JPS59219308A - Production of modified polyvinyl alcohol polymer - Google Patents

Abstract

PURPOSE:To obtain a modified polyvinyl alcohol polymer excellent in adhesion to inorganic materials, by reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide. CONSTITUTION:A modified polyvinyl alcohol polymer having alkyl sulfoxide groups is obtained by reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide. Examples of the sulfoxides include 1-10C alkyl group-containing alkyl vinyl sulfoxides such as methyl vinyl sulfoxide and cyclohexyll vinyl sulfoxide, among which 1-4C lower alkyl vinyl sulfoxides are desirable because of good reactivity. The amount of the sulfoxide is one to provide a molar ratio to the hydroxyl groups in the polyvinyl alcohol polymer, of preferably 0.01 or above.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified polyvinyl alcohol polymer. More specifically, the present invention relates to a method for producing a modified polyvinyl alcohol polymer having excellent adhesion to inorganic substances, which is made from an alkyl sulfoxide by reacting an alkyl vinyl sulfoxide with the hydroxyl groups of the polyvinyl alcohol polymer.

Polyvinyl alcohol-based polymers such as polyvinyl alcohol or vinyl alcohol copolymers obtained by saponifying vinyl esters, especially vinyl acetate alone or copolymers, can be used in molded products such as fibers, films, and sheets, as well as in their strong and durable materials. Taking advantage of its excellent film-forming and adhesive properties, it is widely used as water-soluble adhesives, binder additives, paper processing agents, and textile glues.

As described above, polyvinyl alcohol has good adhesion ability to a wide range of materials, but its adhesion strength may not necessarily be high. For example, adhesive strength to inorganic materials such as glass, asbestos, and concrete is insufficient, and materials with higher adhesive strength are desired.

The present invention was made against these backgrounds, and by reacting an alkyl vinyl sulfoxide to a polyvinyl alcohol-based polymer and introducing an alkyl sulfoxide group, it is possible to create a polyvinyl alcohol polymer with high adhesive strength, especially adhesive strength to inorganic materials. The present invention was achieved by discovering that expensive materials could be used.

As mentioned above, the feature of the present invention is that it uses a modified polyvinyl alcohol polymer that has excellent adhesion to inorganic materials, especially glass. As a method for obtaining a polyvinyl alcohol polymer into which an alkyl sulfoxide group has been introduced, the present inventors have previously applied (Japanese Patent Application No. 58-29956). There is a method of copolymerizing with an ester and then saponifying it, but since the copolymerizability of haalkyl vinyl sulfoxide is not good in this method, in an attempt to obtain a copolymer with a high gold wire of alkyl vinyl sulfoxide units, alkyl vinyl sulfoxide was When copolymerized with vinyl acetate and saponified in large quantities, the polymerization rate and degree of polymerization decrease significantly;
It is difficult to efficiently obtain a modified polyvinyl alcohol polymer with a high degree of modification and a high degree of polymerization. In contrast, the method of the present invention easily reacts a polyvinyl alcohol-based polymer with a high degree of polymerization using various alkyl vinyl sulfoxides, and produces a highly modified polyvinyl alcohol-based polymer with a high content of alkyl sulfoxide groups. This is an advantage that can be gained.

Further, the present invention can easily be made into a high value-added material with new properties by using a polyvinyl alcohol gourd aggregate, which is industrially produced and sold in large quantities, through a post-reaction button. For example, surface properties can be improved by reacting polyvinyl alcohol polymer fibers, films, molded products, and other molded products with alkyl vinyl sulfoxide while maintaining their shape, and introducing alkyl vinyl sulfoxide groups onto their surfaces. This has the advantage that molded material or molded articles can be obtained.

The modified polyvinyl alcohol polymer with a multi-sleeved alkyl sulfoxide group introduced by the method of the present invention has an increased ability to adsorb polar substances, especially due to the property of having both hydrophilicity and lipophilicity of the alkyl sulfoxide group. Furthermore, when this is used as a pesticide dispersant, it exhibits unique effects such as increasing the permeability of pesticides into insect skin, and has excellent performance.

The present invention will be specifically explained below.

What is the polyvinyl alcohol polymer used in the present invention?
A polymer having H2-C-)-(R is H or a methyl group, preferably H) unit, including a homopolymer, a normal copolymer, a block copolymer, a graft polymer, a formal, It includes all polymers such as post-reacted polymers such as butyralized polymers.

Among these, polyvinyl alcohol obtained by polymerizing and saponifying vinyl esters such as vinyl acetate, or vinyl esters such as vinyl acetate are used as comonomers.
Preferred are polyvinyl alcohol copolymers which are obtained by copolymerizing with gin, alkyl vinyl ether, methyl acrylate, Ikucon, maleic anhydride, etc. and saponifying the copolymer. Since the unsaponified residual vinyl ester units of polyvinylalyl-based RK consume the alkali compound of the catalyst used in the reaction with the alkyl vinyl ester, it is preferable that the degree of saponification of the vinyl ester units is high. , 80 molti or more is desirable. The degree of polymerization of these polyvinyl alcohols or polyvinyl alcohol copolymers is not particularly limited, but is 10 to 100.
00, preferably 200 or more. The form of the polymer during the alkylvinyl sulfoxytotono reaction is not particularly limited, and may be in any form such as solution, melt, powder, film, Kawa-Hisui, and foam.

Suitable alkyl vinyl sulfoxides include alkyl vinyl sulfoxides containing an alkyl group having 1 to 10 carbon atoms, such as methyl vinyl sulfoxide, enal vinyl sulfoxide, butyl vinyl sulfoxide, cyclohexyl vinyl sulfoxide, and benzyl vinyl sulfoxide (~ Among them, methyl, enal,
Lower alkyl vinyl sulfoxides having from i to 4 carbon atoms, such as butyl, have good reactivity and are preferred. The reaction between the polyvinyl alcohol polymer and the alkyl vinyl sulfoxide is not particularly limited and may be carried out in any manner as long as both substances can undergo a catalytic reaction. However, usually a solution method involves reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide in an aqueous solution, or if the polyvinyl alcohol polymer is water-immiscible, the polymer is immersed in an aqueous solution containing an alkyl vinyl sulfoxide. , reaction methods, etc., aqueous reactions are preferred because the reaction speed is as high as 1 ship. In addition, polar solvents such as dioxane, detrahydrofuran, diethyl ether, acetone, dimethyl sulfoxide, dimethyl formamide, and formamide can also be used. Other solvents can also be used as long as they do not inhibit the reaction.

In the reaction between a polyvinyl alcohol polymer and an alkyl vinyl sulfoxide, an alkali or alkali metal hydroxide is used as a reaction catalyst, especially sodium hydroxide,
Potassium hydroxide is preferred.

-i The alkali concentration is preferably 0.005 to 5, preferably 0.01 to 3 in molar ratio to the hydroxyl groups of the polyvinyl alcohol polymer. If the molar ratio is less than 0.005, the reaction rate is low, and if the amount of alkali is too large, side reactions such as decomposition or coloring of the polymer will occur, which is not preferable. The amount of alkyl vinyl sulfoxide used is preferably 0.001 or more in molar ratio to the hydroxyl group of the polyvinyl 7/l/coal subcombination, preferably 6J: o
, 01 or more. There is no particular upper limit to the amount of alkyl vinyl sulfoxide used, but even if it is used in a larger amount than necessary, it will be difficult to react all of the hydroxyl groups.
It is usually applied at a molar ratio of 10 or less.

The reaction temperature and time are determined as appropriate, taking into account the desired reaction rate, shape retention of the reactants, etc., but from the viewpoint of side reactions, an appropriate reaction rate I (y and decomposition coloration of the polymer <1i, The reaction temperature is 20-100°C1 (~30-8
5°C, reaction time is 1 minute to 10 hours, preferably 30 force to
It is 5 hours. After the reaction, the unreacted alkylvinyl sulfoxide and the unreacted alkyl vinyl sulfoxide are separated and purified by washing, etc., and then post-treated by drying.

Amount u of alkyl sulfoxide group introduced: h Can be controlled by adjusting the reaction conditions mentioned above. The amount of alkyl sulfoxide groups to be introduced is at least 0.1 mole, preferably at least 1 mole, most preferably at least 5 mole, based on the hydroxyl group of the polyvinyl alcohol polymer. The upper limit is not particularly limited, but is about 80 mol. If it is desired to introduce alkyl sulfoxide groups only onto the surface of a molded product of polyvinyl alcohol polymer, the same amount as above may be introduced to the hydroxyl groups on the surface of the molded product.

The thus obtained modified polyvinyl alcohol polymer (1, 1) has poor adhesion to inorganic materials such as glass, so it can be used in applications that take advantage of these properties. For example, stone board, glass (31,
It can be effectively used as a binder, adhesive, or coating agent for inorganic materials such as glass fibers, rock wool, and ceramics, and as an additive or surface finishing agent for C↓cemen i and mortar. In addition, the 11i2 1iV agent for fibers, fiber processing agent, surface sizing of paper 11, binder for pigment coating, papermaking Kawauchi correction, improving agent for amine resin adhesive, protective colloid for emulsion, photosensitive resin, molded article (film, sea 1-, pipe, tube,
It can also be used as an adhesive for materials such as fibers, wood, paper, aluminum foil, and plastics, and as a binder for nonwoven fabrics.

The modified polyvinyl alcohol polymer of the present invention has excellent affinity and permeability to the skin and epidermis of animals and plants, and is effective as a spreading agent or binder for medical materials such as dialysis membranes, etc. Furthermore, by combining a medicinal ingredient with the modified polyvinyl alcohol polymer of the present invention,
It can also be used as a so-called polymer drug.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Note that the section indicates the Mt section unless otherwise specified.

Example 1 Polymerization degree = 1750 in a reaction vessel equipped with a stirrer and a thermometer
, degree of saponification 98.2 mol - 5 of polyvinyl alcohol
．． 845 parts of an aqueous solution of 2.5% was added thereto, and the temperature was raised to 60° C. while stirring. To this, 400 parts of a 10% aqueous sodium hydroxide solution was added (the molar ratio of sodium hydroxide to the hydroxyl group of polyvinyl alcohol was 1.0), and after adding 90 parts of methyl vinyl sulfoxide to the slurry, the mixture was stirred at 60°C for 5 hours. I reacted to it. After cooling the reaction container from the outside and cooling the reaction solution to 25° C., the reaction solution was poured into a large amount of methanol, and the precipitated modified polymer was separated from P. The catalyst and unreacted methylvinyl sulfoxide were removed by thoroughly washing the polymer (combined product) with methanol, and then it was dried at 70°C for 5 hours.The weight of the obtained polymer was 55 parts. In the infrared absorption spectrum of
Absorption based on the secondary alcohol of vinyl alcohol was observed, and it was found that this polymer was modified polyvinyl alcohol modified with methyl vinyl sulfoxide. Furthermore, when the polymer was dissolved in deuterated water and subjected to proton nuclear magnetic resonance spectroscopy, it was found that the hydroxyl group of vinyl alcohol decreased, the absorption of methyl proton of methyl sulfoxide was reduced to 2.5 prMiCu, and that of methyl vinyl sulfoxide. Since no proton signal of the vinyl group was observed, it was found that the reaction was an addition reaction of the vinyl group of methylvinyl sulfoxide to the hydroxyl group, and modified polyvinyl alcohol into which a methyl sulfoxide group was introduced was preferable. From the results of S elemental analysis, it was found that the methyl sulfoxide unit (7) was 14.3 mol% (denatured mol% of vinyl alcohol units).

Examples 2 to 6 400 parts of a 4.5% aqueous solution of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 99.2 mol. The molar ratio of the amount of methyl vinyl sulfoxide to the hydroxyl group of polyvinyl alcohol is 0.5.1.0.1.
5.2.0.3.0 and reacted, modified polyvinyl alcohol having the modified amount (introduced amount) shown in Table 1 was obtained. The obtained 5% aqueous solution of modified polyvinyl alcohol was prepared and cast onto a glass plate so that the film thickness after drying was 50 μm, and dried at room temperature. After that, 20℃×6
After conditioning the humidity at 5% RH for more than 7 days, apply cellophane tape to the film to reinforce it, cut it into 2 cm wide pieces, peel it at 9o0 at a head speed of 100+a/min, and use the peeling stress as the adhesive force of 2/( 7) Measured in units. Table 1 shows the amount (mole ratio) of methyl vinyl sulfoxide used during the reaction, the amount of methyl sulfoxide modified, and the adhesive strength to the glass surface. For comparison, modified polyvinyl alcohol modified with anti-phoxite was found to have excellent adhesion to glass.

Table 1 Example 7 Instead of polyvinyl alcohol in Example 1, polymerization degree 55
When methyl vinyl sulfoxide was reacted under the same conditions as in Example 1 except that polyvinyl alcohol with a saponification degree of 97.5 mol was used, the amount of modification of methyl sulfoxide was changed to 13.5 mol of modified polyvinyl alcohol. fc.

Examples 8 and 9 Reactions were carried out under the same conditions as in Example 1, except that the amount of sodium hydroxide used in Example 1 was adjusted to a molar ratio of 0.5 (Example B) and 0.1 (Example 8) to hydroxyl groups. However, when the modified amount of methyl sulfoxide was 12.5 mol (Example 8)
and 7.7 mol modified polyvinyl alcohol (Example 9).

Examples 10 and 11 The reaction temperature of Example 1 was changed to 30°C (Example 10) and 75°C.
℃ (Example 11), the reaction was carried out under the same conditions as in Example 1, and the modification time of methyl sulfoxide was 6.1 mol%.
(Example 10) and 14.5 mol of modified polyvinyl alcohol (Example 11) were obtained.

Example 12 5 parts of an ethylene-vinyl alcohol copolymer film having an ethylene content of 50 molt and a degree of polymerization of 800 was poured into 50 parts of an aqueous solution containing 2 parts of potassium hydroxide and 12 parts of isopropyl vinyl sulfoxide, and the mixture was heated at 50°C for 1 hour. A heating reaction occurred.

After the reaction, the film was taken out, thoroughly washed with methanol, and dried.The amount of modification of isopropylsulfoxide units on the surface was determined by total infrared analysis, and it was found to be 12 moles.

Example 13 800 parts of a 5% aqueous sodium hydroxide solution was added to 150 parts of a 30% aqueous solution of polyvinyl alcohol with a degree of polymerization of 50 and a saponification level of 92 molt in a reaction vessel, and 200 parts of ethyl vinyl sulfoxide was added thereto, and the mixture was heated at 60°C. It reacted for 1 hour. The same post-treatment as in Example 1 was carried out, and 12 mol of modified polyvinyl alcohol was used.

Example 14 Example except that an itaconic acid-vinyl alcohol copolymer with an itaconic acid content of 2 mol (degree of polymerization 17 (10, saponification i 98.5 mol%) was used instead of the polyvinyl alcohol of Example 1) The reaction was carried out under the same conditions as in 1 to obtain an X-type polyvinyl alcohol copolymer having a modified amount of methyl sulfoxide of 12.5 moles.

Patent applicant Rira Co., Ltd. Patent attorney Honda Ken Procedural amendment (spontaneous) July 2, 1980 Patent application No. 58-94669 2 Name of the invention Process for producing polyvinyl alcohol polymer Kurashiki Ichizakeoki 1
Address 62j (108) RiRashi Co., Ltd. Representative Director Satoko Kami et al. - 14th Director 2045-1 Aoeyama, Sakaoki, Kurashiki City RiRashi Co., Ltd. Telephone: Tokyo 03 (277131, 82 5 of the specification subject to the 5th amendment) Detailed Description of the Invention Column 6, Contents of Amendment (1) Between the 5th and 6th lines of page 11 of the specification, the following sentences in parentheses should be changed accordingly.

Claims (1)

[Scope of Claims] (1) A method for producing a modified polyvinyl alcohol polymer into which an alkyl sulfoxide group has been introduced, which comprises reacting a polyvinyl alcohol polymer with an alkyl vinyl sulfoxide. (2) tF+Fr, wherein the alkyl vinyl sulfoxide is an alkyl vinyl sulfoxide having 1 to 10 carbon atoms.The method for producing a modified polyvinyl alcohol polymer according to claim 1. (8) Alkyl vinyl sulfoxide is carbon 1 + < number 1 ~
4. A method for producing a modified polyvinyl alcohol polymer according to claim 1, which is a lower alkyl vinyl sulfoxide of No. 4. (4) The modified polyvinyl alcohol system according to claims 41 to 3, wherein the amount of alkyl sulfoxide groups introduced into the modified polyvinyl alcohol polymer is 0.1 mole or more based on the hydroxyl group of the modified polyvinyl alcohol polymer. Polymer manufacturing method. (5) The method for producing a modified polyvinyl alcohol polymer according to claims 1 to 4, wherein the polyvinyl alcohol polymer is a polyvinyl alcohol having a degree of saponification of 80 molar or more. (6) Claim 1, wherein the polyvinyl alcohol polymer is a saponified vinyl acetate-ethylene copolymer.
A method for producing a modified polyvinyl alcohol polymer according to items 4 to 4.