JPS62277149A - Composite structure - Google Patents

Abstract

PURPOSE:To obtain the title composite structure useful as a separating agent, a filler, etc., by forming the thin film of a polymer having a reactive group on the surface of a specified porous carrier, and then cross-linking the polymer with use of the reactive group in an insoluble solvent. CONSTITUTION:The polymer having a reactive group is deposited on the porous carrier (e.g., silica, etc.) having 1mum-1cm particle diameter and 10Angstrom -100mum mean pore diameter and wherein the ratio of the pore diameter to the particle diameter is controlled to <=1/10. The deposited polymer is then cross-linked in an inactive solvent not dissolving the polymer, and insolubilized to obtain the composite structure. The composite structure different from the material obtained by granulating the polymer itself is hard and pressure-tight, and the resistance to solvent is improved as compared with the material obtained by physically adsorbing the polymer on the carrier.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention is useful for composite structures, particularly as a separating agent, filler, etc., in which a polymer is supported on a carrier. It concerns composite structures.

(Prior Art and Problems) Conventionally, synthetic or natural polymers have been made into granules and are expected to be used in a wide range of fields such as separating agents and cosmetics.

However, these granules are often difficult to synthesize and, even if possible, require relatively long processes. Furthermore, these materials are generally soft, which has significantly narrowed their range of use. The present inventors have arrived at the present invention as a result of extensive research in order to overcome the above-mentioned drawbacks and make it possible to utilize polymers in granular form without impairing the useful properties of these polymers. .

(Means for Solving the Problems) That is, the present invention has a particle size of 1 μm to 1 cm and an average pore size of 1 μm to 1 cm.
After forming a film of a polymer having a reactive group on the surface of a porous carrier having a diameter of 0 Å to 100 μm and a ratio of pore size to particle size of 1710 or less, the polymer is coated in an insoluble solvent using the reactive group. The present invention provides a composite structure in which an insolubilized polymer is supported on a porous carrier that is insolubilized by crosslinking.

The composite structure of the present invention is composed of a polymer and a carrier, and first, the carrier used in the present invention will be explained.

The carrier may be a porous organic carrier or a porous inorganic carrier, preferably a porous inorganic carrier. Polymeric materials include polystyrene, polyacrylamide, acrylate suitable as a polyporous organic carrier, and the like. Suitable porous inorganic supports include synthetic or natural materials such as silica, alumina, magnesia, titanium oxide, glass, silicates, and kaolin, which may be surface-treated to improve their compatibility with the polymer. It's okay.

Surface treatment methods include silanization using organic silane compounds and plasma treatment.

Although it is not necessary for the surface of the carrier and the polymer to be chemically bonded via a crosslinking agent due to the nature of wood, there is no problem even if some chemical bonding occurs depending on the presence or absence of reactive groups on the surface of the carrier. The particle size of the carrier is 1
It is μm to 1 cm, preferably 1 μm to 1 mm, and more preferably 1 μm to 300 μm. The average pore diameter is 10 Å to 100 μm, preferably 50 λ to 500 μm.
There are 00 people. Further, the ratio of pore size to particle size is 1/10 or less.

Next, the polymer in the present invention will be explained.

Polymers in the present invention include synthetic polymers, natural polymers,
Any modified natural polymer may be used as long as it has a reactive group, and it may be a single component, a mixture of multiple components, or a copolymer. That is,
A copolymer of a component having a reactive group and a component not having a reactive group may also be used. Synthetic polymers include esters of acrylic acid or methacrylic acid, amides of acrylic acid or methacrylic acid, polymers of vinyl compounds such as styrene derivatives, vinyl alcohol and its derivatives, allyl alcohol and its derivatives, or copolymers thereof. Examples include ring-opening polymers such as lactams, lactones, oxetanes, and epoxides, polyhydric alcohols, dicarboxylic acids and their derivatives, amino alcohols, amino acids, hydroxy acids, diamines, diisocyanates, and other condensates in any combination. .

Examples of natural polymers include polysaccharides and proteins, and examples of modified natural polymers include polysaccharides that do not have a high degree of substitution, and those obtained by chemically or physically treating these. When these polymers are optically active, the resulting composite structure is expected to be used as an optical resolution agent. Examples of optically active polymers include polymers containing optically active polymers such as triphenylmethyl methacrylate, amide of optically active amine and acrylic acid, or amide of optically active amine and methacrylic acid, polyamino acids and derivatives thereof. , proteins, polysaccharides and their derivatives. More specific examples of polysaccharides include cellulose, amylose, chitin, chitosan, mannan, xylan, inulin, and curdlan. Its derivatives include acetate, benzoate, cinnamate, carbamate,
benzyl ethers, and substituted derivatives thereof.

Moreover, the composite structure in which the polymer is insolubilized can be used as a separation agent in cases such as supercritical chromatography, where an elution medium with a large dissolving power is used.

Examples of the reactive groups of these polymers include amino groups, hydroxy groups, thiol groups, carboxyl groups, ester groups, amide groups, isocyanate groups, aldehyde groups, epoxy groups, silyl ether groups, and silanol groups. Therefore, a polymer having a reactive group refers to one containing the above group.

Any soluble and insoluble solvent may be used in the present invention.

Crosslinking in the present invention refers to crosslinking of a polymer by using a polyfunctional compound that covalently bonds with the above-mentioned reactive group, a polyfunctional compound that forms an ionic bond with the above-mentioned reactive group, or a polyvalent metal compound. /Or refers to the direct bonding of polymers without a crosslinking agent by a normal crosslinking reaction and heating, far infrared ray irradiation, ultraviolet irradiation, radiation irradiation, or plasma treatment to bond between molecules.

Next, a method of supporting the polymer on the polymer hair carrier will be explained.

The polymer is dissolved in a solvent and added to the carrier. Thereafter, the solvent is removed by distillation or transferred into a large amount of solvent that does not dissolve the polymer to disperse the soluble solvent, and the polymer is supported on the carrier. The polymer supported on the carrier is crosslinked in an inert solvent that does not dissolve the polymer. Furthermore, the remaining reactive groups may be treated with another reactant.

In the composite structure obtained in this way, it is not necessary that a bond be formed between the carrier and the polymer, but there is no problem even if a portion of the bond is formed.

(Effects of the Invention) The composite structure in which the polymer of the present invention is supported on a carrier is hard and pressure-resistant, unlike conventional granular polymers, and it also physically adsorbs the polymer on the carrier. It is expected to be used in a wide range of applications because it has superior solvent resistance compared to other materials. For example, when used as a separating agent, it is now possible to use solvents that were previously impossible to use, so separation of a wider range of compounds is expected. It is also expected to be used as a filler, cosmetic powder, sustained release carrier, etc.

(Examples) Next, the present invention will be explained with examples, but the present invention is not limited to these examples.

Synthesis example 1゜Microcrystalline cellulose (Avicel, E, manufactured by Merck & Co.) 4.8
95 g in 100 ml of dry pyridine.
React with 9.64 g of phenyl isocyanate at °C.

After reacting for 8 hours, the mixture was returned to room temperature and transferred into 1 liter of methanol to precipitate the polymer. The precipitate was collected in a glass filter and dried, then dissolved again in 200 ml of acetone and reprecipitated in 1.7 ml of methanol. The amount of polymer obtained was 10.3 g. 7.0g of this polymer
was dissolved in 100 ml of acetone, and 1/2 of the solution was uniformly added to 21 g of silane-treated silica gel with a particle size of 10 μm and an average pore size of 1000 (Licrospher-9I 1000° 10 μm SE, manufactured by Merck & Co., Ltd.), and then the acetone was distilled off.

Thereafter, the remaining a7tone solution is added to the silica gel and the acetone is distilled off again to obtain a silica gel on which approximately 90% substituted cellulose is supported.

Example 1゜Synthesis example 1. 15 g of the obtained silica gel was dried in vacuo and dispersed in 70 ml of dry toluene, heated under reflux for 1.5 hours, then 1 ml of 1,6-diisocyanate hexane was added and reacted for an additional 3 hours. - After standing overnight at room temperature, 3 ml of phenyl isocyanate is added and heated under reflux for 9 hours. Thereafter, the temperature was returned to room temperature, and 10 ml of methanol was added to destroy excess isocyanic acid. Followed by methanol,
Wash with acetone to remove soluble polymer. The elemental analysis values of the obtained filler were as follows.

C: 9.48%, H: 1.17%, N: 1.09%. The elemental analysis values of the carrier silica gel before supporting the polymer were as follows.

C: 1.51%, H: 0.42%, N: 0.24%.

Example 2゜Synthesis Example 1. 15 g of the obtained silica gel was dried in vacuo, dispersed in 70 ml of dry toluene, and heated under reflux for 1.5 hours.
Add 5 ml and react for an additional 3 hours. - After standing overnight at room temperature, 3 ml of phenyl isocyanate is added and heated under reflux for 9 hours. Thereafter, the temperature was returned to room temperature, and 10 ml of methanol was added to destroy excess isocyanic acid. Next, wash with methanol and acetone to remove soluble polymers. The elemental analysis values of the obtained filler were as follows.

C: 9.62%, H: 0.98%, N: 1.02%. The elemental analysis values of the carrier silica gel before supporting the polymer were as follows.

C: 1.51%, H: 0.42%, N: 0.24%.

Application example 1゜The silica gel filler obtained in Example 1o was 25 cm long.
, packed in a stainless steel column with an inner diameter of 0.46 cm, and optically resolved various racemic compounds.The optical resolution was similar to that of conventional cellulose trisphenyl carbamate physically adsorbed onto silanized silica gel. Furthermore, even when using an eluent containing 20% or more of methylene chloride, which could not be used to dissolve cellulose trisphenyl carbamate, the polymer did not elute, and even with this eluent, good resolution results were obtained. gave. It was also possible to clean the dirt inside the column using acetone. Table 1 shows the results of optical resolution of racemic compounds using this packed column. The solvent is hexane and 2
- Propatool 9:1 mixed solvent at a flow rate of 0.5ml/m
in, (20°C).

In the table, kl indicates the retention capacity of the first eluting enantiomer, and k'2 indicates the retention capacity of the second eluting enantiomer. Further, α indicates the degree of separation, and Rs indicates the separation coefficient.

Table-1 Racemic body k'1 k'2 α-tracis-still-heon-site 0.32 0.40
1.242-phenylschiff 0 hex force 0
．． 86 0.99 1.15Co(a
cac)3 1.61 2.00
1.242.2.2-Tori sword l o-1-0
, 730,991,24 (9-7thryl) Ethanol Trager base 0.50 0.67 1.33 Binaphthol 2,67 2,83 1.06 1,3.5-1'liter as void volume (Vo) A retention time of 8.89 minutes for live-butylbenzene was used.

Application example 2゜Example 2. The silica gel filler obtained by
When various racemic compounds were optically resolved using a stainless steel column with an inner diameter of 0 to 46 cm, the results showed that the optical resolution was similar to that of conventional cellulose trisphenyl carbamate physically adsorbed onto silanized silica gel. Moreover, even when using an eluent containing more than 20% methylene chloride, which could not be used conventionally to dissolve cellulose trisphenyl carbamate, the polymer did not elute, and even with this eluent, good resolution results were obtained. gave. Table 2 shows the optical resolution results of racemic compounds using this packed column. Solvents include hexane and 2-propanol
:1 mixed solvent was used at a flow rate of 0.5 ml/min (20.degree. C.).

In the table, kt indicates the retention capacity of the first eluting enantiomer, and k'2 indicates the retention capacity of the second eluting enantiomer. Further, α indicates the degree of separation, and Rs indicates the separation coefficient.

Table-2 Racemic body k'1 k'2 α tracys-
Still hen oxide 0.21 0.28
1.32 Table-2 continued Racemic form k'+ k'2 α2-phenylcyclohexanone 0.68 0,
79 1.17Co(acac)3
1,40 1.73 1.242
．． 2.2-trifluoro0-1-0.44 0.
69 1.56 (9-7 cis January 1) Ethanol Traeger base 0.25 0,38 1.54 Binaphthol 2,01 2.38 1.18 Phenyl 11 Heini;l Sulfoxide 2.17
2.34 1.08 void volume (7 mouths)
A retention time of 11°0 minutes for 1,3.5-) tertiary butylbenzene was used as the holding time.

Claims (1)

[Claims] The particle size is 1 μm to 1 cm, and the average pore size is 10 Å to 100 Å.
After forming a film of a polymer having a reactive group on the surface of a porous carrier having a pore size to a particle size ratio of 1/10 or less, the polymer is coated in an insoluble solvent using this reactive group. A composite structure characterized by being insolubilized by crosslinking.