JPWO2006043428A1 - Method for producing polyolefin graft copolymer - Google Patents

Abstract

An object of the present invention is to suppress the generation of scale and improve productivity in the production of a graft copolymer of a latex-like macromonomer and a liquid olefin monomer. In the method for producing a polyolefin graft copolymer in which an olefin monomer is polymerized by a late transition metal-based coordination polymerization catalyst in a macromonomer latex, the macromonomer latex is emulsified in advance in the macromonomer latex. It can be achieved by the production of a polyolefin-based graft copolymer characterized by being added to the inside.

Description

  The present invention relates to a polyolefin graft copolymer produced by polymerizing an olefin monomer with a coordination polymerization catalyst in a macromonomer latex.

  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 a polar compound reacts or coordinates with a complex or a catalytically active species to lose or decompose its activity. 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 (Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3), when such a catalyst is used, a polar solvent such as tetrahydrofuran, ether, acetone, ethyl acetate, water or the like is used. Polyolefin can be polymerized without losing activity even in the presence, and a copolymer with a polar monomer such as a polar vinyl monomer such as an alkyl acrylate 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. For this reason, a technique capable of obtaining a polyolefin copolymer having a high content of polar monomers has been desired.

In order to solve these problems, Patent Document 1 discloses a copolymer obtained by copolymerizing a macromonomer and an olefin monomer. In this technique, a (meth) acrylic macromonomer or isobutylene macromonomer produced by solution polymerization, emulsion polymerization or the like can be used as an example of a macromonomer. However, when the macromonomer is used in a latex state, the dispersibility of the olefin monomer is poor and the reaction becomes non-uniform, so that part of the product may become scale.
Chemical Review, 2000, 100, 1169 Journal of Synthetic Organic Chemistry, 2000, 58, 293 Angwante Chemie International Edition, 2002, 41, 544 JP 2003-147032 A

  Accordingly, an object of the present invention is to suppress the generation of scale and improve productivity in the production of a graft copolymer of a latex-like macromonomer and a liquid olefin monomer.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, they have found that the amount of scale generated in the product can be suppressed by improving the preparation method of the olefin monomer, and completed the present invention.

  That is, the present invention relates to a method for producing a polyolefin graft copolymer in which an olefin monomer is polymerized by a late transition metal coordination polymerization catalyst in a macromonomer latex, and the olefin monomer is pre-emulsified. And adding the macromonomer to the latex in a method for producing a polyolefin-based graft copolymer.

  As a preferred embodiment, the late transition metal complex-based coordination polymerization catalyst is a complex composed of a ligand having two imine nitrogens and a transition metal selected from groups 8 to 10 of the periodic table. The present invention relates to a method for producing a polyolefin graft copolymer.

  As a preferred embodiment, a polyolefin, wherein the late transition metal complex coordination polymerization catalyst is a complex comprising an α-diimine type ligand and a transition metal selected from Group 10 of the periodic table. The present invention relates to a method for producing a graft copolymer.

  As a preferred embodiment, the late transition metal complex-based coordination polymerization catalyst is an active species represented by the following general formula (1) or (2) after reaction with the cocatalyst. And a method for producing a polyolefin-based graft copolymer.

(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 hetero atom capable of coordinating to M, and may be connected to R ₅ , or X may not be present, L ⁻ is any anion .)

  In a preferred embodiment, the macromonomer is a poly (meth) acrylic monomer composed of a monomer having a group capable of copolymerizing with a (meth) acrylic monomer and an olefinic monomer. The present invention relates to a method for producing a copolymer.

  As a preferred embodiment, the present invention relates to a method for producing a polyolefin graft copolymer, wherein the polyolefin in the polyolefin graft copolymer has a 1, ω-structure.

  As a preferred embodiment, the present invention relates to a method for producing a polyolefin graft copolymer, wherein the olefin monomer is 1-hexene.

  According to the production method of the present invention, generation of scale can be suppressed when a macromonomer and an olefin monomer are copolymerized. As a result, it is possible to improve the production efficiency of the polyolefin-based copolymer.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a method for producing a polyolefin-based graft copolymer obtained by copolymerizing an olefin-based monomer with a macromonomer using a coordination polymerization catalyst in a macromonomer latex. The olefin-based monomer is added to the macromonomer latex in a pre-emulsified state.

  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. In order for the macromonomer used in the present invention to graft copolymerize with the olefin monomer, the macromonomer needs to have a group capable of copolymerizing with the olefin. From the viewpoint of good graft efficiency, it is preferable to have a group capable of copolymerizing with at least one, preferably 10 or more olefins, per macromonomer molecule. The group that can be copolymerized with the olefin is not particularly limited by any functional group, but from the viewpoint of high coordination polymerization reactivity, an allyl group, a cycloalkenyl group, a styryl group, and a (meth) acryl group are included. A (meth) acryl group, an allyl group, or a dicyclopentenyl group is particularly preferable. These functional groups are preferably at the molecular chain ends.

  Various types of main macromonomer main chain structures, functional group introduction positions, and production methods are known. The main chain structure is known to be linear, cyclic, or branched. When the macromonomer is in the form of particles, there are various types such as crosslinked particles, non-crosslinked particles, single layer structured particles, multilayer structured particles, and multiphase structured particles. The thing of a simple structure is 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 production method can be synthesized by various methods such as anionic polymerization, cationic polymerization, radical polymerization, coordination polymerization, polycondensation, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In the present invention, since the macromonomer is copolymerized with the olefin in the latex state, emulsion polymerization is preferred as a method for producing the macromonomer used in the present invention. When the macromonomer used in the present invention is in the form of particles, it may be crosslinked particles or non-crosslinked particles. The particles may be uniform particles having only a single layer, or may be multi-layered particles composed of a plurality of layers. Salami-like multiphase structure particles in which other resin phases are dispersed in the matrix resin phase may be used.

  When the macromonomer used in the present invention is a uniform particle having only a single layer, such macromonomers include various ones such as (meth) acrylic, aromatic vinyl, and vinyl cyanide. Any known (meth) acrylic macromonomer having a poly (meth) acrylic acid ester as a main component is preferable. In addition, (meth) acryl in this specification means both methacryl and acryl.

  When the macromonomer used in the present invention is a macromonomer having a multilayer structure, all layers may be produced by radical polymerization, and other monomers capable of radical polymerization in a layer polymerized by a method other than radical polymerization. A macromonomer obtained by copolymerization of The macromonomer having a multilayer structure used in the present invention is a polymer obtained by emulsion polymerization of at least one monomer capable of emulsion polymerization, and a monomer having a different type or composition is obtained by emulsion polymerization. It is a macromonomer obtained by graft copolymerization. Techniques for producing a polymer having a multilayer structure by emulsion polymerization are known, and are disclosed in JP-A No. 2001-89648, JP-A No. 2002-363372, JP-A No. 10-316724, and the like.

  A (meth) acrylic macromonomer composed of a single layer, which is an example of the macromonomer used in the present invention, is composed of (A) (meth) acrylic monomer (hereinafter sometimes referred to as compound (A)) and (B ) A (meth) acryl obtained by copolymerizing a monomer (hereinafter referred to as compound (B)) having at least one radical polymerizable unsaturated group and a group copolymerizable with at least one olefin monomer in the molecule. It is preferable that it is a system macromonomer, and if necessary, (C) a monomer having a radically polymerizable unsaturated group copolymerizable with the compound (A) and / or the compound (B) (hereinafter referred to as compound ( C)) may be contained. There is no restriction | limiting in particular in the usage-amount of each component, Although you may use it in arbitrary quantity, Compound (A) becomes like this. Preferably it is 50-99.99 weight%, More preferably, it is 75-99.9 weight. %. If the amount is too small, the properties expected from the characteristics of the (meth) acrylic polymer when the resulting polyolefin-based graft copolymer is added to a thermoplastic resin such as a polyolefin resin, such as low contact angle and high surface tension. There is a possibility that the effect of improving the physical properties exhibiting polarity or the physical properties that appear as a result of polarity, such as wettability, adhesiveness, paintability, dyeability, high dielectric constant, oil resistance, and high-frequency sealing properties, may be reduced. The compound (B) is preferably used in an amount of 0.01 to 25% by weight, more preferably 0.1 to 10% by weight. If the amount is too small, grafting with the olefinic monomer will be insufficient. If the amount is too large, the compound (B) is generally expensive, which is economically disadvantageous. Compound (C) is preferably used in an amount of 0 to 50% by weight, more preferably 0 to 25% by weight. If the amount is too large, the effect of improving physical properties expected from the characteristics of the (meth) acrylic polymer when the polyolefin graft copolymer is added to the polyolefin resin may be reduced. However, the total of these compound (A), compound (B) and compound (C) is 100% by weight.

  The compound (A) is a component for forming the main skeleton of the (meth) acrylic macromonomer. Specific examples of the compound (A) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid. Acrylic acid alkyl esters such as 2-hydroxypropyl and methoxytripropylene glycol acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, glycidyl methacrylate, methacrylic acid Examples include, but are not limited to, alkyl methacrylates such as hydroxyethyl; (meth) acrylic acid such as acrylic acid and methacrylic acid, and acid anhydrides and metal salts thereof.Among these, (meth) acrylic acid alkyl ester having an alkyl group having 2 to 18 carbon atoms is preferable, and acrylic acid n is more preferable from the viewpoint of availability and economical efficiency of the obtained (meth) acrylic macromonomer. -Butyl, t-butyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate are preferred. These compounds (A) may be used independently and may use 2 or more types together.

  The component (B) is copolymerized with the component (A) and optionally the component (C) by the radically polymerizable unsaturated group that it has to form a copolymer, and as a result, the side chain of the copolymer or It is a component for introducing a group capable of copolymerizing with an olefin monomer at the terminal and enabling graft copolymerization of the copolymer and the olefin monomer. The group that can be copolymerized with the olefinic monomer is not particularly limited as long as it is any functional group, and may be contained either inside or at the end of the monomer molecule, but it has high coordination polymerization reactivity. Therefore, an allyl group (α-olefin structure), a cycloalkenyl group, a styryl group, and a (meth) acryl group are preferable, and a (meth) acryl group, an allyl group, and a dicyclopentenyl group are particularly preferable. These functional groups are preferably at the molecular chain ends.

  When the group that can be copolymerized with the olefin monomer is a group that has both radical polymerizability and coordination polymerizability, the radical polymerizable unsaturated group of the component (B) and the group that can copolymerize with the olefin monomer are The same group may be sufficient and a different group may be sufficient. When they are the same group, the component (B) contains two or more radically polymerizable unsaturated groups (and also a group copolymerizable with the olefin monomer) in one molecule. When only a part of these radically polymerizable unsaturated groups undergo radical polymerization during the synthesis of acrylic macromonomer, the reaction is stopped, and the unreacted radically polymerizable unsaturated group in the resulting (meth) acrylic macromonomer The reaction can be controlled to leave (and also a group copolymerizable with the olefinic monomer).

  Representative examples of the compound (B) include, for example, allyl methacrylate, allyl acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, ethylene glycol dicyclopentenyl ether methacrylate, ethylene glycol diacrylate. Examples include cyclopentenyl ether, dicyclopentenyl methacrylate, and dicyclopentenyl acrylate. These compounds (B) may be used independently and may use 2 or more types together. Among these, allyl methacrylate, ethylene glycol dicyclopentenyl ether, ethylene glycol dicyclopentenyl ether, dicyclopentenyl methacrylate, dicyclopentenyl from the point that the grafting efficiency with polyolefin-based monomer is good. Acrylate is preferred.

  The compound (C) is a component for adjusting various physical properties such as elastic modulus, Tg, and refractive index of the (meth) acrylic macromonomer. As the compound (C), any monomer that can be copolymerized with the compound (A) and / or the compound (B) can be used without particular limitation, and one kind may be used alone, or two or more kinds may be used in combination. Also good. Specific examples of such compound (C) include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,3-butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl. Although ethyl ether etc. are mentioned, it is not limited to these.

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

  In the emulsion polymerization, the entire amount of the raw material may be charged at once, or the remaining part may be added continuously or intermittently after part of the raw material has been charged. For example, by reacting the compound (A) and then adding the compound (B) to react, it is possible to design a structure in which the coordination polymerizable unsaturated groups are unevenly distributed in the surface layer portion of the (meth) acrylic macromonomer particles. it can. In addition, a method in which any one of the compound (A), the compound (B), the compound (C) or a mixture thereof is preliminarily emulsified with an emulsifier and water, a compound (A), a compound (B), A method of adding an emulsifier or an aqueous solution of an emulsifier continuously or divided separately from any of the compounds (C) or a mixture thereof can be employed.

  There is no restriction | limiting in particular about the quantity of the water used for emulsion polymerization, What is necessary is just an amount required in order to emulsify a compound (A), a compound (B), and a compound (C), and a compound (A) and a compound (B ) And the compound (C) may be used in a weight of 1 to 20 times the total amount. If the amount of water used is too small, the proportion of the hydrophobic compound (A), compound (B) and compound (C) will be too high and the emulsion will not phase invert from water-in-oil to oil-in-water, Water is less likely to be 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 the 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 (meth) acrylic macromonomer, but is preferably 0.1 to 10 with respect to 100 parts by weight of the monomer. Parts by weight. In addition, the average particle diameter of the (meth) acrylic macromonomer can be controlled using a normal emulsion polymerization technique such as increase / decrease in the amount of emulsifier used. The average particle diameter of the (meth) acrylic macromonomer is preferably 20 to 20000 nm, more preferably, from the viewpoint that a good dispersion state is obtained when the polyolefin graft copolymer obtained after copolymerization is blended with a thermoplastic resin. It is desirable to be in the range of 50 to 2000 nm, more preferably 100 to 1000 nm.

  The polymerization initiator used for emulsion polymerization is not particularly limited, and known ones can be used. 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.

  In addition to the pyrolytic method, a redox catalyst comprising a polymerization initiator and an activator (metal salt or metal complex), a chelating agent, and a reducing agent can also be used as these initiators. 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 bisulfite, 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 include polyaminocarboxylates such as ethylenediamine diacetate, oxycarboxylic acids such as citric acid, those that form water-soluble chelate compounds such as condensed phosphates, and oil-soluble chelates such as dimethylglyoxime, oxine, and dithizone. Those that form compounds. Of these, polyaminocarboxylates such as ethylenediamine diacetate and oxycarboxylic acids such as citric acid are preferred.

  Examples of the activator include metal salts or metal chelates such as iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, and cobalt. Preferred examples include ferrous sulfate and sulfuric acid. Copper, hexacyano iron (III) potassium, etc. are 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 monomer. A preferable amount of the chelating agent 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 monomer. The preferable use amount of the activator is 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer. 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.

  In the emulsion polymerization, a chain transfer agent may be used as necessary. The chain transfer agent is not particularly limited, and known ones can be used. 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 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.

  When the macromonomer used in the present invention is a macromonomer having a multilayer structure, the type and combination of polymers constituting each layer are not particularly limited, and conventionally known ones may be used. There is no restriction | limiting in the number of layers, You may have two or more arbitrary numbers of layers. The polymer constituting each layer may be crystalline or non-crystalline. It may be a rubbery polymer or a hard polymer. The combination of the polymers in each layer can be arbitrarily selected. A multilayer structure containing at least one layer of a rubbery polymer and at least one layer of a hard polymer is preferable from the viewpoint that the resulting copolymer has good handling properties. A two-layer structure having a hard polymer shell layer around is particularly preferred. The rubbery polymer and the hard polymer mentioned here are the same as those generally meaning in the core-shell polymer field.

  The main chain skeleton of the polymer constituting each layer of the multilayer structure may be linear or branched, and may have a three-dimensional network structure by crosslinking. From the viewpoint that an appropriate elastic modulus can be imparted, it is preferable to take a three-dimensional network structure by crosslinking.

  The macromonomer having a multilayer structure used in the present invention can be produced by a general emulsion polymerization technique. For example, after forming a first layer by emulsion polymerization of a monomer capable of radical polymerization, a second layer can be formed by adding and polymerizing the monomer to obtain a macromonomer having a two-layer structure. Alternatively, a two-layer macromonomer can be obtained by adding a monomer capable of radical polymerization and a radical initiator to a latex of polysiloxane having a radical reactive group. Furthermore, it is also possible to increase the number of layers by repeating the polymerization by adding monomers. You may add an emulsifier, a polymerization initiator, a chain transfer agent, etc. as needed.

  The same type of emulsifier, polymerization initiator, and chain transfer agent used for polymerization of each layer of the macromonomer having a multilayer structure may be used for each layer, or different types may be used for each layer.

  The particle size of the macromonomer having a multilayer structure used in the present invention is 20 to 20000 nm, preferably 50 to 2000 nm, and more preferably 100 to 1000 nm. When a macromonomer having this particle size is used, the dispersibility of the obtained polyolefin graft copolymer in a thermoplastic resin such as a polyolefin resin is particularly excellent. The average particle size of the macromonomer as used in the present invention is measured by a dynamic light scattering method with a Submicron Particle Size Model 370 (manufactured by NICOMP, laser wavelength 632.8 nm) using a sample in which the macromonomer is dispersed in water. The volume average particle diameter.

When the macromonomer having a multilayer structure used in the present invention contains a rubber-like polymer and a hard polymer, the polymer constituting the rubber-like polymer layer has a glass transition temperature of 20 ° C. or lower. More preferably, it is preferably 0 ° C. or lower, particularly preferably −20 ° C. or lower. The polymer constituting the hard polymer layer preferably has a glass transition temperature of 30 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably 80 ° C. or higher. The glass transition temperature (Tg) of the polymer and the measurement method thereof are determined from the data of POLYMER HANDBOOK FORTH EDITION (John Willy & Sons) for the homopolymer, and the copolymer. Using the data, the Fox equation Tg ⁻¹ = w ₁ Tg ₁ ⁻¹ + w ₂ Tg ₂ ⁻¹
Is required. Here, Tg ₁ and Tg ₂ are glass transition temperatures of the respective components, and w ₁ and w ₂ are weight fractions of the respective components.

  The rubber-like polymer and the hard polymer may have a core-shell structure in which the rubber-like polymer layer is inside and the hard polymer layer is outside, or the rubber-like polymer layer is outside and the hard polymer layer is inside. The core shell structure may be taken. A partially covered core-shell structure in which the shell layer covers only a part of the core layer may be used, or a salami-like structure in which a plurality of core particles are dispersed in the shell layer may be used. From the viewpoint that the handleability of the resulting polyolefin-based graft copolymer can be further improved, a core-shell structure in which the rubber-like polymer layer is on the inner side (core) and the hard polymer layer is on the outer side (shell) is preferable.

  The weight ratio of the rubbery polymer / hard polymer is excellent in the balance between the handleability of the resulting polyolefin-based graft copolymer and the low elastic modulus of the thermoplastic resin composition containing the graft copolymer. From a viewpoint, 70 / 30-95 / 5 are preferable, More preferably, it is 80 / 20-90 / 10.

  Specific examples of the polymer constituting the rubber-like polymer layer include diene rubber, (meth) acrylic rubber, silicone rubber, styrene-diene copolymer rubber, (meth) acrylic-silicone composite rubber, and the like. Of these, (meth) acrylic rubber and silicone rubber are preferred. The (meth) acrylic rubber referred to in the present invention is a rubbery polymer composed of 50% by weight or more of (meth) acrylic monomer and less than 50% by weight of monomer copolymerizable therewith. The (meth) acrylic monomer constituting the (meth) acrylic rubber is preferably 75% by weight or more, more preferably 90% by weight or more, and the monomer copolymerizable therewith is preferably less than 25% by weight. More preferably, it is 10% by weight. The silicone rubber referred to in the present invention is a rubber-like polymer composed of 50% by weight or more of organosiloxane and less than 50% by weight of a monomer copolymerizable therewith. The organosiloxane constituting the silicone rubber is preferably 75% by weight or more, more preferably 90% by weight or more, and the monomer copolymerizable therewith is preferably less than 25% by weight, more preferably 10% by weight. It is.

  Hereinafter, a rubbery polymer core-hard polymer shell structure, which is a preferred example of a macromonomer having a multilayer structure, will be described.

  A (meth) acrylic rubber, which is a preferred example of a polymer constituting the rubbery polymer core, is composed of (D) (meth) acrylic monomer (hereinafter referred to as compound (D)) and (E) at least 2 in the molecule. It is preferably a (meth) acrylic rubber obtained by copolymerizing a monomer having two radical polymerizable unsaturated groups (hereinafter referred to as compound (E)), and if necessary, (F) the compound (D ) And / or a monomer copolymerizable with the compound (E) (hereinafter referred to as compound (F)). There is no restriction | limiting in particular in the usage-amount of each component, Although you may use it in arbitrary quantity, Compound (D) becomes like this. Preferably it is 50-99.99 weight%, More preferably, it is 75-99.9 weight. %. As the amount of the compound (D) used is larger, an increase in elastic modulus when the polyolefin-based graft copolymer is added to the polyolefin resin can be suppressed. The compound (E) is preferably 0.01 to 25% by weight, more preferably 0.1 to 10% by weight. When the amount used is in this range, the balance between the graft efficiency and the low elastic modulus of the rubber-like polymer and the hard polymer is particularly good. The compound (F) is preferably 0 to 50% by weight, more preferably 0 to 25% by weight. However, the total of these compound (D), compound (E) and compound (F) is 100% by weight.

  The compound (D) is a component for forming the main skeleton of the (meth) acrylic rubber. Specific examples of the compound (D) include (meth) methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and the like. Examples include, but are not limited to, acrylic esters. When polymerized alone, such as t-butyl acrylate, hexadecyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and methacrylic acid, The (meth) acrylic monomer to be combined can also be used if the amount used is adjusted so as to be copolymerized with other (D) component, (E) component, and (F) component to form a rubbery polymer. . Among these, (meth) acrylic acid alkyl esters having an alkyl group having 2 to 18 carbon atoms are preferable, and more preferably n-acrylic acid n-, from the viewpoint of availability and economical efficiency of the obtained (meth) acrylic rubber. Butyl is preferred. These compounds (D) may be used independently and may use 2 or more types together.

  The compound (E) is a component for enabling graft copolymerization of a rubber-like polymer serving as a core and a hard polymer serving as a shell. A part of the compound (E) is copolymerized with the compound (D) and the compound (F), and only one of the radical polymerizable unsaturated groups in the molecule is unreacted in the (meth) acrylic rubber. The radical polymerizable unsaturated group is introduced to enable copolymerization with a hard polymer. In the remainder, a plurality of radically polymerizable unsaturated groups in the molecule react to introduce a crosslinked structure into the (meth) acrylic rubber.

  Specific examples of the compound (E) include, for example, allyl methacrylate, allyl acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, and the like. These compounds (E) may be used independently and may use 2 or more types together. Of these, allyl methacrylate is preferred.

  The compound (F) is a component for adjusting various physical properties such as elastic modulus, Tg, and refractive index of the (meth) acrylic rubber. As the compound (F), any monomer that can be copolymerized with the compound (D) and / or the compound (E) can be used without particular limitation, and one kind may be used alone, or two or more kinds may be used in combination. Also good. Specific examples of such compound (F) include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,3-butadiene, isoprene, chloroprene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl. Although ethyl ether etc. are mentioned, it is not limited to these.

  The (meth) acrylic rubber can be produced by radical (co) polymerization by an ordinary emulsion polymerization method and can be obtained as a latex.

  In the emulsion polymerization, the whole amount of the raw materials may be mixed at one time, or after a part is mixed, the rest may be added continuously or intermittently. A method of adding any of compound (D), compound (E), compound (F) or a mixture thereof after emulsification with an emulsifier and water, compound (D), compound (E), compound Apart from any one of (F) or a mixture thereof, a method of adding an emulsifier or an aqueous solution of the emulsifier continuously or in a divided manner can be employed.

  There is no restriction | limiting in particular about the quantity of water used for emulsion polymerization, What is necessary is just an amount required in order to emulsify a compound (D), a compound (E), and a compound (F), and a compound (D), a compound (E ) And the total amount of compound (F) may be 1 to 20 times the weight.

  As the emulsifier, the initiator, and the chain transfer agent used for the emulsion polymerization, those mentioned as preferred examples in the method for producing the (meth) acrylic macromonomer can be used.

  Silicone rubber, which is another preferred example of the polymer constituting the rubber-like polymer core, comprises an organosiloxane (hereinafter referred to as compound (G)) and a functional group capable of reacting with the compound (G) in the molecule. And a silicone-based rubber obtained by reacting a monomer having a radically polymerizable unsaturated group (hereinafter referred to as compound (H)), and if necessary, the compound (G) and / or compound A compound having a functional group capable of reacting with (H) (hereinafter referred to as compound (I)) may be contained. The amount of each component used is not particularly limited and may be used in any amount, but the preferred amount used is preferably 50 to 99.99% by weight of compound (G), more preferably 75 to 99.90% by weight. It is. The more the copolymer, the better the release characteristics, moldability, gas permeability, water repellency, weather resistance, surface lubricity, softness, low temperature brittleness, etc., which are the characteristics of silicone. Compound (H) is preferably 0.01 to 25% by weight, more preferably 0.1 to 10% by weight. When the amount used is within this range, the graft efficiency of the rubbery polymer and the hard polymer is particularly good. When using compound (I), it is preferably 0 to 50% by weight, more preferably 0 to 25% by weight. However, the total of these compound (G), compound (H) and compound (I) is 100% by weight.

  The compound (G) is a component for constituting the main skeleton of the silicone rubber. The compound (G) may be of any molecular weight as long as it can be emulsion-polymerized, but preferably has a molecular weight of 1000 or less, particularly preferably 500 or less. As the compound (G), linear, cyclic or branched compounds can be used. From the economical point of the emulsion polymerization system, a cyclic siloxane is preferred. Specific examples of such cyclic siloxane include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 1 2,3,4-tetrahydro-1,2,3,4-tetramethylcyclotetrasiloxane and the like. Bifunctional alkoxysilanes can also be used as the compound (G), and specific examples thereof include dimethoxydimethylsilane and diethoxydimethylsilane. Furthermore, cyclic siloxane and bifunctional alkoxysilane can be used in combination. These compounds (G) may be used independently and may use 2 or more types together. Compound (H) reacts with compound (G) by the functional group that it has. As a result, a radically polymerizable unsaturated group can be introduced into the side chain or terminal of the resulting silicone rubber. This radically polymerizable unsaturated group is a component for enabling graft copolymerization of the silicone rubber and the hard polymer shell.

  As the group for reacting with the compound (G), a hydrolyzable alkoxy group or silanol group bonded to a silicon atom, or a group having a cyclic siloxane structure capable of ring-opening copolymerization with the compound (G) is preferably used. .

  Specific examples of compound (H) include, for example, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- Alkoxysilane compounds such as (meth) acryloxypropyltriethoxysilane, and 1,3,5,7-tetrakis ((meth) acryloxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1, Examples include organosiloxanes such as 3,5-tris ((meth) acryloxypropyl) -1,3,5-trimethylcyclotrisiloxane, among which 3- (meth) acryloxypropylmethyldimethoxysilane has good reactivity. It is particularly preferable in that it is. These compounds (H) may be used independently and may use 2 or more types together.

  Compound (I) is a component for reacting with compound (G) and / or compound (H) to adjust the physical properties of the silicone rubber. For example, when a polyfunctional silane compound having at least three hydrolyzable groups bonded to a silicon atom or a partially hydrolyzed condensate thereof is used, a crosslinked structure is introduced into the silicone rubber, and Tg, elastic modulus, etc. Can be adjusted. Specific examples of such polyfunctional silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, methyltri (methoxyethoxy) silane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and the like. Examples thereof include alkoxysilanes and hydrolysis condensates thereof; acetoxysilanes such as methyltriacetoxysilane, ethyltriacetoxysilane and tetraacetoxysilane, and hydrolysis condensates thereof. These compounds (I) may be used independently and may use 2 or more types together.

  The silicone rubber can be produced by a usual polymerization method performed under acidic or basic conditions. For example, the compound (G), the compound (H), and the compound (I) used as necessary are made into an emulsion together with an emulsifier and water using a homomixer, a colloid mill, a homogenizer, etc., and then the pH of the system is changed to alkylbenzenesulfonic acid. It can be prepared by a method such as adjusting to 2 to 4 with or sulfuric acid and polymerizing by heating and then neutralizing by adding an alkali component such as sodium hydroxide or potassium hydroxide.

  In addition, after adding all the raw materials collectively, after stirring for a fixed time, pH may be made small, and the remaining raw materials may be added sequentially to the emulsion which prepared a part of raw materials and made pH low. When adding sequentially, it may be added as it is or mixed with water and an emulsifier to form an emulsified liquid, but it is preferable to use a method of adding in an emulsified state from the viewpoint of polymerization rate. Although there is no restriction | limiting in particular in reaction temperature and time, 0-100 degreeC is preferable and 50-95 degreeC is more preferable from the ease of reaction control. The reaction time is preferably 1 to 100 hours, more preferably 5 to 50 hours.

  When polymerization is carried out under acidic conditions, the Si—O—Si bond forming the polyorganosiloxane skeleton is usually in an equilibrium state between cleavage and bond formation. This equilibrium changes depending on the temperature, and the lower the temperature, the easier the formation of high molecular weight polyorganosiloxane. Therefore, in order to obtain a high molecular weight polyorganosiloxane, it is preferable to polymerize the compound (G) by heating and then perform aging by cooling to a polymerization temperature or lower. Specifically, the polymerization is carried out at 50 ° C. or higher, and when the polymerization conversion rate reaches 75 to 90%, more preferably 82 to 89%, the heating is stopped and the temperature is cooled to 10 to 50 ° C., preferably 20 to 45 ° C. Then, aging can be performed for about 5 to 100 hours. In addition, the polymerization conversion rate said here means the conversion rate to the low volatile matter of the compound (G) in a raw material, a compound (H), and the compound (I) depending on the case.

  The amount of water used for the emulsion polymerization is not particularly limited, and may be any amount necessary for emulsifying and dispersing the compound (G), the compound (H), and the compound (I). What is necessary is just to use a 1-20 times weight with respect to the total amount of (H) and compound (I).

  As the emulsifier used for the emulsion polymerization, any known emulsifier can be used without particular limitation as long as it does not lose the emulsifying ability in the pH range where the reaction is carried out. Examples of such emulsifiers include, for example, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, and the like. Further, the amount of the emulsifier used is not particularly limited, and may be appropriately adjusted according to the particle size of the target silicone rubber. It is preferable to use 0.05 to 20% by weight in the emulsion from the viewpoint that sufficient emulsifying ability is obtained and the physical properties of the resulting silicone rubber and the polyolefin graft copolymer obtained therefrom are not adversely affected. It is particularly preferable to use 0.1 to 10% by weight. The particle diameter of the silicone rubber can be controlled using a normal emulsion polymerization technique such as increase or decrease in the amount of emulsifier used. From the viewpoint of good dispersibility of the polyolefin graft copolymer obtained after copolymerization in a thermoplastic resin such as a polyolefin resin, the particle diameter of the silicone rubber is preferably 20 to 20000 nm, and more preferably. Is in the range of 50 to 2000 nm, particularly preferably 100 to 1000 nm.

  Examples of polymers constituting the hard polymer shell include polycyanide vinyl, polyaromatic vinyl, poly (meth) acrylic acid alkyl ester, maleimide polymer, etc. Among them, poly (meth) acrylate alkyl Esters are preferred.

  The poly (meth) acrylic acid alkyl ester, which is a preferred example of the polymer constituting the hard polymer, contains at least (J) (meth) acrylic monomer (hereinafter referred to as compound (J)) and (K) in the molecule. It is preferably a hard polymer obtained by copolymerizing a monomer having a group capable of copolymerizing with one radical polymerizable unsaturated group and at least one olefin monomer (hereinafter referred to as compound (K)), As needed, the compound (L) may contain a monomer copolymerizable with the compound (J) and / or the compound (K) (hereinafter referred to as the compound (L)). The amount of each component used is not particularly limited and may be used in any amount, but the compound (J) is preferably 50 to 99.99% by weight, more preferably 75 to 99.9% by weight. The greater the amount of compound (J), the better the handling properties of the resulting macromonomer and further the copolymer after grafting the olefin. Compound (K) is preferably used in an amount of 0.01 to 25% by weight, more preferably 0.1 to 10% by weight. When the amount used is within this range, the grafting efficiency and handling properties with the olefinic monomer are particularly good. The compound (L) is preferably used in an amount of 0 to 50% by weight, more preferably 0 to 25% by weight. However, the total of these compound (J), compound (K) and compound (L) is 100% by weight.

  The compound (J) is a component for forming the main skeleton of poly (meth) acrylic acid alkyl ester and improving the handling property of the copolymer after grafting the macromonomer and further the olefin. Specific examples of the compound (J) include t-butyl acrylate, hexadecyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate ( (Meth) acrylic acid ester; (meth) acrylic acid such as acrylic acid and methacrylic acid, and acid anhydrides and metal salts thereof may be used, but the present invention is not limited thereto. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 2 to 18 carbon atoms is preferable from the viewpoint of availability and economical efficiency of the obtained hard polymer, and among these, t-butyl acrylate, methacrylic acid are preferred. Methyl acid and glycidyl methacrylate are particularly preferred. These compounds (J) may be used independently and may use 2 or more types together. Monomers that become a rubbery polymer when polymerized alone, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, It can be used by adjusting the amount used so that it becomes a hard polymer by copolymerizing with other (J) component, (K) component, and (L) component.

  The compound (K) itself is copolymerized with the component (J) and optionally the component (L) by the radically polymerizable unsaturated group it has, and as a result, a macromonomer having a multilayer structure is formed. It is a component for introducing a group copolymerizable with an olefin monomer and enabling graft copolymerization of the copolymer and the olefin monomer. There are no particular restrictions on the group that can be copolymerized with the olefinic monomer, but allyl, cycloalkenyl, styryl, and (meth) acrylic groups are highly reactive because coordination polymerization is highly reactive. Of these, a group is preferable, and a (meth) acryl group, an allyl group, and a dicyclopentenyl group are particularly preferable. These functional groups are preferably at the molecular chain ends.

  When the group copolymerizable with the olefin monomer is a group having both radical polymerizability and coordination polymerizability, the radical polymerizable unsaturated group of the component (K) can be copolymerized with the olefin monomer. May be the same group or different groups. When they are the same group, the component (K) contains two or more radically polymerizable unsaturated groups (and also a group that can be copolymerized with an olefin monomer) in one molecule. ) The reaction is stopped when only a part of the radical polymerizable unsaturated groups undergo radical polymerization during the synthesis of acrylic hard shell, and unreacted radical polymerizable unsaturated groups (and olefins) are obtained in the resulting macromonomer. The reaction can be controlled so that a group that can be copolymerized with the monomer is left.

  Specific examples of the compound (K) include, for example, allyl methacrylate, allyl acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, ethylene glycol dicyclopentenyl ether methacrylate, ethylene glycol diacrylate. Examples include cyclopentenyl ether, dicyclopentenyl methacrylate, and dicyclopentenyl acrylate. These compounds (K) may be used independently and may use 2 or more types together. Among these, allyl methacrylate, ethylene glycol dicyclopentenyl ether, ethylene glycol dicyclopentenyl ether, dicyclopentenyl methacrylate, dicyclopentenyl from the point that the grafting efficiency with the olefin monomer is good. Acrylate is preferred.

  The compound (L) is a component for adjusting various physical properties such as the elastic modulus, Tg, and refractive index of the poly (meth) acrylic hard shell, and a preferred specific example is the compound (F) in the (meth) acrylic rubber. This is the same as the preferred specific example.

  The poly (meth) acrylic acid alkyl ester can be produced by the same method as the above-described (meth) acrylic rubber. A macromolecule having a multilayer structure is obtained by mixing and polymerizing a latex of a rubber-like polymer, a compound (J), a compound (K), and if necessary, a compound (L), a polymerization initiator, an emulsifier, a chain transfer agent and the like. Monomers can be obtained.

  Known polymerization initiators, emulsifiers, chain transfer agents and the like used for the emulsion polymerization can be used, and those exemplified as preferred examples in the above-described method for producing (meth) acrylic rubber can be preferably used.

  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, 58, 293, Angwante Chemie International Edition, 2002, 41, 544-561, Chemical Communication (Chem. Commun.), 2000, 301, Macromolecular Symposia, 2000, 150, 53, Macromolecules, 2003, 36, 67 No. 11-6715, Macromolecules, 2001, Vol. 34, p. 1165, WO 97/17380 pamphlet, WO 97/48740 pamphlet. However, it is not limited to these. 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 .) The hydrocarbon group having 1 to 4 carbon atoms represented by R ₁ and R ₄ is preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, and more preferably a methyl group. An isopropyl group is 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 illustrated. 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.

The counter anion represented by L ⁻ is produced together with a cation (M ⁺ ) by the reaction of 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. This is because the cation (Q ⁺ ) of the cocatalyst described later extracts a halogen or the like from the metal-halogen bond, metal-hydrogen bond or hydrogen-carbon bond of the catalyst to produce a salt, while the catalyst produces active species. 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. Because. 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.

Furthermore, 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. As 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 because they are simple to synthesize and easily available industrially. 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.

  As the olefin monomer used in the present invention, among olefin compounds having a coordination-polymerizable carbon-carbon double bond, those which are liquid at room temperature and normal pressure are preferable in that the effects of the present invention are easily exhibited.

  Preferable examples of the olefin monomer include olefins having a boiling point of 25 ° C. or higher and a carbon number of 5 to 20, such as 1-pentene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-eicosene, 4- Examples thereof include methyl-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 examples include 1-hexene and 1-octene. . 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 such as 2-norbornene, ethylidene norbornene, 5-phenyl-2-norbornene, dimethanooctahydronaphthalene or dicyclopentadiene may be used in combination. The amount of diene used is preferably 0 to 10 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 has a molar ratio of 10 to 10 ⁹ , more preferably 100 to 10 ⁹ . ⁷ , in particular 1000 to 10 ⁵ .

  The polyolefin in the polyolefin-based graft copolymer obtained by the present invention has a branched structure, 1, ω-inserted structure (Chem. Rev. 2000, 100, 1169, compared to the previous transition metal complex system. (See Journal of Synthetic Organic Chemistry, 2000, Vol. 58, p. 293), or an atactic structure. In the late transition metal complex system, the insertion direction of the olefinic monomer having 3 or more carbon atoms cannot be controlled so much by the steric factor of the ligand, so that stereoregularity is hardly expressed (atactic). For this reason, an amorphous polymer is often obtained and is soluble in a solvent. Therefore, after polymerization, there is an advantage that the catalyst or its residue can be easily removed by filtration, washing, adsorption or the like.

  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 by dispersing a pre-emulsified olefin monomer and a coordination polymerization catalyst in a macromonomer latex. If the olefin monomer is added directly without emulsification, the latex particles may aggregate to generate scale, or the amount of free polyolefin that is not copolymerized with the macromonomer may increase.

  The method for emulsifying the olefinic monomer is not particularly limited, and a conventionally known method may be used. For example, a mixture of water, an emulsifier and an olefinic monomer is emulsified using a stirrer, a homogenizer, an ultrasonic oscillator, or the like. be able to. Although there is no restriction | limiting in particular in the quantity of the water used for emulsification of an olefinic monomer, Preferably it is 30-2000 weight part with respect to 100 weight part of olefinic monomers, More preferably, it is 100-1000 weight part. If the amount is too small, emulsification becomes insufficient. If the amount is too large, the amount of liquid to be charged increases and the production efficiency decreases. As the emulsifier used for emulsification of the olefin-based monomer, known ones can be used. For example, those mentioned as preferred examples in the description of the emulsifier used for the production of the macromonomer described above can be used. Although there is no restriction | limiting in particular in the quantity of an emulsifier, Preferably it is 0.05-20 weight part with respect to 100 weight part of olefinic monomers, More preferably, it is 0.1-10 weight part. If the amount is too small, emulsification becomes insufficient. If the amount is too large, the quality of the resulting olefinic graft copolymer may be adversely affected.

  There is no restriction | limiting in particular in the addition method of a coordination polymerization catalyst. Those dissolved in a water-soluble organic solvent may be added, or those dissolved in a water-insoluble organic solvent may be added as they are or after emulsification. From the viewpoint that generation of scale can be further suppressed, a coordination polymerization catalyst dissolved in a water-insoluble organic solvent is preferably added after being emulsified with water and an emulsifier.

  There is no restriction | limiting in particular in the addition order of a macromonomer, an olefin type monomer, and a coordination polymerization catalyst. They may be added in any order, may be added in parallel at the same time, or may be added alternately in a plurality of times. The whole amount may be added to the reaction vessel in a lump, or after a part is added, the rest may be added continuously or intermittently. You may add additives, such as an emulsifier and an organic solvent, as needed.

  The use ratio of the macromonomer and the olefin monomer can be arbitrarily set, but it is preferable to use 1 to 100 parts by weight of the olefin monomer, and 2 to 33 parts by weight is used with respect to 100 parts by weight of the macromonomer to be used. Further preferred. It is also possible to add a large excess of the olefin monomer, stop the reaction when the above preferred amount is polymerized, and remove the unreacted monomer by heating or decompression. When the olefin monomer is used in a large excess, it is preferable to add 1 to 10 times the amount to be reacted.

  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, with respect to the volume of the entire 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, normal conditions under which general emulsion polymerization is performed are preferred. The reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 95 ° C, and still more preferably 30 to 80 ° C. The reaction pressure is preferably 0.05 to 3 MPa, more preferably 0.09 to 0.11 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.

  The polyolefin graft copolymer obtained by the present invention is usually obtained as a latex. As for the particle size of the latex, the particle size of the raw material macromonomer used and the amount of the reacted olefin monomer can be obtained. From the viewpoint that the dispersibility in thermoplastic resins such as polyolefin resins is particularly excellent, it is preferably 20 nm to 20000 nm, more preferably 50 to 2000 nm, and more preferably 100 to 1000 nm. Depending on the reaction conditions, some of the latex particles may aggregate and precipitate, or free polyolefin may be produced as a by-product, and it is preferable to carry out the reaction under conditions without such a precipitate. In the present invention, such precipitation is suppressed by adding the olefin monomer in a pre-emulsified state.

  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 the polyolefin-based graft copolymer and recovering a solid component. As a method for recovering solid components from latex, for example, a method of adding an electrolyte such as calcium chloride, magnesium chloride, calcium sulfate, magnesium sulfate, aluminum sulfate, or calcium formate to cause aggregation (salting out), hydrophilicity such as methanol, etc. By agglomeration by mixing with an organic solvent, or by agglomeration of solids by mechanical operations such as sonication, high-speed stirring, and centrifugation, or by drying operations such as spray drying, heat drying, freeze drying, and vacuum drying Although the method of removing a water | moisture content etc. is mentioned, it 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. By processing the dried product into pellets using an extruder or Banbury mixer, etc., or by passing the water-containing (solvent-containing) resin obtained through dehydration (desolvation) from the aggregate via a press dehydrator, It can also be processed into a pellet and collected. From the viewpoint of good handling properties, it is preferable to collect the powder preferably.

  By blending the polyolefin-based graft copolymer of the present invention into various thermoplastic resins, thermoplastic resin compositions having various functions derived from the functional groups contained in the macromonomer can be produced. .

  As the thermoplastic resin, 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, Polyolefins such as ethylene glycidyl methacrylate copolymer and 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 Styrene complexes, polyacetal, polyether ether ketone, engineering plastics such as polyether sulfone are preferably exemplified. These thermoplastic resins may be used independently and may use 2 or more types together. 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 blending ratio of the thermoplastic resin and the graft copolymer may be appropriately determined so that the physical properties of the molded product can be obtained in a balanced manner. In order to obtain sufficient physical properties, the amount of the graft copolymer is the amount of the thermoplastic resin. In order to maintain the properties of the thermoplastic resin, the amount of the graft copolymer relative to 100 parts by weight of the thermoplastic resin is 0.1 parts by weight or more with respect to 100 parts by weight, preferably 5 parts by weight or more. 500 parts by weight or less, preferably 100 parts by weight or less.

  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.

  When a (meth) acrylic macromonomer having a single layer structure or a (meth) acrylic rubber- (meth) acrylic hard shell multilayered macromonomer is used as a raw material, the polyolefin graft copolymer of the present invention is It shows physical properties that express polarity or physical properties that appear as a result of polarity, such as low contact angle, high surface tension, surface wettability, adhesion, paintability, dyeability, high dielectric constant, oil resistance, and high-frequency sealability. Polarizing agents for thermoplastic resins, especially polyolefins (adhesiveness, paintability, dyeability, oil resistance, high frequency sealing properties, 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.

  When a multilayer rubber macromonomer having a silicone rubber- (meth) acrylic hard shell is used as a raw material, the polyolefin graft copolymer of the present invention is derived from excellent low temperature characteristics and silicon content derived from low Tg. Excellent functionality such as releasability, moldability, gas permeability, water repellency, weather resistance, surface lubricity, low temperature brittleness improver, plasticizer, flame retardant for thermoplastic resin, especially polyolefin , Impact resistance improvers, slidability imparting agents and the like.

  Further, the thermoplastic resin composition containing the graft copolymer of the present invention is a conventional additive known in the plastics and rubber industries, such as plasticizers, stabilizers, lubricants, ultraviolet absorbers, antioxidants, It can contain compounding agents such as flame retardants, flame retardant aids, pigments, glass fibers, fillers, polymer processing aids and the like.

  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. The coalescence and optionally the additive component are produced by melt-kneading using a heat kneader, for example, a single screw extruder, twin screw extruder, roll, Banbury mixer, Brabender, kneader, high shear mixer, etc. be able to. 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 an emulsion polymerization method, the thermoplastic resin and the graft copolymer are both blended in a latex state and then coprecipitated (coaggregated). It is also possible to obtain.

  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, each physical property and characteristic was measured according to the following methods.

(Synthesis example 1) Synthesis | combination of PBA macromonomer latex Water 2.0L, butyl acrylate 457.9g, allyl methacrylate 9. In a 3L glass separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. 07 g and 2.0 g of sodium dodecyl sulfate were charged and bubbled with nitrogen, followed by stirring and emulsification. The mixture was heated to an internal temperature of 70 ° C. under a nitrogen stream, and 9.07 g of 10% ammonium persulfate aqueous solution was added and reacted for 4 hours. A latex of polybutyl acrylate (PBA) was obtained.

(Example 1) Copolymerization of n-butyl polyacrylate and 1-hexene (emulsification preparation)
The following chemical formula (3)

A palladium complex having the following structure (hereinafter also referred to as [N ^ N] PdMeCl), Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, Vol. 117, p. Synthesized by known methods described in the literature. 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 ₆ F _{5) 4} ^- was prepared 40 mmol / L diethyl ether solution 16mL of the complex. Put a diethyl ether solution of [N ^ N] PdMe ⁺ · B (C ₆ F ₅ ) ₄ ^- complex in a Schlenk tube, remove the diethyl ether under reduced pressure at room temperature, add methylene chloride and dissolve, [N ^{^ N] PdMe + · B (} C 6 F 5) 4 - was adjusted 4 mmol / L methylene chloride solution of the complex.

Charged into a four-neck flask was replaced with argon water 300 mL, of sodium dodecyl sulfate 3g, [N ^ N] PdMe + · B (C 6 F 5) 4 - and 4 mmol / L methylene chloride solution 30mL of complex addition, ultrasonic oscillator Was emulsified. Moreover, 120 mg of sodium dodecyl sulfate, 60 mL of water, and 60 mL of 1-hexene were placed in a 4-neck flask purged with argon, and emulsified using an ultrasonic oscillator.

Put PBA latex 1.5L to 3L separable ^{flask, [N ^ N] PdMe +} · B (C 6 F 5) 4 - was added and stirred emulsion of 4 mmol / L methylene chloride solution of the complex. Further, 1-hexene emulsion was added and stirred at room temperature for 7 hours to polymerize 1-hexene. The product was obtained in the latex state with very little scale generation (Table 1). A 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 the polyolefin graft copolymer of the present invention was obtained.

(Comparative Example 1) Copolymerization of n-butyl polyacrylate and 1-hexene (non-emulsification charge)
Adjusting the 4 mmol / L methylene chloride solution of the complex ^{- [N ^ N] PdMe +} · B (C 6 F 5) 4 in the same procedure as adjusted in Example 1.

Put PBA latex 2L to 3L separable ^{flask, [N ^ N] PdMe +} · B (C 6 F 5) 4 - was added and stirred 4 mmol / L methylene chloride solution 40mL of the complex. Further, 80 mL of 1-hexene was added and stirred at room temperature for 7 hours to polymerize 1-hexene. Most of the product was obtained in a latex state, but a part of the product was scaled and adhered to the inner wall of the container (Table 1). The product latex was salted out with an aqueous calcium chloride solution, filtered, washed with water, and dried after treatment to obtain a polyolefin graft copolymer.

  When a (meth) acrylic macromonomer having a single layer structure or a (meth) acrylic rubber- (meth) acrylic hard shell multilayered macromonomer is used as a raw material, the polyolefin graft copolymer of the present invention is It shows physical properties that express polarity or physical properties that appear as a result of polarity, such as low contact angle, high surface tension, surface wettability, adhesion, paintability, dyeability, high dielectric constant, oil resistance, and high-frequency sealability. Polarizing agents for thermoplastic resins, especially polyolefins (adhesiveness, paintability, dyeability, oil resistance, high frequency sealing properties, 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.

  When a multilayer rubber macromonomer having a silicone rubber- (meth) acrylic hard shell is used as a raw material, the polyolefin graft copolymer of the present invention is derived from excellent low temperature characteristics and silicon content derived from low Tg. Excellent functionality such as releasability, moldability, gas permeability, water repellency, weather resistance, surface lubricity, low temperature brittleness improver, plasticizer, flame retardant for thermoplastic resin, especially polyolefin , Impact resistance improvers, slidability imparting agents and the like.

Claims (7)

  In a method for producing a polyolefin-based graft copolymer in which an olefin-based monomer is polymerized by a late transition metal-based coordination polymerization catalyst in a macromonomer latex, the macromonomer latex is preliminarily emulsified. A method for producing a polyolefin-based graft copolymer, characterized by being added to the inside.   The coordination polymerization catalyst of the late transition metal complex system is a complex comprising a ligand having two imine nitrogens and a transition metal selected from Groups 8 to 10 of the periodic table. A method for producing a polyolefin graft copolymer.   The polyolefin-based polyolefin according to claim 2, wherein the coordination polymerization catalyst of the post-period transition metal complex system is a complex composed of an α-diimine type ligand and a transition metal selected from Group 10 of the periodic table. A method for producing a graft copolymer. The late transition metal complex-based coordination polymerization catalyst is an active species represented by the following general formula (1) or general formula (2) after reacting with the cocatalyst. A method for producing a polyolefin-based graft copolymer.

(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 hetero atom capable of coordinating to M, and may be connected to R ₅ , or X may be absent, L ⁻ is any anion .)   The macromonomer is a poly (meth) acrylic monomer composed of a monomer having a group capable of copolymerizing with a (meth) acrylic monomer and an olefinic monomer. The manufacturing method of the polyolefin-type graft copolymer of description to term.   The method for producing a polyolefin graft copolymer according to any one of claims 1 to 5, wherein the polyolefin in the polyolefin graft copolymer has a 1, ω-structure. The method for producing a polyolefin graft copolymer according to any one of claims 1 to 6, wherein the olefin monomer is 1-hexene.