WO2018088677A1 - Résine thermoplastique et composition de résine thermoplastique - Google Patents

Résine thermoplastique et composition de résine thermoplastique Download PDF

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WO2018088677A1
WO2018088677A1 PCT/KR2017/008347 KR2017008347W WO2018088677A1 WO 2018088677 A1 WO2018088677 A1 WO 2018088677A1 KR 2017008347 W KR2017008347 W KR 2017008347W WO 2018088677 A1 WO2018088677 A1 WO 2018088677A1
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weight
thermoplastic resin
parts
seed
shell
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PCT/KR2017/008347
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English (en)
Korean (ko)
Inventor
채주병
전태영
정유성
김종범
김창술
박은선
김영민
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(주) 엘지화학
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Priority claimed from KR1020170094026A external-priority patent/KR102044364B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to EP17866372.0A priority Critical patent/EP3363833B1/fr
Priority to JP2018528558A priority patent/JP6810147B2/ja
Priority to US15/775,340 priority patent/US11352495B2/en
Priority to CN201780004324.4A priority patent/CN108368210B/zh
Publication of WO2018088677A1 publication Critical patent/WO2018088677A1/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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a thermoplastic resin and a thermoplastic resin composition, and more particularly, to a thermoplastic resin having a composition capable of improving graft density, and a thermoplastic resin composition having high glossiness, including high dispersion.
  • ABS resins may be used in automotive, electrical, and electronic applications due to the stiffness and chemical resistance of acrylonitrile, the processability of butadiene and styrene, the mechanical strength, and the beautiful appearance. It is widely used in electronic products and office equipment. Surface gloss and dispersion in the various blending resins of these ABS resins are one of the important factors that determine the quality of processed molded articles.
  • the surface gloss and dispersion in various blending resins of ABS resins are affected by various factors, such as unreacted monomer and emulsifier, during processing by high temperature extrusion and injection as well as particle size and distribution. If the additive is low, but additives such as compatibilizers are added separately, in this case, there is a disadvantage such as poor workability or increase the amount of gas generated during the processing, it is a technique of improving the surface gloss and dispersion in various blending resins of ABS resin Development continues to be required in the industry.
  • Patent Document 1 US Patent No. 4,360,618
  • thermoplastic resin having a composition capable of improving graft density and a thermoplastic resin composition having high glossiness, including a high dispersion.
  • the present invention provides a graft copolymer having a seed-shell structure, a large diameter rubber polymer having an average particle diameter of more than 2,000 GPa to 3,500 GPa and a small diameter rubber polymer having an average particle diameter of 500 GPa to 2,000 GPa
  • a bimodal seed comprising an aromatic vinyl-vinylcyan polymer shell surrounding the seed, wherein the vinylcyan compound is included in the range of 5 to 28% by weight relative to the total weight of the shell; Provide resin.
  • the present invention provides a thermoplastic resin composition
  • a thermoplastic resin composition comprising the thermoplastic resin and polyarylene ether, wherein the thermoplastic resin is 15 to 50% by weight, the polyarylene ether is contained in 50 to 85% by weight.
  • thermoplastic resin composition having a high glossiness by providing a composition of a thermoplastic resin which can improve graft density, thereby increasing dispersion.
  • Example 1 is a SEM photograph of the dispersion degree of the specimen prepared from the thermoplastic resin composition according to the Examples and Comparative Examples. Respective examples are (a) Example 1, (b) Comparative Example 1, and (c) Comparative Example 2.
  • thermogravimetric analysis (TGA) graph comparing the thermal stability of each emulsifier.
  • thermoplastic resin according to the present invention is a graft copolymer having a seed-shell structure, comprising a large diameter rubber polymer having an average particle diameter of more than 2,000 mm 3 and less than 3,500 mm 3 and a small diameter rubber polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3
  • a modal seed comprising an aromatic vinyl-vinylcyan polymer shell surrounding the seed, wherein the vinylcyan compound is included in the range of 5 to 28% by weight relative to the total weight of the shell.
  • the graft copolymer of the seed-shell structure may include, for example, (a) a seed comprising a bimodal conjugated diene rubber polymer; And (b) a shell surrounding the seed and polymerized with an aromatic vinyl compound and a vinyl cyan compound, and a fatty acid dimer or a metal salt thereof.
  • the conjugated diene rubber polymer of the seed is, for example, a 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 polymerized including at least one conjugated diene-based compound selected from.
  • the seed may be emulsion polymerized, and in this case, there is an effect of excellent mechanical properties, and is not particularly limited as long as it is manufactured according to a conventional emulsion polymerization method.
  • the seed may be in the form of a latex in which the polymerized rubbery polymer is dispersed in water in a colloidal state.
  • the seed has, for example, an average particle diameter of more than 2,000 kPa to 3,500 kPa or less, 2,500 kPa or more to 3,500 kPa or less, or 3,000 kPa or more and 3,500 kPa or less, and a gel content of 60 to 95 wt%, 65 to 80 wt%, or 65 To 75% by weight large diameter seeds, for example, with an average particle diameter of 500 kPa to 2,000 kPa, 1,000 kPa to 2,000 kPa, or 1,000 kPa to 1,500 kPa, with a gel content of 60 to 95 wt%, 70 to 95 wt%, or 80 It may be bimodal of the small diameter seed to 95% by weight, and within this range there is an excellent impact strength and mechanical properties.
  • the average particle diameter is measured by a dynamic laser light skating method using a Nicomp 370HPL device manufactured by Nicomp.
  • the gel content is determined by coagulation of polybutadiene rubber latex with dilute acid or metal salt, washing, drying in a vacuum oven at 60 ° C. for 24 hours, and then crushing the obtained rubber mass with scissors, and then removing 1 g of rubber sections. 100 g of toluene was stored in a dark room at room temperature for 48 hours, separated into sol and gel, dried, and then measured by the following equation.
  • the large-diameter seed and the small-diameter seed constituting the seed may be 50:50 to 90:10, 60:40 to 75:25, 60:40 to 70:20, or 70:30 to 75:25 by weight, for example. Within this range, the dispersion and the surface properties are excellent.
  • the seed may be included in an amount of 30 to 80 wt%, 40 to 75 wt%, or 50 to 70 wt% based on 100 wt% of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. Mechanical properties and surface properties are excellent within.
  • the shell is emulsified graft polymerized to include the fatty acid having a mean carbon number and molecular weight or a metal salt thereof surrounding the bimodal seed, for example 100% by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound It may be included in 20 to 70% by weight, 25 to 60% by weight, or 30 to 50% by weight on the basis, there is an excellent effect of mechanical and physical properties balance within this range.
  • the aromatic vinyl compound includes, for example, styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene and derivatives thereof. It may be at least one selected from the group, and the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.
  • the derivative may mean a compound in which one or two or more hydrogen atoms of the original compound are substituted with a halogen group, an alkyl group, and a hydroxy group.
  • the vinylcyan compound is 5 to 28% by weight, 5 to 20% by weight or less, 5 to 20% by weight, 5 to 15% by weight, or 5 to 28% by weight of the total weight of the shell (aromatic vinyl-vinylcyan polymer shell). It may be preferable to be included in 10% by weight, there is an effect that the mechanical properties and physical properties balance within this range.
  • the content of the aromatic vinyl compound and the vinyl cyan compound included in the shell may be included, for example, in the range of 90:10 to 99: 1 based on the weight ratio.
  • the fatty acid may be, for example, two or more kinds, two to ten kinds, or two to five kinds of fatty acid dimers, metal salts thereof, or mixtures thereof having different carbon numbers in the chain.
  • the average carbon number of the chain of the fatty acid may be, for example, 10 or more, 33 or more, 33 to 44, or 33 to 36, and excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. have.
  • the fatty acid may include, for example, an unsaturated fatty acid dimer having an unsaturation of 1 to 20, 1 to 10, 1 to 5, or 2 to 3, and has a low volatile content during extrusion injection molding within this range.
  • the molecular weight of the fatty acid may be, for example, 500 g / mol or more, 500 to 2000 g / mol, or 500 to 1000 g / mol, and has excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. It is effective to let.
  • the molecular weight here refers to the average molecular weight or weight average molecular weight measured by a gel permeation chromatography (GPC) instrument after drying for 15 minutes in a 120 °C oven to obtain a solid content, 0.2% by weight solution in THF solvent.
  • GPC gel permeation chromatography
  • the fatty acid may include, for example, one or more selected from the group consisting of oleic acid, oleic acid-based dimer, myristoleic acid, linoleic acid, and metal salts thereof.
  • the metal of the metal salt is, for example, an alkali metal, and in particular, may be potassium or sodium.
  • the fatty acid is, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. It can be included as a portion, there is an effect to increase the polymerization stability and storage stability of the polymer within this range.
  • the fatty acid may include, for example, 50% by weight or more, 60 to 100% by weight, or 61 to 100% by weight of an oleic acid-based dimer, and excellent thermal stability within this range, so that the gas during extrusion and injection processing There is an effect of reducing the amount of generation.
  • the fatty acid is, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. It can be included as a wealth.
  • thermoplastic resin of the present invention may have a graft ratio of 50% or more, 60 to 90%, or 70 to 85%, and excellent surface gloss and dispersion in this range, and excellent mechanical properties.
  • the thermoplastic resin of the present invention may, for example, have a weight average molecular weight of 20,000 to 200,000 g / mol, 20,000 to 150,000 g / mol, 20,000 to 100,000 g / mol, 30,000 g / mol or more and less than 85,000 g / mol, or 30,000 to 70,000 g It may be / mol, excellent surface gloss and dispersion in this range, and excellent mechanical properties.
  • thermoplastic resin of the present invention may have a weight average molecular weight of 100,000 to 200,000 g / mol, 120,000 to 180,000 g / mol, or 130,000 to 170,000 g / mol, and have excellent surface gloss and dispersibility within this range. In addition, the mechanical properties are excellent.
  • a weight average molecular weight refers to the molecular weight measured by gel permeation chromatography (GPC).
  • thermoplastic resin of the present invention may have a graft density ( ⁇ ) of more than 0.12 to 0.80 or less, 0.20 to 0.70, or 0.30 to 0.64, and excellent surface gloss and dispersibility within this range, and excellent mechanical properties. have.
  • g d is the graft ratio (%) calculated by Equation 2 below
  • D is the average particle diameter measured by the light scattering method
  • ⁇ is the density value of butadiene rubber particles measured by the ASTM D792 method
  • ⁇ P given in the above formula.
  • N A is Avogadro's constant
  • Mg is dissolved dry matter of sol separated from supernatant of sol-gel separation in TFT solution.
  • Next molecular weight measured by GPC in the range of 20,000 to 150,000 g / mol.
  • the weight of the grafted monomer is (the weight of the precipitate remaining after the sol-gel separation (g))-(rubber weight (g)), the rubber weight is theoretically the solid content basis weight (g) of the rubber polymer injected)
  • sol-gel separation method for example, 1 g of the thermoplastic resin on the powder obtained is placed in 50 g of acetone, and stirred for 24 hours to dissolve, and the solution is separated by using a centrifuge at 20,000 rpm and -20 ° C. Separating the supernatant may be separated by sol-gel.
  • thermoplastic resin on the powder is excellent in thermal decomposition stability obtained by agglomeration using a salt, thereby reducing the amount of gas generated during extrusion and injection processing.
  • the salt may be, for example, a sulfate such as MgSO 4 , a calcium salt such as CaCl 2 , a carbonate, or a mixture thereof.
  • a sulfate such as MgSO 4
  • a calcium salt such as CaCl 2
  • a carbonate or a mixture thereof.
  • the volatilization temperature of the residual emulsifier increases due to the bonding, so that the gas may be caused by the residue during processing at high temperature. Since the amount of generation is reduced, the formation of deposits on the surface of the injection molding is suppressed and the surface smoothness is improved, which is advantageous in obtaining a beautiful appearance during secondary processing such as plating.
  • thermoplastic resin of the present invention provides a composition for improving the graft density
  • the dispersion resin has a high glossiness by increasing the dispersion degree.
  • thermoplastic resin of the present invention is not specific to the manufacturing method, for example, the step of polymerizing the seed; And a fatty acid or a metal salt thereof having an average carbon number of 10 or more and a molecular weight of 500 to 2000 g / mol in the shell, and preparing an shell by emulsion graft polymerization.
  • the seed may include, for example, a large diameter rubbery polymer having an average particle diameter of more than 2,000 mm 3 and up to 3,500 mm 3 and a small diameter rubbery polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3.
  • the seed polymerization may be carried out, for example, by emulsion polymerization.
  • the seed polymerization and emulsion graft polymerization method is not particularly limited in the case of seed polymerization and emulsion graft polymerization generally used in the production method of ABS resin.
  • the thermoplastic resin manufacturing method of the present invention is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters and metal salts of unsaturated fatty acids as emulsifiers during seed polymerization and / or emulsion graft polymerization. It may further comprise more than one species, the amount may be, for example, 1.0 to 3.0 parts by weight based on a total of 100 parts by weight of the monomer (including rubbery polymer during emulsion graft polymerization).
  • a water-soluble initiator or a fat-soluble initiator may be used as an initiator during seed polymerization and / or emulsion graft polymerization, and the water-soluble initiator may include sodium persulfate, potassium persulfate, ammonium persulfate, or the like.
  • the fat-soluble initiator includes cumene hydro peroxide, diisopropylbenzene hydro peroxide, tertiary butyl hydro peroxide, paramethane hydro peroxide, benzoyl peroxide, and the like, and if necessary, the combination thereof may be used. It is possible.
  • the initiator may be used in an amount of 0.01 to 0.5 parts by weight or 0.1 to 0.3 parts by weight, for example, based on a total of 100 parts by weight of a monomer (including a rubbery polymer during emulsion graft polymerization), and does not cause an overreaction within the above range, It can be a polymer having a desired particle size and size distribution.
  • thermoplastic resin production method of the present invention is, for example, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrrole as an oxidation-reduction catalyst during seed polymerization and / or emulsion graft polymerization. It may include one or more selected from the group consisting of sodium phosphate, sodium sulfite.
  • the redox-based catalyst may be used in an example of 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight or 0.01 to 0.2 parts by weight based on a total of 100 parts by weight of the monomer (including rubbery polymer during emulsion graft polymerization). Within this range, the polymerization reaction can be promoted to produce the thermoplastic resin in a short time.
  • the reactants it is preferable to add the reactants, and then graft polymerization by reacting at 60 to 90 ° C. or 60 to 80 ° C. for 3 to 5 hours or 2 to 4 hours. This is because the polymerization reaction is initiated by the activation of the initiator within the above-mentioned range, and the heat removal is easy.
  • a polymer having a uniform size distribution can be prepared.
  • Emulsion graft polymerization of the shell may be performed by using a molecular weight modifier, if necessary, based on 100 parts by weight of the total content of the conjugated diene rubbery polymer, aromatic vinyl compound and vinyl cyan compound, 0.1 to 1 part by weight, 0.2 to 0.6 part by weight or It may further comprise 0.3 to 0.5 parts by weight, it may be advantageous to form a polymer having a desired average particle diameter in the case of further comprising a molecular weight regulator in the above-described range, there is an effect that the size of the polymer is uniform.
  • a molecular weight modifier if necessary, based on 100 parts by weight of the total content of the conjugated diene rubbery polymer, aromatic vinyl compound and vinyl cyan compound, 0.1 to 1 part by weight, 0.2 to 0.6 part by weight or It may further comprise 0.3 to 0.5 parts by weight, it may be advantageous to form a polymer having a desired average particle diameter in the case of further comprising a molecular weight regulator in the above-
  • mercaptan compounds such as tertiary dodecyl mercaptan, can be used as an example.
  • Another example of the present invention is that the total amount of the initiator and the redox-based catalyst used in the graft polymerization reaction can be added at the beginning of the reaction, but when the initiator and the redox-based catalyst are separately added as described above, It is easy to remove the heat and suppress the side reactions while reducing the content of unreacted monomer can improve the quality and productivity of the polymer.
  • the secondary graft polymerization reaction may be performed by raising the temperature to 60 to 100 ° C., or 70 to 90 ° C. under a temperature increase rate of 5 to 30 / hr, or 10 to 20 / hr.
  • a temperature increase rate of 5 to 30 / hr, or 10 to 20 / hr.
  • the polymerization reaction may be preferably terminated at a polymerization conversion rate of 90 to 99%, 95 to 99%, or 97 to 99%.
  • a polymer having a low unreacted monomer content and a high degree of polymerization in the product may be used.
  • the polymerization conversion rate is 1.5 g of the graft copolymer latex in a 150 ° C. hot air dryer, and then weighed to obtain a total solids content (TSC), which is measured by the following equation.
  • TSC Total solids content (parts by weight)
  • reaction conditions such as graft rate, reaction pressure, etc.
  • graft rate reaction pressure, etc.
  • reaction pressure reaction pressure
  • the graft copolymer latex prepared according to the present invention is prepared in the form of a powder through conventional processes such as salt agglomeration, washing, and drying, and the powder is mixed with a nonpolar resin such as a poly (arylene ether) resin. And extruded and injected to produce a molded article.
  • a nonpolar resin such as a poly (arylene ether) resin.
  • thermoplastic resin composition of the present invention is characterized by including the thermoplastic resin and the polyarylene ether resin.
  • thermoplastic resin composition may be in a form in which the thermoplastic resin is dispersed in a matrix resin made of a polyarylene ether resin (see FIG. 1), and in this case, an excellent balance of physical properties such as impact strength and gloss is excellent.
  • the poly (arylene ether) resin may be, for example, a homopolymer of a compound represented by Formula 1 or Formula 2, or a copolymer including a compound of Formula 1 or Formula 2.
  • R a , R 1 , R 2 , R 3 and R 4 are substituents of arylene group (Ar) or phenylene group, each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl , Methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro group, n is an integer of 4 to 20, Ar is an arylene group having 7 to 20 carbon atoms.
  • R 1 and R 2 may be an alkyl group or an alkyl group having 1 to 4 carbon atoms
  • R 3 and R 4 may be hydrogen.
  • the poly (arylene ether) resin may be, for example, a poly (phenylene ether) resin.
  • the poly (phenylene ether) -based resin means a poly (arylene ether) resin that can be represented by the following [Formula 3].
  • W, X, Y and Z are hydrogen or a substituent, n is a repeating unit.
  • W, X, Y and Z are each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, memeth Oxy, phenoxy or nitro group, wherein n is an integer from 4 to 20.
  • the homopolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenyl Ethylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl -1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2, 6-dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether and poly (2,5-dimethyl-1,4-phenylene) ether It may be one or more selected from the group consisting of.
  • the copolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol It may be one or more selected from the group consisting of a copolymer of and a copolymer of 2,3,6-trimethylphenol and o-cresol.
  • the poly (arylene ether) resin may be 50 to 85% by weight, or 50 to 80% by weight based on the total weight of the resin composition according to the present invention, for example, impact strength, mechanical properties and surface gloss within this range This has an excellent effect.
  • the poly (arylene ether) resin may have a weight average molecular weight of 10,000 to 100,000 g / mol, 10,000 to 70,000 g / mol, or 15,000 to 45,000 g / mol, within this range the dimensional stability and physical property balance Excellent effect.
  • thermoplastic resin composition may further include additives such as heat stabilizers, light stabilizers, antioxidants, antistatic agents, antibacterial agents, or lubricants, for example, in a range that does not affect the physical properties.
  • additives such as heat stabilizers, light stabilizers, antioxidants, antistatic agents, antibacterial agents, or lubricants, for example, in a range that does not affect the physical properties.
  • the surface glossiness may have a high glossiness of more than 66, more than 80, 85 to 99, or 88 to 96.
  • the specimens may have improved mechanical properties of greater than 32%, greater than 40%, or between 42 and 65% tensile elongation measured according to ASTM D 638.
  • the specimen may be manufactured by injection molding or extruding the thermoplastic resin composition at a processing temperature of 250 to 300 ° C., or by extruding to produce pellets.
  • thermoplastic resin composition of the present invention is not only excellent in mechanical strength but also excellent in gloss and is expected to be able to replace the existing blending material.
  • a nitrogen-substituted polymerization reactor 100 parts by weight of ion-exchanged water, 80 parts by weight of 1,3-butadiene as a monomer, 3.0 parts by weight of a mixed emulsifier of the oleic acid dimer and rosin soap shown in Table 1 as emulsifiers, potassium carbonate (K 2 CO 3 ) 0.5 parts by weight, 0.4 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.3 parts by weight of potassium persulfate (K 2 S 2 O 8 ) as a polymerization initiator and polymerization at a reaction temperature of 70 °C After reacting up to 30-40% conversion, 20 parts by weight of 1,3-butadiene was continuously administered, and 0.2 parts by weight of potassium persulfate (K 2 S 2 O 8 ) was collectively administered after reaction at 75 ° C.
  • K 2 CO 3 potassium carbonate
  • TDDM ter
  • a nitrogen-substituted polymerization reactor 100 parts by weight of ion-exchanged water, 50 parts by weight of polybutadiene rubber latex (large diameter seed) polymerized in the seed polymerization step (based on solids), and polybutadiene rubber latex polymerized in the seed polymerization step (small Caliber seed) 5 parts by weight (based on solids) was added, followed by 5 parts by weight of a mixture of styrene and acrylonitrile monomers (5% by weight of acrylonitrile), and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator.
  • TDDM tertiary dodecyl mercaptan
  • t-butyl hydroperoxide 0.2 part by weight was sequentially added as a polymerization initiator, stirred at 50 ° C. for 30 minutes, and then an oxidation-reduction catalyst composed of 0.035 part by weight of dextrose, 0.06 part by weight of sodium pyrolate, and 0.0015 part by weight of ferrous sulfate.
  • the batch was administered and polymerization was performed while raising the temperature at 70 ° C. for 1 hour.
  • the polymerization conversion rate was 95% level, followed by a batch dose of 0.05 parts by weight of cumene hydroperoxide together with an oxidation-reduction catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate and an additional 75 Further polymerization was carried out for 1 hour while the temperature was raised to ° C.
  • the polymerization conversion rate of the final polymer was 98.8%.
  • the obtained seed-shell structured ABS graft copolymer latex was coagulated with 2 parts by weight of sulfate, followed by washing to obtain powder (a1).
  • ABS graft copolymer powder (a2) was obtained by the same method as Example 1 except 20 parts by weight were added instead of 5 parts by weight.
  • Example 2 Furthermore, the present invention was carried out in the same manner as in Example 1 except that the ABS graft copolymer powder (a2) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. Two specimens A2 were produced.
  • thermoplastic resin composition manufacturing step of Example 1 50 parts by weight of the ABS graft copolymer powder (a1) instead of 25 parts by weight of the ABS graft copolymer powder (a1), 50 parts by weight of polyphenylene ether instead of 75 parts by weight
  • a specimen A3 of Example 3 was prepared in the same manner as in Example 1, except that parts were added.
  • ABS graft copolymer powder (a4) instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1 was carried out in the same manner as in Example 1 Four specimens (A4) were produced.
  • Example 5 The polymerization was carried out in the same manner as in Example 2 and in a rubber composition, except that a large diameter particle diameter of 3600 mm 3 and a small diameter particle diameter of 900 mm were used to obtain the ABS graft powder (a5) by polymerization in the same manner as in Example 2.
  • the specimen A5 of Example 5 was prepared through the processing of the method.
  • ABS graft powder (a6) was obtained by polymerization in the same manner as in Example 1 except that the same amount of myristic oleic acid dimer was used instead of the oleine phase dimer in the cell polymerization step of Example 1, and the processing of the same method was carried out. Specimen (A6) was produced.
  • a redox catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate and 0.0015 parts by weight of ferrous sulfate was added in a batch, and 70 The polymerization was carried out while raising the temperature at 1 ° C for 1 hour.
  • the polymerization conversion rate was 95% level, followed by a batch dose of 0.05 parts by weight of cumene hydroperoxide together with an oxidation-reduction catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate and an additional 75 Further polymerization was carried out for 1 hour while the temperature was raised to ° C.
  • the polymerization conversion rate of the final polymer was 98.8%.
  • the obtained seed-shell structured ABS graft copolymer latex was solidified with 2 parts by weight of sulfate, followed by washing to obtain a powder (a7).
  • Example 7 Furthermore, the present invention was carried out in the same manner as in Example 1, except that the ABS graft copolymer powder (a7) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. 7 specimen (A7) was produced.
  • a redox catalyst consisting of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate and 0.0015 parts by weight of ferrous sulfate was added in a batch, and 70 The polymerization was carried out while the temperature was raised at 1 ° C. for 1 hour.
  • the polymerization conversion rate was 95%, and then 0.05 parts by weight of cumene hydroperoxide was added together with an oxidation-reduction catalyst composed of 0.035 parts by weight of dextrose, 0.06 parts by weight of sodium pyrolate, and 0.0015 parts by weight of ferrous sulfate, and further Further polymerization was carried out for 1 hour while the temperature was raised to 75 ° C.
  • the polymerization conversion rate of the final polymer was 98.8%.
  • the obtained seed-shell structured ABS graft copolymer latex was solidified with 2 parts by weight of sulfate, followed by washing to obtain powder (a8).
  • Example 2 Furthermore, the present invention was carried out in the same manner as in Example 1, except that the ABS graft copolymer powder (a8) was added instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1. 8 specimen (A8) was produced.
  • Example 2 Further Comparative Example was carried out in the same manner as in Example 1 except that the ABS graft copolymer powder (b1) instead of the ABS graft copolymer powder (a1) in the thermoplastic resin composition manufacturing step of Example 1 was added. 1 specimen (B1) was produced.
  • Comparative Example 1 was carried out in the same manner as in Example 1, except that 25 parts by weight of the product name SG910 (LG Chem) was added as a high-impact polystyrene (hereinafter referred to as HIPS) without undergoing the thermoplastic resin polymerization step .
  • HIPS high-impact polystyrene
  • Comparative Example 2 50 parts by weight of polyphenylene ether instead of 75 parts by weight, 50 parts by weight instead of HIPS 25 parts by weight was carried out in the same manner as in Example 1, the specimen of Comparative Example 3 (B3) was produced.
  • ABS graft copolymer powders (a1, a2, a4, a5, a6, a7, a8, b1, b2, b3) obtained in Examples 1 to 2, 4 to 8 and Comparative Examples 1, 4 and 5. was measured by the following method, and the results are shown in Tables 1 and 2, respectively.
  • Graft rate A value expressed by the following Equation 6 is an index indicating how many polymers are grafted to the total weight of rubber added during graft polymerization. This shows the value for the weight ratio of the grafted polymer and has a different meaning from the graft density. For example, at the same graft rate, the smaller the molecular weight, the higher the graft density.
  • TSC Total solids content (parts by weight)
  • Coagulum content (Coagulum, weight%): The weight of the coagulum produced in the reaction tank, the total rubber weight and the monomer weight was measured, and the coagulum content was calculated by the following equation (5).
  • Graft Rate Weight of Grafted Monomer (g) / Rubber Weight (g) x 100
  • Weight of grafted monomer (weight of sediment remaining after sol-gel separation)-(rubber weight)
  • the dried product of the sol separated from the supernatant was dissolved in a TFT solution and measured by GPC to determine the molecular weight (Mw).
  • graft density ⁇ was calculated according to the following equation.
  • g d is the graft ratio (%) calculated by the above equation (2), D is the average particle diameter measured by the light scattering method.
  • p is a density value of butadiene rubber particles measured by the ASTM D792 method, where p is represented by a large diameter PBL 0.94 g / cm 3 and a small diameter PBL 0.97 g / cm 3 .
  • N A is Avogadro's constant.
  • Mg is a molecular weight measured by GPC and is in a range of 20,000 to 150,000.
  • graft ratio 0.7, NA 6.02x10 23 (mol -1 ), average particle diameter (P / S) 292.7273 nm, density (g / cm 3 ) 0.943182, molecular weight (Mw / 10 3 ) 30 g /
  • the graft density calculated in mol is 0.64.
  • Gas generation amount (ppm) The gas generation degree for each powder was measured by using a TGA device was measured by weight loss when left for 60 minutes under nitrogen, 250 degree isothermal conditions.
  • thermoplastic resin composition specimens A1, A2, A3, A4, A5, A6, A7, A8, B1, B2, and B3 of Examples 1 to 8 and Comparative Examples 1 to 3 were measured by the following methods, The results are shown in Table 3 below.
  • the average carbon number of the chain of the oleic acid-based dimer emulsifier included in the shell polymerization step is lower than in the content range of the present invention Compared to the molded article blended with the polyphenylene ether, it was confirmed that the impact strength, mechanical properties and gloss were excellent.
  • FIG. 1 is an SEM result in which a thermoplastic resin composition is dispersed in a domain in each of the polyphenylene ether matrices of Example 1, Comparative Example 1, and Comparative Example 2 of Table 3 described above. Referring to Figure 1, in the case of the thermoplastic resin composition prepared according to the present invention it can be confirmed that the dispersion effect improved than Comparative Example 1 or Comparative Example 2.
  • TGA thermogravimetric analysis
  • thermoplastic resin having a composition capable of improving graft density by blending a thermoplastic resin having a composition capable of improving graft density, the dispersion degree is improved, so that glossiness and mechanical properties equal to or higher than those of conventional blending resins in extrusion and injection molding are improved. It can provide a blending material having a.

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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)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine thermoplastique, et plus précisément une résine thermoplastique qui est un copolymère greffé présentant une structure noyau-coque, et qui comprend : un noyau bimodal comprenant un polymère de caoutchouc de grand diamètre présentant un diamètre moyen supérieur à 2000 Å et inférieur ou égal à 3500 Å, et un polymère de caoutchouc de petit diamètre présentant un diamètre moyen de 500 à 2000 Å ; et une coque vinylaromatique-cyanovinylique, dans laquelle un composé cyanovinylique est présent en une quantité de 5 à 28 % en poids par rapport au poids total de la coque. La présente invention présente des effets consistant à procurer : une résine thermoplastique présentant une composition permettant d'améliorer la densité de greffage ; et une composition de résine thermoplastique contenant cette dernière, et présentant un brillant élevé grâce à une augmentation de la dispersité.
PCT/KR2017/008347 2016-11-11 2017-08-02 Résine thermoplastique et composition de résine thermoplastique WO2018088677A1 (fr)

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EP17866372.0A EP3363833B1 (fr) 2016-11-11 2017-08-02 Résine thermoplastique et composition de résine thermoplastique
JP2018528558A JP6810147B2 (ja) 2016-11-11 2017-08-02 熱可塑性樹脂及び熱可塑性樹脂組成物
US15/775,340 US11352495B2 (en) 2016-11-11 2017-08-02 Thermoplastic resin and thermoplastic resin composition
CN201780004324.4A CN108368210B (zh) 2016-11-11 2017-08-02 热塑性树脂和热塑性树脂组合物

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KR1020170094026A KR102044364B1 (ko) 2016-11-11 2017-07-25 열가소성 수지 및 열가소성 수지 조성물
KR10-2017-0094026 2017-07-25

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EP3770192A4 (fr) * 2018-12-20 2021-09-01 Lg Chem, Ltd. Latex de caoutchouc diénique, son procédé de fabrication, et copolymère greffé à structure noyau-enveloppe le comprenant

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KR20000009217A (ko) * 1998-07-22 2000-02-15 유현식 스티렌계 열가소성 수지 조성물
KR20010078716A (ko) * 1999-02-04 2001-08-21 고지마 아끼로, 오가와 다이스께 열가소성 수지조성물
KR20050069908A (ko) * 2003-12-30 2005-07-05 주식회사 엘지화학 내충격성 및 흐름성이 우수한 고분자 라텍스 및 이의 제조방법
KR100570430B1 (ko) * 2003-11-26 2006-04-11 주식회사 엘지화학 열가소성 수지 조성물 및 그의 제조방법
KR20110019443A (ko) * 2008-09-04 2011-02-25 히다치 가세고교 가부시끼가이샤 포지티브형 감광성 수지 조성물, 레지스트 패턴의 제조 방법 및 전자 부품

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Publication number Priority date Publication date Assignee Title
US4360618A (en) 1981-11-19 1982-11-23 Monsanto Company Low acrylonitrile content styrene-acrylonitrile polymers blended with polyphenylene oxide
KR20000009217A (ko) * 1998-07-22 2000-02-15 유현식 스티렌계 열가소성 수지 조성물
KR20010078716A (ko) * 1999-02-04 2001-08-21 고지마 아끼로, 오가와 다이스께 열가소성 수지조성물
KR100570430B1 (ko) * 2003-11-26 2006-04-11 주식회사 엘지화학 열가소성 수지 조성물 및 그의 제조방법
KR20050069908A (ko) * 2003-12-30 2005-07-05 주식회사 엘지화학 내충격성 및 흐름성이 우수한 고분자 라텍스 및 이의 제조방법
KR20110019443A (ko) * 2008-09-04 2011-02-25 히다치 가세고교 가부시끼가이샤 포지티브형 감광성 수지 조성물, 레지스트 패턴의 제조 방법 및 전자 부품

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3770192A4 (fr) * 2018-12-20 2021-09-01 Lg Chem, Ltd. Latex de caoutchouc diénique, son procédé de fabrication, et copolymère greffé à structure noyau-enveloppe le comprenant
US11932709B2 (en) 2018-12-20 2024-03-19 Lg Chem, Ltd. Diene-based rubber latex, method for preparing thereof and graft copolymer with core-shell structure comprising the same

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