JP3059320B2 - Reactive olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymer having high reactivity, and is particularly useful as a compatibility improver for various polymers.

[0002]

2. Description of the Related Art Generally, blending an ethylene-vinyl alcohol copolymer with a polyolefin improves the performance of the polyolefin such as gas barrier properties and solvent resistance, and blending an olefin elastomer with the ethylene-vinyl alcohol copolymer. The performance of ethylene-vinyl alcohol copolymer such as flexibility and impact resistance is improved, and the addition of a high-melting olefin polymer such as polypropylene improves the hot water resistance of ethylene-vinyl alcohol copolymer. Is done. However, polyolefins and ethylene vinyl alcohol-based copolymers generally have poor compatibility, and thus this composition does not exhibit the above-mentioned performance sufficiently, or the transparency and uniformity are impaired, and as a result, the appearance of the film is reduced. Often becomes bad. On the other hand, it is known that a resin obtained by graft polymerization of vinylphenylboronic acid onto polypropylene by radiation is useful as an adhesive. (US Pat. No. 3,291,861) and US Pat.
No. 0 describes a product obtained by a hydroboration reaction between a polyolefin having a terminal double bond and a borane as a reaction intermediate for synthesizing a block copolymer. Among the many borane exemplified here, there is a description of diethoxymonoborane, and a reaction product obtained by hydroboration using the same is a polyolefin having a diethyl ester of a boronic acid group at a terminal. . However, this reaction intermediate is merely a reaction intermediate for obtaining a block copolymer, and is not used alone and is not described for use in blending with other resins. .

[0003]

However, in general, a phenylboronic acid group is relatively easily cleaved by a compound having a hydroxyl group such as water or alcohols at a high temperature of 100 ° C. or more, As apparent from the comparative examples described later, when the polyolefin having a phenylboronic acid group was melt-kneaded with a polymer having a hydroxyl group such as an ethylene-vinyl alcohol copolymer, sufficient compatibility was not obtained. An object of the present invention is to provide an olefin polymer having a boron-containing group having good reactivity and compatibility with a thermoplastic resin having a polyvalent hydroxyl group such as an ethylene-vinyl alcohol polymer.

[0004]

The object of the present invention is to provide a boronic acid group or a boron-containing group which can be converted to a boronic acid group in the presence of water, and a repeating structural unit represented by the following formula (I). An olefin-based polymer, wherein the boronic acid group or boron-containing group is achieved by providing an olefin-based polymer bonded to an sp ³ carbon atom in the polymer.

[0005]

Embedded image

(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
And 20 alkyl groups. )

In the present invention, the boronic acid group is represented by the following formula (I)
I).

[0008]

Embedded image

The boron-containing group which can be converted to a boronic acid group in the presence of water (hereinafter abbreviated as boron-containing group) includes boron represented by the above formula (II) after hydrolysis in the presence of water. Any boron-containing group that can be converted to an acid group may be used.
A boronic ester group represented by the formula (II):
And a boronic acid anhydride group represented by V) and a boronic acid group represented by the following general formula (V).

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

In the formula, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (such as a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms), and an alicyclic hydrocarbon group (cyclo). Alkyl group, cycloalkenyl group, etc.), aromatic hydrocarbon group (phenyl group, biphenyl group, etc.)
X and Y may be the same or different. In addition, X and Y may be bonded. However, it is excluded when both X and Y are hydrogen atoms. R ² , R ³ , R ⁴
Is the same hydrogen atom or aliphatic hydrocarbon atom as in X or Y above,
Alicyclic hydrocarbon group, an aromatic hydrocarbon group, R ^2,
R ³ and R ⁴ may be the same or different. M represents an alkali metal or an alkaline earth metal.
Further, X, Y, R ² , R ³ , and R ⁴ may have other groups, for example, a hydroxyl group, a carboxyl group, and a halogen atom. ｝

Specific examples of the boronic ester groups, boronic anhydride groups and boronic acid groups represented by the general formulas (III) to (V) include dimethyl boronate ester group, diethyl boronate group and dibutyl boronate group. Ester group, dicyclohexyl boronate group, ethylene glycol ester boronate group, propylene glycol ester boronate group (1,2-propanediol ester boronate, 1,3-propanediol ester boronate), neoboronate Boronic ester groups such as pentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, boronic acid trimethylolethane ester group, and boronic acid diethanolamine ester group; boronic anhydride group; Alkaline metal base, alkaline earth gold of boronic acid Bases and the like. The above-mentioned boron-containing group that can be converted into a boronic acid group in the presence of water refers to the olefin polymer of the present invention in water or a liquid mixture of water and an organic solvent (toluene, xylene, acetone, etc.) It means a group that can be converted into a boronic acid group when hydrolyzed under the conditions of a reaction time of 10 to 2 hours and a reaction temperature of room temperature to 150 ° C.

[0015] The above-mentioned sp ³ carbon atom is referred to in the literature {for example, identification method of organic compound by spectrum (4th edition)
As is clear from page 189, page 244, sp
A carbon atom having ^three hybrid orbitals, that is, a tetravalent carbon atom having four single bonds bonded. For example, all carbon atoms in the repeating structural unit represented by the formula (I) of the olefin polymer of the present invention are sp ³ carbon atoms. Accordingly, the present invention includes an olefin-based polymer in which an arbitrary hydrogen atom in the repeating structural unit represented by the formula (I) is substituted with a boronic acid or a boron-containing group.

The sp ³ sp ³ which can be converted into a boronic acid group in the presence of a boronic acid group or water bonded to a carbon atom of the present invention
The boronic acid group in the olefin polymer having a boron-containing group bonded to a carbon atom or the boron-containing group that can be converted to a boronic acid group is any of the sp ³ carbon atoms at the terminal, side chain, or main chain of the olefin polymer. May be bonded to Examples of suitable bonding forms of a boronic acid group or a boron-containing group that can be converted to a boronic acid group to an olefin-based polymer include the following formulas (VI) to (IX).

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

Wherein Z in the formulas (II) to (V) represents a boronic acid group or a boron-containing group which can be converted to a boronic acid group in the presence of water. W is an ether bond or a thioether bond. Represents a divalent saturated hydrocarbon group which may be interrupted by a bond containing a non-carbon atom such as an oxygen atom such as an amide bond or an ester bond, a nitrogen atom or a sulfur atom, or may have a branch. P represents an olefin polymer having a repeating structural unit represented by the formula (I), wherein P- in the formulas (VI) and (VII) represents a bond to a terminal site of the olefin polymer, Formula (VII)
In the I) and the formula (IX), / P /-means a bond to a side chain of the olefin polymer. )

Here, the linking group W has 1 to 30 carbon atoms.
And a divalent saturated hydrocarbon group which may have a branch. Specific examples include a linking group represented by the following formula (X).

[0023]

Embedded image

Wherein R ⁵ and R ⁶ are a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 30.

In the bonding forms of the above formulas (VI) to (IX), the linking group is a functional group in the bonding forms of the formulas (VI) and (VIII) and the bonding forms of the formulas (VII) and (IX). Is preferable in the case of a saturated hydrocarbon group having no, and particularly preferable is the case of the formula (VII) in which an olefin polymer or a boron-containing group is directly bonded.

The range of the total amount of the boronic acid group and the boron-containing group in the olefin polymer of the present invention is not particularly limited, but is 0.00001 to 1 milliequivalent / g (constituent units per 1 g of the olefin polymer). Is preferably in the range of 0.0001 to 0.3 meq / g, and more preferably in the range of 0.001 to 0.1 meq / g.

R ² in the formula (I) represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Such a structural unit can be obtained by using an olefin monomer as a starting material. Here, specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene,
-Heptene, 1-octene, 1-nonene, 1-decene and the like. The olefin polymer of the present invention is a homopolymer of one monomer selected from the above olefin monomers or a copolymer of the above olefin monomers (random copolymer, block copolymer) ) Or a copolymer containing a monomer other than the above-mentioned monomers as a copolymer component (random copolymer, block copolymer). A preferred olefin polymer is polyethylene (ultra low density). , Low density, medium density, high density), polypropylene, and ethylene-propylene copolymer. The content of the olefin monomer in the polymer is preferably 50% by weight or more, more preferably 80% by weight or more. Examples of the copolymerization component other than the olefin monomer include olefin monomers other than the above monomers such as norbornene, and acrylate monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate; Methacrylate monomers such as methyl acrylate, ethyl methacrylate and butyl methacrylate; vinyl ester monomers such as vinyl acetate and vinyl pivalate; vinyl chloride, vinylidene chloride and vinyl fluoride.

The molecular weight of the olefin polymer having a boronic acid group and a boron-containing group according to the present invention is determined by using orthodichlorobenzene as a solvent at a measurement temperature of 140 ° C.
200 as weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC).
It is preferably 0 or more, more preferably in the range of 2000 to 3,000,000, and more preferably in the range of 10,000 to 1,000,000.

Next, a typical method for producing an olefin polymer having a boronic acid group and a boron-containing group used in the present invention will be described. An olefin polymer having a boronic acid group or a boron-containing group that can be converted to a boronic acid group in the presence of water can be obtained by adding a borane complex and a trialkyl borate to an olefin polymer having a carbon-carbon double bond under a nitrogen atmosphere. After reacting the ester, to obtain an olefin polymer having a boronic acid dialkyl ester group,
It is obtained by reacting water or alcohols. When an olefin polymer having a double bond at a terminal is used as a raw material in this production method, an olefin polymer having a boronic acid group at the terminal or a boron-containing group that can be converted into a boronic acid group by the presence of water can be obtained. When an olefin polymer having a double bond in the side chain or main chain is used as a raw material, an olefin polymer having a boronic acid group or a boron-containing group that can be converted to a boronic acid group in the presence of water in the side chain Can be obtained.

As typical processes for producing an olefin polymer having a double bond as a raw material, 1) a method utilizing a trace amount of a double bond at a terminal of a usual olefin polymer;
2) A process for thermally decomposing an ordinary olefin polymer under oxygen-free conditions to obtain an olefin polymer having a double bond at a terminal; 3) An olefin obtained by copolymerizing an olefin monomer and a diene polymer. A method for obtaining a copolymer of a series monomer and a diene monomer. For 1), a known method for producing an olefin polymer can be used.
Particularly, a production method using a metallocene polymerization catalyst as a polymerization catalyst without using hydrogen as a chain transfer agent (for example, DE40)
30399) is preferred. The method 2) can be obtained by thermally decomposing an olefin-based polymer at a temperature of 300 to 500 ° C. under an oxygen-free condition such as a nitrogen atmosphere or a vacuum condition by a known method (for example, US Pat. Regarding 3), a method for producing an olefin-diene copolymer using a known Ziegler catalyst (for example, JP-A-50-44281, DE302127)
3) can be used.

As the borane complex, borane-tetrahydrofuran complex, borane-dimethylsulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine and the like are preferable. Among these, a borane-triethylamine complex and a borane-trimethylamine complex are more preferred. The amount of the borane complex to be charged is preferably in the range of 1/3 equivalent to 10 equivalent relative to the double bond of the olefin polymer. As the trialkyl borate, a lower alkyl borate such as trimethyl borate, triethyl borate, tripropyl borate and tributyl borate is preferable. The amount of trialkyl borate to be charged is preferably in the range of 1 to 100 equivalents based on the double bond of the olefin polymer. The solvent does not need to be particularly used, but when used, a saturated hydrocarbon solvent such as hexane, heptane, octane, decane, dodecane, cyclohexane, ethylcyclohexane, and decalin is preferable.

The reaction for introducing a boronic acid dialkyl ester group into an olefin polymer having a double bond is performed at a reaction temperature of room temperature to 300 ° C., preferably 100 to 250 ° C., and a reaction time of 1 to 10 hours, preferably 5 to 5 hours. It is better to do it for hours.

As a condition for reacting water or alcohols, an organic solvent such as toluene, xylene, acetone or ethyl acetate is usually used as a reaction solvent, and water or alcohols such as methanol, ethanol, butanol; ethylene glycol, 1,2-propanediol, 1,3
-Propanediol, neopentyl glycol, glycerin, trimethylolethane, pentaerythritol,
Using a large excess of 1 to 100 equivalents or more of polyhydric alcohols such as dipentaerythritol with respect to the boronic acid group,
It is obtained by performing the reaction at a temperature of room temperature to 150 ° C. for about 1 minute to 1 day. In addition, the boron-containing group which can be converted into a boronic acid group among the above-mentioned functional groups refers to a reaction time of 10 minutes to 2 hours in water or a mixed solvent of water and an organic solvent (toluene, xylene, acetone, etc.). , Reaction temperature from room temperature to 150
It means a group that can be converted into a boronic acid group when hydrolyzed under the condition of ° C.

The reactive olefin polymer of the present invention is excellent in compatibility with a hydroxyl group-containing thermoplastic resin, particularly, an ethylene-vinyl alcohol copolymer, and is a polyolefin and an ethylene-vinyl alcohol copolymer. Useful as a compatibility improver for the composition. Further, the reactive olefin polymer of the present invention is useful as a modifier for an ethylene-vinyl alcohol copolymer. In particular, when the base polymer of the reactive olefin polymer of the present invention is an ethylene polymer such as low-density polyethylene, ultra-low-density polyethylene, or ethylene-propylene copolymer, the present invention obtained by using these base polymers. By blending the reactive olefin polymer of the present invention with an ethylene-vinyl alcohol copolymer, it is possible to improve the properties of the ethylene-vinyl alcohol copolymer, particularly the flexibility, impact resistance and stress crack resistance. it can. When the base polymer of the present invention is a polyolefin having a high melting point such as polypropylene or poly (4-methyl-1-pentene), the hot water resistance of the ethylene-vinyl alcohol copolymer can be improved.

[0035]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In the following Synthesis Examples and Examples, unless otherwise specified, the ratio means the weight ratio, and “%” means “% by weight”. The molecular weight of the polyolefin is Wa
It is a weight average molecular weight in terms of polystyrene measured at 140 ° C. using GPC manufactured by ters, and orthodichlorobenzene as a measurement solvent. The amount of double bonds in the polyolefin was determined using heavy para-xylene as a solvent at 270 M
It was quantified by Hz ¹ H-NMR. The amount of boronic acid groups in the polypropylene and polyethylene in Examples 1 and 3 was 270 MHz ¹ using a mixed solution of heavy para-xylene: heavy chloroform: ethylene glycol = 8: 2: 0.01 as a solvent. Quantified by ¹ H-NMR, and quantified by 270 MHz ¹ H-NMR using a mixed solution of heavy chloroform: ethylene glycol = 10: 0.01 in the ethylene-propylene copolymer of Example 2 at a weight ratio of 10: 0.01 as a solvent. did. The amount of boron-containing groups in the polypropylenes of Examples 4 to 6 was 270 M using heavy para-xylene as a solvent.
It was quantified by Hz ¹ H-NMR. The amount of the boron-containing group in the ethylene-propylene copolymers of Examples 7 and 8 was determined using deuterated chloroform as a solvent at 270 MHz ¹ H-.
Quantified by NMR. Haze measurement method JISK710
5.

Synthesis Example 1 Synthesis of Polypropylene Having a Double Bond at the Terminal: 200 g of polypropylene (polystyrene-equivalent weight average molecular weight: 780,000) was charged into a separable flask, heated at 250 ° C. for 1 hour in a vacuum, and further heated under vacuum. Bath temperature 33
After heating to 0 ° C., heating was performed for 2 hours. After cooling, the polypropylene was taken out and pulverized to obtain a polystyrene-equivalent weight average molecular weight of 180,000 and a double bond at a terminal of 0.080.
A polypropylene having 18 meq / g was obtained.

Synthesis Example 2 Synthesis of ethylene-propylene copolymer having a double bond at the end: A separable flask was charged with 250 g of an ethylene-propylene copolymer having a propylene content of 26% and a weight average molecular weight in terms of polystyrene of 260,000, and was placed under vacuum. Bath temperature at 280 ℃ 3
After heating for 0 minutes, the bath temperature was further increased to 320 ° C. and
By heating for 0 minutes, the propylene content is 26%,
An ethylene-propylene copolymer having a polystyrene-equivalent weight average molecular weight of 130,000 and having a terminal double bond of 0.035 meq / g was obtained.

Synthesis Example 3 Synthesis of Low-Density Polyethylene Having a Double Bond at the Terminal: A separable flask was charged with 200 g of low-density polyethylene having a weight average molecular weight of 230,000 in terms of polystyrene, and heated under vacuum at a bath temperature of 260 ° C. for 30 minutes. And the bath temperature 3
By raising the temperature to 40 ° C. and heating for 2 hours, a low-density polyethylene having a weight average molecular weight in terms of polystyrene of 80,000 and having a double bond at a terminal of 0.06 meq / g was obtained.

Synthesis Example 4 Synthesis of Polypropylene Having Phenylboronic Acid Ethylene Glycol Ester Group: A maleic anhydride-modified polypropylene (maleic anhydride content 0.014 meq / m) synthesized in a separable flask having a stirrer and a cooler by a known method. g, polystyrene equivalent weight average molecular weight 190,000) 20 g, xylene 50
g in a separable flask. Separately, 10 g of xylene, 155 of 3-aminophenylboronic acid monohydrate
and a 3-aminophenylboronic acid ethylene glycol ester / xylene solution prepared by dehydration distillation of 62 mg of ethylene glycol and 62 mg of ethylene glycol.
Heat for 3 hours. After cooling, the precipitate was purified by reprecipitation with acetone and then dried to obtain a polystyrene-equivalent weight average molecular weight of 19.
Have 0.013 meq / g of phenylboronic acid ethylene glycol ester group, and the boronic acid group has sp ²
An atom-bonded polypropylene was obtained.

Example 1 Synthesis of polypropylene having a boronic acid group at a terminal: 100 g of the polypropylene obtained in Synthesis Example 1 and 200 g of decalin in a separable flask equipped with a condenser and a stirrer.
g), and the atmosphere was replaced with nitrogen. 2.3 g of trimethyl borate and 380 mg (mg) of triethylamine borane were added thereto, and the mixture was reacted at 180 ° C. for 4 hours, and then cooled to room temperature. The obtained gel-like polypropylene is thoroughly washed with a mixture of methanol and acetone at a ratio of 1: 1 and then washed and dried with a mixture of water and acetone at a ratio of 1: 1 to obtain a polystyrene-equivalent weight average molecular weight of 180,000. Polypropylene (the following formula (XI)) having a boronic acid group content of 0.013 meq / g and the boronic acid group bonded to the sp ³ carbon atom was obtained.

[0041]

Embedded image

270 MHz ¹ HN of the obtained polymer
The MR chart is shown in FIG. 1, where a peak at 3.8 ppm indicates the presence of boronic acid ethylene glycol ester formed by reacting the boronic acid in the polymer with ethylene glycol in the solvent. ing.

Example 2 Synthesis of an ethylene-propylene copolymer having a boronic acid group at a terminal: 30 g of the ethylene-propylene copolymer obtained in Synthesis Example 2 and 145 mg of a borane-pyridine complex in a separable flask equipped with a condenser. And 1.12 g of tributyl borate were charged and purged with nitrogen. After performing the reaction at 170 ° C. for 40 minutes, the temperature was raised to 220 ° C., and the reaction was performed for 1 hour.
Cool to room temperature, dissolve the resulting polymer in toluene,
After reprecipitation with a mixed solvent of methanol: acetone = 1: 1, a solution is again prepared in toluene, which is reprecipitated with a mixed solvent of acetone: water = 9: 1, and further dried under vacuum at 80 ° C. for 12 hours. With a polystyrene-equivalent weight average molecular weight of 130,000, a boronic acid group at a terminal is 0.018 meq / g.
An ethylene-propylene copolymer having a boronic acid group bonded to a sp ³ carbon atom was obtained.

Example 3 Synthesis of low-density polyethylene having a boronic acid group at a terminal: 30 g of low-density polyethylene obtained in Synthesis Example 3 and borane-pyridine complex 30 were placed in a separable flask equipped with a condenser.
0 mg, tributyl borate 2.25 g, decalin 50 g
, And the mixture was reacted at 190 ° C. for 3 hours after purging with nitrogen. After cooling to room temperature, the resulting gel-like polyethylene is thoroughly washed with a mixed solvent of methanol: acetone = 1: 1, and further washed with a mixed solvent of acetone: water = 1: 1, and dried to obtain polystyrene. Converted weight average molecular weight 8
Have 0.035 meq / g of boronic acid groups at the terminals,
In addition, polyethylene having a boronic acid group bonded to an sp ³ carbon atom was obtained.

Example 4 Synthesis of Polypropylene Having a Boronic Acid Ethylene Glycol Ester Group at the Terminal: 2 g of the boronic acid group-terminated polypropylene obtained in Example 1 was charged into a flask and purged with nitrogen.
After adding 124 mg of ethylene glycol and 20 ml of acetone, the mixture was reacted at room temperature for 24 hours, washed with acetone, and dried in vacuo to obtain a polystyrene-equivalent weight average molecular weight of 180,000 and a boronic acid ethylene glycol ester group of 0.012 meq / g and polypropylene having the boronic ester group bonded to the sp ³ carbon atom.

Example 5 Synthesis of polypropylene having a boronic acid 1,3-propanediol ester group at the terminal: 152 mg of 1,3-propanediol was used instead of 124 mg of ethylene glycol, and the other conditions were the same as in Example 4. As a result of the reaction, a 1,3-propanediol boronic acid group having a weight average molecular weight of 180,000 in terms of polystyrene was provided at a terminal with 0.012 meq / g, and the boronic ester group was bonded to an sp ³ carbon atom. Got polypropylene.

Example 6 Synthesis of Polypropylene Having Boronate Glycerin Ester Group at the End: Glycerin 1 instead of 124 mg of ethylene glycol
The same reaction as in Example 4 was carried out except for using 84 mg, and a polystyrene-equivalent weight average molecular weight of 180,000 was obtained.
0.013me boronic acid glycerin ester group at the terminal
A polypropylene having q / g and the boronate group bonded to the sp ³ carbon atom was obtained.

Example 7 Synthesis of an ethylene-propylene copolymer having a boronic acid ethylene glycol ester group in the side chain: An ethylene-propylene-ethylidene synthesized by a known method in a separable flask having a stirring group and a condenser. 20 g of a norbornene copolymer (propylene content 28%, ethylidene norbornene content 1%, polystyrene-equivalent weight average molecular weight 80,000) and decalin 150 ml were charged into a separable flask and subjected to nitrogen substitution. 4.6 g of borate were added. After reacting at 200 ° C. for 3 hours, the mixture was cooled to room temperature, and the obtained polymer solution was reprecipitated with a mixed solvent of methanol: acetone = 1: 1, dissolved in 100 ml of toluene, and further dissolved in 1 ml of ethylene glycol.
Was added and stirred at room temperature for 5 hours. This solution was reprecipitated with acetone, and further vacuum-dried at 100 ° C. for 12 hours to obtain 0.07me of boronic acid ethylene glycol ester having a weight average molecular weight of 100,000 in terms of polystyrene and a side chain.
An ethylene-propylene copolymer having q / g and having the boronic ester group bonded to the sp ³ carbon atom was obtained.

Example 8 Synthesis of an ethylene-propylene copolymer having a boronic acid ethylene glycol ester group at a terminal: 20 g of the ethylene-propylene copolymer obtained in Example 2 in a separable flask having a stirrer and a condenser. ,
100 ml of toluene and 1 g of ethylene glycol were charged and the atmosphere was replaced with nitrogen. After heating and dissolving at 80 ° C. with stirring, the mixture was further heated for 30 minutes. The resulting solution was reprecipitated with acetone, and then dried under vacuum to obtain a polystyrene-equivalent weight average molecular weight of 130,000, having a boronic acid ethylene glycol ester group at a terminal of 0.018 meq / g and the boronic ester group being An ethylene-propylene copolymer bonded to sp ³ carbon atoms was obtained.

Example 9 In Example 4, 5 g of a polypropylene having a boronic acid ethylene glycol ester group at the terminal and EVAL (registered trademark) -F101 manufactured by Kuraray (ethylene content: 32 mol%, saponification degree: 99.5%, hydrous phenol) Using 45 g of an ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 1.1 dl / g at 30 ° C. in a medium, melt kneading was performed under the following conditions. Machine used: Plastograph Rotor shape: Roller type Number of revolutions: 80 rpm Kneading temperature: 220 ° C. Kneading time: 10 minutes The resin composition obtained by the above method was hot pressed at 220 ° C. to form a 100 μm thick film. did. This film was broken in liquid nitrogen, and the fracture surface was 14
After extraction with xylene at 0 ° C., the fracture surface was observed with a scanning electron microscope. As a result, the average particle size of the polypropylene was 0.3 μm, and the haze of this press film was 13%. This piece of film was treated with hot water at 110 ° C. for 30 minutes under pressure, but the shape of the film was hardly changed.

Comparative Example 1 The procedure of Example 8 was repeated, except that 5 g of the polypropylene having a phenylboronic acid ethylene glycol ester group of Synthesis Example 4 was used instead of 5 g of the polypropylene having an ethylene glycol ester boronate group at the end. When the film was obtained, the average dispersed particle size of the polypropylene was 0.1.
6 μm, haze was 22%. When the film was treated with hot water at 110 ° C. for 30 minutes, the shape of the film was hardly changed.

Comparative Example 2 A film was prepared in the same manner as in Example 8, except that 5 g of a polypropylene having a double bond at the end of Synthesis Example 1 was used instead of 5 g of a polypropylene having a boronic acid ethylene glycol ester group at the end. As a result, the average dispersed particle size of the polypropylene was 5 μm, the haze of the film was 38%, and both the compatibility and the transparency were poor. 110 ° C
Was partially deformed by hot water treatment.

Comparative Example 3 Kuraray Eval (registered trademark) -F101 alone was used for 220
After hot pressing at 0 ° C., hot water treatment was performed under the same conditions as in Example 8, and as a result, the original shape was not completely retained.

Example 10 In place of the polypropylene having a boronic acid ethylene glycol ester group at the end, 10 g of an ethylene-propylene copolymer having a boronic acid group at the end of Example 2 was used, and further, EVAL (registered trademark) manufactured by Kuraray was used. -F101
(Ethylene content 32 mol%, intrinsic viscosity in water-containing phenol at 30 ° C. 1.1 dl / g) A film was obtained in the same manner as in Example 9 except that 40 g of EVAL® was used instead of 45 g. As a result, the average dispersed particle size of the ethylene-propylene copolymer in the film was 0.3 μm, and the haze of the film was 40%. Further, a notched Iz of a sample piece obtained by molding the above composition by a small injection molding machine is used.
When the od impact strength was measured according to the method of JIS K7120, it did not break.

Comparative Example 4 The procedure of Example 10 was repeated except that 10 g of the ethylene-propylene copolymer having a double bond at the terminal was used instead of 10 g of the ethylene-propylene copolymer having a boronic acid group at the terminal. When a film was obtained in the same manner, the average dispersed particle size of the ethylene-propylene copolymer in the film was 6 μm.
m, the haze of the film was 78%, and the notched Izod impact strength of the injection-molded sample piece was 8 Kgfc.
m / cm ² .

Comparative Example 5 Notched Iz of a sample piece injection-molded in the same manner as in Example 10 using only KURARAY® EVAL (registered trademark) -F101
The od impact strength was 2.1 kgfcm / cm ² .

Example 11 5 g of low-density polyethylene having a boronic acid group at the end of Example 3 instead of 10 g of an ethylene-propylene copolymer having an ethylene glycol ester boronic acid terminal at the end
And EVAL (registered trademark) -F10 manufactured by Kuraray
1 (Ethylene content 32 mol%, in water-containing phenol at 30 ° C
A film was obtained in the same manner as in Example 3 except that 45 g of Kuraray's EVAL (registered trademark) -F101 was used instead of 40 g of the intrinsic viscosity of 1.1 dl / g in Example 1, and the average dispersed particle size of polyethylene in the film was obtained. Is 0.4 μm, the haze of the film is 12%, and the notched Izod of the sample is
The impact strength was 12 kgfcm / cm ² .

Comparative Example 6 A film was obtained in the same manner as in Example 11, except that 5 g of low-density polyethylene (weight average molecular weight in terms of polystyrene: 160,000) was used instead of 5 g of low-density polyethylene having a boronic acid group at the terminal. The average dispersed particle size of polyethylene in the film was 4 μm, the haze of the film was 20%, and the notched Izod impact strength of the injection-molded sample piece was 3.5 kgfcm / cm ² .

[0059]

According to the present invention, an olefin polymer having good compatibility with various thermoplastic resins, particularly a polymer having a polyvalent hydroxyl group such as an ethylene-vinyl alcohol copolymer can be obtained. Further, the olefin polymer of the present invention is useful for improving the performance of the ethylene-vinyl alcohol copolymer such as impact resistance and hot water resistance.

[Brief description of the drawings]

FIG. 1 shows a 270 MHz ¹ H-NMR chart of a polypropylene having a boronic acid group at a terminal obtained in Example 1.

Claims (4)

(57) [Claims] 1. A boronic acid group represented by the following formula (II): Alternatively, at least one selected from the group consisting of a boronic ester group represented by the following general formula (III), a boronic anhydride group represented by the following general formula (IV), and a boronic acid salt group represented by the following general formula (V) A boron-containing group of the formula: Embedded image Embedded image Ｘ In the formula, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (such as a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms), and an alicyclic hydrocarbon group (a cycloalkyl group, A cycloalkenyl group) or an aromatic hydrocarbon group (phenyl group, biphenyl group, etc.), and X and Y may be the same or different. In addition, X and Y may be bonded. However, it is excluded when both X and Y are hydrogen atoms. R ² , R ³ , and R ⁴ represent the same hydrogen atom, aliphatic hydrocarbon atom, alicyclic hydrocarbon group, and aromatic hydrocarbon group as those of X and Y, and R ² , R ³ , and R ⁴ represent The same group or different groups may be used. M represents an alkali metal or an alkaline earth metal. In addition, X,
Y, R ² , R ³ , and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group, and a halogen atom. ｝
Having at least one functional group of the following formula (I): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), which is an olefin polymer having a repeating structural unit represented by the formula: wherein the boronic acid group or the boron-containing group is A compatibility improver consisting of an olefin polymer bonded to sp ³ carbon atoms in the coalescence. 2. It has a boronic ester group obtained by reacting a boronic acid group with a polyhydric alcohol, and has the following formula (I): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), which is an olefin polymer having a repeating structural unit represented by the following formula: Olefinic polymer bonded to sp ³ carbon atoms. 3. A boronic acid ethylene glycol ester group, a boronic acid propylene glycol ester group (a boronic acid 1,2-propanediol ester group, a boronic acid 1,2).
3-propanediol ester group), neopentyl glycolate boronate group, catechol ester boronate group, glycerol boronate group, trimethylol ethane boronate group, diethanolamine boronate group. Having a selected boronic ester group and having the following formula (I): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), which is an olefin polymer having a repeating structural unit represented by the following formula: Olefinic polymer bonded to sp ³ carbon atoms. 4. A boronic acid group represented by the following formula (II): Alternatively, at least one selected from the group consisting of a boronic ester group represented by the following general formula (III), a boronic anhydride group represented by the following general formula (IV), and a boronic acid salt group represented by the following general formula (V) A boron-containing group of the formula: Embedded image Embedded image Ｘ In the formula, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (such as a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms), and an alicyclic hydrocarbon group (a cycloalkyl group, A cycloalkenyl group) or an aromatic hydrocarbon group (phenyl group, biphenyl group, etc.), and X and Y may be the same or different. In addition, X and Y may be bonded. However, it is excluded when both X and Y are hydrogen atoms. R ² , R ³ and R ⁴ represent the same hydrogen atom, aliphatic hydrocarbon atom, alicyclic hydrocarbon group and aromatic hydrocarbon group as those of X and Y, and R ² , R ³ and R ⁴ represent The same group or different groups may be used. M represents an alkali metal or an alkaline earth metal. In addition, X,
Y, R ² , R ³ , and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group, and a halogen atom. ｝
Having at least one functional group of the following formula (I): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), which is an olefin polymer having a repeating structural unit represented by the formula: wherein the boronic acid group or the boron-containing group is A method for producing an olefin polymer bonded to an sp ³ carbon atom in a coalescence, comprising reacting a borane complex and a trialkyl borate with an olefin polymer having a carbon-carbon double bond. A method for producing the olefin polymer.