WO2017095099A1 - Procédé de fabrication de résine san thermorésistante - Google Patents

Procédé de fabrication de résine san thermorésistante Download PDF

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Publication number
WO2017095099A1
WO2017095099A1 PCT/KR2016/013824 KR2016013824W WO2017095099A1 WO 2017095099 A1 WO2017095099 A1 WO 2017095099A1 KR 2016013824 W KR2016013824 W KR 2016013824W WO 2017095099 A1 WO2017095099 A1 WO 2017095099A1
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Prior art keywords
weight
heat
parts
san resin
resistant san
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PCT/KR2016/013824
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English (en)
Korean (ko)
Inventor
채주병
정유성
김종범
김창술
김영민
박은선
전태영
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(주) 엘지화학
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Priority claimed from KR1020160159007A external-priority patent/KR101957666B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to US15/560,897 priority Critical patent/US10266627B2/en
Priority to CN201680022599.6A priority patent/CN107531843B/zh
Priority to EP16870995.4A priority patent/EP3260478B1/fr
Priority to JP2017549612A priority patent/JP6481047B2/ja
Publication of WO2017095099A1 publication Critical patent/WO2017095099A1/fr

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    • 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
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles

Definitions

  • the present disclosure relates to a method for manufacturing a heat resistant SAN resin, and more particularly, to a method for preparing a heat resistant SAN resin having excellent productivity and improved heat resistance and fluidity without generating adverse smell during processing, and a heat resistant SAN resin composition prepared therefrom. It is about.
  • ABS resin acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin
  • a method of preparing by emulsion polymerization by replacing part or all of styrene with ⁇ -methylstyrene is commonly used.
  • Heat-resistant SAN resin is a resin manufactured on the basis of ⁇ -methylstyrene, and has a high glass transition temperature and high molecular weight compared to bulk polymerization, and thus has excellent heat resistance and environmental stress crack resistance (ESCR).
  • ESCR environmental stress crack resistance
  • the glass transition temperature is the most important factor for determining the heat resistance characteristics of the heat-resisting resin.
  • the method of increasing the ⁇ -methylstyrene content or increasing the molecular weight is used in the case of increasing the ⁇ -methylstyrene content. Because of its low reactivity, the proportion of unreacted monomers increases, which leads to a decrease in heat resistance. In addition, a separate device for removing unreacted monomers is required, thereby increasing the cost of the product and lowering productivity. This has the disadvantage of being longer and having a lower conversion rate.
  • the molecular weight is mainly used as a molecular weight regulator.
  • the mercaptans to be used produce a bad smell during processing.
  • Korean Patent Laid-Open Publication No. 199-0021665 discloses a method for preparing a copolymer of ⁇ -alkylstyrene-acrylonitrile by emulsion polymerization in the preparation of a heat resistant SAN copolymer, but this manufacturing method In this case, the polymerization time is longer than 9 hours, there is a disadvantage that the copolymer productivity is lowered.
  • Korean Patent Laid-Open Publication No. 1996-0031486 discloses a method for adding an electrolyte when preparing a heat-resistant SAN copolymer having a high content of latex solids and excellent stability by emulsion polymerization, but also has a polymerization time of 6 hours. There was a disadvantage in that it takes a long time and the copolymer productivity is lowered.
  • the present invention provides a method for producing a heat-resistant SAN resin with excellent productivity and improved heat resistance and fluidity without adverse smell during processing and a heat-resistant SAN resin composition prepared therefrom
  • a heat-resistant SAN resin composition prepared therefrom For the purpose of
  • the present invention is a method for producing a heat-resistant SAN resin by polymerizing the ⁇ -methylstyrene monomer and vinyl cyan monomer, (i) the entire amount of the ⁇ - methyl styrene monomer and part of the vinyl cyan monomer A first polymerization step of polymerizing in the presence of an oxidation-reduction catalyst and a hydroperoxide-based initiator, wherein the polymerization is carried out at the same time as the start of the polymerization or after another part of the vinyl cyan monomer is continuously added after the start of the polymerization; (ii) a second polymerization step in which the oxidation-reduction catalyst and the hydroperoxide-based initiator are polymerized at the time when the polymerization conversion rate reaches 25 to 40% in the first polymerization step; And (iii) a third polymerization step in which the remaining amount of the vinyl cyan monomer and the pyrolysis initiator are polymerized at the time point
  • the present invention also provides a heat resistant SAN resin composition prepared from the method for producing a heat resistant SAN resin.
  • the method for producing a heat-resistant SAN resin of the present disclosure is a method for producing a heat-resistant SAN resin by polymerizing an ⁇ -methylstyrene monomer and a vinyl cyan monomer, wherein (i) the entire amount of the ⁇ -methyl styrene monomer and a part of the vinyl cyan monomer are oxidized.
  • the heat-resistant SAN resin is excellent in productivity while improving the heat resistance and fluidity without generating a bad smell during processing.
  • the method for producing a heat-resistant SAN resin of the present invention is a method for producing a heat-resistant SAN resin by polymerizing the ⁇ -methylstyrene monomer and vinyl cyan monomer, (i) the entire amount of the ⁇ -methylstyrene monomer and the vinyl cyan 20 to 65% by weight of 100% by weight of the monomer is polymerized in the presence of an oxidation-reduction catalyst and a hydroperoxide-based initiator, and 30 to 80% by weight of 100% by weight of the vinyl cyan monomer at the same time as the polymerization start or after the polymerization is started.
  • a first polymerization step of polymerizing while continuously adding 30% or 79% by weight (ii) a second polymerization step in which the oxidation-reduction catalyst and the hydroperoxide-based initiator are polymerized at the time when the polymerization conversion rate reaches 25 to 40% in the first polymerization step; And (iii) polymerization at a time point when the polymerization conversion ratio reaches 80 to 90% in the second polymerization step, by adding 0 to 25 wt% or 1 to 25 wt% of the remaining 100 wt% of the vinyl cyan monomer and a pyrolysis initiator. It is characterized in that it comprises a; the third polymerization step to be made, there is an effect of producing a heat-resistant SAN resin having excellent productivity within this range and does not generate a bad smell during processing and improved both heat resistance and fluidity.
  • the method for producing a heat-resistant SAN resin of the present invention is a method for producing a heat-resistant SAN resin by polymerizing the ⁇ -methylstyrene monomer and vinyl cyan monomer, (i) the entire amount of the ⁇ -methylstyrene monomer and the vinyl cyan 30 to 60% by weight or 33 to 40% by weight in 100% by weight of the monomer is polymerized in the presence of an oxidation-reduction catalyst and a hydroperoxide-based initiator, and at the same time as the polymerization start or after the polymerization start, 100 weight of the vinylcyan monomer A first polymerization step of polymerizing while continuously adding 30 to 60 wt% or 50 to 56 wt% in%; (ii) a second polymerization step in which the oxidation-reduction catalyst and the hydroperoxide-based initiator are polymerized at the time when the polymerization conversion rate reaches 25 to 40% in the first polymerization step; And (iii) polymerization of the
  • the vinyl cyan monomer continuously added in step (i) is, for example, 30 minutes to 5 hours, 1 hour to 4 hours, 2 hours to 3.5 hours, or 2 hours to 3 hours after the initiator is added or after the start of polymerization. It can be continuously injected, there is an effect that the heat-resistant SAN resin is excellent in productivity and improved in both heat resistance and fluidity without generating a bad smell during processing within this range.
  • the vinyl cyan monomer continuously added in step (i) may reach 20 to 90%, 40 to 90%, 60 to 90% or 70 to 88% of the polymerization conversion rate after the initiator is added or after the polymerization is started. Until the continuous injection, there is an effect that the heat-resistant SAN resin is excellent in productivity and improved in both heat resistance and fluidity without generating a bad smell during processing within this range.
  • 'after the start of the polymerization' or 'after the initiator is added' means a time interval such that a person skilled in the art can immediately input the start of the polymerization, and, for example, a time point of 1 second to 10 minutes after the start of the polymerization, Or 10 seconds to 5 minutes, or more than 0% to 5% or less, or more than 0% to 3%.
  • Continuous dosing in the present disclosure is not particularly limited in the case of continuous dosing that is commonly recognized in the art, and for example, materials to be added or drop-by-drop while being continuously connected to each other for a predetermined time. ), It may mean that the droplets are continuously injected for a predetermined time at short intervals.
  • the production method of the heat-resistant SAN resin is, for example, based on a total of 100 parts by weight of ⁇ -methylstyrene monomer and vinyl cyan monomer, (i) 65 to 75 parts by weight of the ⁇ -methylstyrene, 5 to 15 parts by weight of vinyl cyan monomer, molecular weight 0.01 to 0.3 parts by weight of the regulator, 0.01 to 1.0 parts by weight of the redox catalyst, 0.001 to 0.2 parts by weight of the hydroperoxide initiator, and 1.5 to 2.0 parts by weight of the emulsifier are added and polymerized at the same time, or simultaneously with the start of the polymerization or the start of the polymerization.
  • the redox catalyst may be added at 0.01 to 1.0 part by weight, 0.03 to 0.5 part by weight, or 0.05 to 0.3 part by weight together with the hydroperoxide-based initiator, and at a low temperature within this range. Even if the polymerization is shortened the polymerization reaction time has the effect of generating a high molecular weight.
  • the redox catalyst that can be used may be at least one selected from the group consisting of ferrous sulfate, dextrose, sodium pyrophosphate, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediaminetetraacetate. .
  • the heat resistant SAN resin means a copolymer resin of ⁇ -methylstyrene monomer-vinyl cyan compound.
  • the vinyl cyan monomer may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
  • the vinyl cyan monomer to be collectively introduced into the (i) first polymerization step may be 5 to 15 parts by weight, or 7 to 13 parts by weight, and the initial reaction rate is appropriate in this range to facilitate molecular weight control, and polymerization. As the reaction time is shortened, the glass transition temperature is increased.
  • the vinyl cyan monomer to be collectively introduced into the (i) first polymerization step as an example may have a weight ratio of ⁇ -methylstyrene monomer of 0.05 to 0.15, or 0.1 to 0.13, while the polymerization reaction time is shortened within this range There is an effect of increasing the glass transition temperature.
  • the redox catalyst may be at least one selected from the group consisting of ferrous sulfate, dextrose, sodium pyrophosphate, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate.
  • the oxidation-reduction catalyst added in the first polymerization step (i) may be, for example, 0.01 to 1.0 parts by weight, 0.03 to 0.5 parts by weight, or 0.05 to 0.3 parts by weight, and polymerization is carried out at low temperature within this range. As the reaction time is shortened, high molecular weight is produced.
  • redox catalyst (i) introduced in the first polymerization step examples include dextrose, sodium pyrolate, and ferrous sulfate; Or sodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and ferrous sulfate; and polymerization at low temperatures within this range has an effect of shortening the polymerization reaction time and producing a high molecular weight.
  • the oxidation-reduction catalyst added in the second polymerization step (ii) may be, for example, 0.01 to 1.0 parts by weight, 0.03 to 0.5 parts by weight, or 0.05 to 0.3 parts by weight, and polymerization is carried out at low temperature within this range. As the reaction time is shortened, high molecular weight is produced.
  • the oxidation-reduction catalyst introduced in the second polymerization step (ii) includes, for example, dextrose, sodium pyrrolate, and ferrous sulfate; Or sodium ethylenediaminetetraacetate, sodium formaldehyde sulfoxylate, and ferrous sulfate; and polymerization at low temperatures within this range has an effect of shortening the polymerization reaction time and producing a high molecular weight.
  • the hydroperoxide-based initiator may be at least one selected from the group consisting of, for example, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tertiary butylhydroperoxide.
  • the (i) hydroperoxide-based initiator to be added in the first polymerization step may be 0.001 to 0.2 parts by weight, 0.005 to 0.15 parts by weight, or 0.01 to 0.1 parts by weight, the polymerization conversion rate is increased within this range It works.
  • the hydroperoxide-based initiator added in the second polymerization step (ii) may be, for example, 0.01 to 2 parts by weight, 0.01 to 1 parts by weight, or 0.02 to 0.5 parts by weight, and the polymerization conversion rate is increased within this range. It works.
  • the pyrolysis initiator may be at least one selected from the group consisting of, for example, potassium persulfate, ammonium persulfate, sodium persulfate, and potassium persulfate.
  • the pyrolysis initiator may be included only in the (iii) tertiary polymerization step, for example, and may be 0.01 to 0.3 parts by weight, 0.05 to 0.25 parts by weight, or 0.1 to 0.2 parts by weight, and finally within this range. There is an effect of increasing the polymerization conversion rate.
  • the molecular weight modifier may be at least one selected from the group consisting of n-dodecyl mercaptan, tertiary dodecyl mercaptan, n-tetradecyl mercaptan and tertiary tetradecyl mercaptan.
  • the molecular weight modifier that is introduced into the first polymerization step in a batch may be 0.001 to 0.3 parts by weight, 0.1 to 0.25 parts by weight, or 0.1 to 0.2 parts by weight, within this range does not occur inverse odor during processing It has an excellent flowability effect without.
  • the molecular weight regulator included in the emulsion in the first polymerization step may be, for example, 0 to 0.2 parts by weight, 0.01 to 0.2 parts by weight, or 0.1 to 0.2 parts by weight within this range does not cause inverse odor during processing It has an excellent flowability effect without.
  • the molecular weight regulator included in the emulsion in the (i) the first polymerization step may not include a molecular weight regulator, there is an effect that the reverse odor does not occur during processing within this range.
  • Vinyl cyan included in the emulsion in the (i) the first polymerization step may be 10 to 18 parts by weight or 11 to 15, for example, the initial reaction rate is appropriate within this range is easy to control the molecular weight, polymerization reaction As the time is shortened, the glass transition temperature is increased.
  • the emulsifier may be, for example, an anionic emulsifier or a neutral polymer emulsifier having an allyl group, a (meth) acryloyl group, or a propenyl group.
  • the emulsion continuously added from the first polymerization step may be added to the point of reaching a polymerization conversion rate of 25 to 90%, 30 to 90%, 50 to 90%, or 80 to 90%, for example, within this range, polymerization stability is improved and a high molecular weight heat resistant SAN resin is produced.
  • the emulsion is continuously added from the first polymerization step is 1 to 20 parts by weight, hr, 2 to 16 parts by weight, or based on the total weight of the vinyl cyan monomer, emulsifier and molecular weight regulator included in the emulsion It can be added at 3 to 5 parts by weight / hr, the polymerization stability is improved within this range and there is an effect that a high molecular weight heat-resistant SAN resin is produced.
  • the batch injection in (i) the first polymerization step may be carried out at 45 to 55 ° C., for example, and polymerization is efficiently performed even at a low temperature within this range, thereby improving production efficiency.
  • the emulsion may be continuously added, for example, while maintaining ⁇ T (set temperature—exothermic temperature) at less than 4 ° C. at 60 to 70 ° C.
  • the polymerization is carried out at a reaction temperature, that is, a set temperature of 75 to 85 ° C., but the present invention provides a glass transition while the polymerization time is shortened even if the polymerization is performed at a lower temperature, that is, a set temperature of 65 to 75 ° C. There is an effect of increasing the temperature.
  • the ⁇ T (set temperature-exothermic temperature) may be, for example, less than 4 ° C., or less than 2 ° C., and polymerization stability is improved and a high molecular weight heat-resistant SAN resin is produced within this range.
  • the second polymerization step (ii) can be polymerized at, for example, the reaction temperature of 65 to 75 °C, there is an effect of improving the polymerization stability within this range.
  • the (ii) second polymerization may be, for example, a polymerization conversion rate of 25 to 40% or 30 to 35%, and there is an excellent balance of polymerization rate and molecular weight increase within this range.
  • the (iii) tertiary polymerization may be, for example, a polymerization conversion rate of 80 to 90%, or 85 to 90%, and the glass transition temperature is increased within this range, thereby improving heat resistance.
  • the water (i) used for batch feeding in the first polymerization step may be, for example, 100 to 500 parts by weight, 100 to 300 parts by weight, or 130 to 250 parts by weight based on 100 parts by weight of the total monomers.
  • the water included in the emulsion in the first polymerization step (i) may be 50 to 300 parts by weight, 50 to 200 parts by weight, 70 to 150 parts by weight, or 80 to 120 parts by weight based on 100 parts by weight of the total monomer, for example. have.
  • the reaction may be terminated at a polymerization conversion rate of 97% or more, or 97 to 99%.
  • After the third polymerization step (iii) may include a step of agglomeration by adding 1 to 3 parts by weight of a coagulant.
  • An example of a drying step after the aggregation; Or drying and aging step; may further include.
  • the drying may be carried out by, for example, a hot air fluidized bed dryer.
  • the drying step; Or drying and aging step; after the completion of the heat-resistant SAN resin may be prepared as a powder of moisture content of 1% by weight or less.
  • the heat resistant SAN resin may have, for example, a weight average molecular weight of 60,000 to 150,000 g / mol, 70,000 to 130,000, or 80,000 to 120,000 g / mol, and within this range, the glass transition temperature and the heat deformation temperature are increased.
  • the heat-resistant SAN resin may have a glass transition temperature of 140 ° C. or higher, or 140 to 150 ° C., and has excellent heat resistance within this range.
  • the heat-resistant SAN resin is, for example, the sum of the vinyl cyanated monomer-vinyl cyanated monomer- ⁇ -methylstyrene copolymer and the vinyl cyanated monomer-vinyl cyanated monomer-vinyl cyanated monomer copolymer, analyzed by NMR, in an amount of 10% by weight or less and 8% by weight. It may be 1 to 7% by weight or less, and has excellent heat resistance within this range.
  • the heat-resistant SAN resin composition of the present disclosure includes, for example, 20 to 30 parts by weight of the heat-resistant SAN resin and 70 to 80 parts by weight of the vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer resin prepared by the method for producing a heat-resistant SAN resin. can do.
  • the conjugated diene compound is, for example, one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be abnormal.
  • the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, ⁇ -methylstyrene, o-ethylstyrene, p-ethylstyrene, and vinyltoluene.
  • the heat resistant SAN resin composition may include, for example, antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, surfactants, coupling agents, plasticizers, admixtures, colorants, stabilizers, lubricants, antistatic agents, colorants, flame retardants, weather agents, ultraviolet absorbers, and the like. It may further comprise one or more selected from the group consisting of sunscreen.
  • ⁇ T set temperature-exothermic temperature
  • an emulsion comprising 100 parts by weight of ion-exchanged water, 15 parts by weight of acrylonitrile and 1.0 parts by weight of potassium stearate was added through a continuous method for 1.0 hour. Then, additional polymerization was carried out while the temperature was raised to 70 ° C. for 2.5 hours (continuous emulsion input).
  • Example 1 except that 75 parts by weight of ⁇ -methylstyrene and 9 parts by weight of acrylonitrile were added at the start of the polymerization, and the emulsion was made of 13 parts by weight of acrylonitrile in a continuous feeding step in the same manner as in Example 1 above. Was carried out.
  • Example 1 73 parts by weight of ⁇ -methylstyrene and 15 parts by weight of acrylonitrile were added in a batch at the start of polymerization, and 9 parts by weight of acrylonitrile was added thereto, and the emulsion was continuously added for 1 hour in ⁇ T ( Except that the set temperature-exothermic temperature) was not adjusted to less than 4 °C was carried out in the same manner as in Example 1.
  • Example 1 except that the initial polymerization temperature was set at 70 ° C. except that potassium persulfate, which is a pyrolysis initiator other than a hydroperoxide-based initiator, was used as the polymerization initiator and the polymerization reaction time was 1 hour. It carried out by the same method as 1.
  • Comparative Example 1 the same procedure as in Comparative Example 1 was carried out except that tertiary mercaptan, which was a molecular weight regulator, was used at 0.6 part by weight.
  • Polymerization Conversion Rate (%) [ ⁇ (Added Monomer And Subsidiary Parts By Weight) * Total Solid Content (%)-(Extra Monopart Added By Weight Monomer) ⁇ / (Total Monomer Input)] * 100
  • Triad content (% by weight): Bruker AVANCE HD III 700MHz NMR instrument was used and the sample was dissolved in CDCl3 (w / TMS) and the NMR spectrum was measured at room temperature. The measured value was obtained by calibrating TMS to 0 ppm and calculating triad sequence distribution based on the integral value of peaks in the range of 150 to 140 ppm and 125 to 118 ppm, and the vinyl cyanated monomer-vinyl cyanated monomer- ⁇ -methylstyrene copolymer. And the content of vinyl cyanated monomer-vinyl cyanated monomer-vinyl cyanated monomer copolymer.
  • Odor during processing The odor generated during extrusion and injection was evaluated by sensory evaluation, and if the odor did not occur, it was evaluated as good.
  • Fluidity (g / 10min) Measured for 10 minutes at 220 °C, 10Kg load in accordance with ASTM D1238.
  • Examples 1 and 2 according to the present invention did not generate inverse odor during processing, a polymer having a weight average molecular weight of 100,000 g / mol or more was produced, and also a triad content is low glass transition The temperature and the heat deformation temperature were increased, and the heat resistance was excellent, but the fluidity was also good.
  • Comparative Examples 1 and 2 which did not use an oxidation-reduction catalyst, had a very large decrease in the glass transition temperature and the heat deformation temperature, and a sharp increase in the triad content.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerization Catalysts (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une résine SAN thermorésistante, et a pour effet de fournir : un procédé de fabrication d'une résine SAN thermorésistante, qui a une excellente productivité, n'émet pas de mauvaises odeurs pendant la fabrication, et améliore la résistance thermique et la fluidité. La présente invention concerne en outre une résine SAN thermorésistante fabriquée par le procédé.
PCT/KR2016/013824 2015-12-04 2016-11-29 Procédé de fabrication de résine san thermorésistante WO2017095099A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/560,897 US10266627B2 (en) 2015-12-04 2016-11-29 Method of preparing heat-resistant SAN resin
CN201680022599.6A CN107531843B (zh) 2015-12-04 2016-11-29 耐热san树脂的制备方法
EP16870995.4A EP3260478B1 (fr) 2015-12-04 2016-11-29 Procédé de fabrication de résine san thermorésistante
JP2017549612A JP6481047B2 (ja) 2015-12-04 2016-11-29 耐熱ｓａｎ樹脂の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0172718 2015-12-04
KR20150172718 2015-12-04
KR1020160159007A KR101957666B1 (ko) 2015-12-04 2016-11-28 내열 san 수지의 제조방법
KR10-2016-0159007 2016-11-28

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Citations (6)

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Publication number Priority date Publication date Assignee Title
KR100236773B1 (ko) * 1997-03-12 2000-01-15 성재갑 방향족 비닐 화합물-비닐 시안화 화합물 공중합체 수지의 제조방법
KR20020048605A (ko) * 2000-12-18 2002-06-24 안복현 열가소성 니트릴계 공중합체 및 그 제조방법
KR100417061B1 (ko) * 2000-12-13 2004-02-05 주식회사 엘지화학 내열성 공중합체의 제조방법
KR20150004249A (ko) * 2013-07-02 2015-01-12 주식회사 엘지화학 내열 san 수지, 이의 제조방법 및 이를 포함하는 내열 abs 수지 조성물
KR20150037460A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 내열성이 우수한 열가소성 수지의 제조방법
KR20150037459A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 내열성 san 공중합체의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100236773B1 (ko) * 1997-03-12 2000-01-15 성재갑 방향족 비닐 화합물-비닐 시안화 화합물 공중합체 수지의 제조방법
KR100417061B1 (ko) * 2000-12-13 2004-02-05 주식회사 엘지화학 내열성 공중합체의 제조방법
KR20020048605A (ko) * 2000-12-18 2002-06-24 안복현 열가소성 니트릴계 공중합체 및 그 제조방법
KR20150004249A (ko) * 2013-07-02 2015-01-12 주식회사 엘지화학 내열 san 수지, 이의 제조방법 및 이를 포함하는 내열 abs 수지 조성물
KR20150037460A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 내열성이 우수한 열가소성 수지의 제조방법
KR20150037459A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 내열성 san 공중합체의 제조방법

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