Thermoplastic resin composition and molding product thereof

[0024] The polymerization method of the styrene-acrylonitrile copolymer may adopt a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, etc., among which a bulk polymerization method or a solution polymerization method is preferred. In addition, the preparation method of the styrene-acrylonitrile copolymer preferably includes performing a polymerization reaction using a reactor that can perform a continuous block or solution polymerization method. The reactor includes: a columnar flow reactor, a complete mixing reactor (CSTR), or a tube reactor containing a static mixing element, etc., of which a complete mixing reactor is preferred. The number of the reactors used may be one, or two or more may be used in combination.

[0025] In one embodiment, the preparation method of the styrene-acrylonitrile copolymer is carried out by solution polymerization. The solvent used in the solution polymerization reaction is, for example, toluene, ethylbenzene, or methyl ethyl ketone. Preferably, the operating temperature range of the solution polymerization reaction is 70°C to 140°C; more preferably, the operating temperature range of the solution polymerization reaction is 90°C to 130°C.

[0026] In one embodiment, when preparing the styrene-acrylonitrile copolymer, thermal polymerization can be used or a polymerization initiator can be added to the reaction, wherein the polymerization initiator is for example, but not limited to, hydrogen peroxide ( Hydroperoxides) compounds, such as: tert-butyl hydroperoxide or Isopropylcumyl hydroperoxide, etc.; Peroxyketal compounds, such as: 1,1-Di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane or 2,2 -Di(4,4-di(tert-butylperoxy)cyclohexyl)propane (2,2-Di(4,4-di(tert-butylperoxy)cyclohexyl)propane) etc.; Diacyl peroxides ) Compounds, such as: Dilauroyl peroxide, Decanoyl peroxide, Dibenzoyl peroxide (hereinafter referred to as BPO), etc.; Peroxyesters compounds , Such as: t-butylperoxypivalate (t-butylperoxypivalate), 2,5-dimethyl-2,5-bis(2-ethylhexanol peroxy) hexane (2,5-Dimethyl- 2,5-di(2-ethylhexanoylperoxy)hexane), etc.; peroxide ketals, such as: 4,4-diperoxy tert-butyl-valeric acid-n-butyl ester (4,4-di-t-butyl peroxy valeric acid-n-butyl ester (TX-17), etc.; peroxycarbonates (peroxycarbonates) compounds, for example: tert-Amylperoxy 2-ethylhexyl carbonate, 2-ethylhexyl tert-butyl peroxy carbonate (tert-Butylperoxy 2-ethylhexyl carbonate), etc.; or azo compounds with nitro and cyclohexane, etc. Based on 100 parts by weight of the total amount of styrene-based monomers, acrylonitrile-based monomers and other copolymerizable monomers, the addition amount of the polymerization initiator ranges from 0.01 parts by weight to 2.0 parts by weight, preferably It is 0.01 part by weight to 1.0 part by weight.

[0027] The grafting rate of styrene-acrylonitrile copolymers can be controlled by adjusting the conditions of the graft polymerization reaction, such as: polymerization temperature, chemical properties of rubber-like polymers, particle size, monomer addition rate, initiator Factors such as chain transfer agent, emulsifier dosage and type will affect the degree of grafting.

[0028] For example, chain transfer agents may include: n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan ) Or tert-dodecyl mercaptan. In one embodiment, based on 100 parts by weight of the total monomer mixture, the amount of chain transfer agent used ranges from 0.01 parts by weight to 0.1 parts by weight.

[0029] In the thermoplastic resin composition, polycarbonate, styrene-acrylonitrile copolymer, acrylonitrile-diene-styrene copolymer and acrylic-diene-styrene copolymer are used The total amount is 100 parts by weight, and the content of the acrylonitrile-diene-styrene copolymer may be 1 part by weight to 15 parts by weight, preferably 2 parts by weight to 12 parts by weight, more preferably 5 parts by weight To 10 parts by weight.

[0030] The acrylonitrile-diene-styrene copolymer can be formed by polymerizing acrylonitrile-based monomers, diene-based monomers, styrene-based monomers, and other copolymerizable monomers. In an embodiment, the acrylonitrile-diene-styrene copolymer may contain 50wt% to 90wt% of diene monomer units, 1wt% to 30wt% of acrylonitrile monomer units, and 8wt% to 45wt% % Of styrene monomer units and 0wt%-20wt% of other copolymerizable monomer units. In an embodiment, the acrylonitrile-diene-styrene copolymer may contain 55wt% to 85wt% of diene monomer units, 3wt% to 25wt% of acrylonitrile monomer units, and 12wt% to 40wt% % Of styrene monomer units and 0wt%-15wt% of other copolymerizable monomer units. In one embodiment, the acrylonitrile-diene-styrene copolymer may contain 60wt% to 80wt% of diene monomer units, 5wt% to 20wt% of acrylonitrile monomer units, and 15wt% to 35wt% % Of styrene monomer units and 0wt% to 10wt% of other copolymerizable monomer units. Here, the term "monomer unit" refers to a structural unit formed by a polymerization reaction of an acrylonitrile-based monomer, a diene-based monomer, a styrene-based monomer, or other copolymerizable monomers.

[0031] The type of the above-mentioned acrylonitrile-based monomer is the same as the acrylonitrile-based monomer of the aforementioned styrene-acrylonitrile-based copolymer, and the description will not be repeated here.

[0032] The type of the above-mentioned styrene-based monomer is the same as the styrene-based monomer of the aforementioned styrene-acrylonitrile-based copolymer, and the description will not be repeated here.

[0033] The types of the above-mentioned other copolymerizable monomers are the same as the other copolymerizable monomers of the aforementioned styrene-acrylonitrile-based copolymer, and the description will not be repeated here.

[0034] Diene monomers can include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloroprene, 1 ,3-pentadiene, 2-phenylbutadiene, 1,3-hexadiene or 1,3-octadiene, etc., among which 1,3-butadiene, 2-methyl-1,3 -Butadiene, chloroprene or 1,3-pentadiene are preferred. The above-mentioned diene monomers can be used alone or in combination of several kinds.

[0035] In one embodiment, the acrylonitrile-diene-styrene copolymer may be a graft copolymer having acrylonitrile monomer units, butadiene monomer units and styrene monomer units.

[0036] In an embodiment, the acrylonitrile-diene-styrene copolymer may be a graft polymerized by graft polymerization of styrene-based monomers, acrylonitrile-based monomers and other copolymerizable monomers on diene-based rubber. Branch copolymer.

[0037] The diene rubber may be a polymer obtained by polymerizing the above diene monomer, or a copolymer obtained by copolymerizing two or more of the above diene monomer. Among them, polybutadiene is preferred. The diene rubber can also be a copolymer obtained by copolymerizing the above diene monomer and other vinyl monomers, for example: butadiene-styrene copolymer, butadiene-vinyl toluene copolymer Butadiene-styrene copolymers; butadiene-acrylonitrile copolymers and butadiene-methacrylonitrile copolymers; butadiene-nitrile vinyl copolymers; butadiene- Methyl acrylate copolymer, butadiene-ethyl acrylate copolymer, butadiene-butyl acrylate copolymer, butadiene-2-ethyl acrylate copolymer, butadiene-methyl methacrylate copolymer, Butadiene-alkyl (meth)acrylate copolymers such as butadiene-ethyl methacrylate copolymers. The diene rubber may also be a terpolymer with a butadiene content of 50% by weight or more.

[0038] In an embodiment, the weight average particle diameter of the acrylonitrile-diene-styrene copolymer may be 50 nm to 800 nm.

[0039] In an embodiment, the weight average particle diameter of the acrylonitrile-diene-styrene copolymer may be 200 nm to 400 nm, for example, 300 nm.

[0040] The weight average particle diameter of the acrylonitrile-diene-styrene copolymer is measured in a latex state. A laser particle size analyzer (model: MASTERSIZER 2000) manufactured by MALVERN Instruments was used as a measuring device, and the weight average particle size (nm) was measured by the light scattering method.

[0041] Acrylonitrile-diene-styrene copolymers can be prepared by individual block, solution, suspension or emulsion polymerization methods, and can also be prepared by a combination of these polymerizations, such as emulsification-block or block The state-suspension polymerization method is preferably an emulsion polymerization method, a bulk polymerization method, and a solution polymerization method, and an emulsion polymerization method is particularly preferred.

[0042] In one embodiment, the preparation method of the acrylonitrile-diene-styrene copolymer can be a diene rubber emulsion, adding styrene monomer, acrylonitrile monomer and other copolymerizable monomers , And optionally adding additives such as emulsifier, polymerization initiator or chain transfer agent, the graft copolymer is prepared by graft polymerization. The above-mentioned diene rubber emulsion may be prepared by an emulsion polymerization method, or may be further enlarged after the emulsion polymerization reaction.