JPH01102060A - High-stability maleimide composition for heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain the titled composition which is copolymerization in the emulsion or suspension polymerization of an ethylenic unsaturated monomer, shows excellent storage stability and can be transferred with a pump, by using a specific amount of N-substituted maleimide, surface active agents, and colloid protective. CONSTITUTION:The subject composition contains, 5-60wt.% of a compound of the formula (R1, R2 are H, halogen, methyl; R3 is 1-18C alkyl, cycloalkyl or aryl which may be substituted with halogens), 0.1-5wt.% of a cationic surfactant such as sodium oleate, and/or a nonionic surfactant, such as polyoxyethylene stearyl ether, and 15-94.8wt.% of water. The composition is excellent in industry, because the polymerization system is kept stable and no deterioration of the polymer is caused.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a maleimide composition that can be used in the production of heat-resistant resins, and more specifically, a maleimide composition that has excellent storage stability, can be transported by pump, and The present invention relates to a highly stable maleimide composition for heat-resistant resins containing an N-substituted maleimide as a copolymerizable maleimide during emulsion and suspension polymerization of ethylenically unsaturated monomers.

<Prior art and its problems> Since N-substituted maleimide is generally solid at room temperature, it has conventionally been used in the form of powder, water-containing powder, or flakes. However, during operation, the N-substituted maleimide is a powder.

This increases the number of man-hours required for weighing and preparing, and causes a deterioration in work efficiency. Furthermore, since N-substituted maleimides generally have sublimation properties, they are also disadvantageous in terms of hygiene. In order to solve these drawbacks, for example, JP-A-54-3015
No. 7 discloses an aqueous suspension of maleimide.

However, the aqueous suspension of maleimide has insufficient storage stability and contains a cationic surfactant in the polymerization system, which makes the emulsion system and suspension system unstable. In addition, quaternary ammonium salts and amines not only rapidly ionically decompose peroxide, which is a radical polymerization initiator, but also affect the heat resistance and electrical properties of the polymer. There are still many unresolved drawbacks, such as the possibility of significantly reducing the particle size of the maleimide compound to be dispersed, and the need to limit the particle size of the maleimide compound to be dispersed to 5 μm or less.

<Objective of the Invention> An object of the present invention is to provide a highly stable maleimide composition for heat-resistant resins that has excellent storage stability and is suitable for measuring, preparation work, and transportation, especially pump transportation.

Another object of the present invention is to provide a highly stable maleimide composition for heat-resistant resins that stabilizes the polymerization system and prevents deterioration of the physical properties of the resulting polymer.

<Means for solving the problem> (a) The following general formula (1) (wherein R1 and R each represent a hydrogen atom, a halogen atom, or a methyl group, and R3 is an unsubstituted or unsubstituted group having 1 to 18 carbon atoms. 5 to 60% by weight of an N-substituted maleimide represented by a halogen-substituted straight-chain alkyl group, a mono-branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; and (b)
Anionic surfactant and/or nonionic surfactant 0.1-20% by weight and (C) colloid protectant 0.1-5%
(d) 15 to 94.8% by weight of water.

The present invention will be explained in more detail below.

General formula used in the present invention (1> R1 and R in the crane 〇 each represent a hydrogen atom, a halogen atom, or a methyl group, and R3 is an unsubstituted or halogen-substituted linear alkyl group having 1 to 18 carbon atoms, a monobranched alkyl group , the above R3 represents a cycloalkyl group, an aryl group or an aralkyl group
When the carbon number of L's is 19 or more, it cannot be used because it is difficult to manufacture. - methylmaleimide,
N-ethylmaleimide, N-n-propylmaleimide,
i'J-n-butylmaleimide.

N-1-butylmaleimide, N-pentylmaleimide, M-n-hexylmaleimide, N-cyclohexylmaleimide, N-n-hebutylmaleimide, N-n-octylmaleimide, N-2-ethylhexylmaleimide , N-n-dodecylmaleimide, N-laurylmaleimide, N-myristylmaleimide, N-hexadecylmaleimide.

N-octadecylmaleimide, N-phenylmaleimide, N-(2-methyl)phenylmaleimide.

N-(3-methyl)phenylmaleimide, N-(4-methyl)phenylmaleimide, N-(2-ethyl)phenylmaleimide, N-(2-chloro)phenylmaleimide, N-(3-chloro)phenylmaleimide, N-(4-
chloro)phenylmaleimide, N-(2,4-dichloro)phenylmaleimide, N-(2-bromo)phenylmaleimide, N-(2-fluoro)phenylmaleimide,
N-benzylmaleimide, N-methylbenzylmaleimide, N-methyl-α-chloromaleimide, N-methyl-
α-bromomaleimide, N-methyl-α-fluoromaleimide, N-cyclohexyl-α-chloromaleimide,
N-cyclohexyl-α-bromomaleimide, N-cyclohexyl-α, β-dichloromaleimide, N-cyclohexyl-α-methylmaleimide, N-phenyl-α-
Preferred examples include chloromaleimide, N-phenyl-α-methylmaleimide, N-benzyl-α-chloromaleimide, and N-benzyl-α-methylmaleimide. N-substituted maleimide may be used alone or as a mixture of two or more.

In the present invention, the content of the N-substituted maleimide in the composition is 5 to 60% by weight, particularly preferably 10% by weight.
~50% by weight. If the content is less than 5% by weight, a sufficient modifying effect cannot be obtained during copolymerization, which is undesirable. If the content is more than 60% by weight, the viscosity becomes extremely high, making it difficult to handle. This is not preferable because it becomes difficult.

Examples of anionic surfactants used in the present invention include:

For example, aliphatic salts such as sodium oleate and castor oil soap, N-acylamino acid salts, alkyl ether carboxylates, acylated peptides, alkyl sulfonates, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, alkylnaphthalenes, etc. sulfonate, derivatives of naphthalene sulfonate salts, sodium salt of β-naphthalene sulfonic acid formalin condensate,
Higher alcohol sulfate ester salts such as dialkyl sulfosuccinates, α-olefin sulfonates, N-acylsulfonates, and sodium cetyl sulfate.

Polymer surfactants such as polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenol ether sulfates, alkylamide sulfates, alkyl phosphates, alkyl ether phosphates, alkyl allyl ether phosphates, and polycarboxylic acids. Examples of nonionic surfactants include alkyl polyoxyethylene ethers such as polyoxyethylene stearyl ether, alkyl allyl polyoxyethylene ethers such as polyoxyethylene nonylphenol ether, and alkylaryl formaldehyde condensed polyoxy Ethylene ether, block polymers and graft polymers with polyoxypropylene as a lipophilic group, polyoxyethylene ether of glycerin ester, sorbitan ester such as sorbitan monooleate, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester , polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, propylene glycol ester,
Preferred examples include sucrose ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, and the like.

In the present invention, the content of the anionic surfactant and/or nonionic surfactant in the highly stable maleimide composition for heat-resistant resin is 0.1 to 20% by weight, particularly preferably 0. .2 to 10% by weight. If the content is less than 0.1% by weight, the dispersibility of the N-substituted maleimide will be markedly reduced, which is undesirable, and if the content exceeds 20% by weight, the dispersion performance will not improve, making it uneconomical. One or more of the undesirable anionic surfactants and/or nonionic surfactants can be selected depending on the viscosity and storage stability of the composition.

Preferred examples of the colloid protective agent used in the present invention include water-soluble cellulose derivatives such as methylcellulose or carboxymethylcellulose, partially or completely saponified polyvinyl acetate, and the like.

In the present invention, the content ratio of the colloidal protective agent in the highly stable maleimide composition for heat-resistant resin is as follows.

It is 0.1 to 5% by weight. The content ratio is 0.1% by weight
If the content is less than 5% by weight, it is undesirable because no effect as a protective agent can be obtained, and if the content exceeds 5% by weight, the viscosity of the composition becomes extremely high, making it difficult to handle.

In the present invention, water is used as the remainder of the N-substituted maleimide, the anionic surfactant and/or the nonionic surfactant, and the colloidal protective agent, and the water is used in the highly stable maleimide composition for heat-resistant resins. The content ratio is 15 to 94.8% by weight.

In the present invention, as a method for preparing a highly stable maleimide composition for heat-resistant resin, for example, a predetermined amount of water is charged into a container,
Next, the colloid protective agent and the surfactant are mixed and stirred to be dispersed. It can be prepared by a method such as adding N-substituted maleimide after that. Examples of mixing and stirring methods at this time include a normal stirrer, a colloid mill, and a high-speed shearer.

Mixing and stirring can be carried out using an ultrasonic homogenizer, a three-roll mill, a ball mill, or the like.

<Effects of the Invention> The highly stable maleimide composition for heat-resistant resins of the present invention has the following advantages. Firstly, since it is a suspension with excellent storage stability, it is suitable for handling such as measuring and preparing, and transportation, especially pump transportation.Secondly, it does not contain cationic components, so the composition remains unchanged. vinyl chloride,
It can be used as a comonomer for suspension and emulsion copolymerization with esters of vinyl acetate, styrene, acrylic acid, and methacrylic acid, and does not cause destabilization of the polymerization system or deterioration of the physical properties of the resulting polymer. As described above, the present invention can provide an industrially excellent highly stable maleimide composition for heat-resistant resins. - <Examples> Next, the present invention will be specifically explained using Examples and Comparative Examples. However, the present invention is not limited to the following examples.

Pour 680g of water into a 1m211 beaker, then add "Newrex" R (sodium dodecylbenzenesulfonate, manufactured by NOF) to Log and "GOHSENOL JKH1".
7 (partially saponified polyvinyl acetate, manufactured by Nippon Gosei Kagaku Kogyo ■) was charged and dispersed by stirring in a ball mill. Next, 300 g of N-cyclohexylmaleimide powder was added and stirred for 15 minutes. This milky white mixture was homogenized using a ball mill at room temperature for 30 minutes to obtain an N-cyclohexylmaleimide-containing composition. Its composition is shown in Table 1.

Example except that the type and amount of N-substituted maleimide used, the type and amount of surfactant and colloid protectant used, and the equipment used for homogenization were changed. An N-substituted maleimide-containing composition was produced by the same method as in Example 1.

Its composition is shown in Table 1.

N-
A substituted maleimide-containing composition was prepared. The composition is the first
Shown in the table.

The same method as in Example 1 was used except that cationic r-cation BBJ (manufactured by NOF Corporation) was used as the Kaikakasa-Kadan surfactant and no colloid protective agent was used.

An N-substituted maleimide-containing composition was prepared. Its composition is shown in Table 1.

Next, measurements of the average particle diameter and viscosity of N-substituted maleimide and storage stability tests were performed on the compositions of the present invention produced in Examples 1 to 12 and the compositions produced in Comparative Examples 1 to 3. was carried out as follows.

The average particle size of the N-substituted maleimide in each composition was measured using a particle size distribution analyzer (Micron Fortsizer 5, manufactured by Seishin Enterprises).
KC-2000 model).

Claims (1)

[Claims] (a) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R_1 and R_2 each represent a hydrogen atom, a halogen atom, or a methyl group, R_3 represents an unsubstituted or halogen-substituted linear alkyl group, branched alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms. )
0.1 to 20% by weight of anionic surfactant and/or nonionic surfactant and (c) 0.1 to 5% of colloidal protective agent.
% by weight and (d) 15 to 94.8% by weight of water.