CA1293091C - Process for producing high impact styrene resin by continuous bulk polymerization - Google Patents
Process for producing high impact styrene resin by continuous bulk polymerizationInfo
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- CA1293091C CA1293091C CA000542813A CA542813A CA1293091C CA 1293091 C CA1293091 C CA 1293091C CA 000542813 A CA000542813 A CA 000542813A CA 542813 A CA542813 A CA 542813A CA 1293091 C CA1293091 C CA 1293091C
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- high impact
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a process for producing a high impact styrene resin by continuous bulk polymerization and a high impact styrene resin produced by the process. The resin is produced in the presence of a rubbery polymer in a tubular reactor having static mixing means such as a static mixer without using a stirred tank reactor. A part of an initial-stage polymer solution is recycled and joined with a feed material solution. The rubbery polymer and the recycled initial-stage polymer solution are easily divided into fine particles uniformly dispersed. As a result, the grafting ratio is increased and a high impact styrene resin having excellent strength is obtained in which the grafted rubbery polymer is contained with a narrow particle size distribution.
Disclosed is a process for producing a high impact styrene resin by continuous bulk polymerization and a high impact styrene resin produced by the process. The resin is produced in the presence of a rubbery polymer in a tubular reactor having static mixing means such as a static mixer without using a stirred tank reactor. A part of an initial-stage polymer solution is recycled and joined with a feed material solution. The rubbery polymer and the recycled initial-stage polymer solution are easily divided into fine particles uniformly dispersed. As a result, the grafting ratio is increased and a high impact styrene resin having excellent strength is obtained in which the grafted rubbery polymer is contained with a narrow particle size distribution.
Description
~ '9~
This invention relates to a process for produc-ing a high impact styrene resin by continuous bulk poly-merization, and to a high impact styrene resin obtained by this process. More specifically, it relates to a process for producing by continuous bulk polymerization a hi~h impact styrene resin havinq excellent strength in which a grafted rubbery polymer in the resin has a narrow particle size distribution, and to a high impact styrene resin obtained by this process.
In the production of a high impact styrene resin by graft polymerizing a styrene monomer in the presence of a rubbery polymer, how to control the dis-persion of the rubbery polymer uniformly as fine parti-cles and the stabilization of the rubbery polymer parti-cles during the graft polymerization is especially im-portant in determining the quality of the resulting resin. The particle size and particle size distribution of the grafted rubbery polymer particles di~persed in the final resin, and the grafting ratio of styrene greatly affect the impact strength and gloss of the final resin.
For the industrial production o~ high impact styrene re~in, a batchwi~e bulk-suspension polymerization method and a continuous bulk polymerization method have generally been employed. The continuous method, however, has been found to be superior in productivity and economy, and has gained widespread acceptance.
Usually, in the continuous bulk polymerization method, it is general practice to provide a plurality of stirred tank reactors and to perform polymerization while continuously feeding a starting material solution.
More specifically, there was proposed a nethod in which in an initial poly~erization step, the rubbery polymer is divided into fine particles and dispersed by dynamic mixing in a stirred tank reactor with a stirrer, 3~
lZ~3~ 91 and thereafter, the polymer solution is continuously transferred to a plurality of stirred tank reactors, and the polymerization is allowed to proceed with stirring.
It has been pointed out however that the con-tinuous bulk polymerization using the tank reactors hasthe defects atteibuted to the dynamic mixinq by the stirrer. Specifically, when the viscosity of the polymer solution in the tank rise~ as the polymerization proceeds, the power or the strength of the stirring vanes has to be increased. To avoid it~ the polymerization conversion of the styrene monomer in the tank must be inhibited as the polymerization proceed~. Alternatively, if exce~sive stirring and mixing is carried out, an excessive shearing force is exerted on the rubbery polymer dispersed as fine particles. Consequently, the dispersed fine particles of the rubbery polymer are broken, and the particle size distribution of the rubbery polymer particle becomes broad. As a result, the strength of the final product decreases. Another defect is that since the stirred tank reactor has an excessive capacity because of its struc-ture, a long period of time is required, for example, in switching from one brand to another in the production of resins in which the rubbery polymer has different particle diameters. In an attempt to remove these defects of the stirred tank reactor, there have been made some sugges-tions including the structure of stirring vanes, the performance of pre-polymerization, or the combination of it with a tubular reactor or a column-type reactor. But these suggestions have not proved to be sufficient for removing the above defects.
In view of the above state of the art, the present inventors made investigations on a continuous process for producing a high impact styrene resin in a tubular reactor having static mixing means such as a static mixer therein without using the stirred tank reactor.
1~33~ 91 On the utilization of a tubular reactor in a continuous polymerization, U. S. Patent 4,275,177 pro-poses a process which u8e8 a tank reactor having a stirrer for carrying out an initial-stage polymerization and a tubular reactor having static mixing means therein for carrying out main polymerization. In this process, however, the defects attributed to the dynamic mixing by the stirrer within the tank cannot be removed, and an excessively high shear owing to the intense stirring and mixing i8 exerted to broaden the particle size distri-bution of the rubbery polymer particles. The grafting rat~o of styrene is not increased, and the results are still unsatisfactory.
The present inventors then made investigations on a method of finely dividing the rubbery polymer and dispersing it as fine particles by performing polymeri-zation in a tubular reactor having static mixing means therein. Thi8 investigation has revealed the following fact. For the rubbery polymer to be finely divided and dispersed as fine particles, appropriate shearing is required in the early stage of polymerization. For this purpose, the presence of a mixer is essential. The degree of mixing by the static mixing means such as a static mixer within the tubular reactor is determined by the linear speed of the polymer solution in the reactor.
Since it depends upon the flow rate and the tubular diameter, it i~ necessary to increase the flow rate greatly in order to perform sufficient mixing. However, there is a limit to the increasing of the flow rate in the tubular reactor because as the polymerization pro-ceeds the viscosity of the polymer solution increase~
markedly and the pressure drop in the tube increases.
Consequently, sufficient shear cannot be obtained. In an ordinary tubular reactor, this weak shear leads to a failure to obtain a desirable particle size in the rubbery polymer although the rubbery polymer can be dispersed as ~Z~3~9J.
fine particles. A further problem is tbat the rubbery polymer precipitated in the early stage of the pol~meri-zation adheres to the wall of the reactor. If the ad-hering rubbery polymer grows and gets into the high impact styrene resin, it becomes a fish eye in the final product.
Further investigations of the present inventor~
made in view of the above situation have now led to the discovery that when continuous bulk polymerization of a styrene monomer in the presence of a rubbery polymer is carried out in a tubular reactor having static mixing means such as a static mixer therein and part or a greater part of the resulting initial-~taqe polymer solution is recycled and allowed to join a flow of the feed material solution, the rubbery polymer in the feed material solution and the initial-stage polymer solution are easily divided into fine particles and uniformly dis-persed, the grafting ratio is increased, and a high impact styrene resin can be easily obtained which has excellent strength and in which the grafted rubbery polymer has a narrow particle size distribu~ion.
Thus, according to this invention, there i8 provided a process for producing a high impact styrene resin which compri~es continuously polymerizing a styrene monomer in bulk in the presence of a rubberY polymer, wherein a polymerization line is used which i8 com-prised of an initial polymerization line lII) consisting of at least one tubular reactor having an inlet following the outlet of a starting material feed line (I) and static mixing means therein, a main polymerization line lIII) consisting of at lea~t one tubular reactor having an inlet following the outlet of the initial polymeri-zation line lII) and static mixing means, and a recycle line ~IV) which branches on the way in a passage ranging from the outlet of the initial polymerization line to the ~3(:~9i inlet of the main polymerization line (III) and returns to the f ront of at least one tubular reactor in the initial polymerization line ~II); and part or a greater part of a flow of the initial-stage polymer solution leaving the cutlet of the initial polymerization line tII) is eecycled via the recycle line tIV) to allow it to join a flow of a starting material solution fed from the starting material feed line ~I) or the flow of the initial polymerization solu-tion being in the process of initial polymerization andthe initial polymerization is further allowed to proceed in the initial polymerization line (II), and in the meantime, the initial polymerization solution not recycled through the recycle line i8 polymerized in the main polymerization line (III).
Typical examples of the rubbery polymee uæed in this invention include polybutadiene rubber, styrene/
butadiene copolymer rubber, styrene/butadiene/styrene block copolymer rubber, ethylene/propylene terpolymer rubber, butadiene/acrylonitrile copolymer rubber, butyl rubber, acrylic rubber, styrene/isobutylene/butadiene copolymer rubber, and isopeene/acrylic ester copolymer rubbers. They may be used either singly or in combi-nation.
The styrene monomer used in this invention generically denotes styrene, alpha-methyl6tyrene, and styrene derivatives resulting from substitution of a halogen atom or a Cl-C4 alkyl group for a hydrogen atom on the benzene ring. Typical examples are styrene, o-chlorostyrene, p-chlorostyrene, p-methylstyrene, 2,4-dimethylstyrene and t-butylstyrene.
In the present invention, another monomer copolymerizable with the styrene monomer ~to be referred to a~ the ~other monomer~3 may be used in combination with the styrene monomer. Examples of the other monomer are acrylonitrile, acrylic acid, alkyl acrylates, l2s3a-si methacrylic acid, alkyl methacrylates, maleic anhydride and various maleimides.
A suitable amount of a solvent may be used to adjust the viscosity of tbe polymer sQlution in the bulk polymerization in accordance with this invention. The solvent may, for example, be toluene, ethylbenzene or xylene. The amount of the solvent used i8 usually not more than 20 parts by weight per 100 parts by weight of the resin component composed of the rubbery polymer and the styrene monomer and other monomer.
If desired, a known organic peroxide which releases free radicals on decomposition, such as benzoyl peroxide, di-t-butyl peroxide or dicumyl peroxide, may be included as a polymerization initiator into the ~tarting material solution used in this invention. If further required, known additives such as a pla~ticizer, an antioxidant and a chain transfer agent may be incorpo rated.
The tubular reactor used in this invention may be any known tubular reactor having static mixing means therein. Tubular reactors having static mixing means composed of a number of mixing elements, such as a Sulzer-type st~tic mixer, a Kenix-type static mixer, a Toray-type static mixer, are preferred.
Tubular reactors may be incorporated in the initial polymerization line ~II) and the main polymeri-zation line (III) and if required, further in the recycle line ~IV).
The total of the number of tubular reactors in the initial polymerization line ~II) and the number of tubular reactors in the main polymerization line (III) i~
not particularly limited because, for example, in the case of a static mixer of the type exemplified above, it differs depending upon the length, the structure and number of mixing elements, etc. Usually, 4 to 15 ~preferably 6 to 10) static mixers each having at least 5 ~93~91 (preferably 10 to 40) mixing elements are used in combi-nation. The number of static mixers to be incorporated in the initial polymerization line (II) and optionally the recycle line (IV) is 1 to 10, preferably 2 to 6.
In the present invention, it is preferred to set up an in-line mixer having dynamic mixing mea~s in any desired site in a circulating line ~to be referred to as the circulating line) formed of the initial polymeri-zation line ~II) and the recycle line ~IV), preferably in the initial polymerization line ~II) after the association of the recycle line ~IV), bacause the rubbery polymer can be divided finely and dispersed as fine particles within a ~hort period of time and a high impact styrene resin having particularly excellent gloss can be obtained. The dynamic in-line mixer is preferably a dynamic piping mixer comprised of a tubular housing portion, dynamic mixing means for forcibly performing stirring within the hou~ing portion such as propeller-type, turbine-type or anchor-type stirring vanes, and a shaft portion support-ing the mixing means. The clearance between the innerwall of the houfiing and the stirring vanes is usually 0.1 to 2 mm, preferably 0.2 to 1 mm.
Preferred examples of the dynamic in-line mixer are a 6pecial anchor-type mixer made by Satake Chemical Industry Co., Ltd., an angle-type mixer made by Chemineer Company, a pipeline mixer made by Greerco Company, and a kneader-type mixer made by Kurimoto Tekkosho Co., Ltd.
The starting material solution to be fed from the starting material feed line (I) comprises the rubbery polymer and the styrene monomer, and optionally another monomer, a solvent, a polymerization initiator and other known additives.
The proportion of the rubbery polymer used i6 preferably 3 to 15% by weight based on the total weight of the rubbery polymer, the styrene monomer and the other optional monomer because the rise of the viscosity of the ~93~1 polymer solution in the circulating line is little, the particle size can be easily controlled, and a high impact styrene resin having excellent impact strength can be obtained.
The starting material solution fed from the material feed line ~I) is continuously associated and mixed with the initial-stage polymer solution circulating in the recycle line ~IV) and i~ polymerized in a tubular reactor in the initial polymerization line ~II) usually at a reaction temperature of 110 to 140C to precipitate a grafted rubbery polymer. Since the precipitated grafted rubbery polymer i8 suitably mixed and dispersed by the tubular reactor as soon as it is precipitated, its con-version to fine particles and uniform dispersion are effect~vely promoted.
When a tubular reactor is provided in the recycle line ~IV), the initial-stage polymer solution circulating under a suitable ~hearing force and a fresh supply of the starting material solution are very effec-tively mixed.
The recycle ratio (R) of the polymer solutionis usually R~Fl/F2~1 - 20 wherein Fl is the flow rate (liters/hr) of the initial-stage polymer solution flowing in the recycle line (IV), and F2 is the flow rate ~liters/hour) of the initial-stage polymer solution which flows into the main polymerization line ~III) without being recycled or the starting material solution in the starting material feed line (I). Preferably, R is from l.S to 10 because at an R in this range, the recycling 3~ can be carried out stably, no polymer deposit occurs in the reactor wall, and fine particles of the rubbery polymer having a narrow particle ~ize distribution can be obtained.
The extent of the initial polymerization is such that the polymerization conversion (_, ~ by weight) of the monomer component comprising the styrene monomer ~ ~ 3 ~9 ~
and the optional other monomer and the content ~a, % by weight) of the rubbery polymer are usually in the follow-ing relation: b=0.9a to 5a, preferably b=1.5a to 3a.
Since within this range, the rubbery polymer can be ea~ily converted to fine particles and dispersed, there can be obtained a high impact styrene resin in which the grafted rubbery polymer particles having an average particle diameter of 0.5 to 6 micrometer~, preferably 0.8 to 3 micrometers, are uniformly dispersed. When the dynamic in-line mixer is incorporated in the recycle line (IV), the average particle diameter of the grafted rubbery polymer particles is 0.3 to 2 micrometers, preferably 0.5 to 1.5 micrometers.
Part or a greater part of the initial-stage polymer solution obtained is recycled as stated above and associated with the starting material solution or the initial-stage polymer solution in the initial poly~eri-zation. The remainder is fed to the main polymerization line (III), and continuously polymerized usually at a react~on temperature of 130 to 170C until the poly~eri-zation conversion of the monomer component composed of the styrene monomer and the optional othee monomer usually reaches 70 to 90% by weight. The product obtained after the polymerization is pelletized after the unreacted monomers and solvent are removed under reduced pressure in, for example, a devolatilization tank to give the desired high impact ~tyrene resin.
The following Examples and Comparative Examples illustrate the present invention more specifically. In these examples, all parts and percentages are by weight.
The accompanying drawing is a diagram showing the apparatus used in the following examples ~or practic-ing the process of this invention.
~1) Content of the rubbery polymer Infrared absorptions are determined by an infrared spectrophotometer, and the intensity of the lZ93~9~
absorptions is compared with a calibration curve prepared in advance.
~2) Izod impact value Measured in accordance with JIS R-6871 ~3) Surface gloss Measured in accordance with JIS Z-8~41.
(4) Grafting ratio One gram of the refiin is added to 50 ml of a 151 (by weight) mixture of methyl ethyl ketone and acetone, and the mixture i8 vigorously shaken to dissolve and~or swell the resin. The in~oluble matter i8 then sedimented by a centrifugal separator, and by decantation, the supernatant liquid is discarded. The resulting methyl ethyl ketone/acetone-insoluble portion i8 dried at 50C under reduced pressure. It was cooled in a desic-cator, and then weighed. The grafting ratio is calcu-lated in accordance with the following equation.
Methyl ethyl ketone/ Rubbery Grafting acetone-ins_luble portion (g~ ~ polymer (q~
ratio Ru~ery polymer ~9) l5) Average particle size and its distribution of the rubbery polymer in the resin The 50~ median diameter~ of the weight average and the number average are determined by a Coulter counter tModel TA-II made by Coulter Electronics Inc.). The resulting 50~ median diameters are defined respectively as the weight average particle diameter and the number average particle diameter, and the ratio of these, as the distribution of the particle size. The ~maller the value of this ratio, the narrower the particle size distri-bution.
In this example, an apparatus of the type shown in the accompanying drawing was used. A gear pump 1 for feeding the starting material is incorporated in a start-J~Z93~
ing material feed line (I). Tubular reactors 2, 3, 4 and5 having an in~ide diameter of 1 inch and a length of 1 m ~static mixer made by Noritake Co.; including twelve N 10 type mixing elements) are connected in series in an initial polymerization line ~IIl following the starting material feed line (I). Tubular reactors 6, 7, 8 and 9 of the same structure are connected in series in a main polymerization line (III) following the initial polymeri-zation line ~II). A recycle line (IV) connects the otlet portion of the tubular reactor 5 and the inlet portion of the tubular reactor 2, and a gear pump lO is incorporated at its center. An after-treatment device comprised of, for example, a gear pump 11, a heat ex-changer 12, a devolatilization tank 13 and an extruder 14 is connected to the tubular reactor 9. In this apparatus, a circulating path is formed ranging from the outlet of the tubular reactor 5 to the tubular reactors 2, 3, 4 and 5 via the gear pump 10.
A starting material solution composed of 5 parts of polybutadiene ~Diene NF35A, Asahi Chemical Industry Co., LTD. polybutadiene content, a, 5%) and 95 parts of styrene monomer was prepared, and then continu-ously polymerized in bulk in the above apparatus under the following conditions using the polymerization lines mentioned above.
Flow rate ~Fl) of the recycle line ~IV): 25 liters/hr Plow rate ~F2) of the starting material $eed line ~ S liters/hr Recycle ratio tR-Fl/F2): 5 Reaction temperature in the recycle line:
Polymerization conversion ~b) of the monomer component at the outlet portion of the tubular reactor 5:
10%
Reaction temperature in the main polymerization line: 155C.
1~93~91 The resulting polymer solution was heated to 230C by the heat exchanger and volatile components were removed under a reduced pressure of 50 mm~g. The residue wa~ melted, kneaded and pelletized in the ex-truder to obtain a high impact styrene resin in accord-ance with this invention. The various properties of the resin were measured, and the results are shown in Table 1.
A high impact tyrne resin in accordance with this invention was prepared in the same way as in Example 1 except that the reaction temperature in the recycle line was changed to 135C, and the polymerization conversion (b) of the monomer component at the outlet portion of the tubular eeactor 5 was changed to 13%. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention wa~ prepared in the same way as in Example 1 except that a starting material solut$on composed of 10 parts of polybutadiene, 90 parts of styrene and 5 parts of ethylbenzene was used, the recycle ratio ~R) in the recycle line was changed to 5, and the polymerization conversion (b) of the monomer component was changed to 24%. The properties of the resin are shown in Table 1.
A hi~h impact styrene resin in accordance with this invention was prepared in the same way as in Example 3 except that the recycle ratio ~R) in the recycle line was changed to 8; the polymerization conversion tb) of the monomer component, to 18%S and the reaction tempera-ture, to 127C. The properties of the resin are shown in Table 1.
35 - A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 1~93~91 3 except that a starting material solution composed of 6 parts of polybutadiene (polybutadiene content, a, 6%) and 94 parts of styrene was used, and a dynamic in-line mixer (made by Greerco Company, U. S. A.; 6 turbines, clearance O.S mm) was incorporatred in series between the tubular reactors 3 and 4, and the rotating speed of the dynamic in-line mixer was set at 700 rpm. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that the recycle ratio ~R) in the recycle line was changed to 7, and the rotating speed of the dynamic in-line mixer was changed to 1500 rpm. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that a startin~ material solution composed of 12 parts of polybutadiene, 88 parts of styrene and 5 parts of ethylbenzene was used, the recycle ratio ~R) in the recycle line was changed to 8, and the rotating spced of the dynamic in-line mixer was changed to 1800 rpm. The properties of the resin are shown in Table 1.
-EXAMPL~ 8 A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that the recycle ratio (R) in the recycle line was changed to 8 and the reaction temperature waæ changed to 127C 80 that the polymerization conversion ~b) of the monomer component became 18%. The properties of the re~in are shown in Table 1.
CO~PARATIVE EXAMPL~ 1 Polymerization reac~ion was carried out in a continuous reaction apparatus comprised of two 20-liter 1~93~91 tank reactors of the complete mixing type equipped with helical stiering vanes, a heat-exchanger and a volatili-zation tank. The same starting material solution as used in Example 1 was fed continuously into a first tank reactor at a rate of 5 liters/hour with stirring, an polymerized in the initital stage at 130C. The initial-stage polymer solution was continuously withdrawn from the bottom of the reactors at a rate of 5 liters/hour, and fed into a second tank reactor and polymerized there at 155C. The polymeriztion product was worked up as in Example 1 to give a high impact styrene re6in for comparison. The propertles of the resin are shown in Table 1.
A high impact srtyrene resin for comparison was prepared in the same way as in Example 1 except that the initial polymerization was carried out using the first tank reactor used in Comparative Example 1 instead of the recycle line. The properties of the resin are shown in Table 1.
1~ 91 1~ N O N -- N -- N
'~7 ~ ~ ~ tl~
__ _ . O _ ~7 _ ~ _~ ~`i ~O __ ,~ o _1 a~ u7 c~ o~
_~ ~ O ~ U~
_ . . _ .. _ ~o o. ô~ o ~ o. a~
oq _ . .
~ U) -~ O O ~
o--a~ o -- o~
_ ~1 _1 ~ _1 .
~ ~ 3 ~ ~ ~ ~ ~
_ .
. N ~ _ N ~`
_l O. ~ _~ O U~ U~
u-- ô & ~ ~ N = -- U ~
u 1~ ~a. ~0 .0 v~ o~
~ ~v O u N U
This invention relates to a process for produc-ing a high impact styrene resin by continuous bulk poly-merization, and to a high impact styrene resin obtained by this process. More specifically, it relates to a process for producing by continuous bulk polymerization a hi~h impact styrene resin havinq excellent strength in which a grafted rubbery polymer in the resin has a narrow particle size distribution, and to a high impact styrene resin obtained by this process.
In the production of a high impact styrene resin by graft polymerizing a styrene monomer in the presence of a rubbery polymer, how to control the dis-persion of the rubbery polymer uniformly as fine parti-cles and the stabilization of the rubbery polymer parti-cles during the graft polymerization is especially im-portant in determining the quality of the resulting resin. The particle size and particle size distribution of the grafted rubbery polymer particles di~persed in the final resin, and the grafting ratio of styrene greatly affect the impact strength and gloss of the final resin.
For the industrial production o~ high impact styrene re~in, a batchwi~e bulk-suspension polymerization method and a continuous bulk polymerization method have generally been employed. The continuous method, however, has been found to be superior in productivity and economy, and has gained widespread acceptance.
Usually, in the continuous bulk polymerization method, it is general practice to provide a plurality of stirred tank reactors and to perform polymerization while continuously feeding a starting material solution.
More specifically, there was proposed a nethod in which in an initial poly~erization step, the rubbery polymer is divided into fine particles and dispersed by dynamic mixing in a stirred tank reactor with a stirrer, 3~
lZ~3~ 91 and thereafter, the polymer solution is continuously transferred to a plurality of stirred tank reactors, and the polymerization is allowed to proceed with stirring.
It has been pointed out however that the con-tinuous bulk polymerization using the tank reactors hasthe defects atteibuted to the dynamic mixinq by the stirrer. Specifically, when the viscosity of the polymer solution in the tank rise~ as the polymerization proceeds, the power or the strength of the stirring vanes has to be increased. To avoid it~ the polymerization conversion of the styrene monomer in the tank must be inhibited as the polymerization proceed~. Alternatively, if exce~sive stirring and mixing is carried out, an excessive shearing force is exerted on the rubbery polymer dispersed as fine particles. Consequently, the dispersed fine particles of the rubbery polymer are broken, and the particle size distribution of the rubbery polymer particle becomes broad. As a result, the strength of the final product decreases. Another defect is that since the stirred tank reactor has an excessive capacity because of its struc-ture, a long period of time is required, for example, in switching from one brand to another in the production of resins in which the rubbery polymer has different particle diameters. In an attempt to remove these defects of the stirred tank reactor, there have been made some sugges-tions including the structure of stirring vanes, the performance of pre-polymerization, or the combination of it with a tubular reactor or a column-type reactor. But these suggestions have not proved to be sufficient for removing the above defects.
In view of the above state of the art, the present inventors made investigations on a continuous process for producing a high impact styrene resin in a tubular reactor having static mixing means such as a static mixer therein without using the stirred tank reactor.
1~33~ 91 On the utilization of a tubular reactor in a continuous polymerization, U. S. Patent 4,275,177 pro-poses a process which u8e8 a tank reactor having a stirrer for carrying out an initial-stage polymerization and a tubular reactor having static mixing means therein for carrying out main polymerization. In this process, however, the defects attributed to the dynamic mixing by the stirrer within the tank cannot be removed, and an excessively high shear owing to the intense stirring and mixing i8 exerted to broaden the particle size distri-bution of the rubbery polymer particles. The grafting rat~o of styrene is not increased, and the results are still unsatisfactory.
The present inventors then made investigations on a method of finely dividing the rubbery polymer and dispersing it as fine particles by performing polymeri-zation in a tubular reactor having static mixing means therein. Thi8 investigation has revealed the following fact. For the rubbery polymer to be finely divided and dispersed as fine particles, appropriate shearing is required in the early stage of polymerization. For this purpose, the presence of a mixer is essential. The degree of mixing by the static mixing means such as a static mixer within the tubular reactor is determined by the linear speed of the polymer solution in the reactor.
Since it depends upon the flow rate and the tubular diameter, it i~ necessary to increase the flow rate greatly in order to perform sufficient mixing. However, there is a limit to the increasing of the flow rate in the tubular reactor because as the polymerization pro-ceeds the viscosity of the polymer solution increase~
markedly and the pressure drop in the tube increases.
Consequently, sufficient shear cannot be obtained. In an ordinary tubular reactor, this weak shear leads to a failure to obtain a desirable particle size in the rubbery polymer although the rubbery polymer can be dispersed as ~Z~3~9J.
fine particles. A further problem is tbat the rubbery polymer precipitated in the early stage of the pol~meri-zation adheres to the wall of the reactor. If the ad-hering rubbery polymer grows and gets into the high impact styrene resin, it becomes a fish eye in the final product.
Further investigations of the present inventor~
made in view of the above situation have now led to the discovery that when continuous bulk polymerization of a styrene monomer in the presence of a rubbery polymer is carried out in a tubular reactor having static mixing means such as a static mixer therein and part or a greater part of the resulting initial-~taqe polymer solution is recycled and allowed to join a flow of the feed material solution, the rubbery polymer in the feed material solution and the initial-stage polymer solution are easily divided into fine particles and uniformly dis-persed, the grafting ratio is increased, and a high impact styrene resin can be easily obtained which has excellent strength and in which the grafted rubbery polymer has a narrow particle size distribu~ion.
Thus, according to this invention, there i8 provided a process for producing a high impact styrene resin which compri~es continuously polymerizing a styrene monomer in bulk in the presence of a rubberY polymer, wherein a polymerization line is used which i8 com-prised of an initial polymerization line lII) consisting of at least one tubular reactor having an inlet following the outlet of a starting material feed line (I) and static mixing means therein, a main polymerization line lIII) consisting of at lea~t one tubular reactor having an inlet following the outlet of the initial polymeri-zation line lII) and static mixing means, and a recycle line ~IV) which branches on the way in a passage ranging from the outlet of the initial polymerization line to the ~3(:~9i inlet of the main polymerization line (III) and returns to the f ront of at least one tubular reactor in the initial polymerization line ~II); and part or a greater part of a flow of the initial-stage polymer solution leaving the cutlet of the initial polymerization line tII) is eecycled via the recycle line tIV) to allow it to join a flow of a starting material solution fed from the starting material feed line ~I) or the flow of the initial polymerization solu-tion being in the process of initial polymerization andthe initial polymerization is further allowed to proceed in the initial polymerization line (II), and in the meantime, the initial polymerization solution not recycled through the recycle line i8 polymerized in the main polymerization line (III).
Typical examples of the rubbery polymee uæed in this invention include polybutadiene rubber, styrene/
butadiene copolymer rubber, styrene/butadiene/styrene block copolymer rubber, ethylene/propylene terpolymer rubber, butadiene/acrylonitrile copolymer rubber, butyl rubber, acrylic rubber, styrene/isobutylene/butadiene copolymer rubber, and isopeene/acrylic ester copolymer rubbers. They may be used either singly or in combi-nation.
The styrene monomer used in this invention generically denotes styrene, alpha-methyl6tyrene, and styrene derivatives resulting from substitution of a halogen atom or a Cl-C4 alkyl group for a hydrogen atom on the benzene ring. Typical examples are styrene, o-chlorostyrene, p-chlorostyrene, p-methylstyrene, 2,4-dimethylstyrene and t-butylstyrene.
In the present invention, another monomer copolymerizable with the styrene monomer ~to be referred to a~ the ~other monomer~3 may be used in combination with the styrene monomer. Examples of the other monomer are acrylonitrile, acrylic acid, alkyl acrylates, l2s3a-si methacrylic acid, alkyl methacrylates, maleic anhydride and various maleimides.
A suitable amount of a solvent may be used to adjust the viscosity of tbe polymer sQlution in the bulk polymerization in accordance with this invention. The solvent may, for example, be toluene, ethylbenzene or xylene. The amount of the solvent used i8 usually not more than 20 parts by weight per 100 parts by weight of the resin component composed of the rubbery polymer and the styrene monomer and other monomer.
If desired, a known organic peroxide which releases free radicals on decomposition, such as benzoyl peroxide, di-t-butyl peroxide or dicumyl peroxide, may be included as a polymerization initiator into the ~tarting material solution used in this invention. If further required, known additives such as a pla~ticizer, an antioxidant and a chain transfer agent may be incorpo rated.
The tubular reactor used in this invention may be any known tubular reactor having static mixing means therein. Tubular reactors having static mixing means composed of a number of mixing elements, such as a Sulzer-type st~tic mixer, a Kenix-type static mixer, a Toray-type static mixer, are preferred.
Tubular reactors may be incorporated in the initial polymerization line ~II) and the main polymeri-zation line (III) and if required, further in the recycle line ~IV).
The total of the number of tubular reactors in the initial polymerization line ~II) and the number of tubular reactors in the main polymerization line (III) i~
not particularly limited because, for example, in the case of a static mixer of the type exemplified above, it differs depending upon the length, the structure and number of mixing elements, etc. Usually, 4 to 15 ~preferably 6 to 10) static mixers each having at least 5 ~93~91 (preferably 10 to 40) mixing elements are used in combi-nation. The number of static mixers to be incorporated in the initial polymerization line (II) and optionally the recycle line (IV) is 1 to 10, preferably 2 to 6.
In the present invention, it is preferred to set up an in-line mixer having dynamic mixing mea~s in any desired site in a circulating line ~to be referred to as the circulating line) formed of the initial polymeri-zation line ~II) and the recycle line ~IV), preferably in the initial polymerization line ~II) after the association of the recycle line ~IV), bacause the rubbery polymer can be divided finely and dispersed as fine particles within a ~hort period of time and a high impact styrene resin having particularly excellent gloss can be obtained. The dynamic in-line mixer is preferably a dynamic piping mixer comprised of a tubular housing portion, dynamic mixing means for forcibly performing stirring within the hou~ing portion such as propeller-type, turbine-type or anchor-type stirring vanes, and a shaft portion support-ing the mixing means. The clearance between the innerwall of the houfiing and the stirring vanes is usually 0.1 to 2 mm, preferably 0.2 to 1 mm.
Preferred examples of the dynamic in-line mixer are a 6pecial anchor-type mixer made by Satake Chemical Industry Co., Ltd., an angle-type mixer made by Chemineer Company, a pipeline mixer made by Greerco Company, and a kneader-type mixer made by Kurimoto Tekkosho Co., Ltd.
The starting material solution to be fed from the starting material feed line (I) comprises the rubbery polymer and the styrene monomer, and optionally another monomer, a solvent, a polymerization initiator and other known additives.
The proportion of the rubbery polymer used i6 preferably 3 to 15% by weight based on the total weight of the rubbery polymer, the styrene monomer and the other optional monomer because the rise of the viscosity of the ~93~1 polymer solution in the circulating line is little, the particle size can be easily controlled, and a high impact styrene resin having excellent impact strength can be obtained.
The starting material solution fed from the material feed line ~I) is continuously associated and mixed with the initial-stage polymer solution circulating in the recycle line ~IV) and i~ polymerized in a tubular reactor in the initial polymerization line ~II) usually at a reaction temperature of 110 to 140C to precipitate a grafted rubbery polymer. Since the precipitated grafted rubbery polymer i8 suitably mixed and dispersed by the tubular reactor as soon as it is precipitated, its con-version to fine particles and uniform dispersion are effect~vely promoted.
When a tubular reactor is provided in the recycle line ~IV), the initial-stage polymer solution circulating under a suitable ~hearing force and a fresh supply of the starting material solution are very effec-tively mixed.
The recycle ratio (R) of the polymer solutionis usually R~Fl/F2~1 - 20 wherein Fl is the flow rate (liters/hr) of the initial-stage polymer solution flowing in the recycle line (IV), and F2 is the flow rate ~liters/hour) of the initial-stage polymer solution which flows into the main polymerization line ~III) without being recycled or the starting material solution in the starting material feed line (I). Preferably, R is from l.S to 10 because at an R in this range, the recycling 3~ can be carried out stably, no polymer deposit occurs in the reactor wall, and fine particles of the rubbery polymer having a narrow particle ~ize distribution can be obtained.
The extent of the initial polymerization is such that the polymerization conversion (_, ~ by weight) of the monomer component comprising the styrene monomer ~ ~ 3 ~9 ~
and the optional other monomer and the content ~a, % by weight) of the rubbery polymer are usually in the follow-ing relation: b=0.9a to 5a, preferably b=1.5a to 3a.
Since within this range, the rubbery polymer can be ea~ily converted to fine particles and dispersed, there can be obtained a high impact styrene resin in which the grafted rubbery polymer particles having an average particle diameter of 0.5 to 6 micrometer~, preferably 0.8 to 3 micrometers, are uniformly dispersed. When the dynamic in-line mixer is incorporated in the recycle line (IV), the average particle diameter of the grafted rubbery polymer particles is 0.3 to 2 micrometers, preferably 0.5 to 1.5 micrometers.
Part or a greater part of the initial-stage polymer solution obtained is recycled as stated above and associated with the starting material solution or the initial-stage polymer solution in the initial poly~eri-zation. The remainder is fed to the main polymerization line (III), and continuously polymerized usually at a react~on temperature of 130 to 170C until the poly~eri-zation conversion of the monomer component composed of the styrene monomer and the optional othee monomer usually reaches 70 to 90% by weight. The product obtained after the polymerization is pelletized after the unreacted monomers and solvent are removed under reduced pressure in, for example, a devolatilization tank to give the desired high impact ~tyrene resin.
The following Examples and Comparative Examples illustrate the present invention more specifically. In these examples, all parts and percentages are by weight.
The accompanying drawing is a diagram showing the apparatus used in the following examples ~or practic-ing the process of this invention.
~1) Content of the rubbery polymer Infrared absorptions are determined by an infrared spectrophotometer, and the intensity of the lZ93~9~
absorptions is compared with a calibration curve prepared in advance.
~2) Izod impact value Measured in accordance with JIS R-6871 ~3) Surface gloss Measured in accordance with JIS Z-8~41.
(4) Grafting ratio One gram of the refiin is added to 50 ml of a 151 (by weight) mixture of methyl ethyl ketone and acetone, and the mixture i8 vigorously shaken to dissolve and~or swell the resin. The in~oluble matter i8 then sedimented by a centrifugal separator, and by decantation, the supernatant liquid is discarded. The resulting methyl ethyl ketone/acetone-insoluble portion i8 dried at 50C under reduced pressure. It was cooled in a desic-cator, and then weighed. The grafting ratio is calcu-lated in accordance with the following equation.
Methyl ethyl ketone/ Rubbery Grafting acetone-ins_luble portion (g~ ~ polymer (q~
ratio Ru~ery polymer ~9) l5) Average particle size and its distribution of the rubbery polymer in the resin The 50~ median diameter~ of the weight average and the number average are determined by a Coulter counter tModel TA-II made by Coulter Electronics Inc.). The resulting 50~ median diameters are defined respectively as the weight average particle diameter and the number average particle diameter, and the ratio of these, as the distribution of the particle size. The ~maller the value of this ratio, the narrower the particle size distri-bution.
In this example, an apparatus of the type shown in the accompanying drawing was used. A gear pump 1 for feeding the starting material is incorporated in a start-J~Z93~
ing material feed line (I). Tubular reactors 2, 3, 4 and5 having an in~ide diameter of 1 inch and a length of 1 m ~static mixer made by Noritake Co.; including twelve N 10 type mixing elements) are connected in series in an initial polymerization line ~IIl following the starting material feed line (I). Tubular reactors 6, 7, 8 and 9 of the same structure are connected in series in a main polymerization line (III) following the initial polymeri-zation line ~II). A recycle line (IV) connects the otlet portion of the tubular reactor 5 and the inlet portion of the tubular reactor 2, and a gear pump lO is incorporated at its center. An after-treatment device comprised of, for example, a gear pump 11, a heat ex-changer 12, a devolatilization tank 13 and an extruder 14 is connected to the tubular reactor 9. In this apparatus, a circulating path is formed ranging from the outlet of the tubular reactor 5 to the tubular reactors 2, 3, 4 and 5 via the gear pump 10.
A starting material solution composed of 5 parts of polybutadiene ~Diene NF35A, Asahi Chemical Industry Co., LTD. polybutadiene content, a, 5%) and 95 parts of styrene monomer was prepared, and then continu-ously polymerized in bulk in the above apparatus under the following conditions using the polymerization lines mentioned above.
Flow rate ~Fl) of the recycle line ~IV): 25 liters/hr Plow rate ~F2) of the starting material $eed line ~ S liters/hr Recycle ratio tR-Fl/F2): 5 Reaction temperature in the recycle line:
Polymerization conversion ~b) of the monomer component at the outlet portion of the tubular reactor 5:
10%
Reaction temperature in the main polymerization line: 155C.
1~93~91 The resulting polymer solution was heated to 230C by the heat exchanger and volatile components were removed under a reduced pressure of 50 mm~g. The residue wa~ melted, kneaded and pelletized in the ex-truder to obtain a high impact styrene resin in accord-ance with this invention. The various properties of the resin were measured, and the results are shown in Table 1.
A high impact tyrne resin in accordance with this invention was prepared in the same way as in Example 1 except that the reaction temperature in the recycle line was changed to 135C, and the polymerization conversion (b) of the monomer component at the outlet portion of the tubular eeactor 5 was changed to 13%. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention wa~ prepared in the same way as in Example 1 except that a starting material solut$on composed of 10 parts of polybutadiene, 90 parts of styrene and 5 parts of ethylbenzene was used, the recycle ratio ~R) in the recycle line was changed to 5, and the polymerization conversion (b) of the monomer component was changed to 24%. The properties of the resin are shown in Table 1.
A hi~h impact styrene resin in accordance with this invention was prepared in the same way as in Example 3 except that the recycle ratio ~R) in the recycle line was changed to 8; the polymerization conversion tb) of the monomer component, to 18%S and the reaction tempera-ture, to 127C. The properties of the resin are shown in Table 1.
35 - A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 1~93~91 3 except that a starting material solution composed of 6 parts of polybutadiene (polybutadiene content, a, 6%) and 94 parts of styrene was used, and a dynamic in-line mixer (made by Greerco Company, U. S. A.; 6 turbines, clearance O.S mm) was incorporatred in series between the tubular reactors 3 and 4, and the rotating speed of the dynamic in-line mixer was set at 700 rpm. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that the recycle ratio ~R) in the recycle line was changed to 7, and the rotating speed of the dynamic in-line mixer was changed to 1500 rpm. The properties of the resin are shown in Table 1.
A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that a startin~ material solution composed of 12 parts of polybutadiene, 88 parts of styrene and 5 parts of ethylbenzene was used, the recycle ratio ~R) in the recycle line was changed to 8, and the rotating spced of the dynamic in-line mixer was changed to 1800 rpm. The properties of the resin are shown in Table 1.
-EXAMPL~ 8 A high impact styrene resin in accordance with this invention was prepared in the same way as in Example 5 except that the recycle ratio (R) in the recycle line was changed to 8 and the reaction temperature waæ changed to 127C 80 that the polymerization conversion ~b) of the monomer component became 18%. The properties of the re~in are shown in Table 1.
CO~PARATIVE EXAMPL~ 1 Polymerization reac~ion was carried out in a continuous reaction apparatus comprised of two 20-liter 1~93~91 tank reactors of the complete mixing type equipped with helical stiering vanes, a heat-exchanger and a volatili-zation tank. The same starting material solution as used in Example 1 was fed continuously into a first tank reactor at a rate of 5 liters/hour with stirring, an polymerized in the initital stage at 130C. The initial-stage polymer solution was continuously withdrawn from the bottom of the reactors at a rate of 5 liters/hour, and fed into a second tank reactor and polymerized there at 155C. The polymeriztion product was worked up as in Example 1 to give a high impact styrene re6in for comparison. The propertles of the resin are shown in Table 1.
A high impact srtyrene resin for comparison was prepared in the same way as in Example 1 except that the initial polymerization was carried out using the first tank reactor used in Comparative Example 1 instead of the recycle line. The properties of the resin are shown in Table 1.
1~ 91 1~ N O N -- N -- N
'~7 ~ ~ ~ tl~
__ _ . O _ ~7 _ ~ _~ ~`i ~O __ ,~ o _1 a~ u7 c~ o~
_~ ~ O ~ U~
_ . . _ .. _ ~o o. ô~ o ~ o. a~
oq _ . .
~ U) -~ O O ~
o--a~ o -- o~
_ ~1 _1 ~ _1 .
~ ~ 3 ~ ~ ~ ~ ~
_ .
. N ~ _ N ~`
_l O. ~ _~ O U~ U~
u-- ô & ~ ~ N = -- U ~
u 1~ ~a. ~0 .0 v~ o~
~ ~v O u N U
Claims (20)
1. A process for producing a high impact styrene resin which comprises continuously polymerizing a styrene monomer in bulk in the presence of a rubbery polymer, wherein a polymerization link is used which is comprised of an initial polymerization line (II) consisting of at least one tubular reactor having an inlet following the outlet of a starting material feed line [I] and static mixing means therein, a main polymerization line (III) consisting of at least one tubular reactor having an inlet following the outlet of the initial polymerization line (II) and static mixing means, and a recycle line (IV) which branches on the way in a passage ranging from the outlet of the initial polymerization line to the inlet of the main polymerization line (III) and returns to the front of at least one tubular reactor in the initial polymerization line (II); and part or a greater part of a flow of the initial-stage polymer solution leaving the outlet of the initial polymerization line (II) is recycled via the recycle line (IV) to allow it to join a flow of a starting material solution fed from the starting material feed line (I) or the flow of the initial polymerization solution being in the process of initial polymerization and the initial polymerization is further allowed to proceed in the initial polymerization line (II), and in the meantime, the initial polymerization solution not recycled through the recycle line is polymerized in the main polymeriza-tion line (III).
2. The process of claim 1 wherein a dynamic in-line mixer is incorporated in a circulating line formed of the recycle line (IV) and the initial polymerization line (II).
3. The process of claim 2 wherein the dynamic in-line mixer is incorporated in the initial polymeriza-tion line (II).
4. The process of claim 1 or 2 wherein the ratio of the flow rate of the initial-stage polymer solution recycled via the recycle line (IV) to the flow rate of the starting material solution fed from the starting material line (I) is from 1 to 20.
5. The process of claim 1 or 2 wherein the ratio of the flow rate of the initial-stage polymer solution recycled via the recycle line (IV) to the flow rate of the starting material solution fed from the starting material feed line (I) is from 1.5 to 10.
6. The process of claim 1 or 2 wherein the initial polymerization in the initial polymerization line (II) is carried out until a polymerization conversion represented by the formula b=0.9a to 5a, wherein a is the content (% by weight) of the rubbery polymer based on the total weight of the rubbery polymer, the styrene monomer and the other optional monomer, and b is the poly-merization conversion (% by weight), is obtained.
7. The process of claim 1 or 2 wherein the initial polymerization in the initial polymerization line (II) is carried out until a polymerization conversion represented by the formula b=1.5a to 3a, wherein a is the content (% by weight) of the rubbery polymer based on the total weight of the rubbery polymer, the styrene monomer and the other optional monomer, and b is the poly-merization conversion (% by weight), is obtained.
8. The process of claim 1 or 2 wherein the total of the number of tubular reactors in the initial polymer-ization line (II) and the number of tubular reactors in the main polymerization line (III) is from 4 to 15.
9. The process of claim 1 wherein the total of the number of tubular reactors in the initial polymerization line (III) and the number of tubular reactors in the main polymerization line (III) is from 6 to 10.
10. The process of claim 1, 2 or 9 wherein the number of tubular reactors in the initial polymerization line (II) is from 2 to 6.
11. The process of claim 1 or 2 wherein the polymer-ization in the main polymerization line (III) is carried out until the polymerization component of the monomer component reaches 70 to 90 % by weight.
12. A high impact styrene resin obtained by the process of claim 1.
13. A high impact styrene resin obtained by the process of claim 2.
14. A high impact styrene resin obtained by the process of claim 5.
15. A high impact styrene resin obtained by the process of claim 7.
16. A high impact styrene resin obtained by the process of claim 9.
17. The resin of claim 12 which contains dispersed therein grafted rubbery polymer particles having an average particle diameter of 0.5 to 6 micrometers.
18. The resin of claim 12 which contains dispersed therein grafted rubbery polymer particles having an average particle diameter of 0.8 to 3 micrometers.
19. The resin of claim 13 which contains dispersed therein grafted rubbery polymer particles having an average particle diameter of 0.3 to 2 micrometers.
20. The resin of claim 13 which contains dispersed therein grafted rubbery polymer particles having an average particle diameter of 0.5 to 1,5 micrometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000542813A CA1293091C (en) | 1987-07-23 | 1987-07-23 | Process for producing high impact styrene resin by continuous bulk polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000542813A CA1293091C (en) | 1987-07-23 | 1987-07-23 | Process for producing high impact styrene resin by continuous bulk polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1293091C true CA1293091C (en) | 1991-12-10 |
Family
ID=4136130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000542813A Expired - Lifetime CA1293091C (en) | 1987-07-23 | 1987-07-23 | Process for producing high impact styrene resin by continuous bulk polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1293091C (en) |
-
1987
- 1987-07-23 CA CA000542813A patent/CA1293091C/en not_active Expired - Lifetime
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