JPS59102902A - Production of chlorinated copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer useful as heat-resistant ink, etc., having extremely improved heat stability and heat softening properties, by subjecting 4-methylpentene-1, etc. to stereoregular polymerization by a Ziegler-Natta catalyst to give a copolymer, chlorinating uniformly it in a solution state. CONSTITUTION:4-Methylpentene-1 as a main constituent monomer is subjected to stereoregular polymerization using a Ziegler-Natte catalyst, to give a copolymer of 4-methylpentene-1 and another alpha-olefin (e.g., decene-1, etc.), which is dissolved in a solvent (e.g., carbon tetrachloride, etc.). The copolymer is reacted with gaseous chlorine in a solution state while being irradiated with light rays, it is uniformly chlorinated in >=50wt% chlorine content, to give the desired chlorinated alpha-olefin.4-methylpentene-1 copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides chlorinated α-olefin 4-methylpentene-
The present invention relates to a method for producing a copolymer.

The present applicant previously tested the product at 260°C and 5 Ky (with a melt index of 8 to 70 g/10n+in (ASTM
Chlorinated poly-4-methylpentene-1 obtained by uniformly chlorinating crystalline poly-4-methylpentene-1 (D1238-65T) in a solution state to a chlorine content of 50% by weight or more.
A method for producing a chlorinated polymer (Japanese Patent Application No. 54-153909), a coating composition (divisional application: Japanese Patent Application No. 57-211684), and a melt index (conditions: temperature 260°C, Pressure 5 to 9/cm
) is 8~70g/10m1n (ASTMD1238-
Chlorinated poly(4-methylpentene-1) obtained by chlorinating crystalline poly(4-methylpentene-1), which is
A heat-resistant coating composition characterized in that it is used in combination with at least 5 parts per 00 parts by weight (Japanese Patent Application No. 1973-
No. 037997), and the present invention provides a method for producing a chlorinated copolymer that is an extension of this method.

In Japanese Patent Application No. 54-153909, the applicant uniformly chlorinated crystalline poly-4-methylpentene-1 in a solution state to a chlorine content of 50% by weight or more, and compared it with conventionally known chlorinated polymers. Therefore, we have created a material that has significantly superior thermal stability and thermal softening properties.

The applicant has further disclosed copolymerized iphos produced by stereoregular polymerization using a Daegler-Natsuta catalyst using 4-methylpentene-1 as the main heptamer and one or more other α-olefins as monomers. When the chlorination of the copolymerized α-olefin monomer was within 20 mol%, the properties of the solution-method chlorinated product were found to be that of crystalline Vomoboly 4-methylpentene-1. Solution method - expected to be comparable to chlorinated products
The present invention was realized based on these results.

The applicant has already prepared chlorinated poly-4-metalpentene-1,
Other chlorinated polyα-olefins with lower softening temperatures (
J: found that a blend of riso (including diolefin) showed unexpected heat softening resistance and heat discoloration resistance (Japanese Patent Application No. 55-037997); Naturally, in the case of
He was inferior by a step or two. However, in the case of chlorinated copolymers, one or more other copolymerized α-
When the total amount of olefins is within 20 mol%, the properties of the resulting chlorinated copolymers are substantially comparable to those of chlorinated small 4-methylpentene-1 polymers; Since it has excellent solubility in carbon tetrachloride, it also has the advantage that it can easily dissolve chlorinated compounds in a solution method even below its boiling point, which is extremely advantageous economically.

The obtained chlorinated product is used in the above-mentioned Japanese Patent Application No. 54-153909 and "Adhesive Composition" (Japanese Patent Application No. 128104-1982).
Similar to the invention described in No. 1, etc., by taking advantage of its thermal decomposition resistance, high heat softening humidity, and good weather resistance, it can be used alone or in combination with various substances to produce heat-resistant inks, OP varnishes, paints, etc. It was possible to produce an adhesive composition that is useful as a coating composition and has improved adhesive strength and heat creep resistance by blending with a rubber adhesive.

Furthermore, the chlorinated copolymer of the present invention is disclosed in the above-mentioned Japanese Patent Application No. 55-03.
Even when used for 7f, chlorinated homopoly-4-methylpentene-1 shows comparable results with other chlorinated polyolefins such as those described in No. 7997.

As examples of α-olefins to be copolymerized, it has been experimentally confirmed that both short chain monomers such as ethylene and propylene and long jf1 monomers such as octaacene have the characteristics of the product of the present invention. .

The present invention will be explained below based on examples.

Example 1 4-methylpentene-195mol% and decene-15m
O1% was produced by stereoregular polymerization using a Ziegler-Natsuta catalyst, and the null 1 to index was 8 g/1.
Take 200g of 1-decene/4-methylpentene-1 copolymer of 0mln (ASTMD1238-65T), add 5 parts of carbon tetrachloride, and heat at the boiling point of carbon tetrachloride (78°C) under normal pressure. After dissolving in the reactor, gaseous chlorine was blown into the reactor from the bottom after air purging and chlorination was carried out under normal pressure (temperature 78° C.).

The time required for chlorination in this case was 12 hours, but the chlorination was completed in a shorter time than the 15 hours required for chlorination of a homopolymer with the same melt index as described in Japanese Patent Application No. 54-15909. Ta.

Example 2 4-methylpentene-194mol1% and hexadecene-
13 mo1% and octadecene-13 mo1% were produced by stereoregular polymerization using a Ziegler-Natsuta catalyst, and the null 1 to index was 70'J/iomin.
Take 200 g of 4-methylpentene/hexade'cene/octadecene copolymer (A STM D 1238-65T), add carbon tetrachloride of 5 (5), and heat the solution at the boiling point of carbon tetrachloride (78°C) under normal pressure. ) a After understanding,
After air purging, chlorine in the form of scum was blown into the reactor from the bottom of the reactor under a light beam and chlorination was carried out under normal pressure (temperature 78° C.).

In this case, the time required for chlorination was 6 hours, but the chlorination was completed in a shorter time than the 8 hours required for chlorination of a homopolymer with the same melt index in Japanese Patent Application No. 54-15909. It was done.

In Examples 1 and 2, in the case of Japanese Patent Application No. 54-153909, it is difficult to dissolve the homopolymer below the boiling point of carbon tetrachloride (length 0.''i is required 1-), and homogeneous -jM reduction is guaranteed. -4, and from the viewpoint of economical practicality, Th
Dissolution at the J1 point or higher and chlorination under pressure were preferred at least at the initial stage of chlorination.

However, in the case of the present invention, most of the copolymer is easily dissolved even at normal pressure (at the boiling point of carbon tetrachloride), and the copolymer can be uniformly dissolved without chlorination under pressure from the initial stage of the reaction.
Fukusoification was implemented.

Various poly-4-methylpentene-1-based polymers were chlorinated in the same manner as in Examples 1 and 2, and their properties are shown in the table below.
Shown in 1.

As can be seen from Table 1, the substance of the present invention is commercially available and patent application filed in 1973.
It has properties comparable to those of substance No. 4-153909.

Comparative example: Null 1-index is 8g/10m1n
AS TMD-1238-65T) r Aloho E
Ho! J shows a chlorinated product of 4-methylbentene-1.

Explanation of various measurement methods in the table Softening temperature: Measured by melting point measuring device Thermochromic property = 180℃, discoloration ink heated after 30 minutes; Place coated base paper on the ink and heat seal bar set at each temperature. After pressing, it was left to cool for 30 minutes or more, and the paper was judged by the peeled state when it was peeled off.

◎・・・No paper peeling O・・・・・・5% or less △・・・30% or less ×・・・・・・50%
OP varnish: An OP varnish containing 20 parts by weight of commercially available chlorinated paraffin (Toyobara A pencil hardness -40: manufactured by Toyo Soda Co., Ltd.) was prepared, formed into a film, and then its pencil hardness was measured.

Claims (1)

[Claims] A copolymer of 4-methylpentene-1 and other α-olefin monomers produced by stereoregular polymerization with 4-methylpentene-1 as the main constituent monomer using a Ziegler-Natsuta catalyst is prepared in a solution state with zero chlorine content.
A method for producing a chlorinated copolymer, which is a chlorinated α-olefin/4-methylpentene-1 copolymer obtained by uniformly chlorinating 50% by weight or more.