JPH09263608A - Production of boron-containing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a boron-containing resin little in impure substance and excellent in compatibility by reacting a thermoplastic resin containing a fixed amount of double bond with a boron compound containing a boron-hydrogen bond in an extruder and adding a specified compound to the reaction product. SOLUTION: (A) A thermoplastic resin such as a polyethylene containing >=0.0001meq/g double bond amount is reacted with (B) a boron compound such as diborane containing boron-hydrogen bonds and (D) a boric ester such as trimethyl borate in an extruder and then (C) a compound such as methanol or ethylene glycol containing one or two hydroxyl groups in the molecule and having <=300 deg.C boiling point under 760mmHg to give the objective boron- containing thermoplastic resin.

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 and has few impurities.

[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 (special feature: Kaihei 3-11540
2, JP-A-4-45104). There is also known a method of producing a polyolefin having a boronic acid group by reacting an olefin polymer having a double bond with a borane complex and a borate ester (JP-A-7-33820).

[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. Further, it has been difficult to remove impurities such as boron compounds derived from excess reagents. In addition, the conventional method is not suitable for mass production because it is manufactured in a batch system. Therefore, it is an object of the present invention to provide a method for producing a boron-containing thermoplastic resin having less impurities by a simpler process, more preferably without using a solvent.

[0004]

The above object is to provide a thermoplastic resin (A) having a double bond content of 0.0001 meq / g or more with a boron compound (B) having a boron-hydrogen bond in an extruder. React, then add 1 hydroxyl group in the molecule
Have one or two, and have a boiling point of 300 at 760 mmHg
This is achieved by adding the compound (C) at a temperature of not higher than 0 ° C.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a double bond is replaced by 0.
The thermoplastic resin (A) containing 0001 meq / g or more means at least 1 selected from the main chain, side chains or terminals.
It is a thermoplastic resin having a carbon-carbon double bond.
The thermoplastic resin (A) having a double bond content of 0.0001 meq / g or more means 1) a resin having a double bond at the end of a usual olefin polymer or vinyl polymer;
2) An olefin polymer or vinyl polymer having a double bond at a terminal, which is obtained by thermally decomposing an ordinary olefin polymer or vinyl polymer under oxygen-free conditions. ;
3) An olefin-diene copolymer or a vinyl-diene copolymer obtained by copolymerization of an olefin or vinyl polymer and a diene polymer may be mentioned. 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, US
2835659, 3087922) to prepare an olefin-based polymer at 300 under oxygen-free conditions such as under nitrogen or under vacuum.
A method of thermal decomposition at a temperature of ℃ to 500 ℃ and a reaction time of 1 minute to 10 hours 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-50-442).
81, DE 3021273), and a method of obtaining a known vinyl-diene copolymer by radical polymerization or anion polymerization.

The double bond in the thermoplastic resin (A) is 0.0
It is important to contain 001 meq / g or more, and there is no particular upper limit, but it is about 1 eq / g. Suitably 0.001 meq / g or more, and further 0.005 meq
/ G or more. The upper limit is 0.5 meq /
g or less is preferable, and more preferably 0.2 meq / g
It is as follows.

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 borane, and the like. Among them, from the viewpoint of chemical stability, borane-triethylamine complex (triethylamineborane), borane-methylsulfide complex, etc. preferable.

In the present invention, a method of reacting the thermoplastic resin (A) with the boron compound (B) and the borate ester (D) is a more preferable embodiment. Examples of the borate ester (D) include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, ethylene glycol borate ester, propylene glycol borate ester, trimethylene glycol borate ester, 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.

As the boiling point of the compound (C) having one or two hydroxyl groups in the molecule of the present invention, it is important that the boiling point under 760 mmHg is 300 ° C. or less, and the range of 60 ° C. to 300 ° C. is preferable. The range of 60 ° C to 250 ° C is more preferable. Examples of such a compound (C) include methanol, ethanol, 1-propanol, and 2
-Lower alcohols such as propanol, 1-butanol, 2-butanol; ethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, etc. Lower diols of

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. Moreover, you may use the extruder which has one multistage vent, and may use two or more extruders. When using one extruder, from the main body side of the extruder, in order from 1) the feed port of the thermoplastic resin (A), 2)
A multi-stage extruder having an addition port for the boron compound (B) and borate ester (D), 3) a vent port, an addition port for the compound (C) having a hydroxyl group and 5) a vent port is preferable, and the screw shape is It is preferable to have a seal or a reverse threaded screw between the above 2), 3), 4) and 5). When using two extruders, in the first extruder, from the main body side, 1) the feed port of the thermoplastic resin (A), 2) the boron compound (B)
And an extruder having a borate ester (D) addition port and 3) a vent port are preferable, and the second extruder feeds the resin obtained by the first extruder in order from the main body side. An extruder having a feed port for the above, an addition port for the compound (C) having a hydroxyl group, and a vent port is preferable, and the screw shapes of the first and second extruders are between the above 2) and 3). It preferably has a seal or a reverse screw. 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 varies depending on the thermoplastic resin (A) and the boron compound (B) used, but usually (A)
The melting point of (A) to 350 ° C. is preferable, and the melting point of (A) + 10 ° C. to 300 ° C. is more preferable. After reacting the thermoplastic resin (A) with the boron compound (B),
It is preferable to add the compound (C) having a hydroxyl group after removing the unreacted boron compound (B), especially under reduced pressure. Here, the unreacted boron compound is converted into the amount of boron and is 500 ppm or less, and further 100 ppm.
It is better to remove so that: Here, decompression means
Internal vacuum is less than 300mmHg, preferably 50m
mHg or less. Impurities can be removed more efficiently by adding a compound having a hydroxyl group. At the same time, the type of ester of the boronic acid group introduced by the reaction can be changed to the ester of the added compound having a hydroxyl group by transesterification reaction. After adding the compound (C) having a hydroxyl group, it is preferable to further reduce the pressure to remove the unreacted boron compound (B). By this removal, the amount of the boron compound as an impurity is converted into the amount of boron and is 100 ppm or less, further 20
It is preferable to set it to ppm or less.

The boron compound (B) is usually added by a pump in 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. A method of using a dry blending method in combination is mentioned. The amount of the boron compound (B) added is not particularly limited, but it is preferably in the range of 0.001 to 10% by weight, more preferably 0.01 to 5 with respect to the thermoplastic resin (A).
% By weight. Further, the preferable range of the addition amount of the borate ester (D) is 0.0 with respect to the thermoplastic resin (A).
The range of 1 to 100% by weight is preferable, and the range of 0.05 to 10% by weight is more preferable. The amount of the compound (C) having a hydroxyl group is not particularly limited, but is preferably in the range of 0.1 to 100% by weight, more preferably 0.5 to 20% by weight, based on the thermoplastic resin (A). Is the range.

As a representative example of the boron-containing thermoplastic resin obtained by the present invention, at least a boronic acid group, a borinic acid group, and 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).

[0015]

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Further, the boron-containing group which can be converted to 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.

[0017]

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[0018]

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[0019]

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[In the formula, 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 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 ester 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).

[0023]

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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).

[0025]

[Chemical 6]

[0026]

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[0027]

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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, alicyclic hydrocarbon group as X described above, 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 Among the above functional groups, a boronic acid ester group such as a boronic acid ethylene glycol ester group is particularly preferable from the viewpoint of compatibility with a vinyl alcohol copolymer such as an ethylene-vinyl alcohol copolymer. The boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water is a thermoplastic resin (A), or a mixture of water or water and an organic solvent (toluene, xylene, acetone, etc.). liquid,
Further, a group capable of being converted into a boronic acid group or a borinic acid group when hydrolyzed in a mixed solution of an aqueous boric acid solution and the organic solvent under a reaction time of 10 minutes to 2 hours and a reaction temperature of room temperature to 150 ° C. means.

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 and 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 application used, but is 0.00001 to 1 milliequivalent / g (me
q / g) is preferable, and more preferably 0.0001 to
It is 0.3 meq / g.

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 polyolefins of Examples 1 and 2 was 500M using heavy xylene as a solvent.
It was quantified by Hz ↑ 1H-NMR.

Example 1 The following resin feeder (extruder C1 part), liquid feeder 1 (extruder C3 part), liquid feeder 2 (extruder C11 part), vent 1 (extruder C8 part) and vent 2 (extruder). Ethylene-propylene-ethylidene norbornene copolymer (A) (Mitsui Petrochemical's "Mitsui EPT" (trade name) 3 in a 37φ twin-screw extruder having a machine C14 part).
120P, melt index (MI) 4g / 10 minutes (190 ° C, 2160g load), double bond amount 0.4me
After supplying q / g} at a rate of 4 kg / hr, the internal pressure of the vent 1 and the vent 2 was reduced to about 20 mmHg. Then, from the liquid feeder 1, triethylamine borane (B) and boric acid 1,3-butanediol ester (D) were obtained.
A weight ratio of 29:71 was added at a rate of 0.6 kg / hr, and 0.4 kg / hr from the liquid feeder 2.
Ethylene glycol (C) was added at a ratio of. This gives a melt index (MI) of 3 g / 10 minutes (190
℃, 2160g load), impurities converted to the amount of boron 1
5 ppm of an ethylene-propylene copolymer having 0.28 meq / g of boronic acid ethylene glycol ester group on the side chain was obtained. Extruder: TEM-35B (Toshiba Machine, same-direction twin-screw extruder) D = 37 mm, L / D = 53.8 Liquid feeder position: C3 and C11 Vent position: C6 and C14 Nitrogen substitution: 1 L / at feeder part Flow nitrogen gas at a rate of: Screw configuration: seals are placed on C5, C7 and C10 Temperature setting C1 to C6: 200 ° C C7 to C15: 250 ° C Die: 250 ° C Screw rotation speed: 150 rpm

Comparative Example 1 A test was conducted under the same conditions as in Example 1 except that the ethylene glycol was not supplied to the liquid feeder 2. As a result, the melt index (MI) was 3 g / 10 minutes (190 ° C., 2 ° C.).
160 g load), the amount of impurities converted to the amount of boron is 280
An ethylene-propylene copolymer having 0.28 meq / g of boronic acid 1,3-butanediol ester group in the side chain was obtained in ppm.

Example 2 From a resin feeder, ultra low density polyethylene {“Excellen” (trade name) EUL430 manufactured by Sumitomo Chemical Co., Ltd., MI = 4 g)
/ 10 minutes, double bond amount 0.047 meq / g} 10 k
The mixture was added at a ratio of g / hr, and from the liquid feeder 1, a mixed solution of triethylamine borane (B) and boric acid 1,3-butanediol ester (D) in a weight ratio of 29:71 was adjusted to 0.9.
As a result of performing the test under the same conditions as in Example 1 except that the addition was performed at a rate of 4 kg / hr, the melt index (M
I) 4 g / 10 min (190 ° C., 2160 g load), ultra low density polyethylene having 5 ppm of boronic acid ethylene glycol ester group at the end as an impurity in terms of boron amount of 5 ppm was obtained.

[0035]

According to the present invention, a boron-containing thermoplastic resin having good compatibility with a polymer having a polyhydric hydroxyl group such as an ethylene-vinyl alcohol copolymer can be easily produced by an extruder.

Claims (2)

[Claims] 1. The amount of double bonds in an extruder is 0.0001.
Boron is contained in the thermoplastic resin (A) containing meq / g or more.
React with a boron compound (B) having a hydrogen bond, then has one or two hydroxyl groups in the molecule, and 760 m
A process for producing a boron-containing thermoplastic resin, which comprises adding a compound (C) having a boiling point of 300 ° C. or lower under mHg. 2. The amount of double bonds is 0.0001 in the extruder.
Boron is contained in the thermoplastic resin (A) containing meq / g or more.
A boron compound (B) having a hydrogen bond is reacted with a borate ester (D), and then a compound (C) having one or two hydroxyl groups in the molecule and having a boiling point of 300 degrees or less under 760 mmHg is added. A method for producing a boron-containing thermoplastic resin, comprising: