JPS5852305A - Polymer or copolymer containing polar group - Google Patents

Abstract

PURPOSE:To obtain a (co)polymer having excellent oil resistance and reactivity characteristic of an aldehyde, prepared by saponifying a (co)polymer of 1-acetoxy-1,3-butadiene. CONSTITUTION:Part or all of the acetoxy groups of 1-acetoxy-1,3-butadiene polymer or copolymer are saponified. Said 1-acetoxy-1,3-butadiene can be prepared by acetoxylating butadiene in the presence of a noble metal catalyst such as palladium or by heating crotonaldehyde in the presence of acetic anhydride and an alkali metal acetate. The 1-acetoxy-1,3-butadiene (co)polymer can be saponified by hydrolysis or alcoholysis by contact with water or an alcohol in an alkaline range in the presence of an alkali such as sodium hydroxide or a salt showing alkalinity, such as potassium acetate or in an acidic range of below pH2 in the presence of a strong acid such as sulfuric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymers or copolymers having polar groups. More specifically, it is obtained by saponifying a polymer or copolymer (hereinafter abbreviated as (co)polymer) of 1-acetoquine-1,3-butadiene (hereinafter abbreviated as 1-ABD).
(Co) Concerning N coalescence.

Conventionally, saponified products of (co)polymers of vinyl acetate are well known, but these saponified products are (co)polymers with hydroxyl groups.3) Polymers with these hydroxyl groups It has many characteristics such as good hydrophilicity and excellent oil resistance, and the ability to control *notes by changing the degree of saponification, so it has been put into practical use in many fields.

On the other hand, little is known about (co)polymers with aldehyde groups, but since aldehyde groups have a reactivity of %M, (co)polymers with aldehyde groups in the (co)N chain are Many uses are conceivable. The present inventors conducted intensive studies on (co)polymers having hydroxyl groups and aldehyde groups in the polymer chain, and found that (co)polymers of 1-ABD The (co)polymer that has been hydrolyzed or alcoholized is
It has hydroxyl groups and aldehyde groups, the amount of which can be controlled by the degree of hydrolysis or alcoholysis, and the obtained (co)polymer has extremely excellent oil resistance and has the reactivity peculiar to aldehyde groups. We discovered that this is a novel polymer with the following characteristics, and arrived at the present invention.

That is, the present invention provides a (co)polymer obtained by saponifying a part or all of the acetoquine groups of a (co)polymer of 1-ABD.

The present invention will be specifically explained below.

The former of the (co)polymer of the present invention @ (co)polymer is 1-ABD
It is a (co)polymer of

This 1-ABD can be obtained by acetoquination of butadiene in the presence of a noble metal catalyst such as palladium, or by heating in the presence of crotonaldehyde 'f#, hydroacetic acid and an acetate of an alkali metal. 1-ABD obtained by these reactions is a mixture of cis and trans forms, but 1-ABD, which is the precursor (co)polymer of the present invention, is a mixture of cis and trans forms.
The monomer used to produce the (co)N combination of ABD may be the cis or trans form alone, or a mixture thereof. It may also contain impurities to the extent that it does not cause any inconvenience.

1-ABD is capable of being polymerized alone and copolymerized with many monomers such as ethylene, unsaturated dienes, and the like. Examples of co-monomers include alkyl acrylate, alkyl methacrylate,
Acrylonitrile, methacrylaterile, styrene and its substituted products, vinyl acetate, methacrylic acid, acrylics include butadiene, isoprene, chloroprene, etc.
It can be copolymerized with many monomers, not limited to those listed here.

Polymerization of 1-ABD is usually carried out by emulsion polymerization or suspension polymerization in an aqueous medium in the range of -20 to 100°C using a surfactant, a polymerization initiator, a chain transfer agent, etc., but the presence of a 1-ABD initiator However, bulk or solution polymerization can also be carried out.

According to NMR analysis, the 1-ABD unit in the c#) polymer of 1-ABD thus obtained was 1
．． has a 4-bond, a 3,4-bond and a 1,2-bond,
1.4-bonds 50-90%, 3.4-bonds 5-40% and 1.2-bonds 6-20%.

For example, a polymer of 1-ABD alone polymerized at 10°C using a redox polymerization initiator has 71% of 1.4-bonds and 6
．． The binding mode was 18% for 4-bonds and 11% for 1.2-bonds.

In this way, (co)polymers with various 1-ABD bonding modes can be produced by hydrolysis or alcoholysis.
The acetoxy group in the 4-bond and 1,2-bond changes to a hydroxyl group, but in the 6,4-bond, it changes to an aldehyde group by keto-enol conversion. Therefore 1-AB
A (co)polymer having both a hydroxyl group and an aldehyde group is obtained from the (co)11 polymer of D, and the amount of hydroxyl group and aldehyde group depends on the degree of saponification and/or the amount of other monomers added to 1-ABD. It can be controlled by polymerization.

Next, the method of hydrolysis and alcohol rinsing of the (co-)offshore bodies of VC1-ABD will be described.

The (co)N combination of 1-ABD is prepared by ano1. In the potash area,
Alternatively, it can be saponified by water decomposition or alcohol rinsing with water or an alcohol such as methanol, ethanol, or inopropyl alcohol in the presence of a strong acid such as sulfuric acid at a pH of 2 or less.

Hydrolysis or alcoholysis as necessary 1-A
Needless to say, the above reaction can be carried out by dissolving the (co)polymer of BD in a suitable solvent, but the above reaction can also be carried out in the form of an emulsion of the 1-ABDO(co)N polymer. In parallel with this, hydrolysis or alcohol rinsing can also be carried out in the same reaction system.

In reactions in the alkaline region, the reaction rate varies greatly depending on the combination of the type and amount of alkali, the amount of water or alcohol, and the reaction temperature, so conditions cannot be determined unconditionally, but the usual reaction temperature is 0 to 100.
℃. Also, even in reactions in the acidic region of pH 2 or less, the reaction rate varies greatly depending on the reaction conditions, and the reaction temperature is a particularly big factor, preferably 50℃ or higher, and 70℃ or higher.
-100 degreeC is more preferable.

Regardless of the conditions, the rate of hydrolysis of the (co)polymer of 1-ABD or saponification of acetoxy groups by methacrylic acid can be arbitrarily selected by appropriately selecting the combination of the above reaction conditions and reaction time. be able to. In the present invention, the saponification rate of acetoxy groups in the (co)polymer of 1-ABD is not particularly limited, but is usually 1 to 10.
0%, preferably 5 to 100%.

Regarding the hydrolysis or the reaction method in methanol, any method can be selected, such as a one-time charge type and a continuous countercurrent or cocurrent type.

1 of the acetoxy groups of the (co)polymer of 1-ABD of the present invention
(Co)polymers made by saponifying some or all of the parts have extremely excellent oil resistance and excellent adhesive properties, and can be used in many fields that utilize the reactivity of hydroxyl and aldehyde groups. used in

Next, the present invention will be described in more detail with reference to Examples.0 Example 1 40 mL of nitrogen sewage was placed in a glass separable flask with a capacity of 1 t.
Dissolve 6y of sodium dodecylbenzenesulfonate in 0y, stir, and dissolve 0.7y of 1-dode/lumerkabutane.
200y of dissolved 1-ABD was added and emulsified at 8°C.Into this were added 0.04y of sodium bisulfate, 01y of sodium ethylenediaminetetraacetate, ferrous sulfate,
2 f and sodium formaldehyde sulfoxylate 01 were charged. While stirring thoroughly at 8°C, add paramenthane hydroperoxide 2y.
Polymerized for hours. Thereafter, 1.0 y of N,N-diethylhydroxylamine was added to stop the reaction.

An emulsion containing no coagulum was obtained, and the polymerization rate was 98%. When this emulsion 5007 was dropped into 3 tons of methanol with stirring, a white polymer was precipitated.

This polymer was thoroughly washed with methanol and dried.

Dissolve 2 oz of this polymer (B) in 1 part acetone and add 0
, add 1201 cc of 2N sodium hydroxide aqueous solution,
When the reaction was carried out at 50° C. for 5 hours with stirring, a polymer was precipitated, and the polymer was washed with acetone and dried to obtain a pale yellow polymer (C) 12.7y.

When the IR spectrum of the polymer (C) was measured using an infrared spectrophotometer, the absorption related to acetoxy groups disappeared;
Absorption of hydroxyl groups and aldehydes was observed.This is shown in the figure.

Example 2 Example 10 Polymer (B) 0.29 in acetone 20CC
20 cc of 0.2N sodium hydroxide solution in methanol was added to the mixture, and the mixture was reacted at 50° C. for 5 hours with stirring. The product R7.6 of the polymer obtained by this reaction was exactly the same as that shown in Example 1.

Example 3 Polymer Φ) of Example 1 0.2 y acetone 2 Q
The mixture was dissolved in CC, 12 occ of 0.2N aqueous sodium hydroxide solution was added thereto, and the mixture was reacted at 90°C for 5 hours.

The hydrolysis rate of the acetoxy groups in the polymer (g) obtained by this reaction was calculated from IRS = 3.
It was 8X.

Example 4 To 10F of the emulsion (A) obtained in Example 1, 10 ccl of an aqueous potassium hydroxide solution of 021q was added and reacted at 50° C. for 5 hours with stirring. The polymer (F) obtained by this reaction was purified in the same manner as in Example 1.

The hydrolysis rate of acetoxy groups in the polymer (F) was calculated from the engineering formula and was 27%.

Example 5 In Example 1, instead of 1-ABD 200y, 1-ABD 100. A copolymer was polymerized and purified in the same manner as in Example 1 except that F and steel L/7100y were used.

This copolymer 0,2y was dissolved in 20cc of acetone.
Add 2N sodium hydroxide aqueous solution Q 20 CC,
The reaction was allowed to proceed for 5 hours with stirring at 0°C.

When the copolymer obtained by the reaction was purified in the same manner as in Example 1 and its IR spectrum was measured, all absorptions related to acetoxy groups disappeared, and absorptions related to hydroxyl groups and aldehyde groups were observed.

Example 6 100 parts by weight of the polymer (C) obtained in Example 1, 1 part by weight of stearic acid, 750 parts by weight of MAF-Bo manufactured by Tokai Electrode ■, 2.4 parts by weight of tetramethylthiuram disulfide,
3.3 parts by weight of dibenzothiazyl disulfide was kneaded and press vulcanization was performed at 160°C for 20 minutes.
-6301, an oil resistance test was conducted by immersing it in toluene at 150°C for 70 hours. The results are shown in Table-1.

Comparative Example 1 An oil resistance test was conducted in the same manner as in Example 6 except that the polymer (B) obtained in Example 1 was used instead of the polymer (C) in Example 6. The results are shown in Table-1.

Table 1 Example 7 The 94-(C')2y obtained in Example 1 was mixed with IJium and heated at 100°C for 5 hours to produce ethyl ether, butyl acetate, It was a polymer that was completely insoluble in carbon tetrachloride, toluene, acetone, methanol, and isopropyl alcohol.

[Brief explanation of drawings]

The figure shows the strength of the polymer (c) obtained in Example 1. Patent applicant Akira Ito, patent attorney representing Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] A polymer or copolymer obtained by saponifying a part or all of the acetoxy groups of a 1-acetoxy-1,3-butadiene polymer or copolymer