程度の加熱処理が採用
される。高温熱処理によって、オキサゾリンボリマ一部
分が消失するとともに、シリカ部分が焼結されて多孔質
シリカ体へ変換される．得られる多孔質シリカ体は、そ
の細孔径及び孔径分布が良好にコントロールされている
．例えば、細孔径は５〜１００人程度の広範囲にわたっ
て自由にコントロールすることができ、また孔径分布に
ついても揃ったものとすることができる。When converting the silica/polymer composite molded article of the present invention into a porous silica body, it is usually sufficient to perform heat treatment at a high temperature higher than the decomposition temperature of the oxazoline polymer, but for example,
Heat treatment is employed at a temperature of about 00° C. for about 3 to 24 hours. By high-temperature heat treatment, part of the oxazoline polymer disappears, and the silica part is sintered and converted into a porous silica body. The resulting porous silica body has well-controlled pore size and pore size distribution. For example, the pore size can be freely controlled over a wide range of about 5 to 100, and the pore size distribution can also be made uniform.
而して、上記のようにして得られる多孔質シリカ体は，
本発明の複合成形体の形態が保持されているので、その
形態を生かした広範囲の用途に適用され得る。例えば、
繊維状体はマット状フィルター，織物状フィルター，触
媒担体，酵素担体などとして、膜状体や管状体は分離フ
ィルター，敢気板，噴気管，散液板・管などとして、球
状体は吸着材，触媒担体，充填材などとして、またコー
ティング体は液体クロマトグラフィー用担体，酵素担体
などとして、それぞれ採用され得るものである。The porous silica body obtained as described above is
Since the shape of the composite molded article of the present invention is maintained, it can be applied to a wide range of uses that take advantage of that shape. for example,
Fibrous bodies can be used as mat filters, woven filters, catalyst carriers, enzyme carriers, etc. Membrane bodies and tubular bodies can be used as separation filters, air plates, fumarole pipes, liquid dispersion plates/tubes, etc. Spherical bodies can be used as adsorbents , a catalyst carrier, a filler, etc., and the coated body can be employed as a carrier for liquid chromatography, an enzyme carrier, etc.
［実施例］
以下、本発明の実施例についてさらに具体的に説明する
が、かかる説明によって本発明が何ら限定されないもの
であることは勿論である。[Examples] Examples of the present invention will be described in more detail below, but it goes without saying that the present invention is not limited by such explanations.
〈 オキサゾｌンボ１マーの 〉
合成例１〜４．
メチルトシレート（ｃＨｇａｒ−）を開始剤とした２−
メチル−２−オキサゾリンの開環重合、その重合反応で
生成するリビング的重合生長末端オキサゾリニウム塩と
求核剤としての３−アミノブロビルトリエトキシシラン
との反応（アミン基がオキサゾリニウム末端と反応して
アンモニウム塩の形となる）、及び該アンモニウム塩の
塩基性イオン交換樹脂による処理（→末端にトリエトキ
シシリル基を有するポリオキサゾリンの生成）からなる
工程にしたがって、下記第１表に示すような各種の加水
分解重合性シリル基含有オキサゾリンポリマーを合成し
た。<Oxazone 1mer> Synthesis Examples 1 to 4. 2- with methyl tosylate (cHgar-) as an initiator
Ring-opening polymerization of methyl-2-oxazoline, reaction of the living polymer propagating terminal oxazolinium salt produced by the polymerization reaction with 3-aminobrobyltriethoxysilane as a nucleophile (the amine group reacts with the oxazolinium terminal). ammonium salt form), and treatment of the ammonium salt with a basic ion exchange resin (→ production of polyoxazoline having a triethoxysilyl group at the end), various types of products as shown in Table 1 below are prepared. A hydrolytically polymerizable silyl group-containing oxazoline polymer was synthesized.
また、上記のメチルトシレートの代わりに、ビスオキサ
ゾリンとメチルトシレートの反応で得られる二官能性開
始剤（Ｔ．０・・ＯＴ１）を用いる他は、上記と同様の
工程に従って、下記第１表に示すような両末端にトリエ
トキシシリル基を有するオキサゾリンポリマーを合成し
た。In addition, in place of the above methyl tosylate, the following 1. An oxazoline polymer having triethoxysilyl groups at both ends as shown in the table was synthesized.
第ｌ表
なお、上記第１表において、時間は上記工程における開
環重合反応の時間を、収率は同間環重合反応での収率を
、それぞれ示している。また、Ｍｎは特定オキサゾリン
ポリマーの分子量を示し、ｃｏｓｃＮ中８０℃の試料に
ついて ’Ｈ−ＮＭＲから計算したものである．
〈オキサゾ１ンボリマー シ１力 Ａ の 〉調製例
１〜６．
上記合成例と同様の方法で合成した下記第２表に示す特
定オキサゾリンポリマーを用いて、テトラエトキシシラ
ンとの共加水分解重合反応を行なった．特定オキサゾリ
ンポリマーとテトラエトキシシランを下記第２表に示す
仕込比でエタノールに溶かし、均一溶液としたところへ
塩酸を滴下し、数分間撹拌後に数日間放置することによ
り反応させた。得られたガラス状の固体を乳鉢で粉砕し
クロロホルムによるソックスレー抽出で精製した。得ら
れたボリマー／シリカ複合体について、元素分析から計
算したポリオキサゾリンの導入率（ｐｏｚｏ％）及び９
００℃まで加熱した時の熱重量分折ＴＧＡ （窒素気流
下、１０℃／ｍｉｎ．）による重量損失（ Ｗｔ−Ｌｏ
ｓｓ％）を下記第２表に示した．下記第２表において、
ＰＯＺＯ−Ａ， ＰＯＺＯ−Ｂは合成例１〜３に準じた
方法で合成された片末端にトリエトキシシリル基を有す
るポリオキサゾリンであり、ｐｏｚｏ−ｃは合成例４に
準じた方法で合成された両末端にトリエトキシシリル基
を有するポリオキサゾリンである。また、Ｄ． Ｐ．は
原料の特定オキサゾリンポリマー（原料ｐｏｚｏ）の重
合度を示す。さらに、仕込比は、原料ＰＯＺＯ／テトラ
エトキシシランの重量比にて示している．
第２表
参考例１〜１０．
調製例１〜６に準じた方法で得られる下記第３表に示す
オキサゾリンポリマー／シリカ複合体について、ポリオ
キサゾリン導入の効果をみるために、次に示す方法によ
って吸水倍率の測定を行なった．
［吸水倍率の測定方法］
試料としてのオキサゾリンポリマー／シリカ複合体の１
００ｍｇを水中で１０時間膨潤させ、次いでガラスフィ
ルターで２０ｍｍＨｇの減圧下に５分間濾過する．この
ように処理された試料から、複合体に膨潤吸収された水
の重量を算出し、その水の重量をもとの乾燥複合体の重
量で割って吸水倍率を求める．
得られる結果（Ｈ８０含量）及び上記第２表におけると
同様のｐｏｚｏ％を下記第３表に示す。また、第３表に
は、テトラエトキシシランのみから合成したゲル（シリ
カ単体）についても、同様の結果を参考例ｌＯとして示
してある．
また、下記第３表において、ＰＯＺＯ−Ａ， ＰＯＺＯ
−８は合成例１〜３に準じた力法で合成された片末端に
トリエトキシシリル基を有するポリオキサゾリンを示し
ており、ｐｏｚｏ−ｃは合或例４に準じた方法で合成さ
れた両末端にトリエトキシシリル基を有するポリオキサ
ゾリンを示している。また、Ｄ． Ｐ．は原料の特定オ
キサゾリンボリマ−（原料ＰＯＺＯ）の重合度を示すも
のである。Table 1 In Table 1 above, time indicates the time for the ring-opening polymerization reaction in the above step, and yield indicates the yield in the ring-opening polymerization reaction. Moreover, Mn indicates the molecular weight of the specific oxazoline polymer, and is calculated from 'H-NMR of a sample at 80°C in coscN. Preparation Examples 1 to 6. A cohydrolytic polymerization reaction with tetraethoxysilane was carried out using specific oxazoline polymers shown in Table 2 below, which were synthesized in the same manner as in the above synthesis example. The specific oxazoline polymer and tetraethoxysilane were dissolved in ethanol at the charging ratio shown in Table 2 below, and hydrochloric acid was added dropwise to the homogeneous solution, which was stirred for several minutes and left to react for several days. The resulting glassy solid was ground in a mortar and purified by Soxhlet extraction with chloroform. Regarding the obtained polymer/silica composite, the introduction rate of polyoxazoline (pozo%) calculated from elemental analysis and 9
Weight loss (Wt-Lo) by thermogravimetric analysis TGA (under nitrogen flow, 10°C/min.) when heated to 00°C
ss%) are shown in Table 2 below. In Table 2 below,
POZO-A and POZO-B are polyoxazolines having a triethoxysilyl group at one end synthesized by a method according to Synthesis Examples 1 to 3, and pozo-c was synthesized by a method according to Synthesis Example 4. It is a polyoxazoline with triethoxysilyl groups at both ends. Also, D. P. indicates the degree of polymerization of a specific oxazoline polymer (raw material pozo) as a raw material. Furthermore, the charging ratio is expressed as a weight ratio of raw material POZO/tetraethoxysilane. Table 2 Reference Examples 1 to 10. The water absorption capacity of the oxazoline polymer/silica composites shown in Table 3 below, obtained by a method similar to Preparation Examples 1 to 6, was measured by the method shown below in order to examine the effect of introducing polyoxazoline. [Method for measuring water absorption capacity] Oxazoline polymer/silica composite sample 1
00 mg in water for 10 hours and then filtered through a glass filter under reduced pressure of 20 mmHg for 5 minutes. From the sample treated in this way, calculate the weight of water that swells and absorbs into the composite, and then divide the weight of water by the weight of the original dry composite to determine the water absorption capacity. The results obtained (H80 content) and pozo% similar to those in Table 2 above are shown in Table 3 below. Table 3 also shows similar results for a gel synthesized only from tetraethoxysilane (silica alone) as Reference Example IO. In addition, in Table 3 below, POZO-A, POZO
-8 indicates a polyoxazoline having a triethoxysilyl group at one end synthesized by the force method according to Synthesis Examples 1 to 3, and pozo-c indicates a polyoxazoline synthesized by a method according to Synthesis Example 4. It shows a polyoxazoline with a triethoxysilyl group at the end. Also, D. P. indicates the degree of polymerization of a specific oxazoline polymer (raw material POZO) as a raw material.
第３表
実施例ｌ．
上記合成例１に準じて合成された重合度９．０の特定オ
キサゾリンボリマ−０．３９ｔｇとテトラエトキシシラ
ン１．９７ｇを、３ｍｌのエタノールに溶かし均一溶液
としたところへ、１規定の塩酸を０．２ｍｌ滴下し数分
間撹拌した溶液を、フッ素樹脂（ポリテトラフルオロエ
チレン）製基材の表面に流延塗布した．この状態で数日
間放置することにより、共加水分解重合反応を進行せし
めた．その結果、基材表面にガラス状固体からなる厚み
１００ミクロンの透明塗膜を形成することができた．ク
ロロホルムによる抽出操作でエタノール溶媒及び未反応
原料を溶出することにより（あるいは５０℃で加熱乾燥
することにより）該塗膜を精製して、オキサゾリンポリ
マー／シリ力複合体からなる透明な塗膜を得た．
該オキサゾリンポリマー／シリカ複合体塗膜は、フッ素
樹脂製基材の表面から剥がすことにより、複合体薄膜と
することもできる．
実施例２〜５．
実施例１において、使用する特定オキサゾリンポリマー
の種類と量及びテトラエトキシシランの使用量を下記第
４表に示すように変え、その他は同様の条件，手順によ
り、オキサゾリンポリマー／シリカ複合体からなる透明
な塗膜及び薄膜を得ることができた．
第４表
以上の実施例１〜５のようにして得られる塗膜及び薄膜
は、後述の製造例と同様の方法によって、その形状を保
持した状態で容易に多孔質シリカ体へ変換することがで
きる．
実施例６．
上記の合成例４に準じて合成されたところの重合度１６
．１の両末端にトリエトキシシリル基を有するポリオキ
サゾリン３．９２ｇとテトラエトキシシラン１９．６ｇ
を、４０ｍｌのエタノールに溶かし均一溶液としたとこ
ろへ、ｌ規定の塩酸を０．９ｍｌ滴下し数分間撹拌した
溶液を原料液として用いた．この原料液４０ｇを、内径
が２ｃｍ，長さがＬｏａｍの一端を封じたフッ素樹脂（
ポリテトラフルオロエチレン）製バイブ状鋳型内に注入
し、温度２７℃に２日間、さらに温度５０℃に１日間保
持することにより、共加水分解重合反応を進行せしめた
．その結果、長さ８．５ｃｍ，直径１．８ｃｍの透明丸
棒体を得ることができた．該丸棒体を５０℃で加熱乾燥
することにより、オキサゾリンポリマー／シリカ複合体
からなる透明な丸棒体を得た．
実施例７．
上記の合成例１〜３に準じて合成された重合度が９．０
の片末端にトリエトキシシリル基を有するポリオキサゾ
リン２．８６ｇとテトラエトキシシラン２８．６ｇを、
４０ｍｌのエタノールに溶かし均一溶液としたところへ
、１規定の塩酸を０．８ｍｌ滴下し数分間撹拌した溶液
を原料液として用いた．
一端を封じた薄肉のシリコーンゴム製チューブ内に水を
張って膨らませた外径１。５ｃｍの棒状内型及び内径４
ｃｍのフッ素樹脂（ポリテトラフルオロエチレン）製円
筒容器外型を用い、該外型内に該内型を同軸状に挿入し
、該外型の内壁と該内型の外壁との間の空間に上記の原
料液を注入し、温度２７℃に２日間、さらに温度５０℃
に１日間保持することにより、共加水分解重合反応を進
行せしめた．原料液がゲル化して固化したので、棒状内
型内の水を抜き出し、シリコーンゴム製チューブを抜き
取ることにより、内径０． ７ｃｍ，外径３．６ｃｍの
透明バイブ状体を得ることができた．該パイプ状体を５
０℃で加熱乾燥することにより、オキサゾリンポリマー
／シリカ複合体からなる透明なパイプ状体を得た．実施
例８．
上記の合成例４に準じて合成された重合度が１６．１の
両末端にトリエトキシシリル基を有するポリオキサゾリ
ン３．９２ｇとテトラエトキシシラン１９．６ｇを、４
０ｍｌのエタノールに溶かし均一溶液としたところへ、
１規定の塩酸を０．９ｍｌ滴下し数分間撹拌した溶液を
原料液として用いた．該原料液を撹拌下に温度２７℃で
共加水分解重合せしめ、粘度が７０ボアズになったもの
を紡糸液とした．
紡糸装置には、孔径０．１２ｍｍの孔を２００個有する
ノズルロ金（最外周径１２０ｍｍの円板に孔配置密度１
．６個／ ｃ ｍ ”になるように孔が配列されている
）が組み込まれている．上記の紡糸液を１５ｋｇ／ｃｍ
”の圧力で該ノズルロ金から押し出し、下方に設置した
巻取ドラムによって１２０ｍ／分の速度で巻き取ったと
ころ、吐出不良やフィラメント切れがおこることなく、
長時間にわたって連続的にゲル状繊維を得ることができ
た。該ゲル状繊維はオキサゾリンボリマ−／シリ力複合
体からなる透明な繊維状体であり、直径が１０ミクロン
、延伸比がｌ２であった．実施例９．
上記実施例８におけると同様の原料液を用いて共加水分
解重合せしめ、粘度が６０ボアズになったものを紡糸液
とした．孔径０．１０ｍｍの孔を１００個有するノズル
口金から該紡糸液を押し出し、巻取ドラムによって１０
０ｍ／分の速度で巻き取ることにより、オキサゾリンポ
リマー／シリ力複合体からなる直径２０ミクロンの透明
なゲル状繊維が得られた。Table 3 Examples l. 0.39 tg of the specific oxazoline polymer with a degree of polymerization of 9.0 synthesized according to Synthesis Example 1 above and 1.97 g of tetraethoxysilane were dissolved in 3 ml of ethanol to form a homogeneous solution, and then 1 N hydrochloric acid was added. 0.2 ml of the solution was added dropwise and stirred for several minutes, and then cast and coated on the surface of a fluororesin (polytetrafluoroethylene) substrate. By leaving it in this state for several days, the cohydrolysis polymerization reaction was allowed to proceed. As a result, we were able to form a transparent coating film of 100 microns thick made of glassy solid on the surface of the substrate. The coating film is purified by eluting the ethanol solvent and unreacted raw materials through an extraction operation with chloroform (or by heating and drying at 50°C) to obtain a transparent coating film composed of the oxazoline polymer/silica composite. Ta. The oxazoline polymer/silica composite coating film can also be made into a composite thin film by peeling it off from the surface of the fluororesin base material. Examples 2-5. In Example 1, the type and amount of the specific oxazoline polymer used and the amount of tetraethoxysilane used were changed as shown in Table 4 below, and otherwise a transparent material made of an oxazoline polymer/silica composite was prepared under the same conditions and procedures. We were able to obtain a coating film and a thin film. The coating films and thin films obtained as in Examples 1 to 5 in Table 4 and above can be easily converted into porous silica bodies while maintaining their shape by the same method as in the production examples described below. can. Example 6. Polymerization degree 16 synthesized according to the above Synthesis Example 4
．． 3.92 g of polyoxazoline having triethoxysilyl groups at both ends of 1 and 19.6 g of tetraethoxysilane
was dissolved in 40 ml of ethanol to form a homogeneous solution, 0.9 ml of normal hydrochloric acid was added dropwise and stirred for several minutes, and the solution was used as the raw material solution. 40g of this raw material liquid was mixed with a fluororesin (with an inner diameter of 2cm and a length sealed at one end).
The cohydrolytic polymerization reaction was allowed to proceed by injecting the mixture into a mold made of polytetrafluoroethylene and maintaining the temperature at 27°C for 2 days and then at 50°C for 1 day. As a result, a transparent round rod with a length of 8.5 cm and a diameter of 1.8 cm was obtained. By heating and drying the round rod at 50°C, a transparent round rod made of an oxazoline polymer/silica composite was obtained. Example 7. The degree of polymerization synthesized according to the above Synthesis Examples 1 to 3 was 9.0.
2.86 g of polyoxazoline having a triethoxysilyl group at one end and 28.6 g of tetraethoxysilane,
To a homogeneous solution dissolved in 40 ml of ethanol, 0.8 ml of 1N hydrochloric acid was added dropwise and stirred for several minutes, and the solution was used as a raw material solution. A rod-shaped inner mold with an outer diameter of 1.5 cm and an inner diameter of 4
Using an outer mold of a cylindrical container made of fluororesin (polytetrafluoroethylene) of cm, the inner mold is coaxially inserted into the outer mold, and the space between the inner wall of the outer mold and the outer wall of the inner mold is filled. Inject the above raw material liquid and maintain the temperature at 27℃ for 2 days, then further at 50℃.
The cohydrolysis polymerization reaction was allowed to proceed by holding the solution for 1 day. As the raw material liquid gelled and solidified, the water in the rod-shaped inner mold was extracted and the silicone rubber tube was removed to reduce the inner diameter to 0. A transparent vibrator-like body with a length of 7 cm and an outer diameter of 3.6 cm was obtained. 5.
By heating and drying at 0°C, a transparent pipe-shaped body made of an oxazoline polymer/silica composite was obtained. Example 8. 3.92 g of polyoxazoline having a triethoxysilyl group at both ends and 19.6 g of tetraethoxysilane having a polymerization degree of 16.1 synthesized according to Synthesis Example 4 above,
Dissolve it in 0ml of ethanol to make a homogeneous solution.
A solution obtained by dropping 0.9 ml of 1N hydrochloric acid and stirring for several minutes was used as the raw material solution. The raw material solution was co-hydrolyzed and polymerized at a temperature of 27° C. with stirring, and the resulting solution had a viscosity of 70 boads, which was used as a spinning solution. The spinning device was equipped with a nozzle die having 200 holes with a hole diameter of 0.12 mm (a hole arrangement density of 1 on a disk with an outermost circumferential diameter of 120 mm).
．． The holes are arranged so that the number of holes is 6/cm").The above spinning solution is
When the filament was extruded from the nozzle with a pressure of 100 ft and wound up at a speed of 120 m/min by a winding drum installed below, no ejection failure or filament breakage occurred.
It was possible to obtain gel-like fibers continuously over a long period of time. The gel-like fiber was a transparent fibrous body made of an oxazoline polymer/silica composite, and had a diameter of 10 microns and a drawing ratio of 12. Example 9. Co-hydrolysis polymerization was carried out using the same raw material solution as in Example 8 above, and the resulting spinning solution had a viscosity of 60 boads. The spinning solution is pushed out through a nozzle having 100 holes with a hole diameter of 0.10 mm, and is
By winding at a speed of 0 m/min, transparent gel-like fibers of oxazoline polymer/silica composite with a diameter of 20 microns were obtained.
実施例１０．
上記の合成例４に準じて合成された重合度が１６．１の
両末端にトリエトキシシリル基を有するポリオキサゾリ
ン３．９２ｇとテトラエトキシシラン１９．６ｇを、４
０ｍｌのエタノールに溶かし均一溶液としたところへ、
ｌ規定の塩酸を０．９ｍｌ滴下し、２７℃で２日間共加
水分解重合せしめた液を原料液とした．
ガラス製の二流体ノズル（内管径０．５ｍｍ，外管径２
．５ｍｍ）の内管より上記の原料液の４０ｍｌを２ｍ１
／分の速度で、また乾燥Ｎ雪を上記二流体ノズルの外管
より５リットル／分の速度で送り込み、別に設けた液体
Ｎ雪リザーバー中に噴霧した．噴霧終了後に上記リザー
バーを減圧にし、液分を昇華せしめた．得られた微小球
体を５０℃で乾燥することにより、オキサゾリンポリマ
ー／シリカ複合体からなる平均粒径０．ｌｍｌの透明球
状粒子を得た．
実施例１１．
上記合成例１に準じて合成された重合度９．０の片末端
にトリエトキシシリル基を有するポリオキサゾリン２．
８６，とテトラエトキシシラン２８．６ｇを４０ｍｌの
エタノールに溶かし均一溶液としたところへ、１規定の
塩酸０．８ｍｌを滴下し、更に２７℃で２日間共加水分
解重合せしめた液を原料液とした．
この原料液を、回転装置にその長軸が水平になるように
設置された内径５ｃｍ．長さ２０ｃｍのポリテトラフル
オロエチレン製バイブ状鋳型内に注入し、１ ０ ０
０ ｒ．ｐ．ｍ．で３０分間回転させた．更に，その
後５０℃で１日間保持することにより、共加水分解重合
反応を進行せしめた。その結果、外径４．５ｃｍ，肉厚
０．５ｍｍ，長さ１８ｃｍのオキサゾリンポリマー／シ
リカ複合体からなる透明なバイブ状体が得られた。Example 10. 3.92 g of polyoxazoline having a triethoxysilyl group at both ends and 19.6 g of tetraethoxysilane having a polymerization degree of 16.1 synthesized according to Synthesis Example 4 above,
Dissolve it in 0ml of ethanol to make a homogeneous solution.
0.9 ml of normal hydrochloric acid was added dropwise, and the solution was co-hydrolyzed and polymerized at 27°C for 2 days, which was used as a raw material solution. Glass two-fluid nozzle (inner tube diameter 0.5 mm, outer tube diameter 2
．． Pour 40ml of the above raw material solution into 2ml from the inner tube (5mm).
Dry N snow was sent through the outer tube of the two-fluid nozzle at a rate of 5 liters/min and sprayed into a separate liquid N snow reservoir. After the spraying was completed, the pressure in the reservoir was reduced to allow the liquid to sublimate. By drying the obtained microspheres at 50°C, the average particle size of the oxazoline polymer/silica composite was reduced to 0. 1ml of transparent spherical particles were obtained. Example 11. 2. Polyoxazoline having a triethoxysilyl group at one end and having a degree of polymerization of 9.0, synthesized according to Synthesis Example 1 above.
86, and 28.6 g of tetraethoxysilane were dissolved in 40 ml of ethanol to form a homogeneous solution, 0.8 ml of 1N hydrochloric acid was added dropwise, and the resulting solution was co-hydrolyzed and polymerized at 27°C for 2 days. did. This raw material liquid was transferred to a rotating device with an inner diameter of 5 cm installed so that its long axis was horizontal. Injected into a 20 cm long polytetrafluoroethylene vibe-shaped mold, 100
0 r. p. m. I rotated it for 30 minutes. Furthermore, the cohydrolysis polymerization reaction was allowed to proceed by holding the mixture at 50° C. for 1 day. As a result, a transparent vibrator-like body made of an oxazoline polymer/silica composite with an outer diameter of 4.5 cm, a wall thickness of 0.5 mm, and a length of 18 cm was obtained.
以上の実施例６〜１１のようにして得られる各種或形体
についても、後述の製造例と同様の方法によって、その
形状を保持した状態で容易に多孔質シリカ体へ変換する
ことができる．
〈 シ１ 力 の ゛告〉製造例１〜６．
下記第５表に示す原料ＰＯＺＯ （特定オキサゾリンポ
リマー）を用いて上記調製例１〜６に準じて調製された
オキサゾリンポリマー／シリカ複合体を、高温熱処理せ
しめることにより多孔質シリカ体を製造した。高温熱処
理は、上記オキサゾリンポリマー／シリカ複合体を５８
０〜６００℃で２４時間加熱することにより行なった．
得られた多孔質シリカ体の表面積及び細孔容積を窒素吸
着法によって測定した結果を下記第５表に示す。The various shaped bodies obtained in Examples 6 to 11 above can also be easily converted into porous silica bodies while maintaining their shapes by the same method as in the production examples described below. <C1 Power Notice> Production Examples 1 to 6. Oxazoline polymer/silica composites prepared according to Preparation Examples 1 to 6 above using raw material POZO (specific oxazoline polymer) shown in Table 5 below were subjected to high temperature heat treatment to produce porous silica bodies. High-temperature heat treatment reduces the above oxazoline polymer/silica composite to 58
This was done by heating at 0 to 600°C for 24 hours.
The surface area and pore volume of the obtained porous silica body were measured by a nitrogen adsorption method, and the results are shown in Table 5 below.
第５表
上記第５表において、ＰＯＺＯ−Ａ， ＰＯＺＯ−Ｂは
合成例１〜３に準じた方法で合成された片末端にトリエ
トキシシリル基を有するポリオキサゾリンであり、ｐｏ
ｚｏ−ｃは合成例４に準じた方法で合成された両末端に
トリエトキシシリル基を有するポリオキサゾリンである
。また、Ｄ． Ｆ’．は原料の特定オキサゾリンポリマ
ー（原料ｐｏｚｏ）の重合度を示す。さらに、仕込比は
、オキサゾリンポリマー／シリカ複合体調製時の原料ｐ
ＯＺｏ／テトラエトキシシランの重量比にて示している
。Table 5 In Table 5 above, POZO-A and POZO-B are polyoxazolines having a triethoxysilyl group at one end synthesized by a method similar to Synthesis Examples 1 to 3;
zo-c is a polyoxazoline synthesized by a method similar to Synthesis Example 4 and having triethoxysilyl groups at both ends. Also, D. F'. indicates the degree of polymerization of a specific oxazoline polymer (raw material pozo) as a raw material. Furthermore, the charging ratio is the raw material p when preparing the oxazoline polymer/silica composite.
The weight ratio of OZo/tetraethoxysilane is shown.
［発明の効果】
本発明の製造方法は、均一透明のオキサゾリンポリマー
／シリカ複合或形体を円滑有利に与え得るという効果を
達成しているとともに、繊維状，膜状の如き各種用途に
応じた形態の成形体を自由に製造できるという効果をも
有する．これらの効果に基いて、本発明で製造される種
々の形態の複合成形体から、高温熱処理によりその形態
を保持したまま多孔質シリカ体が円滑有利に得られると
いう効果も達成される。[Effects of the Invention] The manufacturing method of the present invention achieves the effect of smoothly and advantageously producing a homogeneous transparent oxazoline polymer/silica composite body, as well as forms suitable for various uses such as fibers and films. It also has the effect of allowing the free production of molded objects. Based on these effects, it is also possible to smoothly and advantageously obtain porous silica bodies from composite molded bodies of various shapes produced by the present invention while maintaining their shapes through high-temperature heat treatment.
Claims (1)
と加水分解重合性シランとを共加水分解重合反応させて
ゲル化せしめ、該ゲル化の前乃至後に賦形を行なうこと
を特徴とするオキサゾリンポリマー／シリカ複合成形体
の製造方法。 ２、加水分解重合性シリル基含有オキサゾリンポリマー
における加水分解重合性シリル基がトリアルコキシシリ
ル基である請求項１に記載の製造方法。 ３、加水分解重合性シランがテトラアルコキシシランで
ある請求項１又は２に記載の製造方法。 ４、賦形がコーティングである請求項１〜３のいずれか
一項に記載の製造方法。 ５、成形体が繊維状体である請求項１〜３のいずれか一
項に記載の製造方法。 ６、成形体が球状体である請求項１〜３のいずれか一項
に記載の製造方法。 ７、成形体が管状体である請求項１〜３のいずれか一項
に記載の製造方法。 ８、成形体が膜状体である請求項１〜３のいずれか一項
に記載の製造方法。[Claims] 1. A hydrolytically polymerizable silyl group-containing oxazoline polymer and a hydrolytically polymerizable silane are co-hydrolytically polymerized to form a gel, and shaping is performed before or after the gelation. A method for producing an oxazoline polymer/silica composite molded article. 2. The manufacturing method according to claim 1, wherein the hydrolytically polymerizable silyl group in the oxazoline polymer containing a hydrolytically polymerizable silyl group is a trialkoxysilyl group. 3. The manufacturing method according to claim 1 or 2, wherein the hydrolytically polymerizable silane is tetraalkoxysilane. 4. The manufacturing method according to any one of claims 1 to 3, wherein the shaping is a coating. 5. The manufacturing method according to any one of claims 1 to 3, wherein the molded body is a fibrous body. 6. The manufacturing method according to any one of claims 1 to 3, wherein the molded body is a spherical body. 7. The manufacturing method according to any one of claims 1 to 3, wherein the molded body is a tubular body. 8. The manufacturing method according to any one of claims 1 to 3, wherein the molded body is a film-like body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19044689A JP2680434B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing oxazoline polymer / silica composite molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19044689A JP2680434B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing oxazoline polymer / silica composite molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0356535A true JPH0356535A (en) | 1991-03-12 |
| JP2680434B2 JP2680434B2 (en) | 1997-11-19 |
Family
ID=16258269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19044689A Expired - Lifetime JP2680434B2 (en) | 1989-07-25 | 1989-07-25 | Method for producing oxazoline polymer / silica composite molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2680434B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002085785A1 (en) * | 2001-04-17 | 2002-10-31 | Tokuyama Corporation | Method for producing inorganic porous material |
| US7361278B2 (en) | 2002-07-18 | 2008-04-22 | Canon Kabushiki Kaisha | Process for producing mass transfer device and apparatus for production thereof |
| US7749606B2 (en) | 2004-03-31 | 2010-07-06 | Nippon Sheet Glass Company, Limited | Article with organic-inorganic composite film and process for producing the same |
| US8013055B2 (en) | 2005-12-13 | 2011-09-06 | Asahi Kasei Chemicals Corporation | Aqueous organic-inorganic hybrid composition |
| US8039111B2 (en) | 2005-10-05 | 2011-10-18 | Nippon Sheet Glass Company, Limited | Article with organic-inorganic composite film |
| US20150329673A1 (en) * | 2012-12-19 | 2015-11-19 | 3M Innovative Properties Company | Reactive polyoxazolines having a perfluorinated group |
| WO2017018121A1 (en) * | 2015-07-27 | 2017-02-02 | ニッポン高度紙工業株式会社 | Method of producing inorganic oxide molded body |
-
1989
- 1989-07-25 JP JP19044689A patent/JP2680434B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045106B2 (en) | 2001-04-17 | 2006-05-16 | Tokuyama Corporation | Method for producing inorganic porous material |
| WO2002085785A1 (en) * | 2001-04-17 | 2002-10-31 | Tokuyama Corporation | Method for producing inorganic porous material |
| US7361278B2 (en) | 2002-07-18 | 2008-04-22 | Canon Kabushiki Kaisha | Process for producing mass transfer device and apparatus for production thereof |
| US7749606B2 (en) | 2004-03-31 | 2010-07-06 | Nippon Sheet Glass Company, Limited | Article with organic-inorganic composite film and process for producing the same |
| US8039111B2 (en) | 2005-10-05 | 2011-10-18 | Nippon Sheet Glass Company, Limited | Article with organic-inorganic composite film |
| EP2816087A1 (en) | 2005-12-13 | 2014-12-24 | Asahi Kasei Chemicals Corporation | Aqueous organic-inorganic hybrid composition |
| US8013055B2 (en) | 2005-12-13 | 2011-09-06 | Asahi Kasei Chemicals Corporation | Aqueous organic-inorganic hybrid composition |
| US9403950B2 (en) | 2005-12-13 | 2016-08-02 | Asahi Kasei Chemicals Corporation | Aqueous organic-inorganic hybrid composition |
| US20150329673A1 (en) * | 2012-12-19 | 2015-11-19 | 3M Innovative Properties Company | Reactive polyoxazolines having a perfluorinated group |
| US9718920B2 (en) * | 2012-12-19 | 2017-08-01 | 3M Innovative Properties Company | Reactive polyoxazolines having a perfluorinated group |
| US10087287B2 (en) | 2012-12-19 | 2018-10-02 | 3M Innovative Properties Company | Reactive polyoxazolines having a perfluorinated group |
| WO2017018121A1 (en) * | 2015-07-27 | 2017-02-02 | ニッポン高度紙工業株式会社 | Method of producing inorganic oxide molded body |
| JP2017024961A (en) * | 2015-07-27 | 2017-02-02 | ニッポン高度紙工業株式会社 | Manufacturing method of inorganic oxide compact |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2680434B2 (en) | 1997-11-19 |
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