JP2006022318A - New polymer and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymer which has an alkylene ether structure having polyolefin on its side chain, a resin composition using it and their use. <P>SOLUTION: This polymer has a structure unit shown in general formula (I). In formula (I), A expresses a 2-20C olefin polymer whose weight average molecular weight is 400-500,000, R is a hydrogen atom, an alkyl group or an aralkyl group. This polymer can be contained in an antistatic agent, an adhesive, a coating composition, a molded item, a compatibilizer and an oxygen-supplementing composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a novel polymer having a (poly) alkylene ether structure having a polyolefin having a weight average molecular weight of 400 to 500,000 in the side chain, and a resin composition and use thereof using the same.

  Ethylene polymers or α-olefin polymers are excellent in cost and mechanical properties, and are most widely used as raw materials for various resin products. However, since the molecular structure is nonpolar and the affinity with other substances is poor, attempts have been made to introduce various functional groups.

  Among them, polymers or oligomers that can be polymerized by the introduced functional groups are collectively referred to as macromonomers, and polymers such as controlled comb polymers having high functions can be obtained by copolymerizing with other monomers. It has been known. Many examples of polymers containing polyolefin macromonomers are known, but polyolefin macromonomers having a polymerizable unsaturated group have a small amount of polar groups. It is difficult to use. As other compounds having a polymerizable functional group, those having a hydroxyl group at the terminal (Patent Document 1) and those having an epoxy group in a polyolefin chain (Patent Document 2) are known. Furthermore, in order to be able to polymerize by reacting with tetracarboxylic acid, the polymer obtained using this macromonomer has a limited structure. In the latter, there are multiple alkylene oxides that have a statistical distribution in one polyolefin chain, so problems such as cross-linking occur during the reaction of alkylene oxide. It was difficult to obtain a polymer having a structure having a polyolefin skeleton and a skeleton composed of polar groups.

Japanese Patent Laid-Open No. 9-3173 JP-A-4-55403

An object of the present invention is to provide a polymer having a polyolefin segment and a controlled structure. Furthermore, it is disclosed that the polymer having such a controlled structure is applied to various uses.

  That is, the present invention provides at least the general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more).

  The present invention also provides at least a general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Is a polymer (II) having a structural unit represented by 1) and having hydroxyl groups at both ends.

  The present invention also provides at least a general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more) and a general formula (III)

（ＩＩＩ）

(III)

(Wherein R ² is a polymer having as a repeating unit a structural unit represented by R ² is a divalent hydrocarbon residue having 1 to 20 carbon atoms which may have a hetero atom).

  The present invention also provides at least a general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more) and a general formula (IV)

（ＩＶ）

(IV)

(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. It is a polymer.

  The present invention also provides at least a general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more) and a general formula (V)

（Ｖ）

(V)

(Wherein R ⁴ represents a divalent divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) and is a polymer having a repeating unit as a repeating unit.

This invention is also a composition containing the said polymer, and is a use.

  According to the present invention, various novel polymers having polyolefin segments can be provided. The polyolefin-based macromonomer that is the base of the polymer is advantageous in terms of economy because it does not use expensive monomer raw materials.

In addition, the novel polymer of the present invention can provide materials suitable for various uses such as antistatic agents, adhesives, coating compositions, molded articles, compatibilizing agents, oxygen scavenging compositions, and the like.

  Hereinafter, embodiments of the present invention will be described.

  The polymer of the present invention contains at least the general formula (I)

ｉ （Ｉ）

i (I)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more).

  Examples of the olefin having 2 to 20 carbon atoms include α-olefins such as ethylene, propylene, 1-butene, and 1-hexene. As the polymer, these olefins are used singly or as a mutual polymer, or the characteristics are impaired. It may be copolymerized with other polymerizable unsaturated compounds within the range. Of these, ethylene, propylene, and 1-butene are particularly preferable.

  In the general formula (I), the weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the group represented by A is 400 to 500,000, preferably 800 to 200,000. More preferably, it is 1000-100000. Here, Mw is a polystyrene equivalent value.

  The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the group represented by A in the general formula (I), that is, the molecular weight distribution (Mw / Mn) is not particularly limited. Although there are 0 to several tens of materials, 4.0 or less, particularly 3.0 or less may be preferable in terms of uniformity of physical properties.

  The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the group represented by A can be measured under the following conditions using, for example, GPC-150 manufactured by Millipore.

Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by mass
Movement speed: 1.0 ml / min Sample concentration: 0.1% by mass
Sample injection amount: 500 microliters Detector: Differential refractometer The molecular weight represented by A is measured by measuring the molecular weight of a polyolefin having an unsaturated group at one end, which will be described later, and subtracting the equivalent molecular weight at the end. it can.

  R is hydrogen or a hydrocarbon residue having 1 to 18 carbon atoms bonded to the double bond of the olefin constituting A, such as hydrogen, a methyl group, an ethyl group, or a propyl group.

  In the polymer of the present invention, the content of the structural unit represented by the general formula (I) is not limited as long as it contains the structural unit represented by (I), and a preferable range varies depending on the use of the polymer. When the polymer is used as an antistatic agent, it is generally 1 to 99 mol%. The same applies to the case where the polymer is a polymer having hydroxyl groups at both ends represented by the general formula (II).

  The polymer of the present invention may be any polymer as long as it has a structural unit of the general formula (I) that can be produced by reacting with a compound that reacts with a hydroxyl group or an epoxy group. For example, a polymer having an ether bond, an ester bond, a urethane bond, an amide bond, or a carbonate bond. Furthermore, a block copolymer reacted with siloxane is specifically exemplified.

  Such a polymer can be obtained by ring-opening polymerization or copolymerization of an epoxy compound obtained by epoxidizing a polyolefin having an unsaturated group at one end, which will be described later. If water or a diol is used as the initiator, a polymer having both hydroxyl groups can be obtained.

  The polymer comprises a structural unit represented by the above general formula (I) and a general formula (III)

（ＩＩＩ）

(III)

(In the formula, R ² is a polymer having a structural unit represented by R ^{2 as a} divalent hydrocarbon residue having 1 to 20 carbon atoms which may have a hetero atom). .

In the general formula (III), the hydrocarbon residue of R ² is not particularly limited, but is an arylene such as an alkylene group such as a methylene group or an ethylene group, a cycloalkylene group such as a cyclohexylene group, a phenylene group or a xylylene group. And a group in which a part of these hydrogen atoms is substituted with a hydrocarbon residue or a hetero atom or a hydrocarbon residue substituted with a hetero atom, and a polymer is a monomer of a commercially available dicarboxylic acid having a corresponding structure. It can be produced by condensation with a diol having a structural unit of the general formula (I) as a unit. In this case, other polymerization components such as hydroxycarboxylic acid or other diols or dicarboxylic acids having different structures may be copolymerized.

  There is no restriction | limiting in particular as a weight average molecular weight of a polymer, Although the preferable range changes with uses, Generally, when using as a molding material, it is about 10000-500000 when using as a molding material.

  Another embodiment of the polymer of the present invention has the structural unit represented by the above general formula (I) and has the general formula (IV).

（ＩＶ）

(IV)

(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. It is a polymer.

In general formula (IV), as the hydrocarbon residue of R ³ , the same hydrocarbon residues as R ² in general formula (III) described above can be exemplified, and the polymer is commercially available. It can be produced by condensing diisocyanate as a monomer unit with a diol having a structural unit of the general formula (I). In this case, other polymerization components such as other diols or diisocyanates having different structures can be copolymerized.

  The weight average molecular weight of the polymer is not particularly limited, and the preferred range varies depending on the use, but is generally 1,000 to 1,000,000, and 10,000 to 500,000 when used as a molding material. It is common to set the degree.

  Another aspect of the polymer of the present invention is the structural unit represented by the general formula (I) and the general formula (V).

（Ｖ）

(V)

(Wherein R ⁴ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom), and is a polymer having a repeating unit as a repeating unit.

In general formula (V), the hydrocarbon residue of R ⁴ is not particularly limited, but is an alkylene group such as a methylene group, an ethylene group, a butylene group or a hexylene group, a cycloalkylene group such as a cyclohexylene group, or a phenylene group. And an arylene group such as a xylylene group and a biphenylene group, and a group in which some of these hydrogens are substituted with a hydrocarbon residue or a heteroatom or a hydrocarbon residue substituted with a heteroatom. An epoxy obtained by epoxidizing a polyolefin having an unsaturated group at one end described later, which is a methylene group that is a polymer of ethylene group, propylene group, and formaldehyde formed by polymerizing alkylene oxide such as ethylene oxide and propylene oxide By ring-opening polymerization of the compound and alkylene oxide It may be a structure that can be manufactured and copolymerized at the same time and randomly copolymerized, or a structure obtained by sequentially polymerizing block copolymers.

  As is clear from the gist of the invention, the ratio may be any ratio as long as both are contained.

  Although there is no restriction | limiting as a whole weight average molecular weight, Generally it is set as the weight average molecular weight of about 1000-100000 in order to set it as 1000-1 million, a compatibilizing agent, an antistatic agent, etc. is there.

  The polymer of the present invention can be produced by the following method.

  First, in the target polymer, as a monomer corresponding to the structure represented by the general formula (I), the general formula (VI)

（ＶＩ）

(VI)

(In the formula, A represents a polymer of olefins having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms). The indicated polyolefin with a double bond at one end is produced.

  This polyolefin can be produced by the following method.

(1) A transition metal compound having a salicylaldoimine ligand as shown in JP-A Nos. 2000-239312, 2001-27331, 2003-73412, etc. is used as a polymerization catalyst. Polymerization method.
(2) A polymerization method using a titanium catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

  Among the above methods (1) to (4), particularly according to the method (1), the polyolefin can be produced with high yield. In the method (1), a polyolefin having a double bond at one end is produced by polymerizing or copolymerizing the olefin described above in the presence of the transition metal compound having the salicylaldoimine ligand. Can do.

  The polymerization of the olefin by the method (1) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Detailed conditions and the like are already known, and the above-mentioned patent documents can be referred to.

Ratio of vinyl or vinylidene type double bond measured by ¹ H-NMR in the low molecular weight ethylene polymer of the present invention (in the following description, this ratio is referred to as “one-end vinyl group content”) ) Is 50% or more of all the ends, more preferably 70% or more, and still more preferably 80% or more. ¹ H-NMR was measured at 120 ° C. after completely dissolving the polymer in deuterated 1,1,2,2-tetrachloroethane serving as a lock solvent and a solvent in a measurement sample tube. . The chemical shift was determined by setting the peak of deuterated-1,1,2,2-tetrachloroethane to 5.92 ppm and determining the chemical shift value of other peaks.

The content of one terminal vinyl group in the low molecular weight polymer consisting only of ethylene is determined by ¹ H-NMR. The peak of each hydrogen of the polymer has a peak for three protons (A) based on the terminal saturated methyl group of 0.65 to 0.85 ppm, and a peak for three protons based on the vinyl group (B) of 4.70. It is observed at ˜5.0 ppm and 5.5 to 5.8 ppm. If each S _A and S _B of the peak area of each peak (A) and (B), the double bond content (U%) is calculated by the following equation.

U (%) = S _B × 200 / (S _A + S _B )

  The molecular weight of the polyolefin obtained by the method (1) can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or changing the type of catalyst used.

  Next, the polyolefin is epoxidized, that is, the double bond at the terminal of the polyolefin is oxidized to obtain a polymer containing an epoxy group at the terminal represented by the general formula (VII).

（ＶＩＩ）

(VII)

(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms)
Although the epoxidation method is not particularly limited, the following methods can be exemplified.

(1) Oxidation with peracid such as performic acid, peracetic acid, perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide ( 4) Oxidation with porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Oxidation with salen complex such as manganese salen and hydrogen peroxide or hypochlorite (6) Manganese- Oxidation with hydrogen peroxide and TACN complex such as triazacyclononane (TACN) complex (7) Oxidation with hydrogen peroxide in the presence of group VI transition metal catalyst such as tungsten compound and phase transfer catalyst

  Among the methods (1) to (7), the methods (1) and (7) are particularly preferable in terms of the active surface.

The epoxy content in all the terminals of the terminal epoxy group-containing polymer is determined by ¹ H-NMR. For example, in the case of a terminal epoxy group-containing polymer obtained by epoxidizing a single-end double bond-containing polymer consisting only of ethylene, the peak (C) for the three protons of the methyl group at the saturated terminal is 0.65 to 0. The peak (D) corresponding to 3 protons at the root of the epoxy group is observed at 2.3 to 2.4 ppm, 2.6 to 2.7 ppm, and 2.8 to 2.9 ppm for each proton. When the epoxy modification is not sufficient, a peak (E) corresponding to 3 protons of the terminal double bond is observed at 2 protons at 4.70 to 5.0 ppm and 1 proton at 5.5 to 5.8 ppm. Each peak (C), if each _S C, _{S D} and _{S E} peak areas of (D) and (E), epoxy group content (Ep (%)) is calculated by the following equation.

_{Ep (%) = S D ×} 200 / (S C + S D + S E)

The terminal epoxy group-containing polymer obtained by the above method can be subjected to ring-opening polymerization to produce a polymer having a structural unit of the general formula (I). For the catalyst, polymerization conditions, etc., known ring-opening polymerization methods of alkylene oxide can be used. For example, Takayuki Otsu, “Chemistry of Revised Polymer Synthesis”, Kagaku Dojin, January 1971, p. . 172-180 discloses an example in which a polyol is obtained by polymerizing various monomers. Catalysts used for ring-opening polymerization include Lewis acids such as AlCl ₃ , SbCl ₅ , BF ₃ , and FeCl ₃ for cationic polymerization, and alkali metal hydroxides for anionic polymerization as disclosed in the above document. Alternatively, alkaline earth metal oxides, carbonates, alkoxides, or alkoxides such as Al, Zn, and Fe can be used for alkoxides, amines, phosphazene catalysts, and coordination anionic polymerization. Here, as the phosphazene catalyst, for example, an anion of a compound disclosed in JP-A-10-77289, specifically, a commercially available tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride is alkalinized. The thing made into the alkoxy anion using the metal alkoxide etc. can be utilized.

  Using the active hydrogen compound such as water, amines, diols, and polyols as an initiator in the presence of the catalyst, the terminal epoxy group-containing polymer is homogenized by ring-opening polymerization of only the terminal epoxy group-containing polymer. A polymer is obtained, and a copolymer can be obtained by ring-opening polymerization of a terminal epoxy group-containing polymer and another alkylene oxide.

  As the reaction solvent, a terminal epoxy group-containing polymer, an inert one for alkylene oxide can be used, alicyclic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, Examples include ethers such as dioxane and halogenated hydrocarbons such as dichlorobenzene.

Except for the phosphazene catalyst, the amount of the catalyst used is preferably 0.05 to 5 mol, more preferably 0.1 to 3 mol with respect to 1 mol of the starting terminal epoxy group-containing polymer e. The amount of the phosphazene catalyst used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol, more preferably 5 × 10, with respect to 1 mol of the terminal epoxy group-containing polymer from the viewpoint of polymerization rate, economy and the like. ⁻⁴ to 1 × 10 ⁻¹ mol.

  The reaction temperature is usually 25 to 150 ° C., preferably 50 to 110 ° C., and the reaction time varies depending on the reaction conditions such as the amount of catalyst used, the reaction temperature, and the reactivity of olefins, but is usually several minutes to 50 hours. .

  By using water or diols as the initiator, a polymer (II) having hydroxyl groups at both ends can be obtained. In addition, when a polyether polyol having a specific molecular weight obtained by polymerizing alkylene oxide in advance is used as an initiator, it becomes possible to introduce a hydrophilic unit having a predetermined molecular weight and has hydroxyl groups at both ends having desired physical properties. Manufacture of a block copolymer becomes easy.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetraethylene glycol and the like. Among these, polyethylene glycol and polypropylene glycol are preferable.

  It has a structural unit represented by the above general formula (I) and has the general formula (III)

（ＩＩＩ）

(III)

(Wherein R ² is a hydrocarbon residue having 1 to 20 carbon atoms which may have a divalent hetero atom) a polymer having a repeating unit as a repeating unit (hereinafter referred to as polymer b) Can be produced by the following method.

(1) Reaction of a polymer having hydroxyl groups at both ends represented by the general formula (II) with a dicarboxylic acid corresponding to the general formula (III).
(2) Reaction of terminal epoxy group-containing polymer with dicarboxylic acid corresponding to general formula (III).
(3) Reaction of polyester polyol obtained by condensation reaction of dicarboxylic acid corresponding to general formula (III) and diols, and a terminal epoxy group-containing polymer.

  Here, general diols in (1) and (2) may coexist.

  The dicarboxylic acid is as described above, and more specifically, various commercially available dicarboxylic acids such as oxalic acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid can be used as they are.

  Examples of the diol include aliphatic diols such as ethylene glycol, propylene glycol, and butanediol, and aromatic diols such as biphenol and bisphenol A. In some cases, glycerin having a trifunctional hydroxyl group can also be used. These diols can be obtained alone or in admixture of two or more.

  A method of forming an ester bond from an alcohol and a carboxylic acid is well known, and a method of removing water in the presence of a dehydration catalyst. There is no particular limitation on the method of reacting carboxylic acid in the presence of alkali such as amine after anhydride or acid chloride. Also, as a method of directly reacting an epoxide and a carboxylic acid, a known method such as a reaction in the presence of an alkali metal salt of carboxylic acid or the like can be disclosed.

  It has a structural unit represented by the above general formula (I) and has the general formula (IV)

（ＩＶ）

(IV)

(In the formula, X represents an oxygen atom or an NH group, and R ³ represents a hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom). Hereinafter, the polymer c) can be produced by the following method.

(1) Reaction of the terminal epoxy group-containing polymer with a diisocyanate corresponding to the general formula (IV).
(2) Reaction of the polymer (II) with a diisocyanate corresponding to the general formula (IV).
(3) Reaction of the polymer (b) with a diisocyanate corresponding to the general formula (IV).

  Examples of the diisocyanate that can be used for the production of the polymer c include, for example, Nobutaka Matsudaira et al., “Polyurethane”, Tsuji Shoten, 1964, p. Among those disclosed in 13-18, those having 3 to 23 carbon atoms can be used, and among them, diisocyanate is usually selected. Specifically, hexamethylene diisocyanate, xylylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and the like can be used, but they may be used alone or in combination.

  Further, a small amount of polyisocyanate such as monoisocyanate or triisocyanate can be used in combination.

  As for the reaction methods of both, many methods are known as disclosed in the above-mentioned literature, and a known method such as heating in the presence of a catalyst such as a tin salt or an amine can be employed.

  Structural unit represented by general formula (I) and general formula (V)

（Ｖ）

(V)

(Wherein R ⁴ represents a hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom), a polymer having a repeating unit as a repeating unit (hereinafter referred to as polymer d) is However, the polymerization is generally carried out by the same method as the polymerization method of the corresponding epoxide and the above-mentioned terminal epoxy group-containing polymer.

  The polymer of the present invention described above, the composition containing the polymer, the resin composition containing the polymer and other thermoplastic resins, the polymer is an antistatic agent, an adhesive, and a coating composition And has an excellent antistatic effect.

  Here, the amount of the polymer of the present invention contained in the composition, resin composition, antistatic agent, adhesive and coating composition is preferably 0.5 to 20% by mass, particularly 1 It is preferable that it is 0.0-10 mass%.

  Examples of other thermoplastic resins in the resin composition include polyolefin resins such as polyethylene and polypropylene, polystyrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethyl methacrylate, and polyacrylic acid. Acrylic resins such as butyl, rubbery (co) polymers such as polybutadiene and polyisoprene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyacetal resins, polycarbonate resins, thermoplastic polyurethane resins, fluorine resins, etc. Or a mixture of two or more thereof.

  The composition or resin composition includes an alkali metal or alkaline earth metal salt, a surfactant, and another polymer antistatic agent (a polymer antistatic agent other than the antistatic agent by the polymer of the present invention). At least one selected from the group consisting of may be included. According to these components, the antistatic property of the composition or resin composition can be further improved.

  Examples of the alkali metal or alkaline earth metal salt include monocarboxylic acid or dicarboxylic acid having 1 to 20 carbon atoms (for example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acid having 1 to 20 carbon atoms (for example, Methanesulfonic acid, p-toluenesulfonic acid, etc.), alkali metals, alkaline earth metals and salts of organic acids such as thiocyanic acid, hydrohalic acids (eg hydrochloric acid, hydrobromic acid, etc.), hydrobromic acid, peroxy Preferred examples include salts of inorganic acids such as chloric acid, sulfuric acid and phosphoric acid. Among these, halides such as lithium chloride, sodium chloride and potassium chloride, acetates such as potassium acetate, and perchlorates such as potassium perchlorate are preferable.

  The content of the alkali metal or alkaline earth metal salt in the composition or resin composition is usually 0.001 to 3% by mass, preferably 0.01 to 2% by mass, based on the total amount of the polymer / resin. is there.

  As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, Examples include fatty acid esters of glycerin, fatty acids of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines, anionic Surfactants include, for example, carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates; Examples of cationic surfactants include alkyltrimethylammonium salts, sulfonic acid salts such as rubenzene sulfonate, alkyl sulfonate, and paraffin sulfonate; and phosphate esters such as higher alcohol phosphates. And the like, and the like. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, which can be used alone or Two or more types can be used in combination.

  Among the surfactants, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.

  Content of surfactant in the said composition or resin composition is 0.001-5 mass% normally with respect to a polymer and resin whole quantity, Preferably it is 0.01-3 mass%.

  As the other polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used, and as a known polyether ester amide, for example, JP-A-7-10989 And polyether ester amides comprising a polyoxyalkylene adduct of bisphenol A described in 1. above.

  As the other polymer antistatic agent, a block polymer having a repeating structure in which the unit of bonding between the polyolefin block and the hydrophilic polymer block is 2 to 50 can be used, and examples thereof include a block polymer described in US6552131. .

  The content of the other polymer antistatic agent in the composition or the resin composition is usually 0 to 40% by mass, preferably 5 to 20% by mass with respect to the total amount of the polymer / resin.

  Moreover, a compatibilizer may be contained in the composition or the resin composition. According to the compatibilizing agent, the compatibility between the polymer of the present invention and another thermoplastic resin can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group, such as And a polymer described in JP-A-258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin portion and an aromatic vinyl polymer portion.

  Content of the compatibilizing agent in the said composition or resin composition is 0.1-15 mass% normally with respect to a polymer and resin whole quantity, Preferably it is 1-10 mass%.

  Other additives for resin can be arbitrarily added to the above composition or resin composition within a range that does not impair the effect of the polymer of the present invention, depending on the application. Examples of such additives for resin include pigments, dyes, fillers, glass fibers, carbon fibers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and the like.

  A molded body formed by molding the resin composition has excellent antistatic properties and good paintability and printability. Examples of the molding method of the resin composition include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.). Depending on the method, it can be formed by any method.

  Examples of the method for coating the molded body include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating. Examples of the paint that can be used include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. Although a coating film thickness can be suitably selected according to the objective, it is 10-50 micrometers (dry film thickness) normally.

  The method for printing on the molded body may be any printing method that is generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, offset printing, and the like. Is mentioned. As the ink in these printings, those usually used for plastic printing can be used.

  The polymer according to the present invention is suitable as an oxygen-supplementing composition. In particular, when the polymer is contained in a polyester resin such as PET, the polyester resin can be imparted with oxygen barrier properties. Thereby, for example, the storage stability of an oxygen sensitive substance contained in a PET bottle or the like can be improved.

  As the resin used for this purpose, a copolymer of a structural unit represented by the general formula (I) and polyesters is most effective. Oxygen supplementation is performed by the radical reaction of the polyolefin segment represented by A in formula (I) with oxygen to form a hydroxyl group via a peroxo radical. Therefore, polyolefins containing more tertiary carbon, such as polypropylene and C3-C2 copolymers, are more effective. A preferred weight average molecular weight for the polyolefin segment is 400 to 10,000. The weight average molecular weight of the polymer used as the oxygen scavenging composition is not particularly limited, but is generally 10,000 to 500,000. The content of the polyolefin segment in the polymer used as the oxygen scavenging composition is 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass.

  The polymer according to the present invention is suitable as an emulsion composition. Lubricating property, friction resistance, separation performance are obtained by stirring a polymer in a molten state and water at high speed using a homomixer, a homogenizer, or a disper under high pressure. An emulsion composition having excellent moldability and antibacterial properties and excellent storage stability can be obtained. The ink composition, coating composition, and fiber treatment composition containing the emulsion composition of the present invention exhibit good dispersibility under acidic conditions, and are excellent in lubricity, friction resistance, mold release, durability, and water resistance. .

The polymer according to the present invention can be used as a compatibilizer between incompatible resins, particularly as a compatibilizer for improving the compatibility between a polyolefin resin and a polar resin such as polyester, polyurethane, and polyester polyurethane resin.
The polymer according to the present invention is useful for various modifier applications such as resin modifiers, rubber modifiers, wax modifiers, cement modifiers, ink and paint modifiers, It exhibits reforming effects such as impact resistance, heat resistance, weather resistance, scratch resistance, transparency, paintability, adhesion, low temperature flexibility, fluidity, and dispersibility.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

  In addition, the weight average molecular weight Mw and Mw / Mn were measured by the method described in the text using GPC. The melting point (Tm) was a peak top temperature obtained by measurement using DSC.

(Synthesis Example 1)
(Synthesis of one-end double bond-containing ethylene polymer (P-1))
Compound (VIII) used as a catalyst was synthesized according to Synthesis Example 6 of JP-A-2003-73412, and single-end double bond-containing polyethylene was synthesized according to Example 9 of the same publication.

A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, and the temperature was raised to 150 ° C. Subsequently, 30 kg / cm ² G was pressurized with ethylene in the autoclave to maintain the temperature. A hexane solution (1.00 mmol / ml in terms of aluminum atom) of MMAO (manufactured by Tosoh Finechem) was injected with 0.5 ml (0.5 mmol), and then a toluene solution (0.0002 mmol / ml) of the following compound (VIII) 0. 5 ml (0.0001 mmol) was injected to initiate the polymerization. After carrying out the polymerization at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

（ＶＩＩＩ）

(VIII)

The obtained polymer was homopolyethylene, and ¹ H-NMR measurement was performed on this one-end double bond-containing ethylene-based polymer. As a result, the integral value S _A = From 3.49, the integrated value S _B of the vinyl group = 3.00, the one-end vinyl group content (U) was 92%. The ¹ H-NMR measurement results and physical properties of this one-end double bond-containing ethylene-based polymer (P-1) (unit) were as follows.
¹ H-NMR: δ (C ₆ D ₆ ) 0.81 (t, 3H, J = 6.9 Hz), 1.10-1.45 (m), 1.93 (m, 2H), 4.80 (dd, 1H, J = 9.2, 1.6 Hz ), 4.86 (dd, 1H, J = 17.2, 1.6 Hz), 5.60-5.72 (m, 1H)
Melting point (Tm) 123 ° C
Mw = 1900, Mw / Mn = 2.24 (GPC)

(Synthesis Example 2)
(Synthesis of terminal epoxy group-containing polymer (E-1))
In a 500 ml separable flask, 100 g of the one-end double bond-containing ethylene polymer (P-1) obtained in Synthesis Example 1 (Mn850, vinyl group 108 mmol), 300 g of toluene, Na ₂ WO ₄ .2H ₂ O 0. 85 g (2.6 mmol), CH ₃ (nC ₈ H ₁₇ ) ₃ NHSO ₄ 0.60 g (1.3 mmol), and 85% phosphoric acid 0.11 g (1.3 mmol) were charged, and the mixture was heated to reflux with stirring for 30 minutes. The polymer was completely melted. After the internal temperature was set to 90 ° C., 37 g (326 mmol) of 30% hydrogen peroxide solution was added dropwise over 3 hours, and the mixture was stirred at an internal temperature of 90 to 92 ° C. for 3 hours. Thereafter, 21.5 g (54.4 mmol) of 40% aqueous sodium thiosulfate solution was added while maintaining the temperature at 85 ° C. and stirred for 30 minutes, and the peroxide in the reaction system was completely decomposed with the peroxide test paper. It was confirmed. Next, after confirming that the temperature was 80 ° C. or lower, 300 g of acetonitrile was added to crystallize the product, and the solid was collected by filtration and washed with acetonitrile. The obtained solid was stirred in a 50% aqueous methanol solution at room temperature, and the solid was collected by filtration and washed with methanol. Further, the solid was stirred in 400 g of methanol, collected by filtration and washed with methanol. By drying at room temperature under reduced pressure of 1 to 2 hPa, 96.3 g of a white solid of the terminal epoxy group-containing polymer (E-1) was obtained (yield 99%, olefin conversion 100%).

When this terminal epoxy group-containing polymer (E-1) was subjected to ¹ H-NMR measurement, the integrated value Sc = 3.6 of terminal methyl groups (shift value: 0.88 ppm) containing saturated polyethylene at both ends as impurities. From the integral value S _D = 3.0 and S _E = 0 of the methylene group and methine group (shift value: 2.38, 2.66, 2.80-2.87 ppm) at the base of the epoxy group, the terminal epoxy group content (Ep) is 90% It turns out that. The ¹ H-NMR measurement results and physical properties of this terminal epoxy group-containing polymer (E-1) (single) were as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 3H, J = 6.92 Hz), 1.18-1.66 (m), 2.38 (dd, 1H, J = 2.64, 5.28 Hz), 2.66 (dd , 1H, J = 4.29, 5.28 Hz), 2.80-2.87 (m, 1H)
Melting point (Tm) 121 ° C
Mw = 2058
Mw / Mn = 1.84 (GPC)
Hardness (Penetration) 0 mm
Melt viscosity 189cp (140 ℃)
Softening point 129.5 ° C
5% weight loss temperature 344 ℃ (TGA)
Structural formula of terminal epoxy group-containing polymer (E-1):

（ＩＸ）

(IX)

(Synthesis Example 3)
(Synthesis of single-end double bond-containing ethylene polymer (P-2))
[Preparation of solid component (A)]
After suspending 30 g of silica (SiO ₂ ) dried at 150 ° C. for 5 hours under nitrogen flow in 466 mL of toluene, 134.3 mL of methylalumoxane in toluene (3.08 mmol / mL in terms of Al atom) was added at 25 ° C. For 30 minutes. After completion of dropping, the temperature was raised to 114 ° C. over 30 minutes, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (A). A part of the obtained solid component (A) was collected and examined for concentration. As a result, the slurry concentration was 0.150 g / mL and the Al concentration was 1.179 mmol / mL.

[Preparation of solid catalyst component (B)]
150 mL of toluene was put into a 300 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (A) prepared above (1.91 g in terms of solid part) was charged with stirring. Next, 50.0 mL of a toluene solution of compound (VIII) (0.0012 mmol / mL in terms of Zr atom) was added dropwise over 15 minutes, and the mixture was reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation, washed 3 times with heptane, and 100 mL of heptane was added to prepare a heptane slurry of the solid catalyst component (B). A portion of the resulting heptane slurry of the solid catalyst component (B) was collected to examine the concentration. As a result, the Zr concentration was 0.058 mmol / mL and the Al concentration was 14.8 mmol / mL.

450 ml of heptane was charged into a stainless steel autoclave with an internal volume of 1000 ml sufficiently purged with nitrogen, and 100 liter / hr of ethylene was circulated at room temperature for 15 minutes to saturate the liquid phase and the gas phase. Subsequently, 23 NL of propylene was introduced, the temperature was raised to 80 ° C., and then the pressure was increased to 8 kg / cm ² G with ethylene to maintain the temperature. 0.5 ml (0.5 mmol) of a decane solution of triisobutylaluminum (aluminum atom conversion: 1.00 mmol / ml) was injected, and then the solid catalyst component (B) was injected as 0.0001 mmol in terms of Zr atoms. Polymerization was started. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C. for 60 minutes. Then, the polymerization was stopped by press-fitting 5 ml of methanol, and the monomer was depressurized after the temperature was lowered. The obtained polymer slurry was mixed with 2 L of methanol and stirred and then filtered. The obtained product was dried under reduced pressure at 80 ° C. for 10 hours to obtain 53.2 g of a terminal double bond-containing polymer (P-2) which is an ethylene-propylene copolymer. The product had Mw = 1730, Mw / Mn = 1.68, melting point 108 ° C., vinyl group / vinylene group / vinylidene group = 78.4 / 17.6 / 3.9 measured by ¹ H-NMR. .

(Synthesis Example 4)
(Synthesis of terminal epoxy group-containing polymer (E-2))
The same as Synthesis Example 2 except that the polymer containing one terminal double bond was changed to the one-terminal unsaturated ethylene-propylene copolymer (P-2) (Mw = 1730, Mn = 994) obtained in Synthesis Example 3. As a result, 23.9 g (olefin conversion rate 100%, yield 94%) of a white solid of the terminal epoxy group-containing polymer (E-2) was obtained.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.64, 5.28 Hz), 2.50 (m), 2.66 (1H, dd, J = 3.96, 5.28 Hz), 2.80-2.86 (1H, m), 2.94 (m)
Mw = 1720 Mw / Mn = 1.58 (GPC)
Melting point (Tm) 99.7 ° C
Hardness (Penetration) 0.2mm
Melt viscosity 32cp (140 ℃)
Softening point 114.5 ℃
5% weight loss temperature 334 ℃ (TGA)

(Synthesis Example 5)
(Production of α, β-dihydroxy polymer (D-1))
One-terminal double bond-containing polymer (P-1) 100 g obtained in Synthesis Example 1 (Mn 850, vinyl group 108 mmol), toluene 300 g, Na ₂ WO ₄ .2H ₂ O 1.79 g in a 1000 ml separable flask (5.4 mmol), CH ₃ (nC ₈ H ₁₇ ) ₃ NHSO ₄ (1.27 g, 2.7 mmol) and 85% phosphoric acid (0.23 g, 2.7 mmol) are charged and heated to reflux with stirring for 30 minutes. It was completely dissolved. After the internal temperature was set to 90 ° C., 37 g (326 mmol) of 30% hydrogen peroxide solution was added dropwise over 3 hours, followed by stirring at an internal temperature of 90 to 92 ° C. for 3 hours. By measuring the reaction mixture by ¹ H-NMR, it was confirmed that the terminal olefin was 100% modified with an epoxy group. Thereafter, 34.4 g (54.4 mmol) of 25% aqueous sodium thiosulfate solution was added while maintaining the temperature at 85 ° C., and the mixture was stirred for 30 minutes. The peroxide test paper confirmed that the peroxide in the reaction system was completely decomposed. After cooling to an internal temperature of 80 ° C., 2-propanol was slowly added over 30 minutes to crystallize the product, and the slurry was stirred at 65 ° C. for 1 hour, then the solid was collected by filtration and washed with 2-propanol. did. The obtained solid was stirred at room temperature in a 50% aqueous methanol solution, and the solid was collected by filtration and washed with methanol. The solid was further stirred in 400 g of methanol, collected by filtration and washed with methanol. By drying at 60 ° C. under reduced pressure of 1 to 2 hPa, 106.6 g of a white solid of α, β-dihydroxy polymer (D-1) was obtained (yield 99%, olefin conversion 100%, epoxy conversion 100). %). The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.89 (t, 3H, J = 6.9 Hz), 1.05-1.84 (m), 3.41 (dd, 1H, J = 5.9, 9.9 Hz), 3.57- 3.63 (m, 2H)
Melting point (Tm) 122 ° C
Hardness (Penetration) 0mm
Melt viscosity 214cp (140 ° C)
Softening point 129 ° C
5% weight loss temperature 297 ° C (TGA)
Structural formula of α, β-dihydroxy polymer (D-1):

（Ｘ）

(X)

[Example 1]
(Synthesis example 1 of polyether resin)
In a flask equipped with a thermometer, a stir bar, a nitrogen introducing tube and a condenser, 98.6 g (88 mmol) of a terminal epoxy group-containing polymer (E-1) (Mn = 1119) synthesized in Synthesis Example 2 and polyethylene glycol (PEG ) 600 (Mn = 598) 30.6 g (51 mmol) and toluene 434 g were inserted all at once, and the temperature was raised to 130 ° C. Azeotropic dehydration was performed while distilling toluene. After 147 g of toluene was distilled off, the temperature was lowered to 110 ° C., 1.4 g (9.9 mmol) of boron trifluoride diethyl ether complex was added, and the reaction was carried out for 11 hours. Thereafter, when the reaction solution was dropped into 790 g of methanol, a white solid was precipitated.

The white solid was filtered, and the residue was washed with methanol and dried to obtain 108.7 g of copolymer (1). When ¹ H-NMR measurement was performed on this copolymer (1), the integration value of the terminal methyl group (shift value: 0.88 ppm) of the terminal epoxy group-containing polymer (E-1) and the alkylene group (shift of PEG 600) Value: 3.52-3.79 ppm), it was found that the terminal epoxy group-containing polymer (E-1): PEG600 = 2 mol: a copolymer having a composition of 1 mol, ¹³ C -From the NMR measurement, there was carbon bonded to the PEG600 terminal hydroxyl group (shift value: 61.7 ppm), and integration of about half of the terminal methyl group carbon (shift value: 13.8 ppm) of the terminal epoxy group-containing polymer (E-1). From this value, it was found that the terminal epoxy group-containing polymer (E-1) was a polymer obtained by ring-opening polymerization of two molecules on one side of PEG. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 6H, J = 6.6 Hz), 1.00-1.57 (m, 320H), 3.52-3.79 (m, 52H)
¹³ C-NMR: δ (C ₆ D ₄ Cl ₂ ) 13.8, 22.6, 25.6, 29.2, 29.3, 29.6, 29.7, 29.9, 31.9, 33.6, 61.7, 64.7, 69.1, 70.3, 70.5, 70.6, 70.7, 71.1, 72.6, 76.0, 81.3
Melting point (Tm) 121 ° C

[Example 2]
(Synthesis Example 2 of Polyether Resin)
In a flask equipped with a thermometer, a stir bar, a nitrogen introducing tube and a condenser, PEG 600 (Mn = 598) 6.13 g (10.25 mmol), terminal epoxy group-containing polymer (E-1) (Mn = 1119) 19. 73 g (17.6 mmol) and 69 g of toluene were collectively inserted, the temperature was raised to 130 ° C., and azeotropic dehydration was performed while distilling toluene. After 19 g of toluene was distilled off, the temperature was lowered to 110 ° C., 0.56 g (3.9 mmol) of boron trifluoride diethyl ether complex was added, and the reaction was performed for 7.5 hours, and then the reaction solution was dropped into 158 g of methanol. As a result, a white solid was precipitated.

The white solid was filtered, and the residue was washed with methanol and dried to obtain 20.1 g of copolymer (2). When ¹ H-NMR measurement was performed on this copolymer (2), the integration value of the terminal methyl group (shift value: 0.88 ppm) of the terminal epoxy group-containing polymer (E-1) and the alkylene group (shift of PEG 600) Value: 3.52-3.79 ppm) From the comparison with the integrated value, it was found that the terminal epoxy group-containing polymer (E-1): PEG600 = 4 mol: a polymer having a composition of 1 mol. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 12H, J = 6.6 Hz), 1.00-1.57 (m, 640H), 3.52-3.79 (m, 52H)
Melting point (Tm) 121 ° C

Example 3
(Polyether resin synthesis example 3)
17.9 g (17.9 mmol) of PEG1000 (Mn = 1000) and 6.7 g (35.8 mmol) of 30 wt% KOH aqueous solution were collectively inserted into a flask equipped with a thermometer, a stirring bar, a nitrogen introduction tube and a condenser. Then, the temperature was raised to 100 ° C. to perform dehydration. After dehydration, the temperature was raised to 120 ° C., 30.7 g (27 mmol) of the terminal epoxy group-containing polymer (E-1) (Mn = 1119) was added, the reaction was performed for 18 hours, and then the reaction product was taken out and cooled at 120 ° C. did.

After cooling, 100 ml of distilled water was added to the obtained solid, and hydrochloric acid was added dropwise for neutralization. After neutralization, filtration was performed, and the filtrate was washed with distilled water and dried to obtain 34.8 g of a copolymer (3) as a white solid. When ¹ H-NMR measurement was performed on this copolymer (3), the integration value of the terminal methyl group (shift value: 0.88 ppm) of the terminal epoxy group-containing polymer (E-1) and the alkylene group (shift of PEG 600) Value: 3.52-3.65 ppm) From the comparison with the integrated value, it was found that the polymer having a composition of terminal epoxy group-containing polymer (E-1): PEG1000 = 4 mol: 1 mol. Further, it was found by atomic absorption analysis that the K content was 1.3% by weight. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 12H, J = 6.6 Hz), 1.18-1.5 (m, 640H), 3.52-3.65 (m, 52H)
Melting point (Tm) 124 ° C

Example 4
(Synthesis Example 4 of Polyether Resin)
A reaction was carried out in the same manner as in Example 1 except that PEG1000 was used instead of PEG600 in Example 1, to obtain a copolymer (4). This copolymer (4) was subjected to ¹ H-NMR measurement and was found to be a polymer having a composition of terminal epoxy group-containing polymer (E-1): PEG1000 = 2 mol: 1 mol. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 6H, J = 6.6 Hz), 1.18-1.5 (m), 3.52-3.65 (m, 90H)

Example 5
(Synthesis Example 5 of Polyether Resin)
The reaction was carried out in the same manner as in Example 2 except that the terminal epoxy group-containing polymer (E-2) was used instead of the terminal epoxy group-containing polymer (E-1) in Example 2, and a copolymer ( 5) was obtained. This copolymer (5) was subjected to ¹ H-NMR measurement, and was found to be a polymer having a composition of terminal epoxy group-containing polymer (E-2): PEG600 = 4 mol: 1 mol. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.82-0.92 (m), 1.00-1.70 (m), 3.25-3.76 (m)
Melting point (Tm) 108 ° C

Example 6
(Synthesis of polyurethane resin)
To a flask equipped with a thermometer, a stir bar, a nitrogen inlet tube and a condenser, 5.03 g (8.36 mmol) of PEG600 (Mn = 598), 5.02 g (ca 1 mmol) of copolymer (2) (Mn = ca 5000) and 40 g of toluene were collectively inserted, the temperature was raised to 130 ° C., and azeotropic dehydration was performed while toluene was distilled. After distilling off 13 g of toluene, the temperature was lowered to 110 ° C., 1.58 g (9.4 mmol) of hexamethylene diisocyanate and 0.01 g of dibutyltin dilaurate as a catalyst were added, and the reaction was carried out for 3.5 hours. When concentrated, 9.39 g of copolymer (6) was obtained. This copolymer (6) was a thermoplastic polyurethane resin. When ¹ H-NMR measurement was performed on this copolymer (6), it was found that the integrated value of the terminal methyl group (shift value: 0.86 ppm) of the terminal epoxy group-containing polymer (E-1) and the nitrogen atom of the carbamate bond. Comparison with the integrated value of the adjacent methylene group (shift value: 3.10 ppm) and the integrated value of the terminal methyl group (shift value: 0.86 ppm) of the terminal epoxy group-containing polymer (E-1) and the oxygen atom of the carbamate bond From the comparison with the integral value of the methylene group adjacent to (shift value: 4.14 ppm), the copolymer (2): hexamethylene diisocyanate: PEG600 = 1 mol: 9 mol: a polymer having a composition of 8 mol found. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.86 (t, 12H, J = 6.6 Hz), 1.05-1.4 (m, 690H), 1.47 (t, 50H, J = 5.6 Hz), 3.10 (t , 50H, J = 5.6 Hz), 3.4-3.74 (m, 620H), 4.14 (t, 50H, J = 5.6Hz)
Melting point (Tm) 121 ° C

Example 7
A 500 mL flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirrer was charged with 10 g of the α, β-dihydroxy polymer (D-1) obtained in Synthesis Example 5 and 80 g of toluene and stirred at 125 ° C. In an oil bath to completely dissolve the solid. After cooling to 90 ° C., 148 mg of 85% KOH previously dissolved in 5.0 g of water was added to the flask and mixed for 2 hours under reflux conditions. Thereafter, water and toluene were distilled off while gradually raising the temperature in the flask to 120 ° C. Furthermore, water and toluene in the flask were completely distilled off by reducing the pressure in the flask while supplying a slight amount of nitrogen into the flask. After cooling to room temperature, the solidified solid in the flask was crushed and taken out.

A stainless steel 1.5 L pressure reactor equipped with a heating device, a stirring device, a thermometer, a pressure gauge, and a safety valve was charged with the obtained solid total amount and 200 g of dehydrated toluene, and the gas phase was replaced with nitrogen, followed by stirring. The temperature was raised to 100 ° C. After 30 minutes, 11.8 g of ethylene oxide was added, and the temperature was gradually raised to 130 ° C. over 3 hours. After further maintaining at 130 ° C. for 7 hours, the mixture was cooled to room temperature to obtain a slurry liquid. The α, β-bis (polyethylene glycol) polymer having a polyethylene glycol group (PEG) bonded to the α, β-position of the α, β-dihydroxy polymer (D-1) by distilling off toluene from the slurry solution 19 .5 g was obtained. From the ¹ H-NMR analysis of the obtained polymer, the integrated value of the terminal methyl group (shift value: 0.88 ppm) of the α, β-dihydroxy polymer (D-1) and the alkylene group of the PEG moiety (shift value: 3.34). -Comparison with the integral value of 3.72 ppm) revealed that an average of 26 ethylene glycol units were combined. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (3H, t, J = 6.75 Hz), 1.04-1.66 (m), 3.34-3.72 (m)
Melting point (Tm) 120 ° C

  In a 30 mL flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirrer, 2.0 g of α, β-bis (polyethylene glycol) polymer synthesized by the above method, 10 g of toluene, and 0.2 g of phthalic dichloride were added. added. The mixture was refluxed for 4 hours under slightly nitrogen pressure. Thereafter, the mixture was stirred at 150 ° C. for 4 hours while distilling off toluene, and further stirred for 2 hours while removing the solvent and the generated gas under reduced pressure conditions, and the α, β-bis (polyethylene glycol) polymer was placed in the reactor. 2.1 g of a polymer in which the terminal hydroxyl group of the polyethylene glycol group was ester-crosslinked with phthalic acid was obtained. The physical properties are as follows.

¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, J = 6.8 Hz), 1.13- 1.50 (m), 3.31-3.79 (m), 4.42 (t, J = 5.3 Hz), 7.48- 7.52 (m), 7.69-7.73 (m)
Melting point (Tm) 119 ° C

Example 8
(Evaluation of antistatic property in LLDPE resin 1)
To 45 g of LLDPE (Mitsui Chemicals Evolution SP2320), 5 g of the copolymer (1) obtained in Example 1 (addition amount 10% by mass) and 0.10 g of sodium perchlorate monohydrate as an alkali salt were added. Then, the mixture was kneaded at 180 ° C. for 10 minutes using a 4C150-01 type lab plast mill manufactured by Toyo Seiki Seisakusho, and the kneaded product was taken out.

  Next, the kneaded product was hot press molded. The molding was performed by a method of pressurizing for 3 minutes while heating to 170 ° C. with a vacuum hot press machine, and then taking it out and rapidly cooling to room temperature to obtain a 130 mmφ × 0.5 mm hot press sheet for evaluation.

The obtained hot press sheet was allowed to stand in a constant temperature and humidity chamber controlled at room temperature 23 ± 2 ° C. and humidity 50 ± 5% RH for 24 hours, and when the surface resistance value was measured at an applied voltage of 500 V, it was 6.42 × 10 6. ¹² Ω. The water contact angle was 70 °.

[Comparative Example 1]
For comparison, LLDPE alone, LLDPE and sodium perchlorate (0.2% by mass of polymer), LLDPE and sodium perchlorate (0.2% by mass of polymer) and PEG 600 used in Example 1 (vs. the total amount of polymer) 10 mass%) was also evaluated. As a result, in all cases, the surface resistance was on the order of 10 ¹⁶ Ω, and only kneaded PEG 600 was obtained as a non-uniform shaped product.

Example 9
(Evaluation of antistatic property in LLDPE resin 2)
The same method as in Example 8, except that the copolymer (2) obtained in Example 2 was used instead of the copolymer (1), and 0.15 g of sodium perchlorate monohydrate was used. When a hot press sheet for evaluation was prepared and evaluated, the surface resistance value was 2.91 × 10 ¹¹ Ω. The contact angle of water was 52 °.

Example 10
(Evaluation of antistatic property in LLDPE resin 3)
Example except that the copolymer (4) obtained in Example 4 was used in place of the copolymer (1) and 0.15 g of potassium acetate was used in place of sodium perchlorate monohydrate. When a hot press sheet for evaluation was prepared and evaluated by the same method as in No. 55, the surface resistance value was 1.37 × 10 ¹¹ Ω. The contact angle of water was 53 °.

Example 11
(Evaluation of antistatic property in LLDPE resin 4)
45 g of LLDPE (Mitsui Chemicals Evolution SP2320) and 5 g of the copolymer (4) obtained in Example 4 (addition amount: 10% by mass) were kneaded at 180 ° C. for 10 minutes by 4C150-01 type lab plast mill manufactured by Toyo Seiki Seisakusho. After that, 0.10 g of sodium perchlorate monohydrate was added as an alkali salt and kneaded for 1 minute, and the kneaded product was taken out.

The hot press molding and the surface resistance value measurement were performed in the same manner as in Example 8. As a result, the surface resistance value was 8.01 × 10 ¹⁰ Ω. The water contact angle was 56 °.

Example 12
(Evaluation of antistatic property in LLDPE resin 5)
Example except that the copolymer (5) obtained in Example 5 was used instead of the copolymer (1), and 0.15 g of potassium acetate was used instead of sodium perchlorate monohydrate. When a hot press sheet for evaluation was prepared and evaluated in the same manner as in No. 8, the surface resistance value was 1.91 × 10 ¹² Ω. The water contact angle was 79 °.

Example 13
(Evaluation of antistatic property in LLDPE resin 6)
The same method as in Example 8, except that the copolymer (6) obtained in Example 6 was used instead of the copolymer (1), and 0.15 g of sodium perchlorate monohydrate was used. When a hot press sheet for evaluation was prepared and evaluated, the surface resistance value was 2.56 × 10 ¹³ Ω. The water contact angle was 64 °.

Example 14
(Antistatic evaluation in polypropylene resin)
22.5 g of polypropylene (Mitsui Chemicals homo PP grade F107BV) 2.5 g of the copolymer (3) obtained in Example 3 (added amount 10%), IRGANOX 1010 (manufactured by Nagase Sangyo Co., Ltd.) as a stabilizer at 1000 ppm, IRGAFOS 168 ( Nagase Sangyo Co., Ltd.) was added at 1000 ppm and calcium stearylate at 500 ppm, and kneaded at 200 ° C. for 5 minutes with a 4C150-01 type lab plast mill manufactured by Toyo Seiki Seisakusho.

Next, the kneaded product was hot press molded. METHOD molding, quenching while heating to 200 ° C. in a hot press 9.8MPa (100kgf / cm ²⁾ for 5 minutes pressurized, thereafter 5 minutes to room temperature while pressurized to 2.45MPa (25kgf / cm ²⁾ The evaluation hot press sheet of 95 mm × 95 mm × 3 mm was obtained.

The obtained heat-pressed sheet was left in a constant temperature and humidity chamber controlled at room temperature 23 ± 2 ° C. and humidity 50 ± 5% RH for 24 hours, and the surface resistance value was measured at an applied voltage of 500 V to be 8.76 × 10 ¹² Ω. Met. Moreover, it was 63.5 degrees when the contact angle of water was measured.

[Comparative Example 2]
Example 5 except that a commercially available polyether ester amide copolymer (Irgastat P18 manufactured by Ciba Specialty Chemicals) was used in place of the copolymer (1), and sodium perchlorate monohydrate was not used. When a hot press sheet for evaluation was prepared and evaluated by the same method, the surface resistance value was 3.67 × 10 ¹⁴ Ω. The water contact angle was 95 °.

The novel polymer of the present invention is useful in various applications such as antistatic agents, adhesives, coating compositions, molded articles, compatibilizing agents, oxygen-supplementing compositions and the like.
The novel polymer according to the present invention and the composition containing the polymer are particularly useful as an antistatic agent, and the resin composition containing the polymer is required to be antistatic. It is useful for molded products that require good paintability and printability.

Claims (16)

At least the general formula (I)

i (I)
(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more). At least the general formula (I)

i (I)
(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more), and a polymer (II) having a hydroxyl group at both ends. At least the general formula (I)

i (I)
(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more) and a general formula (III)

(III)
(Wherein, R ² is a divalent hydrocarbon residue having 1 to 20 carbon atoms that may have a hetero atom) polymer having as a repeating unit a structural unit represented by. At least the general formula (I)

i (I)
(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and i represents A structural unit represented by an integer of 1 or more and a general formula (IV)

(IV)
(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. Polymer. At least the general formula (I)

i (I)
(In the formula, A represents an olefin polymer having 2 to 20 carbon atoms and a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, i Represents an integer of 1 or more) and a general formula (V)

(V)
(Wherein R ⁴ represents a C 1-20 divalent hydrocarbon residue which may contain a hetero atom), and a polymer having a repeating unit as a repeating unit. A composition comprising the polymer according to claim 1. From the group which consists of the polymer of Claims 1-5, a salt of an alkali metal or alkaline earth metal, a surfactant, a compatibilizing agent, and a polymer antistatic agent other than the polymer of Claims 1-5. A resin composition comprising at least one selected. A resin composition comprising the polymer according to claim 1 and another thermoplastic resin. The polymer according to claim 1, another thermoplastic resin, and further an alkali metal or alkaline earth metal salt, a surfactant, a compatibilizing agent, and a polymer other than the polymer according to claim 1. A resin composition comprising at least one selected from the group consisting of antistatic agents. An antistatic agent comprising the polymer according to claim 1. An adhesive comprising the polymer according to claim 1. A coating composition comprising the polymer according to claim 1. The molded article formed by shape | molding the composition formed by containing the polymer of Claims 1-5. A molded article obtained by coating or printing a molded body obtained by molding the composition comprising the polymer according to claim 1. A compatibilizing agent comprising the polymer according to claim 1. An oxygen scavenging composition comprising the polymer according to claim 1.