KR20120030950A - Method for preparing segmented ethylene-propylene-diene copolymers - Google Patents

Abstract

PURPOSE: A manufacturing method of segmented ethylene-propylene-diene copolymer is provided to control grafting efficiency of a segmented ethylene-propylene-diene copolymer not only the length or quantity of graft chain. CONSTITUTION: A manufacturing method of segmented ethylene-propylene-diene copolymer comprises: a step of preparing an trithiocarbonate-based chain transfer agent; a step of synthesizing a vinyl monomers by polymerizing vinyl monomers by reversible addition-fragmentation chain transfer by using a chain transfer agent and a radical initiator under the atmosphere of nitrogen or family 18 elements; and a step of grafting the synthesized vinyl polymer to an ethylene-propylene-diene copolymer.

Description

Process for producing ethylene-propylene-diene-based segment copolymer {METHOD FOR PREPARING SEGMENTED ETHYLENE-PROPYLENE-DIENE COPOLYMERS}

The present invention relates to a method for preparing an ethylene-propylene-diene-based segment copolymer through a reversible addition-fragmentation chain transfer (RAFT) method, and more particularly, to the reversible addition-fragmentation chain transfer method. The present invention relates to a method for producing an ethylene-propylene-diene segmented copolymer which can be easily grafted to an ethylene-propylene-diene-based copolymer by synthesizing a vinyl polymer using a trithiocarbonate-based chain transfer agent.

Controlling the molecular structure of polymers to control their chemical and physical properties is one of the most important challenges in polymer chemistry. Polymer chains are classified into homopolymers and copolymers by their constituents, and variously classified according to the form of linkage between the chains. Since the conversion of these components and the molecular structure is accompanied by a change in the chemical and physical properties of the polymer, it is possible to obtain a polymer having a variety of properties through the synthesis of the appropriate polymer. The study of modifying the existing polymer structure is meaningful because it expresses unique properties different from those of the existing polymer by modifying the existing polymer structure, and these properties can be usefully used. For example, the hydroxy polymer or the carbonyl group is substituted in the olefin polymer chain, which is used most industrially, so that it is hydrophilic or polar. The rate or amount of modification in the chain is then an important measure for achieving the original modification goals. If the degree of modification is not high, the physical properties of the original polymer do not change significantly. However, in addition to physical properties, it is possible to see the effect of improving compatibility or adhesion with insoluble materials. In addition, the crosslinking of the linear polymer material changes the viscosity, glass transition temperature and the like of the polymer.

Bonding of heterogeneous polymer components is mainly focused on bonding components having complementary properties to each other. Existing types of chemically bonding polymer chains and heteropolymers include block copolymers and graft copolymers. Block copolymers use a method of polymerizing heteromonomers at the chain ends, and living polymerization is widely used. The graft copolymers are two kinds of polymerization of the polymer or by using the start point to the repeating unit of the chain uses a - - (onto grafting) etc., using the (grafting from), two kinds of polymer and the main chain of the functional group to create a heterogeneous polymer chain in the main chain .

In the case of olefin polymers, research on reforming has been made for a long time. As a study on the graft copolymer, studies have been carried out to graf the polar polymer to polyethylene (PE), polypropylene (PP), and ethylene-propylene-diene terpolymer (EPDM). A method of preparing a graft copolymer by modifying an olefin polymer is mainly performed by removing hydrogen in a chain of an olefin polymer with a peroxide and then polymerizing a heterogeneous polymer. However, the initiation efficiency of the olefin polymer chain is low and it is difficult to obtain a graft copolymer having a desired structure by bonding the disclosed chains. To this end, research on grafting heterogeneous polymers is needed.

Recently, reforming of olefin polymers, diene polymers, and the like using controlled "iving" radical polymerization (CRP), which has the advantage of synthesizing polymers having a well-designed polymerization reaction, has been studied. . Typical radical polymerizations have a constant molecular weight and a wide distribution of molecules. Living radical polymerization method, which has been studied a lot recently, controls the chain transfer or the stop reaction during the polymerization reaction to easily control the molecular weight and molecular weight distribution, design the structure of the polymer chain and introduce functional groups, and control the copolymer composition, thereby improving the material's high performance and performance. And it is applied to a lot of new polymer material creation.

However, a specific method for preparing an ethylene-propylene-diene-based fragment copolymer efficiently and simply by applying a reversible addition-fragmentation chain transfer (RAFT) method has not yet been proposed.

Accordingly, the present invention has been made to solve the problems of the prior art and the technical problem that has been requested from the past, the graft efficiency as well as the length and number of the graft chain in the ethylene-propylene-diene-based segment copolymer produced It is an object of the present invention to develop a new process for preparing ethylene-propylene-diene-based segment copolymers capable of controlling of the present invention, to provide a new technical platform for living radical polymerization for polymer modification.

As a technical means for achieving the above-described technical problem, a first aspect of the present invention, preparing a trithiocarbonate-based chain transfer agent (chain transfer agent); By using the trithiocarbonate chain transfer agent and a radical initiator, a vinyl monomer is polymerized by stirring under a nitrogen or group 18 element atmosphere by reversible addition-fragmentation chain transfer (RAFT). Synthesizing; And grafting the synthesized vinyl polymer to an ethylene-propylene-diene-based copolymer.

In addition, a second aspect of the present invention provides an ethylene-propylene-diene-based segmented copolymer prepared by the above-mentioned production method.

According to the production method according to the present invention, it is possible to easily synthesize ethylene-propylene-diene-based segmented copolymer successfully by a simple two-step reaction.

Further, according to the production method according to the present invention, by controlling the amount of the radical generator and the vinyl polymer to be grafted, the grafting efficiency as well as the length and number of graft chains in the obtained ethylene-propylene-diene-based segment copolymer This is possible.

Thus, using the preparation method according to the present application, it is possible to synthesize ethylene-propylene-diene-based segmented copolymers having various molecular structures and thus improved physical properties and broad applicability.

1 is a view showing the results of GPC analysis of PEA prepared in the present invention,
2 is a spectrum showing the results of FT-IR analysis of EPAN synthesized according to an embodiment of the present invention.
Figure 3 is a graph showing a correction curve expressed by calculating the ratio of the peak height according to the content of PAN after physically mixing the EPDM and PAN used in the present invention.

Hereinafter, embodiments and embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and it should be understood that the present invention covers all the transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

As used herein, the expression "segmented copolymer" refers to a copolymer containing different polymer segments, and should be interpreted to include graft copolymers and block copolymers. . However, more preferably, it may be interpreted to mean a graft copolymer.

A first aspect of the present invention is to prepare a trithiocarbonate-based chain transfer agent (chain transfer agent) (first step); By using the trithiocarbonate chain transfer agent and a radical initiator, a vinyl monomer is polymerized by stirring under a nitrogen or group 18 element atmosphere by reversible addition-fragmentation chain transfer (RAFT). Synthesizing (second step); And grafting the synthesized vinyl polymer onto an ethylene-propylene-diene-based polymer (third step). It provides a method for producing an ethylene-propylene-diene-based copolymer.

The first step is to prepare a trithiocarbonate-based chain transfer agent. Preparing the trithiocarbonate-based chain transfer agent as the first step includes purchasing a commercialized tricarbonate-based chain transfer agent and / or synthesizing a tricarbonate-based chain transfer agent. The trithiocarbonate-based chain transfer agent may be prepared by purchasing a commodity for sale, and may be prepared by synthesis if necessary.

The second step is to prepare a grafted polymer to introduce desired properties into the ethylene-propylene-diene-based polymer, trithiocarbonate-based having a trithiocarbonate structure in place of a conventional dithioester chain transfer agent It is characterized by synthesizing the grafted polymer using a chain transfer agent, the trithiocarbonate structure (unit) is included in the polymer produced by carrying out the polymerization using such a trithiocarbonate-based chain transfer agent, The third step of grafting can be performed using the grafting.

As described above, the second step is a step of synthesizing the vinyl polymer by polymerizing the vinyl monomer by a reversible addition-fragmentation chain transfer (RAFT) using a trithiocarbonate-based chain transfer agent. Same as 1.

Scheme 1

The trithiocarbonate-based chain transfer agent refers to a compound which has a trithiocarbonate structure in a molecule and may be used as a chain transfer agent in a RAFT polymerization reaction, and preferably may be a compound represented by the following Chemical Formula 1, but is not limited thereto. .

[Formula 1]

In Formula 1, R ¹ and R ² are each independently C ₁ ~ C ₁₈ alkyl group, C ₂ ~ C ₁₈ alkenyl group, C ₆ ~ C ₅₀ aryl group, C ₆ ~ C ₅₀ hetero aryl group, C ₅ ~ C ₃₄ Alkylcyclic group, C ₅ ~ C ₃₄ Saturated or unsaturated carbocyclic groups, C ₅ to C ₃₄ Aromatic carbocyclic groups, C ₅ to C ₃₄ Heterocyclic group, C ₁ to C ₁₈ Alkylthio group, C ₁ to C ₁₈ alkoxy group, or C ₂ to C ₃₆ May be a dialkylamino group,

The C ₁ ~ C ₁₈ alkyl group, C ₂ ~ C ₁₈ alkenyl group, C ₆ ~ C ₅₀ aryl group, C ₆ ~ C ₅₀ heteroaryl group, C ₅ ~ C ₃₄ alkyl ring group, C ₅ ~ C ₃₄ Saturated or unsaturated carbocyclic ring groups, C ₅ to C ₃₄ Aromatic carbocyclic groups, C ₅ to C ₃₄ Heterocyclic ring groups, C ₁ to C ₁₈ Alkylthio group, C ₁ to C ₁₈ alkoxy group, or C ₂ to C ₃₆ The dialkylamino groups are each independently hydrogen, epoxy group, hydroxy group, C ₁ to C ₁₈ alkoxy group, C ₆ to C ₅₀ aryl group, acyl group, acyloxy group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, C ₁ to It may be substituted with one or more selected from C ₁₈ alkylcarbonyloxy group, isocyanato group, cyano group, silyl group, halo group and C ₂ ~ C ₃₆ dialkylamino group.

In addition, the C ₁ ~ C ₁₈ alkyl may be more preferably C ₁ ~ C ₆ alkyl, the C ₅ ~ C ₃₄ carbocyclic ring or C ₅ ~ C ₃₄ Heterocyclic ring is more preferably C ₅ ~ C ₁₄ It may be a heterocyclic ring, but is not limited thereto.

In the method for preparing the ethylene-propylene-diene-based copolymer of the present invention, the trithiocarbonate-based chain transfer agent may be more preferably dibenzyl trithiocarbonate (DBTTC).

The vinyl monomer is a vinyl monomer capable of free radical polymerization, and preferably, a compound represented by the following Formula 2 and a combination thereof, but is not limited thereto.

[Formula 2]

In Formula 2, U is hydrogen, halogen, hydroxy, C ₁ ~ C ₁₈ alkoxy, aryloxy (OR '), carboxy, acyloxy, aroyloxy (O ₂ CR'), alkoxy-carbonyl and aryloxy -C ₁ ~ C ₄ alkyl which may be substituted with one or more selected from carbonyl (CO ₂ R '),

V is selected from hydrogen, R ', CO ₂ H, CO ₂ R', COR ', CN, CONH ₂ , CONHR', CONR ' ₂ , O ₂ CR', OR 'and halogen,

Wherein each R ′ is independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₅₀ aryl, C ₄ -C ₃₂ Heterocyclyl, C ₆ -C ₅₀ Arylalkyl, and C ₆ -C ₅₀ It is selected from alkylaryl, the C ₁ ~ C ₁₈ alkyl, C ₂ ~ C ₁₈ alkenyl, C ₆ ~ C ₅₀ Aryl, C ₄ -C ₃₂ Heterocyclyl, C ₆ -C ₅₀ arylalkyl and C ₆ -C ₅₀ Alkylaryl is each independently an epoxy group, a hydroxy group, a C ₁ to C ₁₈ alkoxy group, a C ₆ to C ₅₀ aryl group, an acyl group, acyloxy group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, C ₁ ~ It may be substituted with one or more selected from C ₁₈ alkylcarbonyloxy group, isocyanato group, cyano group, silyl group, halo group and C ₂ ~ C ₃₆ dialkylamino group.

According to one embodiment of the invention, the vinyl monomer is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, meta Krylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acryl Acrylates, acrylic acid and salts thereof, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene; Glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl meta Acrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, N, N-dimethylaminoethyl Acrylate, N, N-diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butyl methacrylamide, Nn-butyl Methacrylamide, N-methylol methacrylamide, N-ethylol methacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylol acrylamide, N-ethylol acrylamide, Vinyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, p-vinylbenzenesulfonic acid sodium salt, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl Methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate , Dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate , Tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate , Diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, di Isopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, scale fluoride, scale bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone Functionalized methacrylates, acrylates and styrenes selected from the group consisting of N-vinylcarbazole, butadiene, isoprene, chloroprene and propylene; And combinations thereof may be selected from the group, but is not limited thereto.

According to one embodiment of the invention, the vinyl polymer synthesized by the polymerization of the vinyl monomer is a functionalized polystyrene, polystyrene, polyacrylate, polymethacrylate, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, At least one selected from the group consisting of polyacrylonitrile, and combinations thereof, but is not limited thereto.

Wherein the functionalized polystyrene has a molecular structure such that it has a vibration damping, abrasion, paintability, impact resistance, high stiffness, flame retardancy, heat resistance, oil resistance, weather resistance, discoloration resistance, and other functionalities in the main chain of polystyrene or substituted by side chains. It means functionalized polystyrene having the above functionalities.

In addition, a radical initiator may be added in addition to the trithiocarbonate-based chain transfer agent and the vinyl monomer described above in the second step, and the radical initiator may initiate the polymerization of the vinyl monomer and is usually used for RAFT polymerization. If it is a radical initiator used, it will not specifically limit.

2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 1,1-azobiscyclohexanecarbonitrile, di as the radical initiator Cumyl peroxide (DCP), diacyl peroxide, dilauroyl peroxide, ditert-butyl peroxide, peroxydicarbonate, diisopropyl peroxydicarbonate, perester, tert-butyl peroxy- 2-ethylhexanoate, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyliso Butyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis (2-ethyl hexanoyl peroxy)- 2,5-dimethylhexane, tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxy-3,5,5-trimethylhexa 8, 1,1-bis- (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydro Peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 1 , 1-azobiscyclohexanecarbonitrile, diisopropyl peroxydicarbonate, tert-amyl peroxypivalate, di (2,4-dichlorobenzoyl) peroxide, tert-butyl peroxypivalate, 2,2 '-Azobis (2-amidinopropane) dihydrochloride, di (3,5,5-trimethylhexanoyl) peroxide, dioctanoyl peroxide, didecanoyl peroxide, 2,2'-azobis ( N, N'-dimethyleneisobutyramidine) di (2-methylbenzoyl) peroxide, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 2,5-dimethyl-2,5-di (2-ethylhexano Peroxy) hexane, 4,4'-azobis (cyanopentanoic acid) di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxyisobutyrate or mixtures of the above mentioned radical initiators can be used.

In the third step, the vinyl polymer is grafted onto the chain of the ethylene-propylene-diene polymer by reacting the ethylene-propylene-diene polymer and the vinyl polymer synthesized in the second step. Preferably, in the third step, the ethylene-propylene-diene-based polymer may be reacted in the presence of a radical generator to generate a reactive radical site, if necessary.

When the ethylene-propylene-diene-based copolymer (EPDM) and the synthesized vinyl polymer are reacted in the presence of the radical generator, the trithiocarbonate structure is formed due to the radicals generated in the ethylene-propylene-diene-based copolymer. The vinyl polymer contained therein serves as a chain transfer agent and is grafted onto the ethylene-propylene-diene-based copolymer.

Wherein the radical generator is 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 1,1-azobiscyclohexanecarbonitrile , Dicumyl peroxide (DCP), diacyl peroxide, dilauroyl peroxide, ditert-butyl peroxide, peroxydicarbonate, diisopropyl peroxydicarbonate, perester, tert-butyl peroxide Oxy-2-ethylhexanoate, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, Methylisobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis (2-ethyl hexanoyl peroxy ) -2,5-dimethylhexane, tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxy-3,5,5-trimeth Tylhexanoate, 1,1-bis- (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert -Butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile ), 1,1-azobiscyclohexanecarbonitrile, diisopropyl peroxydicarbonate, tert-amyl peroxypivalate, di (2,4-dichlorobenzoyl) peroxide, tert-butyl peroxypivalate, 2,2'-azobis (2-amidinopropane) dihydrochloride, di (3,5,5-trimethylhexanoyl) peroxide, dioctanoyl peroxide, didecanoyl peroxide, 2,2'- Azobis (N, N'-dimethyleneisobutyramidine) di (2-methylbenzoyl) peroxide, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyro Nitrile), 2,5-dimethyl-2,5-di (2-ethyl Hexanoylperoxy) hexane, 4,4'-azobis (cyanopentanoic acid) di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, tert-butyl Peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate or mixtures of the above-mentioned radical generators can be used, and especially if the ethylene-propylene-diene-based polymer can generate reactive radical sites. It is not limited.

According to the present invention, by controlling the amount of the radical generator and the synthesized vinyl polymer, the number and grafting efficiency of the vinyl polymer chain grafted in the obtained ethylene-propylene-diene segment copolymer can be controlled. .

The third step may be performed in a solution phase in a solvent. According to an embodiment of the present invention, the solvent may be, for example, xylene or the like, but is not limited thereto. Various organic solvents may be used as the solvent. In addition, the third step may be performed in a molten phase without using a solvent, and is more economical and environmentally friendly than a method using a solvent.

The second aspect of the present invention provides an ethylene-propylene-diene-based segmented copolymer prepared by the above-mentioned production method. According to the above-described manufacturing method, it is possible to provide a copolymer in which a vinyl polymer is grafted to ethylene-propylene-diene terpolymer, which is widely used industrially, and to be modified into a polymer having desired improved physical properties. It can be applied to various fields.

The production method of the present invention can control the number and grafting efficiency of the vinyl polymer chain grafted in the obtained ethylene-propylene-diene segment copolymer by controlling the amount of the radical generator and the synthesized vinyl polymer. have.

Hereinafter, the configuration of the present invention will be described in more detail with reference to the following examples, but is not limited thereto.

[Example]

<Reagent>

As an ethylene-propylene-diene polymer, ethylene-propylene-diene terpolymer (EPDM) is obtained from KEP 650L (Mn = 120,700 g / mol, Mw / Mn = 2.20, ethylidene norbornene content of Kumho Polychem = 8.9 wt%, per EPDM chain). About 90 ethylidene norbornene units) was used. Dibenzyl trithiocarbonate (DBTTC) as chain transfer agent was obtained from Arkema. Acrylonitrile (AN, 99 wt%, Aldrich), ethylacrylate (EA, 99 wt%, Aldrich) were vacuum distilled under CaH ₂ before use. 2,2'-azobisisobutyronitrile (AIBN, 98 wt%, trielectric chemistry), dicumylperoxide (DCP, 99.0 wt%, Aldrich), tetrahydrofuran (THF, 98 wt%, trielectric chemistry), acetone (95 wt%, Samjeon Chem), methanol (99.5 wt%, Samjeon Chem), dimethylsulfoxide (DMSO, 99 wt%, Ducksan) and Anisole (99 wt%, Aldrich) were used without further purification.

<Analysis method>

Gel Permeation Chromatography  ( GPC )analysis

GPC used RI-detector and UV-detector (RID-10A, SPD-20AV, Shimadzu) and three columns (Styragel HR 5, 4, 2). The molecular weight was calibrated with polystyrene standards, and the molecular weight was determined by injecting 40 μl of a sample using HPLC THF as a solvent at an oven temperature of 40 ° C., a pump pressure of 5 MPa, and a flow rate of 1.0 mL / min.

Gas Chromatography ( GC ) analysis

The column of GC (GC-2010, Shimadzu) used VB-WAX (length 30m, inner diameter 0.32mm ID, film thickness 0.25㎛), the measurement conditions of the column was 40 ℃ temperature, 1.5 minutes equilibration time (equilibration time) . The detector is FID1 with temperature 250 ° C, injection mode is split, sampling time is 1 minute, pressure 48.3 kPa, total flow 83.8 mL / min, purge flow 3.0 mL / min, column N ₂ , H ₂ , air with a purity of 99.99% was used at a column flow of 1.58 mL / min. Gas flow conditions were N ₂ = 30 mL / min, H ₂ = 40 mL / min, and air 400 mL / min.

FT - IR  And 1H- NMR  analysis

Fourier transform infrared spectroscopy (FT-IR) was analyzed by Thermo nicolet 380. In the FT-IR specimen preparation, the grafted polymer was removed from the unreacted material and dried in a vacuum oven for at least 10 hours to prepare a film by using a hot press. It was. 1 H-NMR spectroscopy was measured with a 500 MHz Bruker advance spectrometer. The solvent used was CDCl ₃ , and the peak by TMS (tetramethylsilane) was used as the standard peak.

One. DBTTC Using Polyacrylonitrile  ( PAN Polymerization of

The AN can be homopolymerized using DBTTC. The polymerization reaction of PAN used a 250 mL Schlenk flask. The reaction temperature was maintained by using an oil bath (heat bath) on a temperature controllable heater, and the nitrogen atmosphere in the reactor was maintained. The general experimental procedure for polymerizing PAN was as follows.

AN (100 mL, 1.5 mol), AIBN (0.50 g, 0.0030 mol), DBTTC (2.3 mL, 0.0092 mol), DMSO (200% v / v based on AN), Toluene (10 mL) were added to a Schlenk flask with a magnetic stirrer. Put together and kept nitrogen ([AN]: [AIBN]: [DBTTC] = 500: 1: 3). Oxygen was removed through nitrogen bubbling for 60 minutes, and the mixture was stirred at 80 ° C. and 350 rpm. The resultant was diluted in DMSO and then precipitated in methanol to remove monomer and dried in a vacuum oven at 60 ° C. for 24 hours. The process of generating PAN is briefly shown in Scheme 2.

Scheme 2

2. DBTTC Using Polyethyl acrylate  ( PEA Polymerization of

EA can be homopolymerized using DBTTC as an acrylate-based monomer. The polymerization reaction used a 250 mL Schlenk flask. The reaction temperature was maintained by using an oil bath (heat bath) on a temperature controllable heater, maintaining a nitrogen atmosphere in the reactor. The general experimental procedure for polymerizing PEA was as follows.

EA (150 mL, 1.41 mol), AIBN (0.70 g, 0.0043 mol), DBTTC (1.1 mL, 0.0043 mol), toluene (100% v / v based on EA), Anisole (6.6% v / v based on EA, polymerization Added as a standard for GC monitoring of reaction progress) was placed in a Schlenk flask with a magnetic stirrer and kept in nitrogen ([EA]: [AIBN]: [DBTTC] = 334: 1: 1). Oxygen was removed through nitrogen bubbling for 60 minutes and polymerized by stirring at 350 rpm at 70 ° C. The resultant was diluted with toluene and precipitated three times in a 1: 1 volumetric mixture of methanol and water to remove unreacted monomer, and dried in a vacuum oven at 60 ° C. for 24 hours. Samples were taken during the polymerization, and GC and GPC were used to measure the conversion of monomers to polymers, number average molecular weight, theoretical molecular weight, and molecular weight distribution. The process by which PEA is produced is outlined in Scheme 3.

Scheme 3

3. PAN Of “ Grafting On To ( grafting - onto By reaction Graft  Synthesis of Copolymers ( EPDM -g- PAN )

An internal mixer (Brabender Plasticorder) was used to prepare the graft copolymer through the melting reaction. The general experimental procedure was as follows. EPDM (20 g, 1.66x10-4 mol) and prepared PAN (9.6 g, 9.6x10 ^-4 mol) were added to an internal mixer, and the temperature of the rotor was increased to 130 ° C., and the rotor speed was kneaded at 30 rpm. After mixing for 5 minutes, DCP (0.03 g, 1.11 × 10 ⁻⁴ mol) was added thereto and reacted for 180 minutes. The reaction time was selected as a time sufficient to decompose in consideration of the half-life time of the DCP (75 minutes at 135 ℃). General grafting process by reaction is shown in Scheme 4.

Scheme 4

In order to remove unreacted PAN after the reaction, the final reactant was completely dissolved in THF, and then unreacted PAN was completely precipitated for 2 hours, and the supernatant of the solution was precipitated in excess DMSO. The result was dried for 10 hours in a vacuum oven at 80 ℃ and subjected to FT-IR analysis. Each experimental condition is shown in Table 1 below.

EPDM (g) PAN (g) DCP (g) EPAN1 16 1.8 0.03 EPAN2 20 5 0.03 EPAN3 20 9.6 0.03

4. PEA Of “ Grafting On To ( grafting - onto By reaction Graft  Synthesis of Copolymers ( EPDM -g- PEA )

An internal mixer (Brabender Plasticorder) was used to prepare the graft copolymer through the melting reaction. The general experimental procedure was as follows. EPDM (20g, 1.66x10 ^-4 mol) was added to the internal mixer, the temperature was raised to 140 ° C, and the rotor speed was kneaded at 30 rpm. After mixing EPDM for 5 minutes, DCP (0.03g, 1.11x10 ^-4 mol) was added thereto, and the prepared PEA (2.2g, 1.69x10 ^-4 mol) was slowly added dropwise using a pipette and reacted for 90 minutes. The reaction time was selected as a time sufficient to decompose in consideration of the half-life time of the DCP (75 minutes at 135 ℃). In order to remove unreacted PEA after the reaction, the reactant was dissolved in THF and precipitated in excess acetone. The resultant was dried in a vacuum oven at 60 ° C. for 10 hours and subjected to FT-IR analysis for the structure. Each experimental condition is shown in Table 2 below.

EPDM (g) PEA (g) DCP (g) EPEA1 20 2.2 0.02 EPEA2 20 2.2 0.025 EPEA3 20 2.2 0.03

5. Analysis result

DBTTC Using PAN  And PEA Polymerization

As described above, the polymer of the graft chain was polymerized using DBTTC, a RAFT agent, to prepare the graft copolymer through a “grafting-onto” reaction.

It was found that the conversion rate of the monomers increased linearly ([AN]: [AIBN]: [DBTTC] = 500: 1: 3). As a result, the polymerization had the characteristics of living polymerization and was successfully prepared. there was. The final molecular weight of the polymerized PAN is 10,000 g / mol and Mw / Mn is 1.4.

Figure 1 shows the results of GPC analysis of the prepared PEA. It was confirmed that the EA monomer conversion was linearly increased ([EA]: [AIBN]: [DBTTC] = 334: 1: 1), and as a result, the polymerization had the characteristics of living polymerization and was successfully manufactured. there was. The final molecular weight of the polymerized PEA is 13,600 g / mol and Mw / Mn is 1.3.

Manufactured PAN Of “ Grafting On To  ( grafting - onto By reaction EPDM - graft -PAN synthesis (melt reaction)

As described above, the experiment was performed by grafting to EPDM using a trithiocarbonate structure of PAN polymerized using a chain transfer agent (DBTTC). Brabender Plastograph was used as a device for the reaction, and DCP was added with PAN to remove hydrogen from the EPDM and reacted at a constant temperature (130 ° C.). Experimental composition was as shown in Table 1, after the reaction was dissolved in THF to remove the unreacted PAN and then precipitated in DMSO.

When the EPDM reacts with PAN in the presence of peroxide as in Scheme 3, PAN having a trithiocarbonate structure acts as a chain transfer agent and is grafted to EPDM due to the radicals generated in EPDM. Although quantitative analysis is possible by 1H-NMR analysis, when the rubber is partially cured due to peroxide or heat during the reaction, it cannot be analyzed because it is insoluble in solvent. For this reason, the final result was dried and subjected to FT-IR analysis to determine the structure and degree of branching.

2 shows the results of FT-IR analysis of EPDM and EPAN. As a result of each FT-IR analysis, it was found that the characteristic peaks of EPDM (C = C stretches, 1680 cm-1) and PAN (C≡N stretches, 2240 cm ^-1 ) appeared, which led to the branching of PAN. Could.

In FIG. 3, the peak height ratio according to the content of PAN is calculated by physically mixing EPDM and PAN and expressed as a calibration curve. At this time, the ratio of the peak height according to the PAN content showed a tendency, and the degree of branching of the result was estimated through this curve. Table 3 shows the weight and chain number of PAN grafted to EPDM according to the experimental composition.

EPDM (g) PAN
(g) PAN content in the graft copolymer (FT-IR, wt%) Number of PAN Branches per EPDM Chain in Graft Copolymer (FT-IR) Grafting Efficiency (GE) (FT-IR,%) EPAN1 16 1.8 3.1 0.97 30.6 EPAN2 20 5 4.1 1.32 20.5 EPAN3 20 9.6 5.8 1.96 17.8

In addition, the grafting efficiency (GE) was calculated based on the quantitative analysis of PAN grafted to EPDM. The results are shown in Table 3.

The grafting efficiency was calculated using the following equation 1.

[Equation 1]

Grafting efficiency (GE,%) = (weight of grafted PAN / weight of PAN used for reaction) × 100

The weight of PAN used in the reaction in Equation 1 was determined by the experimental composition and the weight of the grafted PAN was determined by the analysis results of the FT-IR.

As shown in Table 3, as a result of the calibration curve, a graft copolymer having about 1 graft branch per EPDM chain was obtained.

Manufactured PEA Of “ Grafting On To  ( grafting - onto By reaction EPDM - graft -PEA synthesis (melting reaction)

As described above, the experiment of grafting to EPDM using a trithiocarbonate structure of PEA polymerized using a chain transfer agent (DBTTC) was performed using a melt reaction method. As in the previous experiments, an internal mixer (Brabender Plastograph) was used and the results were examined while varying the amount of DCP.

Experimental composition was as shown in Table 2, when the reaction of EPDM and PEA in the presence of peroxide, PEA having a trithiocarbonate structure acts as a chain transfer agent grafted to EPDM due to the radicals generated in EPDM. At this time, PEA having a trithiocarbonate structure was controlled in molecular weight and molecular weight distribution, and quantitative analysis was attempted through FT-IR analysis. After the reaction, it was dissolved in THF to remove unreacted PEA and precipitated in acetone. The final result was dried and subjected to FT-IR analysis to determine the structure and degree of branching. As a result of the FT-IR analysis, it was found that the characteristic peaks of EPDM (C = C stretches, 1680 cm ^-1 ) and PEA (C = O stretches, 1730 cm ^-1 ) appeared, resulting in PEA branching. there was.

In order to determine the degree of branching of PEA grafted to EPDM, the ratio of peak height according to the content of PEA was calculated by physically mixing EPDM and PEA and expressed as a calibration curve. At this time, the ratio of the peak height according to the content of PEA showed a tendency, and the degree of branching of the result was estimated through this curve. Table 4 shows the weight and the number of chains of PEA grafted to EPDM according to the experimental composition.

EPDM (g) PEA
(g) DCP
(g) PEA content in graft copolymer
(FT-IR, wt%) Number of PEA Branches per EPDM Chain in Graft Copolymer (FT-IR) Grafting Efficiency (GE) (FT-IR,%) EPEA1 20 2.2 0.02 1.7 0.3 17.15 EPEA2 20 2.2 0.025 2.3 0.4 23.20 EPEA3 20 2.2 0.03 3.4 1.6 34.30

As shown in Table 4, when the peroxide increases, it can be estimated that there are more sites where PEA can be branched in the chain of EPDM, whereby more PEA is branched. Accordingly, it can be estimated that the grafting efficiency GE has increased.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

Claims (11)

Preparing a trithiocarbonate-based chain transfer agent;
By using the trithiocarbonate chain transfer agent and a radical initiator, a vinyl monomer is polymerized by stirring under a nitrogen or group 18 element atmosphere by reversible addition-fragmentation chain transfer (RAFT). Synthesizing; And,
Grafting the synthesized vinyl polymer onto an ethylene-propylene-diene copolymer;
A method for producing an ethylene-propylene-diene-based segment copolymer comprising a. The method of claim 1, wherein the trithiocarbonate-based chain transfer agent is a compound represented by the following formula (1).
[Formula 1]

In Formula 1, R ¹ and R ² are each independently C ₁ ~ C ₁₈ alkyl group, C ₂ ~ C ₁₈ alkenyl group, C ₆ ~ C ₅₀ aryl group, C ₆ ~ C ₅₀ hetero aryl group, C ₅ ~ C ₃₄ Alkylcyclic group, C ₅ ~ C ₃₄ Saturated or unsaturated carbocyclic groups, C ₅ to C ₃₄ Aromatic carbocyclic groups, C ₅ to C ₃₄ Heterocyclic group, C ₁ to C ₁₈ Alkylthio group, C ₁ to C ₁₈ alkoxy group, or C ₂ to C ₃₆ May be a dialkylamino group,
The C ₁ ~ C ₁₈ alkyl group, C ₂ ~ C ₁₈ alkenyl group, C ₆ ~ C ₅₀ aryl group, C ₆ ~ C ₅₀ heteroaryl group, C ₅ ~ C ₃₄ alkyl ring group, C ₅ ~ C ₃₄ Saturated or unsaturated carbocyclic groups, C ₅ to C ₃₄ Aromatic carbocyclic groups, C ₅ to C ₃₄ Heterocyclic group, C ₁ to C ₁₈ Alkylthio group, C ₁ to C ₁₈ alkoxy group, or C ₂ to C ₃₆ The dialkylamino groups are each independently hydrogen, epoxy group, hydroxy group, C ₁ to C ₁₈ alkoxy group, C ₆ to C ₅₀ aryl group, acyl group, acyloxy group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, C ₁ to It may be substituted with one or more selected from C ₁₈ alkylcarbonyloxy group, isocyanato group, cyano group, silyl group, halo group and C ₂ ~ C ₃₆ dialkylamino group. The method of claim 2, wherein the trithiocarbonate-based chain transfer agent is dibenzyl trithiocarbonate (DBTTC). The method of claim 1, wherein the vinyl monomer is selected from the group consisting of a compound represented by the following formula (2) and combinations thereof.
(2)

In Formula 2, U is hydrogen, halogen, hydroxy, C ₁ ~ C ₁₈ alkoxy, aryloxy (OR '), carboxy, acyloxy, aroyloxy (O ₂ CR'), alkoxy-carbonyl and aryloxy -C ₁ ~ C ₄ alkyl which may be substituted with one or more selected from carbonyl (CO ₂ R '),
V is selected from hydrogen, R ', CO ₂ H, CO ₂ R', COR ', CN, CONH ₂ , CONHR', CONR ' ₂ , O ₂ CR', OR 'and halogen,
Wherein each R ′ is independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₅₀ aryl, C ₄ -C ₃₂ Heterocyclyl, C ₆ -C ₅₀ Arylalkyl, and C ₆ -C ₅₀ It is selected from alkylaryl, the C ₁ ~ C ₁₈ alkyl, C ₂ ~ C ₁₈ alkenyl, C ₆ ~ C ₅₀ Aryl, C ₄ -C ₃₂ Heterocyclyl, C ₆ -C ₅₀ arylalkyl and C ₆ -C ₅₀ Alkylaryl is each independently an epoxy group, a hydroxy group, a C ₁ to C ₁₈ alkoxy group, a C ₆ to C ₅₀ aryl group, an acyl group, acyloxy group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, C ₁ ~ It may be substituted with one or more selected from C ₁₈ alkylcarbonyloxy group, isocyanato group, cyano group, silyl group, halo group and C ₂ ~ C ₃₆ dialkylamino group. The method of claim 4, wherein the vinyl monomer is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, Benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid And salts thereof, benzyl acrylate, phenyl acrylate, and acrylonitrile;
Glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl meta Acrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, N, N-dimethylaminoethyl Acrylate, N, N-diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butyl methacrylamide, Nn-butyl Methacrylamide, N-methylol methacrylamide, N-ethylol methacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylol acrylamide, N-ethylol acrylamide, Nyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, sodium p-vinylbenzenesulfonic acid salt, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl Methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate , Dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate , Tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate , Diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diiso Propoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, scale fluoride, scale bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, Functionalized methacrylates, acrylates and styrenes selected from the group consisting of N-vinylcarbazole, butadiene, isoprene, chloroprene and propylene; And
Method for producing an ethylene-propylene-diene-based segment copolymer, characterized in that at least one selected from the group consisting of a combination of these. According to claim 1, The synthetic vinyl polymer is a group consisting of functionalized polystyrene, polyacrylates, polymethacrylates, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, polyacrylonitrile and combinations thereof Method for producing an ethylene-propylene-diene-based segment copolymer, characterized in that at least one selected from. The method of claim 1, wherein the grafting is carried out in the presence of a radical generating agent for generating a reactive radical site in the ethylene-propylene-diene-based polymers Way. 8. The method according to claim 7, wherein the number of grafting efficiency and the number of vinyl-based polymer chains grafted in the obtained ethylene-propylene-diene-based copolymer are controlled by controlling the amount of the radical generator and the synthesized vinyl-based polymer. A process for producing an ethylene-propylene-diene segment copolymer. The method of claim 1, wherein the grafting is carried out in a solution phase in a solvent. The method of claim 1, wherein the grafting is carried out in a molten phase. Ethylene-propylene-diene segmented copolymer prepared by the process according to any one of claims 1 to 10.

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