JPH0450224A - Ethylene polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a biodegradable ethylene polymer, having specific recurring units and a specified number-average molecular weight by polycondensing a specific ethylene polymer with a specified saturated aliphatic dicarboxylic acid, etc. CONSTITUTION:For example, ethylene is polymerized in the presence of a reaction product of a polymerization catalyst composed of a vanadium chelate compound and a dialkylaluminum dihalide with a 5-20C omega,omega'-diolefin compound and then reacted with the omega,omega'-diolefin compound and a proton donor to provide an ethylene polymer having vinyl groups at both terminals. The resultant ethylene polymer is then hydroxylated, oxygenated, etc., to afford an ethylene polymer, composed of recurring units expressed by formula I and having groups expressed by formula I [X is H, group expressed by formula III (R2 is l-5C hydrocarbon), etc.] at both terminals and 300-300000 number-average molecular weight. The obtained ethylene polymer is subsequently polycondensed with a compound expressed by formula TV (R is bifunctional 1-20C hydrocarbon group; Y is halogen, hydroxyl group, etc.) to provide the objective ethylene polymer having recurring units expressed by formula V (A is polyethylene segments having recurring units expressed by formula VI and 300-300000 number- average molecular weight) and 500-5000000 number-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a biodegradable ethylene polymer having an ester bond in its main chain and a method for producing the same.

Prior Art Polyethylene can be decomposed by microorganisms if it has a low molecular weight. It is also known that ester bonds in molecules are hydrolyzed by microorganisms.

In order to make high molecular weight polyethylene biodegradable, a method is known in which starch is mixed with polyethylene. However, although starch is decomposed, the polyethylene itself is not decomposed.

Problems to be Solved by the Invention The object of the present invention is to provide a biodegradable ethylene polymer.

Means for Solving the Problems Based on the above findings, the present inventors believe that the object of the present invention can be achieved if a polymer having an ester bond in its skeleton and a relatively low molecular weight polyethylene segment can be provided. As a result of intensive research, it was found that the object of the present invention can be obtained by polycondensing an ethylene polymer having an oxy group or a substituent thereof at both ends with a dicarboxylic acid or a derivative thereof. The present invention was completed by discovering that

Summary of the invention That is, the beam of the present invention is a polyethylene segment in which A is a polyethylene segment having a number average molecular weight (1'In) of 300 to 300,000 and consisting of repeating units of →CH2 and C82, l'In500 to 5.0.
00,000 ethylene polymer, [where R is 1 carbon number]
Indicates ~20 divalent hydrocarbon groups. ] (2) → Consists of repeating units of C11, ・CH, and
And li! with XO- groups bonded to both ends! n3QQ~
300.000 ethylene polymer (I) and -formula Y-
The method for producing an ethylene polymer according to (1) above, which comprises polycondensing the compound (II) represented by C-R-C-Y, where Y is Ichino, -0R3, a halogen atom, or -3O,R' , R1, )+2 and R3 each represent a hydrocarbon group having 1 to 5 carbon atoms, and R4 represents a hydrocarbon group having 1 to 20 carbon atoms. R has the same meaning as above. ] Ethylene polymer The ethylene polymer of the present invention is represented by the above repeating unit. R in the repeating unit represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
divalent saturated or unsaturated aliphatic hydrocarbon group or alicyclic hydrocarbon group.

A in the repeating unit consists of a polyethylene segment, and its number average molecular weight (Iiln) is 300 to 300,
000, but from the viewpoint of biodegradability, Mn is 100,
000 or less, preferably 10,000 or less.

The ethylene polymer of the present invention has an ion of 500 to 5,000,000, preferably 1,000 to 500,000.

Method for producing ethylene polymer The ethylene polymer of the present invention is the ethylene polymer (I)
It can be produced by polycondensing and compound (n).

Ethylene polymer (I) Ethylene polymer (I) is composed of repeating units of +CH2.CH, +, and has f1300 to 300,000 with x0- groups bonded to both ends thereof. From the viewpoint of biodegradability, 1iln is 100,000 or less, especially 10,
000 or less is desirable.

In the above, X is a hydrogen atom, -3tR'3 or C-R
' indicates. R1 and R2 are carbon atoms having 1 to 5 carbon atoms; hydrogenated groups, preferably alkyl groups, and particularly preferably methyl groups and ethyl groups.

Production method of ethylene polymer (1) Ethylene polymer (I) in which X is a hydrogen atom can be produced by the following method.

A polymerization catalyst consisting of a vanadium chelate compound and a dialkyl aluminum cybaride, and ω, ω having 5 to 20 carbon atoms
An ethylene polymer having vinyl groups at both terminals ( It can be produced by oxidizing I[[).

In addition, the ethylene polymer (I) in which X is -SiR'3 or -C-R2 can be added to the oxylated ethylene polymer obtained above by formula R'3SIY C, where R1 has the same meaning as above, Y represents a halogen atom. It can be produced by reacting with a silane compound of ] or a carboxylic acid of the formula R''CDOH [where R2 has the same meaning as above].

(1) Reaction between polymerization catalyst and diolefin compound The polymerization catalyst consists of a vanadium chelate compound and dialkyl aluminum cybaride.

The vanadium chelate compound has the following general formula: In this formula, R5-R7 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, at least one of R5-R7 must be a hydrogen atom, but R5-R7
must not all be hydrogen atoms.

Specific examples included in the above formula will be explained below.

- When R6 is a hydrogen atom and R5 and R7 are hydrocarbon groups.

R5/R7: CH3/Cl13, [:H3/C2
H5, C2H5/C2H5゜CH3/C6H5, C2H
5/C61 (S, C6H5/C5Hs.

C) +3/C3H5CH2, C6H5CH2/C6H3
C+(2.

C2H5/C6H5CH2, C6H5/C6H9CH2
- When R6 is a hydrocarbon group, one of R5 and R7 is a hydrogen atom, and the other is a hydrocarbon group.

R6/R5 or R': CH3/CH3, C2)I
s/CH3.

H3/[:2H5, C2H5/C2)+s, C5H
s/CL.

CH3/C6H5, C6H5/C, R5, C, H3/C
,H.

C6H5/C6H5, Ca115CH2/CH3°CH
,/C611SCH,,C3H3C112/C,1lS
CH2.

C6H5CH2/C2H5, C2H5/C6tlSCH
2゜C5HsCL/CaHs, C6H5/C6H5
When CH2 and R6 are hydrogen atoms, one of R5 and R7 is a hydrogen atom, and the other is a hydrocarbon group.

R5 or R': CH3, C2H5, C5Hs,
Examples include Cs1 (sCL), and among these, the following compounds are particularly desirable.

V(acetylacetonato)3 V(1,3 butanedionato)3 dialkylaluminum halide has the above formula R'2
AIX [wherein R'' It is an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom], and specific examples include dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide,
Examples include diethylaluminium iodide and diisobutylaluminum chloride.

The usage ratio of vanadium chelate compound and dialkyl aluminum halide is per mole of the vanadium compound,
The dialkyl aluminum halide is 1 to 1.000 mol.

α,ω-Diolefin compounds are -formula%formula% It is 15. ).

Specific examples of the diolefin compounds include 1°4-pentadiene, 1.5-hexadiene, 1°6-hephtadiene, 1,7-octadiene, 1°8-nonadiene, 1,
9-decadiene, 1,10-undecadiene, 1.11
-dodecadiene, 1゜13-tetradecadiene, 1,1
Examples include 5-hexadecadiene and 1,17-octadecadiene.

The reaction between the polymerization catalyst and the diolefin compound is preferably carried out in a solvent that is inert and liquid during the reaction, and examples of such solvents include propane, butane, pentane, hexane, heptane, toluene, etc. Examples include hydrocarbons.

The reaction is carried out at -50°C or lower, preferably -65°C or lower for 1 minute to 10 hours, preferably 5 minutes to 2 hours.

The reaction ratio between the polymerization catalyst and the diolefin compound is 0.0 to 10 moles, preferably 0.5 to 2.0 moles, of the vanadium compound in the polymerization catalyst per 1 mole of the diolefin compound.
It is 0 mole.

(2) Polymerization of ethylene Ethylene polymerization is carried out in the same manner as in (1) above, preferably by supplying ethylene to the reaction system of (1) above in the presence of the reaction product obtained in (1) above. Above (
This is carried out by reacting for a longer time than in case 1). In particular, when the reaction temperature is set to -65°C or lower, the ratio of I'In (weight average molecular weight)/I'In (number average molecular weight) to -1.05 to 1.
5, a nearly monodisperse polymer was obtained. By increasing the polymerization time, the yield and molecular weight of the polymer can be increased.

(3) Reaction with diolefin compound The reaction between the reaction product in (2) above and the diolefin compound is preferably carried out by introducing the diolefin compound into the reaction system in (2) above, The reaction conditions are as described in (1) above.
The same is true for .

(4) Reaction with a proton donor Water, alcohol, inorganic acid, etc. can be used as the proton donor. Examples of the alcohol include methanol, ethanol, propatool, etc., and examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, etc. The purpose of the proton donor is to act on the terminal end of the polymer to separate the polymerization catalyst and donate protons to precipitate the polymer.

The reaction with the proton donor is -100°C to +200°C,
It is preferably carried out at 0 to 150°C for 1 minute to 10 hours, preferably 0.1 to 2 hours. The proton donor is usually used in large excess.

In this way, it is possible to produce an ethylene polymer (I) having vinyl groups at both ends, but since the above production method is adopted, the polymer (III) can be produced by the polymer used in the production. It is presumed to have the following microstructure containing the diolefin compound skeleton and the alkyl group R8 of the dialkyl aluminum halide.

^-+CH, ・C82 size 7B However, A and B are as specified, and n is an integer corresponding to the number average molecular weight.

■ CH2-CH2 C,ll.

H,C=C)I CH, -CH-R8 C, R2゜ C11=CL ■ 3C-CH -H2- H2C=CH CH-CH, -R8 C-R2゜ CH=CH2 ■ CH, -C1l.

0182m H2C=CH CH2-CH-R8 [:, 11. .

CH=CH.

■ H,C-CH- C.H.

112C=CH -CMCL→koR8 Cm-J2 (a-21 C1l=CIl.

or ■ CH2-CH2 Ch2+a H’, C=CH -CHbeCL→koR8 C11-2L (m-2) CH=C1l.

(5) Oxygenation reaction of ethylene polymer (II[) There are the following three methods for oxidation reaction. In method (2), the α-positions at both ends of the polymer are oxidized (-CH2-CH2-D
H), and in the methods of ■ and ■, its β position is oxidized (-
CH-CH3).

CH 2 Polymer (I) is reacted with diborane and then with alkali hydroxide hydrogen peroxide.

■ Polymer (R9 is reacted with sulfuric acid and water.

(2) Polymer (I) is reacted with mercury acetate and water, and then reacted with sodium poron hydride (NaBtl).

Below, methods ① to ② will be explained.

Method (2) The reaction between polymer (III) and diborane is usually carried out at 100 to 200°C, preferably in the presence of a solvent such as ether.
It is carried out for 1 minute to 10 hours.

The ether preferably has a boiling point of 100 DEG C. or higher, and aliphatic ethers such as di-n-butyl ether, di-S-butyl ether, di-n-amyl ether, and di-i-amyl ether are particularly preferred.

Diborane is usually used as a solution in tetrahydrofuran, and the amount used is 0.2 to 1 mole of the diolefin compound used in (1) and (3) above.
The amount is 100 mol, preferably 0.5 to 20 mol.

The reaction with alkali hydroxide and hydrogen peroxide is 0 to 100
C. for 1 hour to 1 week.

As the alkali hydroxide, sodium hydroxide and potassium hydroxide are commonly used, and their aqueous solutions are usually used.

Further, an aqueous solution of hydrogen peroxide is usually used.

The amounts of alkali hydroxide and hydrogen peroxide to be used may be at least equimolar to the diborane used above, but they are usually used in large excess.

Method (2) The reaction of the polymer (I [I) with sulfuric acid and water is usually carried out at 80 to 150°C for 1 minute to 10 hours in the presence of water or a mixture of water and ether.

Method (2) The reaction of polymer (I) with mercury acetate and water is usually carried out at 80 to 150°C for 1 minute to 1 minute in the presence of a mixture of water and ether.
It will be held for 0 hours.

It is then reacted with sodium boron hydride, and the method may be the same as in the reaction with mercuric acetate and water above.

(6) Reaction with silane compound or carboxylic acid The silane compound used is represented by the formula R', SiY. In the formula, R1 is a hydrocarbon group having 1 to 5 carbon atoms, with methyl and ethyl being particularly preferred. Further, Y is a halogen atom, and examples thereof include chlorine, bromine, fluorine, and iodine.

Carboxylic acids are represented by the formula R''CO.

In the formula, R2 is a hydrocarbon group having 1 to 5 carbon atoms, with methyl and ethyl being particularly preferred.

The reaction between the dioxylated ethylene polymer obtained in the above (5) and the silane compound or carboxylic acid may be the same as the method generally performed when trialkylsilylating or esterifying alcohol.

For example, in the reaction with a silane compound, usually, preferably, in the presence of a solvent such as an amine compound, the two are first reacted at 0 to 50 °C for 1 minute to 5 hours, and then
This is carried out by reacting at 0°C for 1 to 10 hours.

The most suitable amine compound is one having a boiling point of 100° C. or higher, such as pyridine.

Further, in the esterification reaction, in addition to using the carboxylic acid alone, a small amount of concentrated sulfuric acid or dry hydrogen chloride may be used at the same time. Furthermore, a halide of carboxylic acid can be used instead of carboxylic acid.

The amount of the silane compound or carboxylic acid to be used may be at least twice the mole of the ethylene polymer having oxy groups at both ends.

Ethylene polymer (I) can be produced as described above.

It will be done. In the formula, R represents a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably a divalent saturated or unsaturated aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 12 carbon atoms. It is the basis.

Y is -DH, -OR', halogen atom or -3o, R
' indicates. R3 is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group, with methyl and ethyl being particularly desirable.

R4 is a hydrocarbon group having 1 to 20 carbon atoms and may contain a halogen atom. Preferably, it is an aryl or aralkyl group having 6 to 12 carbon atoms.

As a specific example of Y, Otl, -DC)Is, -
[IC21(S.

-O"n-C5Ht, -0-i-C+H1, -0-
i-CnHs, -Ct.

Among these, -DH, -0CH5, -0C2H5,
-CI.

so3→(=) etc. is desirable.

Compound (II) includes saturated aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, and dodecanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid, 1,4-butenedicarboxylic acid, cyclohexanedicarboxylic acid,
Dicarboxylic acids such as saturated alicyclic dicarboxylic acids such as nolic acid dicarboxylic acid: dimethyl ester, diethyl ester, di-n-propyl ester, di-l of the above dicarboxylic acids
- dialkyl esters such as butyl esters, dichlorides of the above-mentioned dicarboxylic acids, cibarides such as dibrosides, and the like.

Polycondensation polymer of ethylene polymer (I) and compound (n) (
The polycondensation reaction between I) and compound (n) is usually carried out in the presence of a solvent. The solvent is preferably a hydrocarbon, particularly an aromatic hydrocarbon such as toluene or xylene having a boiling point of 80° C. or higher.

Both reactions are carried out at 50-250°C, preferably at 100-250°C.
It is carried out at 00°C for 1 to 100 hours, preferably 5 to 50 hours. Furthermore, after removing the solvent, 150~2
It is particularly desirable to carry out the reaction at 00°C.

In the polycondensation reaction, it is also possible to use titanium tetraalkoxides such as titanium tetrapropoxide, titanium tetrabutoxide, titanium tetrahexyl oxide, etc. as a catalyst to promote the reaction. Further, in order to trap the generated by-products, a trapping agent such as an amine can be used in combination.

Furthermore, ammonium salts such as benzyltriethylammonium chloride can also be used as reaction accelerators.

In the polycondensation reaction, the molecular weight of the ethylene polymer of the present invention can generally be increased by increasing the reaction temperature, increasing the reaction time, or using a catalyst.

Effects of the Invention According to the method of the present invention, an ethylene polymer that can be decomposed by microorganisms can be produced.

Example Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 a) Synthesis of ethylene polymer (I') To a 31 flask which had been sufficiently purged with nitrogen gas, 1 toluene was added.
．． Ofl was added and the mixture was cooled to -65°C. 1.7 at the same temperature
-1.2 mmol of octadiene was added. Then 10 mmol of AI (C2H5) 2CI and 1 mmol of V
(2-methyl-1,3-butanedionato)3 was added,
Stirred for 30 minutes. A further 4.5 g of ethylene were introduced over a period of 2 hours, followed by the addition of 1.2 mmol of 1.7-octadiene.

After stirring for 10 minutes, the reaction solution was poured into ethanol and the produced polymer was filtered. The number average molecular weight (shame) of the polymer determined by GPC was 4.9 x 103. Moreover, the yield was 4.3g.

As a result of proton NMR measurement of the above polymer, 5.0
Signals based on protons of terminal double bonds were observed at ppm and 5.8 ppm. Their attributions are as follows.

δ (ppm) Attribution δ (ppm) Attribution 5.0 -CH=CH25,8CH=CH2
The difference between this signal and the presence of a group originating from the ethylene polymer was 4.6×10′.

This value agrees well with the result obtained by GPC.

It was concluded that the obtained polymer was an ethylene polymer having vinyl groups at both ends.

The above polymer was added to 200 ml of n-butyl ether, and a THF solution of diborane was added at room temperature while stirring vigorously under nitrogen flow. The amount of diborane added was 2.5 mmol. After stirring at reflux temperature for 1 hour, the temperature was lowered and 3N aqueous sodium hydroxide solution 200- and 3
200ml of 0% hydrogen peroxide solution was added, and the mixture was further stirred for 1 day. The resulting polymer was washed thoroughly with water, then with acetone, and then dried.

The IR (infrared absorption spectrum) chart of the produced polymer had a broad peak at 3300 to 3500 cm-'. From this, it was concluded that the obtained polymer was an ethylene polymer (I) having oxy groups at both ends.

b) Polycondensation with adipic acid dichloride The ethylene polymer (I) obtained above and 1 mmol of adipic acid dichloride were mixed in 20 mj of toluene at 120°C! dissolved in. 1 mmol of tetramethylethylenediamine was added dropwise to this solution, and the mixture was reacted at 120° C. for 24 hours. After removing by-products by hot filtration, the mixture was cooled to room temperature and the precipitated polymer was recovered.

When the IR of this polymer was measured, no peak based on oxy groups was observed, but an absorption peak based on ester groups was observed at 1740c+n-'.

Further, the distance n determined by GPC was 2.0×10'.

From the above results, it can be concluded that the obtained polyethylene polymer is a polymer consisting of the following repeating units.

n! =i 175 Example 2 a) Synthesis of ethylene polymer (1) An ethylene polymer (I ) was synthesized. The l1lo of this polymer was determined by GPC to be 1.2 x 10'.

b) Polycondensation with succinic acid diethyl ester After mixing 1.2 g of the ethylene polymer (I) obtained above and 1 mmol of succinic acid diethyl ester, 1 drop of titanium tetrabutoxide was added, and the mixture was heated at 180°C under a nitrogen gas stream. It reacted for 1 hour.

Furthermore, treatment was performed at 180° C. for 6 hours under a reduced pressure of 2 mmHH. Thereafter, the temperature was lowered to room temperature to obtain a solid ethylene polymer.

When the IR of this polymer was measured, no absorption peak due to oxy groups was observed.

Furthermore, the n value measured by GPC was 5.0×10'.

From the above results, it can be concluded that the obtained ethylene polymer is a polymer consisting of the following repeating units.

n″=, 43 Example 3 a) Synthesis of ethylene polymer (I) To a flask of 31 which had been sufficiently purged with nitrogen gas, 1 toluene was added.
．． Added Ol and cooled to -78°C. At the same temperature, 0.6 mi of 1.9-decadiene! J mol was added. Next, 100 mmol of AI (C2H5) act and 20 mmol of V
(acetylacetonate) was added and stirred for 30 minutes.

After introducing an additional 1.5 g of ethylene over 30 minutes,
0.6 mi of 1,9-decadiene! J mol was added. 30
After stirring for a minute, the reaction solution was poured into ethanol and the produced polymer was filtered off. The yield of polymer was 1.2g,
The distance n was 2.6×10′.

The same operation as in Example 1 was carried out except that the amount of diborane was changed to 1 mmol, and a double-terminated ethylene polymer (II) was prepared.
was synthesized.

Add the ethylene polymer (I) obtained above and 10 g of trimethylchlorosilane to 250-g of pyridine, and
After stirring for an hour, the reaction was carried out for 4 hours under refluxing of pyridine. The produced polymer was washed with methanol and then dried.

As a result of proton NMR measurement, δ=0. A signal due to protons of -5i(CH3)3 group was observed at O8ppm. Further, as a result of IR measurement, no absorption vector due to oxy groups was observed. Due to this,
It was concluded that the obtained polymer was an ethylene polymer (1) having trimethylsilyloxy groups at both ends.

b) Polycondensation with succinic dichloride 1.3 g of the trimethylsilyloxylated ethylene polymer (I) at both ends obtained above, 0.5 mmol of succinic dichloride, and 1 mol of benzyltriethylammonium chloride.
0'mg was reacted at 150°C until no generation of trimethylsilane chloride was observed, and then at 180°C for 1 hour.

The temperature was lowered to room temperature, and a solid ethylene polymer was obtained.

When the IR of this polymer was measured, it was found to be 1740 cm-'
, an absorption spectrum due to the ester bond was observed near 1150 cm-'. Moreover, the M opening measured by GPC was 1.5×10′.

From the above results, it can be concluded that the obtained ethylene polymer is a polymer consisting of the following repeating units.

Claims (2)

[Claims] (1) Number average molecular weight (@M@n) 300 to 300, where A consists of repeating units of ▲ ▲ There are mathematical formulas, chemical formulas, tables, etc. 0
00 polyethylene segment @M@n500~
5,000,000 ethylene polymer. [However, R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. ] (2) ▲There are mathematical formulas, chemical formulas, tables, etc.＠M＠n300 consisting of repeating units of ▼ and with XO- groups bonded to both ends.
Production of the ethylene polymer described in (1) above, which consists of polycondensing the ethylene polymer (I) of ~300,000 and the compound (II) represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ Law. [However, X is a hydrogen atom, -SiR^1_3 or -C-R
^2, Y is -OH, -OR^3, halogen atom or -
SO_3R^4 is shown, R^1, R^2 and R^3 each represent a hydrocarbon group having 1 to 5 carbon atoms, and R^4 represents a hydrocarbon group having 1 to 20 carbon atoms. R has the same meaning as above. ]