JPH0780844B2 - Highly stable maleimide composition for heat resistant resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a maleimide composition that can be used in the production of a heat-resistant resin, and more specifically, it has excellent storage stability and can be pumped. The present invention relates to a highly stable maleimide composition for a heat-resistant resin, which contains an N-substituted maleimide as a maleimide copolymerizable during emulsion and suspension polymerization of an ethylenically unsaturated monomer.

<Prior Art and Problems Thereof> N-substituted maleimides are generally solid at room temperature, and thus have been conventionally used in the form of powder, hydrous powder or flakes. However, when the N-substituted maleimide is a powder at the time of working, it causes an increase in working man-hours at the time of weighing and charging, and causes deterioration of workability. In addition, N-substituted maleimides generally have sublimation properties, and thus have a sanitary drawback. In order to solve these drawbacks, for example, JP-A-54-30157 discloses an aqueous suspension of maleimide.

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

<Object of the Invention> An object of the present invention is to provide a highly stable maleimide composition for a heat resistant resin, which has excellent storage stability and is suitable for weighing, charging and transportation, particularly for pumping.

Another object of the present invention is to provide a highly stable maleimide composition for a heat resistant resin, which stabilizes the inside of the polymerization system and prevents deterioration of the physical properties of the produced polymer.

<Means for Solving Problems> (a) General Formula (I) (In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a methyl group, and R ₃ represents an unsubstituted or halogen-substituted linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, a cycloalkyl group, an aryl group. Or an aralkyl group) 5) to 5% by weight of N-substituted maleimide represented by the formula (b) and (b) anionic surfactant and / or nonionic surfactant.
There is provided a highly stable maleimide composition for a heat resistant resin, which comprises 1 to 20% by weight, (c) a colloid protective agent (0.1 to 5% by weight), and (d) water (15 to 94.8% by weight).

The present invention will be described in more detail below.

General formula (I) used in the present invention Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a methyl group, and R ₃ represents an unsubstituted or halogen-substituted linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, a cycloalkyl group, an aryl group or aralkyl. Represents a group. The carbon number of R ₃ is
When it is 19 or more, it cannot be used because it is difficult to manufacture.

Examples of the N-substituted maleimide represented by the general formula (I) used in the present invention include N-methylmaleimide and N-methylmaleimide.
-Ethylmaleimide, N-n-propylmaleimide, N
-N-butylmaleimide, Ni-butylmaleimide,
Nn-pentylmaleimide, Mn-hexylmaleimide, N-cyclohexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-2-
Ethylhexyl maleimide, N-n-dodecyl maleimide, N-lauryl maleimide, N-myristyl maleimide, N-hexadecyl maleimide, N-octadecyl maleimide, N-phenyl maleimide, N- (2-methyl) phenyl maleimide, 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) phenyl Maleimide, 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 Preferable examples include -chloromaleimide, N-phenyl-α-methylmaleimide, N-benzyl-α-chloromaleimide and N-benzyl-α-methylmaleimide. The N-substituted maleimide may be used alone or as a mixture of two or more kinds.

In the present invention, the content ratio of the N-substituted maleimide in the composition is 5 to 60% by weight, particularly preferably 10 to 50%.
% By weight. When the content ratio is less than 5% by weight,
It is not preferable because a sufficient modifying effect cannot be obtained during copolymerization. On the other hand, if the content ratio exceeds 60% by weight, the viscosity becomes extremely high and the handling becomes difficult, which is not preferable.

Examples of the anionic surfactant used in the present invention include, for example, sodium oleate, aliphatic salts such as castor oil calicheken, N-acyl amino acid salts, alkyl ether carboxylates, acylated peptides, alkyl sulfonates and dodecylbenzene. Alkyl aryl sulfonates such as sodium sulfonate, alkyl naphthalene sulfonates, derivatives of naphthalene sulfonates, sodium salt of β-naphthalene sulfonic acid formalin condensate, dialkyl sulfosuccinates, α-olefin sulfonates, N- Acyl sulfonate, higher alcohol sulfate ester salts such as sodium cetyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenol ether sulfate, alkyl amide sulfate,
Preferable examples include polymer surfactants such as alkyl phosphates, alkyl ether phosphates, alkylallyl ether phosphates and polycarboxylic acids, and examples of nonionic surfactants include polyoxyethylene stearyl. Alkyl polyoxyethylene ethers such as ethers, alkylallyl polyoxyethylene ethers such as polyoxyethylene nonylphenol ethers, alkylallyl formaldehyde condensed polyoxyethylene ethers, block polymers and graft polymers having polyoxypropylene as a lipophilic group, glycerin ester Polyoxyethylene ethers, sorbitan esters such as sorbitan monooleate, polyoxyethylene ethers of sorbitan esters, polyoxyethylene ethers of sorbitol esters Le, polyethylene glycol fatty acid esters, glycerol esters, polyglycerol esters, propylene glycol esters, sucrose esters,
Preferable examples include fatty acid alkanolamides and polyoxyethylene fatty acid amides.

In the present invention, the content ratio of the anionic surfactant and / or the 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 significantly reduced, which is not preferable. Further, the content is 20% by weight.
Dispersion performance does not improve even if it exceeds, which is uneconomical and not preferable. Further, the anionic surfactant and / or the nonionic surfactant can be appropriately selected from one type or two or more types depending on the viscosity and storage stability of the composition.

Preferable examples of the colloid protective agent used in the present invention include water-soluble cellulose derivatives such as methyl cellulose and carboxymethyl cellulose, and partially or completely saponified polyvinyl acetate.

In the present invention, the content ratio of the colloidal protective agent in the highly stable maleimide composition for heat resistant resins is 0.1 to 5% by weight. If the content is less than 0.1% by weight, the effect as a protective agent cannot be obtained, which is not preferable. On the other hand, if the content exceeds 5% by weight, the viscosity of the composition becomes extremely high and handling becomes difficult, which is not preferable.

In the present invention, water is used as the balance of the N-substituted maleimide, the anionic surfactant and / or the nonionic surfactant, and the colloid protective agent, and the water is used in a 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 adjusting the highly stable maleimide composition for heat-resistant resin, for example, a predetermined amount of water is charged in a container,
Next, the colloid protective agent and the surfactant are mixed and stirred to disperse them. Then, it can be prepared by a method such as adding an N-substituted maleimide. As a mixing and stirring method at this time, for example, an ordinary stirrer, a colloid mill, a high-speed shearing machine, an ultrasonic homogenizer, a three-roll mill, a ball mill, or the like can be used for mixing and stirring.

<Effects of the Invention> The highly stable maleimide composition for heat-resistant resins of the present invention has the following advantages. First, it is a suspension with excellent storage stability, and therefore it is suitable for handling and transportation such as metering and preparation, especially for pump transportation. Secondly, since it does not contain a cationic component, the composition is 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 destabilize the polymerization system or lower the physical properties of the resulting polymer. INDUSTRIAL APPLICABILITY As described above, the present invention can provide an industrially excellent highly stable maleimide composition for heat-resistant resins.

<Example> Next, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

Example 1 A 2 l beaker was charged with 680 g of water, and then 10 g of "Neurex" R (sodium dodecylbenzenesulfonate, manufactured by NOF CORPORATION) and "Gothenol" KH17 (partially saponified polyvinyl acetate, Nippon Synthetic Chemistry) Industrial Co., Ltd.) 10g
Was charged and dispersed by a ball mill. Then N
-300 g of cyclohexylmaleimide powder was added and stirred for 15 minutes. This milky white mixture is ball milled at room temperature for 30
Homogenization treatment was performed for a minute to obtain an N-cyclohexylmaleimide-containing composition. The composition is shown in Table 1.

Examples 2 to 12 The same as Example 1 except that the type and amount of N-substituted maleimide used, the types and amounts of surfactant and colloid protective agent used, and the apparatus used for homogenization were changed. The method produced an N-substituted maleimide-containing composition.
Its composition is shown in Table 1.

Comparative Examples 1-2 An N-substituted maleimide-containing composition was produced in the same manner as in Example 1 except that "Gothenol" KH17 as a colloid protective agent was not used. Its composition is shown in Table 1.

Comparative Example 3 An N-substituted maleimide-containing composition was prepared in the same manner as in Example 1 except that a cationic "cation BB" (manufactured by NOF CORPORATION) was used as the surfactant and no colloid protective agent was used. Manufactured. The composition is shown in Table 1.

Example 13 Next, for the compositions of the present invention prepared in Examples 1 to 12 and the compositions prepared in Comparative Examples 1 to 3, the average particle size and viscosity of N-substituted maleimide and the storage stability test are described below. It was done like.

The average particle size of the N-substituted maleimide in each composition was measured by a particle size distribution analyzer (manufactured by Seishin Enterprise Co., Ltd., Micron Fort Sizer SK
C-2000 type). The viscosity was measured using a B-type viscometer under the conditions of 25 ° C. and a rotation speed of 20 rpm. For storage stability, each composition had an inner diameter of 18 mm and a length of 18 mm.
It was put into a cm test tube from the bottom up to a height of 15 cm, and left still in an incubator kept at 25 ° C. After that water is 1c from the liquid surface
The period until separation of m or more was measured. The results are shown in Table 2.

Claims (1)

[Claims] (A) The following general formula (I): (In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom or a methyl group, and R ₃ represents an unsubstituted or halogen-substituted linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, a cycloalkyl group, an aryl group. Or an aralkyl group) 5) to 5% by weight of N-substituted maleimide represented by the formula (b) and (b) anionic surfactant and / or nonionic surfactant.
A highly stable maleimide composition for a heat resistant resin, which comprises 1 to 20% by weight, (c) a colloid protective agent 0.1 to 5% by weight, and (d) water 15 to 94.8% by weight.