WO2021060833A1 - 공액 디엔계 중합체의 제조방법 - Google Patents
공액 디엔계 중합체의 제조방법 Download PDFInfo
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- 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
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- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/06—Butadiene
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F2/00—Processes of polymerisation
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- 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
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- 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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- C08F4/00—Polymerisation catalysts
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- C08F6/00—Post-polymerisation treatments
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a method for preparing a conjugated diene-based polymer, and specifically, a dimer acid saponified product is used in the polymerization initiation step, and a monomer and an emulsifier are divided and added three or more times after the polymerization reaction is initiated. It relates to a method of manufacturing.
- ABS copolymer resin has relatively good physical properties such as moldability and gloss as well as mechanical strength such as impact resistance. It is widely used in parts and the like.
- ABS resin prepared by the emulsion polymerization method has the advantage of having a relatively good balance of physical properties and excellent gloss. Therefore, ABS resins are mainly manufactured by emulsion polymerization rather than bulk polymerization.
- the ABS resin produced by the emulsion polymerization method can be processed by mixing with a styrene-acrylonitrile (SAN) copolymer to maximize the properties of the composition of the SAN resin to diversify products and create high added value.
- SAN styrene-acrylonitrile
- the gloss or clarity of ABS resin is not only affected by the particle size and particle distribution of the dispersed rubber polymer, but also the emulsifier, residual monomer, oligomer remaining after polymerization of polybutadiene latex (PBL) and ABS during high-temperature injection process. It is affected by gas generated on the surface of the resin by impurities such as heat stabilizers and SAN. In particular, the gas generated from the surface of the resin during the high-temperature injection process affects the roughness of the surface, greatly lowering the gloss or clarity of the resin, and is known to be a limiting factor in improving the quality of the resin.
- Patent Document 1 KR 10-1279267 B1
- the present invention is to solve the problems of the prior art described above, to provide a method of manufacturing a conjugated diene-based polymer that is included in a thermoplastic resin to improve impact strength and surface clarity, and to reduce the amount of gas generated during injection. It is aimed at.
- an object of the present invention is to provide a method for producing a graft copolymer including the conjugated diene polymer and a thermoplastic resin composition including the graft copolymer.
- the present invention is a step of initiating a polymerization reaction by collectively introducing 30 to 50 parts by weight of 100 parts by weight of a conjugated diene-based monomer, 0.1 to 5 parts by weight of a dimer acid saponified product, and a polymerization initiator into the reactor ( S1), step of dividing the remaining conjugated diene-based monomer and emulsifier three or more times according to the polymerization conversion rate after the initiation of the polymerization reaction (S2), and terminating the polymerization reaction at the point of 90 to 99% polymerization conversion rate (S3) It provides a method for producing a conjugated diene-based polymer comprising a.
- the step S2 is a step of introducing a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 20 to 35% (S2-1), and a polymerization conversion rate of 45 to 60%.
- Preparation of a conjugated diene-based polymer comprising the step of introducing a conjugated diene-based monomer and an emulsifier (S2-2) and adding a conjugated diene-based monomer and an emulsifier at a time point of 70 to 80% polymerization conversion (S2-3) Provides a way.
- the impact strength and surface clarity of the thermoplastic resin containing the prepared conjugated diene-based polymer can be improved by increasing the standard deviation of the particle diameter of the prepared conjugated diene-based polymer.
- the conjugated diene-based monomer of the present invention may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, of which 1,3-butadiene may be preferred.
- the aromatic vinyl-based monomer of the present invention may be one or more selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which styrene is preferable.
- the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, of which acrylonitrile This is desirable.
- the "derived unit” refers to a unit derived from the compound, and specifically, may refer to the compound itself or a substituent from which some atoms of the compound have been removed.
- the average particle diameter and standard deviation of the particle size of the conjugated diene-based polymer can be measured through a particle size analyzer of Nicomp. Specifically, the polymer sample to be measured is diluted and measured, and the average particle diameter and the standard deviation of the particle size of Intensity Wt You can read and measure.
- a conjugated diene-based monomer 30 to 50 parts by weight of 100 parts by weight of a conjugated diene-based monomer, 0.1 to 5 parts by weight of a dimer acid saponified product, and a polymerization initiator are collectively added to the reactor to initiate a polymerization reaction (S1), and polymerization after the polymerization reaction is initiated.
- Preparation of a conjugated diene-based polymer comprising the step of dividingly introducing the remaining conjugated diene-based monomer and emulsifier three or more times according to the conversion rate (S2) and terminating the polymerization reaction at the point of 90 to 99% polymerization conversion rate (S3) Provides a way.
- the method for producing a conjugated diene-based polymer provided by the present invention includes 30 to 50 parts by weight of 100 parts by weight of a conjugated diene-based monomer subject to polymerization, a dimer acid saponification product, and a polymerization initiator in batch to initiate a polymerization reaction. Includes steps.
- the conjugated diene-based monomer introduced in this step may be 30 to 50 parts by weight, preferably 35 to 45 parts by weight, based on 100 parts by weight, which is the total amount of the conjugated diene-based monomer to be polymerized.
- the conjugated diene-based monomer is added in the above-described range in the polymerization initiation step, the standard deviation of the particle size of the finally prepared conjugated diene-based polymer can be widened.
- the dimer acid saponification product and the polymerization initiator are added together with the conjugated diene-based monomer.
- the dimer acid saponified product serves as an emulsifier.
- the dimer acid may be one or more selected from compounds represented by the following Formulas 1 to 6:
- the saponified product refers to a metal salt of a carboxylic acid group generated by saponification of an acid, for example, an alkali metal salt or an alkaline earth metal salt, and specifically, may be a sodium salt, potassium salt, magnesium salt, or calcium salt.
- the polymerization initiator serves to initiate a polymerization reaction, and may be at least one of a water-soluble polymerization initiator and a mixture of an oil-soluble polymerization initiator and an oxidation-reduction catalyst, and it is particularly preferable to use a combination thereof.
- the water-soluble polymerization initiator may be one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate
- the oil-soluble polymerization initiator is cumene hydroperoxide, diisopropyl benzene hydroperoxide, It may be one or more selected from the group consisting of azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide
- the oxidation-reduction catalyst is sodium formaldehyde sulfoxylate
- It may be one or more selected from the group consisting of sodium ethylenediamine tetraacetide, ferrous sulfate, dextrose, sodium pyrrole phosphate, and sodium sulfite.
- the polymerization initiator may be added in an amount of 0.01 to 1 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the conjugated diene-based monomer. When the polymerization initiator is used less than this, polymerization initiation may not be performed smoothly, and when more than this is used, the physical properties of the finally prepared conjugated diene-based polymer may be adversely affected.
- the remaining conjugated diene-based monomer and an emulsifier are dividedly added to perform a polymerization reaction.
- the standard of the divided input time may be a polymerization conversion rate.
- the amount of the conjugated diene-based monomer dividedly introduced in this step may be less than or equal to the amount of the conjugated diene-based monomer added immediately before.
- the amount of the conjugated diene-based monomer first dividedly added in the course of the polymerization reaction may be less than or equal to 30 parts by weight, and specifically 25 It may be parts by weight, and the amount of the conjugated diene-based monomer dividedly added to the second part may be less than or equal to 25 parts by weight, and may be, for example, 15 parts by weight.
- the reaction time can be made equal to that of the existing one, and through this, the impact strength of the finally prepared polymer is excellent, Polymers can be made with excellent productivity.
- the step S2 is specifically a step of introducing a conjugated diene-based monomer and an emulsifier at a time point of 20 to 35% polymerization conversion rate (S2-1), a step of introducing a conjugated diene-based monomer and an emulsifier at a time point of 45 to 60% polymerization conversion rate. (S2-2) and the step of introducing a conjugated diene-based monomer and an emulsifier at a time point of 70 to 80% of the polymerization conversion rate (S2-3).
- the S2-1 step 20 to 30 parts by weight of the conjugated diene-based monomer is added
- the S2-2 step is 15 to 25 parts by weight of the conjugated diene-based monomer
- the S2-3 step is 10 to 30 parts by weight of the conjugated diene-based monomer. 20 parts by weight is added, and the total amount of the conjugated diene-based monomer added in the steps S2-1 to S2-3 may be 70 parts by weight or less, and the amount of the conjugated diene-based monomer added in the S2-1 to S2-3 steps May be one that satisfies Equation 1 below:
- M1, M2, and M3 are the amounts of conjugated diene-based monomers added in steps S2-1, S2-2, and S2-3, respectively.
- step S2-1 25 parts by weight of a conjugated diene-based monomer is added at a time point of 20 to 35% polymerization conversion rate
- step S2-2 20 parts by weight of a conjugated diene-based monomer is added at a time point of 45 to 60% polymerization conversion rate
- the step S2-3 may be to add 15 parts by weight of a conjugated diene-based monomer at a time point of 70 to 80% polymerization conversion rate, and more specifically, in step S2-1, 25 parts by weight of a conjugated diene-based monomer at a time point of 30% polymerization conversion rate, and in the step S2-2, 20 parts by weight of the conjugated diene-based monomer may be added at the time point of the polymerization conversion rate of 50%, and the step S2-3 may include 15 parts by weight of the conjugated diene-based monomer at the time point at the polymerization conversion rate of 70%.
- the polymerization reaction may be smooth and the impact strength of the prepared conjugated diene-based polymer may be more excellent.
- the polymerization conversion rate can be calculated by measuring the weight after drying 1.5 g of the prepared conjugated diene-based polymer for 15 minutes in a hot air dryer at 150° C. to obtain the total solid content (TSC), and using Equation 1 below. have.
- Polymerization conversion rate (%) total solids content (TSC) X (weight of monomer and subsidiary material added) / 100-(weight of subsidiary material added outside the monomer)
- the sub-material includes all of the remaining components except for the monomer among the substances introduced into the polymerization reaction, and for example, an initiator or an emulsifier may correspond to the sub-material.
- the emulsifier introduced in step S2 may be one or more selected from the group consisting of saponified rosin acid, saponified fatty acid, saponified dimer, and saponified oleic acid, and the emulsifier is divided and introduced like the conjugated diene monomer. I can.
- a molecular weight modifier may be further added, and the total amount of the molecular weight modifier added in the S1 and S2 steps may be less than 1 part by weight based on 100 parts by weight of the conjugated diene-based monomer.
- the total amount of the added molecular weight modifier is larger than this, the balance of physical properties of the prepared conjugated diene-based polymer may be deteriorated.
- the molecular weight modifier is ⁇ -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram It may be one or more selected from the group consisting of disulfide and diisopropylxanthogen disulfide.
- the method for preparing a conjugated diene-based polymer of the present invention includes a step (S3) of terminating the polymerization reaction at a time point of 90 to 99% of the polymerization conversion rate.
- the final conjugated diene-based polymer is prepared through this step, and the average particle diameter of the conjugated diene-based polymer prepared through the production method of the present invention may be 1000 to 2000 ⁇ , preferably 1000 to 1500 ⁇ .
- the conjugated diene-based polymer obtained in this step can be enlarged through the step (S4) of adding a coagulant or a coagulant and an auxiliary coagulant after completion of the polymerization reaction to make the conjugated diene-based polymer enlarge, , Preferably it may be 2500 to 3500 ⁇ .
- the average particle diameter of the conjugated diene-based polymer and the enlarged conjugated diene-based polymer is within the above-described range, physical properties including the impact strength of the polymer may be excellent.
- An acidic flocculant may be used as the flocculant that can be used in this step, specifically sulfuric acid, acetic acid, MgSO 4 , CaCl 2 or Al 2 (SO 4 ) 3 , and sodium alginate or sodium silicate as the auxiliary flocculant
- a sodium auxiliary coagulant such as, or a polymer-based polymer coagulant may be used.
- the present invention provides a method for preparing a graft copolymer by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to a conjugated diene-based polymer prepared by the above production method.
- the graft copolymer may include 40 to 70% by weight of a conjugated diene-based polymer, 15 to 35% by weight of an aromatic vinyl-based monomer, and 5 to 25% by weight of a vinyl cyano-based monomer.
- the component of the graft copolymer is within the above-described range, the chemical resistance and processability of the graft copolymer may be excellent.
- the graft copolymer may be prepared by mixing an aromatic vinyl-based monomer and a vinyl cyan-based monomer with a conjugated diene-based polymer, adding an emulsifier and an initiator, and graft polymerization.
- the emulsifier and initiator may be the same as those described in the method for preparing a conjugated diene polymer.
- the present invention provides a thermoplastic resin composition
- a thermoplastic resin composition comprising a graft copolymer prepared by the method for producing a graft copolymer described above, and a copolymer including a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer.
- the copolymer including the unit derived from the aromatic vinyl-based monomer and the unit derived from the vinyl cyan-based monomer may be a styrene-acrylonitrile copolymer.
- the content of the graft copolymer in the thermoplastic resin composition may be 10 to 50% by weight.
- thermoplastic resin composition may be extruded and injected to be manufactured into a molded article, and the molded article may be used for various purposes such as electric parts, electronic parts, and automobile parts.
- the average particle diameter of the prepared polybutadiene was 1280 ⁇ , and the standard deviation of the particle diameter was 350 ⁇ .
- Example 2 To the polybutadiene prepared in Example 1, 0.3 parts by weight of sodium alginate and 0.6 parts by weight of acetic acid were added to obtain an enlarged polybutadiene.
- the average particle diameter of the enlarged polybutadiene was 3230 ⁇ , and the standard deviation of the particle diameter was 992 ⁇ .
- the average particle diameter of the prepared polybutadiene was 1260 ⁇ , and the standard deviation of the particle diameter was 282 ⁇ .
- a nitrogen-substituted polymerization reactor 75 parts by weight of ion-exchanged water, 90 parts by weight of 1,3-butadiene as a monomer, 3 parts by weight of a dimer acid saponified product as an emulsifier, 0.1 parts by weight of potassium carbonate as an electrolyte, and t as a molecular weight modifier.
- the prepared polybutadiene had an average particle diameter of 1220 ⁇ and a particle diameter standard deviation of 210 ⁇ .
- 1.5 parts by weight of acetic acid was added to the prepared polybutadiene to be enlarged, and the average particle diameter of the enlarged polybutadiene was 3290 ⁇ , and the standard deviation of the particle diameter was 690 ⁇ .
- the average particle diameter of the enlarged polybutadiene was 3230 ⁇ , and the standard deviation of the particle diameter was 823 ⁇ .
- the prepared polybutadiene had an average particle diameter of 1235 ⁇ and a particle diameter standard deviation of 242 ⁇ .
- To the prepared polybutadiene 0.3 parts by weight of sodium alginate and 1.1 parts by weight of acetic acid were added to obtain an enlarged polybutadiene, and the average particle diameter of the enlarged polybutadiene was 3225 ⁇ , and the standard deviation of the particle diameter was 835 ⁇ .
- ABS acrylonitrile-butadiene-styrene
- the obtained thermoplastic resin composition was extruded and injected to obtain an injection specimen.
- Example 1 In the process of manufacturing the injection specimen of Example 1, instead of 60 parts by weight of a single polybutadiene, the polybutadiene and the enlarged polybutadiene of Example 1 were mixed at 1:2, and a graft copolymer and injection were used using 1.2 parts by weight of MgSO 4. A specimen was prepared, and this was taken as Example 4.
- Example 1 Polybutadiene 1280 350 95.0 95.3 0.7 Non-conversational polybutadiene 3270 920 95.7 One Example 2 Non-conversational polybutadiene 3230 992 95 0.8 Example 3 Polybutadiene 1260 282 95.1 95.8 0.7 Non-conversational polybutadiene 3290 870 95.5 0.8 Comparative Example 1 Polybutadiene 1220 210 95.2 96.1 2 Non-conversational polybutadiene 3290 690 95.7 2 Comparative Example 2 Non-conversational polybutadiene 3230 823 94.9 1.7 Comparative Example 3 Polybutadiene 1235 242 95.3 95.2 1.45 Non-conversational polybutadiene 3225 835 95.0 1.45
- Izod impact strength (IMP, kgfcm/cm): According to ASTM D256, a notch was made in a pellet specimen having a thickness of 1/8 inch and 1/4 inch.
- Sharpness (reflection haze) The sharpness was measured by adding gloss values between 17 to 19° and 21 to 23° according to ASTM E430, standard measurement using a glossy specimen. The lower the sharpness value measured by this method, the better the sharpness of the injection specimen.
- Coagulation content weight of coagulation produced inside the reactor (g) / weight of total polymer and weight of monomer (100g)
- VOC volatile organic compounds
- Example 1 Polybutadiene 1170 Non-conversational polybutadiene 1590
- Example 2 Non-conversational polybutadiene 1260
- Example 3 Polybutadiene 1210 Non-conversational polybutadiene 1520
- Example 4 Polybutadiene/non-conversed polybutadiene 1620 Comparative Example 1 Polybutadiene 1930 Non-conversational polybutadiene 2580 Comparative Example 2 Non-conversational polybutadiene 2310 Comparative Example 3 Polybutadiene 1727 Non-conversational polybutadiene 1840 Comparative Example 4 Polybutadiene/non-conversed polybutadiene 2490
- the injection specimen can have a uniform surface because the amount of gas generated during injection is small compared to the case of using the conventional method or the method of the comparative example when using the manufacturing method according to the embodiment of the present invention.
- Example 1 Polybutadiene 550 Non-conversational polybutadiene 690
- Example 2 Non-conversational polybutadiene 632
- Example 3 Polybutadiene 572 Non-conversational polybutadiene 659
- Example 4 Polybutadiene/non-conversed polybutadiene 780 Comparative Example 1 Polybutadiene 1320 Non-conversational polybutadiene 1370 Comparative Example 2 Non-conversational polybutadiene 1150 Comparative Example 3 Polybutadiene 843 Non-conversational polybutadiene 865 Comparative Example 4 Polybutadiene/non-conversed polybutadiene 1220
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Abstract
Description
평균 입경(Å) | 입경 표준 편차(Å) | PBL 전환율 | ABS 전환율 | MgSO4 투입 중량부 | ||
실시예 1 | 폴리부타디엔 | 1280 | 350 | 95.0 | 95.3 | 0.7 |
비대화 폴리부타디엔 | 3270 | 920 | 95.7 | 1 | ||
실시예 2 | 비대화 폴리부타디엔 | 3230 | 992 | 95 | 0.8 | |
실시예 3 | 폴리부타디엔 | 1260 | 282 | 95.1 | 95.8 | 0.7 |
비대화 폴리부타디엔 | 3290 | 870 | 95.5 | 0.8 | ||
비교예 1 | 폴리부타디엔 | 1220 | 210 | 95.2 | 96.1 | 2 |
비대화 폴리부타디엔 | 3290 | 690 | 95.7 | 2 | ||
비교예 2 | 비대화 폴리부타디엔 | 3230 | 823 | 94.9 | 1.7 | |
비교예 3 | 폴리부타디엔 | 1235 | 242 | 95.3 | 95.2 | 1.45 |
비대화 폴리부타디엔 | 3225 | 835 | 95.0 | 1.45 |
폴리부타디엔 종류 | 1/4인치 IMP | 1/8인치 IMP | 선명도 | |
실시예 1 | 폴리부타디엔 | 5.2 | 6.7 | 0.8 |
비대화 폴리부타디엔 | 23.1 | 23.4 | 1.8 | |
실시예 2 | 비대화 폴리부타디엔 | 23.5 | 24.3 | 1.4 |
실시예 3 | 폴리부타디엔 | 3.8 | 5.7 | 1.0 |
비대화 폴리부타디엔 | 22.7 | 23.3 | 1.4 | |
실시예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 18.2 | 18.3 | 0.9 |
비교예 1 | 폴리부타디엔 | 3.2 | 5.0 | 1.7 |
비대화 폴리부타디엔 | 21.8 | 22.7 | 2.7 | |
비교예 2 | 비대화 폴리부타디엔 | 22.3 | 23.0 | 2.3 |
비교예 3 | 폴리부타디엔 | 3.6 | 5.2 | 1.4 |
비대화 폴리부타디엔 | 22.2 | 22.9 | 2.2 | |
비교예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 16.1 | 15.0 | 1.6 |
폴리부타디엔 종류 | 소구경 제조 응고물 발생량 | 대구경화 응고물 발생량 | |
실시예 1 | 폴리부타디엔 | 0.02 | - |
비대화 폴리부타디엔 | - | 0.043 | |
실시예 2 | 비대화 폴리부타디엔 | - | 0.045 |
실시예 3 | 폴리부타디엔 | 0.0175 | - |
비대화 폴리부타디엔 | - | 0.04 | |
실시예 4 | 폴리부타디엔/비대화 폴리부타디엔 | - | 0.023 |
비교예 1 | 폴리부타디엔 | 0.018 | - |
비대화 폴리부타디엔 | - | 0.041 | |
비교예 2 | 비대화 폴리부타디엔 | - | 0.045 |
비교예 3 | 폴리부타디엔 | 0.021 | - |
비대화 폴리부타디엔 | - | 0.037 | |
비교예 4 | 폴리부타디엔/비대화 폴리부타디엔 | - | 0.021 |
폴리부타디엔 종류 | 가스 발생량(ppm) | |
실시예 1 | 폴리부타디엔 | 1170 |
비대화 폴리부타디엔 | 1590 | |
실시예 2 | 비대화 폴리부타디엔 | 1260 |
실시예 3 | 폴리부타디엔 | 1210 |
비대화 폴리부타디엔 | 1520 | |
실시예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 1620 |
비교예 1 | 폴리부타디엔 | 1930 |
비대화 폴리부타디엔 | 2580 | |
비교예 2 | 비대화 폴리부타디엔 | 2310 |
비교예 3 | 폴리부타디엔 | 1727 |
비대화 폴리부타디엔 | 1840 | |
비교예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 2490 |
폴리부타디엔 종류 | 잔류 Mg 함량(ppm) | |
실시예 1 | 폴리부타디엔 | 550 |
비대화 폴리부타디엔 | 690 | |
실시예 2 | 비대화 폴리부타디엔 | 632 |
실시예 3 | 폴리부타디엔 | 572 |
비대화 폴리부타디엔 | 659 | |
실시예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 780 |
비교예 1 | 폴리부타디엔 | 1320 |
비대화 폴리부타디엔 | 1370 | |
비교예 2 | 비대화 폴리부타디엔 | 1150 |
비교예 3 | 폴리부타디엔 | 843 |
비대화 폴리부타디엔 | 865 | |
비교예 4 | 폴리부타디엔/비대화 폴리부타디엔 | 1220 |
Claims (16)
- 공액 디엔계 단량체 100 중량부 중 30 내지 50 중량부, 다이머산 비누화물 0.1 내지 5 중량부 및 중합 개시제를 반응기에 일괄 투입하여 중합 반응을 개시하는 단계(S1);중합 반응 개시 이후 중합 전환율에 따라 나머지 공액 디엔계 단량체와 유화제를 3회 이상에 걸쳐 분할 투입하는 단계(S2); 및중합 전환율 90 내지 99% 시점에서 중합 반응을 종결하는 단계(S3);를 포함하는 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 S2 단계는 나머지 공액 디엔계 단량체와 유화제를 3회 또는 4회에 걸쳐 분할 투입하는 것인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 S2 단계에서 분할 투입되는 공액 디엔계 단량체의 양은 직전에 투입된 공액 디엔계 단량체의 양보다 작거나 같은 것인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 S2 단계는중합 전환율 20 내지 35% 시점에서 공액 디엔계 단량체 및 유화제를 투입하는 단계(S2-1);중합 전환율 45 내지 60% 시점에서 공액 디엔계 단량체 및 유화제를 투입하는 단계(S2-2); 및중합 전환율 70 내지 80% 시점에서 공액 디엔계 단량체 및 유화제를 투입하는 단계(S2-3);를 포함하는 것인 공액 디엔계 중합체의 제조방법.
- 제4항에 있어서,상기 S2-1 단계는 공액 디엔계 단량체 20 내지 30 중량부를 투입하고,상기 S2-2 단계는 공액 디엔계 단량체 15 내지 25 중량부를 투입하고,상기 S2-3 단계는 공액 디엔계 단량체 10 내지 20 중량부를 투입하고,상기 S2-1 내지 S2-3 단계에서 투입되는 공액 디엔계 단량체의 총량은 70 중량부 이하인 것인 공액 디엔계 중합체의 제조방법.
- 제4항에 있어서,상기 S2-1 내지 S2-3 단계에서 투입되는 공액 디엔계 단량체의 투입량은 하기 식 1을 만족하는 것인 공액 디엔계 중합체의 제조방법:[식 1]M1≥M2≥M3식 중에서, M1, M2 및 M3은 각각 S2-1, S2-2 및 S2-3 단계에서의 공액 디엔계 단량체 투입량이다.
- 제1항에 있어서,상기 중합 개시제는 수용성 중합 개시제, 및 지용성 중합 개시제와 산화-환원계 촉매의 혼합물 중 하나 이상인 공액 디엔계 중합체의 제조방법.
- 제8항에 있어서,상기 수용성 중합 개시제는 과황산 칼륨, 과황산 나트륨 및 과황산 암모늄으로 이루어지 군에서 선택되는 1종 이상이고,상기 지용성 중합 개시제는 큐멘하이드로 퍼옥사이드, 디이소프로필 벤젠 하이드로퍼옥사이드, 아조비스 이소부틸로니트릴, 3급 부틸 하이드로퍼옥사이드, 파라메탄 하이드로퍼옥사이드, 및 벤조일퍼옥사이드로 이루어진 군에서 선택되는 1종 이상이고,상기 산화-환원계 촉매는 소듐포름알데히드 술폭실레이트, 소듐에틸렌디아민 테트라아세테이드, 황산 제1철, 덱스트로즈, 피롤인산나트륨, 아황산나트륨으로 이루어진 군으로부터 선택되는 1종 이상인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 중합 개시제는 공액 디엔계 단량체 100 중량부에 대하여 0.01 내지 1 중량부로 투입되는 것인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 S1 단계 및 S2 단계에서 분자량 조절제가 더 투입되며,S1 단계 및 S2 단계에서 투입되는 분자량 조절제의 총량은 공액 디엔계 단량체 100 중량부에 대해 1 중량부 미만인 것인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 유화제는 로진산 비누화물, 지방산 비누화물, 다이머산 비누화물 및 올레산 비누화물로 이루어진 군에서 선택되는 1종 이상인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,상기 공액 디엔계 중합체의 평균 입경은 1000 내지 2000Å인 공액 디엔계 중합체의 제조방법.
- 제1항에 있어서,중합 반응 종결 후 응집제, 또는 응집제 및 보조응집제를 투입하여 비대화하는 단계(S4);를 더 포함하며,상기 공액 디엔계 중합체의 평균 입경은 2500 내지 4000Å인 공액 디엔계 중합체의 제조방법.
- 제1항 내지 제14항 중 어느 한 항의 제조방법으로 제조된 공액 디엔계 중합체에 방향족 비닐계 단량체 및 비닐 시안계 단량체를 그라프트 중합시키는 것인 그라프트 공중합체의 제조방법.
- 제15항의 제조방법으로 제조된 그라프트 공중합체; 및방향족 비닐계 단량체 유래 단위 및 비닐 시안계 단량체 유래 단위를 포함하는 공중합체;를 포함하는 열가소성 수지 조성물.
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- 2020-09-23 WO PCT/KR2020/012872 patent/WO2021060833A1/ko active Application Filing
- 2020-09-23 CN CN202080039052.3A patent/CN113874405B/zh active Active
- 2020-09-23 US US17/615,386 patent/US20220227987A1/en active Pending
- 2020-09-23 KR KR1020200123063A patent/KR102558312B1/ko active IP Right Grant
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CN113874405B (zh) | 2024-05-07 |
EP4036128A1 (en) | 2022-08-03 |
JP7317431B2 (ja) | 2023-07-31 |
KR102558312B1 (ko) | 2023-07-24 |
KR20210037565A (ko) | 2021-04-06 |
JP2022531966A (ja) | 2022-07-12 |
CN113874405A (zh) | 2021-12-31 |
US20220227987A1 (en) | 2022-07-21 |
EP4036128A4 (en) | 2022-11-30 |
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