CN1027542C - Continuous process for preparing rubber modified high impact resins - Google Patents

Abstract

In a process for preparing rubber modified high impact resins (HI-PS and ABS) by polymerizing a starting monomer containing an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer and added with a rubber-like polymer and by using at least two polymerization reactors and a particle disperser placed between the both reactor, the process obtaining the resins of high grade by specifying the relationships between the concentration of the polymerized monomer in the first reactor and the content of the rubber-like polymer in the first reactor and between the volume occupied by the polyemrizing liquid in the first reactor and the inner volume of the particle disperser, and the peripheral linear velocity of a shearing stirrer in the particle disperser.

Description

Continuous process for preparing rubber modified high impact resins

The present invention relates to prepare the continuation method of rubber modified high impact resins.

What The present invention be more particularly directed to is a kind of method, when being dissolved into by rubbery polymer when comprising the initial soln that obtains in initial monomer aromatic vinyl monomers or that comprise the mixture of being made up of aromatic vinyl monomers and vinyl cyanide monomer and carrying out polymerization by utilizing bulk polymerization or solution polymerization process, used rubbery polymer reaches the predetermined granularity that is dispersed in the reaction solution.

Polymerizing styrene in the presence of rubbery polymer and the impact polystyrene resin (hereinafter being abbreviated as the HI-PS resin) that obtains is a kind of polystyrene resin with high impact.And be widely used in different Application Areass.According to the current trends of the method for producing the HI-PS resin, this resin mainly is to prepare by the successive bulk polymerization.Yet still some still utilizes the discontinuous polymerization of mass polymerization or suspension polymerization to react to prepare this resin.

Up to the present continuous processing like this has been widely used in the preparation rubber-modified styrene resin, rubbery polymer is that the mean particle size with 0.1 to 10 μ is dispersed in the resin, because the granularity of rubbery polymer in the resin of being produced is to the character of resin.For example shock strength and surface luster produce significant effects, and therefore, the operating process of control rubbery polymer granularity in resin has critical role in the technology of preparation rubber modified polystyrene resin.

In general, operational condition in be dispersed in rubbery polymer granularity in the rubber-modified styrene resin and particle shape depend on during the polyreaction promptly forms the operational condition (so in the present invention operational condition hereinafter is referred to as " particle forms operation ") of dispersive rubber grain.The reaction solution that during reaction comprises rubbery polymer becomes the discontinuous phase state from the external phase state in polymerization process.The continuous preparation method of rubber-modified styrene resin is more difficult than the discontinuous method of the continuous preparation method of the common styrene resin that does not contain rubbery polymer or preparation rubber-modified styrene resin, this is because in the continuous preparation method of rubber-modified styrene resin, particle form operation be accompanied by reaction solution from a reactor to another reactor jump operation and polymeric reaction condition under carry out.Therefore, up to the present some complicated methods have been proposed for solving such difficulty.For example, the open No.29793/1977 of Japanese Patent has proposed a kind of like this method, and wherein before particle forms operation, rubbery polymer grafted in advance gives polyreaction and gives earlier and finishing.The open No.7794/1978 of Japanese Patent has proposed a kind of like this method, and the polymeric reaction solution that has reached from 30% to 80% conversion of monomer in this method mixes with the initial monomer that will be aggregated.The open No.17725/1984 of Japanese Patent has proposed a part of polymeric reaction solution and has been recycled to method in the initial monomer system.

As everyone knows, in the slower premature polymerization stage of conversion of monomer, be the step that adds the strong mixing polymerization liquid effective as making the external phase (this paper is abbreviated as " rubber phase ") that contains rubbery polymer become the operating method that is dispersed in the rubber grain in the polymerization liquid.In the open No.9245/1987 of Japanese Patent, know that also it is effective that the polymerization reactor of stirred vessel type forms in the such step of operation at particle.Although it is fairly simple, be 0.6 μ and littler particle in order to form granularity, it needs a large amount of stirring power.

In the presence of rubbery polymer, the so-called ABS resin by polymerizing styrene and vinyl cyanide obtain owing to have good shock strength, chemical resistant properties, thermotolerance, hardness, surface luster and other characteristic, has a lot of applications.ABS resin is normally produced in said emulsion polymerization process.In this process, the emulsion that comprises rubbery polymer is added in vinylbenzene and the acrylonitrile monemer, the mixture polymerization reaction take place that then obtains like this.Usually the emulsion polymerization process has such problem, owing to use the emulsion that is several times as much as polymkeric substance, polymerization stage needs a large amount of equipment, and since in this process as emulsifying step, congealing step and drying step so a series of step be essential, this just makes the control of whole production become complexity.Moreover owing to will use impure emulsifying agent, condensing agent inevitably in this process, the resin that obtains like this is just contaminated.As a kind of mode of improving this emulsion polymerization process, disclose in 35354/1974 and 35355/1974 at Japanese Patent and to have put forward, wherein extract in used emulsion after original rubber constituent sends in the vinylbenzene that will be aggregated and the acrylonitrile monemer, this monomer that comprises rubber constituent is aggregated with the production ABS resin by the continuous bulk polymerization process.Although the process of this method is compared obvious the simplification with traditional emulsion polymerization method, this process has still kept complicated extraction step.

As other the method for preparing ABS resin, the open No.20303/1970 of Japanese Patent, the open No.9144/1972,36201/1980 of Japanese Patent have proposed some continuous bulk polymerization process or solution polymerization process.These methods have the advantage that polyreaction and aftertreatment simply reach the refuse that reduces contaminate environment.Yet also there are some problems in these methods, always are not good with the physical properties of the resin of these methods preparation, one of significant characteristic of ABS particularly, and the surface luster of the resin that forms is inferior, and the special equipment of these methods needs.

Using continuous bulk polymerization process or solution polymerization process to prepare in the ABS resin, the granularity that is dispersed in the rubbery polymer in the resin has tangible influence to the generation resin aspect shock strength, surface luster and other the physical properties.Obviously the operating method of the granularity of control rubbery polymer in resin is occupied important position in the technology of preparation ABS resin.Know that the powerful stirring of polymer fluid in premature polymerization stage slowly is effective as making the external phase (hereinafter being abbreviated as " rubber phase ") that contains rubbery polymer be converted into the operating method that is dispersed in the rubber grain in the polymer fluid to used conversion of monomer.The inventor has proposed a kind of like this mode in the open No.2284/1988 of Japanese Patent, use the reactor that stirs type in this stage.Though this method is fairly simple, be that 0.8 μ or littler rubber grain but need very big power of agitator in order to make granularity.

The open No.18477/1974 of Japanese Patent discloses and has used particles dispersed machinery that the rubber grain that formerly forms in the polymerization liquid is carried out the rubber grain that shearing treatment obtains desired particle size.In this mode, after rubber grain being carried out shearing treatment with dispersion machinery, to contain in the polymer fluid that is sheared rubber grain and polymer fluid is remained on temperature be that the crosslinking reaction of rubbery polymer and all monomeric polyreactions are finished simultaneously in 150-200 ℃ the scope by linking agent is joined.

Yet, recently need improve forming working method such as the particle in the continuous flow procedure of the such rubber modified high impact resins of HI-PS resin or ABS resin, to adapt to since this resin Application Expansion market to the higher needs of the physicals of resin; And adapt to the requirement of the more high efficiency preparation method of ever-increasing use with the production cost that reduces this resin.

The purpose of this invention is to provide a kind of method, to adapt to above-mentioned requirements.Rely on this method can obtain to contain desired particle size.And the rubber modified high impact styrene resin of good appearance is arranged, as HI-PS resin and ABS resin, and can not need a large amount of power of agitator consumption and complicated operations process granularity expeditiously with regard to the may command rubbery polymer.

The present invention is the method for preparing rubber modified high impact resins continuously, it is characterized in that: in this method, used two polymerization reactors and a particle disperser at least, this decollator is that a kind of rubbery polymer that makes is dispersed in equipment in the resin with thin rubber grain form, and the method comprising the steps of (1) by being constituted being dissolved into the initial monomer that is made of at least a aromatic vinyl monomers by rubbery polymer or being dissolved in the mixture of being made up of at least a aromatic vinyl monomers and at least a vinyl cyanide monomer that resulting initial soln infeeds in first polymerization reactor continuously in the initial monomer; (2) polyreaction of initial monomer is carried out always in first reactor, has reached up to the concentration of the polymkeric substance that obtains by initial monomer from first reactor dissolved rubbery polymer is transformed into be dispersed in the needed degree of its particle in the reaction solution; (3) reaction solution is proposed continuously from first reactor, the amount of proposition and to offer the amount of the initial monomer in first reactor consistent; (4) reaction solution that proposes from first reactor is then delivered in the particle disperser, decollator has by rotating blade or cylindrical rotor shear agitation device that form and high speed rotating, so that the particle of the rubbery polymer that forms in reaction solution carries out shearing treatment by the shear agitation device; (5) reaction solution that carried out shearing treatment in particle disperser is transferred in second polymerization reactor, the quantity of the polymkeric substance that forms from initial monomer remains on 25% or more, and with initial monomer to change into the ratio of product the same, reaction solution is proceeded polyreaction in second reactor, if necessary, can then in the 3rd, the 4th polymerization reactor, carry out; Polyreaction is carried out under following operational condition:

(A) should satisfy following formula:

V ₂/V ₁＜0.2

Wherein: V ₁Be the volume that is occupied by reaction solution in first reactor, V ₂It is the internal capacity of particle disperser;

(B) peripheral velocity of shearing rotor maintains 0.5 meter of per second or more more;

(C) should satisfy following formula:

1＜X ₁≤ 20 Hes

1.5X ₁-0.05X ² ₁＜X ₂＜4.5X ₁-0.05X ² ₁

X wherein ₁Be the weight percent of rubbery polymer to the first reactor exit reaction solution, X ₂Be the weight percent of the polymkeric substance of initial monomer formation to the first reactor exit reaction solution.

Rely on the present invention's method recited above, form the inferior processing that the stage can prevent to produce the big rubber grain of so-called " flake " and can prevent molded article surface at its particle.This external application relatively simply prepares equipment, according to the shock strength of market to resin, the needs of the physical properties of surface luster or the like resin, the kind by rubber in the granularity, rubber content and the resin that change rubber grain can obtain a variety of high impact resins satisfactorily.

At least can from following composition group, select a kind of monomer as the aromatic vinyl monomers among the present invention: vinylbenzene, alpha-alkyl phenylethylene such as alpha-methyl styrene, α-ethyl styrene, α-isopropyl benzene ethene, α-t-butyl styrene or the like, halogenated styrenes such as α-chloro-styrene, bromstyrol etc.; Alpha-halogen ring-alkylated styrenes such as α-1-chloro-4-methyl-benzene, α-brooethyl vinylbenzene etc.; S compositions such as o with a phenyl ring that replaces by alkyl ^-, m ^-, p ^-Vinyl toluene, o ^-, m ^-, p ^-T-butyl styrene etc. have the distyryl compound such as the o of a phenyl ring that is replaced by halogen ^-, m ^-, p ^-Chloro-styrene, o ^-, m ^-, p ^-Bromstyrol; Have a distyryl compound such as an o by alkyl in the halogen-substituted ring ^-, m ^-And p ^-1-chloro-4-methyl-benzene, o ^-, m ^-And p ^-Brooethyl vinylbenzene etc.Especially preferentially use vinylbenzene, alpha-methyl styrene and p ^-Vinyl toluene.

At least can from the group of vinyl cyanide and methacrylonitrile composition, select a kind of as the vinyl cyanide monomer in the inventive method.

If desired, can from can carry out a group of compositions such as the acrylate monomer of copolymerization such as methyl methacrylate, maleic anhydride, maleimide, select a kind of appending in the above-described monomer to go at least with above-mentioned monomer.

Under the situation of using aromatic vinyl monomers and vinyl cyanide monomer, the mixture ratio value of aromatic vinyl monomers/vinyl cyanide monomer is chosen in 95/5 to 50/50 the scope in initial soln.The mixture ratio that surpasses above-mentioned scope is not better.Because when the ratio of aromatic vinyl monomers/vinyl cyanide monomer greater than 95/5 the time, the ABS resin chemical resistant properties that generates, hardness and thermotolerance inequality, and on the other hand, when the ratio of aromatic vinyl monomers/vinyl cyanide monomer less than 50/50 the time, the ABS resin of generation is inequality on mobile and molded article surface gloss.

As the rubbery polymer of the inventive method, any traditional rubbery polymer can both use, as long as it can be dissolved in the above-mentioned monomer.Example as such rubbery polymer can be enumerated polybutadiene rubber, butylbenzene copolymer rubber, butadiene-styrene block copolymer rubber, acrylonitrile-butadiene copolymer rubber, neoprene, ethylene-propylene copolymer rubber.These rubber can use separately or several being used in combination.When aromatic vinyl monomers and vinyl cyanide monomer are used in combination, be suitable for use as this rubbery polymer in 25 ℃ of viscosity that have 100 centipoises by weight in its 5% the styrene solution or the lower rubber of viscosity.As everyone knows, in body or solution polymerization process, begin to be dissolved in the initial monomer component and turnover ratio that the rubber constituent that exists with its homogeneous phase solution form is transformed into polymkeric substance when initial monomer just is separated when being higher than certain value and transforms into the particle that is dispersed in the solution.Phenomenon that Here it is so-called " phase transformation ".In the situation that the aromatic vinyl monomers vinyl cyanide monomer is used in combination, when the viscosity of above-mentioned rubber components solution during greater than 100 centipoises, it is big that the rubber grain that forms in first reactor becomes.Even use hereinafter with the particle disperser of describing in detail, big like this rubber grain can not be transformed into enough little granularity, and becomes substandard products at the resin that generates aspect the surface luster of moulded product, therefore, uses the rubber of high like this granularity inadvisable.

Rubbery polymer only is dissolved in the initial monomer of being made up of at least one aromatic vinyl monomers, or be dissolved in a kind of initial monomer of forming by at least one aromatic vinyl monomers and at least one ethene cyanogen monomer that mixture constituted, can obtain being used as the initial soln of the inventive method.Yet if desired, other solvent such as aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, halohydrocarbon, ketone etc. also can join in the initial soln mentioned above.If so, the used amount of these solvents by weight can not be greater than 50% of the initial monomer in adding first reactor.Its reason be the amount of solvent for use by weight greater than 50% o'clock of initial monomer, not only the useful volume of polymerization reactor significantly reduces, and needs very large energy in order to reclaim this solvent, whole production efficient has also descended.Initial soln in the method for the present invention comprises the initial solvent that contains this solvent and other the various additives that hereinafter will narrate.

In the method for the invention, when the mixture of aromatic vinyl monomers and vinyl cyanide monomer during as initial monomer, the polyreaction that infeeds the initial soln of first reactor is continuously carried out along with adding as the free radical polymerization initiator of polymerisation catalysts.As the example of used suitable free radical polymerization initiator, can enumerate a series of organo-peroxides and azo-compound.Yet, in these free radical polymerization initiators, preferentially select for use with the transformation period be that 10 hours corresponding decomposition temperatures are 100 ℃ or lower a kind of initiator, 90 ℃ or lower better.As such polymerization starter the dodecanoyl superoxide arranged, tert-butyl peroxide (2-ethylhexanoate), benzoyl peroxide, 1, two (tert-butyl peroxide)-3,3 of 1-, the 5-trimethyl-cyclohexane, Diisopropyl azodicarboxylate, azo is two-the 2-methylbutyronitrile.These initiators for polymerization can use separately, also can a plurality ofly be used in combination.When the mixture of aromatic vinyl monomers and vinyl cyanide monomer is aggregated as initial monomer, if need not any radical polymerization initiator, but the polyreaction thermic of this initial monomer is finished, but because the rubber particle size that unknown cause forms in first reactor becomes so big, the reaction solution that contains this rubber grain is even handled with particle disperser, and formed particle all can not be transformed into the enough little particle of granularity.Therefore, because the particle size that is generated can not be controlled at needed scope, so can not adopt such operating method.In addition, be higher than under the situation that 100 ℃ radical polymerization initiator exists having with corresponding decomposition temperature of 10 hour transformation period, the polyreaction of being carried out also is worthless, because the demanding polymeric reaction temperature of the pyrolytic of used initiator, and the polymer ratio that the thermal-initiated polymerization thing accounts for whole generations also increases, and consequently uses the effect of initiator thereby reduced in polyreaction.According to the quantity of the initial soln that provides to first reactor, the consumption of the radical polymerization initiator of supplying with in first reactor is with 30ppm or more mostly be desirable, and 50ppm is then better.Use the radical polymerization initiator can not be less than 30ppm, because used initiator just needs higher polymerization temperature very little, and the ratio that the thermal-initiated polymerization thing accounts for the total polymer of generation also will increase, and the effect of used initiator equally also descends in the polyreaction.

The stirring reactor of complete mixed type, any first polymerization reactor that can be used as among the present invention in tower reactor of piston flow ejector half or the like.When the stirring-type reactor is used as first reactor, must remain on and change into the transformation efficiency of polymkeric substance by initial monomer in the reaction solution that is stirred in first reactor, rubbery polymer in the liquid be changed into the needed concentration value of the rubber grain that is dispersed in the liquid so that make the polymer concentration that forms like this in the liquid maintain to be higher than.When tower reactor is used as first reactor, must keep flow out in the reaction solution of first reactor initial monomer to the transformation efficiency of polymkeric substance, the rubbery polymer in the liquid be changed into the needed concentration value of the particle that is dispersed in the liquid so that make in the liquid concentration of formed polymkeric substance maintain to be higher than.

In the method for the invention, need carry out polyreaction under the following formula reaction conditions satisfying:

1＜X ₁≤ 20 Hes

1.5X ₁-0.05X ² ₁＜X ₂＜4.5X ₁-0.05X ² ₁

X in the formula ₁Be rubbery polymer and the weight percent that flows out the first reactor reaction liquid, and X ₂Be the monomer of polyreaction and the weight percent of the reaction solution that flows out first reactor, at X ₁Under≤1 situation, the rubber content in the resin that obtains under the operational condition is so low usually, so that in fact the resin that produces can not be used as rubber modified high impact resins.On the other hand, at X ₁Under＞20 the situation, the concentration of reaction solution is increased to so high value, making obviously increases for the required power of reaction solution that stirs in first reactor, and rubbery polymer can not change into the particle that is dispersed in the reaction solution, rubbery polymer perhaps both made when can change into particle, what produce is huge rubber grain, X ₁Preferential range of choice is 2＜X ₁≤ 15.About X ₂Value, at X ₂≤ 1.5X ₁-0.05X ² ₁Situation under, initial monomer is so low to the transformation efficiency of polymkeric substance, to such an extent as to rubbery polymer can not become rubber grain.When initial monomer changes into the transformation efficiency of polymkeric substance in the reaction solution when too low at first reactor exit, its as a result rubbery polymer can not change into graininess, even reaction solution was with hereinafter handling the particle disperser that is described in detail, and the particulate size can not control to desired value.Therefore can not realize purpose of the present invention.

At X ₂〉=4.5X ₁-0.05X ² ₁Situation under, reaction solution becomes very high in the viscosity of first reactor exit, so that reaction solution becomes very difficult when carrying out subsequent disposal with particle disperser, the effect of processing is also not obvious.

When initial monomer is aromatic vinyl monomers and vinyl cyanide mixture, X ₁And X ₂The value of preferentially choosing should satisfy following formula:

1＜X ₁≤ 15 Hes

2.0X ₁-0.05X ² ₁＜X ₂＜4.0X ₁-0.05X ² ₁

At X ₁Under≤1 the situation, in fact the rubber content in the rosin products that obtains under the operational condition is low usually can not be used as rubber modified high impact resins to formed resin.Not not on the one hand, at X ₁Under＞15 the situation, the viscosity of reaction solution becomes so high in first reactor, so that for stirring reaction liquid desired power is increased to obviously high level, and rubbery polymer can not change into the rubber grain that is dispersed in the liquid in first reactor.Even if rubbery polymer can change into graininess, the particle that is generated also is huge.X ₁Usually preferentially be chosen in 2＜X ₁≤ 12 scope.About X ₂Value, at X ₂≤ 2.0X ₁-0.05X ² ₁Situation under, the transformation efficiency that initial monomer changes into polymkeric substance is very low, makes rubbery polymer can not change into rubber grain in first reactor.Even or rubbery polymer can be fractured into graininess, it is unstable and big that resulting granules becomes.When initial monomer changes into the transformation efficiency of the polymkeric substance in the reaction solution when very low at first reactor exit, rubbery polymer in the consequently this liquid can not change into graininess, even rubbery polymer can change into graininess, the particle that obtains also is unsettled and very big, the size of rubber grain can not be controlled at desired value, even perhaps reaction solution is handled with particle disperser, the particle of generation also is huge.Therefore such reaction conditions does not meet purpose of the present invention.

In addition, at X ₂〉=4.0X ₁-0.05X ² ₁Situation under, reaction solution is very difficult to the processing of reaction solution with particle disperser in the viscosity of the first reactor exit so high back that makes that becomes, and the effect of handling is not clearly.

In first polymerization reactor in the present invention, dissolving rubber shaped polymer in the initial monomer of forming by at least one aromatic vinyl monomers or form by the mixture of at least one aromatic vinyl monomers and at least one vinyl cyanide monomer, can further add solvent if desired, initial soln that obtains like this and radical polymerization initiator are delivered in the reactor together continuously, and finish polyreaction, so that the concentration of the polymkeric substance that generates in the gained reaction solution is higher than rubbery polymer is changed into the needed certain viscosity of the rubber grain that is dispersed in the reaction solution.If desired, the conditioning agent of one mole of weight (arrangement agent) can be added in first reactor as mercaptan.The temperature of polyreaction is usually in 50-150 ℃ of scope.During as initial monomer, temperature of reaction is preferably in 60-130 ℃ of scope at the mixture that uses aromatic vinyl monomers and vinyl cyanide monomer.

In this connection, can offer the material composition of first reactor, the feed rate of the material that provides by changing polymerization temperature, operational conditions such as the quantity of initiators for polymerization control initial monomer changes into polymer ratio, and the weight percent concentration X of polymkeric substance in reaction solution that generates ₂

In first reactor, polyreaction is carried out usually and with agitator stirring reaction liquid simultaneously.When rubbery polymer became rubber grain, the granularity of the rubber grain that generates depended on stirring extent.In the methods of the invention, because the size of rubber grain is finally by the particle disperser decision of back, the intensity that stirs in first reactor can be chosen as and can make total overall reaction liquid be the uniform mixing state or do not have a bit reaction solution to spill the state of reactor.

The reaction solution that takes out continuously from first reactor is quantitatively suitable with the initial soln that offers first reactor.The liquid that is removed is then delivered in the particles dispersed mixing tank that is installed between first and second reactors, and handles in decollator so that be transformed into the rubber grain with required size by the rubber grain that generates in first reactor is sheared.

The particle disperser that is used to shear rubber-like polymer particle in the inventive method is a blocky stirring and blended machinery, the shearing rotor that this mechanical inside has the energy high speed rotating and is made up of blade or cylindrical rotor, when reaction solution in particle disperser during short stay, rotating blade carries out high speed shear to reaction solution.

The internal capacity of particle disperser is selected V to satisfy following formula ₂/ V ₁＜0.2, preferred V ₂/ V ₁＜0.15, V wherein ₂Be the internal volume of particle disperser, V ₁By the occupied volume of reaction solution in first reactor.Work as V ₂/ V ₁Be not less than at 0.2 o'clock, the internal volume of particle disperser is just too big with respect to the quantity of mobile reaction solution.The mean time that makes reaction solution stop in particle disperser is elongated.Initial monomer changes into the transformation efficiency of polymkeric substance and the viscosity of reaction solution has all increased in the residence time that reaction solution prolonged in particle disperser thus, consequently in order to make shear-blade or rotor high-speed rotation energy needed too much.Therefore V/V like this is worthless.

In addition, the peripheral velocity of shear-blade or rotor is 0.5 meter of per second or need more.

Speed V equation expression is:

V=π dn(meter per second)

D(rice wherein) be the external diameter of rotating blade or rotor, n is the revolution of rotating blade or rotor per second.

When the peripheral velocity of rotating blade or rotor during less than 0.5 meter per second, in the particle disperser and institute to handle the velocity of shear that rubber grain in the reaction solution collides be not enough, cause by the use particle disperser rubber grain that forms in first reactor to be become the rubber grain with desired particle size and become very difficult.In the methods of the invention, by using the rubber grain in the reaction solution that is dispersed in of particle disperser by first reactor can be adjusted to required size.Particularly, for example be selected on the suitable value shearing rotor revolutions per second n, the size of the rubber grain that is changed just can be adjusted to needed size.

When the shearing treatment of carrying out with particle disperser does not use pump to make reaction solution carry out pump circulation by the circulation line that contains above-mentioned particle disperser, should select to have three at least, the particle disperser that preferably has four shear agitation devices at least, wherein each all is made up of blade or cylindrical rotor.Under the situation of using this multistage particle disperser processing reaction liquid, reaction solution needs to shear rotors by these one by one, but is worthless by this each part fast.Therefore buffer substrate tablet or catch will be installed in the gap between each shear-blade or rotor, or install one group of arranged in series, respectively the cavity of shear-blade or rotor is housed.

When the quantity of shear-blade or rotor during less than three, shearing number of times to the rubber grain that forms in first reactor is just not enough, makes that these rubber grains that generate in first reactor are difficult by the rubber grain that particle disperser changes into desired particle size.

As long as can satisfy above-mentioned condition and can provide any shearing mechanism of high shear rates all to can be used as particle disperser in the inventive method.For example, can use by three or more at least being contained in the shearing impeller on the same turning axle and between each shearing impeller, the such stirring mixer of buffer substrate tablet being arranged, for example the propeller type, stir type, helical stir type, turbo wheel type or the like, each is sheared impeller and is made up of three or more at least blades or stator.

For example, the stirring mixer that picture is made of the unit combination parts also can be used as particle disperser, the unit combination parts by arrange coaxially to each other, every end is made up of the cylindrical rotor and the catch of pectination opening, and stirring mixer has two such unit combination parts at least, so that make the multilayered structure of these the unit combination parts of arranged in co-axial alignment in a cavity; Perhaps make the series multistage structure that is arranged in these unit combination parts in the different cavitys that have a public rotating shaft; Or make the above-mentioned series multistage structure that multilayered structure constituted that is arranged in the different cavitys that have a public rotating shaft, in this stirring mixer, preferably have three machineries that have the parts of rotor and catch at least as particle disperser.In this respect, the rotor that is installed on the turning axle in this machinery is equivalent to shearing rotor mentioned above.

When the particle disperser of using the parts of being made up of coaxial rotor and catch mentioned above to constitute, corresponding gap length h(is in rice between adjacent rotors and the catch) and above the relativeness of defined peripheral velocity V should satisfy following formula:

V/h 〉=200, excellent V/h 〉=300 of getting.

In the above-mentioned particle disperser of forming by coaxial rotor and catch that parts constituted, between each rotor and catch, produce shearing force.When V/h less than 200 the time, the shearing force that is produced is little, it is difficult that the rubber grain that forms in first reactor with this particle disperser becomes the rubber grain with the granularity that requires.

Can use IKA ULTRA-TURRX-INLINE and IKA DISPAX-PEACTOR(trade(brand)name, the product of IKA company), TK Hi-line Mill and TK PiPe-line Homomixer(trade(brand)name, the product of To Kushu Kika Kogyo company), Ebara Milder(trade(brand)name, the product of Ebara Seisakusho) etc. such stirring mixer is as particle disperser.

In addition, use at least one particle disperser, also can repeat above-mentioned shearing treatment.

The quantity that reaction solution in first reactor is discharged from first reactor is suitable with the quantity of the initial soln that joins first reactor.The reaction solution of discharging is sent in the circulation process, and circulation process is provided with particle disperser with the pump circulating reaction liquid that is arranged in first and second reactors in the round-robin process.The rubber grain that forms in first reactor is processed in circulation process, makes the rubber grain in the reaction solution change the rubber grain that forms again by want granularity.

In this case, the particle disperser that the shearing blade wheel is arranged as the above-mentioned type, the also available particle disperser that has other type shearing impeller, picture propeller type, impeller type, helical runner type, turbo wheel type, steady brace type, propeller blade profile etc., each is all with high speed rotating.

Example as above-mentioned particle disperser, can use so-called line style agitator, as have buffer substrate tablet intersection frame bed (Berth) type (product of MiXing equipment company) agitator, have buffer substrate tablet angle type agitator (Chemineer company product), have buffer substrate tablet eccentric angle type agitator (product of Satake Kagakukogyo company), have the straight pipe type agitator (product of Satake Kagakukogyo company) of aperture etc.With regard to any in using this agitator, because mentioned above, need to limit peripheral velocity (0.5 meter per second or more hurry up).

Handled by particle disperser simultaneously by the circulation line round-robin when reaction solution, selecting the volume of circular flow will satisfy following formula:

1.5＜F ₂/ F ₁＜30, preferential 2.0＜F ₂/ F ₁＜30

Wherein, F ₁Be the volume that time per unit is supplied with the initial soln of first reactor, F ₂Be and F ₁Pass through the volume of the internal circulating load of this circulation line in the identical unit time.F ₂/ F ₁The ratio value representation in particle disperser the average treatment number of times of reaction solution.Work as F ₂/ F ₁Ratio be not more than at 1.5 o'clock, can not expect that circulation process has any effect, because reaction solution residence time in circulation line is too short.On the contrary, work as F ₂/ F ₁Ratio be 30 or bigger, although increase the number of times that internal circulating load and reaction solution are handled again in particle disperser, it is littler that the size of processed rubber grain can not become.Consider equipment, can not consider latter event, because make the reaction solution circular treatment just need too much pump and circulation line with the industrial-scale production resin.

From first reactor, take out, and delivered to continuously in second polymerization reactor subsequently by the reaction solution that particle disperser was handled and to proceed polyreaction.Second reactor is the reaction vessel of stirring-type.The reaction solution in second reactor, the transformation efficiency that need make initial monomer be converted into polymkeric substance remains on 25% or more more (by weight).In this connection, when reactor is not a stirring-type, for example, the reactor of tower, owing to use the piston flow ejector half as second polymerization reactor, it is different with the transformation efficiency of Reactor inlet place reaction solution that then the initial monomer in the reaction solution of its reactor outlet changes into the transformation efficiency of polymkeric substance; Even both used the stirring-type reactor as second polymerization reactor.When the transformation efficiency that changes into polymkeric substance when the initial monomer in the reaction solution in second reactor is less than 25% (by weight), the size-grade distribution that then generates the rubber grain in the resin has just broadened.Therefore, can not choose such reaction conditions.On the other hand, the rubber grain that forms in particle disperser needs wearing or featuring stage armour, and they are delivered to and have higher initial monomer and transfer in the reaction solution of transformation efficiency of polymkeric substance and being stablized.Only need reaction solution in the reactor can be stirred equipment and mix well, make reaction solution all keep uniform compositions and temperature, the reactor of any stirring-type all can be used as second polymerization reactor among the present invention.Such reactor is known by technician arbitrarily, for example can enumerate the reaction vessel with the spiral type stirrer equipment that has air trunking, or the reaction vessel of equipping with the paddle wheel of double-screw type.

The reaction solution of polymerization takes out from reactor continuously in second reactor, in order to evaporate the not monomer of polyreaction and the solvent of adding in the past, and obtain needed modified high impact rubber resin, the reaction solution that is taken out carries out further polyreaction at least one stirring-type that just has as required or originally or tower reactor after, take out this reaction solution, in certain temperature range,, under vacuum, handle as from 180 ℃ to 260 ℃.

In the method for the invention, the chain-transfer agent as mercaptan can be used usually, so that the molecular weight of controlling polymers.Under the situation of using chain-transfer agent, can join whole needed dosage in the initial soln that feeds first reactor.

Various details embodiment.

Embodiment 1

The polyhutadiene of 6 parts of weights (Diene 55, the product of Asahi Kesei company limited) is dissolved in the initial monomer of being made up of the ethylbenzene as solvent of 79.0 parts of heavy vinylbenzene and 15 parts of weights obtains initial soln.After being added to the 2,6 di t butyl phenol of 0.1 part of weight in this initial soln, the speed (F of the initial soln of gained with 13.0 liters/hour ₁) put into continuously in first reactor of full load type.The first inside reactor volume is 24.9 liters of (V ₁) and have the spiral type agitating vane of being with vent-pipe.In first reactor, polyreaction is carried out under the condition that 130 ℃ temperature and agitator speed are 1.5 meter per seconds, and finishes the phase transformation of rubbery polymer, has therefore formed the particle of rubbery polymer in reaction solution.This reaction solution contains 6% rubbery polymer (by weight) and 20.5% polystyrene (by weight) (the monomeric conversion: 25.9%) from initial monomer formation at first reactor exit.

Reaction solution in first reactor takes out continuously from reactor and delivers in the circulation line that is provided with toothed gear pump and particle disperser (line mixer), and processed, and toothed gear pump is used for circulating reaction liquid.Internal volume (the V of particle disperser ₂) be 0.96 liter, and have the shearing rotor, shearing rotor, 4 external diameters are arranged is 0.08 meter inclination agitator.In circulation line, the reaction solution that takes out from first reactor is with flow rate (F ₂) be 100 liters of/hour circulations, the shearing rotor in the particle disperser moves (1000 rev/mins) with 16.7 revolutions per seconds rotating speed.Under such operational conditions, the ratio of the volume that the internal volume of particle disperser and reaction solution occupy in first reactor, V ₂/ V ₁Be 0.039, the ratio of the flow rate in the circulation line and the feed rate of the initial soln of delivering to first reactor, F ₂/ F ₁Be 7.7, and the peripheral velocity of shearing rotor is 4.2 meter per seconds.

The reaction solution of handling in circulation line is delivered in second full load type reactor continuously, and the internal volume of this reactor is 10.2 liters and the helical mixing blade of being with vent-pipe is arranged.The polyreaction of second reactor is to be that 130 ℃ of agitating vane rotating speeds are to carry out under 1.0 revolutions per seconds the condition in temperature of reaction.

The ratio of the own polymerization single polymerization monomer of reaction solution and initial monomer is maintained at 34.2%(by weight in second reactor).The reaction solution that polyreaction is crossed in second reactor takes out from reactor, offers the 3rd, the 4th and the 5th following tower reactor one by one and continue its polyreaction in these reactors.The fluid temperature that these reactors are discharged is respectively 140 ℃, 150 ℃ and 160 ℃.Equipment with well-known separation easy volatile material under high temperature, high vacuum is separated the reaction solution that takes out continuously from the 5th reactor from unconverted monomer and solvent, for the product that obtains the HI-PS resin is made coccoid at last with extrusion machine.

The mean particle size of rubber grain can be measured according to the photo survey volume averaging value of clapping with electron microscope in the resin of producing like this.In addition, a part of product is extruded the thin slice that moulding is 0.1 mm thick, and checks that these thin slices have 0.2 millimeter ²The quantity of area or more large-area flake.The method that is used for measuring mean particle size and calculating flake quantity recited above is used for the following examples or comparative example equally.The result of these measurements is as shown in table 1.(table 1 is seen the literary composition back)

Embodiment 2 and 3

Except the flow rate F in circulation line ₂Outside being changed, repeat the same step among the embodiment 1.

Embodiment 4 and 5

In changing circulation line endoparticle decollator, the rotating speed of stirring rotator, repeat the same step among the embodiment 1.

Embodiment 6

Except the temperature in first reactor is become 127 ℃, repeat the same step among the embodiment 1.

Embodiment 7

Except being the quantitative change of the polyhutadiene in the initial soln 9 parts of weights, be the quantitative change of ethylbenzene 12 parts of weights, and the agitation condition in first reactor and particle disperser become as shown in table 1 outside, repeat the same step among the embodiment 6.

Comparative example 1

Except leaving out the circulation line between first reactor and second reactor and leaving out the particle disperser in the circulation line, repeat same step among the embodiment 1.In the resin of being produced, can be observed big and some huge rubber grain of mean sizes of rubber grain.

Comparative example 2

Except the rotating speed of agitating vane in first reactor is bent is 4.5 revolutions per seconds (270 rev/mins), repeats the same step in the comparative example 1.Though in the resin of being produced, can't see huge particle, just to compare with embodiment 1, it is big that the mean sizes of the rubber grain that obtains becomes.

Comparative example 3

Except the rotating speed of the shearing rotor of circulation line endoparticle decollator being become 1.67 revolutions per seconds (100 rev/mins), repeat the same step among the embodiment 1.

Comparative example 4

Apparatus meaningful long-pending be 9.7 liters and to have one be that the particle disperser of shearing rotor of 0.4 meter dihedral vane replaces the particle disperser among the embodiment 1 with 4 external diameters (d), and use under the rotating speed of 3.3 revolutions per seconds (200 rev/mins).In addition, repeat same step among the embodiment 1.

Comparative example 5

Change the temperature of reaction in first and second reactors, so that make the monomer of polyreaction be not more than 25%(by weight) the ratio of initial monomer in second reactor.In addition, repeat same step among the embodiment 1.

Comparative example 6

Except the temperature of reaction in first reactor is become 110 ℃, repeat same step among the embodiment 1.In this case, the concentration of the polymkeric substance that forms the initial monomer in first reactor can not increase, so that does not have the phase transformation of rubbery polymer to take place, and the reaction solution in first reactor still keeps homogeneous phase.Even after handling in the particle disperser in circulation line and in circulation line, reaction solution still keeps homogeneous phase.Rubber grain does not form, up to the temperature that improves reaction solution in second reactor.

Comparative example 7

Except the temperature of reaction in first reactor is become 138 ℃, repeat same step among the embodiment 1.In this case, the concentration of the polymkeric substance that forms the initial monomer in first reactor is too high, causes big among the size ratio embodiment 1 of the rubber grain that forms in first reactor, and also can see huge particle in these rubber grains.Even in the line mixer in circulation line and in circulation line after the processing reaction solution, the mean particle size of rubber grain is big than among the embodiment 1 also, still can see a spot of huge particle.

Comparative example 8

The composition that changes initial soln is as shown in table 2, and the weight percent of polyhutadiene is 10%.In addition, repeat same step among the embodiment 1.In this case, though can't see huge particle, and the size of the rubber grain that forms is little, rubber content is too low in the product that obtains like this, and the rosin products that obtains like this is as rubber modified high impact resins, and its shock strength is too low.(table 2 is seen the literary composition back)

Comparative example 9

The composition that changes in the initial soln is as shown in table 2, uses 21.0% polyhutadiene (by weight), in addition, repeats same step among the embodiment 1.In this case, the concentration of rubber is high does not produce phase transformation to reaction solution.

Embodiment 8

The polyhutadiene of 6 parts of weights (Asaprene 700A. trade(brand)name, Asahi KeSei company limited product) be dissolved in the initial monomer of being made up of the ethylbenzene of the vinyl cyanide (vinylbenzene is 75/25 to the ratio of vinyl cyanide) of 55.5 parts of heavy vinylbenzene, 18.5 parts of weights and 20.0 parts of weights and obtain initial soln, Asaprene viscosity at 25 ℃ in 5% styrene solution by weight is 45 centipoises.The uncle's base dodecyl mercaptans as molecular weight regulator of 0.2 part of weight, 0.02 part heavy benzoyl peroxide (BPO: it be that 10 hours decomposition temperature is 74 ℃) and 0.2 part heavy with respect to the transformation period as the radical polymerization initiator as 2 of antioxidant, after-DI-tert-butylphenol compounds joined in the initial soln, the gained initial soln was with 15.0 liters/hour speed (F ₁) offering first reactor of full load type, the internal volume of first reactor is 18.0 liters of (V ₁) and the spiral type agitating vane of being with vent-pipe is arranged.Polyreaction in first reactor is under 110 ℃ of temperature, and the revolution of agitating vane is to carry out under 1.5 revolutions per seconds the condition.And finish the phase transformation of rubbery polymer, therefore in reaction solution, formed the particle of rubbery polymer.Reaction solution is at the content (X of the rubbery polymer of first reactor exit ₁) (change ratio: 22.0%) for the polymkeric substance that from monomer, forms of 6% and 16.3% weight by weight.

Reaction solution takes out and delivers to the circulation line of being made up of toothed gear pump and line mixer and processed continuously from first reactor, and the reaction solution that circulates and provided is provided toothed gear pump.In circulation line, the reaction solution that takes out from first reactor is at flow rate (F ₂) be 120 liters/hour and line mixer in the revolution (n) of agitating vane be to circulate under the operational conditions of 16.7 revolutions per seconds (1000 rev/mins).Under such operational condition, the ratio of the internal volume of the internal volume of line mixer and first reactor, V ₂/ V ₁Be 0.053, the flow rate of circulation line is to the ratio F of the feeding rate of delivering to the initial soln in first reactor ₂/ F ₁Be 8.0, the peripheral velocity of agitating vane is 4.2 meter per seconds.

The reaction solution of in circulation line, handling deliver to continuously with embodiment 1 in the employed second identical reactor, polyreaction is carried out continuously.Polyreaction in second reactor is 110 ℃ in temperature of reaction, and the agitating vane revolution is to carry out under 1.0 revolutions per seconds.In second reactor ratio of the monomer of polyreaction and initial monomer be 33.8%(by weight).

The polymeric reaction solution takes out from reactor continuously in second reactor, deliver in the 3rd, the 4th and the 5th following reactor, these reactors be equipped with first and second reactors in used identical spiral type agitating vane and vent-pipe, and be respectively 110 ℃ in temperature, carry out polyreaction continuously under 120 ℃ and 130 ℃.Reaction solution takes out continuously from the 5th reactor and isolates unconverted monomer and solvent with the equipment of well-known separation easy volatile material under the high temperature high vacuum.In order to obtain so-called acrylonitrile-butadiene-styrene resin (ABS resin), be pressed into coccoid at last with extrusion machine.

Mean particle size at rubber grain in the product that obtains is like this measured as survey the volume averaging value according to the photo of clapping with electron microscope.At this moment, a part of product is squeezed into the thin slice of 0.1 mm thick, has 0.2 millimeter with calculating ²Or more large-area flake quantity is checked this thin slice.At last, make a test film with 4 ounces of injectors, and the surface luster of coming the experiment with measuring sheet with 60 ° of input angles according to the method for JISZ-8741.

Operational condition and these measuring results are shown in the table 3.To the evaluation result of the following examples and comparative example respectively as shown in table 3 and table 4.(table 3,4 is seen the literary composition back)

Embodiment 9 and 10

Except changing the flow rate F in the circulation line ₂Outside, repeat the same step among the embodiment 8.

Embodiment 11 and 12

In the line mixer that changes circulation line, the rotating speed of agitating vane, repeat same step among the embodiment 8.

Embodiment 13

The temperature of reaction in changing first reactor, repeat same step among the embodiment 8.

Embodiment 14

Is the quantitative change of the polyhutadiene in the initial soln 8 parts of weights, and the quantitative change of the temperature in first reactor and used vinylbenzene and vinyl cyanide is as shown in table 3.In addition repeat same step among the embodiment 8.

Embodiment 15

Except using styrene-butadiene copolymer (Toughdene 2000A, trade(brand)name, Asahi Kasei company limited product, the viscosity of its 5% styrene solution in the time of 25 ℃ is 50 centipoises) as rubbery polymer outside, repeat the same step among the embodiment 8.

Embodiment 16

(LPO, it is that 10 hours decomposition temperature is 62 ℃ with respect to the transformation period) replaces benzoyl peroxide as the radical polymerization initiator with the laurylperoxide acyl of 0.04 part of weight, and the polymeric reaction temperature of first reactor becomes 105 ℃.In addition, repeat same step among the embodiment 8.

Comparative example 10

Except removing the circulation line and the line mixer in the circulation line between first reactor and second reactor, repeat same step among the embodiment 8.Can be observed big and some huge rubber grains of mean particle size of rubber grain.

Comparative example 11

The revolution of agitating vane becomes 6 revolutions per seconds (360 rev/mins) in first reactor, repeats same step in the comparative example 10.Though can't see huge particle, the mean particle size of comparing rubber grain with the situation of embodiment 8 becomes big.

Comparative example 12

The revolution of the line mixer in circulation line becomes 1.67 revolutions per seconds (100 rev/mins), repeats same step among the embodiment 8.

Comparative example 13

Use exhausted line mixer in comparative example 5 replaces the line mixer among the embodiment 8, and used revolution is 3.3 revolutions per seconds (200 rev/mins).In addition repeat step same among the embodiment 8.

Comparative example 14

Change the temperature of reaction in first and second reactors, make its in second reactor the ratio of polymeric monomer and initial monomer remain on 25% the value (by weight) or smaller.In addition repeat step same among the embodiment 8.

Comparative example 15

Except the temperature of reaction in first reactor is become 95 ℃, repeat same step in the comparative example 14.In this case, the concentration of the polymkeric substance that forms from the initial monomer of first reactor does not increase, so that does not have the phase transformation of rubbery polymer to take place, and the reaction solution in first reactor keeps homogeneous phase.Even after handling in its line mixer in circulation line and in circulation line, rubber grain does not all have to form.After the temperature to 120 that improves second reactor ℃, can see the formation of rubber grain.

Comparative example 16

Except the temperature of reaction in first reactor is become 123 ℃, repeat same step among the embodiment 8.The concentration of the polymkeric substance that forms from initial monomer in this case, is too high; Cause big among the size ratio embodiment 8 of formed rubber grain in first reactor, and in these rubber grains, can see huge particle.Even after in the line mixer in circulation line and in circulation line reaction solution being handled, compare with embodiment 8, the mean particle size of rubber grain is also big, and still can see a spot of huge particle.

Comparative example 17

Vinylbenzene in the initial monomer is become the vinyl cyanide of the heavy vinylbenzene of 4Q/60(29.6 part and 44.4 parts of weights to the content ratio of vinyl cyanide), the quantitative change of uncle's base dodecyl mercaptans is 0.3 part of weight, in addition, repeats same step among the embodiment 8.The ABS resin that obtains like this is inferior in a measure aspect surface luster, and flowability also worsens.

Comparative example 18

With full-bodied polyhutadiene (Diene 55A, trade(brand)name, the product of Asahi Kasei company limited, the viscosity of its 5% styrene solution is 160 centipoises in the time of 25 ℃) replace polyhutadiene among the embodiment 8 as rubbery polymer, in addition, repeat same step among the embodiment 8.It is big that mean particle size in the rosin products that obtains like this becomes, and surface luster is also inferior.

Comparative example 19

Replace benzoyl peroxide with 0.04 part heavy peroxidation butyl two tertiary alcohols (it is that 10 hours decomposition temperature is 124 ℃ with respect to the transformation period) as the radical polymerization initiator, polymeric reaction temperature in first reactor is 126 ℃, in addition, repeat same step among the embodiment 8.Its mean particle size of the rosin products that obtains like this is big, and its surface luster is also inferior.

Comparative example 20

Need not add the radical polymerization initiator, under the temperature of 130 ℃ first reactors, finish polyreaction, in addition repeat step same among the embodiment 8 with the method for heat.The granularity of the rosin products that obtains like this is big, and its surface luster is also inferior.

Comparative example 21

Except initial soln becomes the mixture of the ethylbenzene that contains rubbery polymer used among 16 parts of heavy embodiment 8,16 parts of heavy vinyl cyanide of 48.0 parts of heavy vinylbenzene and 20 parts of weights, repeat same step among the embodiment 8.In this step, the concentration of rubbery polymer is too high in first reactor, makes the granularity of reaction solution in first reactor obviously be increased to the state that is gel, and consequently, being reappointed or reelected consecutively what common rosin products can not obtain.

Comparative example 22

Except initial soln is become contain 1.0 parts heavy, in embodiment 8 used rubbery polymer, the vinylbenzene of 59.3 parts of weights outside the mixture of the ethylbenzene of 19.7 parts of heavy vinyl cyanide and 20.0 parts of weights, repeats same step among the embodiment 8.In this step, though the rubber particle size that forms is little, in rosin products, also can't see huge particle, its rubber content is low, causes as its shock strength of ABS resin too low.

Embodiment 17

The polyhutadiene of 6 parts of weights (Diene 55, trade(brand)name, the product of Asahi Kasei company limited) is dissolved in the initial monomer of being made up of the ethylbenzene as solvent of 79 parts of heavy vinylbenzene and 15.0 parts of weights obtains initial soln.After the 2,6 di t butyl phenol as antioxidant of 0.1 part of weight was joined initial solvent, initial solvent was with 13.0 liters of/hour (F of speed ₁) be sent to continuously in the first identical reactor used among the picture embodiment 1.Polyreaction in first reactor is to be that 130 ℃, the revolution of agitating vane are to carry out under 1.5 revolutions per seconds the condition in temperature.And finish the phase transformation of rubbery polymer, in reaction solution, formed the particle of rubbery polymer thus.Contain 6% rubbery polymer (X at the exit of first reactor reaction solution ₁) (by weight) and 20.8% the polystyrene (X that forms from initial monomer ₂) (by weight).(the polymeric monomer account for initial soln weight 26.3%).

From first reactor, take out reaction solution continuously, and send in the particle disperser and handle.The internal volume of used particle disperser is 0.48 liter of (V ₂), agitator is made up of six groups of blades in the rotating shaft, and each group all has the agitating vane of 4 radial arrangement, and its external diameter (d) is 0.05 meter, circular flat board is housed, so that rotate synchronously with blade spindle between each paddle components.Agitator is to move under the condition of 16.7 revolutions per seconds (1000 rev/mins) at rotating speed.Under such operational condition, the ratio V of the internal volume of particle disperser and the first reactor internal volume ₂/ V ₁Be 0.019, the peripheral velocity of each agitating vane is 2.6 meter per seconds.

Then, the reaction solution of handling in particle disperser is delivered to continuously in the second full load type reactor (its internal volume is 10.2 liters, and the spiral type agitating vane of band vent-pipe is arranged) and is proceeded polyreaction.Polyreaction is to be 130 ℃ in temperature of reaction in second reactor, and the agitating vane rotating speed is to carry out under 1.0 revolutions per seconds the condition.

Reaction solution keeps in second reactor, and the weight ratio of polymeric monomer and initial monomer is 34.1%, the reaction solution that polyreaction is crossed in second reactor takes out from reactor continuously, and deliver in the 3rd, the 4th and the 5th following reactor, their temperature out remains on 140 ℃ respectively, 150 ℃ and 160 ℃, these reactors are without any agitator and be tower shape.Reaction solution is proceeded polyreaction.Take out reaction solution continuously from the 5th reactor, use the equipment of well-known separation easy volatile material then,,, make coccoid at last with forcing machine in order to obtain the HI-PS resin at high temperature with unconverted monomer and separated from solvent.

The mean particle size of rubber grain can be measured according to the photo survey volume averaging value of clapping with electron microscope in the rosin products that obtains like this.In addition, a part of rosin products is squeezed into the thin slice of 0.1 mm thick, has 0.2 millimeter with calculating ²Or more large-area fish-eye number is checked thin slice.In the embodiment of back and comparative example, also use above described same assessment method.These evaluation results are as shown in table 5 and table 6.

Embodiment 18 and 19

Except the agitator speed that changes particle disperser, repeat step same in embodiment 17.

Embodiment 20

Except the temperature of reaction in first reactor is become 127 ℃, repeat step same in embodiment 17.

Embodiment 21

The content of polyhutadiene in the initial soln is become 9.0 parts of weights, and the content of ethylbenzene becomes 12.0 parts of weights, and the agitation condition that changes in first reactor and the particle disperser is as shown in table 5, in addition, repeats step same in embodiment 20.(table 5 is seen the literary composition back)

Embodiment 22

As a kind of particle disperser, used stirring mixer at this, such stirring mixer is made up of three layers of agitator, these three layers of agitators have a common axis that runs through three stir chamber of arranging one by one along the reaction solution flow passage, and each agitator has the cylindrical rotor of pectination and layered component that catch is formed constitutes by two of arranged in co-axial alignment at each end.In addition, repeat same step among the embodiment 17.This stirring mixer is by six parts of being made up of rotor and catch.The internal volume of particle disperser is 0.24 liter of (V ₂).About the rotor in every layer, in each two parts that all constitute by a rotor and catch, the external diameter (do) of its outside rotor is 0.55 meter, and the external diameter of the inside rotor is 0.04 meter (di), and the contiguous mutually rotor and the width in any one gap between the catch are 0.001 meter (h).Rotor speed in this particle disperser is 8.3 revolutions per seconds (500 rev/mins).In this embodiment, the ratio V of particle disperser internal volume and the first reactor internal volume ₂/ V ₁Be 0.010, the peripheral velocity of each outer rotor is 1.44 meter per seconds (Vo) in the particle disperser, the peripheral velocity of each internal rotor is 1.05 meter per seconds (Vi), the relativeness V/h of the gap width between peripheral velocity and rotor and catch, for outer rotor Vo/h=1440, for internal rotor Vi/h=1050.

Embodiment 23 and 24

Except the rotating speed that changes the particle disperser rotor, repeat same step among the embodiment 22.

Comparative example 23

Except removing the particle disperser between first and second reactors, repeat same step among the embodiment 17.Can observe big and some huge rubber grains of mean particle size of rubber grain.

Comparative example 24

Except the rotating speed of agitating vane in first reactor being become 4.5 revolutions per seconds (270 rev/mins), repeat same step in the comparative example 23.Though can't see huge particle, the mean particle size of rubber grain is compared with the situation of embodiment 17 and is become big.

Comparative example 25

Except the rotating speed of agitator in the particle disperser being become 2.0 revolutions per seconds (120 rev/mins), repeat same step among the embodiment 17.

Comparative example 26

Apparatus is meaningful long-pending be 7.6 liters and replace particle disperser among the embodiment 17 by the particle disperser that six wheel members are formed, these six parts, each is that 0.14 meter, rotating speed are that the blade of four radial arrangement of 3.33 revolutions per seconds (200 rev/mins) is formed by being contained in an external diameter (d) on the axle all.In addition, repeat same step among the embodiment 17.

Comparative example 27

Change the temperature of reaction in first and second reactors, make in second reactor polymerization the ratio of monomer and initial monomer remain on 25% value or low (by weight), in addition, repeat same step among the embodiment 17.

Comparative example 28

Except the temperature of reaction in first reactor is become 110 ℃, repeat same step among the embodiment 17.In this case, the concentration of the polymkeric substance that forms from initial monomer in first reactor can not increase fully, cause the phase transformation that does not have rubbery polymer in first reactor to take place, and the reaction soln in first reactor is homogeneous phase.Even after with particle disperser processing reaction liquid, there is not rubber grain to form yet.After the temperature that improves second reactor, can be observed the formation of rubber grain.

Comparative example 29

Except the temperature of reaction in first reactor is become 138 ℃, repeat same step among the embodiment 17.In this case, the concentration of the polymkeric substance that forms from initial monomer in first reactor is too high, makes the rubber grain that forms in first reactor too increase, and can see the particle that some are huge in these rubber grains.After with particle disperser reaction solution being handled, comparing of obtaining among the mean particle size of the rubber grain that obtains like this and the embodiment 17 is also big, and can see the rubber grain that a little is huge.

Comparative example 30

The composition of initial soln becomes as shown in table 6, and uses the polyhutadiene of 1.0% weight, in addition, repeats same step among the embodiment 17.In this case, though can't see huge particle, and the mean particle size of the rubber grain that forms is little, the rubber content in the product that obtains like this is too low, make that the shock strength of this rosin products is too low as a rubber modified high impact resins.

Comparative example 31

Composition in the initial soln becomes as shown in table 6, and uses the polyhutadiene of 21.0% weight, in addition, repeats same step among the embodiment 17.In this case, the concentration of rubber is too high in the reaction solution, and making does not have phase transformation to take place.

Comparative example 32

Rotor in making particle disperser repeats same step among the embodiment 22 running under the rotating speed of 1.67 revolutions per seconds (100 rev/mins).

Comparative example 33

The particle disperser of similar structure among use and the embodiment 22, but has only one deck agitator, agitator is made of two layered component of being made up of cylindrical rotor and catch of arranged in co-axial alignment, catch and rotor have the pectination opening at their each end, the rotating speed of agitator rotor is 8.3 revolutions per seconds (500 rev/mins), in addition, repeat same step among the embodiment 22.

Comparative example 34

Use and embodiment 22 in the particle disperser of same structure, but the width (h) of the every interspace between rotor and stator is 0.01 meter, the rotating speed of rotor be 8.3 revolutions per seconds (500 rev/mins) in addition, same step among the repetition embodiment 22.

Embodiment 25

The polyhutadiene of 6.0 parts of weights (Asaprene 700A, trade(brand)name, the product of Asahi Kasei company limited) is dissolved in vinylbenzene, obtains initial soln in the initial monomer that the ethylbenzene of the vinyl cyanide of 18.5 parts of weights (vinylbenzene is 75/25 than the ratio of vinyl cyanide) and 20.0 parts of weights is formed by 55.5 parts of weights.5% the viscosity of styrene solution in the time of 25 ℃ by weight of Asaprene700A is 45 centipoises.0.2 part of weight as the uncle of molecular weight regulator base dodecyl mercaptans, 0.02 part heavy benzoyl peroxide (BPO: it is that 10 hours decomposition temperature is 74 ℃ with respect to the transformation period) and 0.2 part heavy as the radical polymerization initiator as 2 of antioxidant, the 6-DI-tert-butylphenol compounds joins after the initial soln, is 15.0 liters of/hour (F with speed ₁) continuously initial soln send into embodiment 8 in the used first identical reactor.Polyreaction is under 110 ℃ temperature in first reactor, and the rotating speed of agitating vane is to carry out under 1.5 revolutions per seconds the condition.And finish the phase transformation of rubbery polymer, therefore, in reaction solution, formed the particle of rubbery polymer.In the exit of first reactor, the content that reaction solution contains rubbery polymer is 6.0%(X ₁), the content of the polymkeric substance that forms from initial monomer is 16.4%(X ₂), (by weight) (transformation efficiency is 22.2%).

Reaction solution takes out from first reactor continuously, and sends in the particle disperser and handle.Can use exhausted in embodiment 17, same particle disperser.Paddle wheel in the particle disperser is in rotating speed (n) operation down of 16.7 revolutions per seconds (1000 rev/mins).Under this operational conditions, the ratio V of particle disperser internal volume and the first reactor internal volume ₂/ V ₁Be 0.027, the peripheral velocity of agitating vane is 2.6 meter per seconds.

In particle disperser, the reaction solution of handling is delivered in the second full load type reactor continuously, carries out polyreaction continuously, and the internal volume of second reactor is 10.2 liters, and the spiral type stirrer of band vent-pipe is arranged.In second reactor, polyreaction is to be 1.0 revolutions per seconds at agitator speed, carries out under 110 ℃ the temperature of reaction.In second reactor, monomeric number turnover is 33.2%.

In second reactor, the reaction solution that polyreaction is crossed takes out from reactor continuously, and deliver in the 3rd, the 4th and the 5th reactor of back, each reactor all equip with first and second reactor in used identical helical mixing blade and vent-pipe, polyreaction is proceeded, and temperature of reaction is respectively 110 ℃, 120 ℃ and 130 ℃.Reaction solution takes out from the 5th reactor continuously, and comes out at high temperature and the following unconverted monomer of high vacuum and separated from solvent with the equipment of well-known separation easy volatile material, for obtaining the product of ABS resin, makes coccoid at last with extrusion machine.

The mean particle size of rubber grain can be measured according to the photo survey volume averaging value of clapping with electron microscope in the product that obtains like this.In addition, a part of product is squeezed into the thin slice of 0.1 mm thick, and thin slice has 0.2 millimeter by calculating ²Or more large-area fish-eye number is checked.Then make test film, and be 60 ° of surface lusters of coming the experiment with measuring sheet according to the method input angle of JIS Z-8741 with 4 ounces of injectors.The operational condition and the result of these measurements are as shown in table 7.To the evaluation result of back embodiment and comparative example also respectively shown in table 7 and table 8.(table 7,8 is seen the literary composition back)

Embodiment 26 and 27

In changing particle disperser, the rotating speed of agitator, repeat same step among the embodiment 25.

Embodiment 28

Except the temperature of reaction in first reactor is become 107 ℃, repeat same step among the embodiment 25.

Embodiment 29

Is the quantitative change of polyhutadiene in the initial soln 8.0 parts of weights, and the temperature of reaction in the consumption of vinylbenzene and vinyl cyanide and first reactor becomes as shown in table 7.In addition, repeat same step among the embodiment 25.

Embodiment 30

Except in initial soln, using butylbenzene copolymer (Toughdene 2000A, trade(brand)name, the product of Asahi Kasei company limited, the viscosity in its 5% styrene solution are 50 centipoises in the time of 25 ℃) as rubbery polymer outside, repeat same step among the embodiment 25.

Embodiment 31

Replace benzoyl peroxide with the laurylperoxide acyl (LPO) of 0.04 part of weight as the radical polymerization initiator, it corresponds to the transformation period is that 10 hours decomposition temperature is 62 ℃; Polymeric reaction temperature in first reactor becomes 105 ℃.In addition, repeat same step among the embodiment 25.

Embodiment 32

Use the stirring mixer of forming by three layers of agitator as particle disperser.These three layers of agitators are contained in the public rotating shaft one by one, this root axle runs through three stir chamber that are provided with one by one along the reaction solution flow passage, each agitator is installed in separately the stir chamber, and constitute by two layered component of arranged in co-axial alignment, each layered component has the cylindrical rotor and the catch of arranged in co-axial alignment, and rotor and catch have the pectination opening in their ends separately.In addition, repeat same step among the embodiment 25.This stirring mixer is by six parts of being made up of rotor and catch.The internal volume of particle disperser is 0.24 liter of (V ₂).About the rotor in every layer, all in two coaxial mounted parts that constitute by rotor and catch, the external diameter (do) of its outside rotor is 0.055 meter, and the external diameter of corresponding internal rotor (di) is 0.04 meter, and the width in any one gap between adjacent rotor and catch is 0.001 meter (h).In this particle disperser, rotor moves under the rotating speed of 8.3 revolutions per seconds (500 rev/mins).In this embodiment, the ratio V of particle disperser internal volume and the first reactor internal volume ₂/ V ₁Be 0.013, the peripheral velocity of each outer rotor is 1.44 meter per seconds (Vo) in particle disperser, and the peripheral velocity of each internal rotor is 1.05 meter per seconds (Vi), peripheral velocity is to the ratio V/h of the gap width between rotor and the catch, for outer rotor is Vo/h=1440, for internal rotor Vi/h=1050.

Embodiment 33 and 34

Except the rotating speed that changes the particle disperser rotor, repeat same step among the embodiment 32.

Comparative example 35

Except saving the particle disperser between first and second reactors, repeat same step among the embodiment 25.Can see rubber grain and some huge rubber grains of volume particle size.

Comparative example 36

Except the rotating speed of agitating vane in first reactor being become 6.0 revolutions per seconds (360 rev/mins), repeat same step in the comparative example 35.Though can't see huge particle, the mean particle size of rubber grain is compared with the situation of embodiment 25 and is become big.

Comparative example 37

Except the rotating speed of agitator in the particle disperser being become 2.0 revolutions per seconds (120 rev/mins), repeat same step among the embodiment 25.

Comparative example 38

Replace used particle disperser among the embodiment 25 with used same particle disperser in the comparative example 26, and the rotating speed of rotor is 3.33 revolutions per seconds (200 rev/mins), in addition, repeats same step among the embodiment 25.

Comparative example 39

The temperature of reaction in first and second reactors become in second reactor weight ratio of own polymerization single polymerization monomer and initial monomer can be remained on 25% or the reaction conditions (seeing Table 8) of lower ratio on, in addition, repeat same step among the embodiment 25.(table 8 is seen the literary composition back)

Comparative example 40

Temperature of reaction in first reactor becomes 95 ℃, repeats same step in the comparative example 39.In this case, the concentration from initial monomer formation polymkeric substance in first reactor can not fully increase, and causes the phase transformation that does not have rubbery polymer in first reactor to take place, and is homogeneous phase at the first reactor internal reaction liquid.Even after in particle disperser, reaction solution being handled, there is not rubber grain to form yet.Temperature in second reactor is brought up to after 120 ℃, can be seen the formation of rubber grain.

Comparative example 41

Except the temperature of reaction in first reactor is become 123 ℃, repeat same step among the embodiment 25.In this case, the concentration of the polymkeric substance that forms from initial monomer in first reactor is too high, the rubber grain that forms in first reactor is obviously increased, and can see the particle that some are huge in these rubber grains.After with particle disperser reaction solution being handled, the mean particle size of the rubber grain that obtains like this is also big with comparing of obtaining in embodiment 25, and can see the rubber grain that a little is huge.

Comparative example 42

The weight ratio of vinylbenzene and vinyl cyanide is become the vinyl cyanide of the heavy vinylbenzene of 40/60(29.6 part and 44.4 parts of weights), and the amount of uncle's dodecyl mercaptans also becomes 0.3 part of weight.In addition, repeat same step among the embodiment 25.The ABS resin surface luster that obtains like this is poor and it is mobile also inferior.

Comparative example 43

With high viscosity polyhutadiene (Diene 55A, trade(brand)name, the product of Asahi Kasei company limited, the viscosity of its 5% styrene solution in the time of 25 ℃ is 160 centipoises) replace polyhutadiene among the embodiment 25 as rubbery polymer, in addition, repeat same step among the embodiment 25.The mean particle size of the rosin products that obtains like this is bigger, and its surface luster also becomes inferior.

Comparative example 44

Ditertiary butyl peroxide with 0.04 part of weight replaces benzoyl peroxide as the radical polymerization initiator, ditertiary butyl peroxide is that 10 hours decomposition temperature is 124 ℃ corresponding to the transformation period, and the polymeric reaction temperature in first reactor become 126 ℃, in addition, repeat same step among the embodiment 25.The rosin products that obtains like this have big mean particle size and surface luster inferior.

Comparative example 45

Do not use the radical polymerization initiator, and the polyreaction in first reactor is 130 ℃ in temperature and carries out under the states of heat, in addition, repeat same step among the embodiment 25.The rosin products that obtains like this have big mean particle size and surface luster inferior.

Comparative example 46

Except initial soln being become, repeat same step among the embodiment 25 for the mixture of forming by the ethylbenzene of 16.0 parts of heavy rubbery polymers, 48.0 parts vinylbenzene, 16.0 parts vinyl cyanide and 20.0 parts of weights.In such operation, the concentration of the rubbery polymer in first reactor is too high, causes the viscosity of the first reactor internal reaction liquid significantly to be increased to and is gel state, and consequently common rosin products also can not get.

Comparative example 47

Except initial soln being become the mixture of forming by the ethylbenzene of 1.0 parts of heavy rubbery polymers, 59.3 parts vinylbenzene, 19.7 parts of heavy vinyl cyanide and 20.0 parts of weights, repeat same step among the embodiment 25.Though can't see huge particle, the mean particle size of the rubber grain of formation is also less, and the rubber content in the resin that obtains like this is low, so that too low as its shock strength of ABS resin.

Comparative example 48

Except the rotating speed of particle disperser internal rotor being changed to 1.67 revolutions per seconds (100 rev/mins), repeat same step among the embodiment 32.

Comparative example 49

The particle disperser of similar structure among use and the embodiment 32, but has only one deck agitator, agitator is made up of two layered component of arranged in co-axial alignment, each layered component is to be made of columnar rotor and catch, rotor and catch have the pectination mouth in its end separately, and its rotor moves under the rotating speed of 8.3 revolutions per seconds (500 rev/mins).In addition, repeat same step among the embodiment 32.

Comparative example 50

The particle disperser of used same structure among use and the embodiment 32, but the gap width of every interspace (h) is 0.01 meter between rotor and the catch, its rotor moves under the rotating speed of 8.3 revolutions per seconds (500 rev/mins), in addition, repeats same step among the embodiment 32.

Table 6 is continuous

31 32 33 34

64.0 79.0 79.0 79.0

15.0 15.0 15.0 15.0

21.0 6.0 6.0 6.0

13.0 13.0 13.0 13.0

24.9 24.9 24.9 24.9

130 130 130 130

1.5 1.5 1.5 1.5

25.0 26.3 26.3 26.3

16.3 20.8 20.8 20.8

6 ^＊12 ^＊16 ^＊1

0.24 0.24 0.24

0.055，0.04 0.055，0.04 0.055，0.04

1.67 8.3 8.3

0.29，0.21 1.4，1.1 1.4，1.1

0.010 0.013 0.010

288，209 1440，1050 144，105

130 130 130

33.5 33.6 33.5

1.8 1.6 1.6

0 0 0

^*1: the parts that use cylindrical rotor and catch composition are as shearing in the particle disperser

The shearing impeller of agitator, each rotor and catch are split into pectination at its each end.

Claims (5)

1, use at least two polymerization reactors and particle disperser to prepare the method for rubber modified high impact resins continuously, comprise the following steps: that (1) feeds in first polymerization reactor continuously be dissolved in the initial monomer resulting initial soln by rubbery polymer, wherein initial monomer is by being used to that at least a aromatic vinyl monomers of polymeric constitutes or constituting by being used to a kind of mixture that polymeric is made up of at least a aromatic vinyl monomer and vinyl cyanide monomer; (2) make the initial monomer in first reactor carry out polyreaction, the polymer concentration that is obtained by polymerization in first reactor reaches such value, and under this value, rubbery polymer is transformed into its particle that is dispersed in this reaction solution; (3) reaction solution that will contain rubber-like polymer particle with infeed the amount that the initial soln amount is suitable in first reactor and from first reactor, extract out continuously; (4) then, feeding particle disperser by the reaction solution of extracting out in first reactor, this decollator be equipped with form by revolving stirrer or cylindrical rotor and with the shear agitation device of high speed rotating, in this decollator, the rubber-like particle in the reaction solution is applied shearing treatment by the shear agitation device; (5) will be subjected to the reaction solution of shearing treatment then to feed second reactor in the particle disperser, wherein the amount of the polymkeric substance that is formed by initial monomer and initial monomer form that the transformation efficiency of product is the same to be maintained at 25% or more, reaction solution is then proceeded reaction in second reactor, if necessary, can be (for example: then carry out three, the 4th reactor) at follow-up polymerization reactor, it is characterized in that polyreaction is carried out under the following conditions:

(A) should satisfy following formula:

V ₂/V ₁＜0.2

Wherein: V ₁Be the volume that reaction solution occupies in first reactor, V ₂It is the internal volume of particle disperser;

(B) peripheral velocity of Xuan Zhuan blade or rotor is 0.5 meter per second or faster; With

(C) should satisfy following formula:

1＜X ₁≤ 20 Hes

1.5X ₁-0.05X ² ₁＜X ₂＜4.5X ₁-0.05X ² ₁

Wherein:

X ₁Be rubbery polymer and the ratio of the percentage ratio by weight of the first reactor exit reaction solution, X ₂It is the polymkeric substance that forms by initial monomer and the ratio of the percentage ratio by weight of the first reactor exit reaction solution.

2,, perhaps have at least one to be contained on the turning axle and can be with the round shape ring of high speed rotating according to the process of claim 1 wherein that particle disperser has three each all vaned shearing rotors at least; Wherein said shearing rotor is installed in the cavity that has cushion plate or catch, and cushion plate or catch are installed between two rotors adjacent one another are; Perhaps said shearing rotor is contained in respectively in the different chambeies, and these chambeies are with respect to the flow direction arranged in series of reaction solution, so as in above-mentioned particle disperser processing reaction liquid.

3, according to the method for claim 1, shear agitation device in the wherein said particle disperser comprises three parts at least, each parts is made up of the cylindrical rotor and the catch of mutual arranged in co-axial alignment, gapped between rotor and catch, and the shear agitation device is to turn round satisfying under the condition of following formula.

V/h≥200

Wherein: h is the width (rice) in gap between rotor adjacent one another are and the catch, and V is the peripheral velocity (meter per second) of described rotor.

4, according to the method for claim 1, wherein the reaction solution that takes out from first reactor infeeds in the circulation line that comprises particle disperser, so that make above-mentioned liquid stand shearing treatment, want the round-robin reaction solution by in the above-mentioned circulation line forcing with pump, particle in the described reaction solution is handled by the shear agitation device in the particle disperser, and circulating under the condition that satisfies following formula of described reaction solution carried out:

1.5＜F ₂/F ₁＜30

Wherein: F ₁Be the volume of delivering to the initial soln in first reactor in the unit time, F ₂It is the volume by the described reaction solution of circulation line round-robin in above-mentioned identical unit time.

5, according to claim 1, method described in 2 or 3, wherein the initial soln of being made up of rubbery polymer and initial monomer infeeds in first reactor with the radical polymerization initiator, rubbery polymer viscosity in its styrene solution of 5% weight in the time of 25 ℃ is 100 centipoises, initial monomer is made up of aromatic vinyl monomers and vinyl cyanide monomer, the weight ratio of the two is in from 95/5 to 50/50 scope, the radical polymerization initiator is that 10 hours decomposition temperature is 100 ℃ or low corresponding to the transformation period, the amount that adds the radical polymerization initiator is 30ppm or more more corresponding to the amount that infeeds initial soln in first reactor, so that satisfy following formula:

1＜X ₁≤ 15 Hes

2.0X ₁-0.05X ² ₁＜X ₂＜4.0X ₁-0.05X ² ₁

Wherein: X ₁Be rubbery polymer and the ratio of the percentage ratio by weight of the first reactor exit reaction solution, X ₂It is the polymkeric substance that forms by initial monomer and the ratio of the percentage ratio by weight of first reaction solution.