JP2007131717A - Polyolefin-based graft copolymer, composition and method for producing thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin-based graft copolymer produced by polymerizing an olefin monomer in a macromonomer latex by using a coordination polymerization catalyst composed of a late-periodic transition metal complex, wherein the polyolefin-based graft copolymer imparts a composition excellent in impact resistance by compounding with a thermoplastic resin such as a polypropylene or the like, and to provide a composition comprising the copolymer and to provide a method for producing the same. <P>SOLUTION: The invention relates to the polyolefin-based graft copolymer produced by polymerizing the olefin monomer in the macromonomer latex by using the coordination polymerization catalyst composed of the late-periodic transition metal complex, wherein the impact resistance of the composition is improved by setting the particle diameter of the macromonomers in a specific range. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyolefin graft copolymer produced by polymerizing an olefin monomer with a coordination polymerization catalyst in a latex of a macromonomer, a thermoplastic resin composition, and a method for producing them.

  Polyolefin resins are industrially produced by coordination polymerization. As olefin coordination polymerization catalysts, Ziegler-Natta catalysts and metallocene catalysts are well known. However, when such a transition metal based coordination polymerization catalyst is used, there is a problem that the polar compound reacts or coordinates with the complex or the catalytically active species to lose its activity or decompose. Therefore, it has been difficult to impart functionality by copolymerizing a monomer having a polar functional group to polyolefin or to perform olefin polymerization in an emulsion polymerization system.

  As a coordination polymerization catalyst having high resistance to polar compounds, a late transition metal complex-based coordination polymerization catalyst is known. As exemplified in various reviews (for example, see Non-Patent Documents 1, 2, and 3), polyolefin can be polymerized without losing activity even in the presence of a polar solvent such as tetrahydrofuran, ether, acetone, ethyl acetate, water, Copolymers with polar monomers such as polar vinyl monomers such as alkyl acrylates can also be obtained. However, even with these catalysts, there is a limit to the amount of polar monomer that can be copolymerized with polyolefin. A technique for obtaining a polyolefin copolymer having a high content of polar monomers has been awaited.

In order to solve these problems, for example, there is a technique for producing a graft copolymer by polymerizing an acrylate polymer with an acrylate polymer in the presence of a coordination polymerization catalyst of a previous period transition metal complex (for example, Patent Document 1). This polyolefin-based graft copolymer can function as a polarizing agent for polyolefin, but the impact resistance is not always sufficient.
JP 2003-335828 A Chemical Review, 2000, 100, 1169 Journal of Synthetic Organic Chemistry, 2000, 58, 293 Angewante Chemie International Edition, 2002, 41, 544

  Accordingly, an object of the present invention is to provide a polyolefin-based graft copolymer produced by polymerizing an olefinic monomer in a macromonomer latex with a late transition metal-based coordination polymerization catalyst, and to a thermoplastic resin such as polypropylene. An object of the present invention is to provide a polyolefin-based graft copolymer which gives a composition having excellent impact resistance when blended.

  In order to solve the above problems, the present inventors have intensively studied and found that the impact resistance of the composition is improved by using a vinyl-based macromonomer having a specific particle size as a raw material, thereby completing the present invention. did.

  That is, the present invention relates to a polyolefin graft copolymer produced by polymerizing an olefin monomer with a late transition metal-based coordination polymerization catalyst in a macromonomer latex, and the particle size of the macromonomer is 1 to 5 μm. A polyolefin-based graft copolymer (Claim 1).

  The polyolefin graft copolymer according to claim 1, wherein the macromonomer is a (meth) acrylic macromonomer (claim 2).

  The polyolefin graft copolymer according to any one of claims 1 to 2, wherein the macromonomer is a butyl acrylate macromonomer (claim 3).

  The late transition metal-based coordination polymerization catalyst is a complex comprising a ligand having two imine nitrogens and a late transition metal selected from groups 8 to 10 of the periodic table. The polyolefin-based graft copolymer according to any one of (4).

  The polyolefin graft copolymer according to any one of claims 1 to 4, wherein the olefin monomer is an α-olefin having 2 to 20 carbon atoms (claim 5).

  The manufacturing method of the polyolefin-type graft copolymer of any one of Claims 1-5 (Claim 6).

  A thermoplastic resin composition comprising the polyolefin graft copolymer according to any one of claims 1 to 5 and another thermoplastic resin (claim 7).

  A method for producing the thermoplastic resin composition according to claim 7 (claim 8). About.

  A polyolefin-based graft copolymer obtained by polymerizing an olefin monomer with a macromonomer latex having a specific particle size, and a composition having good impact strength of a molded article obtained by blending with a thermoplastic resin is obtained.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a polyolefin graft copolymer obtained by copolymerizing an olefin monomer with a macromonomer using a coordination polymerization catalyst in a latex of a macromonomer, and a method for producing the same. Furthermore, the present invention relates to a thermoplastic resin composition containing a polyolefin graft copolymer and a method for producing the same. The polyolefin graft copolymer referred to in the present invention is a copolymer obtained by graft copolymerization of an olefin and a macromonomer. The macromonomer referred to in the present invention refers to an oligomer or polymer having a functional group that can be copolymerized with other monomers.

  Various types of main macromonomer main chain structures, layer structures, and functional group introduction positions are known. As the main chain structure, those having various structures such as linear, cyclic, branched, crosslinked particles, non-crosslinked particles, single layer structured particles, multilayer structured particles, and multiphase structured particles are known. Various types of functional groups are known, such as in the main chain, in the side chain, at one or both ends of the linear molecule, inside the single layer structure or multilayer structure particle, or on the particle surface.

  The macromonomer used in the present invention is a crosslinked particle characterized in that the amount of a crosslinking agent (polyfunctional monomer having two or more carbon-carbon double bonds per molecule) is in a specific range. . The macromonomer used in the present invention may be a uniform particle having only a single layer or a multilayer structure particle composed of a plurality of layers. A core-shell two-layer structure having a hard polymer shell layer around a rubber-like polymer core layer, or a salami-like multiphase structure in which other resin phases are dispersed in a matrix resin phase, Also good.

  As a general method for producing a macromonomer, various methods such as anionic polymerization, cationic polymerization, radical polymerization, coordination polymerization, polycondensation, ring-opening polymerization, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization are known. . As a method for producing the macromonomer used in the present invention, any polymerization method may be used. However, in the present invention, since the macromonomer is copolymerized with olefin in a latex state, microsuspension polymerization or emulsion polymerization is particularly preferable.

  The macromonomer used in the present invention is a vinyl macromonomer. From the viewpoint of balance of physical properties, (meth) acrylic macromonomer is particularly preferable among vinyl macromonomers. The vinyl macromonomer referred to in the present invention is mainly composed of a polymer of vinyl monomers typified by (meth) acrylic acid ester, aromatic vinyl compound, diene compound, vinyl cyanide compound, vinyl ester and the like. It is a macromonomer. The (meth) acrylic macromonomer referred to in the present invention is a macromonomer mainly composed of a poly (meth) acrylic acid ester. (Meth) acrylic means both methacrylic and acrylic.

  The vinyl-based macromonomer used in the present invention includes (A) a vinyl-based monomer (hereinafter referred to as compound (A)) and (B) a polyfunctional monomer (hereinafter referred to as “carbon-carbon double bond” per molecule). Compound (B)) can be copolymerized by a known method. The compound (A) is preferably used in an amount of 99 to 99.99% by weight, more preferably 99.5 to 99.9% by weight. The compound (B) is preferably 0.01 to 1% by weight, more preferably 0.1 to 0.5% by weight.

  However, the total of the compound (A) and the compound (B) is 100% by weight. If the amount of the compound (B) used is too large, the impact resistance of the composition obtained by blending a polyolefin-based graft copolymer obtained by copolymerizing the compound (B) with a thermoplastic resin such as polypropylene will be low. This is not preferable. If the amount of the compound (B) used is too small, the grafting efficiency with the olefin monomer may be lowered.

  The compound (A) is a component for forming the main skeleton of the vinyl macromonomer. Specific examples of the compound (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, and (meth) acrylic. 2-methoxyethyl acid, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as benzyl (meth) acrylate, glycidyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate; (meth) acrylic acid and acid anhydrides and metal salts thereof; styrene, α -Fragrances such as methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene Vinyl compounds; diene compounds such as 1,3-butadiene, isoprene, and chloroprene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl acetate, vinyl ethyl ether, and the like, but are not limited thereto. .

Among these, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-methoxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate (Meth) acrylic acid alkyl esters having 2 to 18 carbon atoms such as stearyl methacrylate are preferred, and butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are more preferred. Particularly preferred.
Further, a (meth) acrylic macromonomer using 50% by weight or more of a (meth) acrylic acid ester monomer, and a butyl acrylate macromonomer using 50% by weight or more of a butyl acrylate ester are particularly preferable.

  The compound (B) is a component for creating a crosslinking point in the molecule of the macromonomer, and a component for introducing a carbon-carbon double bond that can be copolymerized with the olefinic monomer into the macromonomer. The carbon-carbon double bonds possessed by the compound (B) may all be the same group or different groups. Preferably, it has at least one radical polymerizable carbon-carbon double bond and at least one coordination polymerizable carbon-carbon double bond in the molecule, or at least two radical polymerizable and coordination polymerizable in the molecule. It is preferable to have a carbon-carbon double bond having both.

  As specific examples of the functional group containing a radically polymerizable carbon-carbon double bond, various groups such as a vinyl group, a vinylidene group, an allyl group, a styryl group, and a (meth) acryl group are known. In view of high reactivity and difficulty in deactivating the coordination polymerization catalyst, (meth) acryl groups and allyl groups are particularly preferable. Specific examples of the functional group containing a carbon-carbon double bond having coordination polymerizability include an allyl group, a cyclic olefin, a styryl group, and a (meth) acryl group. From the viewpoint of high reactivity, a carbon-carbon double bond contained in an allyl group or dicyclopentenyl group is particularly preferable.

  Specific examples of the compound (B) include allyl methacrylate, allyl acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, ethylene glycol dicyclopentenyl ether methacrylate, and the like. However, it is not limited to these. Of these, allyl methacrylate and ethylene glycol dicyclopentenyl ether are particularly preferred. These compounds (B) may be used independently and may use 2 or more types together.

  The vinyl macromonomer used in the present invention can be produced by radical (co) polymerization by an ordinary emulsion polymerization method or microsuspension polymerization method, and can be obtained as a latex.

  In the polymerization, the entire amount of the raw material may be charged at once, or the remaining part may be added continuously or intermittently after a part is charged. For example, it is possible to design a structure in which the coordination polymerizable carbon-carbon double bond is unevenly distributed in the surface layer portion of the vinyl-based macromonomer particle by reacting the compound (A) after adding the compound (B). it can. In addition, a method of emulsifying the compound (A) and / or the compound (B) with an emulsifier and water in advance, or adding an emulsifier or an aqueous solution of the emulsifier separately from the compound (A) and / or the compound (B). Alternatively, a method of adding by dividing can be adopted.

  There is no restriction | limiting in particular about the quantity of the water used for micro suspension polymerization or emulsion polymerization, What is necessary is just an amount required in order to emulsify a compound (A) and a compound (B), and a compound (A) and a compound (B 1) to 20 times the weight of the total amount. If the amount of water used is too small, the proportion of the hydrophobic component is too high, and the emulsion does not invert from the water-in-oil type to the oil-in-water type, making it difficult for water to become a continuous layer. If the amount of water used is too large, the stability will be poor and the efficiency in production will be low.

  Known emulsifiers can be used for microsuspension polymerization or emulsion polymerization, and any anionic, cationic or nonionic emulsifier can be used without particular limitation. From the viewpoint of good emulsifying ability, anionic emulsifiers such as alkali metal salts of alkylbenzenesulfonic acid, alkali metal salts of alkylsulfuric acid, and alkali metal salts of alkylsulfosuccinic acid are preferred. The amount of the emulsifier is not particularly limited, and may be appropriately adjusted according to the average particle size of the target vinyl macromonomer. Preferably, the total amount of the compound (A) and the compound (B) is 100 parts by weight. Is 10 parts by weight or less. If the amount is too large, coloring may occur in the composition obtained by blending the resulting polyolefin-based graft copolymer with a thermoplastic resin.

  The average particle size of the vinyl-based macromonomer can be controlled using a known technique such as increase or decrease in the amount of emulsifier used. The average particle size of the vinyl macromonomer from the viewpoint of good dispersibility and impact resistance of the resulting composition when the polyolefin graft copolymer obtained after copolymerization is blended with a thermoplastic resin such as polypropylene. The (volume average particle diameter) is preferably 1 to 5 μm, more preferably 1.25 to 3 μm.

  A well-known thing can be used for the dispersing agent used for micro suspension polymerization. Specific examples include poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, aluminum hydroxide, and starch silica; nonionic polymer compounds such as polyvinyl alcohol, polyethylene oxide, alkyl cellulose, and hydroxyalkyl cellulose; polyacrylic acid and its salts; Examples include anionic polymer compounds such as polymethacrylic acid and salts thereof, and copolymers of methacrylic acid esters and methacrylic acid and salts thereof.

  The polymerization initiator used for the microsuspension polymerization can be any known one without particular limitation. For example, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and organic peroxides such as diisopropyl peroxydicarbonate, lauroyl peroxide, benzoyl peroxide, t-butylperoxybenzoate, and t-butyl peroxide Things are given.

  The polymerization initiator used for the emulsion polymerization can be any known one without particular limitation. For example, persulfates such as potassium persulfate and ammonium persulfate; alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; diacyl peroxides such as benzoyl peroxide; di-t-butyl peroxide, t- And dialkyl peroxides such as butyl peroxylaurate; azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile. Of these, persulfates and alkyl hydroperoxides are preferred.

  These initiators can also be used as a redox catalyst comprising a polymerization initiator, an activator (metal salt or metal complex), a chelating agent, and a reducing agent, in addition to a pyrolytic method. The polymerization initiator may be a thermal decomposition method or a method using a redox catalyst. The pyrolytic method is suitable for obtaining a polymer having a low metal ion content because it is not necessary to add an additive such as a reducing agent or an activator. The method using a redox catalyst is advantageous in that a high reaction rate can be obtained even at a low reaction temperature, and the reaction can be easily controlled.

  As the reducing agent constituting the redox catalyst, for example, glucose, dextrose, sodium formaldehyde sulfoxylate, sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, ascorbic acid, isoascorbic acid and the like can be preferably used. Of these, sodium formaldehyde sulfoxylate is particularly preferred because of its low cost and high activity.

  Chelating agents that constitute redox catalysts include polyaminocarboxylates such as ethylenediaminetetraacetate, oxycarboxylic acids such as citric acid, those that form water-soluble chelate compounds such as condensed phosphates, and dimethylglyoxime, oxine, and dithizone. And the like that form an oil-soluble chelate compound. Of these, polyaminocarboxylates such as ethylenediaminetetraacetate and oxycarboxylic acids such as citric acid are preferred.

  Examples of the activator constituting the redox catalyst include metal salts or metal chelates such as iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, cobalt, and the like. Iron, copper sulfate, potassium hexacyanoiron (III) and the like can be mentioned. The activator and the chelating agent may be used as separate components, or may be reacted in advance and used as a metal complex.

  There are no particular limitations on the combination of the initiator, activator, chelating agent, and reducing agent, and each may be selected arbitrarily. Preferable examples of the combination of activator / reducing agent / chelating agent include, for example, ferrous sulfate / glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, ferrous sulfate / sodium sulfoxylate formaldehyde / ethylenediamine tetra There are combinations of disodium acetate, ferrous sulfate / sodium sulfoxylate formaldehyde / citric acid, copper sulfate / sodium sulfoxylate formaldehyde / citric acid, etc. The particularly preferred combination is ferrous sulfate / sodium sulfoxylate formaldehyde / ethylenediamine Examples thereof include, but are not limited to, disodium acetate, ferrous sulfate / sodium sulfoxylate, formaldehyde / citric acid, and the like.

  The preferred amount of initiator used is 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of compound (A) and compound (B). The preferred amount of chelating agent used is 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total of compound (A) and compound (B). A preferable use amount of the activator is 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of the compound (A) and the compound (B). When the amount used is within this range, the polymerization rate is sufficiently high and coloring and precipitation of the product can be suppressed to a small extent, which is preferable.

  For micro suspension polymerization or emulsion polymerization, a chain transfer agent may be used as necessary. The chain transfer agent may be any known one without particular limitation. Specific examples include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, n-hexyl mercaptan, and the like.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of microsuspension polymerization or emulsion polymerization, It is 0-100 degreeC, Preferably it is 30-95 degreeC. Although there is no restriction | limiting in particular also about reaction time, Usually, 10 minutes-24 hours, Preferably they are 30 minutes-12 hours, More preferably, they are 1 hour-6 hours.

  Next, the catalyst for producing the polyolefin graft copolymer of the present invention will be described.

  In the present invention, a coordination polymerization catalyst is used as a catalyst for producing a polyolefin-based graft copolymer. A coordination polymerization catalyst is a catalyst that promotes coordination polymerization. The coordination polymerization catalyst used in the present invention is not particularly limited as long as it is a coordination polymerization catalyst having olefin polymerization activity in the presence of water and a polar compound.

  Preferred examples include Chemical Review, 2000, 100, 1169-1203, Chemical Review, 2003, 103, 283-315, Journal of Synthetic Organic Chemistry, 2000. Year 58, page 293, Angelwandte Chemie International Edition, 2002, 41, 544-561, Angelvante Chemie International Edition, 200429. -432, Chemical Communication (Chem. Commun.), 2000, p. 301, Macromol. Symp. 2000, 150, 53, Macromolecules, 2003, 36, 6711-6715, Macromolecules, 2001, 34, 1165-1171, Macromolecules Examples described in Macromolecules, 2001, 34, 2022-2026, and those described in WO97 / 17380 and WO97 / 48740, but are not limited thereto. Absent.

  Among them, a complex composed of a ligand having two imine nitrogens and a late transition metal selected from groups 8 to 10 of the periodic table is preferable, and an α-diimine type is more preferable. More preferably, it is a complex comprising a ligand and a late-period transition metal selected from Group 10 of the periodic table, and more particularly preferably, after reacting with a cocatalyst, the following general formula (1) or general formula (2): The species of the structure shown (active species) are preferably used.

(In the formula, M is palladium or nickel. R ₁ and R ₄ are each independently a hydrocarbon group having 1 to 4 carbon atoms. R ₂ and R ₃ are each independently a hydrogen atom or methyl. R ₅ is a halogen atom, a hydrogen atom, or an organic group having 1 to 20 carbon atoms, X is an organic group having a hetero atom that can be coordinated to M, and may be connected to R _5. Or X may not be present, L ⁻ is any anion.)

(In the formula, M is palladium or nickel. R ₁ and R ₄ are each independently a hydrocarbon group having 1 to 4 carbon atoms. R ₅ is a halogen atom, a hydrogen atom, or 1 to 20 carbon atoms. X is an organic group having a heteroatom capable of coordinating to M and may be connected to R ₅ or X may not be present, L ⁻ is any anion .)
Examples of the hydrocarbon group having 1 to 4 carbon atoms represented by R _1, R _4, a methyl group, an ethyl group, an isopropyl group, t- butyl group, is preferable, n- butyl group, more preferably a methyl group, an isopropyl Groups are preferred.

Examples of molecules capable of coordinating to M represented by X include polar compounds such as diethyl ether, acetone, methyl ethyl ketone, acetaldehyde, acetic acid, ethyl acetate, water, ethanol, acetonitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and propylene carbonate. It can be exemplified, but it is not necessary. When R ₅ has a hetero atom, particularly a carbonyl oxygen such as an ester bond, this carbonyl oxygen may be coordinated as X. Further, it is known that the olefin is coordinated during polymerization with the olefin.

Further, the counter anion represented by L ⁻ is produced together with a cation (M ⁺ ) by the reaction between a catalyst comprising an α-diimine type ligand and a transition metal and a cocatalyst, but is not coordinated in the solvent. Any one can form any ion pair.

An α-diimine type ligand having an aromatic group at both imine nitrogens, specifically, a compound represented by ArN═C (R ₂ ) —C (R ₃ ) ═NAr is easily synthesized. It is preferable because of its high activity. R ₂ and R ₃ are preferably hydrocarbon groups, and in particular, those having a hydrogen atom, a methyl group, and an acenaphthene skeleton represented by the general formula (2) are preferable because they are easy to synthesize and have high activity. Furthermore, it is preferable to use an α-diimine type ligand having a substituted aromatic group at both imine nitrogens because it is sterically effective and tends to increase the molecular weight of the polymer. Therefore, Ar is preferably an aromatic group having a substituent, and examples thereof include 2,6-dimethylphenyl and 2,6-diisopropylphenyl.

The auxiliary ligand (R ₅ ) in the active species obtained from the late transition metal complex of the present invention is preferably a hydrocarbon group, a halogen group or a hydrogen group. The co-catalyst cation (Q ⁺ ) described later extracts a halogen from the metal-halogen bond, metal-hydrogen bond, or hydrogen-carbon bond of the catalyst to produce a salt, while the catalyst is an active species. This is because a cation (M ⁺ ) having a metal-carbon bond, a metal-halogen bond, or a metal-hydrogen bond is generated, and it is necessary to form a non-coordinating ion pair with the anion (L ⁻ ) of the promoter. .

Specific examples of R ₅ include a methyl group, a chloro group, a bromo group, and a hydrogen group. In particular, a methyl group or a chloro group is preferable because synthesis is simple. Incidentally, M + ^- the insertion of the olefin to the halogen bond M ⁺ - and is easily occur towards the insertion of olefins into carbon bond (or hydrogen bond), particularly preferred R ₅ is a methyl group as auxiliary ligand catalyst is there.

Further, R ₅ may be an organic group having an ester bond having a carbonyl oxygen capable of coordinating with M, and examples thereof include a group obtained from methyl butyrate.

The cocatalyst can be expressed as Q ⁺ L ⁻ . Examples of Q include Ag, Li, Na, K, and H. Ag is preferable because the halogen drawing reaction is easily completed, and Na and K are preferable because they are inexpensive. The _{L, BF 4, B (C} 6 F 5) 4, B (C 6 H 3 (CF 3) 2) 4, PF 6, AsF 6, SbF 6, (RfSO 2) 2 CH, (RfSO 2) ₃ C, (RfSO ₂ ) ₂ N, RfSO ₃ . In particular, PF _6, AsF _6, SbF _6, (RfSO ₂ ) ₂ CH, (RfSO ₂ ) ₃ C, (RfSO ₂ ) ₂ N, and RfSO ₃ are preferable from the viewpoint that they tend to be stable to polar compounds. , PF _6, AsF _{6 and} SbF ₆ are particularly preferable from the viewpoint that synthesis is simple and industrially available.

From the height of activity, BF _4, B (C ₆ F ₅ ) _4, B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ are particularly B (C ₆ F ₅ ) _4, B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ is preferred. Rf is a hydrocarbon group containing a plurality of fluorine groups. These fluorines are necessary to make the anion non-coordinating, and the larger the number, the better. Examples of Rf include, but are not limited to, CF ₃ , C ₂ F ₅ , C ₄ F ₉ , C ₈ F ₁₇ , and C ₆ F ₅ . Some may be combined.

  For the reasons of activation described above, the molar ratio of late transition metal complex catalyst / promoter is 1 / 0.1 to 1/10, preferably 1 / 0.5 to 1/2, particularly preferably 1 / 0.1. 0.75 to 1 / 1.25.

  The olefin monomer used in the present invention is an olefin compound having a carbon-carbon double bond capable of coordination polymerization.

  Preferred examples of the olefin monomer include olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-eicosene, 4-methyl- Examples include 1-pentene, 3-methyl-1-butene, vinylcyclohexane, cyclopentene, cyclohexene, cyclooctene, norbornene, and 5-phenyl-2-norbornene.

  Among these, α-olefins (olefin compounds having a carbon-carbon double bond at the terminal), particularly α-olefins having 10 or less carbon atoms, are particularly preferred because of their high polymerization activity, and ethylene, propylene, 1-butene and 1-hexene are preferred. , 1-octene and the like. These olefinic monomers may be used alone or in combination of two or more.

1,3-butadiene, isoprene, 1,4-hexadiene, 3,5-dimethyl-1,5-hexadiene, 1,13-tetradecadiene, 1,5-cyclooctadiene, norbornadiene, 5-vinyl- A small amount of a diene monomer such as 2-norbornene, ethylidene norbornene, 5-phenyl-2-norbornene, dimethanooctahydronaphthalene or dicyclopentadiene may be used in combination. The amount of the diene monomer used is preferably 0 to 20 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the olefin monomer. The amount of the olefin monomer used is not limited, but from the viewpoint that a polymer having a large molecular weight can be obtained in a high yield, the olefin monomer / active species is 10 to 10 ⁹ , more preferably 100 to 10 ⁷ in terms of molar ratio. In particular, it is preferably 1000 to 10 ⁵ .

  Next, the manufacturing method of the graft copolymer of this invention is demonstrated.

  The polyolefin graft copolymer of the present invention is produced under emulsion polymerization conditions in which a coordination polymerization catalyst is dispersed in a latex of a specific macromonomer. You may add additives, such as an emulsifier and an organic solvent, as needed. There are no particular restrictions on the order and method of charging each raw material, but from the viewpoint of ease of reaction control, a co-polymerization catalyst, solvent, emulsifier, etc. are added to the latex of the macromonomer and dispersed, and then the olefin monomer is added. Is preferred.

  The macromonomer latex, the olefinic monomer, and the coordination polymerization catalyst may be added all at once in the reaction vessel or a part thereof may be added continuously or intermittently after a part is charged. Further, it may be charged either as it is or in a state where it is mixed with water and an emulsifier to form an emulsion. When the olefin monomer to be used is a liquid, it is preferable to charge after emulsifying the monomer from the viewpoint that generation of scale can be suppressed. When the olefinic monomer used is a gas at the reaction temperature, it may be charged as it is, or after the olefinic monomer is charged as a liquid or a coagulated solid at a low temperature, the system is heated to the reaction temperature. May be.

  The use ratio of the macromonomer and the olefin monomer can be arbitrarily set, but the olefin monomer is preferably 0.5 to 100 parts by weight, more preferably 1 to 33 parts by weight, based on 100 parts by weight of the macromonomer to be used. Is preferred. When the olefin monomer is a volatile liquid or gas having a boiling point of 100 ° C. or less, the olefin monomer is used in a large excess, and the reaction is stopped when the above preferred amount is polymerized, and the unreacted monomer is heated or reduced in pressure. It is also possible to remove.

  In the polymerization, a small amount of an organic solvent may be added in order to increase the solubility of the olefin monomer and the coordination polymerization catalyst and promote the reaction. Although there is no restriction | limiting in particular as the solvent, An aliphatic or aromatic solvent is preferable and these may be halogenated.

  Examples include toluene, ethylbenzene, xylene, chlorobenzene, dichlorobenzene, pentane, hexane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, butyl chloride, methylene chloride, and chloroform. Further, polar solvents such as tetrahydrofuran, dioxane, diethyl ether, acetone, ethanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate may be used. It is particularly preferred that the solvent is low in water solubility and is relatively easy to impregnate the macromonomer used and in which the catalyst is easily dissolved. Examples of such particularly preferred examples include methylene chloride, chloroform, chlorobenzene and butyl chloride. It is done.

  These solvents may be used alone or in combination of two or more. The total amount of the solvent used is preferably 30% by volume or less, more preferably 10% by volume or less, based on the total volume of the reaction solution. Alternatively, it is preferably 150 parts by weight or less, more preferably 50 parts by weight or less, with respect to 100 parts by weight of the macromonomer used. From the standpoint of improving the reaction rate, it is preferable to use a large amount of solvent, and from the standpoint that the reaction system can be easily maintained uniformly, it is preferable to use a small amount of solvent.

  The reaction temperature, pressure, and time for producing the graft copolymer of the present invention may be arbitrarily selected according to the boiling point and reaction rate of the raw material to be used, and are not particularly limited, but the reaction can be easily controlled and the production cost can be reduced. From the viewpoint of suppression, ordinary conditions under which general microsuspension polymerization / emulsion polymerization is performed are preferable.

  The reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 95 ° C, and still more preferably 20 to 80 ° C. The reaction pressure is preferably 0.05 to 10 MPa, more preferably 0.1 to 4 MPa, and the reaction time is preferably 10 minutes to 100 hours, more preferably 0.5 to 50 hours. The temperature and pressure may be constantly kept constant from the start to the end of the reaction, or may be changed continuously or stepwise during the reaction. When the olefin monomer used is a gas, the pressure may gradually decrease as the olefin monomer is consumed by the polymerization reaction, but the reaction may be performed by changing the pressure as it is, or depending on the amount consumed. The reaction may be carried out by always maintaining a constant pressure by supplying an olefin monomer or heating.

  The polyolefin graft copolymer obtained by the present invention is usually obtained as a latex. As for the particle size of the latex, a product corresponding to the particle size of the raw material macromonomer used and the amount of the reacted olefinic monomer is obtained. From the viewpoint that the dispersibility in a thermoplastic resin such as a polyolefin resin and the impact resistance of the obtained composition are particularly excellent, it is preferable to select a condition for obtaining a resin having a thickness of 20 nm to 20000 nm, more preferably 1 to 10 μm. More preferably, it is 1.5-3 micrometers. Depending on the reaction conditions, some latex particles may aggregate and precipitate, or free polyolefin may be formed as a by-product, and it is preferable to carry out the reaction under conditions without such precipitates.

  The latex containing the polyolefin graft copolymer of the present invention thus obtained may be used as it is, or it may be added with additives, blended with other latexes, diluted / concentrated / heat treated / dehydrated. You may use it, after adding processes, such as Qi processing. It may be applied on a substrate such as plastic, metal, wood, glass, etc. and used as a coating agent, paint, surface treatment agent, etc., or impregnated with fiber, paper, cloth, carbon fiber, glass wool, etc. It may be used as an agent or a curing agent. It may be used as a raw material for fiber reinforced plastics and cast films.

  The polyolefin-based graft copolymer of the present invention can be used for various purposes by dehydrating a latex containing it and recovering the solid component. Methods for recovering solid components from latex include, for example, a method of adding an electrolyte such as calcium chloride, magnesium chloride, calcium sulfate, magnesium sulfate, aluminum sulfate, and calcium formate to cause aggregation (salting out), or a hydrophilic organic material such as methanol. Moisture by mixing with a solvent, agglomerating solids by mechanical operations such as sonication, high-speed stirring, and centrifugation, or drying operations such as spray drying, heat drying, freeze drying, and vacuum drying However, the method is not limited to this. A washing operation with water and / or an organic solvent may be performed at any stage in a series of steps for recovering the polyolefin graft copolymer of the present invention from the latex.

  The polyolefin graft copolymer of the present invention can be recovered as a powder or a lump by aggregating or drying the solid component of the latex to remove moisture. Pellet by processing the dried product into pellets using an extruder or Banbury mixer, or by passing the water-containing (solvent-containing) resin obtained through dehydration (desolvation) from the agglomerates via a press dehydrator It can be processed into a shape and recovered. From the viewpoint of good handling properties, it is preferable to collect the powder preferably.

  The thermoplastic resin composition of the present invention can be produced by blending the polyolefin-based graft copolymer of the present invention with various other thermoplastic resins different from the polyolefin-based graft copolymer of the present invention.

  Other thermoplastic resins include commonly used resins such as polypropylene, polyethylene, ethylene propylene rubber, ethylene propylene diene rubber, ethylene octene rubber, polymethylpentene, ethylene cyclic olefin copolymer, ethylene-vinyl acetate copolymer. Polyolefin such as polymer, ethylene glycidyl methacrylate copolymer, ethylene methyl methacrylate copolymer; polyvinyl chloride, polystyrene, polymethyl methacrylate, methyl methacrylate-styrene copolymer styrene-acrylonitrile copolymer, styrene-acrylonitrile-N -Vinyl polymers such as phenylmaleimide copolymer and α-methylstyrene-acrylonitrile copolymer; polyester, polycarbonate, polyamide, polyphenylene ether- Polystyrene conjugate, polyacetal, polyether ether ketone, engineering plastics such as polyether sulfone are preferably exemplified.

  These other thermoplastic resins may be used alone or in combination of two or more. Among these, polyolefins such as polyethylene and polypropylene are preferable in that the dispersibility of the polyolefin graft copolymer of the present invention is good. The copolymer of the present invention is excellent in the effect of improving impact resistance particularly when blended with a polypropylene resin.

  The blending ratio of the other thermoplastic resin and the graft copolymer may be determined as appropriate so that the physical properties of the molded product can be obtained in a well-balanced manner. In order to maintain the characteristics of other thermoplastic resins, the amount of the graft copolymer is 0.1 parts or more, preferably 5 parts or more with respect to 100 parts of the thermoplastic resin. 500 parts or less, preferably 100 parts or less, with respect to 100 parts.

  Since the polyolefin-based graft copolymer of the present invention contains a polyolefin component, it exhibits good dispersibility even for low-polarity resins such as polyethylene and polypropylene, and has various functions derived from functional groups contained in macromonomers. Functions can be added.

  The polyolefin graft copolymer of the present invention can be used as a modifier for imparting various properties derived from vinyl macromonomers to a thermoplastic resin. For example, when (meth) acrylic macromonomer is used, polarities such as oil resistance, low contact angle, high surface tension, surface wettability, adhesiveness, paintability, dyeability, high dielectric constant, high frequency sealability, etc. Indicates physical properties that appear as a result of physical properties or polarity. Polarizers for thermoplastic resins, especially polyolefins (oil resistance, adhesiveness, paintability, dyeability, high frequency sealability, etc.), compatibilizers, primers, coating agents, adhesives, paints, polyolefin / filler composites It can be used for materials, surfactants for polyolefin nanocomposites, etc., and can also be used for thermoplastic elastomers, impact plastics, etc. having polyolefin as a resin component and (meth) acrylic rubber as a rubber component.

  The thermoplastic resin composition containing the graft copolymer of the present invention may be added to conventional additives known in the plastics and rubber industries, for example, plasticizers, stabilizers, lubricants, UV absorbers, oxidation agents, if necessary. It can contain compounding agents such as an inhibitor, a flame retardant, a flame retardant aid, a pigment, glass fiber, a filler, a polymer processing aid, and a matting agent.

  As a method for obtaining the thermoplastic resin composition containing the graft copolymer of the present invention, a method used for blending ordinary thermoplastic resins can be used, for example, the thermoplastic resin and the graft copolymer of the present invention. By melting and kneading the coalescence and optionally the additive component using a heat kneader, such as a single screw extruder, twin screw extruder, roll, plast mill, Brabender, Banbury mixer, kneader, high shear mixer, etc. Can be manufactured. Moreover, the kneading order of each component is not specifically limited, It can determine according to the apparatus to be used, workability | operativity, or the physical property of the thermoplastic resin composition obtained.

When the thermoplastic resin is produced by a microsuspension polymerization or emulsion polymerization method, the thermoplastic resin and the graft copolymer are both blended in a latex state, and then co-precipitated (co-deposited). It can also be obtained by agglomeration).
As a molding method of the thermoplastic resin composition containing the graft copolymer thus obtained, for example, an injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, which is used for molding a normal thermoplastic resin composition, is used. And the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these. In the following synthesis examples, examples and comparative examples, the solid content was calculated from the amount of the solid content remaining after about 1 mL of latex was put in an ointment can and heated and dried in an oven at 110 ° C. for 1 to 2 hours. The particle size (volume average particle size) was measured with a Microtrac particle size distribution measuring device (manufactured by Nikkiso).

(Synthesis Example 1) Into an 8L glass separable flask equipped with a macromonomer latex synthesis stirrer, thermometer, and reflux condenser, was charged 1.4L of pure water and 226g of sodium nitrite (Wako Pure Chemical Industries, Ltd.) Sodium nitrate was dissolved. Next, 1.7 L of pure water, 1.96 kg of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3.92 g of allyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), stearyl methacrylate (Wako Pure Chemical Industries, Ltd.) 19.6 g, Lauroyl peroxide (Nippon Yushi Co., Ltd., Parroyl L) 10 g, and sodium dodecylbenzenesulfonate aqueous solution (Kao Co., Neopelex G15, 15% by mass) 39.2 g were added to a homogenizer (special The mixture was stirred at 14,000 rpm for 50 minutes to obtain a uniform emulsion.

  Here, the emulsified monomer solution was added to the 8 L glass separable flask. The emulsified liquid adhering to the wall of the stainless steel container was washed out with 200 mL of pure water and poured into the same 8 L separable flask. When this reaction solution was heated to 60 ° C. in a water bath to start the reaction, the reaction was completed in about 5 hours, and a macromonomer latex solution of polybutyl acrylate having a solid content of 35% and a particle size of 1.67 μm was obtained. Obtained.

(Example 1) Copolymerization of macromonomer latex and ethylene The following chemical formula (3)

A palladium complex having the following structure (hereinafter also referred to as [N ^ N] PdMeCl) Am. Chem. Soc. It was synthesized by a known method described in literatures such as 1995, 117, 6414. 8 mL of an 80 mmol / L diethyl ether solution of [N ^ N] PdMeCl and 8 mL of an 80 mmol / L diethyl ether solution of LiB (C ₆ F ₅ ) 4 were mixed to precipitate LiCl, and [N ^ N] PdMe · B (C 16 mL of a 40 mmol / L diethyl ether solution of ₆ F ₅ ) 4 complex was prepared (hereinafter, this palladium complex solution is referred to as a Brookhart catalyst).

  Next, the diethyl ether solution of the Brookhart catalyst was concentrated and dried, and then 16 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to obtain a 40 mmol / L stock solution. In addition, these catalyst preparation was performed by normal Schlenk operation in argon atmosphere.

  After degassing 750 mL of the macromonomer latex of Synthesis Example 1, it was charged into an argon-substituted 1 L autoclave (manufactured by TAIATSU TECHNO, TAS-1 type autoclave, material SUS 316, maximum operating pressure 4 MPa, maximum operating temperature 100 ° C.). A methylene chloride solution (4 mmol / L) of 15 mL of Brookhart catalyst was emulsified with 150 mg of sodium dodecyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of pure water by an ultrasonic homogenizer (manufactured by SMT company, ultrasonic disperser UH-600). In addition, the action time of the ultrasonic wave at the time of emulsification is about 10 seconds. The emulsified Brookhart catalyst solution was introduced with a syringe into a 1 L autoclave in which the latex solution was previously charged.

  Thereafter, ethylene gas (manufactured by Sumitomo Seika Co., Ltd.) was introduced, the inside of the autoclave was set to 3 MPa, and the reaction was performed at room temperature for 5 hours. The ethylene gas used here was purified through a dehydration column (manufactured by Nikka Seiko Co., Ltd., dry column HDF 300-A3) and a deoxygenation column (manufactured by Nikka Seiko Co., Ltd., GASCLEAN GC-HDF 300-M). After the reaction, unreacted ethylene gas was removed to obtain a copolymer latex. After the reaction, unreacted ethylene gas was removed to obtain a copolymer latex. The particle diameter of the latex of the obtained copolymer was 1.7 μm. Further, Turn Over Number (hereinafter abbreviated as TON) indicating the number of ethylene monomer incorporation per unit catalyst in this reaction is TON = 5600 [mol Ethylene / mol cat. ]Met.

  About 100 mL of 10% calcium chloride aqueous solution was added to the latex of the product for salting out, followed by filtration, washing with water and drying, to obtain a polyolefin graft copolymer (copolymer of Example 1).

Example 2 Impact Resistance of Polypropylene Resin Composition with Addition of Macromonomer Latex and Ethylene Copolymer Polyolefin of (Example 1) in 100 parts by weight of polypropylene resin (Prime Polymer, Random Polypropylene, F232DC) 20 parts by weight of the graft copolymer was blended and kneaded at 170 ° C. for 5 minutes at a rotation speed of 17 & 14 using a Φ8 ″ × L20 ″ type mixing roll machine (manufactured by Nippon Roll Manufacturing Co., Ltd.). The material was pulverized by a pulverizer VC-210 (manufactured by Horai Iron Works Co., Ltd.), and an ASTM No. 1 dumbbell was injection-molded at a cylinder temperature of 190 ° C. using an 80 t molding machine (manufactured by Toshiba).

  A test piece having a thickness of 3 mm, a width of 12 mm, and a length of 60 mm was cut out from the dumbbell, a notch was added, and an impact resistance test was performed at 23 ° C. and 50% RH at a test speed of 5 mm / min according to ASTM D-256. As a result, the polypropylene resin composition to which the polyolefin graft copolymer of Example 1 was added had an Izod value of 250 J / m, which was higher than the impact resistance of the polypropylene resin alone (Izod = 192 J / m). It was a big value.

(Comparative Synthesis Example 1) Synthesis of Macromonomer Latex An 8 L glass separable flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 1.4 L of pure water and 226 g of sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) Sodium nitrite was dissolved. Next, 1.7 L of pure water, 1.96 kg of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 9.8 g of allyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), stearyl methacrylate (Wako Pure Chemical Industries, Ltd.) 19.6 g, Lauroyl peroxide (Nippon Yushi Co., Ltd., Parroyl L) 10 g, and sodium dodecylbenzenesulfonate aqueous solution (Kao Co., Neopelex G15, 15% by mass) 39.2 g were added to a homogenizer (special The mixture was stirred at 14,000 rpm for 40 minutes to obtain a uniform emulsion.

  Here, the emulsified monomer solution was added to the 8 L glass separable flask. The emulsified liquid adhering to the wall of the stainless steel container was washed out with 200 mL of pure water and poured into the same 8 L separable flask. When this reaction solution was heated to 60 ° C. in a water bath to start the reaction, the reaction was completed in about 6 hours. A macromonomer latex solution of polybutyl acrylate having a solid content of 35% and a particle size of 0.715 μm was obtained. Obtained.

(Comparative Example 1) Copolymerization of Macromonomer Latex and Ethylene Copolymer latex was prepared in the same manner as in Example 1 except that the macromonomer latex of Comparative Synthesis Example 1 was used instead of the macromonomer latex of Synthesis Example 1. Got. In this reaction, TON = 1600 [mol Ethylene / mol cat. ]Met.
About 100 mL of 10% calcium chloride aqueous solution was added to the latex of the product for salting out, followed by filtration, washing with water and drying, and a polyolefin graft copolymer was obtained.

(Comparative Example 2) Impact Resistance of Polypropylene Resin Composition with Addition of Macromonomer Latex and Ethylene Copolymer An operation according to Example 2 was performed except that the copolymer obtained in Comparative Synthesis Example 1 was used. The Izod value of the molded body obtained was 193 J / m.

Claims (8)

  A polyolefin-based graft copolymer produced by polymerizing an olefinic monomer with a late transition metal-based coordination polymerization catalyst in a macromonomer latex, wherein the macromonomer has a particle diameter of 1 to 5 μm. Polyolefin graft copolymer.   The polyolefin graft copolymer according to claim 1, wherein the macromonomer is a (meth) acrylic macromonomer.   The polyolefin graft copolymer according to any one of claims 1 to 2, wherein the macromonomer is a butyl acrylate macromonomer.   The late transition metal-based coordination polymerization catalyst is a complex comprising a ligand having two imine nitrogens and a late transition metal selected from groups 8 to 10 of the periodic table. The polyolefin-type graft copolymer of any one of these.   The polyolefin graft copolymer according to any one of claims 1 to 4, wherein the olefin monomer is an α-olefin having 2 to 20 carbon atoms.   The manufacturing method of the polyolefin-type graft copolymer of any one of Claims 1-5.   A thermoplastic resin composition comprising the polyolefin graft copolymer according to any one of claims 1 to 5 and another thermoplastic resin.   The manufacturing method of the thermoplastic resin composition of Claim 7.