JPS59122535A - Preparation of concentrated thermoplastic resin composition containing inorganic filler - Google Patents

Abstract

PURPOSE:To prevent the formation of a resin containing only non-fibrous material, and to obtain a concentrated composition in high yield, by carrying out the suspension polymerization of an aromatic vinyl monomer in the presence of a mixture of non-fibrous and fibrous inorganic fillers which are surface-treated with an organic titanate compound. CONSTITUTION:100pts.wt. of an aromatic vinyl monomer or a mixture of the monomer and a monomer copolymerizable therewith is suspended in water together with 5-800pts.wt. of a mixture composed of 0.5-60wt% of a non-fibrous inorganic filler surface-treated with an organic titanate compound (0.01-2pts.wt. per 100pts.wt. of the filler) and 99.5-40wt% of a fibrous inorganic filler, and the monomer is polymerized. The non-fibrous filler is alumina, silica, etc. having an average particle diameter of 1-800mum, and the fibrous filler is glass fiber, etc., preferably strands obtained by collecting 100-several thousands fibers each having a diameter of <=20mum and cutting to a length of 1-15mm..

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of a concentrated thermoplastic resin composition containing an inorganic filler (hereinafter referred to as "concentrate") containing a high concentration of fibrous and non-fibrous inorganic fillers. Regarding the method.

Compositions made of thermoplastic resins and inorganic fibers such as glass fibers and carbon fibers are easy to mold and have excellent mechanical properties such as impact resistance and dimensional stability. It is used as a material for structural and functional parts.

However, such fiber-reinforced thermoplastic resins tend to cause fibers to protrude on the surface of the molded product, deteriorating the surface appearance, and tend to cause fiber orientation, resulting in anisotropy in mechanical properties. There was a problem.

In order to solve these problems, it has been known that non-fibrous inorganic fillers such as Merck and milled fibers are generally added.

Directly adding and kneading the required amount of fibrous or non-fibrous inorganic fillers to a thermoplastic resin will cause scattering of the fillers, clogging wear of the extruder, etc., and will not be uniformly dispersed. Problems such as these arise, so the patent application filed by the applicant should be
As described in Japanese Patent No. 4/77, a method has been proposed in which aromatic vinyl monomers and the like are subjected to suspension polymerization in the coexistence of an inorganic filler. In this method, pellets in which the non-fibrous inorganic filler and thermoplastic resin are fixed around the fibrous inorganic filler are obtained, but when the amount of the non-fibrous inorganic filler added to the polymerization system is deposited, the pellets become Powdered non-fibrous inorganic filler-containing thermoplastic resin that is not included in the process is produced, resulting in problems such as a decrease in the yield of the desired pellet-like composition and complication of post-processing.

The present inventors have conducted intensive research to develop a method for producing a concentrate that does not have the above-mentioned problems, and have arrived at the present invention.

The above object of the present invention is to carry out suspension polymerization of an aromatic vinyl monomer or a monomer mixture consisting of an aromatic vinyl monomer and a monomer copolymerizable therewith in the coexistence of an inorganic filler. In the method for producing a concentrate, 700 parts by weight of the above monomer or monomer mixture is mixed with 0 parts by weight of a non-fibrous inorganic filler surface-treated with an organic titanate compound.
．． t~60 weight ratio fibrous inorganic filler 99. j〜yo
An inorganic filler mixture consisting of l~ and 00 parts by weight is suspended and polymerized in 700 to 3000 parts by weight of water.

The organic titanate compound used in the present invention is Ro
A mononuclear \T1/ compound having the molecular formula O:R, a dinuclear compound in which these mononuclear compounds are bonded by a crosslinking bond using a dish ligand, for example, a compound having the structural formula I are used.

The substituent R used in each of the above formulas is H2OH3-,
C,, H5-, n-03H7-, i-bleached-, n-, V
e alkyl group such as c-04H9-, NH to H2NC2
Sulfonyl group such as C2A-9H2N-00 0000 5O2-, C6H5,1-03H50
Aromatic groups such as 6H4C6H,-, 0H306H4-, (
OnH, fist @* 0) 24
2 degrees.

P-(/≦n≦20), ArO-o-(Ar: aromatic group), etc. 11100 disubstituted phosphate group, OO phosphate group, (CaH2n+10)2F (
Phosphite groups such as /≦n≦,,zo) and )(2Q=
CH2 etc. are exemplified.

Examples include phosphite groups such as 0 lophosphate group, C, 1H2n+, and opQ.

The substituents R and R' do not need to be all the same in one type of titanate compound, and may be used in any combination as appropriate.

For example, (1-03H,O) (n-017H35C-
0)3Ti.

1 (1-C3H50) (CsyHxs C-0)3”'
, (1-c3H5o)100((C8H17)2'')sTi, and the like.

1 In addition, as non-fibrous inorganic fillers, alumina, silica, kaolin, clay, with an average particle size of about 00 μm,
Examples include talc, mica, calcium silicate, calcium carbonate, magnesium oxide, quartz powder, feldspar powder, glass milled fiber, glass flakes, and glass peas.

As the fibrous inorganic filler, glass fibers, carbon fibers, etc. are preferable, and in particular, a strand of several thousand of these fibers with a diameter of 2 μm or less is cut into a length of /~/. chopped strands (choppea)
5trana) is preferred.

In order to surface-treat the non-fibrous inorganic filler with an organic titanate compound, the required amount of the organic titanate compound is added while stirring the non-fibrous inorganic filler using a V-type mixer, Henschel mixer, ribbon blender, etc. ,or,
Add the required amount of organic titanate compound to hexane, heptane,
There is a method in which the required amount is dissolved in a solvent such as toluene and added.

The amount of organic titanate compound used is 1% of the non-fibrous inorganic filler.
It is preferably 0.01 to j parts by weight per 00 parts by weight, and
．． Parts by weight of 0 to 0 are more preferred. If the amount used is less than 0 or 0 parts by weight, there will be no effect, and if it exceeds 0 parts by weight, there will be no particular disadvantage, but 8 the effects and effects of the present invention will not be significantly improved. It is uneconomical.

In addition, the fibrous inorganic filler is a vinyl glycidyl compound,
Since the surface is usually previously treated with a silane coupling agent, etc., only non-fibrous inorganic fillers are treated with organic titanate compounds based on the method of the present invention. However, when using a fibrous inorganic filler that has not been surface-treated in advance, it is preferable to perform an organic titanate compound treatment.

In manufacturing the concentrate according to the present invention, a non-fibrous inorganic filler of 0. Evening ~ 30 weight section and the rest,
That is, an inorganic filler mixture consisting of a fibrous inorganic filler with a 993 tag to θ weight ratio consisting of an aromatic vinyl monomer, or an aromatic vinyl monomer and a monomer copolymerizable therewith. 5 to 200 parts by weight of monomer mixture
Polymerize the monomer or monomer mixture by suspending it in 100 to 3000 parts by weight of water together with the monomer or monomer mixture in an amount corresponding to parts by weight. let

Suitably, the inorganic filler mixture contains o,t-to-weight of the non-fibrous inorganic filler, and if the amount is less than "-" parts by weight, the effect of the addition is almost negligible.

Moreover, if the amount exceeds 60% by weight, the obtained concentrate will not become pellet-like.

The amount of inorganic filler mixture! If the amount is less than 100 parts by weight, there is no effect, and if it exceeds 00 parts by weight, the amount of resin is relatively small and the filler cannot be bound, so it is not suitable.

Examples of aromatic vinyl monomers include monomers in which a vinyl group is directly bonded to an aromatic ring, such as styrene, α-methylstyrene, vinyltoluene, and α-vinylnaphthalene.

Examples of monomers copolymerizable with the aromatic vinyl monomer include acrylonitrile, methacrylate, methyl acrylate, methyl methacrylate, and other alkyl esters of acrylic acid or methacrylic acid.

The appropriate amount of water is 700 to 30 parts by weight based on 700 parts by weight of the monomer or monomer mixture. 1
If the amount is less than 0.00 parts by weight, stirring will be difficult and the polymerization reaction will not be easily controlled. If the amount of water exceeds 3000 parts by weight, the polymerization apparatus will be large-scale and therefore uneconomical.

In order to suspend the above monomers, etc., it is preferable to use polyvinyl alcohol, polyacrylamide, gelatin, or other commonly used viscosity stabilizers. It is carried out according to the method described.

According to the method of the present invention, compared to the case according to the prior art,
Concentrates containing a high concentration of non-fibrous inorganic fillers can be obtained in good yields, so when this concentrate is blended with all polystyrene, ASm resin, polyester, etc., it is possible to improve the anisotropy of the appearance, strength, etc. of molded products. or significantly improved.

In addition, during polymerization, most of the non-fibrous inorganic filler is contained in a concentrate formed into pellets centered on chopped strands of the fibrous inorganic filler.
Powdery residue is significantly reduced. Therefore, processing after completion of polymerization becomes easy.

Next, the method of the present invention will be explained in more detail based on Examples and Comparative Examples.

Example/~Equipped with a stirrer, cooler, nitrogen gas inlet, thermometer, etc.! Ion-exchanged water with a suspending agent dissolved in a glass reactor,
and 2S04 was added. Next, chopped glass fiber strands, heavy calcium carbonate (manufactured by Maruo Calcium ■) surface-treated with an organic titanate compound as a non-fibrous inorganic filler, and styrene ("M" in Tables 1 and 1') were used.
s, R-/J. ), acrylonitrile, initiator (benzoyl peroxide, BPO), molecular weight modifier (terpinolene), and antioxidant were all charged in the reactor.The temperature in the reactor rose to 0°C after replacing the entire reactor with nitrogen. After that/! Styrene ("M" in Tables 1 and 2)
SR-Ω,” said Omotesou Choitsu. ) was added continuously. After completion of the reaction, L6. Monomer was removed by stripping. Product ff: Washed with water on a 3.2 mesh wire mesh.

The washing water was filtered through P paper to obtain all the residue. The resulting residue was mostly calcium bicarbonate.

Other reaction conditions and results are shown in Table 1.

Comparative Example/Ω A reaction was carried out in substantially the same manner as in the Example except that heavy calcium carbonate was used without surface treatment in advance. The reaction conditions and results are shown in Table 1.

Example J As a non-fibrous inorganic filler, katanabonmildophi (direct/'μmN length 700 μm) was used. The reaction conditions and results are shown in Table 1.

Comparative Example 3 Example except that the surface treatment of carbon milled fiber was not performed! The reaction was carried out in the same manner.

The reaction conditions and results are shown in Table 2.

Example g Wollastonite (G grade) was used as a non-fibrous inorganic filler. The reaction conditions and results are shown in Table 2.

COMPARATIVE EXAMPLE A reaction was carried out in the same manner as in the example except for the fish flesh, which was not subjected to any surface treatment.The reaction conditions and results are shown in Table 2.

Y) Polyacrylic acid suspending agent 2) Polyvinyl alcohol, manufactured by Nippon Gosei 3)
(i-C3H50) (n-C, □H35G -0-)3
Surface treatment with Ti (7 parts by weight per 700 parts by weight of calcium carbonate)
Surface treatment with CH300 (7 parts by weight per 700 weight of calcium carbonate) 5) (1-C3H50) (n-C17H3,C-
0) Surface treatment with 3Ti 1 (0°5 parts by weight per 700 parts by weight of calcium carbonate) by Youyo and Rihe Tamari 1) See Table 1 Note 1) 2) See Note 2) Carbon milled fiber/ θON quantity θ, fM
Parts of (1-03H50) (n-C17H35c O
) Surface treatment with 3TiI 4) 0.0% per 100 parts by weight of wollastonite G. Otsu weight part (1-C3H,O) (n-C17H35Co)3
Ti Table 1 Surface treatment S) Vehicle treatment Patent applicant Mitsubishi Monsanto Kasei Co., Ltd. 2 representatives Patent attorney Hase - (7 others)

Claims (1)

[Claims] An aromatic vinyl monomer or a monomer mixture consisting of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer is suspension-polymerized in the coexistence of an inorganic filler. In the method for producing a plastic resin composition, 100 parts by weight of the above monomer or monomer mixture is mixed with 0.5-tO weight % of a non-fibrous inorganic filler surface-treated with an organic titanate compound and a fibrous inorganic filler. Filler 99.3--0
Inorganic filler mixture consisting of % by weight l~! A method characterized in that polymerization is carried out by suspending 700 to 3000 parts by weight of water together with Oθ parts by weight.