Method for preparing diene based rubbery polymer and method for preparing graft polymer comprising the same

Abstract

The present invention relates to a method for producing a diene rubbery polymer comprising the step of initiating and performing polymerization of monomers in the presence of an amine compound and a thermal decomposition initiator, wherein the amine compound is one or more selected from the group consisting of a compound represented by Formula 1 and a compound represented by Formula 2, the content of the amine compound is 0.03 to 0.70 parts by weight per 100 parts by weight of the total amount of monomers added during the production of the diene rubbery polymer, and the monomer is a diene monomer; or a diene monomer and a vinyl aromatic monomer; and the polymerization is initiated at 25 to 50 ℃.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a diene-based rubbery polymer and a method for manufacturing a graft polymer containing the same. More specifically, it relates to a method for manufacturing a diene-based rubbery polymer with excellent polymerization stability and excellent impact resistance, while significantly lowering the polymerization initiation temperature through the synergy of a diamine compound and a thermal decomposition initiator, and a method for manufacturing a graft polymer containing the same. Background Technology

[0003] In the case of diene-based graft copolymers produced by emulsion polymerization, redox initiation systems are the most widely used polymerization initiation systems. Redox initiation systems have the advantage of a low polymerization initiation temperature and a fast polymerization rate, allowing polymerization to be controlled in a relatively short time.

[0004] However, due to the metal oxides and reducing agents in the redox initiation system, polymerization stability may be reduced during the production of diene rubbery polymers, and depending on the amount used, an excess of small-particle diene rubbery polymers may be produced. To resolve these problems, attempts have been made to use thermal decomposition initiators such as potassium persulfate, but the polymerization initiation and execution temperatures are high, the polymerization rate is slow, and there is a high possibility that polymerization stability will be reduced due to the high reaction pressure resulting from the high polymerization initiation and execution temperatures. In addition, there is a problem in that the processability and impact resistance of the graft polymer are reduced due to the decrease in rubber efficiency caused by the increased crosslinking rate of the rubbery polymer.

[0005] Accordingly, research is continuing on methods for manufacturing diene-based rubbery polymers that have excellent properties, a low polymerization initiation temperature, and a fast polymerization rate. The problem to be solved

[0007] The problem that the present invention aims to solve is to provide a method for manufacturing a diene-based rubbery polymer with a low polymerization initiation temperature, excellent polymerization stability, and excellent impact resistance, even when using a pyrolysis initiator, and a method for manufacturing a graft polymer containing the same. means of solving the problem

[0009] To solve the above-mentioned problem, the present invention provides a method for producing a diene-based rubbery polymer comprising the step of initiating and performing polymerization of monomers in the presence of an amine-based compound and a thermal decomposition initiator, wherein the amine-based compound is one or more selected from the group consisting of a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2, the content of the amine-based compound is 0.03 to 0.70 parts by weight per 100 parts by weight of the total amount of monomers added during the production of the diene-based rubbery polymer, and the monomer is a diene-based monomer; or a diene-based monomer and a vinyl aromatic monomer; and the polymerization is initiated at 25 to 50 ℃.

[0010] <Chemical Formula 1>

[0011]

[0012] In the above chemical formula 1,

[0013] R1 to R4 are each independently hydrogen or C1 to C 10 It is an alkyl group of, and

[0014] L is C1 to C 10 It is an alkylene group.

[0015] <Chemical Formula 2>

[0016]

[0017] In the above chemical formula 2,

[0018] R5 to R7 are each independently hydrogen or a C1 to C5 alkyl group, but two or more of R5 to R7 are C1 to C5 alkyl groups.

[0019] In addition, (2) the present invention provides a method for manufacturing a diene-based rubbery polymer, wherein the compound represented by the chemical formula 1 in (1) is one or more selected from the group consisting of N,N,N',N'-tetramethylethylenediamine and ethylenediamine.

[0020] In addition, (3) the present invention provides a method for producing a diene-based rubbery polymer in which, in (1) or (2), the compound represented by the chemical formula 2 is dimethylamine.

[0021] In addition, (4) the present invention provides a method for manufacturing a diene-based rubbery polymer, wherein in any one of (1) to (3), the pyrolysis initiator is one or more selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.

[0022] In addition, (5) the present invention provides a method for manufacturing a diene-based rubbery polymer, wherein, in any one of (1) to (4), the polymerization is initiated at 25 to 35 ℃.

[0023] In addition, (6) the present invention provides a method for manufacturing a diene rubbery polymer, wherein in any one of (1) to (5), the content of the pyrolysis initiator is 0.01 to 3.00 parts by weight per 100 parts by weight of the total monomer content added during the manufacture of the diene rubbery polymer.

[0024] In addition, (7) the present invention provides a method for manufacturing a diene rubbery polymer, wherein, in any one of (1) to (6), the step of initiating and performing the polymerization of the monomer comprises: a step of initiating the polymerization of the monomer in the presence of the amine compound and a pyrolysis initiator; and a step of introducing the monomer and polymerizing it at a time when the polymerization conversion rate is 10 to 50%.

[0025] In addition, (8) the present invention provides a method for manufacturing a diene rubbery polymer, wherein the amount of monomer added in the step of initiating the polymerization of the monomer in (7) is 50 to 90 parts by weight with respect to the total amount of monomer added in the step of manufacturing the diene rubbery polymer, and the amount of monomer added in the step of polymerization is 10 to 50 parts by weight with respect to the total amount of monomer added in the step of manufacturing the diene rubbery polymer.

[0026] In addition, (9) the present invention provides a method for manufacturing a diene-based rubbery polymer, wherein in any one of (1) to (8), the polymerization is an emulsion polymerization.

[0027] In addition, (10) the present invention provides a method for manufacturing a graft polymer comprising the steps of: manufacturing a diene-based rubbery polymer by a manufacturing method according to any one of (1) to (9); and polymerizing a vinyl aromatic monomer and a vinyl cyanide monomer into the diene-based rubbery polymer. Effects of the invention

[0028] According to the method for manufacturing a diene-based rubbery polymer of the present invention, polymerization can be initiated and carried out at a relatively low temperature even when a thermal decomposition initiator is used, and the manufacturing efficiency can be significantly improved due to excellent polymerization stability. In addition, a graft polymer with excellent impact resistance can be manufactured. Specific details for implementing the invention

[0031] 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.

[0033] In the present invention, the 'polymerization conversion rate' represents the degree to which monomers polymerize to form a polymer, and can be calculated using the following formula.

[0034] Polymerization Conversion Rate (%) = {(Total weight of monomers input until polymerization is complete) - (Total weight of unpolymerized monomers at the time of measuring the polymerization conversion rate)} / (Total weight of monomers input until polymerization is complete) × 100

[0036] In the present invention, 'average particle size' may refer to the arithmetic mean particle size in a particle size distribution measured by dynamic light scattering, specifically the scattering intensity average particle size. The average particle size can be measured using the Nicomp 370HPL instrument (product name, manufacturer: PSS Nicomp).

[0038] In the present invention, the 'gel content' can be calculated by coagulating, washing, and drying a diene-based rubbery polymer latex to produce a section, and then separating the section into a sol and a gel.

[0039] Specifically, a diene-based rubbery polymer latex can be solidified with a dilute aqueous sulfuric acid solution and then washed. This washed material can be first dried in a vacuum oven at 60°C for 24 hours and then cut into small pieces with scissors to prepare slices. 1 g of these slices is placed in 100 g of toluene and stored in a dark room at 23°C for 48 hours, after which they are separated into a sol and a gel. The gel is then secondarily dried in an oven at 85°C for 6 hours, the weight of the secondarily dried material is determined, and the gel content can be calculated by introducing it into the following formula.

[0040] Gel content (weight%) = (Weight of secondary dried product) / (Weight of slices used in preparation of secondary dried product) × 100

[0042] In the present invention, the 'diene monomer' may be one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and among these, 1,3-butadiene is preferred.

[0044] In the present invention, the 'vinyl aromatic monomer' may be one or more selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferred.

[0046] In the present invention, the 'vinyl cyanide monomer' may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, among which acrylonitrile is preferred.

[0048] In the present invention, the 'molecular weight regulator' may be one or more selected from the group consisting of α-methyl styrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, n-octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxantogen disulfide. Among these, t-dodecyl mercaptan is preferred.

[0050] In the present invention, the 'peroxide-based initiator' may be one or more selected from the group consisting of cumene hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl hydroperoxide, paramethan hydroperoxide, and benzoyl peroxide.

[0052] In the present invention, the 'azo-based initiator' may be azobis-isobutyronitrile.

[0054] In the present invention, the 'emulsifier' may be one or more selected from the group consisting of sodium dicyclohexyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, potassium di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleyl sulfate, potassium octadecyl sulfate, potassium rosinate, and sodium rosinate, among which sodium dodecyl benzene sulfonate is preferred.

[0056] In the present invention, the 'electrolyte' may be one or more selected from the group consisting of KCl, NaCl, KOH, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO3, K4P2O7, Na4P2O7, K3PO4, Na3PO4, K2HPO4, and Na2HPO4, and among these, one or more selected from the group consisting of KOH and K2CO3 are preferred.

[0058] In the present invention, the ‘oxidation-reduction system catalyst’ may be one or more selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, iron sulfate (II), dextrose, tetrasodium pyrophosphate, anhydrous sodium pyrophosphate, and sodium sulfate, and among these, it is preferable to be one or more selected from the group consisting of iron sulfate (II), dextrose, and tetrasodium pyrophosphate.

[0060] In the present invention, the 'aqueous solvent' may be ion-exchanged water or distilled water.

[0062] In the present invention, 'alkyl group' refers to a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, It may be one or more selected from the group consisting of 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and 3-methyloctan-2-yl.

[0064] In the present invention, 'alkylene group' may mean having two bonding positions in an alkyl group, that is, two groups.

[0066] 1. Preparation of diene-based gum polymers

[0068] A method for manufacturing a diene-based rubbery polymer according to one embodiment of the present invention comprises the step of initiating and performing polymerization of monomers in the presence of an amine-based compound and a thermal decomposition initiator, wherein the amine-based compound is one or more selected from the group consisting of a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2, the content of the amine-based compound is 0.03 to 0.70 parts by weight per 100 parts by weight of the total amount of monomers input during the manufacture of the diene-based rubbery polymer, the monomer is a diene-based monomer; or a diene-based monomer and a vinyl aromatic monomer; and the polymerization is initiated at 25 to 50 ℃:

[0069] <Chemical Formula 1>

[0070]

[0071] In the above chemical formula 1,

[0072] R1 to R4 are each independently hydrogen or C1 to C 10 It is an alkyl group of, and

[0073] L is C1 to C 10 It is an alkylene group.

[0074] <Chemical Formula 2>

[0075]

[0076] In the above chemical formula 2,

[0077] R5 to R7 are each independently hydrogen or a C1 to C5 alkyl group, but two or more of R5 to R7 are C1 to C5 alkyl groups.

[0079] In a method for manufacturing a diene-based rubbery polymer, if polymerization is initiated in the presence of an amine-based compound and a thermal decomposition initiator, due to the synergy between the amine-based compound and the thermal decomposition initiator, polymerization can be initiated and carried out at a relatively low temperature even when using a thermal decomposition initiator, and the polymerization stability is excellent, so the manufacturing efficiency is significantly improved, and a graft polymer with excellent impact resistance can be manufactured.

[0081] In the above chemical formula 1, R1 to R4 are each independently hydrogen or a C1 to C4 alkyl group, and L may be a C1 to C4 alkylene group.

[0082] The compound represented by the above chemical formula 1 may be one or more selected from the group consisting of N,N,N',N'-tetramethylethylenediamine and ethylenediamine.

[0084] In the above chemical formula 2, R5 to R7 are each independently hydrogen or a C1 to C5 alkyl group, but at least two of R5 to R7 are C1 to C5 alkyl groups, and R5 to R7 are each independently hydrogen or a C1 to C4 alkyl group, but at least one of R5 to R7 is hydrogen. If an alkyl group exceeding C5 is introduced, the molecular weight of the compound increases, so the content of N relative to the amount of compound added decreases, and the effect is significantly reduced.

[0085] The compound represented by the above chemical formula 2 may be dimethylamine.

[0087] The content of the above amine-based compound may be 0.03 to 0.70 parts by weight, and preferably 0.10 to 0.50 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the content of the above amine-based compound is less than the conditions described above, polymerization does not begin at 25 to 50 ℃. If the content of the above amine-based compound is excessive compared to the conditions described above, polymerization stability is reduced, and excessive coagulation occurs, resulting in reduced manufacturing efficiency.

[0089] Unlike redox initiation systems, the pyrolysis initiator does not require the combined use of a metal oxide and a reducing agent, thereby preventing a decrease in the thermal stability and whiteness of the graft polymer. The pyrolysis initiator may be one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate, and potassium sulfate is preferred from the perspective of cost and polymerization stability.

[0090] The content of the above pyrolysis initiator may be 0.01 to 3.00 parts by weight, preferably 0.10 to 0.80 parts by weight, based on 100 parts by weight of the total monomer content added during the production of the above diene-based rubbery polymer. If the above conditions are satisfied, a balance between the polymerization rate and polymerization stability can be achieved.

[0092] Since the polymerization of the monomer is initiated in the presence of the above-mentioned amine compound and pyrolysis initiator, the polymerization can be initiated at 25 to 50°C, preferably at 25 to 35°C. If the above-mentioned conditions are satisfied, the energy required to raise the temperature of the reactor can be reduced, and the polymerization efficiency can be improved. In addition, the occurrence of coagulation during the production of the diene-based rubbery polymer is reduced, and the final polymerization conversion rate is increased, so the polymerization stability and polymerization efficiency can be improved. Polymerization is not initiated at temperatures below the above-mentioned temperature. Furthermore, if polymerization is initiated at a temperature exceeding the above-mentioned temperature, excessive energy is consumed to raise the temperature of the reactor, and since polymerization is initiated and performed at a high temperature, the polymerization pressure increases, which increases the degree of crosslinking of the diene-based rubbery polymer and increases the gel content, thereby reducing the impact resistance of the diene-based rubbery polymer.

[0094] The above polymerization may be an emulsion polymerization and may be carried out in the presence of one or more selected from the group consisting of an emulsifier, an electrolyte, a molecular weight regulator, and an aqueous solvent, as well as the above amine-based compound and the thermal decomposition initiator.

[0095] The type of emulsifier is as described above, and the content of the emulsifier may be 0.5 to 5.0 parts by weight, preferably 0.8 to 2.5 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the above conditions are satisfied, not only can a diene-based rubbery polymer of a desired size be manufactured, but polymerization stability can also be improved.

[0096] The type of the electrolyte is as described above, and the content of the electrolyte may be 0.3 to 3.0 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the above conditions are satisfied, polymerization stability can be improved.

[0097] The type of the molecular weight regulator is as described above, and the content of the molecular weight regulator may be 0.1 to 1.0 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the above conditions are satisfied, the manufacturing time of the diene-based rubbery polymer can be shortened.

[0099] Meanwhile, the step of initiating and performing the polymerization of the monomer may include the step of initiating the polymerization of the monomer in the presence of the amine-based compound and the pyrolysis initiator; and the step of introducing the monomer and polymerizing it at a time when the polymerization conversion rate is 10 to 50%.

[0100] When the monomer is introduced at a time when the polymerization conversion rate is 10 to 50%, preferably at a time when the polymerization conversion rate is 20 to 40%, the polymerization pressure and polymerization temperature do not rise rapidly, and the polymerization stability is improved, so that a diene-based rubbery polymer having a desired average particle size can be produced.

[0101] The content of the monomer added at the step of initiating the polymerization of the monomer may be 50 to 90 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. Additionally, the content of the monomer added at the step of polymerization may be 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the above conditions are satisfied, polymerization stability can be improved.

[0103] Additionally, the step of initiating and performing the polymerization of the monomer may include: a step of initiating the polymerization of the monomer in the presence of the amine-based compound and a thermal decomposition initiator; and a step of polymerizing while continuously feeding the monomer from a point in time when the polymerization conversion rate is 10 to 30% until a point in time when the polymerization conversion rate is 40 to 70%.

[0104] If the monomer is continuously fed from the point where the polymerization conversion rate is 10 to 30% to the point where the polymerization conversion rate is 40 to 70%, preferably from the point where the polymerization conversion rate is 10 to 20% to the point where the polymerization conversion rate is 50 to 70%, the rapid progression of polymerization, which is a problem that occurs when the monomer is fed all at once before the start of polymerization, can be prevented, thereby improving polymerization stability and latex stability. In addition, the formation of coagulated material can be minimized, and as a result, manufacturing efficiency can be improved. Furthermore, since the stability of the diene rubbery polymer is improved, graft polymerization can proceed smoothly during the manufacture of the graft polymer.

[0105] The content of the monomer added at the step of initiating the polymerization of the monomer may be 50 to 90 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. Additionally, the content of the monomer continuously added during the polymerization step may be 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. If the above conditions are satisfied, polymerization stability can be improved.

[0107] The above-mentioned diene-based rubbery polymer may have an average particle size of 50 to 500 nm and a gel content of 60 to 85 weight%, and preferably, an average particle size of 100 to 400 nm and a gel content of 65 to 80 weight%. If the above-mentioned conditions are satisfied, a graft polymer with significantly improved impact resistance can be produced.

[0109] 2. Method for manufacturing graft polymer

[0111] A method for manufacturing a graft polymer according to another embodiment of the present invention comprises the step of manufacturing a diene-based rubbery polymer by the method according to one embodiment of the present invention; and the step of polymerizing a vinyl aromatic monomer and a vinyl cyanide monomer into the diene-based rubbery polymer.

[0113] The above-mentioned diene-based rubbery polymer may be in the form of latex dispersed in water in a colloidal state.

[0114] The content of the above-mentioned diene-based rubbery polymer may be 45 to 75 parts by weight, preferably 50 to 70 parts by weight, based on 100 parts by weight of the total content of the above-mentioned diene-based rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer. If the above-mentioned range is satisfied, the impact resistance and processability of the graft polymer can be further improved.

[0116] The content of the vinyl aromatic monomer may be 15 to 45 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total content of the diene rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer. If the above-described range is satisfied, the chemical resistance, rigidity, impact resistance, processability, and surface gloss of the graft polymer can be further improved.

[0117] The content of the vinyl cyanide monomer may be 1 to 20 parts by weight, preferably 3 to 17 parts by weight, based on 100 parts by weight of the total content of the diene rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer. If the above-described range is satisfied, the chemical resistance, rigidity, impact resistance, processability, and surface gloss of the thermoplastic resin composition may be further improved.

[0119] The above polymerization can be carried out in the presence of one or more selected from the group consisting of emulsifiers, initiators, oxidation-reduction catalysts, molecular weight regulators, and ion-exchanged water.

[0120] The content of the emulsifier may be 0.01 to 2.00 parts by weight or 0.10 to 0.60 parts by weight based on 100 parts by weight of the total content of the diene-based rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer, and it is preferable that the content be 0.10 to 1.50 parts by weight. If the above-described range is satisfied, emulsion polymerization is easily performed, polymerization stability and latex stability are improved, and the residual amount in the graft polymer can be minimized.

[0122] The content of the initiator may be 0.010 to 1.000 parts by weight or 0.100 to 0.500 parts by weight with respect to 100 parts by weight of the total content of the diene rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer, and it is preferable that the content be 0.100 to 0.500 parts by weight. If the above-described range is satisfied, emulsion polymerization can be easily performed, and the residual amount in the graft polymer can be minimized.

[0124] The content of the above oxidation-reduction catalyst may be 0.0100 to 0.5000 parts by weight or 0.0500 to 0.4000 parts by weight based on 100 parts by weight of the total content of the above diene rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer, and it is preferable that the content be 0.0500 to 0.4000 parts by weight. If the above-described range is satisfied, the polymerization conversion rate can be further increased.

[0126] The content of the above molecular weight regulator may be added in an amount of 0.01 to 1.00 parts by weight or 0.05 to 0.50 parts by weight per 100 parts by weight of the total content of the above diene rubbery polymer, vinyl aromatic monomer, and vinyl cyanide monomer, and it is preferable to add 0.05 to 0.50 parts by weight. If the above-described range is satisfied, the weight-average molecular weight of the shell can be appropriately controlled.

[0128] 3. Thermoplastic resin composition

[0130] A thermoplastic resin composition according to another embodiment of the present invention comprises a graft polymer prepared according to another embodiment of the present invention and a non-graft polymer comprising vinyl aromatic monomer units and vinyl cyanide monomer units.

[0132] The above-mentioned non-graft polymer can impart heat resistance, rigidity, and processability to the thermoplastic resin composition.

[0134] The above-mentioned non-graft polymer may contain vinyl aromatic monomer units and vinyl cyanide monomer units in a weight ratio of 85:15 to 60:40, preferably 80:20 to 65:35. If the above-mentioned range is satisfied, the thermoplastic resin composition can better achieve a balance of heat resistance, impact resistance, and processability.

[0136] The weight ratio of the graft polymer to the non-graft polymer may be 15:85 to 35:65, preferably 20:80 to 30:70. If the above range is satisfied, the chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, stiffness, and processability of the molded article made from the thermoplastic resin composition may be further improved.

[0138] 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.

[0140] Example 1

[0141] Preparation of diene-based rubbery polymers

[0142] 55 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine, 0.30 parts by weight of potassium persulfate, 1.0 parts by weight of potassium rosinate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 0.5 parts by weight of t-dodecyl mercaptan were added to a nitrogen-substituted reactor. Then, the temperature of the reactor was raised to 25 ℃, and the pressure of the reactor was set to 5 kg / ㎠, after which polymerization was initiated. Polymerization was carried out while simultaneously raising the temperature of the reactor to 35 ℃ at a constant rate at the start of polymerization. At the point when the polymerization conversion rate was 20%, 30 parts by weight of 1,3-butadiene and 0.2 parts by weight of potassium rosinate were added, and polymerization was carried out. At the point when the polymerization conversion rate was 50%, the temperature of the reactor was raised to 50°C and polymerized for 10 hours, after which the polymerization was terminated to produce a diene-based rubbery polymer latex.

[0144] Preparation of Graft Polymers

[0146] A monomer mixture was prepared comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium rosinate, and 0.5 parts by weight of t-dodecyl mercaptan.

[0147] Then, an activator mixture comprising 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron(II) sulfate was prepared.

[0148] 60 parts by weight (based on solid content) of the diene-based rubbery polymer latex and 10 parts by weight of ion-exchanged water were introduced into a nitrogen-substituted reactor, and the reactor was heated to 55°C. Polymerization was carried out by continuously introducing the monomer mixture and the activator mixture into the reactor for 2 hours. After the continuous introduction was completed, 0.0050 parts by weight of dextrose, 0.0050 parts by weight of tetrasodium pyrophosphate, 0.0005 parts by weight of iron(II) sulfate, and 0.1 parts by weight of t-butyl hydroperoxide were introduced into the reactor, and the reactor was heated to 80°C over 1 hour, after which the polymerization was terminated to produce a graft polymer latex.

[0149] The above graft polymer latex was aggregated, aged, washed, dehydrated, and dried to produce graft polymer powder.

[0151] <Preparation of Thermoplastic Resin Composition>

[0152] A thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the above graft polymer powder and 72.5 parts by weight of a vinyl-based non-graft polymer (styrene / acrylonitrile polymer, LG Chem's 92 HR).

[0154] Example 2

[0155] A diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.30 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0157] Example 3

[0158] A diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.70 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0160] Example 4

[0161] A diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.30 parts by weight of ethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0163] Example 5

[0164] In Example 1, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.30 parts by weight of dimethylamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0166] Comparative Example 1

[0167] Preparation of diene-based rubbery polymers

[0168] 55 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.3 parts by weight of potassium persulfate, 1.0 parts by weight of potassium rosinate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 0.5 parts by weight of t-dodecyl mercaptan were added to a nitrogen-substituted reactor. Then, the temperature of the reactor was raised to 70 ℃, and the pressure of the reactor was set to 8 kg / ㎠, after which polymerization was initiated. Polymerization was carried out while simultaneously raising the temperature of the reactor to 80 ℃ at a constant rate at the start of polymerization. At the point when the polymerization conversion rate was 20%, 30 parts by weight of 1,3-butadiene and 0.2 parts by weight of potassium rosinate were added, and polymerization was carried out. At the point when the polymerization conversion rate was 50%, the temperature of the reactor was raised to 85°C and polymerized for 10 hours, after which the polymerization was terminated to produce a diene-based rubbery polymer latex.

[0170] Preparation of Graft Polymers

[0171] A monomer mixture was prepared comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium rosinate, and 0.5 parts by weight of t-dodecyl mercaptan.

[0172] Then, an activator mixture comprising 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron(II) sulfate was prepared.

[0173] 60 parts by weight (based on solid content) of the diene-based rubbery polymer latex and 10 parts by weight of ion-exchanged water were introduced into a nitrogen-substituted reactor, and the reactor was heated to 55°C. Polymerization was carried out by continuously introducing the monomer mixture and the activator mixture into the reactor for 2 hours. After the continuous introduction was completed, 0.0050 parts by weight of dextrose, 0.0050 parts by weight of tetrasodium pyrophosphate, 0.0005 parts by weight of iron(II) sulfate, and 0.1 parts by weight of t-butyl hydroperoxide were introduced into the reactor, and the reactor was heated to 80°C over 1 hour, after which the polymerization was terminated to produce a graft polymer latex.

[0174] The above graft polymer latex was aggregated, aged, washed, dehydrated, and dried to produce graft polymer powder.

[0176] <Preparation of Thermoplastic Resin Composition>

[0177] A thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the above graft polymer powder and 72.5 parts by weight of a vinyl-based non-graft polymer (styrene / acrylonitrile polymer, LG Chem's 92 HR).

[0179] Comparative Example 2

[0180] Preparation of diene-based rubbery polymers

[0181] 55 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 0.05 parts by weight of t-butyl hydroperoxide, 0.0080 parts by weight of dextrose, 0.0800 parts by weight of tetrasodium pyrophosphate, 0.0080 parts by weight of iron(II) sulfate, 1.0 parts by weight of potassium rosinate, 1.0 parts by weight of potassium oleate, 1.5 parts by weight of potassium carbonate, and 0.5 parts by weight of t-dodecyl mercaptan were introduced into a nitrogen-substituted reactor. Then, the temperature of the reactor was raised to 70 ℃, and the pressure of the reactor was set to 8 kg / ㎠, after which polymerization was initiated. Polymerization was carried out while simultaneously raising the temperature of the reactor to 80 ℃ at a constant rate at the start of polymerization. At the point when the polymerization conversion rate was 20%, 30 parts by weight of 1,3-butadiene and 0.2 parts by weight of potassium rosinate were added and polymerization was carried out. At the point when the polymerization conversion rate was 50%, the temperature of the reactor was raised to 85°C and polymerized for 10 hours, after which the polymerization was terminated to produce a diene-based rubbery polymer latex.

[0183] Preparation of Graft Polymers

[0184] A monomer mixture was prepared comprising 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 100 parts by weight of ion-exchanged water, 0.05 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of potassium rosinate, and 0.5 parts by weight of t-dodecyl mercaptan.

[0185] Then, an activator mixture comprising 0.0100 parts by weight of dextrose, 0.0100 parts by weight of tetrasodium pyrophosphate, and 0.0010 parts by weight of iron(II) sulfate was prepared.

[0186] 60 parts by weight (based on solid content) of the diene-based rubbery polymer latex and 10 parts by weight of ion-exchanged water were introduced into a nitrogen-substituted reactor, and the reactor was heated to 55°C. Polymerization was carried out by continuously introducing the monomer mixture and the activator mixture into the reactor for 2 hours. After the continuous introduction was completed, 0.0050 parts by weight of dextrose, 0.0050 parts by weight of tetrasodium pyrophosphate, 0.0005 parts by weight of iron(II) sulfate, and 0.1 parts by weight of t-butyl hydroperoxide were introduced into the reactor, and the reactor was heated to 80°C over 1 hour, after which the polymerization was terminated to produce a graft polymer latex.

[0187] The above graft polymer latex was aggregated, aged, washed, dehydrated, and dried to produce graft polymer powder.

[0189] <Preparation of Thermoplastic Resin Composition>

[0190] A thermoplastic resin composition was prepared by mixing 27.5 parts by weight of the above graft polymer powder and 72.5 parts by weight of a vinyl-based non-graft polymer (styrene / acrylonitrile polymer, LG Chem's 92 HR).

[0192] Comparative Example 3

[0193] In Example 1, a diene-based rubbery polymer was attempted to be prepared in the same manner as in Example 1, except that 0.02 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine, but polymerization was not initiated or carried out. In order to initiate polymerization, the temperature of the reactor was raised to 50°C, but polymerization did not begin.

[0195] Comparative Example 4

[0196] A diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.71 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0198] Comparative Example 5

[0199] A diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.80 parts by weight of N,N,N',N'-tetramethylethylenediamine was added instead of 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine.

[0201] Comparative Example 6

[0202] In Example 1, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 0.03 parts by weight of N,N,N',N'-tetramethylethylenediamine was not added before the start of polymerization, but was added after 3 hours had elapsed following raising the temperature of the reactor to 25°C. Polymerization began from the time N,N,N',N'-tetramethylethylenediamine was added.

[0204] Comparative Example 7

[0205] In Example 1, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were to be prepared in the same manner as in Example 1, except that azobisisobutyronitrile (ABIN) was added instead of potassium persulfate, but polymerization did not start at 25°C. In order to start polymerization, the temperature of the reactor was raised to 50°C, but polymerization did not start.

[0207] Comparative Example 8

[0208] In Example 1, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were to be prepared in the same manner as in Example 1, except that t-butyl hydroperoxide was added instead of potassium persulfate; however, polymerization did not start at 25°C because an oxidation-reduction catalyst was not added. In order to start polymerization, the temperature of the reactor was raised to 50°C, but polymerization did not start.

[0210] Comparative Example 9

[0211] In Example 1, a diene-based rubbery polymer, a graft polymer, and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that tris(2-ethylhexyl)amine was added instead of N,N,N',N'-tetramethylethylenediamine, but polymerization did not start at 25°C. To start polymerization, the temperature of the reactor was raised to 50°C, but polymerization did not start.

[0213] Experimental Example 1

[0214] The maximum polymerization pressure (kg / cm²) applied to the reactor during the preparation of the diene-based rubbery polymers of the examples and comparative examples was measured, and the results are shown in Tables 1 to 3 below. Here, the maximum polymerization pressure refers to the point when the internal pressure of the reactor is highest during polymerization.

[0216] Experimental Example 2

[0217] The physical properties of the diene-based rubbery polymers of the examples and comparative examples were measured by the method described below, and the results are shown in Tables 1 to 3 below.

[0219] 1) Average particle size (nm): Measured using the dynamic light scattering method with a Nicomp 380 instrument from Particle Sizing Systems.

[0221] *

[0222] 2) Gel content (weight%): A diene-based rubbery polymer latex was coagulated with a dilute aqueous sulfuric acid solution and then washed. The washed material was first dried in a vacuum oven at 60°C for 24 hours. Afterward, the first-dried material was cut into small pieces with scissors to make slices. 1 g of a slice was placed in 100 g of toluene and stored in a dark room at 23°C for 48 hours, after which it was separated into a sol and a gel. The gel was secondarily dried in an oven at 85°C for 6 hours, the weight of the second-dried material was determined, and the gel content was calculated by substituting it into the following formula.

[0224] Gel content (weight%) = (Weight of secondary dried product) / (Weight of slices used in preparation of secondary dried product) × 100

[0226] 3) Coagulated product (weight%): After filtering the diene-based rubbery polymer latex through a 100-mesh wire mesh, the reaction product that did not pass through the wire mesh was dried in a hot air dryer at 100°C for 1 hour to measure the weight of the coagulated product, and the result was calculated by substituting it into the following formula.

[0227] Content of coagulated material (weight%) = {Weight of coagulated material (g) / Total weight of reaction product (g)} × 100

[0229] Experimental Example 3

[0230] The thermoplastic resin compositions of the examples and comparative examples were extruded to produce pellets, and the pellets were injection molded to produce specimens. The physical properties of the specimens were measured by the methods described below, and the results are shown in Tables 1 to 3 below.

[0232] 1) Impact strength (kgf·cm / cm, 1 / 4 In): Measured at 25 ℃ according to ASTM D256.

[0233] division Example 1 Example 2 Example 3 Example 4 Example 5 Preparation of diene-based rubbery polymers amine compounds type TMEDA TMEDA TMEDA EDA DMA Content (parts by weight) 0.03 0.30 0.70 0.30 0.30 Input time (Polymerization conversion rate, %) 0 0 0 0 0 Initiator type KPS KPS KPS KPS KPS Content (parts by weight) 0.30 0.30 0.30 0.30 0.30 Polymerization initiation temperature (°C) 25 25 25 25 25 Polymerization temperature (°C) 35 35 35 35 35 Maximum polymerization pressure 8.4 8.4 8.5 8.5 8.4 diene-based gum polymer Average particle size (nm) 310 310 310 310 310 Gel content (weight%) 69 68 71 70 69 Coagulated material (weight%) 0.007 0.008 0.011 0.008 0.009 Psalter Impact strength (kg·cm / cm) 34.5 34.1 34.3 34.1 34.1 TMEDA: N,N,N',N'-Tetramethylethylenediamine EDA: Ethylenediamine DMA: Dimethylamine KPS: Potassium persulfate

[0234] division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Preparation of diene-based rubbery polymers amine compounds type - - TMEDA TMEDA TMEDA Content (parts by weight) 0 0 0.02 0.71 0.80 Input time (Polymerization conversion rate, %) - - 0 0 0 Initiator type KPS t-BHP KPS KPS KPS Content (parts by weight) 0.30 0.50 0.30 0.30 0.30 Polymerization initiation temperature (°C) 70 70 Polymerization × 25 25 Polymerization temperature (°C) 80 80 Polymerization × 35 35 Maximum polymerization pressure 13.5 9.0 Polymerization × 8.5 8.5 diene-based gum polymer Average particle size (nm) 310 280 Polymerization × 295 310 Gel content (weight%) 85 67 Polymerization × 66 66 Coagulated material (weight%) 0.012 0.080 - 0.100 0.120 Psalter Impact strength (kg·cm / cm) 29.1 29.5 - 32.4 33.1 TMEDA: N,N,N',N'-Tetramethylethylenediamine EDA: Ethylenediamine DMA: Dimethylamine KPS: Potassium persulfate t-BHP: t-Butyl hydroperoxide

[0235] division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Preparation of diene-based rubbery polymers amine compounds type TMEDA TMEDA TMEDA TEA Content (parts by weight) 0.30 0.30 0.30 0.30 Input time (Polymerization conversion rate, %) 3 hours after raising the reactor temperature to 25 ℃ 0 0 0 Initiator type KPS AIBN t-BHP KPS Content (parts by weight) 0.30 0.30 0.05 0.30 Polymerization initiation temperature (°C) 25 Polymerization × Polymerization × Polymerization × Polymerization temperature (°C) 35 Polymerization × Polymerization × Polymerization × Maximum polymerization pressure 10.4 Polymerization × Polymerization × Polymerization × diene-based gum polymer Average particle size (nm) 212 Polymerization × Polymerization × Polymerization × Gel content (weight%) 75 Polymerization × Polymerization × Polymerization × Coagulated material (weight%) 0.500 - - - Psalter Impact strength (kg·cm / cm) - - - - TMEDA: N,N,N',N'-Tetramethylethylenediamine EDA: Ethylenediamine DMA: Dimethylamine KPS: Potassium persulfate ABIN: Azobisisobutyronitrile t-BHP: t-butyl hydroperoxide

[0236] Referring to Tables 1 to 3, Examples 1 to 3, in which the polymerization of a diene monomer was initiated in the presence of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, had a polymerization initiation temperature of 25°C. Examples 1 to 3 exhibited excellent polymerization stability, resulting in minimal coagulation; the average particle size of the diene rubbery polymer was appropriate; and the impact resistance of the specimens was also excellent. However, as the content of N,N,N',N'-tetramethylethylenediamine increased, the polymerization stability decreased slightly, and the content of coagulation increased. Example 4, in which the polymerization of a diene monomer was initiated in the presence of ethylenediamine and potassium persulfate, had a polymerization initiation temperature of 25°C. Example 4 exhibited excellent polymerization stability, resulting in minimal coagulation; the average particle size of the diene rubbery polymer was appropriate; and the impact resistance of the specimens was also excellent.

[0237] Example 5, in which the polymerization of a diene monomer was initiated in the presence of dimethylamine and potassium persulfate, had a polymerization initiation temperature of 25°C. Example 5 exhibited excellent polymerization stability with minimal coagulation, appropriate average particle size of the diene rubbery polymer, and excellent impact resistance of the specimen.

[0238] Meanwhile, Comparative Example 1, in which the polymerization of a diene monomer was initiated in the presence of potassium persulfate without the presence of amine compounds, had a polymerization initiation temperature of 70°C. Since both the polymerization initiation and execution temperatures were high in Comparative Example 1, the maximum polymerization pressure was also high; consequently, compared to Examples 2, 4, and 5, in which potassium persulfate was added in the same amount, the polymerization stability was reduced, resulting in an excessive amount of coagulated material. Furthermore, while the average particle size of the diene rubbery polymer was at an equivalent level compared to Examples 2, 4, and 5, the impact resistance of the specimens was significantly reduced.

[0239] Comparative Example 2, in which the polymerization of a diene monomer was initiated in the presence of t-butyl hydroperoxide and an oxidation-reduction catalyst without the presence of amine compounds, had a polymerization initiation temperature of 70°C. Since both the polymerization initiation and execution temperatures were high in Comparative Example 2, the maximum polymerization pressure was also high. Furthermore, compared to Examples 1 to 5, the polymerization stability of Comparative Example 2 was reduced, resulting in an excessive amount of coagulated material. Additionally, the average particle size of the diene rubbery polymer was smaller compared to Examples 1 to 5, and the impact strength of the specimens was not excellent.

[0240] Comparative Example 3, in which the polymerization of a diene monomer was attempted in the presence of 0.02 parts by weight of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, did not initiate polymerization at 35°C or lower.

[0241] Comparative Example 4, in which the polymerization of a diene monomer was initiated in the presence of 0.71 parts by weight of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, had a polymerization initiation temperature of 25°C. However, compared to Examples 1 to 5, the polymerization stability of Comparative Example 4 was reduced, resulting in an excessive amount of coagulated material. Additionally, the average particle size of the diene rubbery polymer in Comparative Example 4 was smaller than that of Examples 1 to 5, and the impact resistance of the specimen was not excellent.

[0242] Comparative Example 5, in which the polymerization of a diene monomer was initiated in the presence of 0.80 parts by weight of N,N,N',N'-tetramethylethylenediamine and potassium persulfate, had a polymerization initiation temperature of 25°C. However, compared to Examples 1 to 5, the polymerization stability of Comparative Example 5 was reduced, resulting in an excessive amount of coagulated material. Additionally, although the average particle size of the diene rubbery polymer was at an equivalent level compared to Examples 1 to 5, the impact resistance of the specimen was not excellent.

[0243] In Comparative Example 6, N,N,N',N'-tetramethylethylenediamine was added after 3 hours had elapsed following raising the reactor temperature to 25°C. Polymerization did not begin before the addition of N,N,N',N'-tetramethylethylenediamine, but began only after the addition of N,N,N',N'-tetramethylethylenediamine. Since the polymerization began late, the polymerization proceeded rapidly, which caused a significant increase in the maximum polymerization pressure. Additionally, as polymerization stability was significantly reduced, an excessive amount of coagulated material was produced. Furthermore, because the physical properties of the diene-based rubbery polymer were significantly degraded due to the excessive amount of coagulated material, specimens were not prepared to verify impact resistance.

[0244] Comparative Examples 7, 8, and 9 raised the temperature of the reactor to 50°C to initiate polymerization, but polymerization did not initiate in any of them.

Claims

Claim 1 A method for producing a diene-based rubbery polymer comprising the step of initiating and performing polymerization of monomers in the presence of an amine-based compound and a thermal decomposition initiator, wherein the amine-based compound is ethylenediamine, the content of the amine-based compound is 0.03 to 0.70 parts by weight per 100 parts by weight of the total content of monomers input during the production of the diene-based rubbery polymer, the monomer is a diene-based monomer; or a diene-based monomer and a vinyl aromatic monomer; and the polymerization is initiated at 25 to 50 ℃. Claim 2 delete Claim 3 delete Claim 4 A method for manufacturing a diene-based rubbery polymer according to claim 1, wherein the pyrolysis initiator is one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate. Claim 5 A method for manufacturing a diene-based rubbery polymer according to claim 1, wherein the polymerization is initiated at 25 to 35 ℃. Claim 6 A method for manufacturing a diene-based rubbery polymer according to claim 1, wherein the content of the pyrolysis initiator is 0.01 to 3.00 parts by weight per 100 parts by weight of the total monomer content added during the manufacture of the diene-based rubbery polymer. Claim 7 A method for producing a diene-based rubbery polymer according to claim 1, wherein the step of initiating and performing the polymerization of the monomer comprises: a step of initiating the polymerization of the monomer in the presence of the amine-based compound and a thermal decomposition initiator; and a step of introducing the monomer and polymerizing at a time when the polymerization conversion rate is 10 to 50%. Claim 8 A method for manufacturing a diene-based rubbery polymer according to claim 7, wherein the content of the monomer introduced in the step of initiating the polymerization of the monomer is 50 to 90 parts by weight with respect to 100 parts by weight of the total monomer content introduced during the manufacture of the diene-based rubbery polymer, and the content of the monomer introduced in the step of polymerization is 10 to 50 parts by weight with respect to 100 parts by weight of the total monomer content introduced during the manufacture of the diene-based rubbery polymer. Claim 9 A method for manufacturing a diene-based rubbery polymer according to claim 1, wherein the polymerization is an emulsion polymerization. Claim 10 A method for manufacturing a graft polymer comprising the steps of: manufacturing a diene-based rubbery polymer according to the manufacturing method of claim 1; and polymerizing a vinyl aromatic monomer and a vinyl cyanide monomer into the diene-based rubbery polymer.

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