Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F6/00—Post-polymerisation treatments
  • C08F6/14—Treatment of polymer emulsions
  • C08F6/22—Coagulation
• • 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
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• the present invention relates to a thermal stabilizer free thermoplastic resin composition and a method of manufacturing the same.
• a method for improving the thermal stability and surface gloss of ABS copolymer resin or similar resin is to increase the amount of thermal stabilizer or to remove residual monomer by applying stripping process to ABS copolymer latex, residual emulsifier In order to minimize the content of the method of adding additional water during aggregation / dehydration has been applied.
• rubber reinforcement resins such as ABS (acrylonitrile-butadiene-styrene), MBS (methacrylate-butadiene-styrene), and ASA (acrylonitrile-styrene-acrylate) are generally rubbers through emulsion polymerization. After reinforcement resin is made, it is agglomerated / dried to make powder, and then, it is put into an extruder together with resins such as styrene-acrylonitrile (hereinafter referred to as SAN) and polycarbonate (PC) and processed into pellets. It is manufactured through the steps. In this case, it is common to inject a rubber-reinforced resin having a moisture content of less than 1% into the extruder. In some cases, the first process is a continuous process of kneading powder with SAN and PC in the extruder, which contains about 30% of the water content after dehydration without the drying process. It causes a problem of deterioration.
• ABS acrylonit
• the present invention relates to a heat stabilizer-free thermoplastic resin composition and a method of manufacturing the same, and an object of the present invention is to improve thermal stability and surface gloss without using a heat stabilizer, and at the same time, to provide excellent impact resistance and impact impact strength. It is to provide a resin composition.
• Another object of the present invention is to provide a manufacturing method capable of maintaining high productivity without undergoing a drying step in the preparation of the thermoplastic resin composition.
• the heat stabilizer free thermoplastic resin composition of the present invention comprises a) a rubber reinforced resin and b) a matrix resin,
• the a) rubber reinforcement resin is an ABS-based thermoplastic resin obtained by graft copolymerization comprising a large diameter rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound and a reactive surfactant as an active ingredient.
• the present invention comprises the steps of: a) preparing the ABS-based thermoplastic resin as a rubber-reinforced resin as a heat stabilizer pre-grafted copolymer latex having a water content of 45 to 70%;
• thermoplastic resin composition characterized in that the graft copolymer latex to adjust the moisture content to 2 to 20% and then kneading the matrix resin and the lubricant.
• the thermoplastic resin composition is excellent in impact resistance, dropping impact, gloss without using a heat stabilizer, and in particular, it is characterized by increasing the production efficiency when applied to the compression dehydrator without undergoing a drying process during manufacturing.
• the heat stabilizer free thermoplastic resin composition of this invention consists of a) rubber reinforced resin and b) matrix resin.
• stabilizer free thermoplastic resin composition refers to a thermoplastic resin composition that does not include a heat stabilizer, unless otherwise specified.
• the a) rubber-reinforced resin corresponds to an ABS-based thermoplastic resin obtained by graft copolymerization including an rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound, and a reactive emulsifier as an active ingredient.
• the rubbery polymer may be a large-diameter rubbery latex obtained by preparing a small-diameter rubbery latex and then enlarging particles using an acid.
• the small-diameter rubber latex is 100 parts by weight of 1,3-butadiene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight modifier, and 90 to ion exchanged water. 130 parts by weight of the batch is reacted at 50 to 65 °C for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of a batch of the molecular weight regulator is prepared by reacting at 55 to 70 °C for 5 to 15 hours.
• the small-diameter rubbery latex thus obtained has an average particle diameter of 600 to 1500 mm 3 and a gel content of 85 to 99% by weight.
• the gel content range corresponds to a range in which graft copolymerization is effectively formed on the outside of the rubber particles to impart excellent impact strength and thermal stability.
• Acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or polymer flocculant is added in an amount of 1 to 4 parts by weight as 0.1 to 5 parts by weight of the small-diameter rubbery latex, and gradually added for 1 hour as another example. To enlarge the particles.
• the large-diameter rubbery polymer latex obtained by particle enlargement has a particle size specifically in the range of 2500 to 5000 mm 3, more specifically in the range of 2500 to 3800 mm 3, and the gel content to satisfy the range of 85 to 99 wt%.
• the particle diameter may be an average particle diameter or a number average particle diameter.
• Such large diameter rubbery polymer latex is included in an amount of 60 to 75 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin to provide a rubber reinforced resin.
• the aromatic vinyl compound used in the present invention is not limited thereto, but styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl toluene, t-butyl styrene, chlorostyrene, or a substituent thereof and the like, or a mixture of two or more thereof.
• Based on 100 parts by weight of the total amount of monomers for rubber reinforcement resin may be specifically used in the range of 18 to 28 parts by weight, more specifically 21 to 25 parts by weight.
• acrylonitrile, methacrylonitrile, or a substituent thereof or the like may be mixed alone or in combination of two or more thereof, specifically 5 to 15 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resins. More specifically, it can be used in 9 to 10 parts by weight.
• Reactive emulsifiers used in the present invention can be included in the rubber reinforcement resin to minimize residual emulsifier content in the rubber reinforcement resin to play a role of improving thermal stability and surface gloss without the addition of a heat stabilizer, as well as later
• the compatibility with the matrix resin to be blended is also enhanced to serve to provide an ABS-based thermoplastic resin excellent in impact resistance and falling impact strength.
• an emulsifier including at least one functional group selected from the group consisting of carbonate, sulfonate, sulfate, and the like, but is not limited thereto.
• alkenyl C16-18 di-succinate di- potassium salt alken
• the reactive emulsifier is included within the range of 0.001 to 2 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resin, which is not easy to ensure the polymerization stability at a content of less than 0.001, the residual emulsifier content is higher than 2 parts by weight This is because the resin thermal stability deteriorates.
• the appropriate residual emulsifier content range in the present invention is not limited to this, but 19,000 ppm or less (in terms of the amount of emulsifier used, for example, about 65% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 19,000 ppm, as another example, 17,500 ppm or less (in terms of the amount of emulsifier used, about 55% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 17,500 ppm is preferable.
• the rubber reinforcement resin may include mercaptans as the molecular weight regulator, specifically n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like or Can be used in combination of two or more, the amount may be used in 0.1 to 1 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin.
• the rubber-reinforced resin is a fat-soluble peroxide type such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide as a polymerization initiator.
• Oxidation consisting of polysaccharide dihydroxyacetone or polyamines such as dextrose, glucose, and plotose as the polymerization initiator and metal salts such as iron (II), iron (III), cobalt (II) or cerium (IV)
• metal salts such as iron (II), iron (III), cobalt (II) or cerium (IV)
• One or more types of reducing-type polymerization initiators may be used, and the amount of the reducing agent may be used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomers for rubber-reinforced resins.
• thermoplastic resin composition 20 to 40 parts by weight of such a) rubber reinforced resin b) 60 to 80 parts by weight of one or more matrix resins selected from styrene-acrylonitrile copolymers and polycarbonate resins as matrix resins, and the thermal stabilizer free of the present invention
• the thermoplastic resin composition is completed.
• the weight average molecular weight is in the range of 60,000 to 200,000 g / mol, and the acrylonitrile content is 15 to 40 weight in the styrene-acrylonitrile copolymer. It is preferably included in%.
• the weight average molecular weight is less than 60,000 g / mol, the mechanical properties of the resin is lowered, when the weight average molecular weight is more than 200,000 g / mol, the compatibility with the ABS resin is not good, the surface properties are lowered, acrylonitrile content is 15% by weight If it is less than the impact resistance and chemical resistance is lowered, because when the acrylonitrile content is more than 40% by weight yellowing (yellowish).
• Comparative Example 2 using an Irganox-based heat stabilizer such as IR1076 confirms the effect of improving the thermal stability to a similar degree as when not using the heat stabilizer of the present invention could.
• thermoplastic resin composition using the heat stabilizer-free thermoplastic resin composition thus provided as follows:
• thermoplastic resin as a) rubber reinforced resin described above is prepared as a heat stabilizer pregrafted copolymer latex having a water content of 45 to 70%.
• the graft copolymerization monomer mixture may be used in a continuous input, batch input, or a mixture of the continuous input and the batch input may be optionally used, and is not particularly limited, but 5 to 40% by weight of the total monomer mixture at the initial stage of the reaction and the rest Continuous addition of the monomer mixture is preferred in view of the reaction efficiency.
• the reactive emulsifier it is preferable to continuously add the polymerization conversion in the range of 65 to 75%. In this case, the polymerization stability is not lowered, so that the amount of coagulum generated is small (see Example 1-4 below). .
• the graft polymerization time is preferably within 3 hours, the polymerization conversion after the reaction is 98.5% or more, the weight average molecular weight (Mw) of the polymer is preferably in the range of 50,000 to 150,000 g / mol.
• the heat stabilizer pre-grafted copolymer latex obtained is then subjected to antioxidant treatment and flocculation to obtain a graft copolymer latex having a water content of 45 to 70%.
• the amount in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the graft rubber latex.
• the agglomeration process refers to a process in which a metal salt or an acid is added to the graft rubber latex and then aged.
• the coagulant used herein includes MgSO 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid, or the like.
• Hydrochloric acid, a polymer flocculant, or the like may be used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the graft rubber latex.
• graft rubber latex having a water content of 20 to 40% has a water content of 2 to 20%, more specifically 2 to 10%, and then a styrene-acrylonitrile copolymer and poly as a matrix resin.
• One of the carbonate resins is kneaded with a lubricant and a post process such as extrusion and / or injection molding is performed. In the case of having such a water content range, the drying process may be omitted.
• the moisture content is controlled to remove water using a dehydrator, more specifically, a compression dehydrator, separated into solids having a water content of 20 to 40%, and then manufactured in a powder form dried using a hot air drying method, followed by an extruder. It may be added or added to the extruder as a solid content in the water-containing state and then adjusted to a water content of 2 to 20% through the dehydration and water evaporation process in the extruder.
• thermoplastic resin composition by blending 60 to 80 parts by weight of the matrix resin to 20 to 40 parts by weight of the graft copolymer having a water content of 2 to 20%
• productivity during subsequent processing such as extrusion molding and / or injection molding is improved. It is preferable because it can improve.
• the molded article obtained by extrusion molding or injection molding the thermoplastic resin composition by the method of the present invention was excellent in both thermal stability and gloss, impact resistance and impact impact strength as described in the following examples.
• the lubricant may be ethylene bissteramide (EBA), magnesium stearate, or the like, and the amount of the lubricant may be 0.1 to 5 parts by weight based on 100 parts by weight of the graft copolymer and the matrix resin.
• EBA ethylene bissteramide
• magnesium stearate magnesium stearate
• the rubber content is maximized and the reactive emulsifier is applied during the ABS graft copolymerization to minimize the residual emulsifier content in the ABS resin, thereby improving thermal stability and surface gloss without adding a thermal stabilizer.
• improved compatibility with the styrene-acrylonitrile copolymer it was possible to produce a thermoplastic resin composition excellent in impact resistance and falling ball impact strength.
• the particle diameter and the particle diameter distribution is measured by using a Nicomp 370HPL device (manufactured by Nicomp, USA) by the dynamic laser light scattering method.
• the gel content of the rubber latex solidified with dilute acid or metal salt washed, dried in a vacuum oven at 60 °C for 24 hours, finely chopped the obtained rubber mass, and then put the 1g rubber section into 100g of toluene for 48 hours It is stored in a dark room at room temperature and then separated into a sol and a gel, the gel content is measured using the following formula.
• the solid coagulation content is measured using the following formula.
• Solid coagulation (%) [weight of coagulum produced in the reactor (g) / weight of total rubber and monomer (g)] x 100
• the graft rate (%) of the graft polymer is obtained by coagulating, washing and drying the graft polymer latex to obtain a powder form, adding 2 g of this powder to 300 ml of acetone and stirring for 24 hours, and then using the ultracentrifuge for the solution. The separated acetone solution is dropped into methanol to obtain an grafted portion. It is dried to measure the weight and then calculated according to the following equation.
• Graft Rate (%) Weight of Grafted Monomer (g) / Rubber Weight (g) x 100
• the glossiness may be lowered, which may be unfavorable.
• the residual emulsifier content (ppm) in the graft copolymer is 0.2g graft copolymer powder accurately taken in 50 ml vials, 10 ml of acetone is added and sonicated for 2 hours to dissolve the sample, and slowly added 30 ml of methanol Precipitate the polymer. After sonication for 1 hour to extract the additives, the supernatant was taken out, filtered and the residual emulsifier content (ppm) was measured using HPLC / DAD / MSD (Agilent 1100 system).
• the water content of the graft rubber latex was in the range of 50 to 60%.
• thermoplastic resin composition
• the powdered graft copolymer having a water content of 30% was first made to have a water content of 5% in a compression dehydrator.
• graft rubber latex of Example 1 70 parts by weight of the polybutadiene rubber latex (based on solids), 140 parts by weight of ion-exchanged water, 4.2 parts by weight of styrene, and 1.8 parts by weight of acrylonitrile were added to the reactor. 0.05 parts by weight of cumene hydroperoxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide were collectively added while maintaining the temperature at 50 ° C.
• Example 1 Except that 0.03 parts by weight of IR1076 as a heat stabilizer according to the prior art in Example 1 was repeated the same experiment as in Example 1 and compounded through a drying process.
• MI Melt flow index
• Tensile strength measured by ASTM D638 method.
• Example 3 using a reactive emulsifier, but with different timings, it was also worse than Example 1-6 in the field of measurement of impact strength, fluidity, surface gloss, whiteness, falling impact strength, etc. I could confirm it.

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

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Citations (5)

• 2012
  • 2012-12-06 WO PCT/KR2012/010548 patent/WO2013105737A1/fr not_active Ceased

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