JPH0881517A - Production of boron-containing thermoplastic resin - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin improved in compatibility with a polymer having hydroxyl groups by reacting a specific thermoplastic resin with a boron compd. having a B-H bond in an extruder. CONSTITUTION: 1kg of a thermoplastic resin having a content of double bonds of 0.0001meq/g or higher and 0.00001-0.1kg of a boron compd. having a B-B bond are fed into an extruder and heated to a temp. higher than the m.p. of the resin but not higher than 350 deg.C to effect a reaction therebetween.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a boron-containing thermoplastic resin which is excellent in productivity and economy.

[0002]

2. Description of the Related Art It is known to react a thermoplastic resin having a carbon-carbon double bond with a boron compound having a boron-hydrogen bond in a reaction vessel such as a flask using a solvent such as tetrahydrofuran (Japanese Patent Laid-Open No. Hei 10 (1999) -31977). 3-11540
2, JP-A-4-45104).

[0003]

However, in the conventional method,
Since it was necessary to use a solvent, operations such as dissolution in the solvent, removal of the solvent, and solvent purification were necessary, and complicated steps were required. Therefore, it is an object of the present invention to provide a method for producing a boron-containing thermoplastic resin by a simpler process, more preferably without using a solvent.

[0004]

The above object is to react a thermoplastic resin (A) having a double bond of 0.0001 meq / g or more with a boron compound (B) having a boron-hydrogen bond in an extruder. Achieved by In the present invention, the thermoplastic resin (A) having a double bond is
It is a thermoplastic resin having a carbon-carbon double bond in at least one selected from a main chain, a side chain or a terminal.

A thermoplastic resin (A) having a double bond
As 1) those having a double bond at the end of a normal olefin polymer or vinyl polymer; 2) obtained by thermally decomposing a normal olefin polymer or vinyl polymer under anoxic conditions. Also, an olefin polymer or vinyl polymer having a double bond at the terminal. 3) An olefin-diene copolymer or a vinyl-diene copolymer obtained by copolymerizing an olefin or vinyl polymer and a diene polymer. Regarding the production method of 1), a known production method of an olefin polymer or a vinyl polymer can be used. In particular, hydrogen is not used as a chain transfer agent, a metallocene polymerization catalyst is used as a polymerization catalyst, and an olefin polymer is used. A production method of polymerizing a monomer (for example, DE4030399) is preferable. Regarding the production method of 2), a known method (for example, US283565).
9, 3087922), an olefin polymer under anoxic conditions such as nitrogen and vacuum conditions at 300 ° C to 500 ° C.
The method of obtaining by thermal decomposition at the temperature of 1 to 10 minutes is preferable. Regarding the production method of 3), a method of obtaining an olefin-diene copolymer using a known Ziegler catalyst is preferable (for example, JP-A-50-44281, DE3).
(021273), and a method of obtaining a known vinyl-diene copolymer by radical polymerization or anionic polymerization.

The double bond in the thermoplastic resin (A) is 0.0
It is important to contain 001 milliequivalent / g (meq / g) or more. It is preferably 0.001 meq / g or more, and more preferably 0.005 meq / g or more. The upper limit is not particularly limited, but is preferably 1 meq / g or less, more preferably 0.5 meq / g or less, and further preferably 0.2 meq / g or less.

Specific examples of the thermoplastic resin (A) having a double bond include polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, etc.), ethylene-
Olefin-based polymers such as propylene copolymer, polypropylene, polybutene and poly (3-methyl-1-pentene); olefin-diene-based copolymers such as ethylene-propylene-ethylidene norbornene copolymer and ethylene-isoprene copolymer Vinyl polymers such as coalesce, polystyrene and polyvinyl chloride; polybutadiene, polyisoprene,
Diene polymers such as butadiene-isoprene block and random copolymers, ptadiene-styrene block and random copolymers, isoprene-styrene block and landan copolymers, and hydrogenated products thereof; polyphenylene ether; polyphenylene sulfide, etc. Is mentioned. Among the above polymers, polyethylene (high density, medium density, linear low density, ultra low density), ethylene-propylene copolymer, and polypropylene are particularly preferable.

The boron compound (B) having a boron-hydrogen bond used in the present invention means at least one boron-
It is a boron compound having a hydrogen bond. Specific examples thereof include boranes such as diborane, tetraborane, pentaborane, hexaborane, and decaborane; borane-tetrahydrafuran complex, borane-triethylamine complex, borane-trimethylamine complex, borane-pyridine complex, borane-t-butylamine complex, Borane-N, N-diisopropylethylamine complex, borane-dimethylamine complex, borane-N, N-diethylaniline complex, borane-
Complexes of borane and Lewis bases such as 4-methylmorpholine complex, borane-methyl sulfide complex, borane-1,4-thioxane complex, borane-tributylphosphine complex; thexylborane, catecholborane, 9-borabicyclo [3,3,3] 1] Hydrocarbons such as nonane, diisoamylborane, and dicyclohexylborane, or hydrocarbon oxy-substituted boranes, and the like, among which triethylamineborane, methylsulfideborane and the like are preferable from the viewpoint of chemical stability.

In the present invention, other compound (C) may be added in addition to the boron compound (B). Examples of the other compound (C) include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, ethylene glycol borate, propylene glycol borate, trimethylene glycol borate, boric acid 1 , 3-butanediol ester, boric acid neopentyl glycol ester and the like are preferable, and among these, boric acid trimethylene glycol ester, boric acid 1,3-butanediol ester, boric acid neopentyl glycol ester are particularly preferable. Etc. are preferred. By adding these boric acid esters, it is possible to prevent the cross-linking that often occurs when the boron compound (B) is added, and at the same time to introduce the boron-containing group in the form of a chemically stable boronic acid ester group.

The extruder used in the present invention is not particularly limited, and any of a single-screw extruder, a twin-screw co-rotating extruder and a twin-screw different-direction rotating extruder may be used. A rotary extruder or a twin-screw counter-rotating extruder is preferred.
Further, it is preferable to provide a vent near the resin outlet of the extruder. As a result, excess boron compound can be removed and recovered. Since the boron compound (B) used in the present invention is decomposed by oxygen in the air or water or oxygen at a high temperature, it is preferable that the concentrations of oxygen and water vapor in the extruder are as low as possible. Therefore, it is preferable to flow nitrogen gas into the feeder of the extruder or to provide a vent port for deaeration in the extruder. The maximum temperature in the extruder is the thermoplastic resin (A) and boron compound (B) used
Although it depends on the melting point, the range from (A) melting point to 350 ° C is usually preferable, and (A) melting point + 10 ° C to 30 ° C.
The range of 0 ° C is more preferable.

The boron compound (B) is usually added by a pump from the middle of the barrel of the extruder, by dry blending with the raw material resin in advance, or by injection in the middle of the above, and in advance. A method of using a dry blending method in combination is mentioned. Although the addition amount of the boron compound (B) is not particularly limited, it is 0.00001 relative to 1 Kg of the thermoplastic resin (A).
The range of Kg to 0.1 Kg is preferable, and the range of 0.0001 Kg to 0.05 Kg is more preferable. The preferred range of the other additive (C) is thermoplastic resin (A) 1K.
With respect to g, it is 0.0001 Kg to 1 Kg, and more preferably 0.0005 Kg to 0.5 Kg.

Typical examples of the boron-containing thermoplastic resin obtained by the present invention include at least a boronic acid group, a borinic acid group, and at least a boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water. A thermoplastic resin having one functional group may be mentioned. Where the boronic acid group,
Heat in which at least one functional group selected from the group consisting of a boric acid group or a boron-containing group capable of being converted to a boronic acid or a boric acid group in the presence of water is bound to the main chain, side chain or terminal by a boron-carbon bond. It is a plastic resin. Of these, a thermoplastic resin having the functional group bonded to the side chain or the terminal is preferable, and a thermoplastic resin bonded to the terminal is most suitable. Here, the term "end" means one end or both ends.

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

[0014]

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Further, the boron-containing group which can be converted into a boronic acid group in the presence of water (hereinafter simply referred to as a boron-containing group) is hydrolyzed in the presence of water and is represented by the above formula (I). Any boron-containing group that can be converted to a boronic 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)
And a boronic acid group represented by.

[0016]

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[0017]

[Chemical 3]

[0018]

[Chemical 4]

[In the formula, X and Y are hydrogen atoms, aliphatic hydrocarbon groups (such as linear or branched alkyl groups having 1 to 20 carbon atoms, or alkenyl groups), alicyclic hydrocarbon groups (cyclo Alkyl group, cycloalkenyl group, etc.), aromatic hydrocarbon group (phenyl group, biphenyl group, etc.),
X and Y may be the same group or different. Also, X and Y lobes may be bonded. However, it is excluded when both X and Y are hydrogen atoms. Also R ↑ 1, R ↑ 2, R
↑ 3 represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group similar to the above X and Y, and R
↑ 1, R ↑ 2 and R ↑ 3 may be the same 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 carboxyl group or a halogen atom. }

Specific examples of the boronic acid esters represented by the general formulas (II) to (IV) include boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid dibutyl ester group, and boronic acid. Hexyl ester group, boronic acid dicyclohexyl ester group, boronic acid ethylene glycol ester group, boronic acid 1,2-propanediol ester group, boronic acid trimethylene glycol ester group, boronic acid 1,3-butanediol ester group, boronic acid neo Boronic acid ester groups such as a pentyl glycol ester group, a boronic acid catechol ester group, a boronic acid glycerin ester group, and a boronic acid trimethylolethane ester group; a boronic acid anhydride group; an alkali metal salt of boronic acid, an alkaline earth acid of boronic acid. Examples include metal salts It is.

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

[0022]

[Chemical 5]

The boron-containing group that can be converted to a borinic acid group in the presence of water is a boron-containing group that can be converted to a borinic acid group of 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).

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

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{In the formulas (V to VIII), X has the same meaning as X in the general formula (II), Z is the same aliphatic hydrocarbon group or alicyclic hydrocarbon group as the above X, Represents an aromatic hydrocarbon group. Further, X and Z may be bonded. Further, R ↑ 1, R ↑ 2 and R ↑ 3 are R of the general formula (IV).
It has the same meaning as ↑ 1, R ↑ 2, and R ↑ 3. Further, M has the same meaning as M in the general formula (IV). }

Specific examples of the borinic acid ester group represented by the general formulas (V) to (VIII) include X, Z, R ↑ 1, R.
Examples include those in which ↑ 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. Representative examples include a methylborinic acid group, a methylborinic acid methyl ester group, an ethylborinic acid group, an ethylborinic acid methyl ester group, a methylborinic acid ethyl ester group, a butylborinic acid methyl ester group, and a 3-methylborinic acid-2-butylborinic acid methyl ester group. To be The boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water is a thermoplastic resin (A).
In water or a mixed liquid of water and an organic solvent (toluene, xylene, acetone, etc.) or a mixed liquid of an aqueous solution of boric acid and the organic solvent, with a reaction time of 10 minutes to 2 hours and a reaction temperature of room temperature to 150 ° C. It means a group that can be converted into a boronic acid group or a borinic acid group when hydrolyzed under the conditions.

The boron-containing thermoplastic resin obtained by the present invention has a high reactivity with a polymer containing a polyhydric hydroxyl group such as an ethylene-vinyl alcohol copolymer or a vinyl alcohol-based polymer. It is useful as a polymer compatibilizer, modifier, adhesive, and the like. Further, a boron-containing group such as a boronic acid group can be easily chemically converted into a functional group such as a hydroxyl group or an amino group, and thus is also useful as a synthetic intermediate for a polymer having such a functional group. The boron content in the boron-containing thermoplastic resin varies depending on the intended use, but is preferably 0.00001 to 1 meq / g, more preferably 0.0001 to 0.3 meq / g.
Is.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The amount of double bonds in the polyolefin was determined by 270 MHz ↑ 1H-NMR using heavy paraxylene as a solvent. The amount of boronic acid groups in the ultra low density polyethylene and the high density polyethylene of Example 1 and Example 2 was quantified by 500 MHz ↑ 1H-NMR using heavy xylene as a solvent.

Example 1 37 having the following resin feeder (entrance of extruder), liquid feeder (middle portion of extruder) and vent (two positions before liquid feeder and before extruder outlet)
Φ twin-screw extruder with super-density polyethylene (“Excellen” (trade name) EUL430 manufactured by Sumitomo Chemical Co., Ltd.) (melt index (MI) 4 g / 10 minutes (190 ° C., 2160 g load), double bond amount 4.7 × 10 ↑ -↑ 2 meq / g, density 0.89 g / cm ↑ 3} was supplied at a rate of 8 Kg / hour, while the liquid feeder supplied triethylamine borane (B) and boric acid 1,3-butanediol ester (C). A 29:71 weight ratio mixed solution was added at a rate of 0.2 Kg / hour (B: 0.058 Kg / hour, C: 0.142 Kg / hour). Thus, an ultra-low density polyethylene having a melt index (MI) of 4 g / 10 min (190 ° C., 2160 g load) and having a boronic acid 1,3-butanediol ester group at the end of 0.03 meq / g was obtained. Extruder: TEM-35B (Toshiba Machinery) D = 37 mm, L / D = 53.8 Liquid feeder position: C8 Vent position: C6 and C14 Temperature setting C1 to C6: 240 ° C. C7 to C15: 260 ° C. Die: 250 ° C. Screw rotation speed: 100 rpm

Example 2 High density polyethylene (Y6050 manufactured by Tonen) (MI 0.5 g / 10 minutes, double bond amount 0.04 meq / g) was used in place of the ultra low density polyethylene, and other conditions were the same as in Example 1. When tested under the conditions, MI 0.4 g / 10
A high-density polyethylene having 0.03 meq / g of boronic acid 1,3-butanediol ester group at the end was obtained.

Example 3 10 parts by weight of ultra-low density polyethylene having a boronic acid 1,3-butanediol ester group at the end obtained in Example 1 and EVAL (registered trademark) -L101 (ethylene content 27 mol%) manufactured by Kuraray Co., Ltd. , Saponification degree 99.5%, phenol /
90 parts by weight of an ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 1.1 dl / g in water = 85/15 was melt-kneaded under the following conditions. Extruder: 25φ segment type extruder Temperature setting: C1 to C5 220 ° C Die 220 ° C Screw rotation speed 100 rpm Discharge rate: 2 Kg / hour Notched Izod of the obtained resin composition injection molded product
When the impact strength was measured (thickness: 3 mm, room temperature), the impact strength was 16 Kg · cm / cm ↑ 2. The obtained resin composition was fractured in liquid nitrogen, extracted with hot xylene, and the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle diameter of ultra-low density polyethylene was 0.15 μm.
It was m.

Comparative Example 1 In place of the ultra low density polyethylene having a boronic acid 1,3-butanediol ester group at the terminal, an ultra low density polyethylene having a double bond at the terminal of the raw material of Example 1 was used. As a result of performing the same test as in Example 3, the notched Izod impact strength was 2.5 Kg · cm / cm ↑ 2 and the average dispersed particle diameter was 5 μm.

Comparative Example 2 The notched Izod impact strength of an injection-molded product of EVAL (registered trademark) -L101 manufactured by Kuraray (thickness: 3 mm, room temperature)
When measured, the impact strength was 3 Kg · cm / cm ↑ 2.

[0036]

According to the present invention, a boron-containing thermoplastic resin having good compatibility with a polymer having a polyvalent hydroxyl group such as an ethylene-vinyl alcohol copolymer can be easily synthesized by an extruder. Further, the thermoplastic resin of the present invention is effective in improving the performance such as impact resistance of the ethylene-vinyl alcohol copolymer.

Claims (1)

[Claims] 1. A double bond of 0.0001 m in an extruder.
A method for producing a boron-containing thermoplastic resin, which comprises reacting a thermoplastic resin (A) having eq / g or more with a boron compound (B) having a boron-hydrogen bond.