JPS61283609A - Production of alpha,beta-unsaturated dicarboxylic acid anhydride polymer - Google Patents

Abstract

PURPOSE:To produce the titled polymer in good yields, by radical-polymerizing an alpha,beta-unsaturated dicarboxylic acid hydride in the presence of a specified copolymer (derivative) and a poor solvent. CONSTITUTION:A 12C or higher alpha-olefin is radical-copolymerized with an alpha,beta-unsaturated dicarboxylic acid anhydride (e.g., maleic anhydride) at 50-200 deg.C and, if necessary, the product is esterified to obtain an alpha-olefin/alpha,beta-unsaturated dicarboxylic acid copolymer or its derivative (A). To 100pts.wt. alpha,beta-unsaturated dicarboxylic acid anhydride, 0.5-10pts.wt. component A and a poor solvent (B) (e.g., butane) for the formed polymer and 1-30pts.wt. catalyst (C) (e.g., cumene hydroperoxide) are added and the mixture is radical-polymerized at 70-200 deg.C for 2-12hr.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing α,β-unsaturated dicarboxylic acid anhydride polymers, and more specifically, to efficiently produce α,β-unsaturated dicarboxylic acid anhydride polymers by slurry polymerization. The present invention relates to a method for producing an acid anhydride polymer.

(Prior Art) Polymers of α,β-unsaturated dicarboxylic acid anhydrides (hereinafter sometimes referred to as polydicarboxylic acids) represented by maleic anhydride can be used as a polymer itself or in the form of alkali metal salts, ammonium salts, and esters. It is known to be used in fields such as hardening agents, ink and adhesive additives, dye and pigment dispersants, detergent builders, textile treatment agents, and water treatment agents.

It is known that such polydicarboxylic acids are generally obtained by dissolving α, β-, β-dicarboxylic acid anhydride in an inert organic solvent and polymerizing it using a radical polymerization catalyst. For example, according to Japanese Patent Publication No. 53-20475, at least 30% of maleic anhydride is reacted using toluene as a solvent and benzoyl peroxide as a polymerization initiator.
Polymaleic anhydride can be obtained in high yield by polymerizing for hours at 70 to 120°C.

However, in such conventional methods, the product generally precipitates from the solution as a black colored tar-like substance, as is clear from the examples. The purification method is complicated, and involves the cumbersome operation of heating and dissolving the tar-like substance in a small amount of methyl ethyl ketone, precipitating the polymer with a large amount of toluene, and then separating it. In addition to complicating the process, there are other problems caused by the tarry nature of the product, such as agitation requiring a huge amount of energy, equipment clogging, and polymer buildup on vessel walls. However, there were problems such as unreacted maleic anhydride mixed into the product, resulting in a decrease in conversion rate.

(Problems to be Solved by the Invention) Therefore, the present inventors have conducted extensive research to solve these drawbacks of the prior art, and have found that by using a specific dispersant, cypolydicaldic acid is not treated as a tar-like substance. It was discovered that it can be manufactured in the form of a powder slurry, and based on this knowledge, the present invention was completed.

(Means for Solving the Problems) Thus, according to the present invention, in the presence of a copolymer of an α-olefin having 12 or more carbon atoms and an α,β-unsaturated dicargenic acid anhydride or a derivative thereof and a poor solvent. , α, β−, β
- Provided is a method for producing an α, β-, β-dicarboxylic acid anhydride polymer characterized by radically polymerizing a dicarboxylic acid anhydride.0 α, β-, β used as a monomer in the present invention. - The dicarboxylic acid anhydride may be any one commonly used in this technical field, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, etc. having 4 to 1 carbon atoms.
An example is one having 0. Among them, reactivity, quality,
Maleic anhydride has been praised for its economic efficiency.

These monomers may be used in combination of two or more types if necessary, and other comonomers that can be copolymerized may be used in combination within a range that does not essentially change the performance of the product. @ Specific examples of comonomers that can be used in combination include ethylene,
Propylene, isobutyne, butene-1, butene-2, pentene-1, pentene-2,2-)methylbutene-1,
2-methylbutene-2, hechusen-1,2,2,4-)
Chain monoolefins such as trimethylpentene-112, 2.4-trimethylpentene-2 and thecene-1, cyclic monoolefins such as cyclopentene, cyclohexene, and cyclooctene, styrene, α-methylstyrene, vinyltoluene, etc. Aromatic monoolefins such as the following are exemplified, and these are used in a proportion of 30 mole or less, preferably 20 mole or less, based on the total monomers.

The polymerization of the present invention is carried out in a poor solvent in the presence of a specific dispersant. The dispersant used is a copolymer of an α-olefin having 12 or more carbon atoms, preferably 20 to 40 carbon atoms, and an α,β-unsaturated decal anhydride, or an ester, amide, imide, or metal of the copolymer. While derivatives such as salts are preferred, copolymers themselves are preferred from the viewpoint of performance and economy.

Such a copolymer usually has a melting point of 40 to 110°C and an intrinsic viscosity of 0.05 to 0.3 at 25°C in a pyridine solvent.
di/I, and these are α-olefins with 12 or more carbon atoms obtained by polymerizing lower monoolefins such as ethylene and propylene using a Ziegler type catalyst, and α, β-unsaturated unsaturated decals. It can be obtained by radical copolymerization with an anhydride according to a conventional method, for example, at a temperature of 50 to 200°C. On this occasion,
Maleic anhydride is preferred as the α,β-unsaturated decal anhydride.

In addition, copolymer esters include methanol, ethanol,
The amide or imide of the copolymer can be obtained by esterification using a monohydric or polyhydric alcohol such as butanol, octatool, stearyl alcohol, ethylene glycol, glycerin, etc. according to a known method. It can be obtained by conventional methods using methylamine, ethylamine, butylamine, stearylamine, aniline, cyclohexylamine, monoethanolamine, ethylenediamine, etc. Further, metal salts of copolymers can be easily obtained using alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and the like.

However, when a copolymer of an α-olefin having less than 12 carbon atoms and an α,β-unsaturated dicardic acid anhydride is used as a dispersant, the effect of suppressing the production of oily substances is not sufficient.

The amount of dispersant used is usually per 100 parts by weight of the monomer components. 90.5 to 10 parts by weight, preferably 1.0 to 5 parts by weight; if the amount used is small, the effect of suppressing the production of oily substances will be small, and if the amount is large, it will not be economical. be at a disadvantage.

Furthermore, in the present invention, a poor solvent, that is, a solvent that does not dissolve the produced polymer, is used as the polymerization solvent. Specific examples of such poor solvents include linear, branched or cyclic aliphatic hydrocarbons such as butane, pentane, hexibane, hegetane, octane, decane, ligroin, cyclohexipne, etc., benzene, toluene, xylene, Examples include aromatic hydrocarbons such as chlorobenzene.

In the present invention, polymerization is carried out according to a conventional method in the presence of the above-mentioned poor solvent and dispersant.

Catalysts used in the reaction are middle hydrocarbon/9-oxycargenate, t-butylhydrono-oxide, di-t-butyl/J-oxidide, benzoyl peroxidide, diisopropyl and monooxydicargenate, t-butyl Organic peroxides such as peroxypivalate, α, α
′-azobisisobutyronitrile, α, α′-azo α
- azobis compounds such as ethylbutyronitrile,
Radical initiators such as redox catalysts,
There are no particular restrictions as long as it is a radical initiator.

The amount of such a catalyst used is usually 91 to 30 parts by weight, preferably 5 to 20 parts by weight per 100 parts by weight of monomer components.

Polymerization is usually carried out at 70-200°C, preferably at 90-150°C.
C. for 2 to 12 hours. (Effects of the Invention) Thus, according to the present invention, it is also possible to solve the problems associated with the production of oily substances as described above. That is, stable operation is possible without cleaning the polymerization mill for a long period of time, and polymers can be obtained efficiently with high yield. In addition, since the polymer can be produced in powder or suspension state, the polymer can be transported, separated, washed,
Purification etc. are easy, and the manufacturing process can be simplified.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and parts in Examples, Comparative Examples, and Reference Examples are based on the weight of an unbroken line. and a catalytic amount of dicumyl peroxide, and a polymerization reaction is carried out in the presence of xylene.
The copolymers shown in the table were obtained.

Example 1 196 parts of maleic anhydride was charged into a 31 autoclave equipped with a stirrer, the autoclave was sealed, and the system was then purged with gold and nitrogen. Then, 1000 parts of n-pentane was added under reduced pressure, and then the temperature was raised to 130°C. At the same temperature, 4.5 parts of the copolymer (II) obtained in Reference Example 1 and 25 parts of di-t-butylperoside were added as a dispersant over a period of 1 hour. Thereafter, polymerization was carried out by heating and stirring at the same temperature for 6 hours. After the polymerization reaction is completed, the produced specific polymer is extracted from the pulp at the bottom of the polymerization can.
The conversion rate was measured. The conditions inside the polymerization system and the occurrence of clogging of the bottom pulp were also observed. The la values are shown in Table 2.

Example 2 Polymerization was carried out in the same manner as in Example 1, except that the copolymer (2) obtained in Reference Example 1 was used as a dispersant.

The results are shown in Table 2.

Example 3 Polymerization was carried out in the same manner as in Example 1, except that the copolymer obtained in Reference Example 1 was used as a dispersant. The results are shown in Table 2.

Example 4 400 parts of maleic anhydride was charged into a 31 autoclave equipped with a stirrer, the autoclave was sealed, and the system was purged with gold nitrogen. The copolymer obtained in Reference Example 1 was added as a dispersant at the same temperature.
2) 9 parts and 50 parts of di-t-butyl peroxide were added over 1 hour. Thereafter, the mixture was heated and stirred at the same temperature for 6 hours to effect polymerization. The results are shown in Table 2.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that no dispersant was used. The results are shown in Table 2.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1, except that the copolymer (I) obtained in Reference Example 1 was used as a dispersant. .

The results are shown in Table 2.

From this result, it can be seen that in the case of the example of the present invention, no oily substances were produced and the conversion rate was high. However, when a copolymer of α-olefin with a small number of carbon atoms is used as a dispersant (Comparative Example 2), the effect of suppressing the formation of oily substances is not necessarily sufficient.

Claims (1)

[Claims] 1. Radical polymerization of α,β-unsaturated dicarboxylic anhydride in the presence of a copolymer of α-olefin having 12 or more carbon atoms and α,β-unsaturated dicarboxylic anhydride or a derivative thereof and a poor solvent. 1. A method for producing an α,β-unsaturated dicarboxylic acid anhydride polymer.