TW593370B - Transparent rubber-modified polystyrenic resin - Google Patents

Abstract

The invention provides a transparent rubber-modified polystyrenic resin composed of a continuous phase of copolymers and a disperse phase of rubbery particles formed by rubbery copolymers. The molded product formed by injecting the resin with a mirror surface mould shows a maximal value of height difference (Delta Hmax) of less than 3200 Å and an average value of height difference (Delta Have) of less than 2000 Å determined by a surface profiler. The rubbery particle having a long diameter of larger than 0.3 mum at a distance 1.8 to 2.2 mum from the surface of the molded product shows a A1(the ratio of long diameter a/short diameter b of the rubbery particle before annealing)/A2(the ratio of long diameter a/short diameter b of the rubbery particle after annealing) ratio of 1.08 to 2.35 observed with a TEM at a annealing condition of 120 DEG C x 40 min. The resin exhibits an excellent transparency and physical properties by the control of the annealing condition.

Description

V. Description of the invention [Field of the invention] The present invention relates to a kind of transparent rubber modification, which refers to a group consisting of a copolymer ^ #, an olefin resin, especially a reverse phase, a phase, and a rubber-like A rubber particle dispersed phase. # 日 目+ / Like /, a rubber formed by the material. Tree with good practical transparency and physical properties [Description of Known Skills] Rubber modified polyethylene resin is a kind of material with good processability. 2, Mechanical strength and used in food ", ... Because of the above advantages, it is widely used for household products such as packaging materials, mouths, and mouthpieces for crossbow tails other than 0Α machines. Month _ a Only because of the general modification of rubber polystyrene tree T. „Ht u & ^ Used in the molding of transparent articles. In order to have strength and transparency and to balance the physical properties of the resin, the method of polystyrene resin and styrene-butadiene block: κ, 、 r 隹 cannot fully improve the resin. The mechanical strength is less than B, and the resin with good transparency is a resin molded product with a human angle of 9G (Please measure with the molded product, its transparency is good. 时 When we look at the molded product from the side slope However, it is often found that the transparency becomes worse, that is, the practical transparency becomes i. Because of this practical transparency, the overall quality of the product is reduced. However, the Japanese Patent Application No. 4_180907 is an application for invention In the presence of a styrene-butadiene block copolymer, a method of copolymerization with styrene and methacrylic acid methyl formaldehyde. Although this method can improve the transparency and mechanical strength of the resin, it cannot satisfy practical transparency. Demand for good sexuality. After intensive research, the inventor of this case found that in the standard paper (CNS) A4 collection (Second Edition Tear Off) made of styrene-based monomers and paper sizes, page 3 593370 A7

V ^), / / _, 0, Λ X ^ $ The copolymer consisting of Μ A ΛΚ 兮 is composed of a continuous, η, shaped co-form rubber particle dispersed phase (B), and is compatible with these Continuous phase, knife phase specific composition and resin molded products

Changing rubber conditions before and after annealing, and the surface roughness of the resin molded product, will make the rubber-modified flat-poor Λ-benzene-based resins have better practical transparency and physical properties. [Summary of the Invention] The present invention is to provide a 1 * H-type transparent rubber modified polystyrene resin which has good consistency and transparency. The transparent rubber modified polystyrene material of the present invention is composed of a rubber particle dispersed phase (A) of 25% by weight of a rubber-like copolymer, and a continuous phase (B) of 99 to 75% by weight of a copolymer. # 中The continuous phase of the copolymer is caused by. 100 parts by weight of the styrenic monomer 20 to 70 parts by weight, (meth) acrylate monomer 30 to 80 parts by weight, and copolymerizable monomers 0 to 40 parts by weight. This month, the molded products of the transparent rubber modified polystyrene resin injected through the mirror mold were measured by the surface roughness meter. The measured height difference was △ h, where the largest difference △ Hmax was less than 3200 A, and the average height The difference △ Have is less than 2000 A, and below the surface of the aforementioned molded product! In the depth of 8 ~ 2 2 // m, the rubber particles with a long diameter larger than 0.3 // m are observed with an electron microscope. Under the annealing conditions of 12 (TC x 40 min), the rubber particles before the annealing are not annealed. Average ratio of long diameter a / short diameter b (A1) and the average ratio of long diameter a / short diameter b of annealed rubber particles (A2), where the ratio of A1 / A2 is 1.08 ~ 2.35 〇 This paper size applies China National Standard (CNS) Α4 Specification (21〇χ 297mm) '--- A7

According to the composition of the resin, a transparent rubber-modified polystyrene resin having good physical transparency and physical properties required by the present invention can be obtained. The rubber-like copolymer used in the present invention may be: in the presence of an organic solvent, using an organic lithium compound as a starter, and performing anionic polymerization with a styrene-based monomer, an olefin-based monomer, and an appropriate amount of a solvent;奴 之 / 、 ♦ 物 ， Muni of the above copolymer (Moon viscosity is ~ 80, solution viscosity is 3 ~ 60cps (under 25t, copolymer content is' 5 wt% styrene Monomer solution), and ^. Ethyl in the diene-based unit, the structural content of 8% by weight or more, the block structure I of the rubbery copolymer is: a homopolymer block structure Structure of random block (random) block, taper-block structure with increasing composition. In addition, the rubbery copolymer may have a linear structure or a branched structure, etc. A rubbery copolymer of the present invention In addition to using the above-mentioned block copolymer 2, it can also be mixed with a small amount of butadiene-based homopolymer or 100% by weight of the block copolymer or a random polymerization of styrene by solution polymerization. The ene rubber is used together, and the butadiene-based homopolymer is a low-cis (Lw- cis) structure, the typical weight composition of cis-vinyl in the structure ranges from 30% to 40% / 5% to 40%, and the solution viscosity is 5 to 40 cps (under 25 C, copolymerization Content of styrene monomer solution is 5% by weight). The method for producing the rubbery copolymer of the present invention is a well-known technology, and the detailed methods are described in: US Nos. 2,975, 160, 3,094, 5 14 and 3, Patent cases No. 135,716, No. 3,244,664, No. 3,3 18,862, and Japanese Patent Publication No. 48-875, Japanese Patent Publication No. 48-46691, Japanese Patent Publication No. 49-3 6957, Japanese Patent Publication No. 55-40734 No., Japanese Patent Laid-Open No. 57- This paper size applies to the Chinese National Standard (CNS) A4 specification (210x 297 mm) Page 5 V. Invention Description 405 13 #b and other patent cases or patent applications. : In addition to the foregoing, it can also be used in combination: 4 to the practical practicality of better transparency /. This ethylene-butadiene copolymer can obtain a transparent plastic modified polystyrene resin that is better than the car. S month Styrene-based copolymers of rubbery copolymers are as follows: specific examples of the early body of Jasmine 7, such as "Methylstyrene, p-methylbenzyl Ethylene, m-meta-benzyl, o-methyl-benzyl & benzene, ethylbenzyl, 2,4-dimethylstyrene, dichun " The above-mentioned styrene-based monomers can be used alone or in combination of several kinds, such as ethylene, styrene-styrene, styrene, 2,4,6-tribromostyrene, etc. Specific examples of the diene monomers according to the present invention. , Such as: 1,3-butadiene, 2-arylene, 3-monoene, 2,3-difluorenyl-1,3 · butadiene, ι, 3-pentadiene, L3-hexadiene, etc. The above-mentioned compounds can be used alone or in combination of two or more kinds. Among them, 1,3-butadiene or 2-methyl · πbutadiene is more preferred. The organolithium compound catalyst used in the rubber-like copolymer of the present invention is a compound containing more than one lithium atom in the molecule, and specific examples thereof are: ^^ n-pentyl bell, isopropyl bell, n-butyl bell, secondary Butyl bell, hexyl lithium, cyclohexyl lithium, phenyl lithium, benzyl lithium, naphthyl lithium, third-butyl lithium, dimethylene dilithium, tetramethylene dilithium, butadiene dilithium And isoprene double chain, etc., one or two or more kinds are mixed and used. The polymerization rate of the rubber-like copolymer of the present invention during the polymerization, the vinyl cover, and the reactivity ratio of the monomeric monomer to the styrene monomer and the disordered state can be determined by polar compounds or disorderly (rand 〇m) chemical agents to adjust, the above polar compounds or disordering agents can be selected from: ethers, amines (ainine), thioethers This paper applies Chinese National Standards (CNS) A4 specifications (210 x 297 mm) 6 pages 593370

Potassium, sodium salts of alkylbenzenes, sulfonic acids, sulfon acids, alkyl oxides. The transparent rubber-modified polystyrene resin of the present invention has a rubber-like copolymer content of 1 to 25% by weight, and when the content is less than 1% by weight. At / q, the impact strength of the resin will decrease, exceeding 25 weight. /. , The resin's transparency and processing formability will decrease.

In addition, the continuous phase (B) of the copolymer of the present invention is composed of 20 to 70 parts by weight of a styrene-based monomer, 30 to 80 parts by weight of a (meth) acrylate-based monomer, and 0 to 40 parts by weight. It is formed by parts of copolymerizable monomers. Among them, specific examples of the styrene-based monomer are the styrene-based monomers of the aforementioned rubber copolymer, and will not be repeatedly listed.

Specific examples of the (meth) acrylate-based monomer include, for example, methacrylic acid esters and acrylates. Among these, fluorenyl acrylates may include, for example, methacrylate and ethyl methacrylate. , Butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, 2-methacrylic acid, ethyl acetate, glycidyl methacrylate, etc., and acrylates are, for example: methyl acrylate, ethyl acrylate , N-butyl acrylate, 2-methylpentyl acrylate, 2-ethylpentyl acrylate, octyl acrylate, etc., among which 'methyl methacrylate and n-butyl acrylate are good. The type of the copolymerizable monomer in the continuous phase (B) of the copolymer of the present invention is not particularly limited, and the content ratio of each copolymerizable monomer can be adjusted as necessary to achieve the adjustment of the inflection rate, and it is necessary to make the final resin transparent, as described above. Specific examples of copolymerizable monomers are: unsaturated fatty acids such as itaconic acid, maleic acid, fumaric acid, succinic acid, cinnamic acid, acrylic acid, and methacrylic acid; acrylic acid, methacrylonitrile, etc. Vinyl cyanide monomer; maleimide imide monomer, Malaysian paper standard applicable to China National Standard (CNS) A4 specification (2 tender tear mm) ------- 593370 A7 B7 V. Description of the invention (6 ) Unsaturated carboxylic acid needles such as anhydride, itaconic anhydride, citraconic anhydride, etc. Among them, acrylonitrile is preferred. The maleimide imide monomer may be selected from the group consisting of N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, and hexylmaleimide , N-octylmaleimide, N-dodecylmaleimide, cyclohexylmaleimide, N-phenylmaleimide, N-2,3-xylyl Malay imine, N-2,4-diethylphenylmaleimide, N-2,3-diethylphenyl maleimide, N-2,4 · diethylphenylmaleimide Fluorenimine, N-2,3-dibutylphenylmaleimide, N-2,4_: butylphenylmaleimide, N-2,6-xylylmaleimide, N-2,3-dichlorophenylmaleimide, N-2,4-dichlorophenylmaleimide, N-2,3-dimophenylmaleimide, ST -2,4-diphenylphenylmaleimide and the like; Among them, N-phenylmaleimide is preferred. The polymer structure of the continuous phase (B) of the copolymer of the present invention may be linear or divergent, and the continuous phase (B) of the divergent copolymer may obtain a better physical balance of impact strength and processability (flowability). The continuous phase (B) of the branched copolymer can be achieved by using or adding one or more polyfunctional unsaturated monomers, a polyfunctional initiator, and a polyfunctional chain transfer agent during polymerization. The weight average molecular weight of the continuous phase (B) of the copolymer of the resin of the present invention is not particularly limited, but it is generally 50,000 to 300,000, preferably 60,000 to 200,000, and more preferably 750,000. 00 ~ 150,00. In addition, the transparent rubber of the present invention changes the rubber particle dispersed phase (A) of the polyethylene resin to 7 τ, and the weight average particle diameter of the rubber particles is 0 · 18 ~ 1 // m, preferably 0 ~ 2 ~ The best is between 0 · 2 3 ~ 0 · 5 # m. The rubber particles in the resin of the present invention are large, and the particle content of 0.78 // m accounts for 0 ~ 2 of all rubber particles. $ I% is more than the size of this paper. It applies the Chinese National Standard (CNS) A4 specification (210x 297 mm). Page 8

It is 0 1 7 mile / o, preferably 1 to 15% by weight. When the rubber particle :: amount: the average particle diameter or the particle distribution of the rubber particle diameter cut 0.88 // m, and the target is described in the inner temple, you can get a resin with better practical transparency, transparency and impact strength. The weight average particle diameter of the rubber particles and the content of the rubber particles having a diameter larger than "are determined by slicing the resin by the ultra-thin sectioning method, observing it with a transmission electron microscope, and measuring the weight average particle diameter by the following formula. Σ niD i4 Weight average particle size = ____ Σ ni D i3 In the above formula, ni is the number of rubber particles of particle control Di. The insoluble content in the resin of the present invention is not particularly limited, and is generally 2 ~ 40 reset%, which is more than It is preferably 8 to 35% by weight, more preferably 12 to 30% by weight. In addition, the swelling index of the resin of the present invention is not particularly limited, and is generally 2 to 25, preferably 3 to 20, and more preferably 5 to 15 The measurement method of the insoluble content (wt%) and swelling index of the above resin is as follows: 1 g of the resin is dissolved in a mixed solvent of toluene and acetone at a temperature of 25 ° C for 24 hours. Centrifuge (15,000 rpm, 20 minutes) for separation, then take the lower layer to obtain the weight of the insoluble matter after swelling, and then vacuum-dry the insoluble matter at 80 C for 1 to 2 hours to obtain the weight of dry insoluble matter. Then calculate the insoluble content (weight 0) / 〇). The weight of dry insolubles is not greater than the content of the grain cutter (reset%) =------------ X 1 〇〇% The weight of the resin This paper size applies to China Standard (CNS) A4 Specification (21〇x 291 ^) $ 9 pages 593370 V. Explanation of the invention, the swelling index of the present invention is calculated by the following formula: Weight of insoluble matter after swelling Swelling index II____ Insoluble after drying The weight of the transparent rubber modified polystyrene resin of the present invention, the maximum height difference ΔHmax and the average height difference △ Have are defined as follows: The measurement method 疋 adopts Akume No. 2 standard for injection molding of Akume Company Mirror mold (see “Mould Hand Book” Chapter 4 _8.2 (2) Grinding Standards for Injection Molding) published by Nikkan Kogyo Shimbun in 1989. The surface of the mirror mold is in accordance with JIS B〇601. The Ra method has a surface roughness of 0.1 // m. The resin is used to form a circular test piece with a thickness of 3 mm and a diameter of 5-5 cm in the aforementioned mirror mold. The injection temperature of the test piece is generally 180 ° C to 3001 :, preferably 200X: to 280C. , And the mold temperature (m〇id temperature)-generally 20 ° C ~ 100 C 'preferably 40 ° C ~ 90 ° C, and then use a surface profiler (surface profiler) to measure the flat surface area of the molded product, each time The measurement range (length) is 〖〇〇〇 # m. The height value (η) in this range is measured. The difference between the maximum height value (Hmax) and the minimum height value (Hmin) in this range is △ m (high and low difference value) 'means △ Hi = Hmax-Hmin. Measure the flat area of the molded product at different locations 20 times, measure △ Hi each time and average them, and take an average height difference △ Have (that is, the average value of △ Hi 20 times). Select the largest △ Hi in 20 measurements and call it the largest △ Hi as the maximum height difference △ Hmax, where the maximum height difference △ Hmax should be less than 3200 A. When ΔΗπ ^ χ is greater than 3 2 0 0 Α, As a result, the practical transparency of the resin is deteriorated, and the paper size of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210x 297 mm). Page 10 593370

The average low difference △ Have should be less than 2000 A. When the average high and low difference △ hires A0f, it will also cause the disadvantage of poor practical transparency. On the surface of the H-type product, H2.2 ... at the surface of the rubber product, the length of the rubber particles was examined with an electron microscope. The rubber knee particles of 0.3 // m were unannealed under the annealing conditions of ml × 40 minutes. The average ratio of the long diameter a / short diameter b of the former rubber particles (thousands of average diameters ⑷) and the average long diameter of the rubber particles after annealing (= 2) 'wherein the ratio of A1 / A2 is 108 to 2 3 5, Preferably u8 ~ 2.2,

: Better to 1. Bu 2.0. When the ratio of t A1 / A2 is within the above range, the resin has good practical transparency and impact strength. The method for producing the modified rubber polystyrene resin of the present invention is not particularly limited, but a block or solution polymerization method is preferred. When a block or solution polymerization method is used, better transparency and better processing can be obtained. Properties, such as: good thermal stability and low mold pollution.

The method for producing a modified rubber polystyrene resin according to the present invention is copolymerizable with a styrene-based monomer, a (fluorenyl) acrylic-acid-based monomer, and a polymerizable copolymer added as needed in the presence of a rubbery copolymer. The monomers are subjected to batch or continuous block / solution graft polymerization. Among them, a continuous method can obtain stable physical properties of transparency and impact strength. Taking continuous solution polymerization as an example, firstly, the above-mentioned rubbery copolymer, monomer, and an appropriate solvent are added to form a raw material mixed solution as required. The raw material mixed solution can be traditionally provided with high shear stress and high creep; Dissolution is carried out in a dissolving tank. This dissolving tank can be used: having a ribbon-shaped spiral stirring blade, a propeller-type stirring blade, or other stirring blades that can generate high shear stress, etc., the rubber-like copolymer can be copolymerized in a sufficient time. The material is completely dissolved into a rubber solution (that is, the feed solution). The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210x 297 mm). Page 11 593370 A7 _ B7 V. State of the invention (10) to facilitate the pump The pumping operation to the reactor is performed. The aforementioned raw material solution or monomer solution is continuously fed into the first reactor and / or the second reactor, and / or subsequent reactors respectively, and the first and / or second and / or In the subsequent reactor, a chain transfer agent and a starter are added to carry out the graft polymerization reaction. The above-mentioned reactor may be a continuous stirred reactor (CSTR), a plug flow reactor (PFR), or a static mixing reactor (same type or a combination of different types). The reaction temperature is controlled at 70 ~ 230 ° C. In the transparent rubber-modified polystyrene resin polymerization method of the present invention, it is preferable that the first reactor adopts a continuous stirring reactor (CSTR), and then the second and / or subsequent reactors are connected, and the above-mentioned subsequent reactions are performed. The reactor may be a continuous stirred reactor, a plug flow reactor, or a static mixing reactor. In terms of achieving good practical transparency, it is better to use a continuous stirred reactor (CSTR) for the first reactor, and a plug flow reactor for the last reactor, and more preferably for the first to third reactors. CSTR, the fourth uses a plug flow reactor. Generally speaking, the monomer conversion of the first reactor is about 1 to 40% by weight, preferably 2 to 35% by weight, and more preferably 3 to 30% by weight. The selection of the monomer conversion rate of the first reactor is adjusted according to the type and viscosity of the rubber copolymer used. The final conversion rate of the monomers during the polymerization of the present invention is generally 60 to 98%. In terms of obtaining good practical transparency, the preferred final conversion rate is 70 to 98%, and more preferably 82 to 97%. When the transparent rubber modified polystyrene resin of the present invention is polymerized, the paper size can be adapted to the Chinese National Standard (CNS) A4 specification (210 x 297 mm). Page 12 A7 B7 V. Solvent used in the description of the invention (ll) The types are: aromatic hydrocarbons, ketones, vinegars, among which 'the best aromatic hydrocarbons are, for example, toluene, ethylbenzene, and dimethyl ketone', and the ketones are most preferably methyl ethyl ketone, and the esters are Ethyl acetate is preferred. In the present invention, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane can also be used as part of the solvent. In the production of the transparent rubber-modified polystyrene resin of the present invention, the amount of the starter that can be used is 0 to 2 parts by weight with respect to 100 parts by weight of the monomer, preferably 0.00 to 1 to 0.7. Parts by weight, and the types of the initiator are as follows: (1) alkyl peroxides: tertiary butyl-t-butyl cumyl peroxide (t-butyl cumyl peroxide, hereinafter referred to as per butyl C), α , Α '-bis (third butyl peroxide) diisopropylbenzene [α, α, -bis- (t-butyl peroxy) di isopropyl benzene, hereinafter referred to as Per butyl P], 1,3-bis (per Oxidized third butyl) _diisopropylbenzene n, 3_bis — (t-butyl peroxy) diisopropyl benzene (hereinafter referred to as PX-14). (Π) Peroxyesters: Di-t-butyl-peroxy-hexahydro-terephthalate (BPHTP) and the like. (Μ) peroxocarbonates: diethylene glycol-bis- (third butyl peroxycarbonate) [1] Bu 61; 11716116817 (: 〇1-bis (t-buty1-peroxycarbonate) ), Li Shik > 0-50] etc. (IV) Diacyl peroxide: m-toluoyl and benzoyl peroxide mixture (m-toluoyl and benzoyl peroxide) (Referred to as Nyper BMT-K40), etc. This paper size applies to the Chinese National Standard (CNS) A4 (210x 297 mm) Page 13 593370 A7 B7 V. Description of the invention (V) Peroxy ketals: 4,4, -di-peroxy first butyl-valeric acid-n-butyl ester (4,4, -di_t-butyl peroxyl ^ acid-n-butyl ester, TX-17 for short), etc. For a resin with good practical transparency, it is preferred to use two or more of the aforementioned five types of initiators in combination, more preferably three or more types, and especially (I), (Π), (W ) The three types are best used in combination. In the production of the transparent rubber modified polystyrene resin of the present invention, the amount of chain transfer agent that can be used is a single amount relative to 1.00 parts by weight. 0 to 2 parts by weight, preferably 0.01 to 0.7 parts by weight, specific examples are: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, hard Stearyl mercaptan, tdodeyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, third-octyl mercaptan, Tertiary-Nonyl mercaptan and other sulfur (mereaptan). Others such as: pentaphenylethane, α-methyl styrene dimer, terpinolene ) ° In the production of the transparent rubber-modified polystyrene resin of the present invention, a polyfunctional unsaturated monomer may be added for copolymerization as required. The added amount is 0 to 1 weight relative to 100 weight parts of the monomer. Parts, preferably from 0 005 to 0.6 parts by weight, specific examples of which are: (I) di vinyl benzene, divinylbenzene (1,2,4-trivinylbenzene) ), 1,3,5-trivinylbenzene (l, 3,5-tri vinyl benzene) and other diethylene type 0 This paper size applies to China National Standard (CNS) A4 specifications (210χ 297 public (%) Page 14 593370 A7 ____B7 V. Description of the invention (13) (Π) ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethyl ether Tri_ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate dimethacrylate), 1,4-butylene glycol dimethacrylate, 1,6- hexanediol dimethacrylate, neopentyl alcohol dipropylene Neo pentyl glycol dimethacrylate »PGDMA for short, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2-bis- (4-methyl Propylene glycol oxy diethoxy phenyl) propane [2,2-bis- (4-methacryloxy diethoxy phenyl) propane] and other dipropionic acid methyl esters 〇 (Π) trimethyl propylene Methyl triacetate rimethylol propane trimethacrylate), triethylol ethane trimethacrylate, and the like. (IV) ethylene glycol diacrylate, diethylene glycol diacrylate, tri ethylene glycol diacrylate, polyethylene glycol diacrylate ( polyethylene glycol diacrylate), 1,3-di-propylene glycol diacrylate, 1,4-di-butylene diacetic acid vinegar (l, 4-di-butylene glycol) Paper size applies Chinese National Standard (CNS) A4 specification (210x 297 mm) Page 15 593370 A7 B7 V. Description of invention (Η) diacrylate), 1,6-hexanediol diacrylic acid S purpose (l, 6-hexylene glycol diacrylate), neoopentyl glycol diacrylate (PGDA), di propylene glycol diacrylate, polypropylene glycol diacrylate, 2, 2-bis (4-acryloxy-propoxy-phenyl) propane [2,2-bis (4-acryloxy propoxy phenyl) propane], 2,2-bis (4-acryloxy propethoxyphenyl) Alkoxy) [2,2-bis (4-acryloxy di ethoxy phenyl) prop ane] and other acrylates. (V) Triacrylates such as trimethylol propane triacrylate, triethylol ethane triacrylate, and triethylol ethane triacrylate. (VI) Tetraacrylates such as tetramethyl〇1 methane tetraacrylate. After the aforementioned polymerization reaction, it is taken out of the reactor, and the unreacted monomers, solvents and other low-volatile components are removed through a preheater and a devolatilization device. Polystyrene tree — υ u, in order to obtain good consistent transparency and hue ', 245 ~ 270t is preferred. And deviating: devolatilization slot and / or single-shaft and / or double-shaft extruder with devolatilization mouth can be added to the extruder according to the needs of the devolatilization of Yako Fushanshan ,, such as water, cyclohexane --- Helium slave 4, the general amount of devolatilization aid used is about 10% (the feeding amount of the milk machine is 100% by weight). His Majesty (compared to the extruder, the extruder can also be equipped with a kneading zone as required)

V. Description of the invention (15) Segment (kneading zone), pushing zone (pumping zone) and other screw speeds are 120 ~ 350rPm, the temperature of the extruder is 160 ~ 300t: based on better practical transparency And hue, 240 ~ 26 (rc is preferred. For the purposes of the present invention, an extruder with a devolatilization port is preferred. In addition, a devolatilization tank with an evacuation device can also be used. One or several fluting tanks can be used in series, and its temperature is controlled at 180 ~ 320 °, preferably 2000 ~ 3000. To obtain good practical transparency and hue, 235 ~ 26 (rc is The vacuum degree of the devolatilization tank is controlled below 300 Torr, preferably below 2000 Torr, more preferably below 100 Torr; other devolatilization equipment such as a thin film evaporator 蒸发 ^ ⑴⑺ evaportor) can also be used. Through the treatment of the aforementioned devolatilization device, the volatile components such as residual monomers and solvents in the resin can be reduced to less than 5% by weight, preferably 0.8% by weight. "Α. 25% by weight or less is the most important thing. The present invention can also complete the devolatilization step as required. Resin: Extruded again in the second or second machine. During extrusion, additives such as: anti-emulsification cut, slip agent, etc. can be added as needed, especially resin σ 〇 ～ 0.5 (100% by weight resin), preferably 〇〇 〇1 ～ 〇2% by weight of the second peroxide of its training system, a transparent rubber modified polystyrene resin with good properties can be obtained. The specific examples of the aforementioned third pentyl peroxide are: amyl Per〇Xy)., Per〇xy) -cyci ° ^ [2,2-d 卜 (t-amyi peroxy) pr〇 pane], ethyl 593370 A7 B7 V. Description of the invention (16) Di- (tertiary ammonium peroxy) butyrate [Ethylene_3,3-di_ (t_amyl peroxy) bixtyrate] Base is better. In order to achieve the purpose of good practical transparency and good impact strength, the present invention can be achieved by regulating at least two of the following polymerization manufacturing conditions: (A) the combination of at least two 1-initiators: the types of initiators, such as peroxidation Burning type, peroxide type, percarbonate type, osmium peroxide type, ketal peroxide type. (B) Selection of specific polymerization reactor or final conversion rate and arrangement of polymerization reactors: Generally, 3 to 6 continuous polymerization reactors are preferred, and the first reactor is preferably a continuous reactor ( CSTR), the last one is a plug flow reactor (PFR), more preferably the first to third reactors are CSTR, and the last one is a plug flow reactor. The final conversion rate is 60 to 98%, more preferably 70 to 98%, and even more preferably 82 to 97%. (C) The resin that has been devolatilized is then extruded by an extruder: especially the third pentyl peroxide is added and mixed with the resin and extruded. (D) Specific devolatilization process and residual volatiles: (Di) Specific devolatilization preheater temperature: generally 200 ~ 280 ° C, preferably 245 ~ 270 ° C. (〇2) The temperature of the devolatilization tank is generally ~ 320 ° C, preferably 235 ~ 260 ° C. (C > 3) Extrusion machine with devolatilization: general temperature 160 ~ 300 ° C, preferably 240 ~ 260 ° C, the above-mentioned devolatilization pressure is below 300 T0rr, it is better to add 丨 〇 weight % Devolatilization aid below, for example: water. Paper size T ¥ iiii (CNS) M gauge 4 (2 runs 297 mm) Page 18

593370 A7 B7 V. Description of the invention (18) In addition, other resins can be further blended without significantly impairing the transparency of the resin of the present invention, and other resins such as: styrene- (meth) acrylic acid can be added Ester-acrylonitrile copolymer, styrene- (meth) acrylate copolymer, styrene- (meth) acrylate-acrylonitrile-maleimide copolymer, benzene Ethylene- (fluorenyl) acrylate-maleimide-based copolymer, (meth) acrylate-maleimide-based copolymer, or the aforementioned copolymer is modified with diene rubber, For example: styrene-based diene- (meth) acrylate-acrylonitrile-based copolymer, styrene-based di-based- (fluorenyl) acrylate-based copolymer, styrene-diene (Aromatic) Acrylic acid esters-Acrylic acid-Malaysian imine fluorene copolymers, Acetophenone-dilute _ (Jiamei) Acrylic acid esters-Maleimine imine copolymers, (A Group) Propanoic acid g-based-diluted-maleimide-based copolymers and the like. The resin of Otomochi chinensis resin is resistant to special restrictions, and the compounding cost of the extruded resin is extruded or granulated. The resin is used in an amount of 100 parts by weight based on 100 parts by weight of the transparent rubber modified polyphenylene resin. 〇 ~ 200 parts by weight, which can adjust or improve thermal properties, rigidity and flow processability. The application of the transparent rubber styrene resin of the present invention is not made, and it can be applied to various molding, injection molding, stretch molding, thermoforming, vacuum molding, and hollow molding finished products such as injection molding and compression molding. Products, and can be formulated according to the requirements of high fluidity and high heat resistance. The aforementioned other ingredients or resins can be added and mixed by a common mixing kneading machine such as a Bragg machine, a Banbury mixer, a kneading-mixing machine, a rolling machine, a uniaxial extruder and the like. Usually take the opportunity to mix and knead, and then cool the extruded material. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). Page 20, Description of the invention (19 The above-mentioned kneading-usually in It is better to have a degree of 160 ～ 280. It is also necessary to fold the week and make it into 仃, and use 〇 ～ 250. (: Temperature. B) There is no special limit on the order of mixing and mixing. [Physical property test] 1 Transparency and practical transparency 3 axis, straight, ... (Working degree 'Haze): Injection resin molding thickness setting, show model ^ degree is 5th generation, and then measuring ^ brightness' observation line and test piece according to Bajia 0_1003 standard (Horizontal plane) is 90 degrees (that is, Γ, directly above the test piece), the measured transparency is Haze (90 °), and the included angle between the gauge line and the test piece (horizontal plane) is 30 degrees (that is, from oblique Observe the test piece at 30 degrees on the side), and the measured transparency is Haze (30.). The practical transparency is HaZe (30.). Haze (90.) The difference between the two, when the difference is smaller, it means Transparency is better when used consistently.-、 Measurement of the surface roughness of resin molded products ·· Acume NO 2 standard used for injection molding by Akume Surface mold, the roughness of the surface of the mirror mold measured by the Ra method of Jls B0601 is 0.1 m. The resin is injection-molded into the aforementioned mirror mold to form a round test piece with a thickness of 3 mm and a diameter of 5.5 cm. A surface meter (surface pr0filer, model Tencor Alpha step 500) measures the surface roughness of the round surface of the test piece a total of 20 times, and obtains the maximum height difference △ Hmax and the average height difference △ Have. Impact resistance (IZOD ) · • Measure the Izod impact strength according to ASTM D-256 (2 3 ° C notched 1 / 4-inch thick test piece). Fourth, the weight average particle diameter of the rubber particles and the diameter of the rubber particles are greater than 0.7 8 # Determination of the particle content of m ·· The resin section is taken with a transmission electron microscope. The paper size is applicable to the Chinese National Standard (CNS) A4 size (210x 297 mm) Page 21 593370 A7 ------____ V. Description of the invention (20) ---'-- = 25, 000 times the photo (12-ηχ 9.5cm), calculated according to the following formula: Σ niD i4 weight average particle size = --- Σ niD i3 ni is the particle size m The number of rubber particles. In addition, in i2emx 9 such as photo +, calculate the rubber particle diameter is larger than the rubber particles The content (% by weight) of all rubber particles. If the rubber particles are non-circular, the particle diameter is calculated by the (long diameter + short diameter) / 2 of the rubber particles. 5. Determination of residual volatile content in the resin (ie, residual Monomer and solvent): Gong resin particles were added together with 10 mi of DMF (Di methyl formamide, Di methyl formamide) to dissolve, and then measured by Gc. 6. Determination of A1 / A2 ratio of rubber particles before and after annealing of the molded product: The resin molded product test piece used in the first physical property test is measured by the TEM (transmission electron microscope) and ultra-thin sectioning method to determine the i under the surface of the molded product. · 8 ~ 2 2 // m, take 250,000 times photo 9 · 5cm) by electron microscope photography, among the rubber particles in the photo, select all rubber particles whose major diameter is greater than 0.3 // m, and measure the length The ratio of diameter a to short diameter b '

Where a is the long diameter of the rubber particles, i is the short diameter of the rubber particles, and η is the number of rubber particles whose long diameter is greater than 0.3 μm. In addition, after the above-mentioned molded product is annealed at 120 ° CX 40mins, it is applied to the above-mentioned ultra-thin paper size to apply the Chinese National Standard (CNS) A4 specification (210x297 mm). Page 22 5. Description of the invention (21) Slice method In the electron microscopy, all rubber particles are selected; :: The rubber particles of 25000 times are transmitted, and the average diameter M of the rubber particles with a long diameter a and a short length greater than 0.3 is measured. Take the foregoing; 'Bu ^ ratio, which is calculated with the previous formula. The so-called long diameter refers to the same-the ratio that she can obtain 2 times. Here, the county of the growth axis (straight line) selects the point shape of the farthest ends on the particles. Also, the short diameter refers to the distance of the rubber particles in the direction perpendicular to the aforementioned long axis. # '土 令 工In terms of length. For the short-axis (straight-line) elliptical rubber particles formed by the ideal ellipse n / point, the length of the rubber particles is controlled by the length and diameter of the ellipse. The morphology of the aforementioned rubber particles is obtained by using the ultra-thin sectioning method, and the thickness of each slice is cut to a depth of 1.8 to 2.2 // m, and the rubber particles are observed under a microscope. Measured on the parallel surface of the molded product in the direction parallel to the surface of the molded product between 〇_〇5 ~ 0.09 # m, and then take the sliced part in this direction and process it with electrons [Description of Examples and Comparative Examples] [ Example 1] parts by weight of a rubber copolymer [styrene-butadiene block copolymer, styrene / butadiene content = 25/75% by weight, 丨, 2-vinyl structure content = 15%, muni Viscosity = 47 (ML1 + 4,100.〇), 40 parts by weight of stupid ethylene monomer, 57 parts by weight of methyl methacrylate, 30 parts by weight of acrylonitrile, 38 parts by weight of ethylbenzene, n-dodecyl sulfur 0.15 parts by weight of alcohol, and 0.018 parts by weight of tertiary butyl-p-cumyl peroxide (Japanese oil Perbutyl c), 0.002 parts by weight of -methylbenzylidene and benzamidine Oxide mixture (Japanese grease Nyper BMT-K40), 0.095 parts by weight-peroxide This paper is sized according to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) Page 23 593370 A7 B7 V. Description of the invention (22) the feed formed by the third butyl-hexahydro · terephthalate The liquid was continuously pumped into 4 continuous continuous mixing reactors (CSTR) in series at a rate of 35 Kg / hr. The capacity of the reactors was 40 liters, and the reaction temperature of each reactor was i0 (rc, i〇6 〇c, 120 C, 130 C 'The stirring speed is 300 rpm, 200 rpm, 150 rpm, 90 rpm. The monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 65%.' The aforementioned polymer solution was heated by a preheater at a temperature of At 25 ° C, the devolatilization tank with a vacuum device was used to control the temperature of the devolatilization tank at 240X: to obtain a granular resin, and the granular resin prepared was further added with 0.02% by weight of di-trimethylperoxide. The transparent rubber modified polystyrene resin of the present invention can be obtained by mixing and extruding with an extruder. The residual volatile content of the obtained transparent rubber modified polystyrene resin is 0.12% by weight, and the measured physical properties , Transparency, practical transparency Haze (30 °) -Haze (90 °) and impact strength are shown in Table 1. [Example 2] 13-7 parts by weight of a rubber copolymer [styrene-butadiene block copolymer, Styrene / butadiene content = 25/75% by weight, 1,2-vinyl knot Content = 25%, Muni viscosity = 49 (ML1 + 4 ,: 10.0), 37 parts by weight of styrene monomer, 60 parts by weight of methyl methacrylate, 30 parts by weight of acrylonitrile, and 38 of ethylbenzene Parts by weight, 0.12 parts by weight of n-dodecyl mercaptan, and 0.6 parts by weight of tertiary butyl-p-cumyl peroxide (Perbutyl c), 0.1 parts by weight Mixture of m-methylphenylfluorenyl and phenylfluorenyl peroxide (Nyper BMMT-K40), 0.02 parts by weight of bis-peroxy third butyl-hexahydro-terephthalic acid Ester (di-t-butyi per〇Xy) This paper size applies to China National Standard (CNS) A4 specification (2ΐ〇χ 297 public love) Page 24 593370 A7

The feed solution formed by the terephthalate) was continuously pumped into a series of continuous continuous mixing reactors (CSTR) at a rate of 35 Kg / hr. The total reactor volume of the reactor was 40 liters. The reaction of each reactor The temperature is 90qc, 100 ° C, and the stirring speed of C 130 C is 250rpm, 200rpm, 150rpm, 90rpm. The monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 66 / 〇 The solution was heated by a preheater at a temperature of 250 ° C, and then passed through a devolatilization tank with a vacuum device. The devolatilization tank temperature was controlled at 23 ° to obtain a granular resin prepared by adding a granular resin. 0.03% by weight of di-peroxy second pentyl 'is mixed and extruded with an extruder to obtain the transparent rubber modified polystyrene resin of the present invention. The residual volatile content of the obtained transparent rubber modified polystyrene resin was 42% by weight. The measured physical properties, transparency, practical transparency, and impact strength are shown in Table 1. [Example 3] 14.4 parts by weight of a rubber copolymer [combined with the following three types of rubbers (1), (2), and (3) at a weight ratio of (1) / (2) / (3) = 9 5/3/2 Made of, including: (1) styrene-butadiene block copolymer, SM / BD = 25/75, 1,2-vinyl structure content = 15%, Muni viscosity = 47 (ML1 + 4,100 ° C). (2) Styrene-butadiene block copolymer, SM / BD = 68/32, 1,2-vinyl structure content = 13% by weight, solution viscosity = 5.5 cps (copolymer content is 5% by weight of toluene Solution, 25 ° C). (3) Styrene butadiene rubber, SM / BD = 25/75, 1,2 vinyl structure content = 13%, solution viscosity = 85cps, Asahi Kasei Corporation Tufdene 2100R], 41 parts by weight of styrene monomer, 55 parts by weight of methyl methacrylate, 4.0 parts by weight of acrylonitrile, 38 parts by weight of ethylbenzene, 0.12 parts by weight of n-dodecyl mercaptan, and 0.02 parts by weight of a third butyl-peroxide pair The isopropyl basic paper size applies the Chinese National Standard (CNS) A4 specification (210x 297 mm) page 25 593370 A7 ___B7 V. Description of the invention (24) Benzene (Perbutyl C), 0.09 parts by weight -Mixture of fluorenylbenzyl and benzamyl peroxide (Japanese grease Nyper BMT-K40), 0.02 parts by weight-third butyl peroxide, tert-butyl-hexahydro-terephthalate The feed solution formed by (di_t_butyl peroxy hexahydro terephthalate) was continuously pumped into 4 continuous continuous mixing reactors (CSTR) in series at a rate of 35 Kg / hr. The reactor capacities were all 40 liters, each The reaction temperature of the reactor was 90 ° C, 100 ° C, 120. 〇, 127 X: Stirring speed is 300 rpm, 200 rPm, 150 rPm, 120 rpm. The monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 68%. The aforementioned polymer solution is heated by a preheater at a temperature of At 260 ° C, a devolatilization tank with a vacuum device is attached. The temperature of the devolatilization tank is controlled at 250 ° C to obtain a granular resin. The pelletized resin is then added with 0-015 wt% di-peroxide third The amyl group can be mixed and extruded with an extruder to obtain the transparent rubber modified polystyrene resin of the present invention. The residual volatile content of the obtained transparent rubber-modified polystyrene resin was 0.16% by weight. The physical properties, transparency, practical transparency, and impact strength measured in Table 1 are shown in Table 1. [Example 4] 19.3 parts by weight of a rubber copolymer [composed of (1) / (2) = 93/7 weight ratio of the following two kinds of rubbers, (1) styrene-butadiene Dilute block copolymer, SM / BD = 25/75, 1,2-vinyl structure content = 15%, Muni viscosity = 47 (ML1 + 4 '100 ° C). (2) Styrene-butadiene rubber, SM / BD = 25/75 '1,2-vinyl structure content = 30%, Muniler sound = 55 (MLi + 4' lOOC) 'Asahi Kasei Corporation Tufdene 2330], 38 parts by weight of ethyl acetate monomer, 58 parts by weight of methyl methacrylate, and 4 parts by weight of acrylonitrile This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 mm) Page 26593370 A7 B7 V. Description of the invention (25) parts, 80 parts by weight of ethylbenzene, 0-14 parts by weight of n-dodecyl mercaptan, and 0,009 parts by weight of ", α, -bis (third butyl peroxide) Diisopropylbenzene (Perbutyl PF), between 0.135 parts by weight-a mixture of methylbenzyl and benzophenoxide (Japanese grease Nyper BMT-K40), 0.005 parts by weight- The feed solution of di_t-butyl peroxy hexahydro terephthalate was continuously pumped into the reactor at a rate of 35 Kg / hr. The reactor system was composed of 4 in series The first to third reactors are continuous complete mixing reactors (CSTR), and the fourth reactor is a plug flow reactor (pFR) The reactor capacity is 40 liters. The reaction temperature of each reactor is 90 °, 100 °, 125 ° C, 128 ° C (inlet) to 1550 ° C (outlet), and the stirring speed is 300. rpm, 200rpm, 150rpm, 30rpm, the monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 90%, the aforementioned polymer solution is heated by a preheater, and the temperature is 230 ° C. Devolatilization tank, whose devolatilization tank temperature is controlled at 220 ° C, and finally extruded through a biaxial extruder with a devolatilization port, and the extrusion temperature is controlled at 250 ° C to obtain the transparent rubber modified polystyrene of the present invention. Resin. The residual volatile content of the obtained transparent rubber modified polystyrene resin was 0.22%. The measured physical properties, transparency, practical transparency, and impact strength are shown in Table 1. [Example 5] Rubber Copolymer, V) Two kinds of rubber (1) / (2) = 93/7 weight ratio are used together, including: acetophenone_butadiene copolymer, SM / BD45 / 75, 1,2-ethylene Basic structure content = 15%, Muni viscosity = 47 (MLl + 4 '100t :). ⑺styrene_ butadiene rubber,

Page 27 593370 A7 B7 V. Description of the invention (26) SM / BD = 25/75 '1,2-vinyl structure content = 30%, Muni viscosity = 55 (ML1 + 4, 100 ° C), Asahi Kasei Corporation Tufdene 2330], 36 parts by weight of acetophenone monomer, 61 parts by weight of methyl methacrylate, 3.0 parts by weight of acrylonitrile, 63.6 parts by weight of ethylbenzene, 0.16 parts by weight of n-dodecyl mercaptan, and 0.005 parts by weight α, α, -bis (third butyl peroxide) diisopropylbenzyl (Japanese oil Perbutyl P), 0.002 parts by weight of -methylbenzyl and benzamyl peroxide compounds (Japan Nyper BMT-K40), 0.13 parts by weight of a feed solution of di-t-butyl peroxy hexahydro terephthalate The pump is continuously pumped into the reactor at a rate of / hr. The reactor is composed of 4 reactors in series. Among them, 1 to 3 reactors are continuous-type complete mixing reactors (CSTR), and the fourth reactor is a plug flow type. Reactor (PFR), the capacity of the reactor is 40 liters, and the reaction temperature of each reactor is 98 ° C, 105. (:, 126 ° C, 128 ° C (inlet) to 150 ° C (outlet), stirring speed is 31 rpm, 210 rpm, 150 rpm, 30 rpm, the monomer conversion rate of the polymer solution at the outlet of the fourth reactor 85%, the aforementioned polymer solution is heated by a preheater at a temperature of 260 ° C, and then passed through a devolatilizing tank equipped with a vacuum device, the devolatilizing tank temperature is controlled at 240 ° C, and finally The shaft extruder is extruded, and the extruding temperature is controlled at 25 ° C, and 1% by weight of water is added to the extruder as an extruding auxiliary to obtain the transparent rubber modified polystyrene resin of the present invention. The obtained transparency The residual volatile content of the rubber-modified polystyrene resin is 0% by weight, and the measured physical properties, transparency, practical transparency, and impact strength are shown in the table-household weight. [Example 6]

Page 28 593370 A7 _ B7 V. Description of the invention (27) Rubber copolymer 1 8.3 parts by weight [Combined with (1) / (2) = 93/7 weight ratio of the following two rubbers (1) and (2) Including: acetophen-butadiene block copolymer, SM / BD = 25/75, 1,2-vinyl structure monomer = 15%, Muni viscosity = 47 (ML1 + 4, 100 ° C). (2) Styrene-butadiene rubber, SM / BD = 25/75, 1,2-vinyl structure content = 30%, Muni viscosity = 55 (ML1 + 4, 100 ° C), Asahi Kasei Tuddene 2330 ], 39 parts by weight of styrene monomer, 58 parts by weight of fluorenyl acrylate, 3 parts by weight of acrylonitrile, 50.7 parts by weight of ethylbenzene, 0.15 parts by weight of n-dodecyl mercaptan, and 0.025 parts by weight of α, α '-Bis (third butyl peroxide) diisopropylbenzene (Perbutyl P), between 0.002 parts by weight-a mixture of methylbenzyl and benzamyl peroxide (Japanese grease Nyper BMT-K40), one of the 0.1 serious injuries-the feed solution formed by di-t-butyl peroxy hexahydro terephthalate, continuously at a rate of 35Kg / hr Pumped into the reactor, the reactor is made up of 4 in series, of which the first to third reactors are continuous complete mixing reactors (CSTR), the fourth reactor is a plug flow reactor (PFR), The reactor capacities were all 40 liters, and the reaction temperature of each reactor was 100 ° C and 106. (3, 124 ..., (inlet) ~ 151 ° C (outlet), stirring speed is 300rpni, 200rpm, 150rpm, 30rpm, the monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 85%, as mentioned above The polymer solution was heated by a preheater at a temperature of 24 ° C, and then passed through a devolatilization tank with a vacuum device. The temperature of the devolatilization tank was controlled at 22 ° t, and finally a biaxial extruder with a devolatilization port was attached. Extruded, the extruded temperature is controlled at 23 ° C, and 0.5 wt.% Of water is used as the extrusion aid, and the transparent rubber modified polystyrene resin of the present invention can be obtained. The obtained transparent rubber modified This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 x 297 publications ^ -------- page 29 593370 A7 ----------------- B7 five 、 Explanation of the invention (28) * 一 ^--Residual impact of poly (phenylene fluorene) resin & 0 /, owing to the amount of zen hair is 0 · 15% by weight. The measured physical properties, transparency and practical transparency are n 1 < The degree of d and the impact strength are as shown in Table 1. [Example 7] 100 parts by weight of the transparent rubber modified polystyrene resin obtained from shell-palladium example 1 and 8 parts by weight Methyl methacrylate-butadiene rubber_ Styrene-based graft copolymer (manufactured by emulsification method, powder, KCB650L from Wu Yu Company) 'The transparent rubber modified polystyrene resin obtained after mixing the two The residual volatile content was 0 · 丨 wt%, and the measured physical properties, transparency, practical transparency, and impact strength are shown in Table 1. [Example 8] Rubber copolymer 1 8 · 3 parts by weight [from the following (丨), ( 2) The two rubbers are combined with (1) / (2) = 93/7 weight ratio, including: (丨) styrene-butadiene block copolymer, SM / BD = 25/75, l, 2-Vinyl structural monomer = 15%, Muni viscosity = 47 (ML1 + 4'100 °). (2) Styrene-butadiene rubber, SM / BD 25/75 '1, 2 -Vinyl structure content = 30%, Muni viscosity = 55 (ML1 + 4, 100 ° C), Asahi Kasei Corporation Tufdene 2330], 40.5 parts by weight of styrene monomer, 58 parts by weight of methyl methacrylate, Butyl monoacrylate 1.5 weight stings, 50.7 parts by weight ethyl, 015 parts by weight of n-dodecyl mercaptan, and 0.025 parts by weight of ", α, _bis (third butyl peroxide) diisopropyl basic Japan oil fat Perbutyl P), 0.002 parts by weight-mixture of fluorenyl benzamidine and benzamyl peroxide (Japanese oil Nyper BMMT-K40), 0.1 parts by weight- The feed solution formed by the oxidation of di-t-butyl peroxy hexahydro terephthalate was continuously pumped into the reactor at a rate of 35 Kg / hr. The reactor was composed of 4 strings Paper size applies to China National Standard (CNS) A4 (210 x 297 mm) Page 30 593370

The first to third reactors are continuous complete mixing reactors (CSTR), and the fourth reactor is a plug flow reactor (pFR). The reactor capacity is 40 liters. The reaction temperature of the reactor was 10 (rc, 106x :, 125 ° C, 127t: (inlet) to 151. (: (outlet), stirring speed was 300 rpm, 200 rpm, 150 rpm, 30 rpm, The monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 86%. The aforementioned polymer solution is heated by a preheater at a temperature of 240 ° C, and the temperature of the devolatilization tank is controlled by a devolatilization tank with a vacuum device. At 220 C, it is finally extruded through a biaxial extruder with a devolatilization, and the extruding temperature is controlled at 2 3 5 C, and 0.5.5% by weight of water is added as an extruding auxiliary to obtain the transparent rubber of the present invention. Modified polystyrene resin. Residual volatile content of the obtained transparent rubber modified polystyrene resin is 0.25% by weight. The measured physical properties, transparency, practical transparency and impact strength are shown in Table 1. [Comparative Example 1]

13 parts by weight of a rubber copolymer [styrene-butadiene block copolymer, SM / BD = 25/75, 1,2-vinyl structure content = 15%, Muni viscosity = 47 (ML1 + 4, l〇 〇 ° C)], 38 parts by weight of styrene monomer, 58 parts by weight of methyl methacrylate, 4 parts by weight of acrylonitrile, 37.7 parts by weight of ethylbenzene, 0.15 parts by weight of n-dodecyl mercaptan, and 0.1 part by weight Bis-di-t-butyl peroxy hexahydro terephthalate, a feed solution formed by di_t-butyl peroxy hexahydro terephthalate, was continuously pumped into 3 serial continuous complete mixing types at a rate of 35 Kg / hr Reactor (CSTR), the capacity of the reactor is 40 liters, the reaction temperature of each reactor is 95 ° C, 105 ° C, 125 ° C, the stirring speed is 300 rpm, 200 rpm, 150 rpm, polymerization at the outlet of the third reactor The monomer conversion rate of the polymer solution is 62%. The size of the aforementioned polymer solution paper is applicable to the Chinese National Standard (CNS) A4 specification (210x 297 mm). Page 31 593370

The liquid is preheated and heated to a temperature of C, and the devolatilization with a vacuum device = 'its devolatilization tank temperature is controlled at 22 (rc), and a transparent rubber modified polystyrene resin can be obtained. The obtained The residual volatile content of the transparent rubber modified polystyrene resin is 0.38% by weight. The measured physical properties, transparency, practical transparency, and impact strength are shown in Table 1. [Comparative Example 2] 14.3 parts by weight of a rubber copolymer [styrene-butyl Diene block copolymer, SM / BD 25/75 '1,2-vinyl structure content = 15%, Muni viscosity 47 (ML1 + 4, IOOC)]' 38 parts by weight of styrene monomer, 60 parts by weight of methyl methacrylate, 2 parts by weight of acrylonitrile, 381 parts by weight of ethylbenzene, 0.115 parts by weight of n-dodecyl mercaptan, and 0.115 parts by weight of bis-peroxide tert-butyl Hexahydro_ di + bUtyi per〇xy hexahydroxyterephthalate feed solution formed by continuous pumping at a rate of 35Kg / hr into 4 continuous continuous mixing reactors (cstr ), The total volume of the reactor is 40 liters, and the reaction temperature of each reactor is 100 ° C, 106 ° c, 124 C, 134 C The stirring speed was 300 rpm, 200 rpm, 150 rpm, and 120 rpm. The monomer conversion rate of the polymer solution at the outlet of the fourth reactor was 6 6 / 〇 '. The polymer solution was heated by a preheater at a temperature of 2 3 0. The devolatilization tank with the vacuum equipment is equipped with a devolatilization tank temperature controlled at 22 (rc, and finally extruded through a biaxial extruder with a devolatilization port, and the extruder temperature is controlled at 225.0, and 1 wt% is added to the extruder. Water can be used as extrusion aid to obtain transparent rubber modified polystyrene resin. The residual volatile content of the obtained transparent rubber modified polystyrene resin is 0.15% by weight. The measured physical properties, transparency, practical transparency and The impact strength is shown in Table 1.

Page 593370 A7

[Comparative Example 3] 17-8 parts by weight of a rubber copolymer [composed of (1) / (2) = 90/10 weight ratio of the following two types of rubber: (1) / (2), including: (1) styrene-butadiene Difluorene block copolymer, SM / BD45 / 75, 1,2-vinyl structure content = 15%, Muni viscosity = 47 (ML1 + 4,100 .. (2) butadiene rubber, ι · 2 —vinyl structure content = 11%, Muni viscosity = 47 (MLl + 4, i〇 (rc), cis structure is 5 / ί > Comex Moda PR255], 36 parts by weight of styrene monomer, 61 parts by weight of methyl methacrylic acid, 3 parts by weight of acrylonitrile, 3 parts by weight of ethylbenzene 39, 0.12 parts by weight of n-dodecyl mercaptan, and 0.005 parts by weight of third butyl p-isopropyl peroxide A feed solution of benzene (Japanese oil perbutyi c), 0.08 parts by weight of methylbenzyl and benzamyl peroxide compounds (Nyper BMT-K40) at a rate of 35Kg / hr Continuously pumped into the reactor. The reactor is composed of 4 reactors in series. Among them, the first to third reactors are continuous complete mixing reactors (CSTR), and the fourth reactor is a plug flow reactor (PFR). , The capacity of the reactor is 40 liters, the reaction temperature of each reaction group is 90. 0, 105 ° C, 124 ° C, 126 ° C (inlet) ~ 150C (outlet) 'Stirring speed is 300rpm, 200rpm, 100rpm, 3Orpm' 4th reaction The monomer conversion rate of the polymer solution at the outlet of the reactor was 84%. The aforementioned polymer solution was heated by a preheater and the temperature was 26 (Γ (:, and then passed through a devolatilization tank with a vacuum device, and its devolatilization tank temperature was controlled). At 2 5 5 t, a rubber-modified polystyrene resin can be obtained. The residual volatile content of the obtained rubber-modified polystyrene resin is 0.24% by weight. The measured physical properties, transparency, practical transparency, and impact The strength is shown in Table 1. [Comparative Example 4] This paper size is in accordance with Chinese National Standard (210x297). Page 33 593370 A7 B7 V. Description of the invention (32) 11.7 parts by weight of rubber copolymer [by the following (1 ), (2), and (3) three types of rubbers are combined with a weight ratio of (1) / (2) / (3) = 60/3 5/5, including: (1) styrene-butadiene block Copolymer, SM / BD = 25/75, 1,2-vinyl structure content = 15%, Muni viscosity = 47 (ML1 + 4, 100 ° C). (2) Butadiene rubber Muni viscosity = 47 (ML1 + 4,100), 1,2-vinyl structure content is 11% by weight, PR255 manufactured by Chi Mei Corporation. (3) Styrene-butadiene block copolymer, SM / BD II 68/32, 1.2 — 13% vinyl structure content, solution viscosity = 5.5 cps (copolymer content of toluene solution of 5% by weight)], 41 parts by weight of styrene monomer, methyl methacrylate 55 parts by weight of ester, 4.0 parts by weight of acrylonitrile, 37.2 parts by weight of ethylbenzene, 5 parts by weight of n-dodecyl mercaptan, 0.005 parts by weight of benzoyl peroxide, and 0.09 by weight of 5 Two parts of the feed solution formed by the third butyl peroxy hexahydroterephthalate (di_t_butyl peroxy hexahydro terephthalate) was continuously pumped into the 4 continuous continuous complete series at a speed of 35 Kg / hr. The capacity of a hybrid reactor (CSTR) is 40 liters, and the reaction temperature of each reactor is 95t, 100t, and 124. (:, 132, agitation speed is 20 rpm, 150 rpm, 100 rpm, 90 rpm, the polymerization% of the fourth reactor outlet, the measured physical properties show 0 monomer conversion of the solution "55% 'the aforementioned polymer The solution is heated through the mouth of the preheater, and the temperature is 225. (: Then, through a devolatilization tank with a vacuum device, the temperature of the basin devolatilization temperature is controlled at 2HTC, and the rubber modified polystyrene system can be obtained. The residual volatile content of the rubber-modified polystyrene resin is 〇45 denier ....... € Brightness' Practical transparency and impact strength 0: Table "[Comparative Example 5]

Page 34 593370 A7 B7 V. Description of the invention (33) 12-4 parts by weight of rubber copolymer [styrene-butadiene block copolymer, SM / BD = 68/32, 1,2-vinyl structure content = 13% , Solution viscosity = 5.5 cps (5% by weight toluene solution of copolymer)], 37 parts by weight of styrene monomer, 60 parts by weight of methyl methacrylate, 3 parts by weight of acrylonitrile, 56.2 parts by weight of ethylbenzene, n 0.16 parts by weight of dodecyl mercaptan and 0.115 parts by weight of a feed solution of di-t-butyl peroxy hexahydro terephthalate 3 5Kg / hr continuous pumping of 4 continuous continuous mixing reactors (CSTR) in series' The capacity of the reactors is 40 liters, and the reaction temperature of each reactor is 100 ° C, 106 ° C, 120 ° c, 130 ° C, stirring speed is 300 rpm, 250 rpm, 150 rpm, 120 rpm, the monomer conversion rate of the polymer solution at the outlet of the fourth reactor is 65%, the aforementioned polymer solution is heated by a preheater, and the temperature is 25 5 ° C, and then through a devolatilization tank with a vacuum device, the devolatilization tank temperature is controlled at 250 ° C, and rubber modification can be obtained. Polystyrene resin. The obtained rubber-modified polystyrene-based resin had a residual volatile content of 0.3% by weight. The measured physical properties, transparency, practical transparency, and impact strength are shown in Table 1. [Comparative Example 6] 14.1 parts by weight of a rubber copolymer [styrene-butadiene block copolymer, SM / BD = 25/75, 1,2-vinyl structure content = 15%], styrene monomer 4 Trauma, 57 parts by weight of ethyl methacrylate, 3 parts by weight of acrylonitrile, 38 parts by weight of ethylbenzene, 0.15 parts by weight of n-dodecyl mercaptan, and 0.8 parts by weight of dibenzoyl peroxide The feed solution formed by 0.15-t parts of bisperoxide tertiary butyl peroxide and / or rat-p-arsuccinic acid g was continuously pumped into 4 reactors, of which 1 to 3, at 35 Kg / hr. Velocity reactor is fully continuous

P.35 593770 A7 B7 V. Description of the invention (34) Hybrid reactor (CSTR), the fourth reactor is a plug flow reactor (PFR), the capacity of each reactor is 40 liters, each reactor The reaction temperature is 102 ° C, 108 ° C, 126 ° C, 128 ° C (inlet) ~ 153 ° C (outlet), the stirring speed is 300rpm, 200rpm, 150rpm, 30rpm, the polymer solution at the outlet of the fourth reactor The monomer conversion rate was 88%. The polymer solution was heated by preheating at a temperature of 260 ° C, and then passed through a devolatilization tank with a vacuum device. The devolatilization tank temperature was controlled at 260 ° C, that is, A rubber modified polystyrene resin can be obtained. The residual volatile content of the obtained rubber-modified polystyrene resin was 0.22% by weight. The physical properties, transparency, practical transparency, and impact strength measured are shown in Table 1. However, the above are only the preferred embodiments of the present invention, and the scope of implementation of the present invention is not limited in this way, that is, the simple equivalent changes and modifications made according to the scope of the patent application and the content of the invention specification of the present invention , All should still fall within the scope of the invention patent. Table 1. Physical property comparison table of each example and comparative example of the present invention. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) Page 36 593370 A7B7 V. Description of the invention (35)

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Claims (1)

D8 VI. Scope of patent application 1 _ A transparent rubber modified polystyrene resin, which is a rubber particle dispersed phase (A) formed of 25% by weight of a rubber-like copolymer, and a copolymerization of 99 ~ + 75% by weight It consists of a continuous phase (B), in which the copolymer phase, "shell phase (B)" consists of a total of 100 parts by weight of styrene-based monomer 20 to 70 parts by weight! Parts, (meth) acrylate Formed from 30 to 80 parts by weight of monomers and 0 to 40 parts by weight of copolymerizable monomers:-Among them, the molded product of 'resin injected through a mirror mold is measured by surface roughness, and the low difference of the measured value is △ H, where the largest difference in height △ Hmax is less than 3200 a, and the average difference in height is less than 2000A, and at a depth of 18 ~ 2.2 m below the surface of the aforementioned molded product, observe the rubber particles with an electron microscope. Among rubber particles with a major diameter greater than 03 # m, under the annealing condition of 12 (TCx 40min), the average ratio of the major particle length a / minor diameter b of the non-annealed rubber particles (A1) to the length of the annealed rubber particles Control the average ratio of a / short diameter b (A2), where the ratio of a1 / a2 is 1.08 ~ 2.35 ° 2 The transparent rubber modified polystyrene resin described in item 丨 of the scope of the patent application, wherein the particles with rubber particles larger than 0 78 # m in the dispersed phase account for 0 to 25% by weight of the total rubber particles. 3. According to the scope of the patent application The transparent rubber modified polystyrene resin according to the first item, wherein the weight average particle diameter of the rubber particles is less than 〇18 ~ 104. The transparent rubber modified polystyrene based on the first item described in the scope of the patent application. Resin, where the ratio of A1 / A2 is 1.08 ~ 2.2. 5 · According to the transparent rubber modified polystyrene described in item 1 of the scope of the patent application, the paper size applies the Chinese National Standard (CNS) A4 specification (210χ 297) (Mm) Page 38 593370 A8 B8 C8 D8 VI. Patent application range 1 _10 ~ 2.0 〇 series resin, in which the ratio of A1 / A2 is applicable to the Chinese National Standard (CNS) A4 specification (210x 297 mm) for this paper size Page 39