JPH01165572A - Treatment of polymerizable powder - Google Patents

Abstract

PURPOSE:To prevent various defects of powder, by suspending a maleimide derivative of polymerizable powder having no ring opening properties through hydrolysis with water into water in a specific blending ratio and transporting or weighing the polymerizable polymer as an inert and stable suspension. CONSTITUTION:A maleimide derivative shown by the formula (R1 and R2 are H, 1-4C alkyl, halogen or 1-4C halogenated alkyl; R2 is 1-12C alkyl, cycloalkyl or phenyl containing nonhydrolyzable substituent group) is dispersed into water in the ratio of 5-200 pts.wt., preferably 10-100 pts.wt. maleimide derivative based on 100 pts.wt. water to form a suspension, which is transported or weighed in a suspended state so that the polymerizable powder is treated. The method is used for raw material powder of heat-resistant plastic resin especially applicable to molding method such as injection molding or extrusion molding. Pollution of operation environment resulting from scattering of powder or toxicity is prevented and generation of static electricity is prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for treating polymerizable powder, particularly injection molding,
The present invention relates to a method for treating polymerizable powder used as a raw material for producing heat-resistant thermoplastic resins applied to molding methods such as extrusion molding.

[Prior Art] In the past, imidized polymers have often been used as thermoplastic resins with improved heat resistance. Specifically, the maleimide derivative unit is styrene, methyl methacrylate, )! !
An imidized polymer obtained by polymerizing a vinyl monomer of vinyl chloride with J (J) is used. As a method for producing such an imidized polymer, for example, maleic anhydride and styrene are copolymerized, and then imidized with aniline, etc. Two methods have been reported: a method (Japanese Patent Publication No. 6O-4S642), and a method of directly copolymerizing an imidized polymer (Japanese Unexamined Patent Publication No. 58-225145).

However, the former method requires a copolymerization step first and then an imidization step, which complicates the process and reduces productivity.

On the other hand, the latter method of directly copolymerizing the imidized polymer has drawbacks in processing methods such as handling of the polymerizable powder in the imidized monomer. That is, in general, monomers of maleimide derivatives are powders, and the operation of accurately weighing such monomers on an industrial scale and then charging them into a polymerization reactor has not yet been established. For example, the polymerizable powder contained in a flexible container pack is suspended above the loading port of the polymerization can, and the polymerization can is supplied directly from the outlet at the bottom of the flexible container pack, or the air is flowed through a pipe directly connected to a storage tank, etc. Possible methods include using a pneumatic conveyor and using thrust transport using a screw conveyor, but none of these methods allow for accurate weighing.

In addition, many maleimide derivatives are toxic to the human body, and the product shape of maleimide derivatives is powder or flakes, so transportation methods such as those described above do not allow for granules to be scattered around. Equipment to protect the human body is required.

Furthermore, when transporting organic compounds such as maleimide derivatives, static electricity is likely to be generated, so another polymerization reaction is carried out in the factory, and vapor from other liquid materials, which are the raw materials, is generated. Considering the safety of the work, it is not preferable to carry out operations that involve handling such polymerizable powder in the vicinity of the polymerization can where the polymerization can be easily carried out.

On the other hand, a large amount of maleimide derivatives, which are polymerizable powders,
Treatment methods include transporting it by dissolving it in a vinyl monomer that is liquid at room temperature, such as methyl methacrylate or styrene, or dissolving it in an organic solvent that is inert to the reaction. Because maleimide derivatives are extremely reactive with the above-mentioned vinyl monomers, they cannot be stored for long periods using general storage equipment, and require equipment that can keep them cool. Both of these methods are impractical due to the necessity of

[Problems to be solved by the invention] The present invention has been made to improve the above-mentioned conventional drawbacks, and is a method of copolymerizing maleimide derivatives of polymerizable powder with other vinyl monomers. In a method for producing a heat-resistant thermoplastic resin, a maleimide derivative, which is a polymerizable powder that does not have hydrolytic ring-opening properties, is suspended in water at a specific mixing ratio to form an inert and stable suspension. By transporting or weighing, it is possible to greatly improve the transportability of maleimide derivatives, which have many problems in handling because they are powders, and to accurately control the weighing. The purpose is to prevent the problematic maleimide derivative powder from scattering and contaminating the working environment due to its toxicity, and to provide a method for processing polymerizable powder that prevents the generation of static electricity. It is.

[Means for Solving the Problems] That is, the present invention provides the following - maximum [I] 5 to 200 maleimide derivatives represented by a halogenated alkyl group of numbers 1 to 4, R3 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group having a non-hydrolyzable substituent The present invention relates to a method for treating polymerizable powder, which comprises transporting or weighing a suspension produced by dispersing J. porridge in 100 parts by weight of water.

The present invention will be explained in detail below.

In order to improve the heat resistance of thermoplastic resins, the present invention involves copolymerizing maleimide derivatives, which are polymerizable powders, with vinyl monomers such as styrene, methyl methacrylate, and vinyl chloride to imidize them. In the method of producing a polymer, it can be widely applied to a treatment method that handles a monomer of a maleimide derivative, which is a polymerizable powder described in I'rg.

In the present invention, a powdered maleimide derivative is dispersed in wood to form a uniform and stable suspension, and this suspension is used in a copolymerization reaction of an imidized polymer, or The concentration is preferably 5 to 200 parts by weight, preferably 10 to 100 parts by weight of the maleimide derivative represented by -maximum [I] per 100 parts by weight of water.

! If the concentration of the maleimide derivative that causes g7Q is less than 5 parts by weight, the transport efficiency will be poor due to the low concentration, and if it exceeds 200 parts by weight, the concentration of the suspension will be high and the transportability will be significantly reduced.

In addition, as the maleimide derivative to be suspended, the above-mentioned -
A compound having no hydrolytic ring-opening property with water represented by [I] at most is used. - at maximum [I] R,, R2
is a hydrogen atom, a methyl group.

Preferred are alkyl groups having 1 to 4 carbon atoms such as ethyl group, halogen atoms such as chlorine and bromine, or halogenated alkyl groups having 1 to 4 carbon atoms such as trichloromethyl group.

R3 has 1 carbon atom such as ethyl group or normal octyl group
~12 alkyl groups, cyclohexyl groups.

A cycloalkyl group such as 4-methylcyclohexyl group, or a phenyl group having a non-hydrolyzable substituent such as 0-chlorophenyl group or 2,6-dimethylphenyl group is preferable.

Specific examples of the maleimide derivatives used in the present invention include phenylmaleimide, which has a large hydrolytic ring-opening reactivity, and is undesirable because it impairs the inherent properties of maleimide; , cyclohexylmaleimide, 2,6-dimethylphenylmaleimide, and other maleimides that are relatively stable even in water are preferred.

The method for preparing a suspension of a maleimide derivative is not particularly limited, and a conventional method of uniformly dispersing powder in water can be applied. This can be carried out by adding powder, or by adding water to the maleimide derivative powder without stirring.

In addition, when suspending maleimide derivative powder in water, some of it may float on the water surface, but in such cases, well-known surfactants,
Adding an organic or inorganic dispersion stabilizer is effective for obtaining a uniform suspension.

Furthermore, the maleimide derivative represented by the maximum [I] above is solid at room temperature and has no self-polymerizability in the solid state. A polymerization initiator may be mixed into the suspension. In addition, the suspension of maleimide derivatives must contain additives that are necessary during the polymerization process or processing process, and must be able to be uniformly dispersed in the suspension, and that adding them at this point will not affect subsequent processes. Items that are not given can also be mixed.

[Function] The method for treating polymerizable powder of the present invention includes dispersing and suspending 5 to 200 parts by weight of the maleimide derivative represented by the above-mentioned maximum [I] in 100 parts by weight of water. producing an inert and stable suspension;
By transporting or weighing it, you can easily handle it during the copolymerization reaction process, and also make it easier to handle it during the copolymerization reaction process. , 11 can be accurately controlled.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the devices shown in the following examples are merely illustrative and do not limit the content of the present invention.

Example 1 FIG. 1 is an explanatory view showing an example of an apparatus used in the method for treating a suspension of a maleimide derivative, which is a polymerizable powder, according to the present invention. Using the apparatus shown in FIG. 1, a maleimide derivative was supplied to the Tamasha can for copolymerization by the method shown below.

4s3 of a suspension (density 1.01 g/cm') prepared by suspending 1 part of 30 parts of cyclohexylmaleimide in 100 parts of water to 100 parts by weight of water was charged into a 5i3 tank with a stirring bowl under stirring. , 6, 8.9 were opened and the diaphragm pump 2 was used to transport the suspension to the polymerization 4 with valves 7 and IO closed. After about 10 minutes had elapsed, when the reading on the integrating rotary flow meter 3 increased by 2 m3, the valve 7 was opened and the valve 8 was closed. Next, valve IO was opened and the suspension remaining in the line was sent to polymerization 4.

While stirring the suspension remaining in tank 1 and circulating the slurry using diaphragm pump 2 to prevent precipitation of cyclohexylmaleimide in the slurry remaining in the line, the internal temperature was kept at 20 to 30°C. ) was analyzed using infrared spectroscopy, but there was no change in the composition compared to when it was prepared.

Comparative Example 1 In the same tank as in Example 1, 4113 cyclohexylmaleimide-styrene cyclohexylmaleimide or 20% by weight solution was charged, and the same operation as in Example 1 was performed.

The solution left for two weeks was precipitated in methanol, and the polymer content was analyzed and found to be 30% polymer.

Comparative Example 2 Thirty containers containing 20 kg of cyclohexylmaleimide powder (total 600 kg) were directly charged into Polymerization 4 from the container. The time required for adding the can was 40 minutes including opening and cleaning up the can. In addition, cyclohexylmaleimide powder n1 was packed around the polymerization area immediately after the completion of the preparation.

Comparative Example 3 Cyclohexylmaleimide was fed into the polymerization using the apparatus shown in FIG.

While passing the air compressed fill''t'N2 gas into the pipe 13.

Supplied mtz hecyclohexylmaleimide: 100 kg was dropped from a flexible container hack and sent to the back filter 14 from the rotary Harz under the feeder. Powdering of cyclohexylmaleimide was observed near the exhaust N2 gas at the outlet of the Haku filter 14 and near the feeder 12.

[Effects of the Invention] According to the present invention, polymerizable powders such as maleimide derivatives are suspended in water and transported or weighed in a suspended state. This greatly improves the transportability of maleimide derivatives, which had previously been used, and makes it possible to accurately control metering, resulting in a significant improvement in workability.

Furthermore, the powder of the maleimide derivative is prevented from scattering and contaminating the working environment due to its toxicity, and the problem of static electricity generation is also solved.

In addition to the above-mentioned advantages of simply using it as a suspension, if the method shown in the example is used, remote control by sequence control is also possible.

[Brief explanation of the drawing]

Figure 1 is an explanatory diagram showing an example of an apparatus used in the method for treating a suspension of a maleimide derivative, which is the polymerizable powder of the present invention, and Figure 2 is a conventional feed for polymerization of polymerizable powder. It is an explanatory view showing a device. l...Tank 2...Diaphragm pump 3...Integrating type rotary flow meter 4...Polymerization 5.6, 7, 8, 9.10...Hartz 11...Air compression a 12 ...Feeder 13...Piping
14...Bag filter-15...Receiver is tank Applicant: Representative for Denki Kagaku Kogyo Co., Ltd. Norihiro Watanabe Procedural amendment 1986 Date of Patent Office Commissioner Kunio Ogawa 1, 1 yen Indication of the matter Patent Application No. 322814 of 1972 2, Name of the invention Process for treating polymerizable powder 3, Relationship with the person making the amendment case - Patent applicant 1-4-1 Yurakucho, Chiyo 11-ku, Tokyo ( 329) Denki Kagaku Kogyo Co., Ltd. Representative Akira Shinohara 4, Agent Kita-Otsuka 2-chome, Raicho-ku, Tokyo] 11-5 Nwado Building 40
Room 3 Telephone: 03 (9] 8) 6686 Watanabe Patent Office (6901) Patent Attorney Norihiro Watanabe 5, "Detailed explanation of IJI" and "Brief explanation of drawings" columns of the specification subject to amendment, and Drawing 6 and Contents of Amendment 6-1 The detailed description of the invention is corrected as follows. (1) Delete "of work" in line 9 of page 4 of specification 3. (2) Specification, page 11, line 1 [density 1.01g/c1J is "density 1.2g/c+s'"
Correct to J. (3) In the specification, page 1+, line 3, and page 1t, line 11, "diaphragm pump" is corrected to "pump." 6-2 The brief description of the drawing is corrected as follows. (1) In the first line of page 14 of the specification, [diaphragm pump] was corrected to "pump". 6-: Correct side 54 of +l' as shown in the attached sheet. (1) Correct the "2-tire flamm pump" in Figure 1 to "2 pumps." 2nd child lJ spring sardine Hsnt-nl:/grade-
'II≦Yabu and γ me 6

Claims (1)

[Claims] The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R_1 and R_2 are hydrogen atoms, and the number of carbon atoms is 1 to 4.
an alkyl group, a halogen atom or a halogenated alkyl group having 1 to 4 carbon atoms, R_3 represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group having a non-hydrolyzable substituent). 1. A method for treating polymerizable powder, which comprises transporting or weighing a suspension prepared by dispersing 5 to 200 parts by weight of the maleimide derivative shown above in 100 parts by weight of water.