WO2019151776A1 - Procédé de préparation de copolymère greffé, copolymère greffé et article moulé en résine thermoplastique - Google Patents

Procédé de préparation de copolymère greffé, copolymère greffé et article moulé en résine thermoplastique Download PDF

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WO2019151776A1
WO2019151776A1 PCT/KR2019/001304 KR2019001304W WO2019151776A1 WO 2019151776 A1 WO2019151776 A1 WO 2019151776A1 KR 2019001304 W KR2019001304 W KR 2019001304W WO 2019151776 A1 WO2019151776 A1 WO 2019151776A1
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weight
parts
graft copolymer
conjugated diene
polymer
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PCT/KR2019/001304
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English (en)
Korean (ko)
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김종범
채주병
정유성
김창술
박은선
전태영
김영민
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주식회사 엘지화학
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Priority claimed from KR1020190011180A external-priority patent/KR102111120B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19747015.6A priority Critical patent/EP3613783B1/fr
Priority to CN201980002501.4A priority patent/CN110662780B/zh
Priority to US16/631,812 priority patent/US11104789B2/en
Publication of WO2019151776A1 publication Critical patent/WO2019151776A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/065—Increasing the size of dispersed rubber particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/02—Alkylation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08F2500/24—Polymer with special particle form or size

Definitions

  • the present invention relates to a graft copolymer manufacturing method, a graft copolymer and a thermoplastic resin molded article, and more particularly to a graft copolymer capable of producing a molded article with improved surface properties and improved plating and coating properties. It is to provide a production method, graft copolymer and a thermoplastic resin molded article.
  • a method of controlling the content of acrylonitrile may be used to improve plating properties.
  • a method of improving the graft ratio or including a high gel content butadiene rubbery polymer is also used.
  • the method of introducing the small particle size butadiene rubbery polymer with a small average particle diameter during a graft reaction can also be used.
  • the method of using the small particle butadiene rubbery polymer can improve the adhesion to the plating, the increase of the content of the small particle butadiene rubbery polymer reduces the impact strength of the graft copolymer, and the graft ratio is lowered to reduce the fluidity. May occur.
  • the present invention includes the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, wherein the first conjugated diene polymer Distribution is 0.346 to 0.404, the second conjugated diene-based polymer provides a method for producing a graft copolymer having a particle size distribution of 0.196 to 0.304.
  • the present invention also provides a graft copolymer prepared by the above-described production method, having a graft ratio of at least 37%, and having a weight average molecular weight of the shell of at least 75,000 g / mol.
  • the present invention is a graft copolymer described above; And a copolymer comprising an aromatic vinyl monomer-derived unit and a vinyl cyan monomer-derived unit, and a thermoplastic resin molded article having a residual amount of volatile organic compound of 1,000 ppm or less.
  • the manufacturing method of the graft copolymer of the present invention it is possible to produce a molded article having excellent surface properties and improved plating and coating properties.
  • the manufacturing method of the graft copolymer of the present invention it is possible to produce a molded article excellent in both fluidity and mechanical properties, and minimized the residual amount of volatile organic compounds.
  • FIG. 1 is a graph showing a particle size distribution of a large particle butadiene rubbery polymer of Preparation Example 3.
  • Figure 2 is a graph showing the particle size distribution of the large particle butadiene rubber polymer of Preparation Example 8.
  • the average particle diameter and particle size distribution of the particles of the conjugated diene-based polymer may be measured using dynamic light scattering, and in detail, may be measured using a Nicomp 380 device (product name, manufacturer: PSS). Can be.
  • Average particle diameter or "Dv” as used in this specification means the arithmetic mean particle diameter in particle size distribution measured by the dynamic light scattering method.
  • the arithmetic mean particle size may be an intensity distribution mean particle size.
  • 90% particle size means the particle size (D 90 ) at the 90% position when the particle size is measured from 0 (minimum) to 100% (maximum) in order from the smaller one in the particle size distribution measured by the above measuring method. .
  • 50% particle size means the particle size (D 50 ) in which the larger and smaller ones become equivalent when the powder is divided into two from the particle size in the particle size distribution measured by the above measuring method.
  • “10% particle size” means the particle size (D 10 ) at the 10% position when the particle size distribution measured by the above-mentioned method is taken from 0 (minimum) to 100% (maximum) in order from the smaller one of the particle size. .
  • the measurement method by the dynamic light scattering method and the calculation method of the particle size distribution can be measured by a method well known in the art, and the particle size distribution in the present invention can also be calculated by the following equation (1).
  • Particle size distribution (PSD) [D 90 -D 10 ] / D 50
  • D 90 , D 50 and D 10 are as described above.
  • the gel content of the conjugated diene-based polymer latex coagulated with methanol washed, dried in a vacuum oven at 60 °C for 24 hours, and then obtained by cutting the lump (sample) obtained by scissors and then taking 1 g Toluene was added to 100 g of toluene and stored in a dark room at room temperature for 48 hours, and then separated into sol and gel.
  • the gel content can be measured by the following formula.
  • the graft rate is 2 g of the graft copolymer powder into 300 ml of acetone and stirred for 24 hours, the solution is added to an ultracentrifuge, the supernatant is separated, and the supernatant is dropped into methanol to be grafted. The unoccupied portion was obtained and dried at 85 ° C. to obtain a dried product. After the weight was measured, the graft ratio can be calculated by the following equation.
  • the weight average molecular weight of the shell of the graft copolymer is dried in a hot air oven at 50 °C of the supernatant obtained in the graft rate measuring method, the dried product in THF to prepare a solution (concentration: 0.1% by weight), It can be hung through a 0.1 ⁇ m filter and finally measured using a GPC.
  • the residual amount of volatile organic compounds can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • the polymerization may be any one selected from the group consisting of suspension polymerization, emulsion polymerization and bulk polymerization, of which emulsion polymerization is preferred.
  • the aromatic vinyl monomer derived unit may be a unit derived from an aromatic vinyl monomer.
  • the aromatic vinyl monomer may be at least one selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which styrene is preferred.
  • the vinyl cyan-based monomer-derived unit may be a unit derived from the vinyl cyan-based monomer.
  • the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, of which acrylonitrile is preferable.
  • the conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, and 1,3-butadiene is preferable.
  • Method for producing a graft copolymer comprises the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, the first The conjugated diene polymer has a particle size distribution of 0.346 to 0.404, and the second conjugated diene polymer has a particle size distribution of 0.196 to 0.304.
  • the first conjugated diene-based polymer has a particle size distribution of 0.346 to 0.404, preferably 0.35 to 0.4. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer is minimized.
  • a graft copolymer that implements excellent surface properties and impact strength may be prepared. If the particle size distribution is less than the above-mentioned range, the impact strength is lowered. If the particle size distribution exceeds the above-mentioned range, excessive surface projections occur.
  • the first conjugated diene polymer has an average particle diameter of 0.2 to 0.4 ⁇ m, 0.25 to 0.35 ⁇ m, or 0.3 to 0.33 ⁇ m, of which 0.3 to 0.33 ⁇ m is preferable. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer can be minimized, and the impact strength and fluidity can be improved.
  • Particles included in the first conjugated diene-based polymer may have a standard deviation of 0.3 to 0.4 or 0.33 to 0.38, of which 0.33 to 0.38 are preferred. If the above conditions are satisfied, the first conjugated diene-based polymer includes particles having relatively various particle diameters, thereby making it possible to prepare a graft copolymer having excellent surface properties and impact strength.
  • the second conjugated diene-based polymer has a particle size distribution of 0.196 to 0.304, preferably 0.2 to 0.3. If the above conditions are satisfied, the graft copolymer can realize excellent impact strength and tensile strength. If the above range is not satisfied, the impact strength of the graft copolymer may decrease.
  • the second conjugated diene-based polymer has an average particle diameter of 0.2 to 0.4 ⁇ m, 0.25 to 0.35 ⁇ m, or 0.28 to 0.30 ⁇ m, of which 0.28 to 0.30 ⁇ m is preferable. If the above range is satisfied, the mechanical properties and fluidity of the graft copolymer may be further improved.
  • Particles included in the second conjugated diene-based polymer may have a standard deviation of 0.2 to 0.29 or 0.24 to 0.26, of which 0.24 to 0.26 is preferable.
  • the second conjugated diene-based polymer includes particles having a uniform particle size, thereby preparing a graft copolymer having excellent impact strength.
  • the first conjugated diene-based polymer and the second conjugated diene-based polymer are each prepared by 1) a method of polymerizing a conjugated diene monomer without performing an enlargement or 2) a small particle conjugated diene system by polymerizing a conjugated diene monomer After the polymer is prepared, the small particle conjugated diene polymer may be prepared by enlarging the polymer.
  • the average particle diameter of the small particle conjugated diene-based polymer may be 0.05 to 0.15 ⁇ m or 0.08 to 0.12 ⁇ m, of which 0.08 to 0.12 ⁇ m is preferred. If the above conditions are satisfied, it may be easy to prepare the first and second conjugated diene-based polymers.
  • the gel content of the small particle conjugated diene-based polymer may be 90% or more, 90% to 95% or 90% to 94%, of which 92% to 94% is preferred. If the above conditions are satisfied, excellent impact strength can be realized.
  • the preparation of the first and second conjugated diene-based polymers may be carried out over one or more steps, and the enlargement may be performed by adding a flocculant to the small particle conjugated diene-based polymer.
  • the flocculant may be acetic acid or phosphoric acid.
  • the flocculant may be added in an amount of 2.75 to 3.75 parts by weight or 3 to 3.5 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer, and 3 to 3.5 parts by weight of the flocculant. It is desirable to. When the above range is satisfied, a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the first conjugated diene polymer can be prepared.
  • the weight ratio of the flocculant added at the time may be 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 is preferable.
  • the weight ratio of the flocculant added during primary and secondary enlargement is 65:35 to 80:20 or 70:30 to 75:25, of which 70:30 to 75:25 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
  • the flocculant may be added in an amount of 2 to 2.73 parts by weight or 2.5 to 2.7 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer when preparing the second conjugated diene polymer, and 2.5 to 2.7 parts by weight. It is preferable to add in a negative amount.
  • a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the second conjugated diene polymer can be produced.
  • the weight ratio of the flocculant added at the time may be 90:10 to 99: 1 or 93: 7 to 97: 3, of which 93: 7 to 97: 3 is preferable.
  • the weight ratio of the flocculant added during the primary and secondary enlargement is 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
  • the second conjugated diene-based polymer when the second conjugated diene-based polymer is prepared by the method 1), it can be prepared by a known method, in order to satisfy the above-described particle size distribution and average particle size, the content of the emulsifier or electrolyte in the known method Can be adjusted appropriately.
  • the emulsifier may be one or more selected from the group consisting of alkali rosin acid metal salts, fatty acid alkali metal salts and fatty acid dimer alkali metal salts, of which fatty acid dimer alkali metal salts are preferred.
  • the rosin acid alkali metal salt may be one or more selected from the group consisting of potassium rosin acid salt and sodium rosin acid salt, and potassium rosin acid salt is preferable.
  • the fatty acid alkali metal salt may be a C 8 to C 20 fatty acid alkali metal salt, alkali metal salt of capric acid, alkali metal salt of lauric acid, alkali metal salt of palmitic acid, alkali metal salt of stearic acid, alkali metal salt and oleic acid and linol
  • alkali metal salts of leinic acid are more preferable.
  • the fatty acid dimer alkali metal salt may be a C 8 to C 20 fatty acid dimer alkali metal salt, preferably a C 8 to C 20 fatty acid dimer potassium salt, and more preferably an oleic acid dimer potassium salt.
  • the emulsifier may be added to 0.3 to 3.0 parts by weight or 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the conjugated diene monomer, of which 0.5 to 2.5 parts by weight is preferably added.
  • the polymerization stability is excellent and the polymerization conversion rate can be increased.
  • the electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 and Na 2 HPO 4 It may be at least one selected from the group consisting of, of which at least one selected from the group consisting of K 2 CO 3 and Na 2 CO 3 is preferred.
  • the electrolyte may be added in an amount of 0.1 to 1 part by weight or 0.2 to 0.5 part by weight based on 100 parts by weight of the conjugated diene-based monomer, of which 0.2 to 0.5 part by weight is preferable.
  • the polymerization stability is excellent and the polymerization conversion rate can be increased.
  • the weight ratio of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 30:70 to 80:20, 50:50 to 80:20, 60:40 to 75:25 or 65:35 to 70:30 It may be, of which 65:35 to 70:30 is preferred.
  • the formation of protrusions on the surface may be minimized to manufacture a molded article having excellent surface characteristics, and thus, a molded article having excellent coating or plating characteristics may be manufactured.
  • the graft ratio is high, the graft copolymer with improved impact strength and fluidity can be prepared.
  • the total sum of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 50 to 50, based on the total weight of the first conjugated diene-based polymer, the second conjugated diene-based polymer, an aromatic vinyl monomer, and a vinyl cyan monomer. It may be 65% by weight or 55 to 60% by weight, preferably 55 to 60% by weight. When the above-mentioned range is satisfied, it is possible to minimize the generation of coagulum during polymerization, and the impact strength of the graft copolymer may be further improved.
  • the first conjugated diene-based polymer and the second conjugated diene-based polymer may be in the form of latex dispersed in water in a colloidal state, and may be first introduced into a reactor before the polymerization starts.
  • the total sum of the aromatic vinyl monomer and the vinyl cyan monomer may be 35 to 50 wt%, based on the total weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. 40 to 45% by weight, of which 40 to 45% by weight is preferred. If the above range is satisfied, the chemical resistance, stiffness, impact strength, processability and surface gloss of the graft copolymer may be further improved.
  • the weight ratio of the aromatic vinyl monomer and the vinyl cyan monomer may be 80:20 to 65:35 or 75:25 to 70:30, of which 75:25 to 70:30 is preferable.
  • the polymerization conversion rate is increased, and the polymerization stability and the latex stability can be further improved.
  • the aromatic vinyl monomer and the vinyl cyan monomer may be emulsion-polymerized while continuously introduced at a constant rate into a reactor in which the first and second conjugated diene polymers are present.
  • the reaction heat generated during the polymerization may be dispersed.
  • At least one selected from the group consisting of a molecular weight regulator, an initiator, an emulsifier, a redox catalyst, and water may be further added to the reactor.
  • the molecular weight modifier may include a large reactive vinyl dimer having a high reactivity, a high decomposition rate mercaptan compound and a low reactivity rate, that is, a low decomposition rate.
  • the mercaptan compound may be at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan and octyl mercaptan, and t-dodecyl mercaptan is preferred.
  • the aromatic vinyl-based dimer may be at least one selected from the group consisting of ⁇ -methyl styrene dimer, ethyl styrene dimer and propyl styrene dimer, of which ⁇ -methyl styrene dimer is preferable.
  • the molecular weight modifier may be 0.30 to 0.50 parts by weight or 0.35 to 0.45 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Of these, 0.35 to 0.45 parts by weight is preferable. If the above-mentioned range is satisfied, the weight average molecular weight of the shell can be properly maintained to further improve the impact strength of the graft copolymer.
  • the mercaptan compound and the aromatic vinyl dimer may be added in a weight ratio of 60:40 to 70:30 or 65:35 to 70:30, and of the mercaptan compounds and 65:35 to 70:30. .
  • the mercaptan compound and the aromatic vinyl-based dimer can adjust the graft ratio of the graft copolymer to increase the falling ball impact strength and the notched Izod impact strength.
  • the initiators include potassium persulfate, sodium photosulphate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramentane hydroperoxide and benzoyl per At least one selected from the group consisting of oxides, and at least one selected from the group consisting of t-butyl hydroperoxide is preferred.
  • the initiator may be added in an amount of 0.5 to 0.8 parts by weight, or 0.6 to 0.7 parts by weight based on 100 parts by weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.6 to 0.7 parts by weight. When the above range is satisfied, the latex stability is excellent and the emulsion polymerization is easily performed, while the residual amount in the graft copolymer can be minimized.
  • the emulsifier may be at least one selected from the group consisting of C 1 to C 20 mono carboxylic acid salts, C 12 to C 18 succinate metal salts, sulfonic acid metal salts and rosin acid alkali metal salts.
  • the mono carboxylate may be a C 8 to C 20 fatty acid soap.
  • the C 12 to C 18 succinate metal salt may be a C 12 to C 18 alkenyl succinate dipotassium salt.
  • the sulfonic acid metal salt may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium lauric sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate. have.
  • the rosin acid alkali metal salt may be at least one selected from the group consisting of potassium rosin salt and sodium rosin salt.
  • an alkali metal rosin salt is preferable, and potassium rosin salt is more preferable.
  • the emulsifier may be added in an amount of 0.5 to 1.2 parts by weight, or 0.8 to 1.0 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.8 to 1.0 parts by weight. If the above range is satisfied, while the emulsion polymerization is easily performed, the residual amount in the graft copolymer can be minimized.
  • the redox catalyst may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate and sodium sulfate.
  • ferrous sulfate, dextrose and sodium pyrophosphate are preferably one or more selected from the group consisting of.
  • the redox catalyst is 0.1 to 0.5 parts by weight, or 0.3 to 0.4 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyan monomer. It may be added, of which 0.3 to 0.4 parts by weight is preferably added. If the above range is satisfied, there is an advantage that the polymerization conversion rate is increased.
  • the water may be ion exchanged water.
  • At least one selected from the group consisting of the molecular weight regulator, the initiator, the emulsifier, the redox catalyst and the water is present in the reactor in which the first and second conjugated diene polymers are present together with the aromatic vinyl monomer and the vinyl cyan monomer. It can be fed continuously at a constant speed. When continuously added, the heat of reaction may be dispersed during polymerization, and thus, heat removal may be facilitated.
  • the graft copolymer prepared by the above-described manufacturing method has a graft ratio of at least 37%, and the weight average molecular weight of the shell is 75,000 g / mol or more, preferably 75,000 to 110,000 g / mol. If the above-mentioned range is satisfied, the surface characteristics may be excellent, and plating and painting characteristics may be further improved.
  • Thermoplastic resin composition according to another embodiment of the present invention is a graft copolymer prepared by the manufacturing method according to an embodiment of the present invention; And a copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit.
  • the copolymer may impart heat resistance, rigidity, and processability to the thermoplastic resin composition.
  • the copolymer may include the aromatic vinyl monomer derived unit and the vinyl cyan monomer derived unit in a weight ratio of 85:15 to 70:30 or 80:20 to 75:25, among which 80:20 to 75: It is preferable to include in the weight ratio of 25. If the above-mentioned range is satisfied, the thermoplastic resin composition can better realize the balance of heat resistance, impact strength and processability.
  • the copolymer may have a weight average molecular weight of 100,000 to 150,000 g / mol or 120,000 to 140,000 g / mol, of which 120,000 to 140,000 g / mol is preferred. When the above range is satisfied, the impact strength of the thermoplastic resin composition may be further improved.
  • the weight average molecular weight may be measured as a relative value for a standard polystyrene (PS) sample through GPC using THF (tetrahydrofuran) as an eluent.
  • PS polystyrene
  • THF tetrahydrofuran
  • the copolymer may be prepared by one or more methods selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization, and preferably, the copolymer is prepared by bulk polymerization.
  • the weight ratio of the graft copolymer and the copolymer may be 20:80 to 35:65 or 25:75 to 30:70, of which 25:75 to 30:70 is preferable. If the above range is satisfied, the chemical resistance, impact strength, thermal stability, colorability, fatigue resistance, rigidity and workability of the molded article manufactured from the thermoplastic resin composition may be further improved.
  • thermoplastic resin molded article produced from the thermoplastic resin composition described above has a residual amount of volatile organic compound of 1,000 ppm or less. If the conditions mentioned above are satisfied, the molded article excellent in odor characteristic can be provided.
  • the residual amount of the volatile organic compound can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • aqueous acetic acid solution containing 2.4 parts by weight of acetic acid (concentration: 7% by weight) was stirred at 30 ° C. at a speed of 10 rpm for 1 hour. After continuous feeding at a constant rate, the mixture was stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.6 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-1. .
  • the large particle size butadiene rubber polymer A-1 had a particle size distribution of 0.34 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-2.
  • the large particle size butadiene rubber polymer A-2 had a particle size distribution of 0.35 and an average particle diameter of 0.3 ⁇ m.
  • the large particle size butadiene rubbery polymer latex A-3 has a wide particle size distribution.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 1.05 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-4. It was.
  • the large-diameter butadiene rubbery polymer latex A-4 had a particle size distribution of 0.4 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing 0.4 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged while stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-5. It was.
  • the large particle butadiene rubber polymer latex A-5 had a particle size distribution of 0.41 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.25 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-6. It was.
  • the large particle size butadiene rubbery polymer latex A-6 had a particle size distribution of 0.19 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing 0.125 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-7. It was.
  • the large particle size butadiene rubber polymer latex A-7 had a particle size distribution of 0.2 and an average particle diameter of 0.3 ⁇ m.
  • ion-exchanged water 100 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 1.5 parts by weight of potassium rosin salt as emulsifier, 0.3 parts by weight of Na 2 CO 3 as electrolyte, t-dodecylmer as molecular weight regulator 0.03 part by weight of captan and 0.5 part by weight of potassium persulfate were added as a batch, the temperature was raised to 50 ° C, and polymerization was started. When the polymerization conversion rate was about 35%, 0.7 parts by weight of potassium rosin salt, 0.5 parts by weight of potassium persulfate and 30 parts by weight of 1,3-butadiene were collectively added as an emulsifier to carry out polymerization.
  • the large-diameter butadiene rubbery polymer latex A-8 has a narrow particle size distribution.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-9. It was.
  • the large-diameter butadiene rubbery polymer latex A-9 had a particle size distribution of 0.3 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.35 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-10. It was.
  • the large particle butadiene rubber polymer latex A-10 had a particle size distribution of 0.31 and an average particle diameter of 0.3 ⁇ m.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition ⁇ Production of the thermoplastic resin composition>
  • thermoplastic resin composition C-1 was prepared by mixing 30 parts by weight of the graft copolymer powder B-1 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • thermoplastic resin composition C-3 was prepared by mixing 30 parts by weight of the graft copolymer powder B-3 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-4 30 parts by weight of the graft copolymer powder B-4 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-4.
  • butadiene rubbery polymer latex A-3 40 parts by weight instead of 24 parts by weight (based on solids) of butadiene rubbery polymer latex Graft copolymer powder B-5 was prepared in the same manner as in Example 1 except for the addition.
  • thermoplastic resin composition C-5 was prepared by mixing 30 parts by weight of the graft copolymer powder B-5 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-6 30 parts by weight of the graft copolymer powder B-6 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-6.
  • Graft copolymer powder B-7 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-2 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-7 30 parts by weight of the graft copolymer powder B-7 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical Co., Ltd. were mixed to prepare a thermoplastic resin composition C-7.
  • Graft copolymer powder B-8 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-4 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-8 was prepared by mixing 30 parts by weight of the graft copolymer powder B-8 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-9 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-7 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-9 was prepared by mixing 30 parts by weight of the graft copolymer powder B-9 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-10 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-9 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-10 was prepared by mixing 30 parts by weight of the graft copolymer powder B-10 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-11 was prepared in the same manner as in 1.
  • thermoplastic resin composition C-11 was prepared by mixing 30 parts by weight of the graft copolymer powder B-11 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-12 was prepared in the same manner as in Example 1, except that 20 parts by weight of butadiene rubbery polymer latex A-9 (based on solids) was added instead.
  • thermoplastic resin composition C-12 was prepared by mixing 30 parts by weight of the graft copolymer powder B-12 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition was prepared by mixing 30 parts by weight of the graft copolymer powder B-13 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-14 was prepared by mixing 30 parts by weight of the graft copolymer powder B-14 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-15 was prepared by mixing 30 parts by weight of the graft copolymer powder B-15 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-16 was prepared by mixing 30 parts by weight of the graft copolymer powder B-16 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-17 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-1 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-17 30 parts by weight of the graft copolymer powder B-17 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-17.
  • Graft copolymer powder B-18 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-5 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-18 was prepared by mixing 30 parts by weight of the graft copolymer powder B-18 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-19 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-6 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-19 30 parts by weight of the graft copolymer powder B-19 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-19.
  • Graft copolymer powder B-20 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-10 was added instead of butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-20 was prepared by mixing 30 parts by weight of the graft copolymer powder B-20 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Polymerization Conversion Rate (%) [Total Solids Content (TSC) ⁇ (parts of monomers and subsidiary materials added) / 100]-(parts of subsidiary materials added to the monomer)
  • Graft rate (%) [(content of grafted SAN copolymer) / (sum of content of large particle butadiene rubbery polymer)] ⁇ 100
  • thermoplastic resin composition of the Example and the comparative example was put into the twin screw extruder set to 210 degreeC, and extruded, and the pellet was manufactured.
  • the physical properties of the pellets were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
  • Residual amount of volatile organic compounds (ppm): The residual amount of volatile organic compounds was measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • the pellet prepared in Experimental Example 1 was injected to prepare a specimen, and the physical properties thereof were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
  • the graft copolymers of Examples 1 to 12 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.35 to 0.4 and a large particle butadiene rubber polymer having a particle size distribution of 0.2 to 0.4 have a graft ratio of 37. It was confirmed that it was% or more and the weight average molecular weight of the shell was 75,000 g / mol or more.
  • the weight average molecular weight of the shell is 65,000 g / mol or less, and when the graft ratio is less than 37%, the weight average molecular weight is 75,000 g / mol or more.
  • the thermoplastic resin compositions of Examples 1 to 12 had a small amount of residual volatile organic compounds, so that the odor characteristics were excellent, and the number of surface protrusions was small, indicating that the surface characteristics were excellent. It was found that the falling ball impact strength and notched Izod impact strength were also excellent in mechanical properties.
  • Examples 1, 7 and 8 have a significantly lower residual amount of volatile organic compounds than Comparative Example 6 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.41 and a large particle butadiene rubber polymer having a particle size distribution of 0.23, and having a surface protrusion.
  • the number was remarkably small, and the fall impact strength and the notched Izod impact strength were excellent.
  • Examples 1, 9, and 10 had a significantly lower residual amount of volatile organic compounds compared to Comparative Example 8 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.37 and a large particle butadiene rubber polymer having a particle size distribution of 0.31.
  • the number of protrusions was remarkably small, and it was confirmed that the falling ball impact strength and the notched Izod impact strength were excellent.
  • Comparative Examples 1 to 4 made of only one type of large-diameter butadiene rubbery polymer, the amount of residual volatile organic compounds compared to the examples is not good because the odor characteristics are not good, and the number of surface projections is large, the surface properties are not good It could not be confirmed that falling ball impact strength and impact strength were reduced.

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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)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un copolymère greffé, un copolymère greffé et un article moulé en résine thermoplastique. Le procédé de préparation comprend une étape de polymérisation d'un premier polymère à base de diène conjugué, d'un second polymère à base de diène conjugué, d'un monomère à base de vinyle aromatique et d'un monomère à base de cyanure de vinyle, le premier polymère à base de diène conjugué ayant une distribution de tailles des particules entre 0,346 et 0,404, et le second polymère à base de diène conjugué ayant une distribution de tailles des particules entre 0,196 et 0,304.
PCT/KR2019/001304 2018-02-02 2019-01-30 Procédé de préparation de copolymère greffé, copolymère greffé et article moulé en résine thermoplastique WO2019151776A1 (fr)

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EP19747015.6A EP3613783B1 (fr) 2018-02-02 2019-01-30 Procédé de préparation de copolymère greffé, copolymère greffé et article moulé en résine thermoplastique
CN201980002501.4A CN110662780B (zh) 2018-02-02 2019-01-30 接枝共聚物的制备方法、接枝共聚物和热塑性树脂模制品
US16/631,812 US11104789B2 (en) 2018-02-02 2019-01-30 Method for preparing graft copolymer, graft copolymer and thermoplastic resin molded article

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CN115427469A (zh) * 2020-11-27 2022-12-02 株式会社Lg化学 制备接枝共聚物的方法、接枝共聚物和包含该接枝共聚物的树脂组合物

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CN115427469A (zh) * 2020-11-27 2022-12-02 株式会社Lg化学 制备接枝共聚物的方法、接枝共聚物和包含该接枝共聚物的树脂组合物

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