WO2020122407A1 - Procédé de préparation d'un copolymère greffé de composé de vinyle aromatique conjugué à un composé cyan vinylique et composition de résine thermoplastique comprenant un copolymère greffé - Google Patents

Procédé de préparation d'un copolymère greffé de composé de vinyle aromatique conjugué à un composé cyan vinylique et composition de résine thermoplastique comprenant un copolymère greffé Download PDF

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WO2020122407A1
WO2020122407A1 PCT/KR2019/013802 KR2019013802W WO2020122407A1 WO 2020122407 A1 WO2020122407 A1 WO 2020122407A1 KR 2019013802 W KR2019013802 W KR 2019013802W WO 2020122407 A1 WO2020122407 A1 WO 2020122407A1
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weight
compound
parts
graft copolymer
conjugated diene
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PCT/KR2019/013802
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English (en)
Korean (ko)
Inventor
석재민
김유빈
김영민
이진형
한수정
정용환
박찬홍
허재원
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(주) 엘지화학
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Priority claimed from KR1020190129090A external-priority patent/KR102297798B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to US16/954,132 priority Critical patent/US11634527B2/en
Priority to EP19880937.8A priority patent/EP3696201B1/fr
Priority to CN201980006748.3A priority patent/CN111566136B/zh
Priority to JP2020542102A priority patent/JP7011073B2/ja
Publication of WO2020122407A1 publication Critical patent/WO2020122407A1/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
    • 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
    • C08F6/18—Increasing the size of the dispersed particles

Definitions

  • the present invention relates to a method for preparing a graft copolymer and a thermoplastic resin composition comprising the graft copolymer, and more specifically, to graft polymerization of an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber latex. Agglomeration of the latex with an acid coagulant and then coagulation with a salt coagulant to produce a graft copolymer having excellent cohesion efficiency and excellent glossiness, color and processing properties, and thermoplastics containing the graft copolymer It relates to a resin composition.
  • ABS-based copolymers represented by vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer are impact resistance, mechanical strength, moldability, gloss Due to its good physical properties such as degree, it is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts.
  • an aromatic vinyl compound and a vinyl cyan compound monomer are grafted to a conjugated diene rubber latex by emulsion polymerization to produce an ABS-based copolymer, it exhibits a good physical property balance compared to an ABS-based copolymer produced by bulk polymerization and exhibits excellent gloss, etc. Since it has the advantage of having an ABS-based copolymer is mainly produced by emulsion polymerization.
  • ABS-based copolymer latex produced by emulsion polymerization is preferably processed into a powder for the reduction of volume, various utilization and ease of handling, and usually, the ABS-based resin latex is agglomerated, aged, dehydrated and dried. An ABS resin powder can be obtained.
  • Aggregation of the ABS-based copolymer latex prepared by emulsion polymerization can chemically aggregate latex particles stabilized by the emulsifier used for emulsion polymerization using various flocculants, and the flocculant may use acid or metal salt.
  • Aggregation of latex using an acid has a disadvantage that the thermal stability of the ABS-based resin is reduced by the residual acid, and the amount of gas generated during the thermoforming process is high, so that the yellowness of the resin is high.
  • agglomeration of latex using a metal salt has a relatively low gas generation amount and yellowness, but has a problem of low productivity.
  • Patent Document 1 Korean Patent Registration No. 10-0463482
  • the present invention is an acid flocculant 0.10 to 0.80 with respect to 100 parts by weight of graft copolymer latex (based on solid content) graft polymerized with an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex.
  • a first agglomeration step of aggregating by adding a weight part And a second agglomeration step in which 0.96 to 1.85 parts by weight of a salt flocculant is added after the first flocculation step to aggregate, and the total weight of the acid flocculant and salt flocculant is adjusted to 1.66 to 2.20 parts by weight, resulting in excellent cohesion efficiency and gloss High and low b value (b value) measured using a Hunter Lab color meter and b value (b value) measured after staying at an injection machine at 250°C for 15 minutes, excellent color, low heat loss, and long scorch time. It is an object to provide a method for producing a graft copolymer having excellent properties.
  • the present invention is a graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight.
  • Preparing a graft copolymer latex A first agglomeration step in which 0.10 to 0.80 parts by weight of an acid coagulant is added to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second coagulation step in which 0.96 to 1.85 parts by weight of the salt coagulant is added after the first coagulation step to aggregate, and the total amount of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight.
  • a method for preparing a compound-aromatic vinyl compound graft copolymer is provided.
  • the present disclosure provides a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer prepared by the above production method.
  • the present description includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and an aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight according to the above production method It provides a thermoplastic resin composition characterized by.
  • the graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber latex is agglomerated with 0.10 to 0.80 parts by weight of an acid coagulant, and then agglomerated with 0.96 to 1.85 parts by weight of a salt flocculant
  • the gloss is high while the cohesive efficiency is high, and the b value measured using a HunterLab color meter and the b value measured after staying at 250°C for 15 minutes are low. This has excellent effect, low heating loss and long scorch time, so it has the effect of excellent processing characteristics.
  • the present inventors agglomerated the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex with an acid coagulant, and then agglomerated with a salt coagulant. The effect of excellent color and processing characteristics was confirmed, and based on this, more research was conducted to complete the present invention.
  • the method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is 20 to 40% by weight of the aromatic vinyl compound and 50 to 70% by weight of the conjugated diene rubber latex having a solid content of 30 to 65% by weight, and vinyl Graft polymerization of 1 to 20% by weight of the cyan compound to prepare a graft copolymer latex;
  • a first agglomeration step in which 0.10 to 0.80 parts by weight of an acid coagulant is added to 100 parts by weight of the prepared graft copolymer latex (based on solid content);
  • a second coagulation step in which 0.96 to 1.85 parts by weight of a salt coagulant is added and then coagulated after the first coagulation step, wherein the sum of the weights of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight, in this case Excellent cohesive efficiency, excellent b-value measured using HunterLab color meter and low b-value
  • the manufacturing method of the conjugated diene rubber latex is, for example, 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, and 0.1 to 0.5 parts by weight of a molecular weight modifier, and It may include the step of preparing 0.1 to 1 part by weight of the initiator and polymerizing to form a conjugated diene rubber latex, and in this case, there is an excellent impact resistance effect.
  • the method for preparing the conjugated diene rubber latex is 100 parts by weight of a conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, and 0.2 to 0.4 parts by weight of a molecular weight modifier. And adding 0.3 to 0.8 parts by weight of the initiator and polymerizing to prepare a conjugated diene rubber latex, in which case there is an excellent impact resistance effect.
  • the manufacturing method of the conjugated diene rubber latex is 30 to 100 parts by weight of ion-exchanged water, 0.3 to 2 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, and a molecular weight modifier 0.1 to 0.5 parts by weight of the initiator and 0.05 to 0.5 parts by weight of the initiator and primary polymerization;
  • the polymerization conversion rate of 35 to 45% at the time of adding 0.05 to 0.5 parts by weight of the initiator, 10 to 25 parts by weight of the conjugated diene compound continuously, and secondary polymerization;
  • the polymerization conversion rate is 70 to 80%, and 0.2 to 1 part by weight of an emulsifier is added, followed by tertiary polymerization; And terminating the polymerization at a polymerization conversion rate of 93 to 99% by weight after the third polymerization step.
  • impact resistance is excellent.
  • the polymerization conversion rate may be defined as the weight percentage of the monomer converted to the polymer until measurement based on 100% of the total weight of the monomers input until the end of polymerization, and the method for measuring the polymerization conversion rate is measured according to this definition.
  • the polymerization conversion rate measurement method it is not particularly limited, and after 1.5 g of the latex prepared in a specific example is dried in a 150° C. hot air dryer for 15 minutes, the weight is measured to calculate the total solid content (Total Solid Content; TSC). It can be obtained and calculated using Equation 2 below. Equation 2 is based on the total weight of the injected monomer is 100 parts by weight.
  • Polymerization conversion rate (%) [Total solids content (TSC) ⁇ (total weight of the added monomers, ion-exchanged water and auxiliary materials) / 100]-(weight of added sub-materials other than monomer and ion-exchanged water)
  • the auxiliary material refers to an initiator, an emulsifier, an electrolyte, and a molecular weight modifier.
  • the injected monomer refers to a conjugated diene compound.
  • the conjugated diene compound is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene. It may be abnormal.
  • the emulsifier may be, for example, one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.
  • the electrolyte is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 and Na 2 HPO 4 .
  • the initiator may be, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and the like, and the water-soluble persulfate polymerization initiator may include, for example, potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the fat-soluble polymerization initiator is, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramethane hydroperoxide and benzoyl
  • the oxidation-reduction catalyst system include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and ah. It may be one or more selected from the group consisting of sodium sulfate.
  • the conjugated diene rubber latex it may be most preferably potassium persulfate.
  • the molecular weight modifier may be, for example, a mercaptan-based molecular weight modifier, and a tertiary dodecyl mercaptan is particularly preferable.
  • the conjugated diene rubber latex of the present base material may have, for example, an average particle diameter of 1,800 to 5,000 mm 2, preferably 2,000 to 4,000 mm 2, more preferably 2,500 to 3,500 mm 2, and has excellent impact resistance within this range.
  • the average particle diameter of the conjugated diene rubber latex is diluted to less than 0.1% of the total solids content (TSC) to prepare a sample, and then the Nicomp TM 380 instrument (USA, PSS, Nicomp) is used by dynamic laser light skating. Can be measured.
  • the step of preparing the graft copolymer latex for example, 20 to 40 wt% of aromatic vinyl compounds and 1 to 20 wt% of vinyl cyan compounds are grafted to 50 to 70 wt% of conjugated diene rubber latex having a solid content of 30 to 65 wt%.
  • the solid content is defined as the content of the active ingredient remaining when all the moisture in the latex is evaporated, and after measuring 2.5g of latex on a balance with an aluminum dish, heat it for 5 minutes with heat at 150°C to evaporate all the moisture. It can be obtained by measuring the weight by the following equation (3).
  • Solid content 100-[(Weight of latex before moisture drying (g)-Weight of powder remaining after moisture drying (g))/Weight of latex before moisture drying]
  • the step of preparing the graft copolymer latex is, for example, 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 70 to 200 parts by weight of ion-exchanged water, 0.1 to 2 parts by weight of an initiator, and 0.1 to 2 parts by weight of an emulsifier.
  • the polymerization reaction may be terminated at a polymerization conversion rate of 93 to 99% by weight.
  • the polymerization conversion rate follows the definition and measurement method of the polymerization conversion rate described above in the preparation step of the conjugated diene rubber latex, but the injected monomer means the conjugated diene compound, the aromatic vinyl compound, and the vinyl cyan compound contained in the rubber latex.
  • the step of preparing the graft copolymer latex includes 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 100 to 170 parts by weight of ion-exchanged water, 0.3 to 1 parts by weight of an initiator, and an emulsifier.
  • the polymerization reaction may be terminated at a polymerization conversion rate of 95 to 98% by weight.
  • the step of preparing the graft copolymer latex comprises 50 to 70% by weight of conjugated diene rubber latex and 30 to 65% by weight of solid content based on 100 parts by weight of the conjugated diene rubber, aromatic vinyl compound, and vinyl cyan compound.
  • the conjugated diene rubber latex may have, for example, a solid content of 30 to 65% by weight, preferably 40 to 60% by weight, more preferably 55 to 60% by weight, and in this case, the polymerization reaction proceeds uniformly There is.
  • the aromatic vinyl compound is, for example, styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ⁇ -brobo styrene, ⁇ -bro It may be one or more selected from the group consisting of parent styrene, m-bromo styrene, ⁇ -chloro styrene, ⁇ -chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene and vinyl naphthalene.
  • the vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.
  • the emulsifier, initiator and molecular weight modifier may be used, for example, within the range used in the preparation of the conjugated diene rubber latex.
  • additives such as electrolytes, etc., which are not specifically mentioned in the present description, may be appropriately selected as needed, and are particularly limited in the range generally applicable to the production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex. Does not work.
  • reaction conditions such as reaction time, reaction temperature, pressure, reactant input time, etc. in the method for preparing a graft copolymer other than the above-described substrates, are not particularly limited if they are within the range commonly used in the technical field to which the present invention pertains. It can be carried out by appropriately selecting according to.
  • the graft copolymer latex prepared above is aggregated by a flocculant to form a graft copolymer slurry.
  • the agglomeration step is a first agglomeration step to agglomerate by adding 0.10 to 0.80 parts by weight of an acid coagulant with respect to 100 parts by weight of the graft copolymer latex prepared as an example (based on solid content); And a second agglomeration step in which 0.96 to 1.85 parts by weight of a salt flocculant is added after the first flocculation step to aggregate, and the sum of the acid flocculant and the salt flocculant may be 1.66 to 2.20 parts by weight,
  • the gloss is high and the b value measured using a Hunter Lab color meter and the b value measured after staying at 250° C. for 15 minutes have low color, excellent heating, low scorch time, and excellent processing characteristics.
  • the first coagulation step may be, for example, an acid flocculant added to the graft copolymer latex at 75 to 85° C., and then a temperature of 5 to 10° C. from 5 to 35° C. may be increased.
  • the flocculant is added at 78 to 82° C., it may be a step of raising the temperature over a period of 10 to 30 minutes by 6 to 8° C. In this case, coagulation is uniformly performed and coagulation efficiency is excellent.
  • a salt coagulant is introduced at 80 to 95° C., from which it can be heated over 5 to 35 minutes by 5 to 10° C., preferably a salt coagulant is added at 84 to 90° C. , From this, the temperature can be increased over a period of 10 to 30 minutes by 6 to 8°C, and in this case, there is an effect that aggregation is uniformly performed, and aggregation efficiency is excellent and aged.
  • the temperature at which the first agglomeration step ends and the temperature at which the second agglomeration step starts may be the same.
  • the first agglomeration step and the second agglomeration step may be performed under conditions of, for example, agitation speeds of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm. , But is not limited thereto. Productivity is excellent within the stirring speed range, and cohesion efficiency is high, and there is an effect of excellent physical property balance.
  • the acid flocculant is, for example, 0.10 to 0.80 parts by weight, preferably 0.15 to 0.75 parts by weight, more preferably 0.20 to 0.70 parts by weight, even more preferably 100 parts by weight of the graft copolymer latex (based on solid content) 0.20 to 0.50 parts by weight, or 0.50 to 0.70 parts by weight can be agglomerated, excellent cohesive efficiency within this range, high gloss, and a b value measured using a HunterLab color meter and 250°C for 15 minutes It is excellent in color, low color loss, long scorch time, and excellent processing characteristics.
  • the salt coagulant is, for example, 0.96 to 1.85 parts by weight, or 0.96 to 1.80 parts by weight, preferably 1.00 to 1.80 parts by weight, more preferably 1.25 to 1.80 parts by weight based on 100 parts by weight of the graft copolymer latex (based on solid content). Part, more preferably, it can be agglomerated by including 1.30 to 1.50 parts by weight, within this range is excellent glossiness, low heating loss and long scorch time, there is an effect of excellent processing characteristics.
  • the total amount of the acid coagulant and the salt coagulant is, for example, 1.66 to 2.20 parts by weight, or 1.70 to 2.10 parts by weight, preferably 1.70 to 2.00 parts by weight, more preferably 100 parts by weight of the graft copolymer latex (based on solid content).
  • the acid coagulant may be, for example, one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid, preferably sulfuric acid, in this case at a b value and 250° C. measured using a HunterLab colorimeter. The b-value measured after 15 minutes of residence has an excellent effect.
  • the salt coagulant may be, for example, one or more selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, and aluminum chloride, preferably magnesium sulfate, and in this case, aggregation efficiency is good. It has an excellent glossiness effect.
  • the acid coagulant and the salt coagulant contain a solvent such as water
  • their weight means the weight excluding the solvent
  • the agglomeration step may further include, for example, antioxidants, stabilizers, or a mixture thereof, and in this case, there is an excellent effect in physical properties balance after extrusion.
  • the agglomerated graft copolymer latex may be dehydrated and dried to obtain a graft copolymer powder.
  • a powder refers to an object in a state in which a large number of solid particles are aggregated.
  • an object having an average particle diameter in a state in which a large number of solid particles are aggregated may be 1 to 10,000 ⁇ m or 10 to 2,000 ⁇ m. have.
  • the average particle diameter of the powder can be measured by a DP caking test.
  • the DP caking test specifically compresses 10 g of powder with a weight of 20 kg for 10 minutes, and then stacks layers from #8 mesh (2380 ⁇ m) to #625 mesh (20 ⁇ m) on a sieve vibrator (Analysette 3) of Fritsch, Germany. After installing a stainless steel container capable of collecting powder that passes through 625 mesh at the bottom of #625 mesh, apply vibration to the sieve vibrator for 20 minutes, check the particle size distribution of the powder remaining in the mesh, and accumulate in the particle size distribution. The diameter of particles passing through 50% by weight is taken as the average particle size of the powder.
  • the dehydration and drying step is not particularly limited when it is a method generally used in the art.
  • the slurry obtained after the agglomeration can be dehydrated using a centrifugal dehydrator, a press-type dehydrator, for example, to obtain a wet powder graft copolymer.
  • the dehydration may be preferably performed at least once, preferably 1 to 3 times, more preferably 2 to 3 times as an example, and in this case, the residual emulsifier content is reduced to improve surface properties such as glossiness. It has the effect.
  • the graft copolymer in the wet powder state obtained after the dehydration has a water content of, for example, 40% by weight or less, preferably 10 to 40% by weight, more preferably 10 to 35% by weight or 10 to 30% by weight. %, in this case, there is an advantage in that productivity is increased by increasing efficiency in a drying step, which is a post-process.
  • the drying is not particularly limited in the case of a known drying process that is commonly practiced in the technical field to which the present invention pertains.
  • a fluidized bed dryer After supplying and drying, a graft copolymer powder can be obtained.
  • the graft copolymer powder obtained by drying the wet powder-type graft copolymer may have a water content of, for example, 2% by weight or less, preferably 0.1 to 2% by weight, and more preferably 0.1 to 1% by weight.
  • a water content of, for example, 2% by weight or less, preferably 0.1 to 2% by weight, and more preferably 0.1 to 1% by weight.
  • the water content can be measured using a moisture analyzer, specifically, it can be measured with a moisture analyzer from METTLER TOLEDO of Switzerland.
  • the graft copolymer powder can be extruded after melt-kneading with an aromatic vinyl compound-vinyl cyan compound copolymer as an example, and in this case, has excellent impact resistance, chemical resistance, moldability, etc., excellent glossiness, and Hunter wrap color.
  • the b-value measured using a meter and the b-value measured after staying at 250° C. for 15 minutes can be low to produce a beautifully colored thermoplastic resin composition.
  • the melt kneading and extrusion steps may be performed under 220 to 240° C. and 250 to 400 rpm, for example, 225 to 235° C. and 300 to 400 rpm, for example, but are not limited thereto.
  • the melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader, etc., and is not particularly limited.
  • one or more additives selected from the group consisting of colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight It can be injected within the sub-range.
  • the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is characterized by being manufactured by the above manufacturing method, and in this case, a b value and 250 measured using a HunterLab colorimeter. After staying at °C for 15 minutes, the measured b value is low and the gloss is high, so the color is excellent. It works.
  • thermoplastic resin composition of the present disclosure is 20 to 40% by weight of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, preferably 25 to 35% by weight, and aromatic vinyl compound-vinyl cyan compound copolymer 60 It characterized in that it contains 80 to 80% by weight, preferably 65 to 75% by weight, in this case it is excellent in impact resistance, chemical resistance, moldability and gloss, b value measured using a Hunter Lab color meter and After staying at 250°C for 15 minutes, the measured b-value is low, so the color has a beautiful effect.
  • the thermoplastic resin composition is, for example, a glossiness of a specimen having a thickness of 1/8 inch (3.2 mm) measured at a 45° angle with a gloss meter in accordance with ASTM D523. It may be from 110 to 110, preferably from 92 to 102, more preferably from 96 to 100, and within this range, physical properties and color are excellent.
  • thermoplastic resin composition may have a b value of 3.6 or less, preferably 3.0 to 3.6, more preferably 3.2 to 3.5, measured using a HunterLab color meter, and excellent in physical property balance and color within this range. It works.
  • the thermoplastic resin composition has a b value of 9 or less, preferably 3 to 9, more preferably 5 to 9, and more preferably 5 to 9, measured using a HunterLab colorimeter after 15 minutes of residence at 250°C, for example. It may be 8, and within this range, the physical properties balance and color are excellent.
  • the thermoplastic resin composition may have, for example, a scorch time by a scorch test at 190° C. for 60 minutes or more, or 80 minutes or more, preferably 80 to 180 minutes, more preferably 80 to 150 minutes. There is an effect of excellent processing properties and physical properties balance within this range.
  • the scorch time is the time when the flow stops in the mold and the rubber starts to ripen. If the scorch time is short, the unvulcanized compound is vulcanized during molding at a high temperature, thereby increasing the frequency of molding failure.
  • the scorch time is a scorch time by placing the thermoplastic resin composition powder having a water content of 1% by weight or less in an aluminum foil in a state where it can be contacted with oxygen in the air, leaving it in a hot air oven at 190°C and measuring the time at which carbonization starts. .
  • the water content can be measured using a moisture analyzer, specifically, it can be measured with a moisture analyzer from METTLER TOLEDO of Switzerland.
  • the thermoplastic resin composition may have a heating loss of 0.8% by weight or less, or 0.1 to 0.8% by weight, preferably 0.1 to 0.6% by weight, more preferably 0.4 to 0.6% by weight, and processing characteristics within this range. And it has the effect of excellent physical properties balance.
  • the reduction in heating is a decrease in weight generated during heating of a substance under certain conditions, and is heated under a nitrogen atmosphere at a heating rate of 20° C./min from 80° C. to 250° C., and then maintained under 250° C. for 60 minutes.
  • the weight before and after heating can be determined by measuring by thermogravimetric analysis (TGA). The lower the heating loss, the better the processing characteristics.
  • Heating loss ⁇ (Weight before heating-Weight after heating)/Weight before heating ⁇ 100
  • ion-exchanged water in a nitrogen-substituted polymerization reactor 55 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 85 parts by weight of 100 parts by weight of 1,3-butadiene as a monomer, 1.5 parts by weight of a fatty acid metal salt of C16 to C18 as an emulsifier, potassium carbonate as an electrolyte (K 2 CO 3 ) 0.15 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and 0.3 parts by weight of potassium persulfate as an initiator were collectively administered and polymerized at a reaction temperature of 70°C.
  • TDDM tertiary dodecyl mercaptan
  • the prepared conjugated diene rubber latex had an average particle diameter of 3,000 ⁇ and a solid content of 55 to 60% by weight.
  • ABS graft copolymer ⁇ Production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as "ABS graft copolymer")>
  • Example 1 the contents of sulfuric acid and magnesium sulfate were changed in the same manner as in Example 1, except that the contents of Table 1 were changed.
  • Comparative Example 1 it was carried out in the same manner as in Comparative Example 1, except that 2 parts by weight of magnesium sulfate was added instead of 2 parts by weight of sulfuric acid.
  • Comparative Example 1 it was carried out in the same manner as in Comparative Example 1, except that 1 part by weight of sulfuric acid and 1 part by weight of magnesium sulfate were mixed instead of 2 parts by weight of sulfuric acid.
  • Comparative Example 1 it was carried out in the same manner as in Comparative Example 1, except that sulfuric acid and magnesium sulfate were mixed and added in the contents shown in Table 2 below.
  • Example 1 it was carried out in the same manner as in Example 1, except that the input order and content of sulfuric acid and magnesium sulfate were changed and input as shown in Table 3 below.
  • thermoplastic resin composition having a water content of 1% by weight or less was put in an aluminum foil in a state where it can be contacted with oxygen in the air, and a time at which a hot air oven at 190°C was left to stand and carbonization was measured was measured.
  • Heating loss (% by weight): Under a nitrogen atmosphere, the temperature rises from 80°C to 250°C at a rate of 20°C/min, and then heats under conditions maintained at 250°C for 60 minutes to analyze the weight of the resin before and after heating by thermal gravimetric analysis (TGA It was measured by) and calculated by the following equation (4).
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Coagulant input method After adding the first coagulant, adding the second coagulant First flocculant (parts by weight) H 2 SO 4 0.2 H 2 SO 4 0.3 H 2 SO 4 0.5 H 2 SO 4 0.7 H 2 SO 4 0.7 H 2 SO 4 0.45 Second flocculant (parts by weight) MgSO 4 1.8 MgSO 4 1.7 MgSO 4 1.5 MgSO 4 1.3 MgSO 4 1.0 MgSO 4 1.4 Total flocculant (parts by weight) 2.0 2.0 2.0 2.0 2.0 1.7 1.85 b value 3.2 3.2 3.2 3.2 3.3 3.2 B value after stay 9 9 8 8 8 8 Glossiness 97 97 97 97 96 97 Scorch time (min.) 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more 80 minutes or more Heating loss (% by weight) 0.4 0.4 0.5 0.4 0.6 0.5
  • Examples 1 to 6 according to the present invention have high gloss, and a b value measured using a HunterLab color meter and a b value measured after a 15 minute stay at 250° C. Not only was the color excellent, but the scorch time was long and the heating loss was low, so the processing characteristics were excellent.
  • Comparative Examples 1 and 2 containing the acid flocculant or the salt flocculant alone and the acid flocculant and the salt flocculant were mixed in batches, and Comparative Examples 3 to 7 were measured for gloss and b values measured using a HunterLab color meter. After staying at 250°C for 15 minutes, the measured b value, scorch time, and heating loss were poor.
  • Comparative Examples 8 to 12 in which the acid coagulant was added after the salt coagulant was agglomerated and the glossiness, the b value measured using a Hunter Lab color meter, and the b value measured after 15 minutes of residence at 50° C. and scorch time. Or the heating loss was poor.

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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)
  • Dispersion Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un copolymère greffé et une composition de résine thermoplastique comprenant le copolymère greffé et, plus spécifiquement, un procédé de préparation d'un copolymère greffé, comprenant l'étape consistant à ajouter un coagulant acide par rapport à 100 parties en poids (sur la base de la teneur en matières solides) d'un latex de copolymère greffé dans lequel un composé vinyle aromatique et un composé de cyan vinylique sont polymérisés par greffage avec un latex de caoutchouc de diène conjugué pour provoquer la coagulation, puis l'ajout à nouveau d'un coagulant de sel à celui-ci pour provoquer la coagulation. Selon la présente description, lorsqu'une préparation est réalisée selon le procédé décrit ci-dessus, il y a des effets d'une excellente efficacité de coagulation, d'un degré élevé de brillance, d'une excellente couleur due à une faible valeur b mesurée à l'aide d'un colorimètre HunterLab et à une faible valeur b mesurée après un temps de rétention de 15 minutes à 250 °C, et d'excellentes propriétés de traitement dues à une faible perte de chauffage et un long temps de grillage.
PCT/KR2019/013802 2018-12-14 2019-10-21 Procédé de préparation d'un copolymère greffé de composé de vinyle aromatique conjugué à un composé cyan vinylique et composition de résine thermoplastique comprenant un copolymère greffé WO2020122407A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/954,132 US11634527B2 (en) 2018-12-14 2019-10-21 Method of preparing vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and thermoplastic resin composition including graft copolymer
EP19880937.8A EP3696201B1 (fr) 2018-12-14 2019-10-21 Procédé de préparation d'un copolymère greffé de composé de vinyle aromatique conjugué à un composé cyan vinylique et composition de résine thermoplastique comprenant un copolymère greffé
CN201980006748.3A CN111566136B (zh) 2018-12-14 2019-10-21 乙烯基氰化合物-共轭二烯化合物-芳香族乙烯基化合物接枝共聚物的制备方法和组合物
JP2020542102A JP7011073B2 (ja) 2018-12-14 2019-10-21 ビニルシアン化合物－共役ジエン化合物－芳香族ビニル化合物グラフト共重合体の製造方法、及びそのグラフト共重合体を含む熱可塑性樹脂組成物

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KR20180161808 2018-12-14
KR10-2018-0161808 2018-12-14
KR1020190129090A KR102297798B1 (ko) 2018-12-14 2019-10-17 비닐시안 화합물-공액디엔 화합물-방향족 비닐 화합물 그라프트 공중합체의 제조방법 및 이 그라프트 공중합체를 포함하는 열가소성 수지 조성물
KR10-2019-0129090 2019-10-17

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US5514772A (en) * 1993-02-16 1996-05-07 Mitsubishi Rayon Co., Ltd. Method for producing powdery and granular polymers
KR19990017231A (ko) * 1997-08-22 1999-03-15 사공수영 내열성이 우수한 열가소성 수지 분말의 제조방법
KR100463482B1 (ko) 2001-08-06 2004-12-29 제일모직주식회사 고무라텍스의 응집입자 제조방법
KR20090079372A (ko) * 2008-01-17 2009-07-22 주식회사 엘지화학 열안정성이 우수한 열가소성 수지 분체의 제조방법
KR20180051839A (ko) * 2016-11-09 2018-05-17 주식회사 엘지화학 Abs계 수지 분체의 제조방법 및 표면특성이 향상된 abs계 수지 조성물의 제조방법
KR20190129090A (ko) 2017-03-28 2019-11-19 가부시키가이샤 고베 세이코쇼 타이어 시험 방법 및 타이어 시험 장치

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KR930012958A (ko) * 1991-12-14 1993-07-21 유영학 열안정성이 우수한 열가소성 수지의 제조방법
US5514772A (en) * 1993-02-16 1996-05-07 Mitsubishi Rayon Co., Ltd. Method for producing powdery and granular polymers
KR19990017231A (ko) * 1997-08-22 1999-03-15 사공수영 내열성이 우수한 열가소성 수지 분말의 제조방법
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