CN1118787A - Rubber modified styrene resin compound and its production method - Google Patents

Abstract

The method includes dissolving 2-20 wt.% rubber in 98-80 wt.% monomer of styrene series, and removing volatilizing components when the conversion rate of the polymer reaches 55 wt.%. It is characterized in that 0.02-1.0 wt.% thiodipropionate compound (B1) is added in the course of polymer reaction and 0.002-0.8 wt.% organic polysiloxane (B2) is added before the reversion of the rubber polymer to maintain the good impact strength and tensile strength and enhance the surface impact strength for the initial product and the recovered product.

Description

Rubber-modified styrene resin composition and manufacture method thereof

The present invention relates to a kind of rubber-modified styrene resin composition and manufacture method thereof, be meant a kind of good face shock strength that has especially, composition is when recycling, and the impact polystyrene that still has good strength and rerum natura is a resin.

General industrial community is in order to improve the shock-resistance of phenylethylene resin series, have plenty of polystyrene and the fusion of rubber-like polymer, have plenty of the rubber-like polymer is dissolved in and carry out graft polymerization reaction in the styrenic monomers, obtain the state that grafting rubbers polymer (disperse phase) and polystyrene (matrix external phase) are mixed by this; The shock-resistance of the polystyrene resin gained behind the above-mentioned modified rubber is preferable, therefore, and the shock-resistance that is otherwise known as phenylethylene resin series (hereinafter to be referred as HIPS); Generally speaking, this impact polystyrene is the testing method of resin, mainly be that the test film that utilizes compressed moulding or ejection formation to make carries out the test of Izod impact strength, though above-mentioned Izod impact strength is a kind of of phenylethylene resin series mechanical properties, but on actual moulding product, the face shock strength also is a kind of considerable test index; Therefore, the producer is when discussing the shock-resistance of polystyrene resin in recent years, though the Izod impact strength emphasis for discussing still, the face shock strength is similarly that the producer emphasizes and very important mechanical properties.

In traditional skill, general industrial community is in order to promote the impact strength of HIPS, can add a spot of organopolysiloxane class, for example: Japan special permission disclose clear 57-No. 172948, clear 57-No. 170949, clear 57-No. 187346 etc. in the disclosed Japanese patent of invention case all similar exposure, and still this mode there is no help for the face shock strength of product.

In order to improve the face shock strength of HIPS, in traditional technology, Japan's clear 55-No. 30525 patent cases of special permission bulletin once disclosed, special divinyl rubber (containing 1,2-vinyl of 15～35%) is added polymerization in the vinylbenzene, can obtain the preferable HIPS of face shock strength, but the prepared HIPS of this method, it up to more than 350%, can cause the shortcoming that flowability is not good, processing is difficult for as the glue percentage of grafting, is restricted in the use.

In addition, No. the 3945976th, U.S.'s patent of invention, once record in the patent cases such as No. 4294937 and No. 4451612, in the process of HIPS with continous way body or solution polymerization, in order to make resin possess good color and luster, thermostability, the antioxidant that adds a spot of phenol system or phosphorus system in the charging of the styrenic monomers of being everlasting, for example: 2,6-di-t-butyl-4-sylvan, octadecyl-3-(3,5-di-t-butyl-4-hydroxyl-phenyl) propionic salt, three nonyl phosphorous acid benzene fat (tris-nonyl phenylphosphite) etc., though above-mentioned processing mode can make resin obtain good look and translate, the opposite shock strength is not still improved.

And generally the processor is when the actual production moulding, and what can produce some poor products or chip (Scrap), and in order to reduce cost, metropolitan pulverizes utilization, moulding more again with poor products and chip; The resin of above-mentioned recycling is because the effect of hot resume and friction shear stress can cause the reduction of finished product shock-resistance; Though but the interpolation of status mat antioxidant and minor betterment Izod impact strength, this does not have much effects for the face shock strength, obviously in practice at present, the HIPS resin make or processing on often face the insufficient awkward situation of face shock strength.

This case contriver remakes research in order to solve aforementioned problems at the relation between rubber size distribution and specific compound, through going deep into discussion with keen determination, finishes the present invention then.

Therefore, the purpose of this invention is to provide a kind of composition when moulding and recycling, all have the composition and the manufacture method thereof of the rubber modified styrene series resin of good face shock strength.

The invention is characterized in: utilize specific rubber size distribution, dispersity, be added in the phenylethylene resin series with the thiodipropionate based compound and the organopolysiloxane of specified proportion, can when keeping resin Izod impact strength and tensile strength, promote the face shock strength of first moulding of product and recycling.

Rubber-modified styrene resin composition of the present invention comprises:

(A) in phenylethylene resin series 100 weight parts of modified rubber, rubber with 2～20 weight parts, it is to be distributed in the phenylethylene resin series matrix of 98～80 weight parts with particle state, and the particle size dispersion degree is more than or equal to 0.8, this is that it is defined as follows with the laser light scattering method as micelle footpath dispersity:

(B ₁) the thiodipropionate based compound of 0.02～1.0 weight part; With

(B ₂) organopolysiloxane of 0.002～0.8 weight part.

The manufacture method of rubber modified styrene series resin of the present invention be with: the rubber of 2～20 weight parts is dissolved in the styrenic monomers of 98～80 weight parts, its polymerization temperature is between 90～250 ℃, and stirred, reach more than 55% up to transformation efficiency, remove volatile component again, to form the phenylethylene resin series of modified rubber: this manufacture method is characterised in that, the 100 weight part pan feedings that rubber-like polymer and styrenic monomers add up to add among its polymerization process whole process: the thiodipropionate based compound (B of 0.02～1.0 weight part in forming ₁);

And before the phase reversion of rubber-like polymer, add the organopolysiloxane (B of 0.002～0.8 weight part ₂).

Below the present invention is described in further detail, and enumerate embodiment for your guidance.

The so-called rubber modified styrene series resin of the present invention is meant: the rubber-like polymer is dissolved in the vinyl aromatic monomers, with body or solution or bulk solution and the mode polymerization of hanging turbid and usefulness; Be applicable to that vinyl aromatic monomers of the present invention has: vinylbenzene, neighbour-vinyl toluene, right-vinyl toluene ,-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, the vinylbenzene that alkyl such as t-butyl styrene are replaced, with the vinylbenzene that replaces such as: the α of α-vinyl toluene, α-methyl-right-vinyl toluene etc.-alkyl, perhaps bromine-vinylbenzene, dibromo-vinylbenzene, 2,4,6-tribromo-vinylbenzene etc.; Above-mentioned styrenic monomers can be used separately or several merge use; Except above-mentioned styrenic monomers, the present invention also can add other copolymerizable monomers, and for example: nitrile (as: vinyl cyanide), (methyl) esters of acrylic acid (as: methyl methacrylate, butyl acrylate), acrylic acid or the like, maleic anhydride, maleimide monomers such as (as: N-phenyl maleimides) are closed in insatiable hunger.

The polymeric kind of rubber used in the present invention there is no particular restriction, the rubber that was applied in HIPS in the past and is resin all can use, and for example: one or more rubber polymer such as the polymkeric substance of natural rubber, polyhutadiene, polyisoprene, vinylbenzene-divinyl rubber shape, the polymkeric substance of vinylbenzene-synthetic polyisoprene shape, isoprene-isobutylene rubber, ethene-acrylic rubber merges and uses; Wherein polybutadiene rubber can be divided into the polyhutadiene of high-cis content and the polyhutadiene of low cis content again.

The benzene Class B of modified rubber of the present invention is the rubber that resin contains 2～20 weight parts, is good with 3～15 weight parts especially; That is to say, the rubbery polymer of 2～20 weight parts is dissolved in polymerization in the styrenic monomers of 98～80 weight parts; Form particulate state after polymerization is finished, and the rubber particles and the styrene resin that are grafted with styrenic are the external phase at the end; The median size of above-mentioned graft rubber particle is between 0.5～10 μ m, and be preferable with 0.6～5 μ m, especially being the best between 0.7～3.0 μ m, the median size Dave of alleged here rubber obtains its size distribution with laser light scattering method (lightscattering), just measure earlier the pairing population n of each particle diameter Di _i, the average formula with Sauter Mean Diameter on average obtains again. $\mathrm{Dave}=\frac{{\mathrm{\Σ}{n}_i\mathrm{Di}}^3}{{\mathrm{\Σ}{n}_i\mathrm{Di}}^2}$

In the present invention, the particle size dispersion degree of the graft rubber particle in the HIPS resin is not less than 0.8, and to be preferable greater than 0.9, optimum regime is at 0.9～2.8; When the particle size dispersion degree was lower than 0.8, the face shock strength of HIPS resin recycling was relatively poor, when this numerical value is higher than 2.8, can cause the decline of resin tensile strength; The aforementioned particle size dispersity can be by stirring velocity, the thiodipropionate based compound (B of polyreaction ₁) and organopolysiloxane (B ₂) factor such as addition, interpolation opportunity, temperature of reaction regulated and obtained.

Rubber size dispersity of the present invention, with aforementioned laser light scattering method, it is defined as follows:

Wherein:

D (V, 0.1) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 10 weight %, pairing rubber size numerical value.

D (V, 0.5) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 50 weight %, pairing rubber size numerical value.

D (V, 0.9) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 90 weight %, pairing rubber size numerical value.

Laser light diffuse transmission measuring method: 0.1 gram sample is seated in methyl-ethyl ketone of 10 milliliters, sways dissolving fully, insert in the laser light scatterometer again, focal length is 100mm, can get size distribution figure; Perhaps 1.0 gram samples are dissolved in methyl-ethyl ketone of 10 milliliters, after the dissolving focal length are adjusted into 45mm, can get size distribution figure.

That is to say,, represent that the distribution of size is narrow more, otherwise the distribution of size is wide more when the numerical value of particle size dispersion degree is more little.

Rubber content in the HIPS resin of the present invention's 100 weight parts is good with 3～15 weight parts especially between 2～20 weight parts, that is to say, the rubber of 2～20 weight parts is scattered in the styrenic of 98～80 weight parts; When the amount of aforementioned rubber is lower than 2 weight parts, face shock strength deficiency when this numerical value is higher than 20 weight parts, will cause degradation shortcoming under mobile low, the tensile strength.

Be used for thiodipropionate based compound (B of the present invention ₁), its concrete typical example has: (Di-stearyl thio dipropionate also can be called sulfo-distearyl acyl group propionic ester: DSTDP, chemical formula: C ₁₈H ₃₇OOCCH ₂CH ₂-S-CH ₂CH ₂COOC ₁₈H ₃₇), sulfo-dilauryl propyl sulfide acid esters (Di-lauryl thiodipropionate), sulfo-two-tridecyl dipropionate (Di-tridecyl thiodipropionate), sulfo-two-tetradecyl dipropionate (Di-myristyl thiodipropionate) etc., its usage quantity is 0.02～1.0 weight part with respect to 100 weight part HIPS resins, is preferable with 0.04～0.4 weight part again; As thiodipropionate based compound (B ₁) addition when being lower than 0.02 weight part, face shock strength for resin is improved poor effect, when addition during greater than 1.0 weight parts, not only can cause the not good of face shock strength, more can cause the rubber size dispersity greater than 3, and further cause the decline of resin tensile strength.

Organopolysiloxane (B used in the present invention ₂) can following structural represent:

Wherein, m, n are integer, R ₁～R ₂Be alkyl or aromatic base.

Under 25 ℃, organopolysiloxane (B used in the present invention ₂) kinetic viscosity is 10～10,000 centistoke (Centistoke), especially with 20～2000 centistokes for better; Above-mentioned organopolysiloxane (B ₂) with respect to the HIPS resin of 100 weight parts, its addition between 0.002～0.8 weight part, especially with 0.04～0.3 weight part for better; As organic polysiloxane (B ₂) addition when being lower than 0.002 weight part, the face shock strength of resin is not good, when the addition of organic polysiloxane during greater than 0.8 weight part, can cause the decline of HIPS resin tensile strength, this secondary processing for synthetic resin (for example: chemistry is property, printing, coating etc. then) can cause the not good phenomenon of processing.

Organopolysiloxane (B among the present invention ₂) interpolation opportunity, must be before the phase reversion of HIPS resin polymerization reaction, preferable interpolation be opportunity: the rubber composition is not finished phase reversion as yet in the polyreaction, and the transformation efficiency of styrenic monomers arrives before the 12 weight %; So-called here phase reversion is meant: the mixing solutions of rubber and styrenic monomers is at the polymerization initial stage, the form that with the rubber phase is external phase exists, when the transformation efficiency of styrenic monomers increases gradually and the mixing effect of complex reaction system, rubber is instead surrounded by styrenic monomers and polymkeric substance, and become discrete particles shape (discontinuous phase), this time styrenic monomers and polymer formation external phase, above-mentioned phenomenon is exactly so-called " phase reversion "; Among the present invention in order to significantly improve the face shock strength of resin, except aforementioned organopolysiloxane (B ₂) must before the phase reversion of polyreaction, add outside, also must be engaged in the polymerization process, with thiodipropionate based compound (B ₁) add, just can achieve the above object; In addition, control speed of reaction, grafting rubbers state that can be suitable according to need in polymerization process cooperate suitable stirring this time again, just can the appropriateness control rubber size dispersity; And, lack any in the aforesaid compound on this opportunity, can't obtain sufficient face shock strength.

Employed thiodipropionate based compound (B among the present invention ₁) or organopolysiloxane (B ₂) can send into reactive tank with pump of constant delivery type respectively, in addition, also can be with thiodipropionate based compound (B ₁) or organopolysiloxane (B ₂) be added in reaction monomers and/or solvent and the solution that the rubber-like polymer is become, send into reactive tank again.Organopolysiloxane (B particularly ₂) interpolation need before the phase reversion of polyreaction, just can reach good face shock strength period, therefore, organopolysiloxane (B ₂) addition manner need special consideration, for example with embolism formula reactive tank during as the polymerization reaction trough in phase reversion zone, organopolysiloxane (B ₂) be added in monomer and/or solvent and the pan feeding that rubber is become, mix the back and add reaction, the interpolation in this time is 0% monomer conversion period, also can add in the conversion zone of some specific monomer transformation efficiencys; And with complete hybrid reactive tank during as the polymerization reaction trough in phase reversion zone, organopolysiloxane (B ₂) must be added in monomer and/or solvent and the solution feed stream that the rubber-like polymer is become, be 0% monomer conversion interpolation period in this time.

The manufacture method of HIPS resin of the present invention can body, solution or body (solution)-outstanding turbid two-section type polymerization process polymerization, is good with body (solution) polymerization.The polymeric temperature is good between 90～250 ℃, especially with 95～210 ℃ for better, the not special restriction of the reactive tank that the present invention uses, for example can be hybrid or embolism formula reactive tank fully, also can use several reactive tank serial or parallel connections, perhaps hybrid fully and embolism formula the two and usefulness, above-mentioned reactive tank can add agitator or additional agitator, if additional its stirring velocity of agitator is preferable with 8～45rpm at 5～55rpm especially; In reaction feed or reaction can add molecular weight regulator, initiator, antioxidant, plasticizer, lubrication prescription, inert solvent etc. according to need in carrying out; After polyreaction to phase reversion produces, can further continue reaction, more than the transformation efficiency of styrenic monomers is up to 55 weight %, comparatively ideal transformation efficiency is more than 70 weight %, afterwards polymers soln is delivered to preheater, be heated to 180～300 ℃, polymers soln be discharged in the vacuum devolatilization groove again and remove unreacted residual monomer, solvent and other volatile components, recovered solvent, monomer etc. can be assigned in according to suitable proportion and use in the charging; Through the process of this devolatilization, resulting polymer residue fugitive constituent is lower than 1 weight %, with toothed gear pump it is extruded continuously and makes granular resin.

Be applicable to that molecular weight regulator of the present invention has: just-lauryl mercaptan, α-methyl styrene dimer thing, uncle-lauryl mercaptan, 1-phenyl butyl-2-fluorenes, penta dioxane (thio-alcohol of di-pentane), trichloromethane etc., indenes alkene class, halohydrocarbon etc.; Have and be fit to polymerization initiator of the present invention: 1,1-two (tert-butyl peroxide) hexanaphthene (1,1-bis-t-butyl peroxy cyclohexane) etc. ketal peroxide class (peroxyketal), the two isopropyl benzenes (dicumyl peroxide) of peroxidation, peroxidation is two-two alkyl peroxide classes (dialkyl peroxide) of the tertiary butyl (di-t-butyl peroxide) etc., the peroxidation two acyl classes (diacylperoxide) of dibenzoyl peroxide (bis-benzoyl peroxide) etc., peroxidation is two-the peroxidation carbonate (peroxy carbonate) of tetradecyl carbonate (di-myristyl peroxycarbonate) etc., the peroxycarbonates class (peroxyester) of the tertiary butyl-peroxidation isobutyl-carbonate (t-butyl peroxy isopropyl carbonate), the ketone peroxide (ketone peroxide) of cyclohexanone peroxide (cyclo hexanoneperoxide) etc., the hydroperoxide type (hydroperoxide) of right-terpane base hydroperoxide (P-menthane hydroperoxide) etc., the usage quantity of above-mentioned polymerization initiator is many below 0.6 weight %.

The spendable plasticizer of the present invention has: mineral oil, polyoxyethylene glycol etc.; Spendable lubrication prescription has: stearic acid, Zinic stearas, calcium stearate, stearylamide, ethene-two stearylamides etc.; And antioxidant can adopt: 2,6-dual-tert-butyl-4-sylvan, octadecyl-3-(3,5-di-t-butyl-4-hydroxyl-phenyl)-phenol such as propionic ester are antioxidant and for example: the phosphorous antioxidant of three-nonyl phenyl phosphite, the inferior acid esters of three (2,4-di-tert-butyl-phenyls) etc.; The spendable inert solvent of the present invention has: ethyl benzene,toluene,xylene, methyl ethyl ketone, benzene, isopropyl benzene etc., its addition depends on the needs, and reaches as high as 40 weight %.

In addition, HIPS resin of the present invention also can add various conventional lubrication prescription, antioxidant, plasticizer, fire retardant, photostabilizer, tinting material etc. according to need, further add: glass fibre, inorganic filling agent etc., also can be according to need and other polymkeric substance fusion, for example: PPO, Nylon 11, Nylon 12, Nylon 6, PC, ABS, AS, resins such as PE, PP.

＜embodiment 〉

＜embodiment 1 〉

Comprise the following table composition in the incoming flow of present embodiment: composition use amount styrene 83 weight portion ethylo benzenes 10 weight portion polybutadiene rubbers 6 weight portion sulfo-distearyl acyl group dipropionates 0.2 weight portion dimethyl silicone polymer 0.004 weight portion initiator (0.02 weight portion of trigonox D-E50)

The chemical name of trigonox D-E50 initiator is: 2,2-two-(tert-butyl peroxide)-butane (2,2-di-(t-butyl peroxy) butane).

Above-mentioned incoming flow feeds with in first reactive tank of whipping appts continuously with the flow velocity of 40l/hr, the volume of this first reactive tank is: 100 liters, temperature are set between 100～120 ℃, stirring velocity is 40rpm, phase reversion produces when the styrene monomer conversion rate reaches 14 weight %, and in the exit of first reactive tank, its transformation efficiency is greatly about about 22 weight %; Afterwards it is sent in the subsequent reactions groove and proceed polymerization, this moment, polymerization temperature was controlled between 125～220 ℃, when the polymkeric substance transformation efficiency arrives the 80 weight % left and right sides, polymers soln is sent into the processing that the devolatilization groove removes fugitive constituent, afterwards again with toothed gear pump through the porous dies extruding pelletization.

Measure its rerum natura with following method again after the manufacturing:

Izod impact strength: ASTM D-256

Tensile strength: ASTM D-638

Particle size dispersion degree: laser light scattering method

Face shock strength: according to the ball falling impact strength detection of ASTM D-3763

The face shock strength of recycling: be that HIPS resin granular feedstock is heavily covered the extrusion secondary with twin screw extruder, its face shock strength is tested in the ejection formation test piece of going again.

＜embodiment 2 〉

Manufacture and composition are approximately identical to embodiment 1; difference is: and polydimethylsiloxane in the composition and sulfo-distearyl acyl group dipropionate (hereinafter to be referred as: DSTDP) when reaching 4 weight %, the styrene conversion rate adds the opportunity of adding reactive tank; and the addition of DSTDP changes 0.05 weight part into, and the addition of polydimethylsiloxane changes 0.25 weight part into.

＜embodiment 3 〉

Manufacture and composition are approximately identical to embodiment 1, difference is: when polydimethylsiloxane in the composition and DSTDP adding change the styrene conversion rate into reach 8 weight % opportunity, and the addition of DSTDP changes 0.6 weight part into, and the addition of polydimethylsiloxane changes 0.5 weight part into.

＜comparative example 1 〉

Manufacture and composition also are approximately identical to embodiment 1, and difference has three:

One. polydimethylsiloxane in the composition and DSTDP joining day are when reaching 10 weight % in the styrene conversion rate.

The addition of two .DSTDP changes 1.2 weight parts into.

Three. the addition of polydimethylsiloxane changes 0.1 weight part into.

＜comparative example 2-1 〉

Composition and polymerizing condition are approximately identical to embodiment 1 equally, and difference has following 3 points:

One. when polydimethylsiloxane and DSTDP joining day are changed into the styrene conversion rate and reach 80 weight %.

The addition of two .DSTDP changes 0.4 weight part into.

Three. the addition of polydimethylsiloxane changes 0 into.

＜comparative example 2-2 〉

Composition and polymerizing condition are same as comparative example 2-1, and difference is: change the addition of DSTDP into 0, the addition of polydimethylsiloxane changes 1.2 weight parts into.

＜embodiment 4 〉

Comprise the following table composition in the incoming flow of present embodiment: composition usage quantity vinylbenzene 83 weight part ethylbenzenes 8 weight part sulfo-distearyl acyl group dipropionates 0.15 weight part polybutadiene rubber 8.0 weight part polydimethylsiloxanes 0.4 weight part initiator (0.01 weight part of Tx-29A)

The chemical name of Tx-29A initiator is: 1, and 1-two-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane.

Above-mentioned incoming flow feeds with in first reactive tank of whipping appts continuously with the flow velocity of 36l/hr, the volume of this first reactive tank is that 100 liters, temperature are set between 105～130 ℃, stirring velocity is 30rpm, phase reversion produces when the styrene monomer conversion rate reaches 17 weight %, and at the exit of first reactive tank transformation efficiency greatly about about 28 weight %; Send into afterwards and carry out polymerization in the subsequent reactions groove, this moment, polymerization temperature was controlled between 130～220 ℃, when the transformation efficiency of polymkeric substance arrives the 87 weight % left and right sides, polymers soln is sent into the processing that the devolatilization groove removes fugitive constituent, all the other are all identical with embodiment 1.

＜embodiment 5 〉

Manufacture and composition are approximately identical to embodiment 4, difference is: polydimethylsiloxane in the composition and DSTDP add and add when the styrene conversion rate reaches 10 weight % opportunity, the addition of DSTDP changes 0.4 weight part into, and the addition of polydimethylsiloxane changes 0.1 weight part into.

＜embodiment 6 〉

Manufacture and composition are approximately identical to embodiment 1, difference is: the DSTDP in the composition adds opportunity when the styrene conversion rate reaches 55 weight %, the addition of DSTDP changes 0.2 weight part into, the addition of polydimethylsiloxane changes 0.2 weight part into, and the stirring velocity of first reactive tank changes 30rpm into.

＜comparative example 3 〉

Manufacture and composition are approximately identical to embodiment 4, and difference is as follows:

One. when polydimethylsiloxane and DSTDP joining day are changed into the styrene conversion rate and reach 50 weight %.

Two. the addition of polydimethylsiloxane changes 0.004 weight part into.

Three. the stirring velocity 45rpm of reactive tank.

Four. the ethylbenzene usage quantity changes 10 weight parts into.

＜comparative example 4 〉

Manufacture and composition are same as embodiment 4, but the DSTDP addition in the charging changes 0 into, and the addition of polydimethylsiloxane changes 0.4 weight part into.

＜comparative example 5 〉

Manufacture and composition are same as embodiment 4, but the cancellation of the DSTDP in the charging changes TNPP (being exactly three nonyl phosphorous acid benzene fat (tri-nonyl phenylphosphite)) 0.15 weight part into, and the addition of polydimethylsiloxane changes 0.6 weight part into.

＜conclusion 〉

Show as can be known by embodiment 1～6, when polydimethylsiloxane added before phase reversion, especially cinnamic transformation efficiency added before 12 weight %, and be engaged in when adding DSTDP in the polymerization process, can when keeping good Izod impact strength and tensile strength, obtain excellent face shock strength; When the resin recycling, also can keep good face shock strength.

Can be understood by comparative example 1 demonstration, when the amount of DSTDP surpassed 1.0 weight parts, the face shock strength was not good, and causes the particle size dispersion degree greater than 3.0 yet, and tensile strength also can descend; No matter shown by comparative example 2-1, comparative example 2-2 and comparative example 4, be to lack DSTDP or polydimethylsiloxane, all can't obtain good face shock strength; Show as for comparative example 3: when the particle size dispersion degree is lower than 0.8, the face shock strength extreme difference of product recycling; Comparative example 5 shows that DSTDP is changed with phosphorous antioxidant TNPP, and the face shock strength can't be improved.

Data by above explanation and embodiment, comparative example are provable, the specific rubber size dispersity that is defined according to the present invention, and cooperation contains the composition that sulfo-dipropionate based compound and organopolysiloxane are constituted, except can keeping moulding product good tensile strength and Izod impact strength, more can obtain the splendid face shock strength of practicality, when the resin recycling, also can possess good face shock strength; Moreover, when organic polysiloxane adds in the polymerization process before phase reversion, and cooperate the thiodipropionate based compound in polyreaction, to add, more can obtain wonderful shock strength; Therefore, rubber-modified styrene resin composition of the present invention and manufacture method thereof, not only composition, method for making novelty have more the utility value on the industry.

Table 1 Single position: weight part

Experiment numbers		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
								The vinylbenzene weight part		????86	????86	????86	????83	????83	????86
The ethylbenzene weight part		????10	????10	????10	????8	????8	????10
								Pan feeding rubber content weight part		????6.0	????6.0	????6.0	????8.0	????8.0	????6.0
DSTDP(B 1) weight part		????0.2	????0.05	????0.6	????0.15	????0.4	????0.2
								DSTDP(B 1) Tian Jia Time styrene conversion rate (%)		????0	????4	????8	????0	????10	????55
Polydimethylsiloxane (B 2) weight part		????0.004	????0.25	????0.5	????0.4	????0.1	????0.2
								(B 2) Tian Jia Time styrene conversion rate (%)		????0	????4	????8	????0	????10	????0
The final rubber content weight part of resin combination		????8.0	????8.0	????8.0	????10.0	????10.0	????8.0
								Average particle size (μ m)		????2.8	????1.0	????2.5	????1.5	????0.9	????1.6
The particle diameter dispersity		????2.1	????1.5	????2.6	????1.0	????1.4	????1.0
								Rerum natura	Face shock strength (Kg-cm)	????150	????145	????160	????170	????175	????140
Reclaim the face shock strength (Kg-cm) of system again	????130	????115	????140	????140	????145	????115
							Tensile strength (Kg/cm 2)		????265	????250	????235	????250	????240	????270
Izod impact strength (Kg.cm/cm)	????7.5	????8.2	????8.5	????9.3	????8.5	????8.0

Note: DSTDP is: sulfo-distearyl anilide dipropionate.

Table 2

Single position: weight

Experiment numbers		Comparative example 1	Comparative example 2-1	Comparative example 2-2	Comparative example 3	Comparative example 4	Comparative example 5
								The vinylbenzene weight part		????86	????86	?????86	?????83	?????83	????83
The ethylbenzene weight part		????10	????10	?????10	?????8	?????8	????8
								Pan feeding rubber content weight part		????6.0	????6.0	?????6.0	?????8.0	?????8.0	????8.0
DSTDP(B 1) weight part		????1.2	????0.4	?????0	?????0.15	?????0	????0
								The TNPP weight part		????0	????0	?????0	?????0	?????0	????0.15
DSTDP(B 1) or TNPP Tian Jia Time styrene conversion rate (%)		????10	????80	?????0	?????50	?????0	????0
								Polydimethylsiloxane (B 2) weight part		????0.1	????0	?????1.2	?????0.004	?????0.4	????0.6
(B 2) Tian Jia Time styrene conversion rate (%)		????10	????80	?????0	?????50	?????0	????0
								The final rubber content weight part of resin combination		????8.0	????8.0	?????8.0	?????10.0	?????10.0	????10.0
Average particle size (μ m)		????3.6	????1.8	?????1.4	?????1.7	?????1.2	????2.7
								The particle diameter dispersity		????3.2	????0.95	?????1.2	?????0.7	?????1.1	????1.2
Rerum natura	Face shock strength (Kg-cm)	????120	????100	?????110	?????110	?????100	????110
								Reclaim the face shock strength (Kg-cm) of system again	????85	????70	?????75	?????60	?????70	????70
	Tensile strength (Kg/cm 2)	????220	????270	?????215	?????240	?????250	????240
								Izod impact strength (Kg.c/cm)	????8.2	????7.0	?????8.0	?????8.0	?????8.5	????9.0

Note: DSTDP is: sulfo-distearyl anilide dipropionate.

TNPP is: three nonyl phosphorous acid benzene fat.

Claims (5)

1. rubber-modified styrene resin composition, its be by:

(A) contain in the rubber modified styrene series resin of 100 weight parts: it is in the resinous substrates that the rubber of 2～20 weight parts is dispersed in 98～80 parts by weight of styrene with particle state, and the particle size dispersion degree of rubber particles is more than or equal to 0.8;

Above-mentioned rubber size dispersity is with the laser light scattering method, and it is defined as follows:

Wherein:

D (V, 0.1) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 10 weight %, pairing rubber size numerical value;

D (V, 0.5) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 50 weight %, pairing rubber size numerical value;

D (V, 0.9) representative: be transverse axis with the rubber size, accumulation particle weight percentage is the longitudinal axis, by small particle size in the integral distribution curve of big particle diameter, during accumulation particle weight percentage 90 weight %, pairing rubber size numerical value;

(B ₁) the thiodipropionate based compound of 0.02～1.0 weight part;

(B ₂) organopolysiloxane of 0.002～0.8 weight part forms.

2. rubber-modified styrene resin composition as claimed in claim 1, wherein the particle size dispersion degree of rubber particles is at 0.9～2.8.

3. rubber-modified styrene resin composition as claimed in claim 1, wherein, the thiodipropionate based compound can be sulfo-distearyl acyl group propyl sulfide acid esters.

4. the manufacture method of a rubber modified styrene series resin, its be with: the rubber of 2～20 weight parts is dissolved in the styrenic monomers of 98～80 weight parts, and between 90～250 ℃, carry out polymerization, transformation efficiency up to styrenic monomers reaches more than the 55 weight %, remove volatile component again, form the phenylethylene resin series of modified rubber;

It is characterized in that: add up to 100 weight parts with respect to rubber and styrenic monomers, in above-mentioned polymerization process, add thiodipropionate based compound (B ₁) 0.02～1.0 weight part and before the phase reversion of rubber polymer, add organopolysiloxane (B ₂) 0.002～0.8 weight part.

5. manufacture method as claimed in claim 4 wherein, before the polyreaction phase reversion, adds above-mentioned organopolysiloxane (B ₂) interpolation opportunity at the styrenic monomers transformation efficiency before 12 weight %.