JPS5891716A - Production of modified thermoplastic polymer particle - Google Patents

Abstract

PURPOSE:To produce modified thermoplastic polymer particles at high production rates by a simple process, by impregnating thermoplastic polymer pellets with a vinyl monomer and an initiator under specified conditions and reacting the both. CONSTITUTION:Modified thermoplastic polymer particles are produced by impregnating (A) 50-99.9pts.wt. thermoplastic polymer particle, average particle diameter of about 1-8mm.,[e.g., ethylene (co)polymer pellet]with (B) 50- 0.1pt.wt. vinyl monomer (e.g., styrene) and (C) 0.0005-0.2wt%, based on component B, initiator (e.g., 2,4-dichlorobenzoyl peroxide) in the absence of water in a mixing and heating apparatus not equipped with any propeller (e.g., a double cone mixer equipped with a heating device) under conditions not causing fusion of the thermopolastic polymer, and then polymerizing the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making IJ'I modified thermoplastic polymers in which the process is streamlined and productivity is significantly improved.

A modified thermoplastic polymer obtained by subjecting a thermoplastic polymer and a vinyl monomer to graft polymerization conditions has color characteristics that thermoplastic polymers do not have due to the S group of the vinyl monomer and the amount of modification. Because of this, it is used in various application fields.

Various methods have been known to date for this graft polymerization condition. For example, a solution craft method in which a thermoplastic polymer and a vinyl monomer are polymerized by dissolving them in a good solvent;
Bulk grafting method in which a thermoplastic polymer is dissolved in a vinyl monomer and polymerized; Melting method in which a thermoplastic polymer is melted at high temperature and polymerized in the coexistence of a vinyl monomer and a thermoplastic polymer. Grafting method: Aqueous suspension grafting method in which polymerization is carried out while or after impregnating thermoplastic polymer particles with vinyl monomer in an aqueous suspension system; thermoplastic polymer powder and vinyl monomer and optionally Radiation grafting method in which polymerization is carried out by irradiating radiation to a slurry consisting of a suitable solvent; polyolefin powder and vinyl monomer (in particular, dalicidyl acrylate-based or vinyl silane-based monomers are used for the purpose of completely improving the adhesion between polyolefin and glass). ) and organic peroxide into a mixer;
Powder grafting methods, in which vinyl monomers are graft-polymerized onto powder by mixing, are generally used. However, each of these grafting methods has its own drawbacks. For example, the solution grafting method requires complicated equipment and processes because it uses Daichi's solvent, the bulk grafting method is difficult to use as a molding material unless a granulation step is added afterward, and the molten ground method requires the use of thermoplastic polymers. Deterioration and polymerization occur, requiring efforts to control quality.
The radiation grafting method requires expensive radiation generation and irradiation equipment, and the aqueous suspension grafting method uses water as a dispersion agent, which complicates the equipment and drying process and also prevents vinyl monomers from reacting with water. If the powder is soluble or water-soluble, it is difficult to manufacture, and in the powder graft method, the powder surface area is increased (that is, the powder diameter is decreased) for the special purpose of adhesion to glass, so powder explosion etc. It also has other disadvantages, such as the risk of oxidation and the fact that only small amounts of specific monomers can be introduced.

The present invention solves these drawbacks and provides a method for producing a thermoplastic polymer of good quality, which can easily and safely obtain a homogeneous modified thermoplastic polymer, and which has significantly improved productivity. It was done with the purpose of doing so.

That is, in the present invention, in the absence of water, the average particle size is 1 to 8 m.
The thermoplastic polymer particles are impregnated with a vinyl monomer and a polymerization initiator at a mIf that does not substantially decompose the polymerization initiator, and then the temperature is raised to complete the polymerization of the vinyl monomer. In the method for producing high-quality thermoplastic polymer particles, the component ratio in the system before merging is (a) #Plastic polymer particles: 50 to 99.9 (h
) Vinyl pellets: 50 to 0.1 parts by weight (c) Polymerization initiator: 0.05 to 20 parts by weight per 100 parts by weight of the vinyl precursor; (2) Impregnation and polymerization The process is characterized in that the process is carried out in a single device equipped with mixing equipment and heating equipment without using stirring blades, and (3) the process is carried out under conditions in which the thermoplastic polymer particles are not substantially dissolved or melted throughout the entire process. This is a method for producing modified thermoplastic polymer particles.

According to the method of the present invention, many unexpected effects and advantages can be achieved, such as:

(1) Since thermoplastic polymer particles with a fixed particle size are used,
It is possible to prevent secondary aggregation of particles during impregnation with vinyl monomer and to uniformly wet the particle surface.

There is also almost no risk of powder explosion.

(2) Since thermoplastic polymer particles of Irf fixed particle size are used and the particles are processed without substantially dissolving or melting,
The particles after the modification treatment can be used as a molding material as they are.

(3) Essentially using radiation and solvents (including solvents) 6
- Since there is no need to mix and match, equipment and supply mixing processes can be omitted.

(4) Since no water is used, the drying step can also be omitted or simplified.

(5) Since the treatment is carried out in the absence of water, even water-reactive or soluble vinyl monomers can be used in a stable form. The vinyl monomer can be sufficiently dispersed in the interior 1 of the plastic polymer particles, and homogeneous modified particles can be obtained.

Further, it is possible to introduce a large amount of vinyl monomer, and it is also possible to introduce a volume of vinyl monomer that is difficult to mix with a thermoplastic polymer by impregnation.

(7) The amount of vinyl monomer used is such that an impregnation step is necessary to uniformly infiltrate the thermoplastic polymer particles, but preferably L< It is better not to use so much beforehand that it is always in suspension (eg even after impregnation). That is, substantially the entire amount of the element used in advance can be impregnated into the thermoplastic polymer particles.

Therefore, the remaining liquid vinyl monomer does not need to be removed and can be efficiently treated.

(8) Since the impregnation and polymerization conditions are mild, deterioration and polymerization of the thermoplastic polymer can be prevented.

(9) Since the impregnation and polymerization steps are performed in one device (if necessary, the drying step can also be performed in the same device), there are no environmental hygiene problems such as odors, and production can significantly improve sexual performance.

00 Since the mixing equipment provided in the equipment for the impregnation and polymerization processes does not use stirring blades, the thermoplastic polymer particles will not be damaged or cracked by the rotation of the blades.

The present invention will be explained in detail below.

Components in the System and Their Ratios The essential components used in the present invention are thermoplastic polymer particles, a vinyl monomer, and a polymerization initiator.

The dimensions of the thermoplastic polymer particles do not change much before and after the modification treatment, so any size that is normally used as a 5V-shaped material is sufficient. Generally, the average particle size is 1 to 8 mm, preferably 3 to 7 mm. Therefore,
What is called a beret can be used.

The types of thermal WJ plastic polymer particles include ethylene, propylene, butene-11pentene-1,4-methylpentene-1, and hexene-1% α-olefin (including ethylene), either singly or copolymerized. In addition, block, random or duraft copolymers of these α-olefins and other unsaturated compounds, co-electric so-called olefin polymers in which α-olefin accounts for the majority of the weight; acrylonitrile-butadiene-styrene copolymers (ABS vinyl chloride resin; polycarbonate; thermoplastic polyester; polyamide; polystyrene; styrene-butadiene-styrene block copolymer; 9-styrene-butadiene rubber; polyacrylonitrile; Ru.

Regarding the olefin polymer of upper = r, other unsaturated compounds that can be copolymerized with α-olefin include vinyl esters such as vinyl acetate; acrylic acid and methacrylic acid;
Unsaturated organic acids such as maleic acid and itaconic acid or derivatives thereof such as esters, amines, amides, salts and anhydrides; vinylsilanes such as vinyltrimethoxysilane and vinyltriacetoxysilane; and the like.

Next, as the vinyl monomer, any radically polymerizable vinyl monomer can be used. Specifically, it is appropriately used depending on the properties of various monomers and the properties of the copolymer, but for example, styrene monomers, vinyl esters, unsaturated carboxylic acid esters, etc. are suitable.

Examples of styrene-based monomers include styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-mer 10-tylstyrene, α-ethylstyrene, and the like.

It is possible to improve the moldability of the thermoplastic polymer, the adhesion with styrene resin, the blend compatibility, etc. Among them, styrene is most preferred.

Vinyl acetate is a typical vinyl ester monomer. It can be used for purposes such as improving the flexibility of these thermoplastic + L1 polymers, imparting adhesion to vinyl chloride, and improving high frequency welding properties.

As the unsaturated carboxylic ester, acrylic esters or methacrylic esters are suitable, such as aliphatic acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, acrylic #2 ethylhexyl, and perfluorobutyl acrylate. Examples include perfluoroacrylate esters. These can be used for purposes such as internal plasticization of thermoplastic polymers, improvement of adhesion with acrylic resins, and improvement of surface properties.

In addition to fl, etc., water bathing monomers and hydrophobic monomers can also be used as special monomers.

Examples of water-bathable monomers include unsaturated carboxylic acids such as acrylic acid and maleic acid, 2-hydroxy-γ-IJ L/
-), hydroxyalkyl acrylate of 2-hydroxymethacrylate, N-vinyl-2-pyrrolidone, vinylpyridine, and the like. These thermoplastic polymers can be used for purposes such as adhesion to metals and improvement of water wettability.

Examples of hydrophobic monomers include maleic anhydride, which is ring-opened by water, N,N-dimethylamine ethyl methacrylate, N,N-diethylaminoethyl methacrylate, and vinyltrimethoxysilane, which are hydrolyzed by water.
Buy. These can be used for purposes such as adhesion with metals, adhesion with other thermoplastic resins, and improvement of electrical properties, printability, and crosslinking properties.

In particular, the vinyl monomer is a styrene monomer and the component ratio in the system before polymerization is (a) Thermoplastic polymer particles; 50 to 90 parts by weight (t
)) Styrenic monomer; 50 to 10 parts by weight (c) Polymerization initiator: 0.
05 to 20 parts by weight, or the vinyl monomer is unsaturated carboxylic acid Nisdel, and the component ratio in the system before polymerization is (a) Thermoplastic polymer particles: 50 to 90 parts by weight (b ) Unsaturated carboxylic acid ester: 50 to 10 parts by weight (c) Polymerization initiator: 0.05 to 20 parts by weight per 100 parts by weight of unsaturated carboxylic acid ester, and vinyl polymer is preferably a vinyl ester.

Moreover, these vinyl monomers can also be used in combination. For example, acrylonitrile, methacrylate,
It is preferable to use methylene geltalonitrile or the like together with a styrenic monomer.

These vinyl monomers can be used alone, but they do not have good impregnating properties into thermoplastic polymer particles, for example, because they are water-soluble or hydrophilic and are not very compatible with thermoplastic polymer particles. Regarding the vinyl monomer, it is possible to improve or control the impregnation speed, R ratio, yield, etc. by using a suitable solvent as a carrier to promote impregnation.

As this carrier, a solvent is selected that dissolves the vinyl monomer, is compatible with the thermoplastic polymer, and has good impregnating properties. Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n
-Hexane, cyclohexane, heptane, etc. Chlorobenzene, dichloroethylene, carbon tetrachloride, etc. can be mentioned as logenated hydrocarbons. Because of the need for the carrier to be used and for the thermoplastic polymer particles to dissolve or not melt, the total amount of the vinyl monomer and carrier solvent is 50 to 0 parts by weight based on 50 to 99.9 parts by weight of the thermoplastic polymer particles.
．． 1% by weight is good, but even in this case, the vinyl monomer needs to be in an amount of 50 to 0.1% by weight based on 50 to 99.9 parts by weight of the thermoplastic polymer particles.

When using a carrier solvent, it is preferably used in an amount of 5 parts by weight or more within the above range.

Furthermore, if the polymerization initiator has a low decomposition temperature in order to obtain a half-life of 10 hours, polymerization of the vinyl=14=monomer may proceed during impregnation, making it difficult to produce homogeneous modified polymer particles. Therefore, it is preferable that the decomposition temperature is 50°C or higher. It is also possible to polymerize efficiently by appropriately combining materials with low decomposition temperatures and materials with low decomposition temperatures to carry out decomposition stepwise or continuously at each temperature.

Here, [the decomposition temperature to obtain a half-life of 10 hours] means that when 0.1 mol of a polymerization initiator is added to benzene lt and left for 10 hours, the decomposition rate of the polymerization initiator is 50%. %, meaning the temperature.

Since the polymerization initiator is used together with the vinyl monomer, it is preferable that the polymerization initiator is soluble in the vinyl monomer.

Examples of such degree initiators include 2,4-dichlorobenzoyl peroxide (54°C), t-butylbaroxybiparate (56°C), O-methylbenzoylperoxide (57°C), bis- 3,5,5-)dimethylhegisanoylno;-oxide (6(1'C), octano-r rubber oxide (61°C), benzoyl peroxide (74°C), t-butyl peroxide 2-
Ethylhexanoate (74°C), cyclohexanone peroxide (97°C), 2,5-dimethyl-2,5-
Dibenzoyl peroxyhexane (100°C), t-butyl peroxybenzoate (104°C), di-t-butyl diperoxyphthalate (105°C), methyl ethyl ketone peroxide (109°C), dicumyl peroxide (117°C) , organic peroxides such as di-t-butyl peroxide (124°C), azo compounds such as azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), and water purple peroxide. can.

The value in parentheses is each ]O time half-life.

The blending ratio of the above thermoplastic polymer particles, vinyl monomer, and polymerization initiator in the system before polymerization is as follows: (a) thermoplastic polymer particles: 50 to 99.9 parts; Preferably 50 to 98 parts by weight, particularly preferably 50 to 90 parts by weight
Part by weight α]) Vinyl monomer: 50 to 0.1 part by weight, preferably 50 to 2 parts by weight, particularly preferably 50 to 10 parts by weight (C) Polymerization initiator: 1 part by weight of 100 parts by weight of vinyl monomer The amount is 05 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

If the thermoplastic polymer particles are below this range (the vinyl extender exceeds the above range), unimpregnated vinyl monomer will occur, making it difficult to obtain homogeneous modified thermoplastic polymer particles; If it exceeds the range (the vinyl monomer is less than the range -1), the reforming effect of the introduced vinyl monomer will be insufficient and the desired modified product will not be obtained, which is not preferable.

Furthermore, if the polymerization initiator is less than the above range, the vinyl monomer cannot be sufficiently polymerized, and conversely, if it exceeds the range, reactions other than the polymerization reaction, such as polymer deterioration and gelation, are likely to occur. Undesirable.

Impregnation and polymerization process In the present invention, the impregnation and polymerization processes are carried out in a non-aqueous system in one apparatus equipped with stirring equipment and heating equipment, and the thermoplastic polymer particles are completely absorbed. Throughout the process, it is necessary to conduct the process under conditions that do not substantially melt or melt.

A typical method for impregnating thermoplastic polymer particles with vinyl monomer is to add vinyl monomer in which a polymerization initiator (and other additives as necessary) is dissolved into the thermoplastic polymer particles. Another method is to add thermoplastic polymer particles to the polymerization initiator and vinyl monomer and mix them together.

In the impregnation step, impregnation must be carried out efficiently by heating under conditions in which the polymerization initiator does not substantially decompose and the thermoplastic polymer particles do not substantially dissolve or melt, and is generally heated to 100°C or less, preferably. is carried out at 40-90°C.

In this step, more than 50% of the vinyl monomer in the above blending ratio, preferably substantially the entire amount, is impregnated into the thermoplastic polymer particles. That is, the monomers are impregnated so that the age of the unimpregnated vinyl monomers is less than 18-5, preferably substantially eliminated, than the age of the unimpregnated vinyl monomers at the above-mentioned blending ratio.

Since thermoplastic polymers are relatively compatible with vinyl monomers, even if less than 50% of the vinyl monomer is impregnated with the above blending ratio before the start of polymerization, the above blending ratio can be used during polymerization. As the remaining monomers impregnate the thermoplastic polymer particles, the vinyl monomer polymer particles obtained by polymerizing these monomers precipitate independently from the modified thermoplastic polymer particles. Never. If a large amount of vinyl monomer is used in excess of the above blending ratio, unimpregnated material may remain, in which case it is discharged from the system before proceeding to the next step.

The impregnation time is usually about 2 to 8 hours.

When impregnating thermoplastic polymer particles with vinyl monomer (and polymerization initiator), auxiliary materials such as plasticizers, lubricants, and antioxidants can be impregnated at the same time (these auxiliary materials are thermoplastic In some cases, it is already added to the polymer particles, or it can be added after trench polymerization).

Further, in order to adjust the molecular weight of the polymer produced as a result of polymerization of vinyl monomers, a chain transfer agent such as n-butylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan or the like may be added.

If the thermoplastic polymer particles impregnated in this way are heated to a temperature above which the polymerization initiator used decomposes at an appropriate rate, the impregnated vinyl monomer will polymerize and be modified. High quality thermoplastic polymer particles are produced. Since radical polymerization is to be carried out, it is preferable to carry out heating in an atmosphere that does not substantially contain oxygen, and it is also preferable to mix appropriately during the progress of polymerization.

Since it is necessary to polymerize under conditions in which the thermoplastic polymer particles are not substantially dissolved or melted, the polymerization temperature is 60 to 150℃.
The temperature should be appropriately selected within the range of °C, but it does not need to be constant throughout the polymerization process. If the polymerization temperature is 150° C., not only gelation is likely to occur, but also particle fusion and agglomeration are likely to occur. The polymerization time is usually about 0.5 to 10 hours. Polymerization pressure is normal pressure to 1oKr
/- The degree is normal.

The impregnation and polymerization process 8 as described above is carried out in a non-aqueous system in one apparatus equipped with mixing equipment and heating equipment without using stirring blades.

In order to achieve uniform impregnation and even distribution of heat, it is desirable that the components in the system remain balanced during the impregnation and polymerization steps.

If the mixing is carried out by stirring, the thermoplastic polymer particles may be damaged or cracked, or the mixing may not be carried out sufficiently, which is not preferable.

Therefore, it is necessary to use a device that moves itself without using wings, that is, a device that rotates, vibrates, or rotates and vibrates. The device may be equipped with a baffle plate inside to increase the mixing rate.

Among these, a type in which the device rotates on its own axis by a rotating shaft is particularly preferable, and a device in which the rotating shaft is at an angle of 80° or less with respect to the horizontal axis is particularly preferable. The most common type is one with a horizontal axis of rotation, and is suitable for use as a device. In addition, the heating equipment provided in this device includes a method in which a 21-jacket is provided in the device and a suitable heating medium such as steam, hot water, oil, etc. heating equipment is available.

As such a device, a double conical mixer, a V-type mixer, a cylindrical mixer, and a spherical mixer, which are generally used as rotary solid mixers, can be used.

Even if simple drying or deodorizing treatment is required after polymerization,
Post-processing can be carried out directly within the above-mentioned apparatus by blowing air or reducing pressure without relying on other equipment.

The modified thermoplastic polymer particles obtained can be used immediately as a molding material.

The modified thermoplastic polymer particles of the present invention are thermoplastic polymers containing homogeneously dispersed vinyl monomers, or vinyl monomers grafted onto a thermoplastic polymer backbone, or It is presumed to be a mixture, and the polymer particles unique to vinyl monomers do not exist separately from the thermoplastic polymer particles.

The modified thermoplastic polymer particles 22- thus obtained have particularly excellent tensile strength, fluidity during molding, appearance of molded products, and compatibility with other polymers, and also exhibit excellent paintability and adhesion mediating properties. Also, depending on the type of vinyl monomer, it has excellent mixing compatibility with thermoplastic polymers or has crosslinking properties, so it is used in a wide range of fields including electric wire coating materials and thin film molding materials. Application is possible.

Example 1 An autorotating reactor (contents @ 20
1) 8.4 Kf of polypropylene particles (Mitsubishi Noprene FX-4) having an average #1 diameter of about 3 mm were charged into the container. Separately, 28.8 f of benzoyl peroxide was dissolved in 3.6 [9] of styrene, and this was added into the same reactor through the inlet tube that had been used in the previous reactor, and the system was purged with nitrogen.

Next, heat the inside of the system to 60℃ by passing hot water through the jacket.
, the reactor is rotated (approximately 10 rpm) at this temperature,
This mixing was continued for 3 hours, and almost the entire amount of styrene containing the polymerization initiator was impregnated into the polypropylene particles.Then, the system was heated to 90℃, and polymerization continued at this temperature for 5 hours. completed.

During immersion, the product in the system was simply dried under reduced pressure (approximately 10 Torr) using a filtration and decompression device attached to the reactor to remove a very small amount of unreacted residual monomer, and after cooling, the produced styrene-modified polypropylene Particle 12 K9 was taken out. This particle had no fusion, agglomeration, damage, or gas, and was ready to be used for molding.

Comparative Example 1 3Kq of pure water in a stirred autoclay with a content of 101 cm
, tricalcium phosphate 609 as a Nfli agent, and sodium dodecylbenzenesulfonate 0 as a filtration aid.
．． 09 f to make an aqueous medium. After adding and suspending 1.2 liters of styrene in which 9.6 f of benzoyl peroxide was dissolved, 1.8 Kf of polypropylene particles (Mitsubishi Noblen FX-4) were added, and the system was purged with nitrogen.

Next, the temperature inside the system was raised to 60° C., and stirring was continued at this temperature for 3 hours to impregnate almost the entire amount of styrene containing the polymerization initiator into the polypropylene particles.

Next, the temperature inside the system was raised to 90° C., and after stirring was continued at this temperature for 5 hours to complete polymerization, the system was cooled and the produced contents were taken out.

This product is pickled to remove the suspending agent, further washed with water, dehydrated by centrifugation, and finally dried with hot air.
Styrene-modified polypropylene particles 3 K9 were obtained.

The weight ratio of the combined amount of styrene and polypropylene particles to water was about 1:11, and the total charging capacity of the raw materials was about 60% of the reactor.

Comparing this result with Example 1, it is found that by using water, the production amount is reduced, the post-treatment process is complicated, and the production efficiency is significantly reduced. (Instead, the same amount of ethylene-vinyl acetate copolymer (styrene E)
VA50M), and the same amount of t-butyl peroxy 25-pivalate was used instead of benzoyl peroxide, and the temperature inside the system during impregnation was 45°C, and the temperature inside the system during polymerization was 75°C. In the same manner as in Example 1, 12 groups of styrene-modified ethylene-vinyl acetate copolymer particles were obtained.

The obtained particles were as good as in Example 1.

Comparative Example 2 Polypropylene particles 5.4 Kg, styrene 6, (iK
9. Polymerization was carried out under the same conditions as in Example except that the amount ratio of benzoyl peroxide was 52.8 F. The obtained particles showed agglomeration due to several fusions, and when the particles were molded, the dispersion of the styrene polymer was non-uniform.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1, except that the impregnation step, which was performed at 60° C. for 3 hours in Example 1, was not performed and the polymerization step was immediately performed.

The obtained product showed agglomeration due to fusion of several particles and formation of polystyrene on the particle surface due to poor impregnation, making it impossible to use it as a molding resin. Ta.

Comparative Example 4 A reaction was carried out under the same conditions as in Example 2 except that 28.8 f of t-butyl peroxybenzoate was used as a polymerization initiator, the impregnation v1 degree was 90°C, and the reaction temperature was 125°C. However, during the reaction, the ethylene-vinyl acetate copolymer particles melted and agglomerated, resulting in the modified product'f:? There was nothing I could do.

Comparative Example 5 Into the reactor used in Example 1, 120 V of tricalcium phosphate as a suspending agent and 120 V of tricalcium phosphate as a suspending agent and dodecylbenzenesulfonate 01]82 as a suspension aid were added to prepare an aqueous medium.

To this, 9.9 to 2.4 styrene in which 19.2 f of benzoyl peroxide was dissolved was added, and after being suspended by mixing by rotation, polypropylene particles (Mitsubishi Noblen FX-4) 3.
Added 9 to 6. After purging the system with nitrogen, impregnation and polymerization steps were carried out under the same conditions as in Example 1.

After that, the inside of the system is cooled, and the water is removed using the all-mesh partition and discharge pipe attached to the reactor, and the contents are pickled! The V clouding agent was removed and washed with water. The product was kept in the reactor and dried for a long time in an attached vacuum device to obtain 6 Ky of styrene-modified polypropylene particles.

Note that the total amount of styrene and polypropylene and water were used in approximately equal weights.

Comparing this example with Example 1, even if a rotating reactor was used, in an aqueous suspension system, post-treatment was complicated and productivity was low.

Example 3 In Example 1, the raw materials were aromatic polycarbonate particles (manufactured by Teijin Kasei Co., Ltd. [Tijin Panlite L1250J) 1O, 8 kg, and styrene 3.2 kg as raw materials.
Next, a reaction was carried out under the same conditions as in Example 1 except that benzoyl peroxide 3f was used to obtain styrene-modified polycarbonate resin particles 12-.

These particles showed no fusion or agglomeration, and could be used immediately for molding.

Example 4 In Example 1, the same amount of polyethylene terephthalate particles (“Polyester Chip RP-BJ” manufactured by Mitsubishi Kasei Corporation) with an average particle diameter of about 3 m was added to the polypropylene particles.
) was used in the same manner as in Example 1 to obtain 12Kf of styrene-modified polyethylene terephthalate particles. The obtained particles were of good quality with no fusion or agglomeration observed.

Example 5 In Example 1, polyamide (nylon 6-6) particles (rAmila manufactured by Toshisha Co., Ltd.
n 0M3001 N J ) l (1.8Kg, styrene-modified polyamide particles 1 were prepared in the same manner as in Example 1 except that styrene was 1.2 to 9 and benzoyl peroxide was 62.
I got 1 for 2. The obtained particles were of good quality with no fusion or agglomeration observed.

Example 6 In Example 1, styrene-modified polybutylene terephthalate particles were produced in the same manner as in Example 1, except that instead of polypropylene particles, polybutylene terephthalate particles with an average particle size of about 3 mm in the concave portion were used. Got 9 on 12.

The obtained particles were of good quality with no fusion or agglomeration observed.

Example 7 In Example 2, the vinyl monomer was vinyl acetate, and t
- Polymerization was carried out under the same conditions as in Example 2, except that the amount of butyl peroxyvivalate was changed to 362, and vinyl acetate-modified EVA was obtained.□The pellet did not show any fusion or clumping, and was immediately molded. It was in a condition that could be used as a commercial resin.

The vinyl acetate content of this product was determined according to JIS-6730-
The total vinyl acetate content was determined to be 43.1% by weight as determined by the saponification method according to 1973, which was in good agreement with the mass balance. When the vinyl acetate content of PACE EVA was subtracted from this vinyl acetate content, it was found that about 95% by weight of the raw vinyl acetate was introduced.

Example 8 In the same autorotating reactor as used in Example 1, 30-ripropylene particles (Mitsubishi Noblen MH-8) 8.0K were added.
g was added. Separately t-butyl perbenzoate I 6
o y was dissolved in 400v of maleic anhydride and Toluev 1680 as a carrier solvent, and this was introduced into the reactor, and after replacing the inside of the system with 9 cables, the temperature in the reactor was raised to 90°C. The polypropylene particles were allowed to stand for 3 hours at this temperature with continued mixing by rotation to impregnate the maleic anhydride toluene solution containing peroxide into the polypropylene particles.

Next, the temperature inside the reactor was raised to 125° C., and mixing by rotation was maintained at this temperature for 5 hours to complete polymerization. After the reaction, the inside of the reactor was reduced to a reduced pressure (approximately 10 Torr) using the filtration and decompression equipment attached to the reactor [7] The product was dried, and after cooling, the solid content was taken out and maleic anhydride-modified polypropylene particles were removed. Got 9 on 8.4. The MFR of this pellet was 6.02/10 minutes.The maleic anhydride content of this product was determined by infrared spectroscopy and was approximately 4.8% by weight. It turns out that it has been widely adopted.

Comparative Example 6 A modification corresponding to Example 8 was carried out using an extruder (melt grafting method). That is, 100 parts by weight of polypropylene (Mitsubishi Noblen TA-8), 5 parts by weight of maleic anhydride, and 2 parts by weight of t-butyl peroxybenzoate were blended, mixed for 2 minutes using a mixer, and then L/D at 40 seismic diameter.
An attempt was made to produce modified polypropylene grafted with maleic anhydride by melt-kneading it at 210°C using a No. )
I couldn't.

Example 9 Polyethylene particles (Yukalon H
D JX-10) 9.6 to 9 and N,N-dimethylamine ethyl methacrylate 400f and toluene 400F
Then, 1-butylperoxybenzoe) 2 (l 9) was added as a polymerization initiator, and the impregnation temperature was maintained at 90°C for 3 hours and the reaction temperature was maintained at 125°C for 5 hours to complete the polymerization, and the polymerization was further dried and modified. 10Kf of polyethylene particles were obtained.The pellets did not show any fusion or agglomeration, and were ready to be used as a molding resin.When the nitrogen content I of this material was measured, it was 2550 ppm, and the monomer content was It was confirmed that the number of needles was approximately 4%, which is almost quantitative.

Claims (1)

[Claims] 1. In the absence of water, a vinyl monomer and a polymerization initiator are added to thermoplastic polymer particles having an average particle size of 1 to 8 mm at a temperature at which the polymerization initiator does not substantially decompose. In a method for producing modified thermoplastic polymer particles by impregnation and subsequent wetting to complete polymerization of a vinyl monomer, (1) the proportion of components in the system before polymerization is (a) Thermoplastic polymer particles °50 Example 9.9 Okihobe (
b) Vinyl part: 5o-t+, 1 heavy R part (
C) Polymerization initiator: vinyl monomer B) (0.05 to 20 parts per + g); (2) mixing equipment that does not use stirring blades throughout the impregnated glue and polymerization process; A modified thermoplastic polymer characterized in that the treatment is carried out in one apparatus equipped with a heating membrane 4+Hi, and (3) the process is carried out under conditions in which the thermoplastic polymer particles are not substantially dissolved or melted throughout the entire process. Method for producing particles. 2 The vinyl monomer is a styrene monomer, and the component ratio in the system before polymerization is (a) thermoplastic polymer particles; 50 to 90 parts by weight (b)
) Styrenic monomer: 50 to 10 parts (c) Polymerization initiator; Styrenic monomer ILI (l) 0.05 to 20 M! parts as described in item 1 relative to the top part. Method. 3. The method according to item 1, wherein the vinyl moiety is a vinyl ester. 4. The vinyl moiety is an unsaturated carboxylic acid ester,
The component proportions in the system before polymerization are (a'l) Thermoplastic polymer particles: 50 to 90 parts by weight (b) Unsaturated carboxylic acid ester: 50·-10 parts by weight (c) Polymerization initiator: Unsaturated carboxylic acid ester 10
The method according to item 1, wherein the ratio is 0.05 to 20 parts by weight to 0 parts by weight.