JP2021161275A - Method for producing composition of inorganic compound component and resin component - Google Patents

Abstract

To provide a method for producing a polymer composition that does not impair the original properties of various polymers and can improve other performances such as elongation.SOLUTION: After an inorganic compound such as an inorganic filler is brought into contact with a polymer such as an olefinic elastomer, the polymer is removed with a good solvent for cleaning, resulting in an inorganic compound. The inorganic compound is brought into contact with a polymer, preferably one similar to the above-mentioned polymer, to give a polymer composition. The resultant composition shows an excellent balance of properties unlike the polymer compositions of the conventional structure.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a composition of an inorganic compound and a resin component using the inorganic compound and the resin component.

Ethylene / α-olefin rubber such as ethylene / propylene copolymer rubber (EPR) and ethylene / propylene / diene copolymer rubber (EPDM), aromatic rubber such as styrene-butadiene rubber and isoprene rubber, so-called butyl rubber and the like. A polymer composition using a combination of an elastomer and a crystalline resin such as polypropylene or polyethylene or an amorphous resin such as polystyrene can realize various physical properties, and can realize various physical properties, such as automobile parts, electric wire materials, and electrical / electronic parts. , Widely used for construction civil engineering materials, industrial material parts, etc. For the purpose of strengthening synthesis, it is also possible to further enhance rigidity, impact resistance, dimensional stability, etc. by combining inorganic compounds such as talc, mica, glass fiber, and carbon fiber.

In recent years, there has been an increasing need for weight reduction and long life of various parts, and there is a strong demand for higher performance and higher quality of raw polymer materials. Furthermore, quality control standards for parts are becoming stricter, and there is a strong demand for material design to eliminate kneading defects and extrusion defects that cause product defects.

On the other hand, since the properties of the above-mentioned components are significantly different, the interaction at the interface is poor, and the original physical properties may not be sufficiently exhibited due to interfacial peeling or the like. For example, it is known that interfacial peeling is likely to occur between the inorganic compound and the polymer composition. Therefore, in many cases, the inorganic compound is used by surface-treating it with a polymer having a polar moiety or the like.

On the other hand, even if a mixture of an inorganic compound and polyethylene or polystyrene is washed with a good solvent of each polymer, the polymer is not completely removed from the surface of the inorganic compound, and a layer of several nanometers is formed on the surface. There are reports that it will be formed. (Non-Patent Documents 1 and 2)

M. Asada, N. Jiang, L. Sendogdular, P. Gin, Y. Wang, MK Endoh, T. Koga, M. Fukuto, D. Schultz, M. Lee, X. Li, J. Wang, M. Kikuchi , A. Takahara, Heterogeneous Lamellar Structures Near the Polymer / Substrate Interface, Macromolecules 45 (17) (2012) 7098-7106. H. Tsuruta, Y. Fujii, N. Kai, H. Kataoka, T. Ishizone, M. Doi, H. Morita, K. Tanaka, Local Conformation and Relaxation of Polystyrene at Substrate Interface, Macromolecules 45 (11) (2012) 4643-4649.

The method of treating the inorganic compound with the polymer having the polar moiety may not exhibit sufficient performance because the compatibility with the polymer composition to be combined may be insufficient. Therefore, it is necessary to develop a method that can improve the physical properties more effectively.

Therefore, the present invention has been made with the object of providing a resin composition containing an inorganic compound having a more excellent balance of physical properties.

As a result of studies to solve the above problems, the present inventors have brought the inorganic compound into contact with the polymer, and then used a liquid compound (sometimes referred to as a good solvent) capable of dissolving the polymer once to obtain the weight. The present invention has been completed by finding that the inorganic compound obtained by dissolving the coalescence and removing most of it has an excellent modifying effect on the resin composition. Therefore, the present invention can be specified by the following requirements.

[1] Step of contacting the inorganic compound with the polymer (I) (1),
Step (2) of removing the polymer (I) using an organic compound having a dissolving ability of the polymer (I).
Step (3) of contacting the inorganic compound obtained in step (2) with the polymer (II) to form a composition.
A method for producing a polymer composition, wherein the above steps are sequentially carried out.

[2] The method for producing a polymer composition according to [1], wherein the mass ratio of the inorganic compound to the polymer (I) in the step (1) is 1/20 to 100/1.

[3] The method for producing a polymer composition according to [1], wherein the mass ratio of the inorganic compound to the polymer (II) in the step (3) is 1/1000 to 3/1.

[4] The method for producing a polymer composition according to [1], wherein the step (2) is carried out at 10 to 250 ° C.

Since the present invention uses the inorganic compound obtained by the above method, a polymer composition having an excellent balance of physical properties can be obtained.

It is a schematic diagram which illustrates the reactor with a stirrer.

The present invention is a method for producing a polymer composition in which the polymer (I) is brought into contact with an inorganic compound by a specific method and then combined with the polymer (II). Hereinafter, each component and each step will be described.

(Inorganic compound)
The inorganic compound used in the present invention is not particularly limited as long as it is a known inorganic compound such as a metal, a metal oxide, an inorganic salt or carbon, but generally, those having a shape such as particles, fibers or fillers are mentioned. Can be done. More specifically, various reinforcing materials and inorganic fillers can be mentioned.

Specific examples of the reinforcing agent include commercially available "Asahi # 55G" and "Asahi # 50HG" (manufactured by Asahi Carbon Co., Ltd.), "Silica (trade name)" series: SRF, GPF, and the like. Carbon blacks such as FEF, MAF, HAF, ISAF, SAF, FT, MT (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks surface-treated with a silane coupling agent, silica, activated calcium carbonate, fine powder Examples include talc and fine powdered silicic acid. Of these, carbon black of "Asahi # 55G", "Asahi # 50HG", and "Seast HAF" is preferable.

Specific examples of the "inorganic filler" include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. Of these, heavy calcium carbonate is preferable. As the heavy calcium carbonate, commercially available "Whiten SB" (trade name: Shiraishi Calcium Co., Ltd.) or the like can be used.

It is preferable that the surface of the inorganic compound used in the present invention has micro-level or nano-level irregularities.

(Polymer (I), Polymer (II))
The polymer (I) and the polymer (II) used in the present invention are not particularly limited as long as they are known polymers. Suitable examples include styrene-based polymers typified by various polystyrenes, various acrylic-based polymers typified by polymethyl methacrylate, methacrylic polymers, polyethylene, polypropylene and ethylene-based elastomers (ethylene and carbon). Examples thereof include olefin-based polymers typified by (copolymers with α-olefins, polyene compounds, etc.) having 3 or more atoms. Among these, if the method of the present invention is used, even a composition of an olefin polymer and an inorganic compound, which has no polarity and has a low affinity for the above-mentioned inorganic compound, tends to show an excellent balance of physical properties. .. Further, the polymer (I) and the polymer (II) may be the same or different, but preferably the same type of polymer has a higher temperament effect in many cases.

Hereinafter, the ethylene / α-olefin / polyene compound copolymer (hereinafter, may be referred to as an ethylene-based copolymer) used in the examples of the present invention will be introduced in detail as an example.

The method for producing the ethylene-based copolymer used in the present invention includes a metallocene-based catalyst described later, particularly a metallocene compound (α) having a structure represented by the formula (i), and a group 13 element-containing compound (β) in the periodic table. ) Is preferably used. First, the metallocene compound (α) and the Group 13 element-containing compound (β) in the periodic table will be introduced.

[Metallocene compound (α)]
The metallocene compound (α) used in the present invention preferably has the structure of the following formula (i). As a specific structure, the one disclosed in the above-mentioned International Publication No. 2009/72503 can be mentioned.

(In formula (i), R'represents a hydrogen atom, a hydrocarbyl group, a di (hydrocarbylamino) group or a hydrocarbyleneamino group, which groups have up to 20 carbon atoms.
R'' represents a hydrocarbyl group or a hydrogen atom having 1 to 20 carbon atoms.

M represents titanium.

Y represents −O−, −S−, −NR ^* −, −PR ^* −, −NR ₂ ^* or −PR ₂ ^* .

Z ^{* _{is, -SiR * 2 -, - CR}} * 2 -, - SiR * 2 SiR * 2 -, - CR * 2 CR * 2 -, - CR * = CR * -, - CR * 2 SiR * 2 - Or -GeR ^* _2- represents.

When ^{there are a plurality of R *} , each is independently a hydrogen atom; or at least one group selected from the group consisting of a hydrocarbyl group, a hydrocarbyloxy group, a silyl group, an alkyl halide group and an aryl halide group. The R ^* contains atoms having 2 to 20 atoms, and the two R ^* (when R ^{* is not a hydrogen atom) possessed by Z *} may arbitrarily form a ring, and Z ^* may form a ring. and R ^* having R ^* and Y have may form optionally ring.

X represents a monovalent anionic ligand group having up to 60 atoms excluding the class of ligands which are cyclic delocalized π-binding ligand groups.

X'represents a neutral connected group having up to 20 atoms.

X ″ represents a divalent anionic ligand group having up to 60 atoms.

p represents 0, 1 or 2, q represents 0 or 1, and r represents 0 or 1.

However, when p is 2, q and r are 0, M is in the +4 oxidation state (or, when Y represents -NR ^* ₂ or -PR ^* ₂ , M is in the +3 oxidation state. Yes), X is a halide group, a hydrocarbyl group, a hydrocarbyloxy group, a di (hydrocarbyl) amide group, a di (hydrocarbyl) phosphide group, a hydrocarbyl sulfide group and a silyl group, derivatives in which these groups are halogen-substituted, these groups. Represents an anionic ligand selected from di (hydrocarbyl) amino-substituted derivatives, derivatives in which these groups are hydrocarbyloxy-substituted, and derivatives in which these groups are di-(hydrocarbyl) phosphino-substituted, and up to 30. It has an atom other than a hydrogen atom.

However, when r is 1, p and q represent 0, M is an oxidized state of +4, and X'' is selected from the group consisting of a hydrocarbazil group, an oxyhydrocarbyl group and a hydrocarbylenedioxy group. Represents the dianionic ligand to be produced and has atoms other than hydrogen atoms up to 30.

However, when p is 1, q and r represent 0, M is a +3 oxidized state, and X is an allyl group, a 2- (N, N-dimethylamino) phenyl group, 2- (N,). Represents a stabilizing anionic ligand group selected from the group consisting of an N-dimethylaminomethyl) phenyl group and a 2- (N, N-dimethylamino) benzyl group.

However, when p and r are 0, q represents 1, M is a +2 oxidized state, and X'is a neutral conjugated diene or neutral optionally substituted with one or more hydrocarbyl groups. Represents a non-conjugated diene, where X'has up to 40 carbon atoms and forms a π-complex with M. )

In the general formula (i), any of the following aspects (1) to (4) is preferable.

(1) p represents 2, q and r represent 0, M represents a +4 oxidized state, and X independently represents methyl, benzyl or halide.

(2) q and q represent 0, r represents 1, M is a +4 oxidized state, and X ″ represents a 1,4-butadienyl group forming a metallocyclopentene ring with M.

(3) p represents 1, q and r represent 0, M represents a +3 oxidized state, and X represents 2- (N, N-dimethylamino) benzyl.

(4) p and r represent 0, q represents 1, M is an oxidized state of +2, and X'represents 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

In any of the above aspects (1) to (4), it is more preferable that R ″ further represents a hydrogen atom or a methyl group, and it is particularly preferable that R ″ represents a hydrogen atom.

The above-mentioned formula (ii) is, (t-butylamido) - dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane titanium (II) 1,3-pentadiene (also known as: [N-(1, 1 -Dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-tetrahydro-2-methyl-S-indacene-1-yl] Silaneamine (2-) -κN] [(1,2,3,4-η) -1,3-pentadiene] -titanium) of the metallocene compound (α) having the structure of the above formula (i). This is a preferred embodiment.

When a metallocene-based catalyst having a structure represented by the above formula (ii) is used, the polymerization reaction for obtaining an ethylene-based copolymer is a copolymerization of non-conjugated polyenes (component [C] and component [D]) described later. It is particularly excellent in copolymerizability, and for example, it is possible to efficiently incorporate the double bond at the terminal of vinylnorbornene (VNB) and introduce a long chain branch at a high rate. Further, since the obtained ethylene-based copolymer has a narrow molecular weight distribution and composition distribution and an ethylene-based copolymer having an extremely uniform molecular structure can be prepared, rubber molding is a concern with the formation of long-chain branches. The formation of gel-like lumps on the body surface is significantly suppressed. As a result, it is considered that the rubber molded product containing such an ethylene-based copolymer has excellent surface appearance because it does not contain gel-like lumps, and has excellent shape retention, so that production stability is also good. Further, by adopting the method of using the compound (β) described later, the effect can be further enhanced.

The metallocene compound (α) having the above-mentioned structure can be prepared by using a well-known synthetic method. For example, it is disclosed in International Publication No. 98/49212 Pamphlet. If necessary, a reducing agent can be used to produce a complex in a lower oxidized state (metallocene-based catalyst). Such a method is disclosed in USSN8 / 241,523.

In the present invention, the metallocene compound (α) is used in combination with a solvent such as an olefin, a polyene compound, or a hydrocarbon compound described later. Its usage in the reactor (concentration) in the terms of metal atom per liter of the reaction volume, usually ¹⁰ -10 ^{to 10 -1} mole, such amount as preferably ¹⁰ -9 ^{to 10 -2} mol Used in.

When the metallocene compound (α) is supplied to the reaction system, the concentration (αf) of the metallocene compound (α) supplied to the reaction device is usually higher than the concentration (αr) in the reaction device. Is common. In a preferred embodiment, the molar ratio of (αf) and (αr) described above preferably satisfies the following requirements.

100 ≧ (αf) / (αr) ≧ 1.5

When the above range is satisfied, it is expected that the effect of the molar ratio relationship between (βf) and (βr), which will be described later, will be further enhanced. It may be possible to improve more effectively.

[Compound containing Group 13 elements of the periodic table (β)]
Examples of the compound (β) containing the Group 13 element in the periodic table used in the present invention include the following boron-containing compounds (also referred to as boron-based compounds) and known organic aluminum compounds.

Examples of the "boron-based compound" include trimethylammonium tetrakis (pentafluorophenyl) borate, di (taloalkyl hydride) methylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and tripropylammonium. Tetrax (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) Borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-) Butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-Dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis ( Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3) , 4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6) -Tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, di- (i-propyl) ammonium tetrakis (pentafluoro) Phenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2, Alkylammonium salts such as 3,4,6-tetrafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate;
Tri-substituted phosphoniums such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, etc. salt;
Diphenyloxonium tetrakis (pentafluorophenyl) borate, di- (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl) borate, etc. Oxonium salt;
Diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and other disubstituted sulfonium salts. And so on.

As the "organoaluminium compound", known trialkylaluminum, dialkylaluminum halide, and alkylaluminum dihalide are preferable examples. Specifically, triisobutylaluminum (hereinafter, also referred to as "TIBA") and the like are particularly preferable examples.

In the present invention, the amount (concentration) of the compound (β) containing a Group 13 element in the periodic table in the reaction apparatus is usually ^10-9 to 1 liter of the reaction volume in terms of the group 13 atoms in the periodic table. It is used in an amount such that it is 10 ² mol, preferably ^10-8 to 10 ^{1 mol.}

In the case of the above-mentioned boron-based compound, the molar ratio with the transition metal atom in the metallocene compound (α) is usually 1 to 50, preferably 1 to 20, particularly preferably 1 to 10.

In the case of the above-mentioned organoaluminum compound, the molar ratio of the aluminum atom (Al) to the transition metal atom in the metallocene compound (α) is usually 10 to 5,000, preferably 20 to 2,000. Used in quantity.

When the group 13 element-containing compound (β) in the above periodic table is supplied to the reaction system, the concentration (βf) of the compound (β) supplied to the above reaction device is usually the concentration (βr) in the reaction device. It is common to make it higher than. In the present invention, the above-mentioned molar ratio of (βf) and (βr) is characterized by satisfying the following requirements.
100 ≧ (βf) / (βr) ≧ 1.5

When the above range is satisfied, the ethylene-based copolymer (described later) obtained by the above-mentioned catalyst can effectively improve the appearance of the unfoamed sheet of the obtained ethylene-based copolymer, for example. It becomes. At the same time, it may be more preferable to satisfy the relationship between the supply concentration of the metallocene compound (α) and the concentration in the reactor.

The reason why the appearance of the molded product using the ethylene-based copolymer obtained later is improved when the above requirements are satisfied is not clear at present, but the present inventors speculate as follows. doing.

As mentioned above, compound (β) is usually supplied at a concentration higher than the concentration in the reactor. This is partly because the amount of solvent used in the reaction, such as hydrocarbon compounds, tends to be reduced. In addition, there is a tendency that it is preferable from the viewpoint of equipment cost, condition change, and degree of freedom in solvent selection. On the other hand, if the supply concentration is too high, the concentration of the compound (β) may be partially or momentarily too high. The compound (β) is known to have an effect of easily increasing the polymerization activity. Therefore, a region where the polymerization activity tends to increase locally may occur. At that time, it is considered that the reactivity of the polyene compound described later may increase and a cross-linking reaction or the like may occur at the same time. Since such a crosslinked product may be an insoluble and insoluble component, poor dispersion may occur and the appearance may be deteriorated.

By controlling the supply concentration of the compound (β) to be relatively low as in the present invention, it is possible to suppress the increase in the local polymerization activity, so that the generation of the poorly dispersed component can also be suppressed. There will be.

For the same reason, it may be preferable to reduce the supply concentration of compound (α) into the reactor. However, since the amount of moles used in compound (β) is generally larger than that in compound (α), it can be considered that the effect of suppressing the supply concentration is high.

In the method for producing an ethylene-based copolymer, ethylene [A] and an α-olefin having 3 to 20 carbon atoms such as propylene are present in the presence of a catalyst containing the compound (α) and the compound (β) as described above. It is preferable to copolymerize [B] with the non-conjugated polyene compound [C] and the non-conjugated polyene compound [D] in combination with a solvent such as a hydrocarbon.

(Α-olefin [B])
Examples of the α-olefin [B] having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-. Examples thereof include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are particularly preferable. Such α-olefins are suitable because the raw material cost is relatively low and the obtained rubber molded product exhibits excellent mechanical properties.

(Non-conjugated polyene)
The ethylene-based copolymer preferably has a structural unit derived from the non-conjugated polyene component [C]. Specifically, one double bond (also referred to as "C = C" or "carbon-carbon double bond") between adjacent carbon atoms that can be polymerized by a metallocene catalyst is provided in one molecule. The non-conjugated polyene [C] having is used.

Such a non-conjugated polyene [C] _{does not contain a chain polyene having vinyl groups (CH 2} = CH-) at both ends, and one carbon-carbon double bond exists as a vinyl group at the molecular end. However, it is preferable that other carbon-carbon double bonds are present in the molecular chain (including the main chain and the side chain) in the form of an internal olefin structure.
The polymerization mode of the metallocene catalyst is coordination anion type polymerization, and when the non-conjugated polyene [C] has a terminal vinyl group, the terminal vinyl group is involved in the polymerization.
Examples of the component [C] include the following aliphatic polyenes and alicyclic polyenes.

Specific examples of the "aliphatic polyene" include 1,4-hexadien, 1,5-heptadiene, 1,6-octadien, 1,7-nonadien, 1,8-decadien, 1,12-tetradecadien, 3 -Methyl-1,4-hexadien, 4-methyl-1,4-hexadien, 5-methyl-1,4-hexadien, 4-ethyl-1,4-hexadien, 3,3-dimethyl-1,4-hexadien , 5-Methyl-1,4-Heptadien, 5-Ethyl-1,4-Heptadien, 5-Methyl-1,5-Heptadien, 6-Methyl-1,5-Heptadien, 5-Ethyl-1,5-Heptadien , 4-Methyl-1,4-octadien, 5-Methyl-1,4-octadien, 4-ethyl-1,4-octadien, 5-ethyl-1,4-octadien, 5-methyl-1,5-octadien , 6-Methyl-1,5-octadien, 5-ethyl-1,5-octadien, 6-ethyl-1,5-octadien, 6-methyl-1,6-octadien, 7-methyl-1,6-octadien , 6-Ethyl-1,6-octadien, 6-propyl-1,6-octadien, 6-butyl-1,6-octadien, 7-methyl-1,6-octadien, 4-methyl-1,4-nonadien , 5-Methyl-1,4-Nonadiene, 4-Ethyl-1,4-Nonadiene, 5-Ethyl-1,4-Nonadiene, 5-Methyl-1,5-Nonadiene, 6-Methyl-1,5-Nonadiene , 5-Ethyl-1,5-Nonadiene, 6-Ethyl-1,5-Nonadiene, 6-Methyl-1,6-Nonadiene, 7-Methyl-1,6-Nonadiene, 6-Ethyl-1,6-Nonadiene , 7-Ethyl-1,6-Nonadiene, 7-Methyl-1,7-Nonadiene, 8-Methyl-1,7-Nonadiene, 7-Ethyl-1,7-Nonadiene, 5-Methyl-1,4-Decadien , 5-Ethyl-1,4-Decadien, 5-Methyl-1,5-Decadien, 6-Methyl-1,5-Decadien, 5-Ethyl-1,5-Decadien, 6-Ethyl-1,5-Decadien , 6-Methyl-1,6-decadien, 6-ethyl-1,6-decadien, 7-methyl-1,6-decadien, 7-ethyl-1,6-decadien, 7-methyl-1,7-decadien , 8-Methyl-1,7-Decadien, 7-Ethyl-1,7-Decadien, 8-Ethyl-1,7-Decadien, 8-Methyl-1,8-Decadien, 9-Methyl-1,8-Decadien , 8-Ethyl-1 , 8-Methyl-1,6-undecadien, 9-methyl-1,8-undecadien and the like. In the present invention, these aliphatic polyenes can be used alone or in combination of two or more. Of these, 7-methyl-1,6-octadien and the like are preferable.

The "alicyclic polyene" is composed of an alicyclic portion having one carbon-carbon double bond (unsaturated bond) and a chain portion having an internal olefin bond (carbon-carbon double bond). Specific examples thereof include 5-ethylidene-2-norbornene (ENB), 5-propyriden-2-norbornene, and 5-butylidene-2-norbornene represented by the following formula (iii). Of these, 5-ethylidene-2-norbornene (ENB) is preferable because it has good sulphurization reactivity (high-speed sulphurability). Specific examples of other alicyclic polyenes include 2-methyl-2,5-norbornadiene and 2-ethyl-2,5-norbornadiene.

The ethylene-based copolymer contains a structural unit derived from at least one kind of component [C], and may contain a structural unit derived from two or more kinds of component [C].

なお、ＥＮＢのエチリデン由来の二重結合は、メタロセン系触媒による重合では反応しない場合が多い。

It should be noted that the ethylylidene-derived double bond of ENB often does not react in the polymerization with a metallocene catalyst.

The ethylene-based copolymer may contain the following structural units derived from non-conjugated polyene [D]. Such a compound has a structure having two double bonds between adjacent carbon atoms in one molecule, which can be polymerized by a metallocene catalyst described later.

Specific examples of such a non-conjugated polyene [D] include 5-alkenyl-2-norbornene such as 5-vinyl-2-norbornene (VNB) and 5-allyl-2-norbornene represented by the following formula (iv). Norbornene; alicyclic polyenes such as 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [4,5,0,1 ^2.5 , 1 ^7.10 ] deca-3,8-diene; 1 , 7-Octadiene, α, ω-diene, etc. such as 1,9-decadene, etc. can be mentioned.

Of these, 5-vinyl-2-norbornene (VNB), 2,5-norbornadiene, dicyclopentadiene (DCPD), 1,7-octadien, and 1,9-decadien are preferable, and they are excellent in introducing long-chain branches. Therefore, 5-vinyl-2-norbornene (VNB) is particularly preferable.

Further, two or more kinds of the above-mentioned non-conjugated polyene [D] may be used in combination.

Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the "aliphatic hydrocarbon" include pentane, hexane, heptane, etc. Among these, the obtained ethylene-based polymer can be dissolved, and separation and purification at the time of recovery of the polymer can be performed. From this point of view, hexane is a preferable example.

As a production method having the above characteristics, a metallocene compound (α) is used as a main catalyst, and a group 13 element-containing compound (β) in the periodic table such as a boron-based compound and / or an organic aluminum compound such as a trialkyl compound is used as a co-catalyst. , Hexane and other aliphatic hydrocarbons are used as a solvent, and the method can be carried out by a continuous method using a reactor with a stirrer as shown in FIG.

The reaction temperature is preferably in the range of room temperature or higher and 150 ° C. or lower, for example.

The polymerization pressure is in the range of more than 0 to ~ 8 MPa (gauge pressure), preferably more than 0 to ~ 5 MPa (gauge pressure).

The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. Is.

Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used.

The molar ratio ([A] / [B]) of the charged ethylene [A] to the α-olefin [B] is preferably 25/75 to 80/20, more preferably 30/70 to 70/30. be.

The molar ratio ([A] / [C]) of the charged ethylene [A] to the non-conjugated polyene [C] is preferably 70/30 to 99/1, more preferably 80/20 to 98/2. ..

The molar ratio ([A] / [D]) of the charged ethylene [A] to the non-conjugated polyene [D] is preferably 70/30 to 99.9 / 0, similarly to the above [A] / [C]. .1, more preferably 80/20 to 99.5 / 0.5.

By polymerizing using the above catalyst, copolymers having various compositions having a non-conjugated polyene having a double bond and the like can be obtained.

<Ethylene copolymer>
The ethylene-based copolymer used in the present invention contains a structural unit derived from ethylene [A], an α-olefin [B] having 3 to 20 carbon atoms, a non-conjugated polyene component [C] and / or a component "D". What you have can be exemplified. Such an ethylene-based copolymer can be produced by using a metallocene-based catalyst described later. The various preferred requirements are introduced below.

[(1) Molar ratio of structural units ([A] / [B])]
The molar ratio ([A] / [B]) of the structural unit derived from ethylene [A] to the structural unit derived from the α-olefin [B] is preferably 40/60 to 85/15. , More preferably 55/45 to 75/25.

When the molar ratio is within the above range, it is preferable from the viewpoint of the flexibility of the obtained rubber molded product and the mechanical properties at low temperature.

[(2) Molar amount of structural unit derived from component [C] + [D]]
The total molar amount of the structural unit derived from the non-conjugated polyene [C] and the structural unit derived from the non-conjugated polyene [D] is 0.5 to 10.0 mol% of the total structural units. Is preferable, more preferably 1.5 to 4.0 mol%, still more preferably 2.0 to 3.8 mol%.

When the "sum of molar amounts" is within the above range, the obtained rubber molded product is suitable because it is excellent in compression set and foaming characteristics.

[(3) Extreme viscosity [η]]
The ultimate viscosity [η] measured in 135 ° C. decalin is preferably 1.0 to 5.0 dL / g, more preferably 1.5 to 4.0 dL / g, still more preferably 2.0 to 2.0 dL / g. It is 4.0 dL / g.

When the ultimate viscosity [η] is within the above range, the rubber composition is excellent in kneading processability, and the obtained rubber molded product is excellent in compression set, which is preferable.

[(4) Molar ratio of structural units ([C] / [D])]
In the case of an ethylene-based copolymer having both the non-conjugated polyene [C] -derived structural unit and the non-conjugated polyene [D], the molar ratio of the structural units derived from them ([C] / [D] ]) Is 85/15 to 99.5 / 0.5, preferably 90 / 10-99 / 1.

When the molar ratio is within the above range, it is preferable from the viewpoint of kneading stability and foaming characteristics of the obtained rubber composition.

[(5) Mooney viscosity [ML _{1 + 4} ]]
The Mooney viscosity [ML _{1 + 4} ] measured at 160 ° C. is preferably 40 to 160, preferably 50 to 150.

The Mooney viscosity shall be measured using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation) under the condition of 160 ° C. in accordance with JIS K6300.

Further, a rule of thumb, a Mooney viscosity measured at 160 ° C. [ML 1 _{+ 4],} the Mooney viscosity measured at 100 ° C. [ML 1 _{+ 4],} observed correlation below, for example, Mooney viscosity measured at 160 ° C. When [ML _{1 + 4} ] is 40, the Mooney viscosity [ML _{1 + 4} ] at 100 ° C. is 95.

{Moony viscosity at 100 ° C [ML _{1 + 4} ]} = 2.38 × {Moony viscosity at 160 ° C [ML _{1 + 4} ]}

(Step (1) of bringing the inorganic compound into contact with the polymer (I))
The method for producing a polymer composition of the present invention first requires a step of bringing the inorganic compound into contact with the polymer (I). This step is not particularly limited as long as the inorganic compound and the polymer (I) are brought into contact with each other. It is preferable that the method is such that the polymer (I) comes into contact with the entire surface of these inorganic compounds. For example, a method of kneading the inorganic compound and the polymer (I) with a mixer or an extruder to form a polymer composition can be mentioned. Further, for example, a method in which the polymer (I) is dissolved in a liquid hydrocarbon compound and then the inorganic compound is charged into the solution can be mentioned. The inorganic compound to be charged into the solution of the polymer (I) may be charged as it is, or may be charged as a dispersion liquid in which the inorganic compound is dispersed in the liquid hydrocarbon compound. Specific examples of the liquid hydrocarbon compound will be described later.

The mass ratio of the inorganic compound and the polymer (I) in this step (1) is 1/2 to 100/1. It is preferably 1/15 to 90/1, and more preferably 1/1 to 80/1.

(Step (2) of obtaining an inorganic compound from which the polymer (I) has been removed by using an organic compound having a dissolving ability of the polymer (I)).
Most of the polymer (I) is removed from the inorganic compound and the polymer (I) brought into contact with each other in the step (1) by using an organic compound having a dissolving ability of the polymer (I). Step (2). The organic compound having a dissolving ability of the polymer (I) can be considered as a generally-called "solvent". (Hereinafter, it may be simply referred to as a solvent.) In the step of dissolving the polymer (I) in the solvent and removing the polymer (I) in this way, most of the polymer (I) is separated from the inorganic compound. It is known that the polymer (I) is slightly constrained on the surface of the inorganic compound and takes a mode like a restraint layer. (For example, Non-Patent Document 1 and Non-Patent Document 2) Such a restraining layer may be more likely to be formed when the surface of the inorganic compound has minute irregularities.

In the step (2), the polymer (I) is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the solvent, although it depends on the solubility of the polymer (I) in the solvent. It is used in an amount such that it is by mass, more preferably 0.8 to 30% by mass. The total amount of the inorganic compound and the polymer (I) is 0.05 to 60% by mass, more preferably 0.1 to 50% by mass, and further preferably 0.2 to 40% by mass with respect to the solvent. The quantity. This ratio is the same in the method using the solution of the polymer (I) or the dispersion liquid of the inorganic compound in the above step (1).

This step (2) is preferably carried out at 10 ° C. to 200 ° C., although it depends on the solubility of the polymer (I) in the solvent and the polymer concentration. A more preferable lower limit is 20 ° C. On the other hand, a more preferable upper limit value is 180 ° C., more preferably 170 ° C., and particularly preferably 160 ° C.

As the organic compound having a dissolving ability in the polymer (I), a known liquid organic compound (solvent) can be used without limitation as long as it is not a so-called poor solvent of the polymer (I).

Specific examples of such compounds depend on the type and structure of the polymer used, but are aliphatic hydrocarbons such as hexane, heptane, octane, decane, and dodecane, branched aliphatic hydrocarbons, and alicyclic hydrocarbons such as cyclohexane. Liquid aromatic hydrocarbons such as hydrogen, benzene, toluene, ethylbenzene and xylene and ketones such as acetone, methylethylketone and methylisobutylketone are good examples. Further, depending on the structure of the polymer, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monopropyl ether acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3- Examples thereof include ethyl ethoxypropionate, ethyl 3-methoxypropionate, butyl acetate, methyl pyruvate, ethyl pyruvate and the like. In addition, N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone. , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether A high boiling point solvent such as acetate can also be used. Further, liquids such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, and dialkylene glycol dialkyl ether can also be used.

In this step of removing the polymer (I), a usual solid-liquid separation method can be used without limitation. For example, known general methods such as filtration, hot filtration, and decantation method can be mentioned as preferable examples. Of course, after the removal step, so-called cleaning can be performed using a new solvent.

(Step (3) of contacting the inorganic compound (III) obtained in the step (2) with the polymer (II) to form a composition)
It is considered that the inorganic compound (III), which is considered to have a thin layer of the polymer (I) on the surface, was obtained by the steps (1) and (2). The step (3) is a step of contacting the inorganic compound (III) with the polymer (II) to form a polymer composition. In this step, the same method as the method of contacting a polymer with a conventionally known inorganic filler, glass fiber, carbon fiber or the like to form a polymer composition can be used without limitation. For example, a method of contacting and mixing the inorganic compound (III) obtained in the above step (2) with the polymer (II) to obtain a polymer composition using a mixer or an extruder can be given as a suitable example. You can. At this time, it is preferable to carry out at a temperature at which the polymer (II) melts. Specifically, it is preferable to make contact at a temperature 10 to 50 ° C. higher than the temperature at which the melting point of the polymer (II) or the glass transition temperature is higher. At this time, it is preferable that the inorganic compound (III) is dispersed as uniformly as possible with the polymer (II).

In this step (3), the weight ratio of the inorganic compound (III) to the polymer (II) is preferably 1/1000 to 3/1. It is more preferably 1/8000 to 2/1, and even more preferably 1/6000 to 3/2.

The polymer composition obtained as described above tends to have an improved balance of tensile strength, elongation, breaking point strength, etc. of the polymer (II), and a composition having an unprecedented balance of physical properties tends to be obtained. This is because the inorganic compound (III) obtained through the steps (1) and (2) probably has a restraining layer of the polymer (I), and this is the interface between the polymer (II) and the inorganic compound. It can be considered that the adhesive strength is increased extremely efficiently, and the above-mentioned rigidity and / or flexibility is improved. In particular, the restraint layer may be strongly constrained by the inorganic compound.

(Other ingredients)
The polymer composition produced by the present invention may appropriately contain other components depending on the intended purpose.

"Other components" include, for example, various additives such as foaming agents, foaming aids, reinforcing agents, inorganic fillers, softeners, antiaging agents (stabilizers), processing aids, activators, and hygroscopic agents. Can be mentioned.

Further, other polymers can be additionally introduced into the polymer composition of the present invention. The content of the other polymer in the entire polymer composition is preferably 20% by mass or less.

The "rubber composition" can be prepared by kneading the "ethylene copolymer" and other components at a predetermined temperature using, for example, a conventionally known kneader such as a mixer, a kneader, or a roll. can. Since the above-mentioned "ethylene-based copolymer" is excellent in kneadability, the rubber composition can be satisfactorily prepared.

(Foaming agent)
Further, in the present invention, examples of the "foaming agent" to be blended as needed include inorganic foaming agents such as sodium bicarbonate and sodium carbonate; N, N'-dinitrosopentamethylenetetramine, N, N'. -Nitroso compounds such as dinitrosoterephthalamide; azo compounds such as azodicarboxylicamide and azobisisobutyronitrile; hydrazide compounds such as benzenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide); calcium azide, 4, Examples thereof include organic foaming agents such as azide compounds such as 4'-diphenyldisulfonyl azide.

The blending amount of the foaming agent is 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight, and more preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer (II). ..

(Effervescent aid)
In the present invention, a "foaming aid" can be blended together with the foaming agent, if necessary. The foaming aid exhibits actions such as lowering the decomposition temperature of the foaming agent, promoting decomposition, and homogenizing bubbles.

Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid, and citric acid, salts thereof, urea, and derivatives thereof.

(Softener)
The "softener" can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more. Specific examples of the softener include process oil (for example, "Diana Process Oil PS-430" (trade name: manufactured by Idemitsu Kosan Co., Ltd.)), lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, vaseline, etc. Petroleum-based softeners; Coultal-based softeners such as Coultal and Coultal pitch; Fatty oil-based softeners such as mash oil, flaxseed oil, rapeseed oil, soybean oil and palm oil; waxes such as beeswax, carnauba wax and lanolin. Kind; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate or salts thereof; naphthenic acid, pine oil, rosin or derivatives thereof; terpene resin, petroleum resin, atactic polypropylene, k. Synthetic polymer substances such as malon inden resin; ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; other microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon synthetic lubricating oil, tall Examples include oil and sub (factis). Of these, petroleum-based softeners are preferable, and process oils are particularly preferable.

The blending amount of the softener can be appropriately selected depending on the intended use, and is usually preferably a maximum of 200 parts by weight, preferably a maximum of 150 parts by weight, and more preferably a maximum of 130 parts by weight with respect to 100 parts by weight of the polymer (II).

(Anti-aging agent (stabilizer))
The above-mentioned polymer composition is similar to a normal polymer composition in that the product life can be extended by blending an "anti-aging agent (stabilizer)", and such anti-aging As the agent, conventionally known anti-aging agents, for example, amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, and the like can be used.

More specifically, aromatic secondary amine-based antiaging agents such as phenylbutylamine, N, N-di-2-naphthyl-p phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene (3,5-di-t-butyl). -4-Hydroxy) hydrocinnamate] Phenolic anti-aging agents such as methane; thioether-based anti-aging agents such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide Agent: Dithiocarbamate-based anti-aging agent such as nickel dibutyldithiocarbamate; Sulfur-based anti-aging agent such as 2-mercaptobenzoylimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc. Examples include agents.

These anti-aging agents can be used alone or in combination of two or more, and the blending amount of such anti-aging agents is usually 0.3 with respect to 100 parts by weight of the polymer (II). It is 10 parts by weight, preferably 0.5 to 7.0 parts by weight, and more preferably 0.7 to 5.0 parts by weight. When the blending amount of the anti-aging agent is within the above range, there is no bloom on the surface of the obtained polymer composition, and further, vulcanization inhibition does not occur, which is preferable.

(Processing aid)
As the "processing aid" that can be blended in the present invention, one that is generally blended with an elastomer or the like as a processing aid can be widely used.

Examples of such processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters and the like. Of these, stearic acid is preferred.

The processing aid can be appropriately blended in an amount of 10 parts by weight or less, preferably 8.0 parts by weight or less, and more preferably 5.0 parts by weight or less with respect to 100 parts by weight of the polymer (II). When the blending amount of the processing aid is within the above range, there is no bloom on the surface of the obtained polymer composition, and vulcanization inhibition does not occur, which is preferable.

(Activator)
In the present invention, the "activator" to be blended as needed can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.

Examples of such activators include di-n-butylamine, dicyclohexylamine, monoeranolamine, "Acting B" (trade name: manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and "Acting SL" (trade name; Yoshitomi Pharmaceutical Co., Ltd.). Amines such as (manufactured by Co., Ltd.); diethylene glycol, polyethylene glycol, lecithin, triarilute melilate, zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids (specifically, "Structol activator 73", "Structor IB 531" , Activators such as "Structor FA541" (trade name: Schill & Seilacher), etc .; Zinc peroxide modifiers such as "ZEONET ZP" (trade name: Nippon Zeon Co., Ltd.); Cutadecyltrimethylammonium bromide, synthetic Examples thereof include hydrotalcites and special quaternary ammonium compounds (specifically, "Arcard 2HF" (trade name: manufactured by Lion Akzo Co., Ltd.)). Of these, "Alucard 2HF" is preferable.

The blending amount of the activator is 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, and more preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the rubber component.

(Hydraulic agent)
In the present invention, the "moisture absorbing agent" to be blended as needed can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.

Examples of such a hygroscopic agent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, white carbon and the like. Of these, calcium oxide is preferred.

The blending amount of the hygroscopic agent is 0.5 to 15 parts by weight, preferably 1.0 to 12 parts by weight, and more preferably 1.0 to 10 parts by weight with respect to 100 parts by weight of the polymer (II).

In addition, when the polymer (II) is a material for rubber, sulfur, a cross-linking agent, or the like can be used in combination.

Additives usually used for rubber can be arbitrarily blended within a range that does not impair the object of the present invention.

Such a polymer composition can be used for various purposes as an injection molded product. For example, structural members of automobiles and home appliances (bumpers, instrument panel materials, outer panel members of home appliances, etc.). If the polymer composition of the present invention is a rubber composition, a sponge material for weather strips such as a sponge for door sponge, a sponge for opening trim, a sponge for hood seal, and a sponge for trunk seal; Applications such as highly foamed sponge materials can be exemplified. Of course, it is not limited to these uses.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1
(Preparation of xylene solution of ethylene propylene terpolymer (EPT))
Mitsui Chemicals' EPT (brand name: 4045M) and commercially available para-xylene (special grade reagent) are mixed in a glass container at room temperature (20 to 25 ° C.) to obtain 200 g of a solution having an EPT concentration of 3% by mass. rice field.

(Preparation of xylene dispersion of silica fine particles)
Silica fine particles (trade name: AEROSIL200) and commercially available paraxylene (special grade reagent) were mixed in a glass container at room temperature (20 to 25 ° C.) to obtain 200 g of a dispersion having a silica fine particle concentration of 3% by mass. ..

(Contact between EPT and silica fine particles and EPT removal process)
The EPT solution obtained above and the silica fine particle dispersion were mixed at room temperature, stirred with a magnetic stirrer for about overnight (about 12 hours), and then allowed to stand to allow the silica fine particles to settle.

After that, the supernatant liquid is removed, the supernatant liquid is further removed by a centrifuge, the washing with para-xylene and the supernatant removal operation by centrifugation are repeated three times, and then the precipitated solid is vacuum-dried to remove silica fine particles. Obtained.

(Preparation of composition of EPT and silica fine particles)
One part of stearic acid, which is a stabilizer, is added to 100 parts of Mitsui Chemicals EPT (brand name: 4045M), and 50 parts of silica fine particles obtained by the above method are kneaded with a 6-inch biaxial roll to EPT. The composition was obtained.

The composition was formed into a tensile test Specimen having a thickness of 2 mm by melt breath molding (temperature: 180 ° C.), and a tensile test was performed using a tensile test device manufactured by IS Giken Co., Ltd., and the following results were obtained.

Break point strength: 18 MPa, break point elongation: 880%

Comparative Example 1
An EPT composition was obtained in the same manner as in Example 1 except that the trade name: AEROSIL200 was used as it was as the silica fine particles. Further, the same tensile test was performed, and the following results were obtained.

Break point strength: 26 MPa, break point elongation: 870%

Comparative Example 2
A tensile test was carried out in the same manner as in Example 1 except that the EPT was molded as it was, and the following results were obtained.

Break point strength: 1.5 MPa, break point elongation: 170%

From these results, it can be seen that the polymer composition of the present invention exhibits an excellent balance of physical properties that extends without impairing the flexibility of EPT.

Claims (4)

Step (1) of bringing the inorganic compound into contact with the polymer (I),
Step (2) of removing the polymer (I) using an organic compound having a dissolving ability of the polymer (I).
Step (3) of contacting the inorganic compound obtained in step (2) with the polymer (II) to form a composition.
A method for producing a polymer composition, wherein the above steps are sequentially carried out. The method for producing a polymer composition according to claim 1, wherein the weight ratio of the inorganic compound to the polymer (I) in the step (1) is 1/20 to 100/1. The method for producing a polymer composition according to claim 1, wherein the weight ratio of the inorganic compound to the polymer (II) in the step (3) is 1/1000 to 3/1. The method for producing a polymer composition according to claim 1, wherein the step (2) is performed at 10 to 250 ° C.

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