Polyolefin graft copolymer produced using initiator containing azidoformate group and production method therefor

Abstract

Disclosed are a polyolefin graft copolymer produced using an initiator containing an azidoformate group and a production method therefor. Specifically, the present invention provides a polyolefin graft copolymer represented by structural formula 1, comprising: a polyolefin-based main chain; and a graft chain grafted to the polyolefin-based main chain and containing a polar polymer. Through the use of a polar polymer containing an azidoformate group as a terminal, the azidoformate group at the terminal is decomposed by photochemical or thermal energy to allow nitrogen gas to escape, forming a nitrene, and the formed nitrene reacts with a C-H bond of the polymer main chain, thereby achieve efficient grafting.

Description

Polyolefin graft copolymer manufactured using an initiator containing an azido formate group and a method for manufacturing the same

[0001] The present invention relates to a polyolefin graft copolymer prepared using an initiator containing an azido formate group and a method for preparing the same.

[0002] Polyolefins are widely used commercial polymers, accounting for 55% of global polymer production. Representative examples include polyethylene (PE), polypropylene (PP), ethylene-propylene (EPR), and ethylene-propylene-diene monomer rubber (EPDM rubber). Polyolefins' excellent chemical stability, wide range of mechanical properties, and low cost facilitate processing and recycling, leading to their use in tires, containers, hoses, and bumpers. However, polyolefins are typically non-polar polymers with hydrocarbon chains, limiting their use in areas where interaction with other substances, such as compatibilizers and adhesives, is critical. Therefore, modification technologies that introduce polar chains or functional groups into polyolefins while maintaining the properties of the parent material and imparting new, valuable properties have been actively researched for a long time.

[0003] Polyolefin modification methods can be broadly divided into two, the first of which is direct copolymerization between olefin monomers and polar monomers. This method, when producing polyolefins through coordination polymerization using Ziegler-Natta catalysts or the like, has limitations: the polar groups interfere with the coordination positions of the central metal, making copolymerization difficult. Furthermore, when producing polyolefins through radical polymerization, the resulting polymers contain branched molecular structures, resulting in relatively low melting temperatures and low crystallinity.

[0004] The second method is post-polymerization modification, which involves modifying a pre-synthesized polyolefin and imparting functional groups. This method, which is currently the most widely used for the commercial synthesis of functionalized polyolefins, offers the advantages of bulk modification and easy control over the amount and type of functional groups introduced. One of the most commonly used approaches in post-polymerization modification involves the reaction of free radicals with C—H bonds in the polymer backbone. Free radicals are primarily formed by H abstraction via peroxide initiation, and in most cases, maleic anhydride is added to generate anhydride-functionalized polymer chains. However, this method has the disadvantage of causing unintended side reactions such as crosslinking and degradation.

[0005] Therefore, research is needed on polyolefin modification that can suppress side reactions such as chain scission and crosslinking of the target polymer and does not use a catalyst.

[0006] The purpose of the present invention is to solve the above problems, and to provide a method for modifying polyolefin without using a catalyst, which can suppress side reactions such as chain scission and crosslinking of a polymer to be modified.

[0007] According to one aspect of the present invention, a polyolefin graft copolymer represented by structural formula 1 is provided, which comprises a polyolefin-based main chain; and a graft chain grafted onto the polyolefin-based main chain and comprising a polar polymer:

[0008] [Structural formula 1]

[0009]

[0010] In the above structural formula 1,

[0011] R 1 is a valence bond or an alkylene group of C1 to C9,

[0012] R2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0013] R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0014] A is a polar monomer,

[0015] R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group,

[0016] m, n and x are each independently the number of repetitions of the repeating unit,

[0017] The number average molecular weight of the above polyolefin graft copolymer is 1,000 to 10,000,000 g / mol.

[0018] Also, R 1 is an alkylene group of C1 to C7,

[0019] R 2 is a C1 to C5 alkyl group,

[0020] R 3 is a C1 to C5 alkyl group or -CN.

[0021] Also, R 1 is a C2 to C6 alkylene group,

[0022] R 2 is a C1 to C3 alkyl group,

[0023] R 3 is a C1 to C3 alkyl group or -CN.

[0024] Also, R 1 is a C3 to C5 alkylene group,

[0025] R 2 is a C1 to C3 alkyl group,

[0026] R 3 is -CN.

[0027] In addition, the polyolefin-based main chain is selected from the group consisting of polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene rubber), It may include at least one selected from the group consisting of isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber) and copolymers thereof.

[0028] Additionally, the polyolefin graft copolymer may additionally include a compatibilizer.

[0029] In addition, the compatibilizer may include at least one selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butylene-styrene block copolymer (SBS), maleic anhydride styrene-butylene-styrene block copolymer (SEBS-g-MAH), and ethylene oxide-propylene oxide copolymer.

[0030] Additionally, the polar monomer may include a radically polymerizable monomer.

[0031] In addition, the radical polymerizable monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid and its salts, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid and its salts, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N,N-dimethylamino ethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, Itaconic acid and its salts, 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-butylmethacrylamide, Nn-butylmethacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic acid sodium salt, trimethoxysilylpropyl methacrylate, Triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate,Styrenes, acrylates, methacrylates, acrylamides, vinyl acetates, anhydrides, acrylic acids and combinations thereof, such as diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole It may include one or more species selected from the group consisting of:

[0032] According to another aspect of the present invention, a method for producing a polyolefin graft copolymer is provided, comprising the steps of: reacting a polymer having a polyolefin-based main chain represented by structural formula 2 according to reaction formula 1 with a polar polymer having an azido formate terminal represented by structural formula 3 to produce a polyolefin graft copolymer represented by structural formula 1;

[0033] [Reaction Formula 1]

[0034]

[0035] In the above reaction formula 1,

[0036] R 1 is a valence bond or an alkylene group of C1 to C9,

[0037] R 2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0038] R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0039] A is a polar monomer,

[0040] R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group,

[0041] m, n and x are each independently the number of repetitions of the repeating unit,

[0042] The number average molecular weight of the above polyolefin graft copolymer is 1,000 to 10,000,000 g / mol.

[0043] Additionally, the above reaction can be carried out at a temperature of 25 to 300°C.

[0044] In addition, the polymer having the polyolefin main chain is polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene It may include at least one selected from the group consisting of rubber), isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber), and copolymers thereof.

[0045] In addition, the method for producing the polyolefin graft copolymer may further include, before the step of producing the polyolefin graft copolymer, a step of reacting a compound represented by structural formula 4 and a polar monomer represented by structural formula 5 according to reaction formula 2 to produce a polar polymer having an azidoformate group as a terminal, represented by structural formula 3.

[0046] [Reaction Formula 2]

[0047]

[0048] In the above reaction formula 2,

[0049] R 1 Each of the atoms is a bond or an alkylene group of C1 to C9,

[0050] R 2 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0051] R 3 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0052] A is a polar monomer,

[0053] x is the number of repetitions of the repetition unit,

[0054] The number average molecular weight of the above polar polymer is 500 to 5,000,000 g / mol.

[0055] Additionally, the above reaction can be performed at a temperature of -20 to 250°C.

[0056] Additionally, the solvent of the above reaction may include a polar aprotic solvent.

[0057] Additionally, the solvent of the above reaction may include at least one selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), benzene, and toluene.

[0058] The initiator of the present invention polymerizes a monomer through decomposition of an azo group at -20 to 250°C to provide a polar polymer having an azidoformate group as a terminal group. This can be used to modify polyolefins and facilitate mixing with polar substances.

[0059] The polar polymer synthesized through the free radical polymerization of the initiator of the present invention includes an azidoformate group at the terminal, so that the azidoformate group at the terminal is decomposed by photochemical or thermal energy, nitrogen gas is released, and nitrene is formed, and the formed nitrene reacts with the CH bond of the polyolefin polymer main chain, so that efficient grafting can be performed.

[0060] These drawings are for reference in explaining exemplary embodiments of the present invention, and therefore, the technical idea of ​​the present invention should not be interpreted as being limited to the attached drawings.

[0061] Figure 1a is a DSC curve showing the thermal behavior of AFPS according to Manufacturing Example 2 of the present invention.

[0062] Figure 1b shows the azide decomposition ratio according to temperature of AFPS according to Manufacturing Example 2 of the present invention.

[0063] Figure 2a shows the 1600 cm of PF10 after 1 to 4 purifications and PP / AIBN-PS after 1 purification. -1 The IR spectra are shown in .

[0064] Figure 2b shows an FT-IR calibration curve for calculating the amount (wt%) of AFPS grafted onto PP.

[0065] FIG. 3 shows a comparison of the colors of PF10 according to Example 1 of the present invention and HDPE-graft-PSIN samples according to Example 4 of Korean Patent Registration No. 10-2374081.

[0066] Figures 4a to e show FE-SEM images of PP, Comparative Example 2 (PP / AIBN-PS10), Comparative Example 4 (PP / AIBN-PS20), Example 1 (PF10), and Example 2 (PF20), respectively, in that order.

[0067] Figure 5 shows the XRD spectra of PP, Comparative Example 4 (PP / AIBN-PS20), and Example 2 of the present invention (PF20).

[0068] Figure 6a shows the DSC heating curves of samples of PP, comparative example (PP / AIBN-PS), and example of the present invention (PF).

[0069] Figure 6b shows the DSC cooling curves of samples of PP, comparative example (PP / AIBN-PS), and example of the present invention (PF).

[0070] Figure 7 shows the DSC isothermal crystallization curves at 126°C of PP, Comparative Example 2 (PP / AIBN-PS14), and PF20 P2 purified twice in Example 2.

[0071] Figures 8a to 8c show the relative crystallinity (X) according to the isothermal crystallization progress time according to the temperature change of PP, Comparative Example 2 (PP / AIBN-PS14) and PF20 P2 samples, respectively. t ) is shown.

[0072] Figures 9a to 9c respectively show Avrami plots according to temperature change of PP, Comparative Example 2 (PP / AIBN-PS14), and PF20 P2 samples.

[0073] Figure 10a shows the composite viscosity of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0074] Figure 10b shows the storage and loss moduli of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0075] Figure 10c shows the loss tangent of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0076] Figure 10d shows the vGP-plot of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0077] Figure 11a shows the Young's modulus of PP, comparative example (PP / AIBN-PS), and exemplary example (PF) samples.

[0078] Figure 11b shows the elongation of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0079] Figure 11c shows the tensile strength of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0080] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0081] However, the following description is not intended to limit the present invention to a specific embodiment, and when explaining the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description is omitted.

[0082] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

[0083] Additionally, terms including ordinal numbers, such as "first," "second," etc., which will be used hereinafter, may be used to describe various components, but these components are not limited by these terms. These terms are used solely to distinguish one component from another. For example, without departing from the scope of the present invention, a first component could be referred to as a second component, and similarly, a second component could also be referred to as a first component.

[0084] Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

[0085] Hereinafter, a polyolefin graft copolymer prepared using an initiator containing an azido formate group of the present invention and a method for preparing the same will be described in detail. However, these examples are provided by way of example only and the present invention is not limited thereto, and the present invention is defined solely by the scope of the claims set forth below.

[0086] The present invention provides a polyolefin graft copolymer represented by structural formula 1, which comprises a polyolefin-based main chain; and a graft chain grafted onto the polyolefin-based main chain and comprising a polar polymer:

[0087] [Structural formula 1]

[0088]

[0089] In the above structural formula 1,

[0090] R 1 is a valence bond or an alkylene group of C1 to C9,

[0091] R 2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0092] R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0093] A is a polar monomer,

[0094] R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group,

[0095] m, n and x are each independently the number of repetitions of the repeating unit,

[0096] The number average molecular weight of the above polyolefin graft copolymer may be 1,000 to 10,000,000 g / mol, preferably 1,000 to 5,000,000 g / mol, more preferably 1,000 to 1,000,000 g / mol, and even more preferably 5,000 to 500,000 g / mol.

[0097] Here, * may be generated by a hydrogen atom, a C1 to C5 alkyl group, a C1 to C5 alkoxy group, or a radical polymerization terminator added to terminate radical polymerization, and the radical polymerization terminator may be used without limitation as long as it does not impair the properties of the generated polymer.

[0098] Also, R 1 is an alkylene group of C1 to C7,

[0099] R 2 is a C1 to C5 alkyl group,

[0100] R 3 is a C1 to C5 alkyl group or -CN.

[0101] Also, R 1 is a C2 to C6 alkylene group,

[0102] R 2 is a C1 to C3 alkyl group,

[0103] R 3 is a C1 to C3 alkyl group or -CN.

[0104] Also, R 1 is a C3 to C5 alkylene group,

[0105] R 2 is a C1 to C3 alkyl group,

[0106] R 3 is -CN.

[0107] In addition, the polyolefin-based main chain is selected from the group consisting of polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene rubber), It may include at least one selected from the group consisting of isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber) and copolymers thereof.

[0108] Additionally, the polyolefin graft copolymer may additionally include a compatibilizer.

[0109] In addition, the compatibilizer may include at least one selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butylene-styrene block copolymer (SBS), maleic anhydride styrene-butylene-styrene block copolymer (SEBS-g-MAH), and ethylene oxide-propylene oxide copolymer.

[0110] Additionally, the polar monomer may include a radically polymerizable monomer.

[0111] In addition, the radical polymerizable monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid and its salts, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid and its salts, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N,N-dimethylamino ethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, Itaconic acid and its salts, 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-butylmethacrylamide, Nn-butylmethacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic acid sodium salt, trimethoxysilylpropyl methacrylate, Triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate,Styrenes, acrylates, methacrylates, acrylamides, vinyl acetates, anhydrides, acrylic acids and combinations thereof, such as diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole It may include one or more species selected from the group consisting of:

[0112] According to another aspect of the present invention, a method for producing a polyolefin graft copolymer is provided, comprising the steps of: reacting a polymer having a polyolefin-based main chain represented by structural formula 2 according to reaction formula 1 with a polar polymer having an azido formate terminal represented by structural formula 3 to produce a polyolefin graft copolymer represented by structural formula 1;

[0113] [Reaction Formula 1]

[0114]

[0115] In the above reaction formula 1,

[0116] R 1 is a valence bond or an alkylene group of C1 to C9,

[0117] R 2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0118] R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN,

[0119] A is a polar monomer,

[0120] R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group,

[0121] m, n and x are each independently the number of repetitions of the repeating unit,

[0122] The number average molecular weight of the above polyolefin graft copolymer may be 1,000 to 10,000,000 g / mol, preferably 1,000 to 5,000,000 g / mol, more preferably 1,000 to 1,000,000 g / mol, and even more preferably 5,000 to 500,000 g / mol.

[0123] Here, * may be generated by a hydrogen atom, a C1 to C5 alkyl group, a C1 to C5 alkoxy group, or a radical polymerization terminator added to terminate radical polymerization, and the radical polymerization terminator may be used without limitation as long as it does not impair the properties of the generated polymer.

[0124] In addition, the reaction can be carried out at a temperature of 25 to 300°C. If the reaction is carried out at less than 25°C, the melting point of PP is 165°C or higher, which is not preferable, and if it exceeds 300°C, more than 90% of the azide decomposes too quickly within 10 minutes, which is not preferable.

[0125] In addition, the polymer having the polyolefin main chain is polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene It may include at least one selected from the group consisting of rubber), isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber), and copolymers thereof.

[0126] In addition, the method for producing the polyolefin graft copolymer may further include, before the step of producing the polyolefin graft copolymer, a step of reacting a compound represented by structural formula 4 and a polar monomer represented by structural formula 5 according to reaction formula 2 to produce a polar polymer having an azidoformate group as a terminal, represented by structural formula 3.

[0127] [Reaction Formula 2]

[0128]

[0129] In the above reaction formula 2,

[0130] R 1 Each of the atoms is a bond or an alkylene group of C1 to C9,

[0131] R 2 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0132] R 3 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0133] A is a polar monomer,

[0134] x is the number of repetitions of the repetition unit,

[0135] The number average molecular weight of the polar polymer may be 500 to 5,000,000 g / mol, preferably 1,000 to 1,000,000 g / mol, more preferably 1,000 to 100,000 g / mol, and even more preferably 5,000 to 50,000 g / mol.

[0136] Here, * may be generated by a hydrogen atom, a C1 to C5 alkyl group, a C1 to C5 alkoxy group, or a radical polymerization terminator added to terminate radical polymerization, and the radical polymerization terminator may be used without limitation as long as it does not impair the properties of the generated polymer.

[0137] In addition, the reaction may be carried out at a temperature of -20 to 250°C, preferably 25 to 150°C, and more preferably 40 to 120°C. If the temperature is lower than -20°C, the azo group of the initiator is not decomposed, making it impossible to produce a polymer, which is undesirable. If the reaction is carried out at a temperature exceeding 250°C, the azidoformate group of the initiator may decompose, causing a side reaction, which is undesirable.

[0138] Additionally, the solvent of the above reaction may include a polar aprotic solvent.

[0139] Additionally, the solvent of the above reaction may include at least one selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), benzene, and toluene.

[0140] Additionally, the polar monomer may include a radically polymerizable monomer.

[0141] In addition, the radical polymerizable monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid and its salts, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid and its salts, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N,N-dimethylamino ethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, Itaconic acid and its salts, 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-butylmethacrylamide, Nn-butylmethacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic acid sodium salt, trimethoxysilylpropyl methacrylate, Triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate,Styrenes, acrylates, methacrylates, acrylamides, vinyl acetates, anhydrides, acrylic acids and combinations thereof, such as diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole It may include one or more species selected from the group consisting of:

[0142] According to another aspect of the present invention, a method for preparing an initiator is provided, comprising: (a) reacting a first reactant comprising a compound represented by structural formula 5 and a compound represented by structural formula 6 according to reaction scheme 3 to prepare a compound represented by structural formula 7; and (b) reacting a second reactant comprising a compound represented by structural formula 7 and a compound represented by structural formula 8 to prepare an initiator represented by structural formula 4.

[0143] [Reaction Formula 3]

[0144]

[0145] In the above reaction formula 3,

[0146] R is OCF3, OCCl3, OCBr3, Cl, or OR 0 And,

[0147] R 0 is a C1 to C3 alkyl group or a C6 to C14 aryl group,

[0148] R 1Each of the atoms is a bond or an alkylene group of C1 to C9,

[0149] R 2 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0150] R 3 are each a hydrogen atom, a C1 to C5 alkyl group or -CN,

[0151] X is F, Cl, Br, I, or OR 0 And,

[0152] R 0 is a C1 to C3 alkyl group or a C6 to C14 aryl group,

[0153] M is Li, Na or K.

[0154] Additionally, the first reactant of step (a) may additionally comprise a tertiary amine.

[0155] Here, tertiary amine is used as a catalyst for the reaction, and can promote the reaction toward the forward reaction by increasing the reactivity of the OH group, which is a reactant, and neutralizing the HCl produced by the reaction.

[0156] Additionally, the tertiary amine may be represented by structural formula 9:

[0157] [Structural formula 9]

[0158]

[0159] In structural formula 9,

[0160] R 5 Inland R 10 are each independently a hydrogen atom or a C1 to C5 alkyl group.

[0161] In addition, step (a) may include (a-1) preparing a mixture by mixing a compound represented by structural formula 5 and a compound represented by structural formula 6 according to reaction scheme 3; and (a-2) reacting the first reactant mixed with a tertiary amine in the mixture to prepare a compound represented by structural formula 7.

[0162] In addition, the reaction of step (a) may be carried out at -50 to 100°C, preferably -10 to 10°C, and more preferably 0°C. If the temperature is lower than -50°C, the reaction may be too slow, which is undesirable, and if it is carried out at higher than 100°C, the reaction composition may vaporize or the reaction may be too fast, which is undesirable.

[0163] In addition, the reaction of step (b) may be carried out at -50 to 100°C, preferably -10 to 10°C, and more preferably 0°C. If the temperature is lower than -50°C, the reaction may be too slow, which is undesirable, and if it is carried out at higher than 100°C, the reaction composition may vaporize or the reaction may be too fast, which is undesirable.

[0164] Additionally, the reaction solvent of step (a) and the reaction solvent of step (b) may each include a polar aprotic solvent.

[0165] Additionally, the reaction solvent of step (a) may include at least one selected from the group consisting of CHCl3 and CH2Cl2.

[0166] In addition, the reaction solvent of step (b) is acetone, C4H 10 It may include at least one selected from the group consisting of O, CH2Cl2, hexane, and ethyl acetate.

[0167] In addition, the method may further include a step of reacting a compound represented by structural formula 7 and a second reactant including a compound represented by structural formula 8 in step (b), and then purifying the reactant through chromatography using a developing solution containing a mixture of hexane and ethyl acetate (c).

[0168] In the above step (c), the mixing ratio of hexane and ethyl acetate may be 0.1:10 to 5:10, preferably 1:10, and more preferably 2:10.

[0169] In addition, (d) the step of adding the reaction solvent of step (b) to the resultant of step (c), reacting it, and extracting it with the reaction solvent of step (a) to prepare an initiator represented by structural formula 4 may be further included.

[0170] In one or more of the steps (a) to (d) above, moisture can be removed using a desiccant after the reaction, and the reaction solvent can be removed by evaporation.

[0171] The above-mentioned desiccant may include MgSO4.

[0172] The above evaporation can preferably be performed using a rotary evaporator.

[0173] [Example]

[0174] Hereinafter, preferred embodiments of the present invention will be described. However, these are provided for illustrative purposes only and the scope of the present invention is not limited thereby.

[0175] The initiator (AFIN) and polymer (AFPS) used in the present invention are those described in Patent Application No. 10-2023-0075279.

[0176] Manufacturing Example 1: Manufacturing of an initiator (AFIN) having azidoformate groups at both ends

[0177] To prepare the intermediate 5,5'-Diazene-1,2-diylbis(5-cyanohexyl chloroformate) (ABCC), 2,2-(Diazene-1,2-diyl)bis(5-hydroxy-2-methylpentanenitrile) (6.06 g) and dichloromethane (25 mL) were added to a 250 mL round bottom flask, followed by triphosgene solution (7.12 g in 20 mL dichloromethane) and stirring at 0 °C for 20 minutes. N,N-diisopropylethylamine (6.20 g) was slowly added dropwise to the reaction mixture and reacted at 0 °C for 10 hours. After the reaction, ice deionized water was added to terminate the reaction, dichloromethane was added to dilute, and the resultant was extracted with dichloromethane. After removing moisture with MgSO4, dichloromethane was evaporated using a rotary evaporator, and ABCC was obtained as a yellow liquid through a purification process using column chromatography using a developing solution of hexane / ethyl acetate (2:10).

[0178] To synthesize AFIN, ABCC (5.28 g) was dissolved in acetone (65 mL), sodium azide solution (2.79 g in 30 mL deionized water) was added, and the mixture was reacted at 0 °C for 2 hours. After the reaction, acetone was removed by evaporation using a rotary evaporator, deionized water (200 mL) and diethyl ether (250 mL) were added, and the resultant was extracted with diethyl ether. After removing moisture with MgSO4, diethyl ether was evaporated using a rotary evaporator, and finally AFIN was obtained as a yellow liquid.

[0179]

[0180] Manufacturing Example 2: Manufacturing of a polymer (AFPS) having an azidoformate group at the terminal.

[0181] A polymer having an azidoformate group at the terminal was prepared using AFIN manufactured according to Manufacturing Example 1. Polystyrene was selected as a model polymer. The synthesis of polystyrene (AFPS) using AFIN was carried out as follows. Styrene (10 g), AFIN (0.47 g), and DMSO (15 ml) were placed in a 250 ml round bottom flask, and nitrogen bubbling was performed for 30 minutes. The reaction was carried out for 9 hours in an oil bath heated to 75 °C. The resultant was diluted with THF and precipitated in methanol to remove unreacted substances, and finally, a polymer (AFPS) having an azidoformate group at the terminal was prepared.

[0182]

[0183] Manufacturing Example 3: Initiator (AIBN) not containing an azido formate group at the terminal

[0184] 2,2'-azobis-isobutyronitrile (AIBN) without an azidoformate group was used in Manufacturing Example 3.

[0185] Manufacturing Example 4: Manufacturing of high molecular weight polystyrene (AIBN-PS) without an azidoformate group at the terminal.

[0186] Polystyrene without terminal groups was also synthesized by a free radical polymerization method using 2,2'-azobis-isobutyronitrile (AIBN) as an initiator (Preparation Example 3). The synthesis of polystyrene (AIBN-PS) using AIBN was as follows. Styrene (15 g), AIBN (0.295 g), and DMSO (20 ml) were placed in a 250 ml round bottom flask, and nitrogen bubbling was performed for 30 minutes. The reaction was carried out on a magnetic stirrer in an oil bath heated to 75 °C for 12 hours. The reactant was diluted with THF and then precipitated in methanol to remove unreacted substances, ultimately producing polystyrene (AIBN-PS) without terminal azidoformate groups.

[0187] Manufacturing Example 5: Initiator containing sulfonyl azide at the terminal (IN) azide )manufacturing

[0188] IN same as Example 1 described in Korean Patent Registration No. 10-2374081 azide was manufactured.

[0189] Manufacturing Example 6: Manufacturing of a polar polymer (PSIN) having a sulfonyl azide group at the terminal.

[0190] A polar polymer having a sulfonyl azide group at the terminal was synthesized by a free radical polymerization method. Specifically, 30 g of styrene and an initiator (IN) prepared according to Preparation Example 5 were used. azide) 3.7 g and 40 mL of DMSO (Dimethyl sulfoxide) were placed in a 250 mL round flask, and nitrogen bubbling was performed for 30 minutes. The reaction was performed using a magnetic stirrer for 11 hours in an oil bath heated to 75 °C. The reactant was diluted with tetrahydrofuran (THF) and precipitated in methanol to remove unreacted substances, thereby producing a polar polymer (PSIN) having a sulfonyl azide group at the terminal.

[0191] Example: Preparation of graft copolymer (PP-graft-AFPS) by mixing high molecular polystyrene (AFPS) having an azidoformate group at the terminal and PP.

[0192] Example 1: PF10 (AFPS 10 wt%)

[0193] A polyolefin graft copolymer was prepared through a CH bond insertion reaction in the melt phase, and the reaction was performed in an internal mixer (Brabender Plasticorder 50 EHT). Specifically, the internal mixer was preheated to 170°C and the rotor speed was set to 50 rpm. PP (33.82 g) and Ethanox®310 (0.38 g, 1 wt.%) were added to the preheated internal mixer, and when melted, AFPS (3.8 g, 10 wt.%) was added, and the reaction was performed for a total of 30 minutes. After the reaction, the mixture (PF series) was cooled to room temperature to prepare graft copolymer PF10.

[0194] Example 2: PF20 (AFPS 20 wt%)

[0195] Graft copolymer PF20 was prepared in the same manner as in Example 1, except that PP (30.02 g) and AFPS (7.6 g, 20 wt.%) were used instead of PP (33.82 g) and AFPS (3.8 g, 10 wt.%).

[0196] Comparative example: Manufacturing of a PP / AIBN blend by mixing PP with high molecular weight polystyrene (AIBN-PS) that does not have an azidoformate group at the end.

[0197] Comparative Example 1: PP / AIBN-PS7 (AIBN-PS 7 wt%)

[0198] A PP / AIBN-PS7 mixture was prepared in the same manner as in Example 1, except that PP (34.96 g) and AIBN-PS (2.66 g, 7 wt.%) prepared in Preparation Example 4 were used instead of PP (33.82 g) and AFPS (3.8 g, 10 wt.%).

[0199] Comparative Example 2: PP / AIBN-PS10 (AIBN-PS 10 wt%)

[0200] A PP / AIBN-PS10 mixture was prepared in the same manner as in Example 1, except that PP (33.82 g) and AIBN-PS (3.80 g, 10 wt.%) prepared in Preparation Example 4 were used instead of PP (33.82 g) and AFPS (3.8 g, 10 wt.%).

[0201] Comparative Example 3: PP / AIBN-PS14 (AIBN-PS 14 wt%)

[0202] A PP / AIBN-PS14 mixture was prepared in the same manner as in Example 1, except that PP (32.30 g) and AIBN-PS (5.32 g, 14 wt.%) prepared in Preparation Example 4 were used instead of PP (33.82 g) and AFPS (3.8 g, 10 wt.%).

[0203] Comparative Example 4: PP / AIBN-PS20 (AIBN-PS 20 wt%)

[0204] A PP / AIBN-PS20 mixture was prepared in the same manner as in Example 1, except that PP (30.02 g) and AIBN-PS (7.60 g, 20 wt.%) prepared in Preparation Example 4 were used instead of PP (33.82 g) and AFPS (3.8 g, 10 wt.%).

[0205] Comparative Example 5: High-density polyethylene graft copolymer (HDPE-graft-PSIN) using a polar polymer containing sulfonyl azide at the terminal

[0206] A polyolefin graft copolymer was prepared through a CH bond insertion reaction in the melt phase, and the reaction was performed in an internal mixer (Brabender Plasticorder 50 EHT). Specifically, the internal mixer was preheated to 170°C and the rotor speed was set to 50 rpm. 30 g of commercially available crystalline high-density polyethylene (HDPE) was added to the preheated internal mixer, and when melted, 3.33 g of PSIN prepared according to Manufacturing Example 6 and 0.303 g of ethanox310, an antioxidant, were added, and the reaction was performed for a total of 18 minutes to prepare a high-density polyethylene graft copolymer (HDPE-graft-PSIN).

[0207] Table 1 below summarizes the experimental conditions according to Examples 1 to 3 and Comparative Examples 1 to 4.

[0208] Classification PP(g) AFPS AIBN-PS gwt% gwt% Example 1 (PF10) 33.82 3.80 10--Example 2 (PF20) 30.02 7.60 20--Comparative Example 1 (PP / AIBN-PS7) 34.96--2.667 Comparative Example 2 (PP / AIBN-PS10) 33.82--3.80 10 Comparative Example 3 (PP / AIBN-PS14) 32.30--5.32 14 Comparative Example 4 (PP / AIBN-PS20) 30.02--7.60 20

[0209] [Example Exam]

[0210] Test Example 1: Confirmation of the thermal behavior of AFPS

[0211] Figure 1a shows the endothermic peak at which the decomposition of azidoformate begins at 120°C as a result of DSC measurement of AFPS, and Figure 1b shows the degree of decomposition calculated from the change in the size of the azide peak by calcining a small amount of AFPS at each temperature (130, 150, 170, 190°C) over time and performing FT-IR measurement to more precisely analyze the thermal behavior of azidoformate over time in the corresponding temperature range.

[0212] Referring to Figure 1, 70% of the azide was decomposed after 60 minutes at 130°C, and 80% was decomposed after 25 minutes at 150°C, which took a long time to decompose, and PP did not melt because its melting point was higher than 165°C, which was not suitable. On the other hand, 190°C was not suitable because more than 90% was decomposed too quickly within 10 minutes. At 170°C, more than 90% was decomposed within 15 to 20 minutes, which was the most suitable temperature for performing a melting reaction, and therefore, 170°C was applied as the temperature condition for the melting process to be performed in the future.

[0213] Test Example 2: Characterization of PP-graft-AFPS (PF)

[0214] Figure 2a shows the result of the grafting reaction of AFPS of Manufacturing Example 2 of the present invention onto PP, and Figure 2b shows a calibration curve through FT-IR measurement according to the polystyrene content.

[0215] Referring to Fig. 2a, to confirm whether AFPS was grafted onto PP, the reaction product was dissolved in xylene at 137°C and then precipitated in a THF solution, and the purification process was performed four times to remove unreacted polystyrene. The FT-IR measurement results showed that the product was obtained at 1600 cm -1Successful grafting was confirmed by the appearance of the C=C stretching peak of styrene. The amount (g) of polystyrene grafted onto PP can be calculated using the grafting efficiency (GE, %) and FT-IR analysis results, as shown in Equation 1 below.

[0216] [Formula 1]

[0217]

[0218] Table 2 shows the grafting efficiency (%) of PF according to reaction time.

[0219] DesignationReaction Time(min)H 1600 / H 2721 Grafted AFPSGE(%)PF10-5P250.12411.6443.17PF10-10P2100.15382.0253.24PF10-15P2150.16182.1355.98PF10-20P2200.17912.356 1.83PF10-30P2300.20572.6970.86PF10-40P2400.20022.6268.99PF10-60P2600.20532.6970.71PF10-80P2800.16602.1857.39

[0220] Referring to Fig. 2b and Table 2, the characteristic peak of polystyrene in the PP / AIBN-PS sample is 1600 cm -1 The C=C stretching peak and the characteristic peak of PP at 2721 cm -1The PP backbone peak was selected and a calibration curve was created through FT-IR measurement according to the polystyrene content. As a result of measuring the grafting efficiency according to the reaction time, a high value of ~43% was shown after 5 minutes of reaction time, and the grafting efficiency value tended to increase as the reaction time increased, and the highest value of ~71% was shown at 30 minutes of reaction time. In addition, it was confirmed that the grafting efficiency no longer increased or decreased after 40 minutes of reaction time, so 30 minutes of reaction time was the most optimal reaction time.

[0221] Test Example 3: Color comparison with HDPE-graft-PSIN (Korean Patent No. 10-2374081) manufactured using PS terminated with sulfonyl azide group.

[0222] FIG. 3 shows a comparison of the colors of PF10 according to Example 1 of the present invention and HDPE-graft-PSIN (Korean Patent No. 10-2374081) samples according to Example 4 of Korean Patent No. 10-2374081.

[0223] Referring to FIG. 3, when the color of the sample of Example 1 (PF10) of the present invention and the HDPE-graft-PSIN sample, which is a polyolefin modified sample using CH insertion of a sulfonyl azide group, were compared, the HDPE-graft-PSIN was colored dark brown, whereas the PF10 was slightly yellow. This comparison was made between samples that were not subjected to reprecipitation purification and was therefore indicated as P0 in the sample name. When samples after two reprecipitation purifications (indicated as P2 in the sample name) were compared with each other, the HDPE-graft-PSIN showed a beige color, whereas the PF10 was confirmed to be almost white.

[0224] Through this, it was confirmed that the azidoformate group caused less coloring of the manufactured modified polyolefin compared to sulfonyl azide.

[0225] Test Example 4: Morphology Analysis of PP-graft-AFPS (PF)

[0226] Figures 4a to e show FE-SEM images of PP, Comparative Example 2 (PP / AIBN-PS10), Comparative Example 4 (PP / AIBN-PS20), Example 1 (PF10), and Example 2 (PF20), respectively.

[0227] Referring to Fig. 4, FE-SEM was measured for morphology analysis of Example 1 (PF10) and Example 2 (PF20), which are the results of the reaction of PP and AFPS, and unlike Comparative Example 2 (PP / AIBN-PS10) and Comparative Example 4 (PP / AIBN-PS20), which are physical mixtures of PP and AIBN-PS, Example 1 (PF10) and Example 2 (PF20) showed no polystyrene domains and a uniform phase, indirectly proving that they were graft copolymers rather than physical mixtures.

[0228] Test Example 5: Analysis of crystal structure and thermal properties of PP-graft-AFPS (PF)

[0229] Test Example 5-1: Crystal structure analysis of PP-graft-AFPS (PF)

[0230] Figure 5 shows the XRD spectra of PP, Comparative Example 4 (PP / AIBN-PS20), and Example 2 of the present invention (PF20).

[0231] Referring to FIG. 5, X-Ray Diffraction (XRD) was measured to analyze the crystal structure of Example 2 (PF20) and Comparative Example 4 (PP / AIBN-PS20), and it was confirmed that the characteristic peaks of polypropylene appeared at the same position for all of PP, Comparative Example 4 (PP / AIBN-PS20), and Example 2 (PF20).

[0232] FWHM (degree)Crystallite size (nm)(110)(040)(130)(110)(040)(130)PP0.400.360.3619.7922.0622.11Comparative Example 4(PP / AIBN-PS20)0.460.450.3817.2117.6520.95Example 2(PF20)0.490.450.4016.1617.6519.90

[0233] Referring to Table 3, it can be seen that in the case of Example 2 (PF20), the peak intensity is somewhat reduced and the peak width is somewhat increased compared to PP or Comparative Example 4 (PP / AIBN-PS20), which suggests that the crystallinity and crystal size of PP are somewhat reduced due to the grafted polystyrene side chain.

[0234] Test Example 5-2: Thermal Characterization of PP-graft-AFPS (PF) (DSC)

[0235] Figure 6a shows the DSC heating curves of samples of PP, comparative example (PP / AIBN-PS), and example (PF) of the present invention, and Figure 6b shows the DSC cooling curves.

[0236] Referring to Fig. 6, in the thermal property analysis through DSC, a sample purified twice from the PF sample (P2 after the sample name) was used to minimize the influence of unreacted polystyrene and observe the thermal properties unique to the PP graft copolymer. The comparison between Comparative Example 1 (PP / AIBN-PS7) and PF10 P2 purified twice from Example 1 was made by matching the PS content after purification in consideration of grafting efficiency. The same applies to the comparison between Comparative Example 2 (PP / AIBN-PS14) and PF20 P2 purified twice from Example 2.

[0237] DesignationT m (℃)ΔH f (J / g)X c (%)T c(℃)PP167.194.145.0114.5Comparative Example 1166.292.244.1116.8Comparative Example 2165.887.041.6117.52 times purified Example 1165.691.743.9117.02 times purified Example 2165.375.536.1119.6

[0238] As shown in Table 4, PF20 (Xc, 36.1%) is higher than PP (X c , 45.0%) and PP / AIBN-PS14 (X c , 41.6%), it was estimated that the PS chain was grafted and hindered the movement of the PP chain. Referring to Fig. 6a, the melting temperature values ​​of PP / AIBN-PS and PF were slightly reduced compared to PP, and referring to Fig. 6b, PF20 had a crystallization temperature (T ) lower than PP / AIBN-PS14. c ) has increased.

[0239] Through this, it was estimated that the grafted polystyrene side chains reduce the crystal size of polypropylene, but act as micronucleating agents as non-uniform points during crystallization from a molten state, thereby promoting crystallization.

[0240] Test Example 5-3: Confirmation of isothermal crystallization behavior and crystallization rate of PP-graft-AFPS (PF)

[0241] Figure 7 shows the DSC isothermal crystallization curves at 126°C of PP, Comparative Example 2 (PP / AIBN-PS14), and PF20 P2 purified twice in Example 2, and Figures 8a to 8c respectively show the relative crystallinity (X) according to the isothermal crystallization progress time according to the temperature change of PP, Comparative Example 2 (PP / AIBN-PS14), and PF20 P2 samples purified twice in Example 2. t) and Figs. 9a to 9c respectively show Avrami plots according to temperature changes of PF20 P2 samples purified twice in PP, Comparative Example 2 (PP / AIBN-PS14) and Example 2.

[0242] Referring to Fig. 7, in order to confirm the isothermal crystallization behavior and crystallization rate, all samples were first heated at 190 ℃ for 5 minutes to remove the thermal history to remove fine crystal nuclei, and then rapidly cooled at a cooling rate of 40 ℃ / min to reach the isothermal crystallization temperatures (124, 126, 128, 130 ℃), and the obtained DSC curves were examined. Fig. 7 shows the crystallization exotherm curves during isothermal crystallization, in which PF20 P2 crystallizes faster than PP and PP / AIBN-PS14 blends, indicating that the grafted polystyrene chains promote the crystallization of PP.

[0243] Referring to Figure 8, the relative crystallinity (X) according to the crystallization progress time t ) was measured, and X t was calculated using Equation 2 below, and dH t is the enthalpy change over time during crystallization, and t and ∞ represent the elapsed time during crystallization and the time until crystallization is completed, respectively.

[0244] [Formula 2]

[0245]

[0246] Also X t It can be expressed through the Avrami equation and is shown in Fig. 9 through equation 4 expressed as log t and log(-ln(1-Xt)).

[0247] [Formula 3]

[0248]

[0249] [Formula 4]

[0250]

[0251] Here, n is the Avrami exponent, which represents the nuclear growth process, and K is the crystal growth rate constant, and these values ​​are shown in Table 5 below.

[0252] DesignationT c (℃)NK·10 -2 (min -1 )t 1 / 2 (min)PP1242.6957.91.071262.5128.21.431282.7810.21.991302.728.32.18Comparative Example 2 (PP / AIBN-PS14)1242.8088.10.921262.8041.81.201282.7719.11.591302.814.82.59PF20 P21242.69172.00.711262.7790.20.901282.5953.21.111302.7918.11.62

[0253] Here, t 1 / 2 is defined as the time at which the relative decision-making power becomes 50% (t 1 / 2 =(ln2 / K) 1 / n )

[0254] The n value was not significantly different between 2.51 and 2.81, indicating that the introduction of polystyrene did not significantly affect the crystallization mechanism of PP. Since the n value was between 2 and 3, it indicated two-dimensional or three-dimensional crystal growth. The K value was the highest for PF20, and conversely, the time for 50% of crystal growth to be completed, t 1 / 2 was the fastest. This was presumed to be due to the presence of a branch structure resulting from the introduction of AFPS.

[0255] Test Example 6: Rheological Characteristics of PP-graft-AFPS (PF)

[0256] Figure 10a shows the complex viscosity of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples, Figure 10b shows the storage and loss moduli of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples, Figure 10c shows the loss tangent of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples, and Figure 10d shows the vGP-plot of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples.

[0257] Referring to Fig. 10, since rheology is sensitive to the molecular structure of polymers, the rheological behavior of PF samples was investigated using a rheometer. Fig. 10a shows the complex viscosity (n*) behavior according to each frequency of PP, PP / AIBN-PS, and PF at 190°. In the low frequency region, the n* value of PF is obviously higher than those of PP and PP / AIBN-PS, and the n* value increases as the AFPS content increases. On the other hand, it can be seen that the n* value of PP / AIBN-PS is lower than that of PP. This is because the immiscibility of PP and PS limits interfacial slip and stress transfer through the interface.

[0258] Referring to Fig. 10b, the storage modulus (G') and loss modulus (G'') values ​​provide information on the elastic properties of the sample. As the AFPS content increases, relatively higher G' and G'' values ​​are observed at low frequencies. The chain entanglement caused by the AFPS branch structure combined with PP results in a longer relaxation time and higher melt elasticity, resulting in a high G' value.

[0259] Referring to Fig. 10c, the loss tangent (tan δ, G'' / G') is another indicator of chain characteristics reflecting the relaxation process. For PP and PP / AIBN-PS, tan δ values ​​were relatively high at low frequencies, decreased with increasing AFPS content, and showed a flatter curve with frequency. This indicates that the terminal relaxation time of PF increased with the amount of AFPS.

[0260] Referring to Fig. 10d, the characteristics of the branched polymer structure can also be described through the van Gurp-Palmen (vGP) plot using the phase angle (δ). At low complex modulus, the δ value decreases as the amount of AFPS increases, indicating more elastic properties in the molten state.

[0261] Test Example 7: Tensile property analysis of PP-graft-AFPS (PF)

[0262] Figure 11a shows the Young's modulus of PP, comparative (PP / AIBN-PS), and exemplary (PF) samples, Figure 11b shows the elongation, and Figure 11c shows the tensile strength.

[0263] Referring to Fig. 11, the tensile properties of PP, PP / AIBN-PS, and PF analyzed according to ASTM D638 are shown. PF with the same PS content exhibits a relatively higher Young's modulus and lower elongation than PP / AIBN-PS, suggesting that this is due to the covalent bonding of hard AFPS. In addition, tensile strength can be affected by particle size, and the reason why PF has a higher tensile strength than PP / AIBN-PS is that as the AIBN-PS content increases, the domain size of PP / AIBN-PS increases, resulting in a decrease in tensile strength, whereas PF shows almost no change in tensile strength because a homogeneous phase is formed and no domains are observed even when the AFPS content is high.

[0264] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. Polyolefin main chain; and A graft chain that is grafted onto the polyolefin-based main chain and includes a polar polymer; A polyolefin graft copolymer represented by structural formula 1, which comprises: [Structural formula 1] In the above structural formula 1, R 1 is a valence bond or an alkylene group of C1 to C9, R 2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN, R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN, A is a polar monomer, R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group, m, n and x are each independently the number of repetitions of the repeating unit, The number average molecular weight of the above polyolefin graft copolymer is 1,000 to 10,000,000 g / mol.

2. In paragraph 1, R 1 is an alkylene group of C1 to C7, R 2 is a C1 to C5 alkyl group, R 3 A polyolefin graft copolymer characterized by having a C1 to C5 alkyl group or -CN.

3. In paragraph 2, R 1 is a C2 to C6 alkylene group, R 2 is a C1 to C3 alkyl group, R 3 A polyolefin graft copolymer characterized by having a C1 to C3 alkyl group or -CN.

4. In paragraph 3, R 1 is a C3 to C5 alkylene group, R 2 is a C1 to C3 alkyl group, R 3 A polyolefin graft copolymer characterized in that it is -CN.

5. In paragraph 1, The above polyolefin main chain is selected from the group consisting of polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene rubber), A polyolefin graft copolymer characterized by comprising at least one selected from the group consisting of isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber) and copolymers thereof.

6. In paragraph 1, A polyolefin graft copolymer characterized in that the polyolefin graft copolymer further comprises a compatibilizer.

7. In paragraph 6, A polyolefin graft copolymer characterized in that the compatibilizer comprises at least one selected from the group consisting of a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-butylene-styrene block copolymer (SBS), a maleic anhydride styrene-butylene-styrene block copolymer (SEBS-g-MAH), and an ethylene oxide-propylene oxide copolymer.

8. In paragraph 1, A polyolefin graft copolymer characterized in that the polar monomer comprises a radically polymerizable monomer.

9. In paragraph 8, The above radical polymerizable monomers are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid and its salts, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid and its salts, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N,N-dimethylamino ethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, Itaconic acid and its salts, 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-butylmethacrylamide, Nn-butylmethacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert-butylacrylamide, Nn-butylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid, diethylaminostyrene, alpha-methylvinyl benzoic acid, diethylamino alpha-methylstyrene, p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic 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,A composition characterized by comprising at least one selected from the group consisting of styrenes, acrylates, methacrylates, acrylamides, vinyl acetates, anhydrides, acrylic acids and combinations thereof, such as trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole. Polyolefin graft copolymer., 10. A method for producing a polyolefin graft copolymer, comprising: a step of reacting a polymer having a polyolefin-based main chain represented by structural formula 2 according to reaction formula 1 with a polar polymer having an azido formate terminal represented by structural formula 3 to produce a polyolefin graft copolymer represented by structural formula 1; [Reaction Formula 1] In the above reaction formula 1, R 1 is a valence bond or an alkylene group of C1 to C9, R 2 is a hydrogen atom, a C1 to C5 alkyl group, or -CN, R 3 is a hydrogen atom, a C1 to C5 alkyl group, or -CN, A is a polar monomer, R 4 and R 5 are the same or different from each other, and each independently represents a hydrogen atom or a C1 to C6 alkyl group, m, n and x are each independently the number of repetitions of the repeating unit, The number average molecular weight of the above polyolefin graft copolymer is 1,000 to 10,000,000 g / mol.

11. In paragraph 10, A method for producing a polyolefin graft copolymer, characterized in that the above reaction is performed at a temperature of 25 to 300°C.

12. In paragraph 10, The polymer having the above polyolefin main chain is polyethylene, polypropylene, poly α-olefin, polybutadiene, ethylene-α-olefin copolymer, ethylene-propylene copolymer (EPR), ethylene-propylene-diene rubber (EPDM), styrene butadiene styrene copolymer (SBS), styrene butadiene rubber (SBR, styrene butadiene rubber), stereospecific styrene butadiene rubber (stereospecific SBR, stereospecific styrene butadiene rubber), styrene butadiene styrene copolymer, polychloroprene rubber (CR, polychloroprene rubber), cis-chlorobutadiene rubber (cis-chlorobutadiene rubber), acrylonitrile butadiene rubber (NBR, acrylonitrile butadiene rubber), butadiene rubber (BR, butadiene rubber), isoprene rubber (IR, isoprene rubber), A method for producing a polyolefin graft copolymer, characterized in that it comprises at least one selected from the group consisting of isobutylene isoprene rubber (IIR, isobutylene isoprene rubber, butyl rubber) and copolymers thereof.

13. In paragraph 10, The method for producing the above polyolefin graft copolymer includes, before the step of producing the polyolefin graft copolymer, A method for producing a polyolefin graft copolymer, characterized in that it further comprises a step of producing a polar polymer having an azidoformate group as a terminal, represented by structural formula 3, by reacting a compound represented by structural formula 4 and a polar monomer represented by structural formula 5 according to reaction formula 2. [Reaction Formula 2] In the above reaction formula 2, R 1 Each of the atoms is a bond or an alkylene group of C1 to C9, R 2 are each a hydrogen atom, a C1 to C5 alkyl group or -CN, R 3 are each a hydrogen atom, a C1 to C5 alkyl group or -CN, A is a polar monomer, x is the number of repetitions of the repetition unit, The number average molecular weight of the above polar polymer is 500 to 5,000,000 g / mol.

14. In paragraph 13, A method for producing a polyolefin graft copolymer, characterized in that the above reaction is performed at a temperature of -20 to 250°C.

15. In paragraph 13, A method for producing a polyolefin graft copolymer, characterized in that the solvent of the above reaction comprises a polar aprotic solvent.

16. In paragraph 13, A method for producing a polyolefin graft copolymer, characterized in that the solvent of the above reaction comprises at least one selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), benzene, and toluene.

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