JPH0725918A - Reactive polymer - Google Patents

Abstract

PURPOSE:To obtain a reactive polymer useful as compatibility improver for various polymers, having a boron-containing functional group, convertible into a boronate group or borinate group mixture boronate group, borinate group and water, at the end and high reactivity. CONSTITUTION:Sodium boron hydride, benzophenone and metal sodium are added to dried THF, incorporated with trifluoroboron-diethyl ester complex, 2-propene-1-thiol is dripped and reaction is carried out to give 3- mercaptopropylboronic acid ethylene glycol ester. Then, this compound is mixed with styrene, heated to 120 deg.C and reacted with azobiscyclohexanecarbonitrile. Methanol is poured into the reaction mixture, the precipitated polymer is recovered and dried to give the objective polymer containing a functional group composed of a boron-containing group convertible to boronate group or borinate group in the presence of a boronate group, borinate group and water, at the end.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Styrene-based polymers, acrylamide-based polymers, acrylic-based polymers and vinylpyrrolidone-based polymers having a boronic acid group in the side chain are known. {For example, JP-A-4-124145, JP-A-4-124144, Macr
OMOLECULES, 24 volumes, 4224-4226 pages (1991), Macromolecules, 2
Volume 3, pages 4525-4527 (1990), JP-A-59-223706, Journal of of Poly.
mer, Science, Polymer, Chemi
story, Edition, 20 volumes, 1949-195
2 page (1982), JP-A-55-66910}.

[0003]

However, in a blend of a boronic acid thermoplastic resin having a boronic acid group in a side chain and a thermoplastic resin having a hydroxyl group in a side chain such as an ethylene-vinyl alcohol copolymer, crosslinking occurs. Therefore, the gelation tends to deteriorate the appearance of the film. However, the object of the present invention, when melt-kneading with a thermoplastic resin having a hydroxyl group, or when melt-kneading a vinyl-based polymer or a diene polymer and a thermoplastic resin having a hydroxyl group, compatibility is good. Another object of the present invention is to provide a polymer which gives a composition having good transparency and mechanical properties.

[0004]

The above object is to provide a functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boronic acid group or a boron-containing group which can be converted into a boric acid group in the presence of water. It is achieved by providing a vinyl-based or diene-based polymer having an end.

The vinyl-based polymer having a functional group selected from the group consisting of a boronic acid group used in the present invention, a boric acid group, and a boron-containing group convertible into a boronic acid group or a boric acid group in the presence of water at the end. What is a polymer or diene polymer?
A boronic acid group, a borinic acid group, or a functional group selected from the group consisting of a boronic acid group or a boron-containing group that can be converted to a boric acid group in the presence of water is bound to one or both ends by a boron-carbon bond, It is a vinyl-based or diene-based polymer composed of a vinyl-based monomer or a diene-based monomer. In the present invention, the boronic acid group is represented by the following formula (I).

[0006]

[Chemical 1]

The boron-containing group which can be converted to a boronic acid group in the presence of water (hereinafter abbreviated as boron-containing group) is a boron-containing group represented by the above formula (I) which is hydrolyzed in the presence of water. Any group containing a boron-containing group that can be converted into an acid group may be used, but as a representative example, the following general formula (I
A boronic acid ester group represented by I), represented by the following general formula (II
A boronic acid anhydride group represented by I), the following general formula (IV)
The boronic acid group represented by

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[Wherein, X and Y are hydrogen atoms, aliphatic hydrocarbon groups (straight chain or branched alkyl groups having 1 to 20 carbon atoms, alkenyl groups, etc.), alicyclic hydrocarbon groups (cyclo It represents an alkyl group, a cycloalkenyl group, etc.) or an aromatic hydrocarbon group (phenyl group, biphenyl group, etc.), and X and Y may be the same or different.
Further, X and Y may be combined. However, it is excluded when both X and Y are hydrogen atoms. Also R ↑ 1, R ↑
2 and R ↑ 3 represent the same hydrogen atom, aliphatic hydrocarbon atom, alicyclic hydrocarbon group and aromatic hydrocarbon group as those of X and Y, and R ↑ 1, R ↑ 2 and R ↑ 3 are the same. It may be a base or different. M represents an alkali metal or an alkaline earth metal. Also, the above X, Y, R ↑ 1, R ↑
2, R ↑ 3 may have another group such as a hydroxyl group, a carboxyl group, or a halogen atom. }

Specific examples of the boronic acid ester group represented by the general formulas (II) to (IV) include a boronic acid dimethyl ester group, a boronic acid diethyl ester group, a boronic acid dibutyl ester group, a boronic acid dicyclohexyl group, and a boronic acid ethylene group. Glycol ester group, boronic acid propylene glycol ester group (boronic acid 1,2-propanedio-
Ester ester group, boronic acid 1,3-propanediol ester group), boronic acid neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, boronic acid trimethylolethane ester group, boronic acid diethylanol group. A boronic acid ester group such as a ruamine ester group and a boronic acid triethanolamine amine group; a boronic acid anhydride group; an alkali metal base of boronic acid,
Examples thereof include alkaline earth metal bases of boronic acid.

In the present invention, the borinic acid group is represented by the following formula (V).

[0014]

[Chemical 5]

The boron-containing group which can be converted to a borinic acid group in the presence of water is a boron-containing group which can be converted to a borinic acid group represented by the above formula (V) by being hydrolyzed in the presence of water. Any of them may be used, but as a representative example, a borinic acid ester group represented by the following general formula (VI),
Examples thereof include a borinic acid anhydride group represented by the following general formula (VII) and a borinic acid group represented by the following general formula (VIII).

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

{In the formula, X has the same meaning as X in the above general formula (II), and Z is the same aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group as the above X, Amino group,
Represents an amide group. Further, X and Z may be bonded.
Further, R ↑ 1, R ↑ 2, and R ↑ 3 have the same meanings as R ↑ 1, R ↑ 2, and R ↑ 3 in the general formula (IV). Further, M has the same meaning as M in formula (IV). }

Specific examples of the borinic acid ester group represented by the general formulas (VI) to (VIII) include X, Z, R ↑ 1,
Examples thereof include those in which R ↑ 2 and R ↑ 3 represent a lower hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 1-methylpropyl group, a pentyl group, a hexyl group and a phenyl group. As typical examples, methylborinic acid group, methylborinic acid methyl ester group, ethylborinic acid ethyl ester group, butylborinic acid methyl ester group, 3-methyl-2
-Butylborinic acid methyl ester group. The boron-containing group which can be converted into a boronic acid group or a borinic acid group among the above functional groups means that the reaction time is 10 minutes in water or a mixed solvent of water and an organic solvent (toluene, xylene, acetone, etc.). It means a group which can be converted to a boronic acid group or a borinic acid group when hydrolyzed under the conditions of a reaction temperature of room temperature to 150 ° C. for ˜2 hours.

It is preferable that the functional group is bonded to substantially only terminals (one terminal or both terminals) of the vinyl or diene polymer, and the total amount thereof is 0.0001 to.
The range of 1 milliequivalent / g of polymer (meq / g) is preferable, and 0.001 to 0.1 meq / g is particularly preferable.

The bonding form of the functional group to the vinyl polymer or diene polymer may be either directly bonded to the carbon atom of the monomer unit at one end or both ends of the polymer, or one end thereof. Alternatively, it may be one bonded to the carbon atom of the divalent linking group bonded to the monomer units at both ends. The type of the linking group is not particularly limited, and examples thereof include an alkylene group and a phenylene group, and particularly, an alkylene group {the following formula (I
X) or a group represented by (X)} is preferable. These divalent linking groups may contain oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of such a divalent linking group include linking groups of the following formulas (IX) to (XI).

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

The monomer units constituting the vinyl polymer or diene polymer of the present invention include vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl pivalate; methyl acrylate and ethyl acrylate. −
Acrylate ester monomers such as butyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate -Methacrylate ester monomers such as-, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, etc .;
Acrylamides such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N
-Methacrylamides such as dimethylmethacrylamide;
Vinyl halides such as vinyl chloride, vinylidene chloride and vinyl fluoride; aromatic vinyl monomers such as styrene and α-methylstyrene; acrylonitrile monomers such as acrylonitrile and methacrylonitrile; butadiene; Examples thereof include diene-based monomers such as isoprene, cyclopentadiene, and chloroprene. Here, the monomer constituting the vinyl polymer does not mean an olefin monomer. However, it is free to use an olefinic monomer as another monomer component in a small amount, for example, in a range of less than 50% by weight.

The vinyl polymer or diene polymer of the present invention comprises one, two, or three or more of these monomers. In the case of a copolymer of two components or three or more components, the chain distribution is not particularly limited, and may be a random copolymer, a block copolymer or a graft copolymer.

Suitable base polymers of the present invention include:
Polystyrene, polymethyl (meth) acrylate, hydrogenated product of styrene-diene block polymer (styrene-isoprene block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene) Hydrogenated products such as block copolymers) are particularly preferred.

The molecular weight of the vinyl polymer or diene polymer of the present invention is not particularly limited, but the styrene-equivalent weight average molecular weight by gel permeation chromatography (hereinafter abbreviated as GPC) is 1000 or more, preferably. It is 1,000 to 1,000,000, and more preferably 10,000 to 300,000.

Next, a typical method for producing a vinyl polymer and a diene polymer having a functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group according to the present invention will be described. The first production method; the vinyl-based polymer and the diene-based polymer having at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group at the terminal are boronic acid groups,
It can be obtained by polymerizing a vinyl monomer and / or a diene monomer in the presence of a thiol having a functional group selected from a borinic acid group or a boron-containing group.

The thiol having a boronic acid group or a boron-containing group as a raw material is obtained by reacting a thiol having a double bond with a diborane or borane complex in a nitrogen atmosphere, and then adding an alcohol or water. To be Further, a thiol having a borinic acid group or a boron-containing group is reacted with a thiol having a double bond, a diborane or a borane complex and an olefin in a nitrogen atmosphere, and then an alcohol
It can be obtained by adding rutile or water. Here, as the thiol having a double bond, 2-propene-1-thiol, 2-methyl-2-propen-1-thiol, 3
-Butene-1-thiol, 4-pentene-1-thiol and the like, among which 2-propen-1-thiol and 2-methyl-2-propen-1-thiol are preferable. As the borane complex, borane-tetrahydrofuran complex, borane-dimethylsulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine complex are preferable, and among them, borane-tetrahydrofuran complex is particularly preferable. The amount of diborane or borane complex added is preferably about the same as the amount of thiol having a double bond. The reaction conditions are room temperature to 200 ° C.
Is preferred. Tetrahydrofuran (TH
F), ether solvents such as diglyme; saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane, decalin, etc., among which THF is preferred. The alcohols added after the reaction include methanol.
Lower alcohols such as alcohol and ethanol are preferable, and particularly,
Methanol is preferred. The olefins added when producing a thiol having a borinic acid group are not particularly limited, but ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl- 1-
Lower olefins such as butene, 2-methyl-2-butene, 1-hexene and cyclohexene are preferred.

In the presence of the thus obtained thiol having a functional group selected from a boronic acid group, a borinic acid group and a boron-containing group, it is selected from vinyl-based monomers and diene-based monomers. A polymer having the functional group at the terminal is obtained by radically polymerizing at least one kind. As the polymerization conditions, an azo-based or peroxide-based initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C.
The addition amount of the thiol having the functional group is 1 g of monomer
The amount of thiol added is not particularly limited, but if a monomer such as vinyl acetate or styrene that is easily chain-transferred is used, it may be added during the polymerization. It is preferable to feed thiol, and when a chain transfer-resistant substance such as methyl methacrylate is used, it is preferable to add thiol from the beginning.

The end groups of the vinyl polymer and the diene polymer having a functional group selected from the boronic acid group, the borinic acid group and the boron-containing group at the end as described above generally have high reactivity and ester. It can be converted into another boron-containing group by a reaction such as exchange or hydrolysis. For example, a boronic acid dimethyl ester group is easily hydrolyzed to a boronic acid group by moisture in the air, and a boronic acid group is converted to a boronic acid ethylene glycol ester by reacting ethylene glycol with the boronic acid group. Dehydrated and condensed to form boronic anhydride. When the terminal group of the polymer is a boronic acid group, the terminal groups are condensed with each other by heating to form a boronic acid anhydride, and the melt viscosity increases, but such increase in melt viscosity is caused by ethylene glycol, 1,3-
It can be prevented by reacting a polyhydric alcohol such as propanediol and esterifying.

Second method: Boronic acid, borinic acid,
Among vinyl-based polymers having a functional group selected from a boron-containing group at the end, diene-based polymers and hydrogenated products thereof, vinyl-based polymers and diene-based polymers are vinyl-based monomers or diene-based monomers. It is obtained by anionically polymerizing the body with an organic alkali metal and then terminating the anionic living end with a borate ester.

Further, by hydrogenating (hydrogenating) the carbon-carbon double bond in the diene component of these diene polymers, and further the copolymer of vinyl monomer and diene monomer. It is possible to obtain a hydrogenated product of a diene-based polymer having a functional group selected from boronic acid, boric acid, and a boron-containing group at the terminal, or a copolymer of a vinyl monomer and a diene-based monomer. Specifically, n-butyllithium, s
-Using an anionic polymerization initiator such as butyllithium,
A saturated aliphatic hydrocarbon compound such as hexane, heptane, or cyclohexane, or an aromatic hydrocarbon compound such as benzene or toluene is used as a solvent and added dropwise at a temperature condition of 30 to 60 ° C. to have a boronic acid at a terminal. A vinyl-based polymer, a diene-based polymer, and a copolymer thereof can be obtained. Subsequently, a boric acid polymer having a boronic acid ester at the end is added by dropping boric acid ester such as triethyl borate to the anion living terminal at a temperature condition of 30 to 60 ° C. in the system. , A diene-based polymer, and a copolymer thereof can be obtained. Further, by hydrogenating the obtained diene-based polymer and diene-based copolymer, a diene-based polymer having a boronic acid at a terminal and a hydrogenated product of these copolymers can be produced. As the hydrogenation catalyst, a homogeneous catalyst or a heterogeneous catalyst can be used. For example, as a homogeneous catalyst, a saturated aliphatic hydrocarbon compound such as hexane or heptanecyclohexane, or an aromatic hydrocarbon compound such as benzene or toluene is used as a solvent, and an organic transition metal catalyst (for example, nickel acetoacetonate or cobalt acetylacetoate) is used. Nate, nickel naphthenate, cobalt naphthenate, etc.) and a Ziegler catalyst, which is a combination of an alkyl compound of a metal such as aluminum, an alkali metal, or an alkaline earth metal, etc. per double bond of the polymer subjected to hydrogenation. About 001 to 0.1 mol% is used.
Hydrogenation reaction is from room temperature to 150 ° C, normal pressure to 50 kg / cm ↑ 2
Under hydrogen pressure of 1 hour to 50 hours. After completion of the hydrogenation reaction, the hydrogenation catalyst is dissolved in water by adding acidic water in a container and stirring vigorously. By removing the aqueous phase of the two phases that have been phase-separated and further removing the solvent, a diene polymer having a boronic acid group at the terminal and a hydrogenated product of the copolymer thereof are obtained.

The hydrogenation rate of the above polymer is not particularly limited,
The range of 10 to 100% is preferable, and the range of 50 to 100% is more preferable. The hydrogenated reactive polymer of the present invention has good weather resistance, good compatibility with ethylene-vinyl alcohol copolymer, and softness of ethylene-vinyl alcohol copolymer. It is useful as an additive for the purpose of improving the properties and impact resistance.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, in the following synthesis examples and examples, unless otherwise specified, a ratio means a weight ratio and “%” means “% by weight”. The weight average molecular weight is measured by using tetrahydrofuran as a solvent unless otherwise specified.
Is a polystyrene-equivalent weight average molecular weight. The amount of boronic acid groups in the resin was quantified by 270 MHz ↑ 1H-NMR using a mixed solution of deuterated chloroform: ethylene glycol = 10: 0.02 as a solvent.
The amount of borinic acid and its ester group was quantified by 500 MHz ↑ 1 NMR using deuterated chloroform as a solvent. The haze was measured according to JIS K7105.

Synthesis Example 1 Synthesis of 3-mercaptopropylboronic acid ethylene glycol ester: 19.26 g of sodium borohydride (NaBH ↑ 4) in a flask equipped with a condenser and a dropping funnel.
Was charged and the atmosphere was replaced with nitrogen. 500 ml of THF, which was dried and distilled over benzophenone and sodium metal.
Was charged, and the mixture was cooled to 0 ° C. in an ice bath, then, while being stirred, boron trifluoride-diethyl ether complex 99.
95 g was added dropwise over 30 minutes. After 2 hours, 45.61 g of 2-propene-1-thiol was added dropwise at 0 ° C. over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C. and stirring was further performed for 3 hours. After cooling to 0 ° C, 100 mL of methanol was added dropwise over 40 minutes. The reaction solution was filtered to remove solids, the solvent was distilled off, 38 g of ethylene glycol was added, and the mixture was extracted with methylene chloride-water to remove excess ethylene glycol, dried over magnesium sulfate, and distilled under reduced pressure. This gave 46.7 g of a 4: 1 mixture of 3-mercaptoboronic acid ethylene glycol ester and 2-mercapto-1-methylethylboronic acid ethylene glycol ester. Boiling point 70 ° C (4mmHg)

Synthetic Example 2 Synthesis of 3-mercaptopropylboronic acid dimethyl ester After purging a flask equipped with a condenser and a dropping funnel with nitrogen, a 1 mol / l THF solution of a commercially available borane-THF complex (A
(manufactured by ldrich) was charged, cooled to 0 ° C. in an ice bath, and 23 g of 2-propene-1-thiol was added to 3 ml.
Dropping was performed over 0 minutes. After stirring for 1 hour, the temperature was raised to 60 ° C, and after further stirring for 3 hours, the mixture was cooled to 0 ° C and methanol 5 was added.
0 ml was added dropwise over 30 minutes. After distilling off the solvent, distillation under reduced pressure gave 24 g of a 4: 1 mixture of 3-mercaptoboronic acid dimethyl ester and 2-mercapto-1-methylethylboronic acid dimethyl ester glycol ester. Boiling point 50 ° C (1mmHg)

Synthesis Example 3 Synthesis of 4- (2-mercaptoethyl) phenylboronic acid ethylene glycol ester: 2.92 g of 4-vinylphenylboronic acid, 1.38 g of ethylene glycol in a flask equipped with a dehydration distillation tube. Charge 50 ml of benzene, 80
It heated at 30 degreeC for 30 minutes, and distilled water was removed. To this reaction solution, 3.18 g of thioacetic acid and 47 mg of azobisisobutyronitrile were added, and the mixture was heated at 75 ° C for 2 hours. After distilling off the reaction solvent, the residue was extracted with methylene chloride / sodium hydrogen carbonate aqueous solution, the methylene chloride layer was dried over magnesium sulfate, and then the solvent was distilled off. 5 g of crude 4- (2-acetylthioethyl) phenylboronic acid ethylene glycol ester thus obtained, 20 ml of methanol,
Triethylamine (10 ml) was charged into a flask, reacted under nitrogen at 65 ° C. for 20 hours, and then distilled under reduced pressure to obtain 4- (2-mercaptoethyl) phenylboronic acid ethylene glycol ester (3.55 g). Boiling point 135 ° C (0.2mmH
g)

Synthesis Example 4 Synthesis of 3-mercaptopropyl (3-methyl-2-butyl) borinic acid methyl ester: A flask equipped with a dropping funnel and a stirrer was purged with nitrogen, and 1 mol / l borane THF was used. 310 ml of solution was charged. After cooling to 0 ° C. with an ice bath, 21.74 g of 2-methyl-2-butene was added dropwise over 6 minutes while stirring. After 30 minutes at 0 ° C., 22.79 g of 2-propene-1-thiol was added to 30
Dropping was carried out over a period of minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C. and stirring was further performed for 1 hour. After cooling to 0 ° C., 50 ml of methanol was added dropwise over 12 minutes. After distilling off the solvent, 3-mercaptopropyl (3-methyl-2-butyl) borinic acid methyl ester 2 was obtained by distillation.
7.2 g was obtained. Boiling point 50 ° C (0.5mmHg)

Example 1 Synthesis of polystyrene having a boronic acid ethylene glycol ester group at the end: 500 g of styrene in a flask equipped with a stirrer and a reflux condenser and the 3-mercaptopropylboronic acid ethyleneglycol obtained in Synthesis Example 1. Then, 0.0765 g of luster (MPBE) was charged and deaeration under reduced pressure was performed. After heating to 120 ° C, MPBE 0.394
%, Azobiscyclohexanecarbonitrile 0.069
% Styrene solution first at 7.2 ml feed, then at 0.
Feeding was performed at a rate of 5 ml / min, and after 210 minutes, the reaction and feeding were stopped. The polymerization rate at this time was 45%. This polystyrene was purified by reprecipitation with methanol and then dried to obtain a boronic acid group content of 0.0
Polystyrene having 13 meq / g and a weight average molecular weight of 130,000 and having a boronic acid ethylene glycol ester at the end was obtained.

Example 2 Synthesis of polymethyl methacrylate having a boronic acid ethylene glycol ester ester group at the end: Methyl methacrylate 15 in a flask equipped with stirrer and condenser.
0 g, 0.876 g of 3-mercaptoboronic acid ethylene glycol ester obtained in Synthesis Example 1 was charged, deaeration was performed by blowing nitrogen, and then the temperature was raised to 80 ° C. and separately prepared azobisisobutyrate. 0.2 of ronitrile
After the first addition of 1.5 ml of 3% toluene solution, 0.5 ml was added every 30 minutes. After 5 hours, it was cooled and the polymerization was stopped. The polymerization rate at this time was 47%. The obtained polymethylmethacrylate was reprecipitated with methanol and then dried to obtain a boronic acid ethylene glycol ester group at the terminal having a boronic acid group amount of 0.03 meq / g and a styrene-converted weight average molecular weight of 58,000. Having polymethyl methacrylate {the following formula (XII) and the following formula (XII)
I) about 8: 2 mixture} was obtained.

[0044]

[Chemical 12]

[0045]

[Chemical 13]

270 MHz ↑ 1H- of the obtained polymer
The NMR chart is shown in FIG.
Indicates the presence of a boronic acid ethylene glycol ester represented by (XII), and a peak of 4.2 ppm indicates (XI
The presence of the boronic acid ethylene glycol ester represented by II) is shown.

Example 3 Synthesis of polymethyl methacrylate having a boronic acid ethylene glycol ester ester group at the terminal: The mercapto obtained in Synthesis Example 3 instead of the 3-mercaptoboronic acid ethylene glycol ester in Synthesis Example 1. Polymerization and post-treatment were carried out under the same conditions as in Example 2 using 1.248 g of ethylene glycol ethylphenylboronic acid. As a result, polymethylmethacrylate having a boronic acid group content of 0.03 meq / g and a styrene-equivalent weight average molecular weight of 57,000 and a boronic acid ethylene glycol ester at the terminal was obtained.

Example 4 Synthesis of polymethylmethacrylate having a borinic acid group at the end: 150 g of methylmethacrylate in a flask equipped with a stirrer and a condenser, 3-mercaptopropyl obtained in Synthesis Example 2 After charging 1.225 g of (3-methyl-2-butyl) borinic acid methyl ester and performing deaeration by blowing nitrogen, the temperature was raised to 80 ° C., and azobisisobutyronitrile (0.1%) was separately prepared. After adding 1.5 ml of 23% toluene solution first, 0.5 ml every 30 minutes
Was added. After 5 hours, it was cooled and the polymerization was stopped. The polymerization rate at this time was 61%. The obtained polymethyl methacrylate is reprecipitated with methanol and then dried to obtain a polymethyl methacrylate having a boric acid group content of 0.03 meq / g and a weight average molecular weight of 53000 and having a boric acid group at the end. Got

Example 5 Synthesis of polyvinyl acetate having a boronic acid group at the end: Vinyl acetate 580 in a flask equipped with stirrer and condenser.
g, 0.033 g of 3-mercaptopropylboronic acid dimethyl ester (MPBDM) obtained in Synthesis Example 2 was charged and heated to 70 ° C. After 20 g of a separately prepared 0.12% vinyl acetate solution of azobisisobutyronitrile was added, a separately prepared 13 g / L ethyl acetate solution of MPBDM was fed at a rate of 0.6 ml / min. 180
Polymerization and feed were stopped after minutes. The polymerization rate at this time was 36%. The obtained polymer was reprecipitated with hexane, and the polymer was boiled in 500 ml of distilled water for 1 hour and dried to give a boronic acid group content of 0.045.
Polyvinyl acetate having a meq / g and a styrene-equivalent weight average molecular weight of 35,000 was obtained.

Example 6 Synthesis of Hydrogenated Product of Polystyrene-Polyisoprene Block Copolymer Having Boronic Acid Group at Terminal: 500 g of cyclohexane and 0.003 mol of s-butyllithium were charged in a pressure vessel having an internal capacity of 1.5 l. After heating to 500 ° C., this temperature was maintained, and 60 g of the styrene monomer was appropriately charged and then 120 g of the isoprene monomer was appropriately driven and driven. Then, 0.7 ml of sufficiently dehydrated trimethyl borate was added to the system (2 times the mole of the anion living end).
It dripped and was driven in for 1 hour. Furthermore, the Ziegler catalyst prepared outside the system was used to adjust the carbon-carbon double bond in the polymer to 0.0
After 1-fold addition, hydrogen pressure was 10 kg / cm ↑ 2 and hydrogenation temperature was 70 ° C. for 5 hours. After the completion of hydrogenation, the catalyst was decatalyzed by the addition of acidic water and then dried to obtain a styrene block having a molecular weight of 20000, a styrene content of 33%, a hydrogenation ratio of 90%, and a boronic acid group content of 0.013 meq / g. A polystyrene-polyisoprene block copolymer having an acid group was obtained.

Example 7 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester at the end of Example 3 and EVAL (registered trademark) -F101 manufactured by Kuraray (ethylene content 32 mol%, saponification degree 99.5%, Using 45 g of ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 1.1 dl / g at 30 ° C. in water-containing phenol, melt kneading was performed under the following conditions. Machine used: Plastograph Rotor shape: Roller type Rotational speed: 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 film having a thickness of 100 μm. did. This film was fractured in liquid nitrogen and the fracture surface was
After extraction with 0 ° C. xylene, the fracture surface was observed with a scanning electron microscope. As a result, the average particle size of polymethylmethacrylate was 0.08 μm, the haze of the film was 8%, and the compatibility and transparency were good.

Comparative Example 1 A film was prepared in the same manner as in Example 1 except that 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the terminal was used instead of 5 g of polymethyl methacrylate having a polystyrene equivalent weight average molecular weight of 56000. As a result, the average dispersed particle diameter of polypropylene was 2.
The film had a haze of 5 μm, a haze of 72%, and poor compatibility and transparency.

Example 8 In place of 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the end, 5 g of polystyrene-polyisoprene-block copolymer having a boronic acid group at the end of Example 6 was used. A film was obtained in the same manner as in Example 7. The polystyrene-polyisoprene block copolymer had an average dispersed particle size of 0.4 μm.
m, the haze of the film was 14%, and the compatibility and transparency were good. Further, the notched Izod impact strength of a sample piece obtained by molding the above composition with a small injection molding machine was measured by JI.
When measured according to the method of SK7120, the notched Izod impact strength was 18 Kgf / cm ↑ 2.

Comparative Example 2 Instead of 5 g of the polystyrene-polyisoprene block copolymer having a boronic acid group at the terminal, a polystyrene-polyisoprene block copolymer (styrene block molecular weight 20000, styrene content 33%, hydrogenation rate 95) was used. %)
A film was obtained in the same manner as in Example 8 except that 5 g was used. The average dispersed particle diameter of the polystyrene-polyisoprene block copolymer was 5 μm, and the haze of the film was 30.
%, And notched Iz of the injection-molded sample piece
The od impact strength was 4.5 Kgf / cm ↑ 2.

[0055]

INDUSTRIAL APPLICABILITY The vinyl polymer or diene polymer having a boron-containing group at the end of the present invention is used when melt-kneading with a thermoplastic resin having a hydroxyl group, particularly an ethylene-vinyl alcohol copolymer, or The base polymer of the present invention of the present invention is useful as a compatibility improver when melt-kneading with a vinyl polymer or a diene polymer having no boron-containing group, and the polymer of the present invention is ethylene- When melt-kneaded with a vinyl alcohol-based copolymer,
A resin composition having good gas barrier properties, compatibility, transparency and mechanical properties can be obtained.

[Brief description of drawings]

1 shows a 270 MHz ↑ 1H-NMR chart of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the terminal obtained in Example 2. FIG.

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[Procedure amendment]

[Submission date] October 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Further, by hydrogenating (hydrogenating) the carbon-carbon double bond in the diene component of these diene polymers, and further the copolymer of vinyl monomer and diene monomer. It is possible to obtain a hydrogenated product of a diene-based polymer having a functional group selected from boronic acid, boric acid, and a boron-containing group at the terminal, or a copolymer of a vinyl monomer and a diene-based monomer. Specifically, n-butyllithium, s
-Using an anionic polymerization initiator such as butyllithium,
Hexane, heptane, saturated aliphatic hydrocarbon compounds such as cyclohexane, or benzene, by the aromatic hydrocarbon compounds such as toluene is added dropwise at a temperature of 30 to 60 ° C. using a solvent, the terminal boronic acid group It is possible to obtain the vinyl-based polymer, the diene-based polymer, and the copolymer thereof. Subsequently, a boric acid ester having a boronic acid ester group at the end is added by dropping a boric acid ester such as triethyl borate in an equimolar amount or more to the anion living terminal under the temperature condition of 30 to 60 ° C. A coalesced product, a diene-based polymer, and a copolymer thereof can be obtained. Further, by hydrogenating the obtained diene-based polymer and diene-based copolymer, the boronic acid is added to the terminal.
A diene polymer having a group and a hydrogenated product of a copolymer thereof can be produced. As the hydrogenation catalyst, a homogeneous catalyst,
Alternatively, a heterogeneous catalyst can be used. For example, as the homogeneous catalyst hexane, heptane, saturated aliphatic hydrocarbon compounds such as cyclohexane, or benzene, an aromatic hydrocarbon compound such as toluene as a solvent, the organic transition metal catalyst (e.g., Nikkeruase chill acetonate,
Cobalt acetylacetonate, nickel naphthenate,
0.001 to 0.1 mol per double bond of a polymer subjected to hydrogenation of a Ziegler catalyst or the like by a combination of an alkyl compound of a metal such as cobalt naphthenate) and aluminum, an alkali metal or an alkaline earth metal Use about%. Hydrogenation reaction is from room temperature to 150 ° C, normal pressure to 50 kg
It is performed under a hydrogen pressure of / cm ↑ 2 and is completed in 1 to 50 hours. After completion of the hydrogenation reaction, the hydrogenation catalyst is dissolved in water by adding acidic water in a container and stirring vigorously. By removing the aqueous phase of the two phases that have been phase-separated and further removing the solvent, a diene polymer having a boronic acid group at the terminal and a hydrogenated product of the copolymer thereof are obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Example 2 Synthesis of polymethylmethacrylate having a boronic acid ethylene glycol ester ester group at the end: methylmethacrylate 15 in a flask equipped with stirrer and condenser.
0 g, were charged the obtained 3-mercapto-propyl rag <br/> phosphate ethylene glycol ester 0.876g in Synthesis Example 1, after performing degassed by blowing nitrogen, 8
After raising the temperature to 0 ° C. and adding 1.5 ml of a separately prepared 0.23% toluene solution of azobisisobutyronitrile,
0.5 ml was added every 30 minutes. 5 hours later, cool down,
The polymerization was stopped. The polymerization rate at this time was 47%. The obtained polymethylmethacrylate was reprecipitated with methanol and then dried to obtain a boronic acid group content of 0.03 m.
As a result, a polymethyl ester having a boronic acid ethylene glycol ester group at the end and having a weight average molecular weight of 58,000 in terms of eq / g (a mixture of the following formula (XII) and the following formula (XIII) of about 8: 2) was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Example 6 Synthesis of Hydrogenated Product of Polystyrene-Polyisoprene Block Copolymer Having Boronic Acid Group at Terminal: 500 g of cyclohexane and 0.003 mol of s-butyllithium were charged in a pressure vessel having an internal capacity of 1.5 l. After heating to 50 ° C. , 60 g of styrene monomer was added dropwise while keeping this temperature, and then 120 g of isoprene monomer was added dropwise and driven in.
Subsequently, 0.7% of fully dehydrated trimethyl borate was added to the system.
ml (2 times mol relative to the anion living end) was added dropwise, and the mixture was driven for 1 hour. Further, after adding the Ziegler catalyst prepared outside the system by 0.01 times the carbon-carbon double bond in the polymer, hydrogen pressure was 10 Kg / cm ↑ 2, hydrogenation temperature was 70
Hydrogenated at ℃ for 5 hours. After completion of the hydrogenation, the catalyst was decatalyzed by the addition of acidic water and then dried to obtain a styrene block having a molecular weight of 20,000, a styrene content of 33% and a hydrogenation ratio of 9
0%, a polystyrene having a boronic acid group at the end of the boronic acid group amount 0.013meq / g - was obtained hydrogenated product of polyisoprene block copolymer.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

Comparative Example 1 Instead of 5 g of polymethylmethacrylate having a boronic acid ethylene glycol ester group at the end. A film was obtained in the same manner as in Example 7 except that 5 g of polystyrene-converted weight average molecular weight of 56,000 was used to obtain a film. The average dispersed particle diameter of polymethyl methacrylate was 2.5 μm, and the haze of the film was 72%. Yes,
The compatibility and transparency were poor.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

[0055]

INDUSTRIAL APPLICABILITY The vinyl polymer or diene polymer having a boron-containing group at the end of the present invention is used when melt-kneading with a thermoplastic resin having a hydroxyl group, particularly an ethylene-vinyl alcohol copolymer, or The base polymer of the present invention is useful as a compatibility improver when melt-kneading with a vinyl polymer or a diene polymer having no boron-containing group, and the polymer of the present invention is an ethylene-vinyl alcohol-based polymer. When melt-kneaded with the copolymer, a resin composition having good gas barrier properties, compatibility, transparency and mechanical properties can be obtained.

Claims (2)

[Claims] 1. A vinyl-based polymer or a diene-based polymer having a functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borin group in the presence of water at the end. Polymer. 2. A polymer obtained by hydrogenating the diene polymer according to claim 1.