JP3474525B2 - Reactive polymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly reactive vinyl polymer or diene polymer, and is particularly useful as an agent for improving the compatibility of various polymers. . 2. Description of the Related Art It is common practice to introduce a small amount of a functional group in order to impart new performance to a polymer material. In particular, the introduction of a reactive functional group has a large effect of improving compatibility with other resins, adhesiveness, and the like.
This is one of the important technologies when performing lamination and the like. Boron-containing groups such as boronic acid groups have extremely high reactivity and are one of useful functional groups, and various polymers having the functional groups are known. For example, Jou
rnal of Polymer Science, P
oligomer Chemistry Edition,
20, Vol. 1949-1952 (1982), Ma
cromolecules, 23, 4525-452
7 pages (1990), Macromolecule
s, Vol. 24, pages 4224-4226 (1991),
JP-A-55-66910 and JP-A-59-2237.
06, JP-A-4-124145, JP-A-4-124145
JP-A-124144. [0003] However, boron-containing groups such as boronic acid groups are liable to gel due to their high reactivity, and increase in viscosity when melt-kneaded with other resins. And when the obtained composition is formed into a film, poor appearance such as fish eyes occurs. Thus, an object of the present invention is to increase the viscosity when melt-kneading with a thermoplastic resin having a hydroxyl group, or when melt-kneading a vinyl-based polymer or a diene-based polymer with a thermoplastic resin having a hydroxyl group. An object of the present invention is to provide a polymer which exhibits stable melting behavior, has good compatibility, and has good transparency and mechanical properties. The above objects can be attained by providing a vinyl polymer or a diene polymer having a functional group comprising a polyhydric alcohol ester of boronic acid. In the present invention, the functional group comprising a polyhydric alcohol ester of boronic acid is represented by the following general formula (I). [0006] 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), an alicyclic hydrocarbon group (cyclo An alkyl group, a cycloalkenyl group, etc.) or an aromatic hydrocarbon group (a phenyl group, a biphenyl group, etc.), and X and Y may be the same or different.
X and Y may be bonded, provided that X and Y
Are excluded when both are hydrogen atoms. The above X
And Y are other groups, for example, a hydroxyl group, a carboxyl group,
It may have a halogen atom or the like. Specific examples of the functional group comprising a polyhydric alcohol ester of boronic acid represented by the above general formula (I) include an ethylene glycol boronate group and a propylene glycol boronate group (boronic acid 1,2). -Propanediol ester group, boronic acid 1,3-propanediol ester group), neopentyl glyconate boronate
And a catechol boronate ester group, a glycerin boronate ester group, a trimethylolethane boronate group, a diethanolamine boronate group, and a triethanolamine boronate group. The amount of these functional groups is preferably in the range of 0.0001 to 1 meq / g of polymer (meq / g), more preferably 0.001 to 0.1 meq / g. The bonding form of the functional group to the vinyl polymer or diene polymer may be, for example, a form directly bonding to a carbon atom of a monomer unit of the polymer, or a form bonding to a carbon atom of a monomer unit. Examples include a form of bonding to a carbon atom of a valent linking group, but the present invention is not limited thereto. The divalent linking group is not particularly limited, and may be a group consisting of only a carbon chain, or may contain an oxygen atom, a sulfur atom, a nitrogen atom, or the like. However, the functional group is a terminal of the polymer.
The form connected only to the above is excluded. Specific examples of such a divalent linking group include an alkylene group, a phenylene group and the following general formula (II)
To (IV). [0011] Embedded image [0013] Among these, the linking groups represented by the general formulas (II) and (III) are preferred. 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, ethyl acrylate To
Acrylic ester monomers such as butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate Methacrylate monomers such as butyl methacrylate, octyl methacrylate, dodecyl methacrylate; acrylamides such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide Monomer: methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N
-Methacrylamide monomers such as dimethyl methacrylamide; vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; aromatic vinyl monomers such as styrene and α-methylstyrene; acrylonitrile; Nitrile monomers such as methacrylonitrile; butadiene,
Examples include diene monomers such as isoprene, cyclopentadiene, and chloroprene. Here, the monomer constituting the vinyl polymer does not mean an olefin monomer.
However, the olefin monomer as another monomer component,
It is free to use in small amounts, for example in the range of less than 50% by weight. The vinyl polymer or diene polymer of the present invention comprises one or more of these monomers. In the case of a copolymer of two or more components, the chain distribution is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer. When a diene monomer is contained as a monomer, a part or all of the diene monomer may be hydrogenated. Among the polymers comprising such monomers, polystyrene, polymethyl acrylate, polymethyl methacrylate, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene- Preferred are hydrogenated isoprene-styrene block copolymer and hydrogenated styrene-butadiene-styrene block copolymer. The molecular weight of the vinyl polymer or diene polymer of the present invention is not particularly limited, but the weight average molecular weight in terms of styrene by gel permeation chromatography (hereinafter abbreviated as GPC) is usually 1,000 or more, and is preferably Is from 1000 to 1,000,000, more preferably from 10,000 to 300,000. Next, a typical method for producing a vinyl polymer or a diene polymer having a functional group comprising a polyhydric alcohol ester of a boronic acid according to the present invention will be described. First Production Method: A vinyl-based polymer and a diene-based polymer having a functional group consisting of a polyhydric alcohol ester of a boronic acid are prepared in the presence of a thiol having the functional group in the presence of a vinyl-based monomer and / or It is obtained by polymerizing a diene monomer. The thiol having a functional group consisting of a polyhydric alcohol ester of boronic acid as a raw material is prepared by reacting a thiol having a double bond with a diborane or a borane complex under a nitrogen atmosphere, and then adding an alcohol or water to the borane. It is obtained by reacting it with an acid or boronic ester and further reacting with a polyhydric alcohol. 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 is preferred. As the borane complex, a borane-tetrahydrofuran complex, a borane-dimethylsulfide complex, a borane-pyridine complex, a borane-trimethylamine complex, and a borane-triethylamine complex are preferable, and among them, a borane-tetrahydrofuran complex is particularly preferable. The amount of diborane or borane complex to be added is preferably approximately equimolar to thiol having a double bond. The reaction temperature is preferably in the range from room temperature to 200 ° C. As a solvent, tetrahydrofuran (T
Ether solvents such as HF) and diglyme; and saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane and decalin. Of these, THF is preferable. As alcohols added after the reaction, lower alcohols such as methanol and ethanol are preferable, and in particular,
Methanol is preferred. Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, and 1,3-
Propanediol, neopentyl glycol, catechol
Glycerin, trimethylolethane, diethanolamine, triethanolamine and the like, but are not limited thereto. Radical polymerization of at least one selected from vinyl monomers and diene monomers in the presence of a thiol having a functional group comprising a boronic acid polyhydric alcohol ester thus obtained. Thereby, a polymer having the functional group is obtained. As the polymerization conditions, an azo- or peroxide-based initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C. The amount of the thiol having a functional group to be added is preferably about 0.0001 mmol to 1 mmol per 1 g of the monomer. The method of adding the thiol is not particularly limited. However, when a monomer that easily undergoes chain transfer such as vinyl acetate or styrene is used as the monomer, it is preferable to introduce the thiol during polymerization, and the chain transfer such as methyl methacrylate is performed. When using a material that is difficult to perform, it is preferable to add thiol from the beginning. Boronic acid groups and boronic ester groups are generally highly reactive. For example, a boronic acid dimethyl ester group is easily hydrolyzed to a boronic acid group by moisture in the air, and the boronic acid group is dehydrated and condensed by heating to form a boronic anhydride. When the functional group of the polymer is a boronic acid group, the functional groups condense upon heating to form a boronic anhydride, and the melt viscosity increases. On the other hand, in the polymer having a functional group composed of a polyhydric alcohol ester of boronic acid of the present invention, such an increase in melt viscosity does not occur, and when melt kneading with another resin, for example, shows a stable melting behavior. There is an advantage. Second Production Method: A vinyl polymer and a diene polymer having a functional group comprising a polyhydric alcohol ester of boronic acid are prepared by converting a vinyl monomer and / or a diene monomer to an organic alkali metal. Anion polymerization using
Subsequently, the anion living terminal is terminated with a borate ester, and further obtained by reacting with a polyhydric alcohol. Specifically, n-butyllithium, sec
-Using an anionic polymerization initiator such as butyl lithium,
In a solvent such as a saturated aliphatic hydrocarbon compound such as hexane, heptane, or cyclohexane, or an aromatic hydrocarbon compound such as benzene or toluene, a vinyl monomer and / or a diene monomer is added at 30 to 60 ° C. Anionic polymerization is carried out under temperature conditions, and then a boric acid ester such as triethyl borate in an amount of at least equimolar to the anionic living terminal is dropped into the system at a temperature of 30 to 60 ° C. to form a boronic ester at the terminal. By adding a group and further reacting a boronic ester group with a polyhydric alcohol, a vinyl polymer, a diene polymer, or a copolymer thereof having a functional group consisting of a polyhydric alcohol ester of boronic acid is obtained. Obtainable. The obtained diene-based polymer or diene-based copolymer can be hydrogenated by a known method. 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, heptane, and cyclohexane, or an aromatic hydrocarbon compound such as benzene and toluene is used as a solvent, and an organic transition metal catalyst (for example, nickel acetylacetonate, cobalt acetyl) is used. Acetonate, nickel naphthenate, cobalt naphthenate, etc.) and a Ziegler catalyst, etc., obtained by combining a metal alkyl compound such as aluminum, alkali metal, alkaline earth metal, etc. It is used in an amount of about 0.001 to 0.1 mol%. The hydrogenation reaction is carried out at normal temperature to 150 ° C. under a hydrogen pressure of normal pressure to 50 kg / cm ² , and is completed in 1 to 50 hours. After the completion of the hydrogenation reaction, acidic water is added to the system, and the mixture is vigorously stirred to dissolve the hydrogenation catalyst in the water. By removing the aqueous phase of the two phases that are phase-separated and further removing the solvent,
A diene polymer having a functional group consisting of a polyhydric alcohol ester of boronic acid or a hydrogenated product of a diene copolymer is obtained. Although the hydrogenation rate of the above polymer is not particularly limited,
From the viewpoint of weather resistance, a range of 10 to 100% is preferable, and 5
The range of 0 to 100% is more preferable. The polymer obtained in this manner is melt-kneaded with a thermoplastic resin having a hydroxyl group, particularly an ethylene-vinyl alcohol copolymer, or has a thermoplastic resin having a hydroxyl group and a boron-containing functional group. It is useful as a compatibility improver when melt-kneading a vinyl polymer or a diene polymer which is not used. The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the following Synthesis Examples and Examples, unless otherwise specified, the ratio means the weight ratio, and “%” means “% by weight”. The weight average molecular weight was calculated by GPC measurement using tetrahydrofuran as a solvent and converted to standard polystyrene. The amount of boronic ester groups and the amount of boronic acid groups in the resin were calculated from ¹ H-NMR spectra measured using a mixed solution of chloroform / ethylene glycol = 10: 0.02 as a solvent. The haze was measured according to JIS K7105. Synthesis Example 1 Synthesis of ethylene glycol 3-mercaptopropylboronic acid: 19.26 g of sodium borohydride (NaBH ₄ ) was charged into a flask equipped with a condenser and a dropping funnel, followed by purging with nitrogen. THF500 dried and distilled using benzophenone and sodium metal
After cooling to 0 ° C. in an ice bath, the mixture was mixed with boron trifluoride-diethyl ether complex 99.9 with stirring.
5 g was added dropwise over 30 minutes. Two hours later, while maintaining the system at 0 ° C, 45.61 g of 2-propene-1-thiol was added dropwise over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C., and the mixture was further stirred for 3 hours. Cool to 0 ° C and methano-
100 mL was added dropwise over 40 minutes. After 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 and water to remove excess ethylene glycol, dried over magnesium sulfate, and distilled under reduced pressure. As a result, 46.7 g of a 4: 1 mixture of ethylene glycol 3-mercaptopropylboronic acid ester and ethylene glycol 2-mercapto-1-methylethylboronic acid ester was obtained. Boiling point: 70 ° C. (4 mmHg) Synthesis Example 2 Synthesis of ethylene glycol 4- (2-mercaptoethyl) phenylboronic acid: 2.92 g of 4-vinylphenylboronic acid, ethylene glycol in a flask equipped with a dehydration fractionating tube -1.38 g of toluene and 50 ml of benzene
The mixture was heated at 0 ° C. for 30 minutes to remove distilled water. 3.18 g of thioacetic acid and 47 mg of azobisisobutyronitrile were added to the reaction solution, and the mixture was heated at 75 ° C. for 2 hours. After the reaction solvent was distilled off, the residue was extracted with a methylene chloride / aqueous sodium hydrogen carbonate solution. The methylene chloride layer was dried over magnesium sulfate, and the solvent was distilled off. 5 g of crude 4- (2-acetylthioethyl) phenylboronic acid ethylene glycol ester thus obtained, 20 m of methanol
l, 10 ml of triethylamine was charged into a flask and reacted at 65 ° C. for 20 hours under nitrogen.
3.55 g of-(2-mercaptoethyl) phenylboronic acid ethylene glycol ester was obtained. Boiling point 135 ° C
Example 1 Synthesis of polystyrene having boronic acid ethylene glycol ester group: In a flask equipped with a stirrer and a reflux condenser, 500 g of styrene and 3-
0.0765 g of mercaptopropyl boronic acid ethylene glycol ester (MPBE) was charged and degassed under reduced pressure. After heating to 120 ° C., MPBE 0.394
%, Azobiscyclohexanecarbonitrile 0.069
% Of styrene solution at first, and then 0.5 ml
The mixture was charged at a rate of ml / min, and the polymerization was stopped after 210 minutes.
At this time, the polymerization rate was 45%. The reaction solution was reprecipitated with methanol, and the solid was dried to obtain polystyrene having a boronic acid ethylene glycol ester group of 0.013 meq / g and a weight average molecular weight of 130,000. Example 2 Synthesis of polymethyl methacrylate having boronic acid ethylene glycol ester group: In a flask equipped with a stirrer and a cooler, 150 g of methyl methacrylate was prepared. 0.876 g of a 4: 1 mixture of ethylene glycol ester of mercaptopropylboronic acid and ethylene glycol ester of 2-mercapto-1-methylethylboronic acid was charged, and the mixture was purged with nitrogen.
After initially charging 1.5 ml of a 0.23% toluene solution of azobisisobutyronitrile separately prepared,
0.5 ml was charged every 30 minutes. After 5 hours, the system was cooled to stop the polymerization. At this time, the polymerization rate was 47%.
The reaction solution was reprecipitated with methanol, and the solid was dried.
0.03me of boronic acid ethylene glycol ester group
polymethyl methacrylate represented by the following formulas (V) and (VI) having q / g and a weight average molecular weight of 58,000: Formula (V): Formula (VI) = 4: 1, molar ratio ｝
I got Embedded image Embedded image 270 MHz ¹ HN of the obtained polymer
FIG. 1 shows the MR chart. A peak at 4.18 ppm indicates the presence of ethylene glycol ester boronate in formula (V), and a peak at 4.2 ppm indicates the presence of ethylene glycol ester boronate in (VI). . Example 3 Synthesis of polymethyl methacrylate having boronic acid ethylene glycol ester group: In place of ethylene glycol 3-mercaptopropylboronic acid ester obtained in Synthesis Example 1, it was obtained in Synthesis Example 2. Using 1.248 g of ethylene glycol 4- (2-mercaptoethyl) phenylboronic acid, polymerization and post-treatment were carried out under the same conditions as in Example 2. As a result, polymethyl methacrylate having a boronic acid ethylene glycol ester group of 0.03 meq / g and a weight average molecular weight of 57000 was obtained. Example 4 5 g of the polymethyl methacrylate having a boronic acid ethylene glycol ester group obtained in Example 3 and EVAL®-F101 manufactured by Kuraray (ethylene content: 32
Mol%, saponification degree 99.5%, in water-containing phenol at 30 ° C
And melt kneading under the following conditions using 45 g of an intrinsic viscosity 1.1 dl / g ethylene-vinyl alcohol copolymer). Machine used: Plastograph rotor Shape: Roller type rotation 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 sheet having a thickness of 100 μm. did. This sheet was broken in liquid nitrogen, and the fracture surface was 140
After extraction with xylene at ℃, the fracture surface was observed with a scanning electron microscope. As a result, the average particle size of the polymethyl methacrylate was 0.08 μm, and the haze of the sheet was 8%. Comparative Example 1 Instead of 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group, a weight average molecular weight of 5 g was used.
A sheet was obtained in the same manner as in Example 4 except that 5 g of 6000 polymethyl methacrylate was used. The average particle size of the polymethyl methacrylate was 2.5 μm, and the haze of the sheet was 72%. Comparative Example 2 Instead of 5 g of polymethyl methacrylate having an ethylene glycol ester boronate group, a styrene-isoprene-block copolymer having a boronic acid group (styrene block molecular weight: 20,000, styrene content: 33%, hydrogenation rate: 90%, boronic acid group amount 0.013 meq / g) 5 g
A sheet was obtained in the same manner as in Example 4 except that the styrene-isoprene block copolymer was used. The average particle size of the styrene-isoprene block copolymer was 0.4 μm, and the haze of the sheet was 14%. Comparative Example 3 Instead of 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group, a styrene-isoprene block copolymer (styrene block having a molecular weight of 20
000, styrene content 33%, hydrogenation rate 95%) except that 5 g was used to obtain a sheet in the same manner as in Example 4.
The average particle size of the styrene-isoprene block copolymer is 5
μm, and the haze of the film was 30%. From the results of Example 4 and Comparative Examples 1 to 3, the polymer of the present invention has better compatibility with EVAL and higher transparency of the obtained composition than the conventional polymer. I understand. The vinyl polymer or diene polymer having a functional group comprising a polyhydric alcohol ester of boronic acid according to the present invention is a thermoplastic resin having a hydroxyl group, particularly an ethylene-vinyl alcohol copolymer. When melt-kneading with, or when melt-kneading a thermoplastic resin having a hydroxyl group and a vinyl-based polymer or a diene-based polymer having no boron-containing functional group, a stable melting behavior without a rise in viscosity occurs. And is also useful as a compatibility improver. Also,
When the polymer of the present invention is melt-kneaded with a thermoplastic resin having a hydroxyl group, a resin composition having good gas barrier properties, compatibility, transparency, and mechanical properties can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a 270 MHz ¹ H-NMR chart of polymethyl methacrylate having a boronic acid ethylene glycol ester group obtained in Example 2.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (1)

(57) [Claim 1] A vinyl polymer or diene polymer having a functional group comprising a polyhydric alcohol ester of boronic acid , wherein the vinyl polymer or diene polymer is used.
Means polystyrene, polymethyl acrylate, polymethyl
Methacrylate, styrene-isoprene block copolymer
Merged hydrogenated product, styrene-butadiene block copolymer water
Additive, styrene-isoprene-styrene block copolymer
Body hydrogenated product and styrene-butadiene-styrene block
Polymer selected from the group consisting of hydrogenated copolymers
And the functional group is a carbon atom of a monomer unit of the polymer.
Divalent, which is directly bonded to
Characterized by being attached to a carbon atom of the linking group of
Coalescing. However, a polymer having the functional group only at the terminal is excluded.
Good.