Method for preparing rubbery polymer, rubbery polymer, graft copolymer and resin composition

Abstract

The present invention relates to a method for manufacturing a rubbery polymer, comprising the step (S10) of polymerizing a conjugated diene monomer to produce a conjugated diene polymer latex containing a conjugated diene polymer, wherein the step (S10) is carried out by including a crosslinking agent represented by Formula 1 (see description of the invention) and a crosslinking agent represented by Formula 2 (see description of the invention). The invention also relates to a rubbery polymer, a graft copolymer, and a resin composition.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a rubbery polymer, and specifically to a method for manufacturing a rubbery polymer that can be used in the manufacture of a graft copolymer, a rubbery polymer, a graft copolymer comprising a rubbery polymer, and a resin composition comprising a graft copolymer. Background Technology

[0002] Acrylonitrile-butadiene-styrene (ABS) copolymers are manufactured by graft copolymerizing styrene and acrylonitrile onto a butadiene rubbery polymer. Compared to conventional high-impact polystyrene (HIPS), ABS copolymers have superior impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, stiffness, and processability, and are used in automotive interior and exterior materials, office equipment, parts for various electrical and electronic products, and toys.

[0003] Among these, for ABS copolymers intended for use in fields requiring high impact resistance, it is necessary to use large-diameter rubbery polymers or manufacture rubbery polymer latex with appropriately controlled gel content in order to improve impact resistance through rubbery polymers.

[0004] Here, in order to introduce a large-diameter rubbery polymer, there is a method of polymerizing a small-diameter rubbery polymer and then enlarging the small-diameter rubbery polymer through a coagulant such as a polymer coagulant, or polymerizing a large-diameter rubbery polymer separately and mixing them. However, this has the problem of low production efficiency because, after polymerizing the small-diameter rubbery polymer, a polymer coagulant or a large-diameter rubbery polymer must be polymerized separately.

[0005] In addition, regarding the control of gel content, in order to improve the productivity of rubbery polymers, it is necessary to increase the polymerization conversion rate during the polymerization of rubbery polymers. However, if the polymerization conversion rate is increased, the gel content also increases, and consequently, there is a problem in that the impact resistance actually decreases.

[0006] As a solution to this problem, a method has been proposed to control the polymerization conversion rate and gel content by introducing a molecular weight regulator during the polymerization of rubbery polymers. However, when the molecular weight regulator is added excessively, the polymerization reaction is delayed, which leads to a decrease in productivity, and there is a problem in that the polymerization conversion rate cannot be increased to over 90% in order to maintain the gel content at an appropriate level. Prior art literature

[0007] JP1996-259777A The problem to be solved

[0008] The present invention was devised to solve the problems of the prior art described above, and aims to provide a method for manufacturing a rubbery polymer that can improve impact resistance by controlling the gel content of the rubbery polymer, while ensuring productivity by increasing the polymerization conversion rate during the polymerization of the rubbery polymer, and lowering the crosslinking density through thermal decomposition of the crosslinking agent during the processing of a resin composition containing a graft copolymer produced by graft polymerization from the rubbery polymer.

[0009] In addition, the present invention aims to provide a rubbery polymer produced from the above method for producing a rubbery polymer, a graft copolymer graft-polymerized from the rubbery polymer, and a resin composition comprising the graft copolymer. means of solving the problem

[0010] To solve the above problem, the present invention provides a method for manufacturing a rubbery polymer comprising the step (S10) of polymerizing a conjugated diene monomer to produce a conjugated diene polymer latex containing a conjugated diene polymer, wherein the step (S10) is carried out by including a crosslinking agent represented by the following chemical formula 1 and a crosslinking agent represented by the following chemical formula 2.

[0011] [Chemical Formula 1]

[0012]

[0013] In the above chemical formula 1, R 1 and R 5 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is not simultaneously hydrogen, and R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and

[0014] [Chemical Formula 2]

[0015]

[0016] In the above chemical formula 2, R 6 is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each is independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 30, where a+b+c is an integer selected from 1 to 30.

[0017] In addition, the present invention provides a rubbery polymer comprising a conjugated diene monomer unit; a crosslinking agent unit represented by Formula 1; and a crosslinking agent unit represented by Formula 2.

[0018] In addition, the present invention provides a graft copolymer comprising a rubbery polymer, wherein the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by Formula 1; and a crosslinking agent unit represented by Formula 2, and the graft copolymer comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0019] In addition, the present invention provides a resin composition comprising a graft copolymer, wherein the graft copolymer comprises a rubbery polymer, wherein the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by Formula 1; and a crosslinking agent unit represented by Formula 2, and wherein the graft copolymer comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit. Effects of the invention

[0020] According to the method for manufacturing a rubbery polymer of the present invention, it is possible to manufacture a rubbery polymer with a high polymerization conversion rate during the polymerization of a rubbery polymer, thereby improving the productivity of the rubbery polymer.

[0021] In addition, since the rubbery polymer produced according to the method for producing a rubbery polymer of the present invention includes a pyrolytic crosslinking agent unit, when processing a resin composition containing a graft copolymer graft-polymerized from the rubbery polymer, the pyrolytic crosslinking agent unit is pyrolytically decomposed by the heat source of the processing process, thereby lowering the crosslinking density of the rubbery polymer and controlling the gel content of the rubbery polymer, and accordingly, the impact resistance of the molded article formed from the resin composition is improved.

[0022] In other words, according to the method for manufacturing a rubbery polymer of the present invention, there is an effect of simultaneously improving the productivity of the rubbery polymer and securing impact resistance. Specific details for implementing the invention

[0023] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0024] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0025] In the present invention, the term 'monomer unit' may refer to a component, structure, or the material itself derived from a monomer, and as a specific example, may refer to a repeating unit formed within a polymer by a monomer introduced during the polymerization of a polymer and participating in the polymerization reaction.

[0026] In the present invention, the term 'crosslinking agent unit' may refer to a component, structure, or the material itself derived from the crosslinking agent, and, as a specific example, may refer to a unit formed by the crosslinking agent during a crosslinking reaction by the crosslinking agent.

[0027] The term 'composition' as used in the present invention includes reaction products and decomposition products formed from the materials of the said composition, as well as mixtures of materials containing said composition.

[0028] In the present invention, 'polymerization conversion rate' indicates the degree to which monomers are polymerized by a polymerization reaction to form a polymer, and may be calculated by taking a portion of the polymer from the reactor during polymerization and using the following mathematical formula 1.

[0029] [Mathematical Formula 1]

[0030] Polymerization conversion rate (%) = [(Total content of input monomers - Total content of unreacted monomers) / Total content of input monomers] × 100

[0032] The present invention provides a method for manufacturing a rubbery polymer.

[0033] According to one embodiment of the present invention, the method for manufacturing a rubbery polymer comprises the step (S10) of polymerizing a conjugated diene monomer to produce a conjugated diene polymer latex comprising a conjugated diene polymer, and the step (S10) may be carried out by including a crosslinking agent represented by the following chemical formula 1 and a crosslinking agent represented by the following chemical formula 2.

[0034] [Chemical Formula 1]

[0035]

[0036] In the above chemical formula 1, R 1 and R 5 Each can independently be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but may not simultaneously be hydrogen, and R 4 It may be a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0037] [Chemical Formula 2]

[0038]

[0039] In the above chemical formula 2, R 6 Silver may be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each may independently be a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c may each independently be an integer selected from 0 or 1 to 30, and a+b+c may be an integer selected from 1 to 30.

[0040] According to one embodiment of the present invention, the step (S10) is a step for producing a conjugated diene polymer latex comprising a conjugated diene polymer by polymerizing a conjugated diene monomer, and can be carried out by emulsion polymerization as a specific example.

[0041] According to one embodiment of the present invention, the conjugated diene monomer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and more specifically, 1,3-butadiene may be used.

[0042] According to one embodiment of the present invention, in step (S10), the conjugated diene monomer may be introduced in its entirety before the start of polymerization, or a portion may be introduced before the start of polymerization and the remainder during the polymerization. When performing step (S10), if the conjugated diene monomer is introduced in a divided manner before the start of polymerization and during the polymerization, it has the effect of increasing the average particle size of the rubbery polymer while improving the particle size uniformity of the rubbery polymer being produced. As a specific example, in step (S10), 30% to 70% or 40% to 60% by weight of the conjugated diene monomer may be introduced before the start of polymerization, and 30% to 70% or 40% to 60% by weight may be introduced during the polymerization. As a more specific example, in step (S10) above, the conjugated diene monomer may be introduced in an amount of 30% to 70% or 40% to 60% by weight before the start of polymerization, in an amount of 15% to 35% or 20% to 30% by weight at a time when the polymerization conversion rate is 40% to 60%, and in an amount of 15% to 35% or 20% to 30% by weight at a time when the polymerization conversion rate is 65% to 80%.

[0043] According to one embodiment of the present invention, the emulsion polymerization of step (S10) may be carried out in the presence of an emulsifier, and the emulsifier may be a fatty acid-based emulsifier or a fatty acid dimer-based emulsifier.

[0044] According to one embodiment of the present invention, the content of the emulsifier in step (S10) may be 0.1 to 10.0 parts by weight, 0.8 to 8.0 parts by weight, or 1.0 to 6.0 parts by weight per 100 parts by weight of the conjugated diene monomer, and within this range, it is possible to produce a rubbery polymer having an average particle size suitable for ensuring impact resistance.

[0045] According to one embodiment of the present invention, in step (S10), the emulsifier may be added in its entirety before the start of polymerization, or a portion may be added before the start of polymerization and the remainder added during the polymerization process. When performing step (S10), if the emulsifier is added in divided portions before the start of polymerization and during the polymerization process, it has the effect of increasing the average particle size of the rubbery polymer while improving the particle size uniformity of the rubbery polymer being produced. As a specific example, in step (S10), a portion of the emulsifier may be added before the start of polymerization and the remainder added during the polymerization process. As a more specific example, in step (S10), a portion of the emulsifier may be added before the start of polymerization, a portion may be added when the polymerization conversion rate is 70% to 79%, and the remainder may be added when the polymerization conversion rate is 80% to 90%. At this time, the types of emulsifier added before the start of polymerization and during the polymerization process may be different from each other.

[0046] According to one embodiment of the present invention, step (S10) may be carried out by radical polymerization using an initiator that can be used in emulsion polymerization, specifically examples such as a water-soluble initiator, a peroxide-based, redox, or azo-based initiator. The water-soluble initiator may be potassium persulfate or ammonium persulfate, and the redox initiator may be one or more selected from the group consisting of, for example, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. In this case, it has the effect of providing a stable polymerization environment. Additionally, when using the redox initiator, ferrous sulfate, dextrose, and sodium pyrrole phosphate may be further included as redox catalysts.

[0047] According to one embodiment of the present invention, the content of the initiator in step (S10) may be 0.01 to 5.00 parts by weight, 0.05 to 3.00 parts by weight, or 0.1 to 1.0 parts by weight per 100 parts by weight of the conjugated diene monomer, and within this range, it is possible to produce a rubbery polymer having an average particle size suitable for ensuring impact resistance.

[0048] According to one embodiment of the present invention, in step (S10), the initiator may be added in its entirety before the start of polymerization, or a portion may be added before the start of polymerization and the remainder added during the polymerization process. When performing step (S10), if the initiator is divided and added before the start of polymerization and during the polymerization process, it has the effect of increasing the average particle size of the rubbery polymer while improving the particle size uniformity of the rubbery polymer being produced. As a specific example, in step (S10), a portion of the initiator may be added before the start of polymerization and the remainder added during the polymerization process. As a more specific example, in step (S10), a portion of the initiator may be added before the start of polymerization, a portion may be added when the polymerization conversion rate is 70% to 79%, and the remainder may be added when the polymerization conversion rate is 80% to 90%. At this time, the types of initiators added before the start of polymerization and during the polymerization process may be different from each other.

[0049] According to one embodiment of the present invention, the step (S10) may be carried out in the presence of a molecular weight regulator, and the molecular weight regulator may be a mercaptan-based molecular weight regulator, and a specific example may be t-dodecyl mercaptan.

[0050] According to one embodiment of the present invention, the content of the molecular weight regulator in step (S10) may be 0.01 to 5.00 parts by weight, 0.05 to 3.00 parts by weight, or 0.1 to 1.0 parts by weight per 100 parts by weight of the conjugated diene monomer, and within this range, it is possible to produce a rubbery polymer having an average particle size suitable for ensuring impact resistance.

[0051] According to one embodiment of the present invention, in step (S10), the molecular weight regulator may be added in its entirety before the start of polymerization, or a portion may be added before the start of polymerization and the remainder added during the polymerization process. When performing step (S10), if the molecular weight regulator is added in divided portions before the start of polymerization and during the polymerization process, it has the effect of increasing the average particle size of the rubbery polymer while improving the particle size uniformity of the rubbery polymer being produced. As a specific example, in step (S10), a portion of the molecular weight regulator may be added before the start of polymerization and the remainder added during the polymerization process. As a more specific example, in step (S10), a portion of the molecular weight regulator may be added before the start of polymerization and the remainder added at a point when the polymerization conversion rate is 40% to 60%. At this time, the types of molecular weight regulators added before the start of polymerization and during the polymerization process may be different from each other.

[0052] According to one embodiment of the present invention, the emulsion polymerization of step (S10) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water. Accordingly, the conjugated diene polymer emulsion polymerized in step (S10) may be obtained in the form of a latex in which conjugated diene polymer particles are dispersed colloidally in an aqueous solvent.

[0053] According to one embodiment of the present invention, the step (S10) can be carried out until the polymerization conversion rate is 90% or more, 90.0% to 99.9%, or 93.0% to 98.0%, and within this range, the productivity of the rubbery polymer can be secured.

[0054] According to one embodiment of the present invention, the step (S10) may be carried out by including a crosslinking agent represented by the following chemical formula 1 and a crosslinking agent represented by the following chemical formula 2.

[0055] [Chemical Formula 1]

[0056]

[0057] In the above chemical formula 1, R 1 and R 5 Each can independently be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but may not simultaneously be hydrogen, and R 4 It may be a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0058] [Chemical Formula 2]

[0059]

[0060] In the above chemical formula 2, R 6 Silver may be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each may independently be a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c may each independently be an integer selected from 0 or 1 to 30, and a+b+c may be an integer selected from 1 to 30.

[0061] Accordingly, the method for manufacturing a rubbery polymer according to the present invention is characterized by simultaneously including a crosslinking agent represented by Formula 1 and a crosslinking agent represented by Formula 2 when manufacturing a conjugated diene polymer latex.

[0062] Here, the crosslinking agent represented by the above chemical formula 1 is R 2 and R 3By including at least one monovalent hydrocarbon group, electron transfer within the molecule to the carboxyl group of an adjacent (meth)acrylate group can easily occur due to thermal energy, and accordingly, the decomposition of the polymer chain from the crosslinking agent unit formed from the crosslinking agent represented by Chemical Formula 1 can be made possible. Therefore, when processing a graft copolymer and a resin composition containing the rubbery polymer, the crosslinking density can be lowered by preventing the decomposition of the polymer chain due to the high temperature of the processing process, and accordingly, the gel content of the rubbery polymer can be controlled during the processing process even after the rubbery polymer has been prepared.

[0063] In addition, compared to using the crosslinking agent represented by Chemical Formula 1 alone, using the crosslinking agent represented by Chemical Formula 2 together can further improve impact strength due to the decrease in crosslinking density. The crosslinking agent represented by Chemical Formula 2 is not simply a crosslinking agent containing a tri(meth)acrylate group, but rather contains -[R 7 It is a tri(meth)acrylate-based crosslinking agent having a polymer chain containing an alkoxylate unit represented by -O]-. Therefore, the crosslinking agent represented by Chemical Formula 2 above performs the role of a crosslinking agent from the tri(meth)acrylate group, and at the same time -[R 7 A free volume can be provided within a rubbery polymer and a graft copolymer containing it from -O]-. In this way, when a free volume is formed within the rubbery polymer and the graft copolymer containing it, the rubbery properties capable of absorbing shock from the rubbery polymer can be further enhanced.

[0064] In addition, in a rubbery polymer having a free volume and a graft copolymer containing the same, if the polymer chain decomposition occurs in the crosslinking agent unit formed from the crosslinking agent represented by Formula 1, the decrease in gel content due to the decrease in crosslinking density is further intensified, thereby maximizing the improvement in impact strength of the rubbery polymer.

[0065] Accordingly, when manufacturing a rubbery polymer according to the present invention, if a crosslinking agent represented by Formula 1 and a crosslinking agent represented by Formula 2 are simultaneously included, it is possible to manufacture a rubbery polymer with a high polymerization conversion rate, thereby improving the productivity of the rubbery polymer. At the same time, when processing a resin composition containing a graft copolymer graft-polymerized from the rubbery polymer, the thermally decomposing crosslinking agent unit is thermally decomposed by the heat source of the processing process, thereby lowering the crosslinking density of the rubbery polymer and controlling the gel content of the rubbery polymer. Accordingly, the impact resistance of the molded article formed from the resin composition is improved.

[0066] According to one embodiment of the present invention, in a crosslinking agent represented by the chemical formula 1, R 1 and R 5 is independently a hydrogen or methyl group, and R 2 and R 3 Each is independently a hydrogen or a methyl group, but is not simultaneously a hydrogen, and R 4 may be an alkylene group having 1 to 5 carbon atoms. As a specific example, R 1 and R 5 are each independently hydrogen, and R 2 and R 3 Each is independently a hydrogen or a methyl group, but is not simultaneously a hydrogen, and R 4may be an alkylene group having 1 to 5 carbon atoms, in which case electron transfer within the molecule to the carboxyl group of an adjacent (meth)acrylate group can easily occur due to thermal energy, and accordingly, the decomposition of the polymer chain from the crosslinking agent unit formed from the crosslinking agent represented by Chemical Formula 1 may be possible.

[0067] According to one embodiment of the present invention, the crosslinking agent represented by Formula 1 may be one or more selected from the crosslinking agents represented by Formulas 1-1 to 1-5 below.

[0068] [Chemical Formula 1-1]

[0069]

[0070] (6-methylheptane-1,6-diyl diacrylate)

[0071] [Chemical Formula 1-2]

[0072]

[0073] (5-methylhexane-1,5-diyl diacrylate)

[0074] [Chemical Formula 1-3]

[0075]

[0076] (4-methylpentane-1,4-diyl diacrylate)

[0077] [Chemical Formula 1-4]

[0078]

[0079] (3-methylbutane-1,3-diyl diacrylate)

[0080] [Chemical Formula 1-5]

[0081]

[0082] (2-methylpropane-1,2-diyl diacrylate)

[0083] According to one embodiment of the present invention, as represented by the formulas 1-1 to 1-5, the crosslinking agent represented by formula 1 is R 2 and R3 This may simultaneously be a methyl group, in which case the transfer of electrons within the molecule to the carboxyl group of the adjacent acrylate group by thermal energy may occur more easily, and accordingly, the decomposition of the polymer chain from the crosslinking agent unit formed from the crosslinking agent represented by Chemical Formula 1 may be easy.

[0084] According to one embodiment of the present invention, the crosslinking agent represented by Formula 1 may be added in its entirety before the start of polymerization in step (S10), or a portion may be added before the start of polymerization and the remainder added during the polymerization process. When performing step (S10), if the crosslinking agent represented by Formula 1 is added in divided portions before the start of polymerization and during the polymerization process, the crosslinking agent units represented by Formula 1 can be evenly distributed within the rubbery polymer, thereby ensuring uniformity when subsequently inducing the decomposition of polymer chains by thermal energy. As a specific example, in step (S10), a portion of the crosslinking agent represented by Formula 1 may be added before the start of polymerization, and the remainder may be added at a point when the polymerization conversion rate is 30% to 70%. At this time, the crosslinking agent represented by Formula 1 added before the start of polymerization and during the polymerization process may have different types of substituents within the range of Formula 1.

[0085] According to one embodiment of the present invention, the crosslinking agent represented by Formula 1 may be added in an amount of 0.01 to 0.50 parts by weight, 0.05 to 0.30 parts by weight, or 0.1 to 0.2 parts by weight per 100 parts by weight of the conjugated diene monomer, and within this range, there is an effect of improving the productivity of the rubbery polymer while simultaneously ensuring impact resistance.

[0086] According to one embodiment of the present invention, in a crosslinking agent represented by the formula 2, R6 is hydrogen or a methyl group, and R 7 and R 8 Each is independently an alkylene group having 1 to 5 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 15, wherein a+b+c may be an integer selected from 10 to 20, in which case it acts as a crosslinking agent from the tri(meth)acrylate group, and at the same time -[R 7 There is an effect of sufficiently securing free volume in rubbery polymers from -O]- and graft copolymers containing them.

[0087] According to one embodiment of the present invention, the crosslinking agent represented by Chemical Formula 2 may be a crosslinking agent represented by Chemical Formula 2-1 below.

[0088] [Chemical Formula 2-1]

[0089]

[0090] In the above chemical formula 2-1, a, b, and c are each independently selected as integers from 0 or 1 to 15, and a+b+c may be integers selected from 10 to 20.

[0091] According to one embodiment of the present invention, as shown in Chemical Formula 2-1, the crosslinking agent represented by Chemical Formula 2 has triacrylate groups each connected by -[CH2-CH2-O]-, thereby forming crosslinking agent units while securing free volume, which can further improve the rubber properties capable of absorbing shock from the rubbery polymer.

[0092] According to one embodiment of the present invention, the crosslinking agent represented by Formula 2 may be added in an amount of 0.01 to 0.50 parts by weight, 0.05 to 0.30 parts by weight, or 0.1 to 0.2 parts by weight per 100 parts by weight of the conjugated diene monomer, and within this range, there is an effect of improving the productivity of the rubbery polymer while simultaneously ensuring impact resistance.

[0093] According to one embodiment of the present invention, the average particle size of the rubbery polymer produced from step (S10) may be 2,500 Å to 3,500 Å, 2,800 Å to 3,300 Å, or 3,000 Å to 3,100 Å, and within this range, the resin composition has excellent impact resistance.

[0094] According to one embodiment of the present invention, the rubbery polymer latex produced from step (S10) may have a gel content of 75.0 wt% to 90.0 wt%, 80.0 wt% to 90.0 wt%, or 85.0 wt% to 90.0 wt%, and within this range, it is easy to control the gel content of the rubbery polymer to ensure productivity by increasing the polymerization conversion rate during polymerization, while also lowering the crosslinking density through thermal decomposition of the crosslinking agent during processing of the resin composition.

[0096] In addition, the present invention provides a rubbery polymer manufactured according to the above method for manufacturing a rubbery polymer.

[0097] According to one embodiment of the present invention, the rubbery polymer may comprise a conjugated diene monomer unit; a crosslinking agent unit represented by the following chemical formula 1; and a crosslinking agent unit represented by the following chemical formula 2.

[0098] [Chemical Formula 1]

[0099]

[0100] In the above chemical formula 1, R 1 and R 5Each can independently be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but may not simultaneously be hydrogen, and R 4 It may be a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0101] [Chemical Formula 2]

[0102]

[0103] In the above chemical formula 2, R 6 Silver may be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each may independently be a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c may each independently be an integer selected from 0 or 1 to 30, and a+b+c may be an integer selected from 1 to 30.

[0104] According to one embodiment of the present invention, the conjugated diene monomer unit, the crosslinking agent unit represented by Formula 1, and the crosslinking agent unit represented by Formula 2 may refer to a monomer unit or a crosslinking agent unit formed by the participation of the conjugated diene monomer, the crosslinking agent represented by Formula 1, and the crosslinking agent represented by Formula 2, as described in the method for manufacturing a rubbery polymer above, in a polymerization reaction.

[0105] According to one embodiment of the present invention, the respective contents of the conjugated diene monomer unit, the crosslinking agent unit represented by Formula 1, and the crosslinking agent unit represented by Formula 2 may also be the same as the contents of each component added during the manufacture of the rubbery polymer.

[0107] In addition, the present invention provides a method for manufacturing a graft copolymer comprising a rubbery polymer manufactured by the above method for manufacturing a rubbery polymer.

[0108] According to one embodiment of the present invention, the method for manufacturing a graft copolymer comprises the step (S10) of polymerizing a conjugated diene monomer to produce a conjugated diene polymer latex containing a conjugated diene polymer; and the step (S20) of introducing an aromatic vinyl monomer and a vinyl cyanide monomer into the conjugated diene polymer latex produced in step (S10) and graft polymerizing to produce a graft copolymer latex containing a graft copolymer, wherein step (S10) may be carried out by including a crosslinking agent represented by the following chemical formula 1 and a crosslinking agent represented by the following chemical formula 2.

[0109] According to one embodiment of the present invention, the step (S10) may be carried out by the same method as the step (S10) of the rubbery polymer manufacturing method described above.

[0110] According to one embodiment of the present invention, the step (S20) may be a step of graft polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer onto a rubbery polymer prepared in the step (S10) in order to produce a graft copolymer.

[0111] According to one embodiment of the present invention, the graft polymerization of step (S20) may be carried out by graft emulsion polymerization. Additionally, the graft polymerization of step (S20) may be carried out on the rubbery polymer latex prepared in step (S10).

[0112] According to one embodiment of the present invention, step (S20) may be carried out by radical polymerization using a peroxide-based, redox, or azo-based initiator that can be used in graft emulsion polymerization, and the redox initiator may be one or more selected from the group consisting of, for example, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide, and in this case, it has the effect of providing a stable polymerization environment. In addition, when using the redox initiator, ferrous sulfate, dextrose, and sodium pyrrole phosphate may be further included as redox catalysts.

[0113] According to one embodiment of the present invention, the graft emulsion polymerization of step (S20) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water, and accordingly, the graft copolymer grafted in step (S20) may be obtained in the form of a latex in which the graft copolymer particles are dispersed colloidally on an aqueous solvent.

[0114] According to one embodiment of the present invention, the aromatic vinyl monomer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0115] According to one embodiment of the present invention, the vinyl cyanide monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, and a specific example may be acrylonitrile.

[0116] According to one embodiment of the present invention, the content of the rubbery polymer latex introduced in step (S20) may be 40% to 90% by weight, 50% to 80% by weight, or 50% to 70% by weight based on the solid content, with respect to the total content of the rubbery polymer latex (based on solid content), aromatic vinyl monomer, and vinyl cyanide monomer, and within this range, the mechanical properties of the graft copolymer can be secured.

[0117] According to one embodiment of the present invention, the content of the aromatic vinyl monomer introduced in step (S20) may be 5% to 50% by weight, 15% to 45% by weight, or 25% to 40% by weight with respect to the total content of the rubbery polymer latex (based on solid content), aromatic vinyl monomer, and vinyl cyanide monomer, and within this range, there is an effect of improving the dispersibility of the graft copolymer in the resin composition while securing the mechanical properties of the graft copolymer.

[0118] According to one embodiment of the present invention, the content of the vinyl cyanide monomer introduced in step (S20) may be 1% to 20% by weight, 3% to 15% by weight, or 5% to 10% by weight with respect to the total content of the rubbery polymer latex (based on solid content), aromatic vinyl monomer, and vinyl cyanide monomer, and within this range, there is an effect of improving the dispersibility of the graft copolymer in the resin composition while securing the mechanical properties of the graft copolymer.

[0120] In addition, the present invention provides a graft copolymer comprising the rubbery polymer prepared according to the graft copolymer manufacturing method.

[0121] According to one embodiment of the present invention, the graft copolymer comprises the rubbery polymer, and the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by the following chemical formula 1; and a crosslinking agent unit represented by the following chemical formula 2, and the graft copolymer may comprise an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0122] [Chemical Formula 1]

[0123]

[0124] In the above chemical formula 1, R 1 and R 5 Each can independently be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but may not simultaneously be hydrogen, and R 4 It may be a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0125] [Chemical Formula 2]

[0126]

[0127] In the above chemical formula 2, R 6 Silver may be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each may independently be a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c may each independently be an integer selected from 0 or 1 to 30, and a+b+c may be an integer selected from 1 to 30.

[0128] According to one embodiment of the present invention, the rubbery polymer and graft copolymer may be the rubbery polymer and graft copolymer described above in the graft copolymer manufacturing method, and the aromatic vinyl monomer unit and vinyl cyanide monomer unit may refer to repeating units formed by the aromatic vinyl monomer and vinyl cyanide monomer described above in the graft copolymer manufacturing method participating in the graft polymerization reaction.

[0129] According to one embodiment of the present invention, the respective contents of the rubbery polymer, aromatic vinyl monomer unit, and vinyl cyanide monomer unit may also be the same as the contents of each component introduced during the manufacture of the graft copolymer.

[0131] In addition, the present invention provides a resin composition comprising the graft copolymer.

[0132] According to one embodiment of the present invention, the resin composition comprises the graft copolymer, and the graft copolymer comprises a rubbery polymer, wherein the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by the following chemical formula 1; and a crosslinking agent unit represented by the following chemical formula 2, and the graft copolymer may comprise an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0133] [Chemical Formula 1]

[0134]

[0135] In the above chemical formula 1, R 1 and R 5 Each can independently be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but may not simultaneously be hydrogen, and R 4 It may be a divalent hydrocarbon group having 1 to 10 carbon atoms.

[0136] [Chemical Formula 2]

[0137]

[0138] In the above chemical formula 2, R 6 Silver may be hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each may independently be a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c may each independently be an integer selected from 0 or 1 to 30, and a+b+c may be an integer selected from 1 to 30.

[0139] According to one embodiment of the present invention, the resin composition may comprise the graft copolymer and the styrene copolymer. The styrene copolymer may be a non-graft copolymer comprising aromatic vinyl monomer units, and as a specific example, may be a copolymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units. Here, the styrene copolymer may be a matrix resin that is kneaded together with the graft copolymer within the resin composition to form a matrix.

[0140] According to one embodiment of the present invention, the aromatic vinyl monomer forming the aromatic vinyl monomer unit of the styrene-based copolymer may be one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and as a specific example, it may be styrene.

[0141] According to one embodiment of the present invention, the vinyl cyanide monomer forming the vinyl cyanide monomer unit of the styrene-based copolymer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and as a specific example, it may be acrylonitrile.

[0142] According to one embodiment of the present invention, the resin composition may comprise 10% to 40% by weight, 15% to 35% by weight, or 20% to 30% by weight of the graft copolymer; and 60% to 90% by weight, 65% to 85% by weight, or 70% to 80% by weight of a copolymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units, and within this range, there is an effect of maximizing mechanical properties, particularly impact resistance, while preventing a decrease in the processability of the resin composition containing the graft copolymer.

[0143] According to one embodiment of the present invention, the graft copolymer and the styrene copolymer each comprise an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, and when the types of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit forming each copolymer are the same, they are mixed and dispersed as the same components during the extrusion process of the resin composition. Therefore, in the actual resin composition and the molded article formed therefrom, a rubbery polymer may exist in a dispersed form within a matrix formed of aromatic vinyl monomer units and vinyl cyanide monomer units. Accordingly, the respective content of the graft copolymer and the styrene copolymer in the resin composition can be determined from the total content of aromatic vinyl monomer units and vinyl cyanide monomer units in the resin composition and the content of the rubbery polymer.

[0144] According to one embodiment of the present invention, the crosslinking agent unit represented by Chemical Formula 1 may undergo thermal decomposition upon processing by a heat source. That is, the crosslinking agent unit represented by Chemical Formula 1 may be a thermally decomposing crosslinking agent unit. As a specific example, the crosslinking agent unit represented by Chemical Formula 1 is R 2 and R 3By including at least one monovalent hydrocarbon group, electron transfer within the molecule to the carboxyl group of an adjacent (meth)acrylate group can easily occur due to thermal energy, and accordingly, the decomposition of the polymer chain from the crosslinking agent unit formed from the crosslinking agent represented by Chemical Formula 1 can be achieved. Therefore, when processing the resin composition, the crosslinking density can be lowered by the decomposition of the polymer chain caused by the high temperature of the processing process, and accordingly, the gel content of the rubbery polymer can be controlled during the processing process even after the rubbery polymer has been manufactured. Accordingly, the resin composition according to the present invention has the effect of improving the impact resistance of the molded article formed from the resin composition by lowering the crosslinking density of the rubbery polymer and controlling the gel content of the rubbery polymer through the thermal decomposition of the thermally decomposing crosslinking agent unit represented by Chemical Formula 1 from the heat source of the processing process.

[0145] According to one embodiment of the present invention, the resin composition has an impact strength of 25.0 kgf·m / m or more, 27.0 kgf·m / m or more, measured at a thickness of 1 / 4 inch according to ASTM D256. Above, or 27.0 kgf·m / m to 30.0 It may be kgf·m / m, and within this range, it has the effect of sufficiently ensuring the impact resistance of the resin composition containing the graft copolymer.

[0146] According to one embodiment of the present invention, the resin composition may have a melt index (220 ℃, 10 kg) measured by ASTM D1238 of 40.0 g / 10 min or more, 45.0 g / 10 min or more, or 46.0 g / 10 min to 48.0 g / 10 min, and within this range, the processability of the resin composition including the graft copolymer can be sufficiently secured.

[0147] According to one embodiment of the present invention, the resin composition has a tensile strength of 400 kgf / cm² as measured by ASTM D638. 2 Above, 420 kgf / cm² 2 Above, or 420 kgf / cm² 2 Up to 435 kgf / cm² 2 It may be possible to ensure sufficient mechanical properties of the resin composition containing the graft copolymer within this range.

[0148] According to one embodiment of the present invention, the resin composition may have a surface gloss of 98.0 or higher, 98.5 or higher, or 98.5 to 99.9 as measured at 45° according to ASTM D2457, and within this range, the appearance characteristics of the resin composition including the graft copolymer can be sufficiently secured.

[0150] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0152] Examples

[0153] Example 1

[0154] <Manufacture of rubbery polymer latex>

[0155] In a nitrogen-substituted polymerization reactor, 55 parts by weight of ion-exchanged water, 50 parts by weight of 1,3-butadiene, 0.15 parts by weight of K2CO3 as an electrolyte, 0.3 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.3 parts by weight of potassium persulfate as an initiator, 1.5 parts by weight of potassium oleate as an emulsifier, 0.1 parts by weight of 4-methylpentane-1,4-diyl diacrylate as a crosslinking agent, and trimethylolpropane (ethoxylate) as a crosslinking agent 150.1 parts by weight of triacrylate were added in a lump sum, and the internal temperature of the polymerization reactor was raised to 70°C to start polymerization. When the polymerization conversion rate reached 55%, 25 parts by weight of 1,3-butadiene and 0.15 parts by weight of t-dodecyl mercaptan, a molecular weight regulator, were added in a lump sum to the polymerization reactor. When the polymerization conversion rate reached 70%, 25 parts by weight of 1,3-butadiene were added in a lump sum to the polymerization reactor. When the polymerization conversion rate reached 75%, 0.07 parts by weight of potassium persulfate, an initiator, and 0.37 parts by weight of potassium rosinate, an emulsifier, were added in a lump sum to the polymerization reactor. When the polymerization conversion rate reached 85%, 0.05 parts by weight of potassium persulfate, an initiator, and 0.15 parts by weight of potassium rosinate, an emulsifier, were added to the polymerization reactor in a lump sum. Subsequently, when the polymerization conversion rate reached 95%, the polymerization reaction was terminated to obtain a rubbery polymer latex. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,030 Å.

[0157] Example 2

[0158] In the above Example 1, the procedure was carried out in the same manner as in Example 1, except that when the polymerization conversion rate reached 55% during the preparation of the rubbery polymer latex, 0.05 parts by weight of the crosslinking agent, 4-methylpentane-1,4-diyl diacrylate, was added to the polymerization reactor. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,019 Å.

[0160] Example 3

[0161] In the above Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.15 parts by weight of 4-methylpentane-1,4-diyl diacrylate, a crosslinking agent, was added instead of 0.1 parts by weight when preparing the rubbery polymer latex. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,021 Å.

[0163] Example 4

[0164] In the above Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.1 parts by weight of 3-methylbutane-1,3-diyl diacrylate was added instead of 4-methylpentane-1,4-diyl diacrylate, which is a crosslinking agent, when preparing the rubbery polymer latex. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,011 Å.

[0166] Comparative Example 1

[0167] In the above Example 1, the procedure was carried out in the same manner as in Example 1, except that 4-methylpentane-1,4-diyl diacrylate, a crosslinking agent, was not added during the preparation of the rubbery polymer latex. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,004 Å.

[0169] Comparative Example 2

[0170] In the above Example 1, when preparing the rubbery polymer latex, the crosslinking agent trimethylolpropane (ethoxylate) 15 The procedure was carried out in the same manner as Example 1 above, except that triacrylate was not added. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,017 Å.

[0172] Comparative Example 3

[0173] In the above Example 1, when preparing a rubbery polymer latex, 4-methylpentane-1,4-diyl diacrylate as a crosslinking agent and trimethylolpropane (ethoxylate) as a crosslinking agent 15 The procedure was carried out in the same manner as Example 1 above, except that triacrylate was not added. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 2,998 Å.

[0175] Comparative Example 4

[0176] In the above Example 1, the process was carried out in the same manner as in Example 1, except that 4-methylpentane-1,4-diyl diacrylate, a crosslinking agent, was not added during the preparation of the rubbery polymer latex, and the polymerization reaction was terminated when the polymerization conversion rate reached 87%. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,010 Å.

[0178] Comparative Example 5

[0179] In the above Example 1, when preparing the rubbery polymer latex, the crosslinking agent trimethylolpropane (ethoxylate) 15 The procedure was carried out in the same manner as Example 1 above, except that 0.1 parts by weight of trimethylolpropane triacrylate was added instead of triacrylate. At this time, the average particle size of the rubbery polymer particles in the prepared rubbery polymer latex was 3,005 Å.

[0181] Experimental Example 1

[0182] For the rubbery polymer latexes prepared in Examples 1 to 4 and Comparative Examples 1 to 5 above, the average particle size of rubbery polymer particles in the rubbery polymer latex was measured by the following method, and the gel content, total solid content, and coagulated content were measured and shown in Tables 1 and 2 below along with the final polymerization conversion rate.

[0184] * Average particle size (Å): 1 g of each rubbery polymer latex prepared in the above examples and comparative examples was diluted in 100 g of distilled water, and then measured by dynamic light scattering using a Nicomp 370 HPL instrument from PSS (Particle Sizing Systems).

[0185] * Gel content (weight%): 10 g of each amorphous polymer latex prepared in the above examples and comparative examples was slowly added to 100 g of ethanol to obtain a precipitate. The obtained precipitate was filtered through an 80-mesh wire mesh and then dried at 55°C for 4 hours to obtain a first dried product. 1 g of the obtained first dried product was added to 100 g of toluene and stored in a dark room for 12 hours. Afterward, the swollen precipitate was filtered through an 80-mesh wire mesh and then dried at 85°C for 4 hours to obtain a second dried product. The gel content was calculated from the weights of the first dried product and the second dried product using the following Equation 2.

[0186] [Mathematical Formula 2]

[0187] Gel content (weight%) = [Weight of secondary dried product (g) / Weight of primary dried product added to toluene (g)] × 100

[0188] * Total solid content (weight%): Approximately 1 g of rubbery polymer latex filtered through a 100-mesh wire mesh prepared in each of the above examples and comparative examples was dried in a hot air dryer at 150°C for 20 minutes to measure the weight of the coagulated material, and the total solid content was calculated using the following mathematical formula 3.

[0189] [Mathematical Formula 3]

[0190] Total solid content (weight%) = [Weight of coagulated material (g) / Total weight of rubbery polymer latex (g)] × 100

[0191] * Coagulated material content (weight%): Each rubbery polymer latex prepared in the above examples and comparative examples was filtered through a 100-mesh wire mesh, dried at 70°C for 10 hours to obtain a coagulated material, and its weight was measured. The coagulated material content was calculated using the following mathematical formula 4.

[0192] [Mathematical Formula 4]

[0193] Coagulated Content (Weight%) = [Weight of Coagulated Material (g) / Total Weight of Reaction Product (g)] × 100

[0195] division Examples 1 2 3 4 Final polymerization conversion rate (%) 94.9 95.1 94.8 94.6 average particle size (Å) 3,030 3,019 3,021 3,011 Gel content (weight%) 87.7 89.5 87.3 88.5 Total solid content (weight%) 57.9 58.7 57.8 58.2 Coagulation content (weight%) 0.08 0.08 0.09 0.08

[0197] division Comparative example 1 2 3 4 5 Final polymerization conversion rate (%) 95.1 94.7 94.8 87.1 94.5 average particle size (Å) 3,004 3,017 2,998 3,010 3,005 Gel content (weight%) 86.9 86.7 87.0 72.5 86.8 Total solid content (weight%) 58.5 58.0 58.1 53.1 57.7 Coagulation content (weight%) 0.09 0.08 0.08 0.08 0.08

[0199] As shown in Tables 1 and 2 above, it was confirmed that the rubbery polymers of Examples 1 to 4, prepared according to the method for preparing a rubbery polymer of the present invention, had an average particle size equivalent to that of Comparative Examples 1 to 3 and 5, in which the polymerization reaction was terminated at the same polymerization conversion rate. Furthermore, it was confirmed that the gel content, total solid content, and coagulated content were also prepared at similar levels. In other words, it was confirmed that the rubbery polymers of Examples 1 to 4, prepared according to the method for preparing a rubbery polymer of the present invention, exhibited the same level of productivity as Comparative Examples 1 to 3 and 5 while applying two types of crosslinking agents.

[0200] On the other hand, in the case of Comparative Example 4, in order to control the gel content, the polymerization reaction had to be terminated when the polymerization conversion rate reached 87%.

[0202] Experimental Example 2

[0203] Graft copolymer and resin compositions were prepared using the rubbery polymer latex prepared in Examples 1 to 4 and Comparative Examples 1 to 5 as follows.

[0204] <Manufacture of Graft Copolymer Latex>

[0205] A first mixture was prepared in which 10 parts by weight of acrylonitrile, 30 parts by weight of styrene, 25 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosinate, and 0.35 parts by weight of t-dodecyl mercaptan were uniformly mixed, and a second mixture was prepared in which 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrole phosphate, and 0.002 parts by weight of ferrous sulfate were uniformly mixed.

[0206] 60 parts by weight (based on solid content) of the prepared rubbery polymer latex and 100 parts by weight of ion-exchanged water were introduced into a nitrogen-substituted polymerization reactor, and the prepared first mixture and second mixture were continuously introduced at a constant rate for 3 hours at 70°C. After the continuous introduction was completed, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrole phosphate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were introduced into the reactor in a lump sum. Subsequently, the temperature of the reactor was raised to 80°C over a period of 1 hour, and then the polymerization reaction was terminated to produce a graft copolymer latex. At this time, the polymerization conversion rate was 97%.

[0208] <Manufacture of Graft Copolymer Powder>

[0209] 2 parts by weight of magnesium sulfate (MgSO4) were added to 100 parts by weight (based on solid content) of the graft copolymer latex prepared above, and aggregated at 82°C. Afterwards, the mixture was aged at 93°C for 30 minutes, and then washed, dehydrated, and dried to produce a graft copolymer powder.

[0211] <Preparation of Resin Composition>

[0212] 23 parts by weight of the above-prepared graft copolymer powder, 77 parts by weight of styrene-acrylonitrile copolymer (manufactured by LG Chem, product name 92HR), 1.5 parts by weight of lubricant, and 0.3 parts by weight of heat stabilizer were fed into a twin-screw extruder and mixed and extruded at 210°C to produce resin composition pellets.

[0214] For the graft copolymer latex prepared above, the coagulation content was measured by the following method and is shown in Tables 3 and 4 below along with the final polymerization conversion rate.

[0215] In addition, the resin composition pellets manufactured above are 210 The impact strength, melt index, tensile strength, and surface gloss were measured by the following method after injection molding at ℃, and are shown together in Tables 3 and 4 below.

[0217] * Coagulated material content (weight%): Each graft copolymer latex prepared in the above examples and comparative examples was filtered through a 100-mesh wire mesh, dried at 70°C for 10 hours to obtain a coagulated material, and its weight was measured. The coagulated material content was calculated using the following mathematical formula 4.

[0218] [Mathematical Formula 4]

[0219] Coagulated Content (Weight%) = [Weight of Coagulated Material (g) / Total Weight of Reaction Product (g)] × 100

[0220] * Impact strength (kgf·cm / cm): The notched izod impact strength was measured for 1 / 4 inch thick specimens according to the ASTM D256 method.

[0221] * Melt index (g / 10 min): Measured according to ASTM D1238 method under conditions of 220 ℃ and 10 kg.

[0222] * Tensile strength (kgf / cm²) 2 ): Measured according to ASTM D638.

[0223] * Surface gloss: According to the ASTM D2457 method, the surface gloss of the specimen at an angle of 45° was measured using a Gloss meter (VG-7000, Nippon Denshoku).

[0225] division Examples 1 2 3 4 Graft copolymer Polymerization conversion rate (%) 93.7 94.3 93.4 94.0 Coagulation content (weight%) 0.06 0.06 0.07 0.06 Resin composition Impact strength (kgf·cm / cm) 27.1 28.5 27.9 27.5 Melt index (g / 10 min) 46.8 46.5 47.1 47.0 tensile strength (kgf / cm 2 ) 430 424 433 428 Surface gloss 98.7 99.0 98.5 98.8

[0227] division Comparative example 1 2 3 4 5 Graft copolymer Polymerization conversion rate (%) 94.7 93.5 93.8 93.8 93.6 Coagulation content (weight%) 0.11 0.10 0.11 0.06 0.10 Resin composition Impact strength (kgf·cm / cm) 22.5 21.9 20.8 27.4 21.6 Melt index (g / 10 min) 47.8 47.3 47.0 47.0 47.5 tensile strength (kgf / cm 2 ) 452 455 461 431 457 Surface gloss 98.1 98.3 97.5 98.8 98.5

[0229] As shown in Tables 3 and 4 above, when a graft copolymer is prepared using the rubbery polymers of Examples 1 to 4 prepared according to the method for preparing rubbery polymers of the present invention, it was confirmed that the content of coagulated material in the graft copolymer latex can be reduced compared to when a graft copolymer is prepared using the rubbery polymers of Comparative Examples 1 to 3 and 5 prepared with the same polymerization conversion rate. This was equivalent to the level in which a graft copolymer is prepared using the rubbery polymer of Comparative Example 4, in which the polymerization reaction was terminated when the polymerization conversion rate reached 87% to control the gel content.

[0230] In addition, it was confirmed that the resin composition containing the graft copolymer prepared using the rubbery polymer of Examples 1 to 4 prepared according to the method for preparing a rubbery polymer of the present invention achieved mechanical properties equivalent to or better than those of the resin composition containing the graft copolymer prepared using the rubbery polymer of Comparative Examples 1 to 3 and 5 prepared with the same polymerization conversion rate, and in particular, the impact strength was significantly improved. This was equivalent to the level of the resin composition containing the graft copolymer prepared using the rubbery polymer of Comparative Example 4, in which the polymerization reaction was terminated when the polymerization conversion rate reached 87% to control the gel content.

[0231] These results are believed to be due to the fact that, even though the gel content increases with increasing polymerization conversion rate when manufacturing rubbery polymers, the crosslinking agent represented by Formula 1 is introduced, and during the processing of the resin composition, the crosslinking agent unit represented by Formula 1 is thermally decomposed by a heat source, thereby lowering the crosslinking density of the rubbery polymer and reducing the gel content.

[0232] That is, it was confirmed that the rubbery polymers of Examples 1 to 4, prepared according to the method for preparing rubbery polymers of the present invention, achieve mechanical properties equivalent to those of the rubbery polymer of Comparative Example 4, in which the polymerization reaction was terminated when the polymerization conversion rate reached 87% to control the gel content, while also being able to produce rubbery polymers with the same polymerization conversion rate as Comparative Examples 1 to 3 and 5, thereby simultaneously securing productivity and mechanical properties.

[0234] From these results, it was confirmed that according to the method for manufacturing a rubbery polymer of the present invention, it is possible to manufacture a rubbery polymer with a high polymerization conversion rate during the polymerization of a rubbery polymer, thereby improving the productivity of the rubbery polymer, and since the manufactured rubbery polymer contains a pyrolytic crosslinking agent unit, when processing a resin composition containing a graft copolymer graft-polymerized from the rubbery polymer, the pyrolytic crosslinking agent unit is pyrolytically decomposed by the heat source of the processing process, thereby lowering the crosslinking density of the rubbery polymer and controlling the gel content of the rubbery polymer, and accordingly, the impact resistance of the molded article formed from the resin composition is improved.

Claims

Claim 1 A method for manufacturing a rubbery polymer comprising the step (S10) of polymerizing a conjugated diene monomer to produce a conjugated diene polymer latex containing a conjugated diene polymer, wherein the step (S10) is carried out by including a crosslinking agent represented by the following Chemical Formula 1 and a crosslinking agent represented by the following Chemical Formula 2: [Chemical Formula 1] In the above chemical formula 1, R 1 and R 5 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is not simultaneously hydrogen, and R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, R 6 is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each is independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 30, where a+b+c is an integer selected from 1 to 30. Claim 2 In claim 1, in the above chemical formula 1, R 1 and R 5 are each independently hydrogen or a methyl group, and R 2 and R 3 Each is independently a hydrogen or a methyl group, but is not simultaneously a hydrogen, and R 4 A method for manufacturing a rubbery polymer in which is an alkylene group having 1 to 5 carbon atoms. Claim 3 Method for preparing a rubbery polymer according to claim 1, wherein the crosslinking agent represented by Chemical Formula 1 is one or more selected from the crosslinking agents represented by Chemical Formulas 1-1 to 1-5 below: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] . Claim 4 A method for manufacturing a rubbery polymer according to claim 1, wherein the crosslinking agent represented by the above chemical formula 1 is partially added before the start of polymerization during the polymerization of step (S10), and the remainder is added at a time when the polymerization conversion rate is 30% to 70%. Claim 5 A method for manufacturing a rubbery polymer according to claim 1, wherein the crosslinking agent represented by the above chemical formula 1 is added in an amount of 0.01 to 0.50 parts by weight per 100 parts by weight of the above conjugated diene monomer. Claim 6 In claim 1, in the above chemical formula 2, R 6 is hydrogen or a methyl group, and R 7 and R 8 A method for producing a rubbery polymer, wherein each is independently an alkylene group having 1 to 5 carbon atoms, a, b, and c are each independently an integer selected from 0 or 1 to 15, and a+b+c is an integer selected from 10 to 20. Claim 7 Method for preparing a rubbery polymer according to claim 1, wherein the crosslinking agent represented by Chemical Formula 2 is a crosslinking agent represented by the following Chemical Formula 2-1: [Chemical Formula 2-1] In the above chemical formula 2-1, a, b, and c are each independently selected from 0 or 1 to 15, and a+b+c is an integer selected from 10 to 20. Claim 8 A method for manufacturing a rubbery polymer according to claim 1, wherein the crosslinking agent represented by the above chemical formula 2 is added in an amount of 0.01 to 0.50 parts by weight per 100 parts by weight of the above conjugated diene monomer. Claim 9 A rubbery polymer comprising: a conjugated diene monomer unit; a crosslinking agent unit represented by the following Chemical Formula 1; and a crosslinking agent unit represented by the following Chemical Formula 2: [Chemical Formula 1] In the above chemical formula 1, R 1 and R 5 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is not simultaneously hydrogen, and R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, R 6 is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each is independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 30, where a+b+c is an integer selected from 1 to 30. Claim 10 A graft copolymer comprising a rubbery polymer, wherein the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by the following Chemical Formula 1; and a crosslinking agent unit represented by the following Chemical Formula 2, and the graft copolymer comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit: [Chemical Formula 1] In the above chemical formula 1, R 1 and R 5 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is not simultaneously hydrogen, and R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, R 6 is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each is independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 30, where a+b+c is an integer selected from 1 to 30. Claim 11 A resin composition comprising a graft copolymer, wherein the graft copolymer comprises a rubbery polymer, wherein the rubbery polymer comprises a conjugated diene monomer unit; a crosslinking agent unit represented by the following Chemical Formula 1; and a crosslinking agent unit represented by the following Chemical Formula 2, and wherein the graft copolymer comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit: [Chemical Formula 1] In the above chemical formula 1, R 1 and R 5 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, but is not simultaneously hydrogen, and R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, [Chemical Formula 2] In the above chemical formula 2, R 6 is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 7 and R 8 Each is independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and a, b, and c are each independently integers selected from 0 or 1 to 30, where a+b+c is an integer selected from 1 to 30. Claim 12 A resin composition according to claim 11, wherein the crosslinking agent unit represented by the above chemical formula 1 decomposes thermally when processed by a heat source.

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