WO2016099129A1 - 디엔계 고무 중합체의 제조방법, 이로부터 제조된 디엔계 고무 중합체 및 이를 포함하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체 - Google Patents
디엔계 고무 중합체의 제조방법, 이로부터 제조된 디엔계 고무 중합체 및 이를 포함하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체 Download PDFInfo
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- WO2016099129A1 WO2016099129A1 PCT/KR2015/013752 KR2015013752W WO2016099129A1 WO 2016099129 A1 WO2016099129 A1 WO 2016099129A1 KR 2015013752 W KR2015013752 W KR 2015013752W WO 2016099129 A1 WO2016099129 A1 WO 2016099129A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/942—Polymer derived from nitrile, conjugated diene and aromatic co-monomers
Definitions
- the present invention provides a method for preparing a diene rubber polymer having a high polymerization conversion rate and a relatively low gel content and a high swelling index, a diene rubber polymer prepared therefrom, and an acrylonitrile-core having a core-shell structure including the core.
- Butadiene-styrene graft copolymer is
- ABS resins In general, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins have relatively good physical properties such as impact resistance, mechanical strength, moldability, glossiness, and are widely used in electrical, electronic parts, office equipment, and automobile parts. .
- the ABS resin is greatly affected by physical properties such as the average particle diameter of the diene rubber latex which is a rubber component.
- the physical properties of the ABS resin may vary depending on the average particle diameter, gel content, and swelling index of the diene rubber latex.
- ABS-based resins are typically manufactured through an emulsion polymerization method.
- diene-based rubber latex is prepared by emulsion polymerization method, and then an aromatic vinyl compound and vinyl cyan compound are added thereto, and graft reaction is performed by emulsion polymerization method to acrylonitrile-butadiene-styrene graft copolymer.
- SAN styrene-acrylonitrile copolymer
- the diene rubber polymer may be advantageously applied to the production of ABS resin when the polymerization conversion is 90% or more, and the gel content of 90 to 95% and 14 when the diene rubber polymer is 90% or more. It may have a swelling index of 20 to.
- the gel content and the swelling index are closely related to the polymerization conversion rate and the polymerization reaction temperature.
- the polymerization is performed at a relatively high temperature.
- the gel content rapidly increases and the swelling index is increased. Is greatly reduced.
- the transparency may be lowered due to a low swelling index, but impact resistance may be lowered.
- impact resistance may be improved, but transparency may be decreased. Therefore, in order to obtain an ABS resin having excellent physical properties, a diene rubber polymer in which polymerization conversion rate, particle diameter, gel content, and swelling index is appropriately controlled is required.
- the present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a method for producing a diene rubber polymer having a high polymerization conversion, a relatively low gel content and a high swelling index.
- Still another object of the present invention is to provide a core-shell acrylonitrile-butadiene-styrene graft copolymer including the diene rubber polymer as a core.
- step 1 50 parts by weight to 75 parts by weight of the conjugated diene monomer, 1 part by weight to 4 parts by weight of the emulsifier and 0.1 parts by weight to 0.5 parts by weight of the molecular weight modifier in the reactor and the first polymerization step (step 1); 25 to 50 parts by weight of the conjugated diene monomer at the time of the polymerization conversion rate of the step 1 is 10% to 40% continuously for 0.5 to 10 hours and the second polymerization (step 2); And terminating the polymerization (step 3) when the polymerization conversion rate of the step 2 is 92% or more.
- the present invention also provides a diene rubber polymer prepared from the above production method.
- the core comprises the diene rubber polymer of the present invention
- the shell comprises an aromatic vinyl compound and a vinylcyan compound
- the weight ratio of the aromatic vinyl compound to the vinyl cyan compound forming the shell provides a weight ratio of 5: 1 to 1: 5 to provide an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure.
- a molecular weight modifier is additionally added at a point of polymerization conversion of 40% to 85%, and the polymerization reaction is carried out at a temperature range of primary and secondary without performing polymerization at a single temperature.
- the crosslinking reaction can be controlled to exhibit a high polymerization conversion.
- the diene rubber polymer prepared according to the present invention may have a low gel content and improve the swelling index, and the acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure may have impact strength characteristics. This can be further improved.
- the process for producing the diene rubber polymer according to the present invention and the core-shell structure acrylonitrile-butadiene-styrene graft copolymer comprising the diene rubber polymer prepared therefrom are particularly necessary for industries, particularly impacts. It can be easily applied to the reinforcement industry.
- the present invention is to produce a diene rubber polymer having a high conversion rate and easy to apply to the rubber component of the acrylonitrile-butadiene-styrene graft copolymer of the core-shell structure while lowering the gel content and the swelling index Provide a method.
- step 1 50 parts by weight to 75 parts by weight of the conjugated diene monomer, 1 part by weight to 4 parts by weight of the emulsifier and 0.1 parts by weight to 0.5 parts by weight of the molecular weight modifier in the reactor and the first polymerization step (step 1);
- step 2 25 to 50 parts by weight of the conjugated diene monomer at a time point of 10% to 40% of the polymerization conversion rate in step 1 was continuously added for 0.5 to 10 hours (step 2);
- step 3 terminating the polymerization (step 3) at the time when the polymerization conversion rate of the step 2 is 92% or more.
- Step 1 is 50 parts by weight to 75 parts by weight of the conjugated diene monomer, 1 part by weight to 4 parts by weight of the emulsifier and 0.1 parts by weight to 0.5 parts by weight of the conjugated diene monomer to start the polymerization by mixing the emulsifier and molecular weight regulator Part by weight is added to the reactor and the first polymerization step.
- the conjugated diene monomer may include a single product of the conjugated diene monomer, or a monomer mixture including the conjugated diene monomer as a main component and an aromatic vinyl monomer and a vinyl cyan monomer.
- the monomer mixture is 55 to 99.7% by weight of the conjugated diene monomer; 0.1 wt% to 40 wt% of an aromatic vinyl monomer; And it may include 0.1% to 40% by weight of vinyl cyanic monomer.
- the conjugated diene monomer is not particularly limited, but may be, for example, one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene. Specifically, it may be 1,3-butadiene.
- the aromatic vinyl monomer is not particularly limited, and for example, may be one or more selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene. Specifically, it may be styrene.
- the vinyl cyan monomer is not particularly limited, and for example, may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. Specifically, it may be acrylonitrile.
- the emulsifier is not particularly limited, but for example, anionic adsorption type emulsifiers such as potassium rosin, potassium fatty acid, sodium lauryl sulfonate, sodium alkylbenzene sulfonate, and nonionic emulsifiers such as polyoxyethylene alkylphenyl ether, sodium Reacting emulsifiers such as dodercell allyl sulfosuccinate, C 16-18 alkenyl benzoate di-potassium salt, sodium acrylamide stearate, polyoxyethylene alkylphenyl ether ammonium sulfate, polyoxyethylene alkyl ether sulfate ester ammonium salt Polymeric reactive emulsifiers such as these may be used alone or in combination.
- anionic adsorption type emulsifiers such as potassium rosin, potassium fatty acid, sodium lauryl sulfonate, sodium alkylbenzene sulfonate, and
- the molecular weight modifier is not particularly limited, but for example, mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide Sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, diisopropylchianthogen disulfide.
- mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide Sul
- the primary polymerization may be carried out in the presence of at least one additive in ion-exchanged water, a polymerization initiator and an electrolyte as necessary.
- the amount of the ion-exchanged water, the polymerization initiator and the electrolyte is not particularly limited.
- the ion-exchanged water is 65 parts by weight to 100 parts by weight
- the polymerization initiator is 0.2 parts by weight to 0.4 parts by weight
- the electrolyte is 0.2 parts by weight. It may be used in parts to 3 parts by weight.
- the polymerization initiator is not particularly limited and may be a conventional one known in the art, but for example, a water-soluble polymerization initiator such as persulfate, a fat-soluble polymerization initiator such as a peroxy compound, or an oxidation-reduction catalyst may be used.
- the persulfate may be potassium persulfate, sodium persulfate, ammonium persulfate, or the like.
- the fat-soluble polymerization initiator may be cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, Paramentane hydroperoxide, benzoyl peroxide, and the like.
- the redox-based catalyst may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite and the like.
- the electrolyte is potassium chloride, sodium chloride, potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate, potassium sulfate, sodium sulfate, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium pyrophosphate, sodium pyrophosphate, potassium phosphate, sodium phosphate, potassium hydrogen phosphate, phosphoric acid Sodium hydrogen and the like.
- the secondary polymerization is a step of continuously adding 25 to 50 parts by weight of the conjugated diene monomer for 0.5 to 10 hours when the polymerization conversion rate of the primary polymerization is 10% to 40%.
- the production method according to the present invention can easily form a diene rubber polymer having an appropriate particle size by dividing the conjugated diene monomer into two stages (batch addition and continuous addition) according to the polymerization conversion time point. have.
- the production method of the present invention may further include the step of additionally adding 0.01 parts by weight to 0.3 parts by weight of the molecular weight regulator when the polymerization conversion rate of the (second step) secondary polymerization is 40% to 85%. More specifically, it can be added further at the time of 55% to 70% of the polymerization conversion rate. Since the preparation method according to the present invention can suppress the crosslinking reaction by additionally adding a molecular weight modifier at the time of 40% to 85% of the polymerization conversion rate, it is possible to suppress the increase of the gel content and the decrease of the swelling index while increasing the polymerization conversion rate. . As a result, it is possible to obtain a diene rubber polymer having a high polymerization conversion, a low gel content and a relatively high swelling index. In addition, the said molecular weight modifier may use the same or different thing as mentioned above.
- the primary polymerization and the secondary polymerization according to the present invention may be a polymerization is performed under different temperature conditions, respectively.
- the primary polymerization may be performed under a temperature condition of 60 °C to 72 °C
- the secondary polymerization may be performed under a temperature condition of 72 °C to 85 °C. That is, the present invention may be to perform the polymerization while gradually increasing the temperature conditions as the polymerization proceeds.
- Step 3 is a step of terminating the polymerization when the polymerization conversion rate of the secondary polymerization is 92% or more in order to obtain a diene rubber polymer.
- the end of the polymerization step may be carried out using a polymerization inhibitor, the polymerization inhibitor may be used a conventional one known in the art.
- the present invention also provides a diene rubber polymer prepared from the above production method.
- the diene rubber polymer according to an embodiment of the present invention may have an average particle diameter (D50) of 2,600 kPa to 5,000 kPa, a gel content of 70% to 84%, and a swelling index of 11 to 25. It may be.
- D50 average particle diameter
- ⁇ represents a unit of the length used to express the wavelength of electromagnetic radiation, where 1 ⁇ is equal to 0.1 nm.
- the gel content indicates the degree of crosslinking in the polymer, that is, the degree of crosslinking of the polymer.
- the greater the gel content value the higher the degree of crosslinking of the polymer.
- the swelling index indicates the degree of swelling of the polymer by the solvent. The higher the crosslinking degree of the polymer, the lower the swelling index.
- the present invention provides an acrylonitrile-butadiene-styrene copolymer comprising the diene rubber polymer.
- the shell comprises an aromatic vinyl compound and a vinylcyan compound
- the weight ratio of the aromatic vinyl compound to the vinyl cyan compound forming the shell provides a weight ratio of 5: 1 to 1: 5 to provide an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure.
- the weight ratio of the core to the shell includes 30 parts by weight to 70 parts by weight: 30 parts by weight to 70 parts by weight.
- the resulting acrylonitrile-butadiene-styrene copolymer may be deteriorated, such as hardening.
- the oil resistance and the tensile strength of the acrylonitrile-butadiene-styrene copolymer may be decreased.
- the oil resistance of the finally produced acrylonitrile-butadiene-styrene copolymer may be lowered, the tensile strength may be reduced, and the shell may exceed 70 parts by weight.
- the core portion may be relatively reduced, resulting in hardening of the resulting acrylonitrile-butadiene-styrene copolymer.
- the copolymer of the present invention may have a graft ratio of 15% to 40%, the weight average molecular weight of the free rubber (free rubber) extracted from the copolymer dry powder may be 25,000 to 65,000.
- the acrylonitrile-butadiene-styrene copolymer according to the present invention is not particularly limited and can be prepared by conventional methods known in the art, such as aromatic vinyl compound, vinyl cyan compound and It may be prepared by adding an additive such as an emulsifier and then emulsion polymerization and coagulation and washing. At this time, each component may be involved in the reaction through a method of adding to the reactor in a batch, a method of adding continuously or a part of the first addition and the divided input after the start of the polymerization.
- Emulsification polymerization may be carried out typically in a temperature range of 10 °C to 90 °C, preferably a temperature range of 25 °C to 75 °C.
- the agglomeration is to agglomerate the acrylonitrile-butadiene-styrene copolymer latex composition formed after the emulsion polymerization to form an acrylonitrile-butadiene-styrene copolymer latex coagulum, in a conventional method known in the art. It can be carried out by, for example, the composition can be carried out by treating the salt aqueous solution or acid aqueous solution and salt agglomeration or acid agglomeration.
- the washing is to remove the impurities (residual emulsifier, flocculant, etc.) from the acrylonitrile-butadiene-styrene copolymer latex coagulum formed through the salt agglomeration or acid agglomeration to obtain an acrylonitrile-butadiene-styrene copolymer.
- the coagulum may be added to an aqueous inorganic salt solution, washed, and dried.
- washing and drying is not particularly limited and may be carried out by a method conventional in the art.
- 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the polymerization reactor and the temperature was raised to 80 ° C. After the temperature was raised over 1 hour, the reaction was terminated.
- the formed acrylonitrile-butadiene-styrene copolymer latex was coagulated with an aqueous sulfuric acid solution, washed and dried to obtain a powdered acrylonitrile-butadiene-styrene copolymer.
- the acrylonitrile-butadiene-styrene copolymer in powder form was prepared in the same manner as in Example 1, except that tertiary dodecyl mercaptan was not added at the time of the polymerization conversion rate of 55% when the diene rubber polymer was prepared. Obtained.
- the reaction temperature of the first polymerization was adjusted to 85 ° C.
- the reaction temperature of the second polymerization was gradually reduced to 70 ° C., except that the reaction temperature of the diene rubber polymer was adjusted to 70 ° C.
- Acrylonitrile-butadiene-styrene copolymer was obtained.
- the reaction temperature of the first polymerization was adjusted to 75 ° C.
- the reaction temperature of the second polymerization was adjusted to 75 ° C., such as the first polymerization, through the same method as in Example 1 above.
- a powdered acrylonitrile-butadiene-styrene copolymer was obtained.
- the weight average molecular weight and molecular weight distribution were determined by dissolving each extracted free rubber in THF (tetrahydrofuran) using a gel permeation chromatography (GPC) analyzer.
- THF tetrahydrofuran
- Impact strength was measured by mixing 72.5 parts by weight of styrene-acrylate copolymer (SAN, 92HR, LG Chem) with 27.5 parts by weight of each acrylonitrile-butadiene-styrene copolymer in a mixer, preparing pellets using an extruder It was.
- SAN styrene-acrylate copolymer
- LG Chem LG Chem
- Example 1 93 21.5 79 17 31242 2.47 36 Comparative Example 1 93 21 85 14 18590 1.81 32 Comparative Example 2 93 22 81 16 28313 2.15 34 Comparative Example 3 93 20 85 13 22307 2.09 31 Comparative Example 4 86 28 74 18 33460 2.68 36
- the polymerization conversion rate is 55% when the secondary polymerization temperature is increased from 70 ° C., which is the first polymerization reaction temperature, to 80 ° C. under the polymerization reaction temperature conditions separated in two steps.
- Example 1 containing 0.05 parts by weight of tertiary dodecyl mercaptan showed a low gel content, high swelling index, and high impact strength even at 93% higher conversion than Comparative Example 1 without tertiary dodecyl mercaptan.
- Comparative Example 2 in which the tertiary dodecyl mercaptan was added at 30% time point was less affected by the gel content and the swelling index than Example 1, and the improvement of the impact strength was low.
- Comparative Example 3 in which the reaction temperature was lowered from 85 ° C. to 70 ° C., the gel content did not decrease, the swelling index did not increase, and the impact strength decreased.
- Comparative Example 4 where the reaction temperature was kept constant at 75 ° C., a low gel content, a high swelling index, and a high impact strength were shown, but the reaction time delay was low.
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Abstract
Description
구분 | 디엔계 고무 중합체 | 아크릴로니트릴-부타디엔-스티렌 공중합체 | |||||
전환율(%) | 반응시간(hr) | 겔 함량(%) | 팽윤지수 | 프리러버 중량평균분자량 | 프리러버 분자량 분포 | 충격강도(kgfcm/cm) | |
실시예 1 | 93 | 21.5 | 79 | 17 | 31242 | 2.47 | 36 |
비교예 1 | 93 | 21 | 85 | 14 | 18590 | 1.81 | 32 |
비교예 2 | 93 | 22 | 81 | 16 | 28313 | 2.15 | 34 |
비교예 3 | 93 | 20 | 85 | 13 | 22307 | 2.09 | 31 |
비교예 4 | 86 | 28 | 74 | 18 | 33460 | 2.68 | 36 |
Claims (22)
- 공액디엔계 단량체 50 중량부 내지 75 중량부, 유화제 1 중량부 내지 4 중량부 및 분자량 조절제 0.1 중량부 내지 0.5 중량부를 반응기에 투입하고 1차 중합하는 단계(단계 1);상기 (단계 1)의 중합 전환율이 10% 내지 40%인 시점에 공액디엔계 단량체 25 중량부 내지 50 중량부를 0.5 내지 10시간 동안 연속투입하고 2차 중합하는 단계 (단계 2); 및상기 (단계 2)의 중합 전환율이 92% 이상인 시점에서 중합을 종료시키는 단계(단계 3);를 포함하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 2차 중합 단계의 중합 전환율이 40% 내지 85%인 시점에 0.01 중량부 내지 0.3 중량부의 분자량 조절제를 추가로 투입하는 단계를 포함하는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 2에 있어서,상기 2차 중합 단계의 중합 전환율이 55% 내지 70%인 시점에 0.01 중량부 내지 0.3 중량부의 분자량 조절제를 추가로 투입하는 단계를 포함하는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 1차 중합은 60℃ 내지 72℃의 온도 범위에서 수행되는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 2차 중합은 72℃ 내지 85℃의 온도 범위에서 수행되는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 1차 중합은 이온교환수, 중합개시제 및 전해질 중 적어도 하나 이상의 첨가제 존재 하에 수행되는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 공액디엔계 단량체는 공액디엔계 단량체의 단일물, 또는 상기 공액디엔계 단량체를 주성분으로 포함하는 단량체 혼합물인 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 단량체 혼합물은 공액디엔계 단량체 55중량% 내지 99.7중량%; 방향족 비닐계 단량체 0.1중량% 내지 40중량%; 및 비닐시안계 단량체 0.1중량% 내지 40중량%를 포함하는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 7 또는 청구항 8에 있어서,상기 공액디엔계 단량체는 1,3-부타디엔, 이소프렌, 클로로프렌 및 피퍼릴렌(piperylene)으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 8에 있어서,상기 방향족 비닐계 단량체는 스티렌, α-메틸 스티렌, α-에틸 스티렌 및 p-메틸 스티렌으로 이루어진 군으로부터 선택되는 적어도 하나 이상인 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 8에 있어서,상기 비닐시안계 단량체는 아크릴로니트릴, 메타크릴로니트릴 및 에타크릴로니트릴로 이루어진 군으로부터 선택되는 적어도 하나 이상인 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1에 있어서,상기 중합 종료 단계는 중합억제제를 사용하여 수행되는 것을 특징으로 하는 디엔계 고무 중합체의 제조방법.
- 청구항 1의 제조방법에 의하여 제조된 디엔계 고무 중합체.
- 청구항 13에 있어서,상기 디엔계 고무 중합체의 평균입경 (D50)은 2,600Å 내지 5,000Å인 것을 특징으로 하는 디엔계 고무 중합체.
- 청구항 13에 있어서,상기 디엔계 고무 중합체의 겔 함량은 70% 내지 84%인 것을 특징으로 하는 디엔계 고무 중합체.
- 청구항 13에 있어서,상기 디엔계 고무 중합체는 팽윤지수가 11 내지 25인 것을 특징으로 하는 디엔계 고무 중합체.
- 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체로서,상기 코어는 청구항 13의 디엔계 고무 중합체를 포함하고,상기 쉘은 방향족 비닐 화합물 및 비닐시안 화합물을 포함하며,상기 쉘을 이루는 방향족 비닐 화합물 : 비닐시안 화합물의 중량비는 5:1 내지 1:5의 중량비인 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
- 청구항 17에 있어서,상기 코어 : 쉘의 중량비는 30 중량부 내지 70 중량부 : 30 중량부 내지 70 중량부인 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
- 청구항 17에 있어서,상기 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체는 15% 내지 40%의 그라프트율을 갖는 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
- 청구항 17에 있어서,상기 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체는 공중합체 건조 분말로부터 추출된 프리러버(free rubber)의 중량평균분자량이 25,000 내지 65,000인 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
- 청구항 17에 있어서,상기 방향족 비닐 화합물은 스티렌, α-메틸 스티렌, α-에틸 스티렌 및 p-메틸 스티렌으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
- 청구항 17에 있어서,상기 비닐시안 화합물은 아크릴로니트릴, 메타크릴로니트릴 및 에타크릴로니트릴로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 코어-쉘 구조의 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체.
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KR102146370B1 (ko) | 2018-05-25 | 2020-08-20 | 주식회사 엘지화학 | 공중합체의 제조방법 |
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US10385154B2 (en) | 2019-08-20 |
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