JPS6026404B2 - Method for producing derivatives of unsaturated polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method* for producing derivatives of unsaturated polymers.

Specifically, the present invention relates to a method for producing a reactive unsaturated polymer by adding a Q,8 unsaturated carboxylic acid in an ester form to an unsaturated polymer having a carbon-carbon double bond. Conventionally, a method is known in which an unsaturated polymer is reacted with acrylic acid in the presence of an organic peroxide.
In this case, the carbon-carbon double bonds of acrylic acid react as shown in the following formula, and a (poly)acrylic acid adduct of an unsaturated polymer is produced. The method of the present invention involves directly reacting an unsaturated polymer with a Q,8 unsaturated carboxylic acid to form an ester bond between the unsaturated polymer and the Q,8 unsaturated carboxylic acid as shown in the following formula.

That is, in the present invention, by reacting an unsaturated polymer with a Q,8 unsaturated carboxylic acid in the presence of an organic sulfonic acid or an inorganic acid, and introducing a Q,8 unsaturated carboxylic acid ester into the unsaturated polymer, A method of producing a polymer having Q,8 unsaturated ester groups is provided.

The unsaturated polymer used in the present invention is a polymer having a carbon-carbon double bond in its molecule. Examples of these polymers include polymers of DEN, copolymers of DEN and olefins or vinyl compounds, ring-opening polymers of cyclic olefins, and the like. Examples include polymers or copolymers of ptagene, isoprene, and piberylene, and ring-related or ring-opened copolymers of cyclobentene and cyclooctene. Specifically, polybutadiene, polysoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, poly 1,3-pentadiene,
Examples include copolymers of bentadiene and styrene, polybentenamer, polyoctenamer, copolymers of cyclobentene and cyclooctene, and ethylene-bropyrene-gene copolymers.

Examples of the organic sulfonic acids used in the present invention include haloalkyl sulfonic acids such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid, para-toluenesulfonic acid,
Benzene sulfonic acid, naphthalene sulfonic acid, etc. are used, and examples of the inorganic acid include sulfuric acid, fluorosulfonic acid, and chlorosulfone sulfuric acid. In addition, the Q,8 unsaturated carboxylic acids used in the present invention include acrylic acid,
Examples include methacrylic acid, crotonic acid, and cinnamic acid. The reaction in the present invention is usually carried out by adding a Q,8 unsaturated carboxylic acid to an unsaturated polymer in a suitable solvent, and then adding an organic sulfonic acid or an inorganic acid.

Alternatively, an organic sulfonic acid or a mixture of an inorganic acid and a Q,3 unsaturated carboxylic acid can be added to the solution of the unsaturated polymer for reaction. The solvent used in the reaction is not particularly limited as long as it does not inhibit the reaction, but halogenated hydrocarbons such as 1,2 monoethitane dichloride and benzene chloride, and hydrocarbons such as benzene and toluene are preferably used.

The reaction is usually carried out in the range of 0 to 15 qo, preferably 30 to 120 qo.

The reaction can be carried out by adding a small amount of a Q,8 unsaturated carboxylic acid polymerization inhibitor such as P-methoxyphenol.

Since the unsaturated polymer derivative obtained by the present invention contains a reactive Q,8 unsaturated ester group in its molecule, it can be reacted in the presence of an appropriate catalyst or by means of light, heat, etc. It can be used as a polymer.

These are useful in applications such as paints, photosensitive polymers, crosslinking agents, curing agents and other industrial materials. Examples 1 to 10 A solvent was added to the unsaturated polymer shown in the table below to dissolve the polymer, and then acrylic acid (Kiyoshi, Wako Pure Chemical Industries, Ltd., special reagent grade, containing 0.02% quinone compound) was added, and the following Paratoluenesulfonic acid (monohydrate) or sulfuric acid was added to the mixture, and the mixture was stirred and reacted at a predetermined temperature.

The reaction mixture was poured into a large amount of methanol containing a small amount of 2,6-tertiarybutylparazole to precipitate the polymer. The crude polymer was dissolved in toluene and poured into a large amount of methanol containing a small amount of 2,6-di-tert-butyl parazole for precipitation. The produced polymer was vacuum dried at 40qC. The produced polymer was identified by infrared absorption spectrum. The results are shown in Table 1 and FIGS. 1 and 2. Table 1 However, Polymer A: polybutadiene (cis-1.4:77%,
Trans 1.4: 20%, 1.2: 3%)
RBROI) = 2.60 (30qo in toluene)
Polymer C: 1.2 polybutadiene (JSRRB810
) [ri] = 1.28 (30 qo in toluene) Polymer D
: Cis-1.4 polyisoprene (cis-1.4:73%
, transformer 1.4:21%, 3.4:6%) [ri]=
0.47 (3C in toluene) a 30°C in toluene (1 night/day) b Determined from elemental analysis of the produced polymer.

c value (30 oo in toluene) The produced polymer was identified and the results were as follows.

The infrared absorption spectrum of the polymer falsified in Example 4 is shown in FIG. 1, and for comparison, the spectrum of raw material polymer A is shown in FIG. From Figure 1, in the infrared absorption spectrum of the produced polymer, the absorption due to Q,B unsaturated ester is 1725-1,128 quintessence-1,120 quintessence-
It appears strongly in the 1,106 ratio S-1.

On the other hand, since absorption of carboxylic acid, which characteristically appears in the vicinity of 3000 to 250 ratio N-1, was not observed, it was confirmed that an acrylester group was introduced into the produced polymer. Example 11 Benzene sulfonic acid (
The reaction was carried out in the same manner as in Example 4, except that the solution (monohydrate) was used overnight.

The yield of the produced polymer was 1.01 minutes, [ri] = 0.14,
The amount of acrylic acid added was 14.5 mol%. Example
12 Except for using crotonic acid instead of acrylic acid,
The reaction was carried out in the same manner as in Example 4.

The yield of the produced polymer was 1.01 minutes, [ri] = 0.13,
The amount of crotonic acid added was 3.8 mol%. In the infrared absorption spectrum of the produced polymer, the absorption by Q,8 unsaturated carboxylic acid ester is 1720 skin-1,1275
It was recognized in Nuke-1,1195 Ne-1,1047 Arc-1. Example 13 The reaction was carried out in the same manner as in Example 4, except that cinnamic acid was used instead of acrylic acid.

The yield of the produced polymer was 0.83 minutes, [ri] = 0.15,
The amount of cinnamic acid added was 8.1 mol%. From the infrared absorption spectrum of the produced polymer, absorption due to Q,3 unsaturated carboxylic acid ester was observed in 171 ratio Ne-1 and 1190 Hada-1. Example 14 Trifluoromethanesulfonic acid 0.2' instead of sulfuric acid
The reaction was carried out in the same manner as in Example 7 except that .

The yield of produced polymer is 1.11 minutes, [ri] = 0.13
The amount of acrylic acid added was 27.8 mol%. The infrared absorption spectrum of the produced polymer was similar to that of Example 4. Example 15 Crystalline 1,2-polyptadiene used in Example 9.
A mixture of 7.4 liters of acrylic acid and 0.1 liters of trifluoromethanesulfonic acid was gradually added to a mixture of 7.4 liters of acrylic acid and 0.1 liters of trifluoromethanesulfonic acid while heating the mixture, and after stirring at 80 qo for 3 hours, The same treatment as in Example 1 was performed.

The yield of product is 0. Madarayu, the amount of acrylic acid added is 24.
It was 6 mol%.

Example 16 Methacrylic acid (Wako Pure Chemical Industries, Ltd.) instead of acrylic acid
The experiment was conducted in the same manner as in Example 14, except that 7.1 grains (grain, reagent grade 1) were used.

The yield of the produced polymer was 1.31 hours, and the amount of methacrylic acid added was 157 mol%.

Brief Description of the Drawings Figure 1 shows the infrared absorption spectrum of the polymer obtained in Example 4, and Figure 2 shows the infrared absorption spectrum of the unsaturated polymer A used as the raw material.

Figure 1 Figure 2

Claims (1)

[Claims] 1 An unsaturated polymer having a carbon-carbon double bond,
A method for producing an unsaturated polymer derivative, which comprises reacting an α,β unsaturated carboxylic acid in the presence of an organic sulfonic acid or an inorganic acid to introduce an α,β unsaturated carboxylic acid ester group into the unsaturated polymer. .