CN114163576A - Preparation process of bulk matte high-flow ABS resin - Google Patents

Preparation process of bulk matte high-flow ABS resin Download PDF

Info

Publication number
CN114163576A
CN114163576A CN202111418138.XA CN202111418138A CN114163576A CN 114163576 A CN114163576 A CN 114163576A CN 202111418138 A CN202111418138 A CN 202111418138A CN 114163576 A CN114163576 A CN 114163576A
Authority
CN
China
Prior art keywords
reactor
rubber
abs resin
flow
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111418138.XA
Other languages
Chinese (zh)
Inventor
魏丽娟
李永华
张东梅
邵维彧
唐明
肖大君
韩丽君
武天希
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North Huajin Chemical Industries Co Ltd
Original Assignee
North Huajin Chemical Industries Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North Huajin Chemical Industries Co Ltd filed Critical North Huajin Chemical Industries Co Ltd
Priority to CN202111418138.XA priority Critical patent/CN114163576A/en
Publication of CN114163576A publication Critical patent/CN114163576A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

Abstract

The invention belongs to the field of preparation of high polymer materials, and particularly relates to a preparation process of matte high-flow ABS resin. Mixing and dissolving the cut rubber, the solvent, the acrylonitrile and the styrene sol in a kettle until the raw rubber solution is uniform and has no rubber block; the dissolved crude rubber solution, the initiator, the chain transfer agent and the silicone oil are sent to four plug flow reactors connected in series by a conveying device to carry out continuous bulk polymerization reaction; the dosage of the chain transfer agent is 8-10% of the dosage of the raw glue solution, and the stirring speed of the second plug flow reactor is 80-100 rpm; and (3) devolatilizing, extruding and granulating the polymerized material to prepare the matte high-flow ABS resin. The melt index of the ABS resin prepared by the invention is 25-40g/10min, the glossiness is 70-80, and the average particle size of rubber is 0.7 mu m.

Description

Preparation process of bulk matte high-flow ABS resin
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a preparation process of matte high-flow ABS resin.
Background
With the development trend of light weight of automobiles and the universality of application of ABS resin on automobile interior parts, the automobile industry puts higher requirements on the extinction performance and the flow performance of the ABS resin.
Often, incompatible polymers or fillers are added to reduce the surface gloss of ABS articles. For example, SEBS, nitrile rubber (CN1128776A), gelled SAN (CN102108176, US5580924), three-dimensional lattice-structured alkyl (meth) acrylate (CN101724129) and other incompatible polymers are added into the ABS system. The addition of inorganic fillers such as silicates, aluminates, silica and the like also reduces the surface gloss of the resin. However, the above solutions all have certain drawbacks. When the matte effect is achieved by adding an incompatible material, the physical and mechanical properties of the final material are seriously deteriorated, and the mechanical property requirement is high, and when the gelled resin is used as a flatting agent, the product surface is too rough and the glossiness is not uniform because the gelled resin is partially crosslinked.
The gloss of ABS resin is mainly determined by the particle size of butadiene rubber, and the larger the particle size of rubber, the lower the gloss. The rubber particle size of the emulsion polymerization ABS resin is usually within 0.5 μm, so the surface gloss is high, while the rubber particle size of the bulk polymerization ABS resin is usually more than 0.6 μm, so the surface gloss is low. According to the invention, the process conditions are adjusted, the high-viscosity rubber is used for preparing the bulk ABS resin containing the large-particle-size rubber through a bulk polymerization process, and the process formula is adjusted to ensure the high fluidity and excellent mechanical properties of the product, so that the matte high-fluidity ABS resin is prepared.
Disclosure of Invention
The invention provides a preparation method for preparing matte high-flow ABS resin aiming at the characteristics and market demands of the conventional ABS resin, and the material has the characteristics of high flow and low gloss, and is particularly suitable for the field of automobiles.
In order to realize the purpose of the invention, the invention provides a preparation process of bulk-method matte high-flow ABS resin, which comprises the following steps:
(1) mixing and dissolving the cut rubber, the solvent, the acrylonitrile and the styrene sol in a kettle until the raw rubber solution is uniform and has no rubber block;
the rubber is high-viscosity rubber, the Mooney viscosity is 55-60, and preferably one or more of 565T, 97B, 30AF or 700A; the rubber content in the raw rubber solution is 8% -10% of the raw rubber solution;
(2) the dissolved crude rubber solution, the initiator, the chain transfer agent and the silicone oil are sent to four plug flow reactors connected in series by a conveying device to carry out continuous bulk polymerization reaction; the dosage of the chain transfer agent is 8-10% of the dosage of the raw glue solution, and the stirring speed of the second plug flow reactor is 80-100 rpm;
(3) and (3) devolatilizing, extruding and granulating the polymerized material to prepare the matte high-flow ABS resin.
And (3) respectively supplementing acrylonitrile after the second reactor and the third reactor in the step (2), wherein the supplementing amount is 1-2% of the total amount of the reaction liquid.
In the step (2), the polymerization temperature of the first reactor is 80-100 ℃, the polymerization temperature of the second reactor is 95-112 ℃, the polymerization temperature of the third reactor is 115-135 ℃, and the polymerization temperature of the fourth reactor is 135-150 ℃.
The prepared ABS resin has a melt index of 25-40g/10min, a glossiness of 70-80 and an average rubber particle size of 0.7 μm.
The invention has the beneficial effects that:
(1) the high-viscosity rubber is selected in the process formula, the rubber particle size in the prepared bulk ABS resin is larger, and the glossiness of the product is effectively reduced;
(2) the rubber content in the process formula is reduced, so that the fluidity of the product is not influenced while the high-viscosity rubber is used;
(3) the dosage of the chain transfer agent in the process formula is increased, the viscosity of a reaction system can be diluted, and the fluidity of a product is guaranteed;
(4) the stirring speed of the second reactor is reduced to 80-100rpm, so that the viscosity of the rubber phase is increased during phase transition, the viscosity difference between the rubber phase and the matrix resin phase is increased, the formation of large-particle-size rubber particles is facilitated, and the glossiness of a product is reduced;
(5) a small amount of acrylonitrile is supplemented in the second reactor and the third reactor, so that the content of free styrene in reaction liquid is reduced, and the glossiness of the product is further reduced;
(6) the temperature of the fourth reactor is reduced, the crosslinking degree is reduced, the matte property of the product is further ensured, and meanwhile, the reaction liquid viscosity can be reduced by reducing the reaction temperature, and the product fluidity is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1
15kg of 565T g of rubber, 110kg of styrene and 18kg of ethylbenzene were added to the compounding tank, and the mixture was dissolved at room temperature with stirring for 12 hours, and then 18kg of acrylonitrile was added and dispersed with stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.07kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
Example 2
15kg of 97B rubber, 110kg of styrene and 18kg of ethylbenzene mixture were added to the compounding tank, and stirred and dissolved for 12 hours at normal temperature, and then 18kg of acrylonitrile was added and stirred and dispersed for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.07kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
Example 3
13kg of 565T g of rubber, 110kg of styrene and 18kg of ethylbenzene were added to the compounding tank, and the mixture was dissolved at room temperature with stirring for 12 hours, and then 18kg of acrylonitrile was added and dispersed with stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.07kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
Example 4
15kg of 565T g of rubber, 110kg of styrene and 18kg of ethylbenzene were added to the compounding tank, and the mixture was dissolved at room temperature with stirring for 12 hours, and then 18kg of acrylonitrile was added and dispersed with stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.42kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.07kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 136 ℃, 148 ℃ and 135 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
Example 5
15kg of 565T g of rubber, 110kg of styrene and 18kg of ethylbenzene were added to the compounding tank, and the mixture was dissolved at room temperature with stirring for 12 hours, and then 18kg of acrylonitrile was added and dispersed with stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.065kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.08kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
Example 6
15kg of 565T g of rubber, 110kg of styrene and 18kg of ethylbenzene were added to the compounding tank, and the mixture was dissolved at room temperature with stirring for 12 hours, and then 18kg of acrylonitrile was added and dispersed with stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 120 ℃, 124 ℃ and 132 ℃, and 0.07kg/h of acrylonitrile is supplemented after the third reactor;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the matte high-flow ABS resin.
The performance of the test products was analyzed using the corresponding astm d standard as shown in table 1.
TABLE 1 analytical results of examples 1 to 6
Figure BDA0003376375210000071
The ABS resin products of the above examples had a melt index measured according to ASTM D1228, a tensile strength measured according to ASTM d638, an impact strength measured according to ASTM D256, a flexural strength measured according to ASTM D790, and a gloss measured according to GB 8807-88.
The analysis results of comparative examples 1 and 2 show that 565T rubber with high viscosity has lower glossiness; comparing the analysis results of examples 1 and 3, it can be seen that the flow property of the product can be ensured by reducing the rubber content; the comparative results of examples 1 and 4 show that increasing the amount of chain transfer agent in the process recipe and decreasing the fourth reactor temperature can increase the product flowability; comparative results of examples 1 and 5 show that product gloss can be reduced by increasing the amount of acrylonitrile make-up in the second and third reactors; comparing the results of the analyses of examples 1 and 6, it can be seen that increasing the stirring speed of the second reactor is not advantageous for reducing the gloss of the product.
In conclusion, the ABS resin prepared by the method has low gloss, high fluidity and excellent other mechanical properties.

Claims (4)

1. A preparation process of a bulk matte high-flow ABS resin is characterized by comprising the following steps:
(1) mixing and dissolving the cut rubber, the solvent, the acrylonitrile and the styrene sol in a kettle until the raw rubber solution is uniform and has no rubber block;
the rubber is high-viscosity rubber, the Mooney viscosity is 55-60, and specifically is one or more of 565T, 97B, 30AF or 700A; the rubber content in the raw rubber solution is 8% -10% of the raw rubber solution;
(2) the dissolved crude rubber solution, the initiator, the chain transfer agent and the silicone oil are sent to four plug flow reactors connected in series by a conveying device to carry out continuous bulk polymerization reaction; the dosage of the chain transfer agent is 8-10% of the dosage of the raw glue solution, and the stirring speed of the second plug flow reactor is 80-100 rpm;
(3) and (3) devolatilizing, extruding and granulating the polymerized material to prepare the matte high-flow ABS resin.
2. The process for preparing the bulk matte high-flow ABS resin according to claim 1, wherein in the step (2), acrylonitrile is supplemented after the second reactor and the third reactor respectively, and the addition amount is 1-2% of the total amount of the reaction solution.
3. The process for preparing the bulk matte high-flow ABS resin according to claim 1, wherein the polymerization temperature of the first reactor in the step (2) is 80-100 ℃, the polymerization temperature of the second reactor is 95-112 ℃, the polymerization temperature of the third reactor is 115-135 ℃, and the polymerization temperature of the fourth reactor is 135-150 ℃.
4. The process for preparing the bulk matte high-flow ABS resin according to claim 1, wherein the prepared ABS resin has a melt index of 25-40g/10min, a gloss of 70-80 and a rubber average particle size of 0.7 μm.
CN202111418138.XA 2021-11-26 2021-11-26 Preparation process of bulk matte high-flow ABS resin Pending CN114163576A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111418138.XA CN114163576A (en) 2021-11-26 2021-11-26 Preparation process of bulk matte high-flow ABS resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111418138.XA CN114163576A (en) 2021-11-26 2021-11-26 Preparation process of bulk matte high-flow ABS resin

Publications (1)

Publication Number Publication Date
CN114163576A true CN114163576A (en) 2022-03-11

Family

ID=80480987

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111418138.XA Pending CN114163576A (en) 2021-11-26 2021-11-26 Preparation process of bulk matte high-flow ABS resin

Country Status (1)

Country Link
CN (1) CN114163576A (en)

Similar Documents

Publication Publication Date Title
US4009226A (en) Abs moulding compositions
JP6364490B2 (en) High heat resistant ABS resin composition suitable for blow molding and method for preparing the same
CN107298827B (en) Low-gloss heat-resistant ABS resin and preparation method thereof
CA1221786A (en) Continuous process for producing rubber modified high- impact resins
CN111499813B (en) Method for preparing high-flow AES resin by adopting continuous bulk method
CN111378073A (en) Process method for preparing high-fluidity low-gloss ABS resin by continuous bulk method
CN110452472A (en) Expandable polystyrene particle and preparation method
WO2022095363A1 (en) Polycarbonate alloy composition, preparation method therefor and application thereof
CN114163576A (en) Preparation process of bulk matte high-flow ABS resin
CN101050299B (en) Method for preparing alloy between ABS polymer and polycarbonate based on continuous substance law
EP2358773B1 (en) Rubber-reinforced vinyl aromatic (co)polymer, having an optimum balance of physico-mechanical properties and a high gloss
CN110240778A (en) A kind of preparation method of ontology ABS resin
JPS6351460B2 (en)
JPH02115206A (en) Graft polymer suitable for preparation of transparent thermoplastic molding composition
CN108659367B (en) Composition for transparent washing machine cover and preparation method
WO2022095362A1 (en) Pcabs composition, preparation method therefor, and application thereof
CN102099381A (en) Low chloride polybutadiene
EP1447417B1 (en) TRANSPARENT RUBBER−MODIFIED COPOLYMER RESIN AND RESIN COMPOSITION CONTAINING THE SAME
US4426499A (en) Process for the production of graft polymers
JP3978272B2 (en) Damping thermoplastic resin composition
CN108659155B (en) Low-cost cladding agent for core-shell structure resin and preparation method and application thereof
JP3236056B2 (en) Method for producing rubber-modified styrenic resin
CN113980190A (en) Preparation process of anti-impact bulk ABS resin
EP3676302A1 (en) Process for the preparation of low haze and color stable styrenic polymers
KR20000055268A (en) Styrenic thermoplastic composition with good low temperature impact resistance

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination