JPS58201814A - Synthesis of novel copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer capable of regulating easily the introduction ratio and position of a functional group, by polymerizing a compound containing an unsaturated double bond with a fumaric dialkyl ester having a specific molecular structure. CONSTITUTION:A compound containing a polymerizable unsaturated double bond is polymerized with an unsymmetrical fumaric dialkyl ester (e.g., fumaric acid methyl t-butyl diester, etc.) shown by the formula (X and Y are alkyl and one or more are bulky branched alkyl) in the presence of a polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of copolymerizing diester dicarboxylic acid in order to introduce a functional group into a polymer. This invention relates to a method for producing a copolymer having unique and excellent performance by combining the compound and difurkyl heptalate in one unit when polymerizing the compound using various radical polymerization initiators as a raw material.

Conventionally, examples of compounds having single unsaturated double deposits include ethylene, boopylene, isoptylene, 1-propylene, vinyl chloride, styrene, and Aku! Ip+2)! Compounds such as Jru are in practical use,
Many polymerization and copolymerization methods are known. In addition to being used as they are in various products, these polymers can also be used with other organic compounds, inorganic compounds, or composites thereof, such as in the form of laminates, emulsions, etc. is produced and used.

However, these polymers, especially homopolymers, have many performance drawbacks along with their advantages. For example, polyolefins such as polyethylene and polypropylene have a common property that they do not have reactive functional groups in their molecular chains. This makes mixing processing with other organic compounds, inorganic compounds, and their composites impossible or difficult. ◎ Other polymers, such as polystyrene and polyvinyl chloride, also have problems in terms of dyeability, adhesion, etc. There are many points that should be improved.

In general, many techniques have been published to improve these drawbacks. For example, in the polymerization of polyolefins and substituted polyolefins, in order to make them reactive to heavy metals, they have a specific functional group and have polymerization performance. Examples include a method in which a compound is added and then copolymerized with the olefin by an appropriate polymerization method.

However, when applying these known methods, it is necessary to ensure that the added compound having a suitable functional group and polymerization performance simultaneously imparts desired performance without reducing the advantages of the original polyion fin. is required.

Unsaturated compounds such as carboxylic acids and carboxylic esters are well known as such additives, such as acrylic acid, acrylic esters, methacrylic acid, methacrylic acid-esters, and vinyl esters such as vinyl acetate. These additives are not necessarily preferable in terms of single-component reactivity with the olefin.

For example, when acrylic acid, methacrylic acid, or their esters are added during the polymerization of ethylene or propylene, the monoheavy metal properties of the additives are too large and the compound added at the desired position and ratio in the resulting copolymer is It is difficult to introduce functional groups.

Also, first synthesize polyolefins using an appropriate polymerization method. A method in which an additive having a functional group is subsequently added to the polyolefin by an appropriate method is also often used, but this method involves the use of maleic anhydride, fumaric acid, maleic acid esters, etc., which have relatively low polymerization performance. Fumaric acid esters are used.

Journal on Polymer Science
al of Polymer science) A
- 1 Volume 5.

On page 1539 there is an example of addition reaction between polyethylene and maleic anhydride. In addition, an example of an addition reaction between polypropylene and maleic anhydride is found in Kogyo Ihigaku Zasshi Vol. 71, 7432N, but it is clear that it is difficult to adjust the preferred introduction ratio and position of additives having functional groups.

The present inventors conducted intensive studies to improve the shortcomings of these conventional methods, and found that by using a fumaric acid dialkyl ester with a specific molecular structure as a polymerizable additive with a functional group, it was possible to combine it with various compounds. The present invention was completed based on the discovery that a copolymer can be easily synthesized and that the introduction ratio and position of functional groups can also be easily adjusted.

The present invention provides a copolymer characterized in that an asymmetric heptalic acid dialkyl ester having at least one bulky branched alkyl group is used when polymerizing a compound having a polymerizable unsaturated double bond. It concerns the synthesis method of

Examples of the compound having a polymerizable unsaturated double bond used in the present invention include ethylene, propylene, imbutylene, 1-butene, and 1-pentene.

Olefinic hydrocarbons such as l-hexene. butadiene,
Diolefin hydrocarbons such as isoprene, vinyl chloride, chlorinated melefins or diolefin hydrocarbons such as chloroprene, cyclic olefins or diolefins such as cyclohexene, cyclopentadiene, vinylcyclohexene, 7ran, vinylpyridine, vinylcarbazole, etc. Heterocyclic compounds containing a carbon-carbon 5- double bond, aromatic compounds containing a novinyl group such as styrene, α-methylstyrene, divinylbenzene, etc. Aromatic compounds containing vinyl groups such as vinyl chloride and vinylphenanthrene; unsaturated carboxylic acids such as acrylic acid, fumaric acid, and methacrylic acid; and methyl alkuroates.

Unsaturated carboxylic acid esters such as methyl methacrylate and methyl fumarate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl acetate, vinyl benzoate and vinyl butyrate, cyanated olefins or diolefins such as acrylonitrile and methacrylonitrile. Compound. Unsaturated carboxylic acid amides such as acrylamide and methacrylic acid amide can be used, but mixtures thereof can also be used.

The fumaric acid dialkyl ester used in the present invention is a compound represented by the following chemical formula.

1 〇 61 In the formula, X and Y are different alkyl groups.

For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5ec-butyl group, -butyl group, neopentyl group, 5ee-pentyl group.

Examples include isopentyl group, and X.

It is an essential requirement that at least one of Y is a bulky branched alkyl group. Various combinations of alkyl groups are possible for such asymmetric 7-malate diesters, such as methyl isopropyl fumarate diester, methyl t-7'f diester fumarate, methyl neopentyl fumarate diester, ethyl isopropyl fumarate diester. , ethyl t-butyl 7-malate diester, ethyl neopentyl fumarate diester, isopropyl t-butyl fumarate, and the like.

The fumaric acid dialkyl ester used in the present invention can be synthesized by various known esterification methods. For example, fumaric acid is first esterified with alcohol.2. Furthermore, there is a method of synthesizing the fumaric acid dialkyl ester by subjecting the obtained fumaric acid monoalkyl ester to other branch alcohols. Alternatively, it can be obtained from maleic anhydride or maleic acid by esterification and isomerization reactions.

The fumaric acid diester used in the present invention is preferably purified in advance by a method such as distillation.

In the present invention, copolymerization of a compound having a polymerizable unsaturated double bond and a fumaric acid dialkyl ester is carried out by a conventional method, for example, in the presence of a suitable radical polymerization initiator, in a solvent or without a solvent. The purpose can be achieved by heating as necessary at atmospheric pressure, elevated pressure or reduced pressure.

In that case, a method of replacing the reaction system with an inert gas such as nitrogen, helium, argon, etc. can also be implemented.

Radical initiators used in the present invention include, for example, various organic peroxides, redox reagents, perhalides, and oxygen, as well as heat, light, radiation, etc., and combinations thereof are also possible. .

When using a solvent, the polymerization methods used for radical polymerization include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization,
Any method of gas phase polymerization can be used. Regardless of which polymerization method is used, functional groups can be introduced into the resulting copolymer by changing the mixing ratio of the raw material compound having a polymerizable unsaturated double bond and fumaric acid dialkyl ester. Proportion and position can be easily adjusted.

According to the synthesis method of the present invention, a copolymer having a predetermined amount of functional groups can be easily obtained. Desirable processing properties such as dyeability, adhesion, internal solubility,
Comes with anti-static material.

improved. Furthermore, the ester group introduced into the copolymer is a must! ! Saponified to give various properties.

It can be subjected to reactions such as ester substitution and amidation.

Specific examples of the present invention are illustrated below, but these are not intended to limit the scope of the present invention. 9- The lower part indicates the weight.

Example 1-1 A predetermined amount of methyl t-butyl diester fumarate was charged into a 1 ton autoclave equipped with a stirrer and a thermometer, and the system was sufficiently purged with nitrogen and then replaced with ethylene gas. Then, 1.00 c of pure oxygen was added as a polymerization initiator.
o was introduced into the autoclave using a gas syringe, and ethylene 280y was further introduced. This was maintained at 160°C and polymerized for 6 hours while stirring. After the reaction was completed, the reaction mixture was cooled to room temperature and unreacted ethylene gas was released to obtain a reaction product.

The obtained reaction product was dissolved in hot decalin, poured into hexane, reprecipitated, and separated by filtration to obtain a polymer size. Table 1 shows the measurement results for the yield of the obtained polymer, the addition rate of fumaric acid dialkyl ester, and the molecular weight.

110-Table-1 Methyl fumarate The addition rate of t-butyl diester was calculated from the elemental analysis values. The molecular weight of the polymer was determined by Staudinger's limiting viscosity method.

The same applies to the following Examples and Comparative Examples.

Comparative Example 1 In the example, maleic acid or tsumarate was used instead of methyl t-butyl diester fumarate. The results are shown in Table-2 and Table-3.

As shown in Table 2 and Table 3, although the Examples showed a high addition rate, maleic acid hardly reacted and the addition rate of fumaric acid dimethyl ester was also extremely low.

Implementation-P2 A predetermined amount of styrene 20y and methyl t-butyl fumarate diester, which had been distilled and purified in advance, was charged into a sealed polymerization tube made of Pyrex glass, and a predetermined amount (2X 10” mol/l) of bezoyl peroxide (BPO) was added. The sealed tube was melt-sealed by thoroughly purging with nitrogen according to the usual method.The sealed tube for polymerization was placed in a shaking water bath at 80°C.
The mixture was kept at ±0.2°C and reacted for 6 hours. After polymerization,
The contents of the sealed tube were washed with methanol and reprecipitated with benzene-hydrochloric methanol to obtain a polymer. Table 4 shows the results for the obtained polymer.

Table 4 Comparative Example 2 The bounty reaction was carried out in the same manner as in Example 1-2 except that maleic acid or dimethyl fumarate was used instead of methyl t-butyl fumarate in Example 2. It became. The results are shown in Table-5 and Table-6.

13-Table 6 As can be seen, although the examples showed a high addition rate, maleic acid hardly reacted and the addition rate of fumaric acid dimethyl ester was also extremely low.

Example 1-3 Using an autoclave similar to that used in Example 1-1, a predetermined amount of methyl t-butyl diester fumarate and 0.5 g of lauroyl peroxide were charged therein, and the system was heated to -20°.
Temporary vinyl chloride 300F, which had been cooled and replaced with nitrogen, was introduced into C. This was polymerized for 6 hours while maintaining the temperature at 60°C and stirring. After the reaction was completed, the polymer was washed with water and passed through the mouth to obtain a polymer. The results for the obtained polymer are shown in Table-7.

14- Table-7 Example-1-4 Mix 150-dimethylformamide, predetermined amounts of methyl t-butyl fumarate diester, and acrylonitrile 120F in a 500 ml four-bottle flask equipped with a stirrer, temperature needle, and cooling tube. After the system was sufficiently purged with nitrogen, a solution of 3% by weight of azobisisobutyronitrile in dimethylformamide (20%) was added, and the temperature was maintained at 60°C for polymerization for 6 hours. After the reaction was completed, unreacted acrylonitrile was removed under reduced pressure using an aspirator, and the resulting polymer solution was added to a large amount of water to precipitate the polymer to obtain a produced polymer. Table 8 shows the results for the obtained polymer.

Table-8 Example-1-5 In an autoclave similar to that used in Example 1-1,
Predetermined amount of methyl t-butyl diester malate and 10 parts of rhodium chloride 2y sodium dodecylbenzenesulfonate,
400 mg of water was added, cooled, and 200 mg of butadiene was added. Next, polymerization was carried out at 80° C. for 4 hours without stirring, and after completion of zero polymerization, the mixture was cooled to room temperature and unreacted butadiene was removed.

The resulting polymer was obtained by adding the contents into methanol and precipitating it. Table 9 shows the results for the obtained polymer.

15-Table-9 However, the intrinsic viscosity was measured in 1-traline solvent, and the same applies below.

Example 1-6 In an autoclave similar to that used in Example 1-1, formamide 360 jE, methyl fumarate in a predetermined amount of monobutyl diester, styrene 25F, and butadiene 15
0 and sodium lauryl sulfate as an emulsifier.
Using 05F, 1.5y of dodecyl mercaptan was added, the system was sufficiently purged with nitrogen, and potassium persulfate I
P was added, stirred, and reacted at 50°C for 25 hours. After the reaction was completed, unreacted butadiene was removed, and phenyl β-naphthylamine was added to the resulting polymer in an amount of 2% by weight based on the polymer, followed by pouring into 25% brine to coagulate the polymer, washing with water, and drying to obtain a polymer.

17- 16- The results for the produced polymers are shown in Table-io.

Table 10 Examples 2-1 to 2-6 In Examples 1-1 to 1-6, ethyl neopentyl 7-malate was used as a substitute for methyl t-butyl fumarate as shown in Table 11. In each case, polymers were obtained by polymerization under similar reaction conditions corresponding to each case. The results are shown in Table-11.

18- Table-11 Examples 3-1 to 3-6 In Examples 1-1 to 1 to 6, methyl fumarate t-
When using isopropyl t-butyl fumarate as a substitute for butyl diester as shown in Table 12,
Polymers were obtained by polymerization under similar reaction conditions corresponding to each. The results are shown in Table-12.

Table-12 patent applicant Nihon Yugetsu-4 non-member λ soil

Claims (1)

[Claims] A method for synthesizing a copolymer, which comprises using an asymmetric 7-malate dialkyl ester having at least one bulky branched alkyl group when polymerizing a compound having an unsaturated double bond that can be superimposed. .