JPH05310915A - Copolymerization of ethylene-carbon monoxide - Google Patents

Abstract

PURPOSE:To produce a copolymer having a remarkably high degree of polymerization by polymerizing ethylene and carbon monoxide in the presence of a free radial initiator in a carbonate. CONSTITUTION:Ethylene and carbon monoxide are polymerized in the presence of a free radial initiator in a carbonate so as to produce an ethylene-carbon monoxide copolymer having a high polymerization degree. As the carbonate, a dialkyl carbonate, preferably diethyl carbonate is used. As the free radical initiator, a peroxydicarbonate-based initiator, a peroxy ester-based initiator or an azo-based initiator is preferably used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an ethylene-carbon monoxide copolymer useful as an engineering resin.

[0002]

2. Description of the Prior Art A method for producing an ethylene-carbon monoxide copolymer in the presence of an organic peroxide is disclosed in US Pat.
286 and JP-A-53-128690.
It is disclosed in each of Japanese Patent Laid-Open No. 53-128691,
Examples of the polymerization solvent include water, benzene, isooctane, dioxane, n-hexane, acetonitrile and propylene oxide.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ethylene-carbon monoxide copolymer having a high degree of polymerization.

[0004]

The feature of the present invention resides in that ethylene and carbon monoxide are copolymerized in the presence of a specific solvent. That is, the present invention is an ethylene-carbon monoxide copolymerization method in which ethylene and carbon monoxide are polymerized in a carbonic acid ester in the presence of a radical initiator.

In the present invention, a dialkyl carbonate can be used as the carbonic acid ester. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and the like, and a mixture containing them can also be used,
Dimethyl carbonate and diethyl carbonate are preferably used. In the present invention, a peroxydicarbonate-based, peroxyester-based, diacyl peroxide-based or azo-based initiator is preferably used as the radical initiator. Here, each system has --O--O-- bond or --N in one molecule.
= A monoradical initiator containing one N-bond, a biradical initiator containing two -O-O- bonds or -N = N-bonds in one molecule, a -O-O- bond in one molecule, or −
Included are polymeric initiators containing three or more N = N-bonds.

Examples of monoradical initiators include di-2-ethylhexyl peroxydicarbonate and t-
Butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide and 2,2'-azobisisobutyronitrile are preferably used. Examples of the biradical initiator include 2,5-dimethyl-2,5-bis (2-ethylhexylperoxy) hexane and 2,5-dimethyl.
Dimethyl-2,5-bis (neodecanoylperoxy)
Hexane is preferably used.

As the polymeric peroxide, for example, polyperoxydicarbonate represented by the general formula (1) is used.

[0008]

[Chemical 5]

Here, n is a natural number of 3 to 200, R ₁ is an ether group, a carbonate group, an ester bond, a saturated carbon ring or an aromatic ring, and both ends of which have 3 to 50 carbon atoms are primary. It represents a hydrocarbon group which is a secondary or tertiary carbon. In the formula (1), n is preferably in the range of 3-100. When n is less than 3, a copolymer having a high degree of polymerization cannot be obtained, and when n exceeds 200, the solubility in a solvent is lowered, which is not preferable.

R ₁ has 3 to 50 carbon atoms, preferably 3 to 2 carbon atoms.
It is a hydrocarbon group of 0. A substance having a carbon number of R ₁ of less than 3 is unstable and difficult to handle, while a substance having a carbon number of more than 50 is not preferable because the amount of the initiator used must be increased. R ₁ is composed of a hydrocarbon group in which groups at both ends bonded to an oxygen atom are primary, secondary or tertiary carbons. This hydrocarbon group may contain an ether group, a carbonate group, an ester bond, a saturated carbon ring or an aromatic ring. Examples of such R ₁ include the following formulas (5) to (9).

[0011] _{-C 2 H 4 - (O-} C 2 H 4) 1 - (1 is 1 or 2) (5) - (CH 2) 6 -O-CO-O- (CH 2) 6 - (6 _{) - (CH 2) 2 -O} -CO- (CH 2) 4 -COO- (CH 2) 2 - (7)

[0012]

[Chemical 6]

[0013]

[Chemical 7]

Preferred R₁As-(CH₂)_m−
(M is a natural number of 3 to 10), -CH ₂-C (CH₃)₂
-CH₂-And-C (CH₃)₂-CH₂-CH (C
H₃)-And other straight-chain aliphatic hydrocarbons having 3 to 10 carbon atoms
Group or branched aliphatic hydrocarbon group, represented by formula (H)
An aliphatic hydrocarbon group containing such a saturated carbocycle, and -C ₂
H_Four-(OC₂H_Four)₁-(1 is 1 or 2)
Examples thereof include an aliphatic hydrocarbon group containing an ether group. This
These R₁The polyperoxydicarbonate having
Raw material diol is easy to obtain at the time of synthesis, and safety is high
Which point is preferable.

Another example of the polymeric peroxide is a polyperoxy ester represented by the general formula (2).

[0016]

[Chemical 8]

Here, n is a natural number from 2 to 200, R ₂
And R ₃ represents an ether group, a saturated carbon ring or a hydrocarbon group having 2 to 50 carbon atoms which may contain an aromatic ring.
In the formula (2), when n is less than 2, a copolymer having a high degree of polymerization cannot be obtained, and when it exceeds 200, the solubility in a solvent is lowered, which is not preferable. n is preferably in the range of 2 to 100.

R₂And R₃Has 2 to 50 carbon atoms, preferred
Or 2 to 20 hydrocarbon groups. R₂Or R₃Charcoal
A substance with a prime number of 1 is unstable and difficult to handle. one
However, if the carbon number exceeds 50, do not increase the amount of initiator used.
It has to be unfavorable. R₂And R₃Is ete
It may contain a ring group, a saturated carbocycle or an aromatic ring.
R like this₂, R₃Is, for example, -CH (CH
₃) -CH (CH₃)-, -CH (CH₃) -CH₂−
CH (CH₃)-And -C (CH₃)₂-(CH₂)
₂-C (CH₃)₂-C3-10 branched fatty oil
Aliphatic hydrocarbon group, -CH₂-O-CH₂-And-C
(CH₃)₂-CH₂-O- (CH₂) ₃-O-CH₂
-C (CH₃)₂Aliphatic carbonization containing ether groups such as
Hydrogen group, containing a saturated carbocycle represented by the following formula (10)
A group and an aromatic ring represented by the following formula (11)
Examples include groups.

[0019]

[Chemical 9]

Preferred polyperoxyesters used in the present invention include those represented by the following formulas (12) to (19).

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical formula 12]

[0024]

[Chemical 13]

The polyperoxy ester of the formula (2) used in the present invention is a dichloride represented by Cl-CO-R ₁ -CO-Cl and a hydroperoxide represented by HO-O-R ₂ -O-OH. It is obtained by esterifying. Another example of the polymeric peroxide is a diacyl-type polymeric peroxide represented by the general formula (3).

[0026]

[Chemical 14]

Here, n is a natural number of 3 to 50, and R ₄ is
It represents a hydrocarbon group having 3 to 50 carbon atoms, which may contain an ether group, an ester bond, a saturated carbon ring or an aromatic ring. Suitable diacyl type polymeric peroxides include those represented by the following formulas (20) to (25).

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

Examples of the macroazo initiator that can be used in the present invention include compounds represented by the general formula (4).

[0032]

[Chemical 18]

Here, n is a natural number of 3 to 50, and R ₅ is-(CH ₃ ) C (CN)-or-(CH ₃ ) C at both ends.
(COOCH ₃ )-, which represents a cyano group, an ether group or a hydrocarbon group having 8 to 20 carbon atoms and optionally containing an ester bond. Examples of suitable R ₅ include those represented by the following formulas (26) to (29).

[0034]

[Chemical 19]

[0035]

[Chemical 20]

The compound of formula (26) contains 2,2'-azobis (2-cyanopropanol) and saturated fatty acid dichloride having 1 to 8 carbon atoms, and the compound of formula (27) has 2 carbon atoms.
8 saturated aliphatic dialcohol and 4,4'-azobis and (4-cyanovaleric acid dichloride), a compound of formula (28) is _{- (CH 2 CH 2 O)} - of repeating units 2-4
Ethylene glycol and 4,4'-azobis (4
-Cyanovaleric acid dichloride) and the compound of formula (29) are condensed with 2,2'-azobis (2-methylcarboxyl propanol) and a saturated fatty acid dichloride having 1 to 8 carbon atoms and dehydrochlorinated. can get. The carbon number of R ₅ is preferably 13 to 20.

The ratio of ethylene to carbon monoxide in the reaction mixture is from 1 to 4 to 4 to 1, preferably from 1 to 3 to 3 to 1. Further, the polymerization is carried out in the range of 50 to 90 ° C., though it depends on the initiator used.

[0038]

EXAMPLES The present invention will be described below with reference to examples.

[0039]

[Reference example]

(1) Synthesis of polyperoxydicarbonate 96 g (0.24%) of a 10 wt% sodium hydroxide aqueous solution.
12.5 g (0.1 mol) of 30 wt% hydrogen peroxide solution (0.1 mol)
A solution A containing 1 mol) and a solution B containing 24.3 g (0.1 mol) of 1,6-hexanediol bischloroformate dissolved in 100 g of cyclohexane were prepared. Both solutions A and B were added to a 1 liter four-necked flask which was vigorously stirred and kept at 1 to 4 ° C. by ice cooling. The resulting precipitate was filtered off, washed with water and dried under reduced pressure at 5 to 10 ° C. to obtain powdery poly (hexamethylene peroxydicarbonate) 19.
4 g was obtained.

Analysis of this powder by GPC revealed that
1.3 × 10 in terms of weight average molecular weight in terms of ethylene^FourAnd
It was This is n in the repeating unit represented by the formula (1).
= 64. In addition, active oxygen determined by the KI method
Was 94% of theory. In the same way, equation (1)
R in₁Is the formula (8), -CH₂-C (CH₃)₂
-CH₂-,-(CH₂)_Four-, -C₂H_Four-OC₂
H_Four-, And -C ₂H_Four-(O-C₂H_Four)₂−
Polyperoxydicarbonate was synthesized. (2) Synthesis of polyperoxy ester 236 g (4.2 mol) of 35 wt% potassium hydroxide
Put in a 1 liter 4-necked flask and stir under stirring ClOCC
H₂OCH₂COCl 34g (2.0mol) at 10 ° C
Dropping was performed while maintaining the following. HOOC under strong stirring
(CH₃)₂CH ₂CH₂C (CH₃)₂COOH 3
Drop 6 g (2.0 mol) while keeping the liquid temperature at 5-10 ° C.
Defeated After raising the liquid temperature to 15 ° C and stirring for 30 minutes,
While maintaining the temperature at 10 ° C., 500 g of cold water was added and the mixture was left to stir.
The organic layer was separated, washed with water and dried to obtain 55 g of a liquid. this
As a result of analyzing the liquid by GPC, the polystyrene equivalent weight
Average molecular weight is 3.3 × 10³Met. This is formula (2)
It corresponds to n = 12 in the repeating unit represented by.

Polyperoxyesters represented by the formulas (12) to (19) were synthesized by the same method.

[0042]

Example 1 A SUS autoclave equipped with a stirrer having a capacity of 1 liter was charged with 800 ml of dimethyl carbonate as a solvent and 1.6 g of poly (hexamethylene peroxydicarbonate) of n = 64, which was synthesized according to the reference example, followed by CO / ethylene pressure. Gas phase pressure of 45 kg / c at room temperature
It was prepared to be m ² G. While stirring at 100 rpm, the autoclave was heated with a heat medium to raise the temperature to 60 ° C. After reacting for 6 hours while adding a mixed gas so as to keep the gas phase pressure at 50 kg / cm ² , the autoclave was cooled to 40 ° C. or lower, and the pressure was reduced to atmospheric pressure. Acetone was added to the content, the solid was filtered off, and dried under reduced pressure at room temperature to obtain a white powder. The viscosity of a 0.5 g / dl m-cresol solution of this powder was measured at 60 ° C. using an Ubbelohde viscosity tube to obtain a reduced viscosity ηsp / c value defined below.

[0043]

[Equation 1]

The results are shown in Table 1.

[0045]

Examples 2 to 13 Copolymerization of ethylene and carbon monoxide was carried out under the same conditions as in Example 1 except that the initiators shown in Tables 1 and 2 were used and the charged amount and temperature were changed. The results are shown in Tables 1-2.

[0046]

Example 14 As a radical initiator,-(OC- (C
H₂)₆-CH (C₂H_Five)-(CH ₂)₉-CO-O
-O)_n-(Example 1 of JP-B-63-32089)
Was synthesized based on. ) 2.7 g and a polymerization temperature of 80
Polymerization was carried out under the same conditions as in Example 1 except that the temperature was changed to ° C.
As a result, the reduced viscosity of the copolymer ηsp / c = 0.40dl / g
Got

[0047]

Example 15 As a radical initiator, a product obtained by condensing 2,2′-azobis (2-cyanopropanol) and sebacic acid dichloride in DMF in the presence of triethylamine was used. As a result of GPC analysis, the weight average molecular weight of this initiator was 3 × 10 ³ in terms of polystyrene,
This corresponds to n = 8. Using 2.9 g of this initiator,
As a result of carrying out the polymerization under the same conditions as in Example 1 except that the polymerization temperature was 90 ° C., the reduced viscosity ηsp / c of the copolymer was 0.
41 dl / g was obtained.

[0048]

Example 16 Example 1 except that the substances and amounts shown in Table 3 were used as the radical initiator and the conditions shown in Table 3 were used.
Polymerization was carried out under the same conditions as above. The results are shown in Table 3.

[0049]

Comparative Examples 1 and 2 Polymerization was carried out under the same conditions as in Example 17, except that n-hexane and 1,4-dioxane were used as the solvent. The results are shown in Table 4.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

According to the present invention, ethylene having a high degree of polymerization
A carbon monoxide copolymer can be obtained.

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[Procedure amendment]

[Submission date] June 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

R ₂ and R ₃ are hydrocarbon groups having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms. A substance having 1 carbon atom in R ₂ or R ₃ is unstable and difficult to handle. On the other hand, if the carbon number exceeds 50, the amount of the initiator used must be increased, which is not preferable. R ₂ and R ₃ may contain an ether group, a saturated carbocycle or an aromatic ring.
As such R ₂ , for example, —CH (CH ₃ ) —
_{CH (CH 3) -, -} CH (CH 3) -CH 2 -CH
(CH ₃₎ - and _{-C (CH 3) 2 - (} CH 2) 2 -C
(CH _{3) 2} - branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, such as, -CH ₂ -O-CH ₂ - and -C (C
_{H 3) 2 -CH 2 -O- (} CH 2) 3 -O-CH 2 -C
The aliphatic hydrocarbon group containing an ether group such as (CH ₃ ) ₂ — is, for example , a group containing a saturated carbocycle represented by the following formula (10) as R ₃ , and an aromatic group represented by the following formula (11). Examples include groups containing a ring.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

As a result of GPC analysis of this powder, the weight average molecular weight in terms of polystyrene was 1.3 × 10 ⁴ . This is n in the repeating unit represented by the formula (1).
= 64. In addition, the active oxygen determined by the KI method was 94% of the theoretical value. In the same way, equation (1)
R ₁ in formula (8), —CH ₂ —C (CH ₃ ) _{2
-CH 2 -, - (CH 2} ) 4 -, - C 2 H 4 -O-C 2
Polyperoxydicarbonates that were H ₄ − and —C ₂ H ₄ — (O—C ₂ H ₄ ) ₂ — were synthesized. (2) Synthesis of polyperoxyester 236 g (4.2 mol) of 35 wt% potassium hydroxide was placed in a 1-liter four-necked flask and stirred under ClOCC.
H ₂ OCH ₂ COCl 34 g (2.0 mol) at 10 ° C.
Dropping was performed while maintaining the following. HOOC under strong stirring
(CH ₃ ) ₂ CH ₂ CH ₂ C (CH ₃ ) ₂ OOH 36g
(2.0 mol) was added dropwise while maintaining the liquid temperature at 5 to 10 ° C. After raising the liquid temperature to 15 ° C and stirring for 30 minutes, 5 to 10
While maintaining the temperature at 0 ° C, 500 g of cold water was added and the mixture was left to stir. The organic layer was separated, washed with water and dried to obtain 55 g of a liquid. As a result of analyzing this liquid by GPC, the weight average molecular weight in terms of polystyrene was 3.3 × 10 ³ . This corresponds to n = 12 in the repeating unit represented by the formula (2).

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

Example 1 A SUS autoclave equipped with a stirrer having a capacity of 1 liter was charged with 800 ml of dimethyl carbonate as a solvent and 1.6 g of poly (hexamethylene peroxydicarbonate) of n = 64, which was synthesized according to the reference example, followed by CO / ethylene. Gas mixture with a pressure ratio of 1 at room temperature has a vapor phase pressure of 45 kg / c.
It was prepared to be m ² G. While stirring at 100 rpm, the autoclave was heated with a heat medium to raise the temperature to 60 ° C. After reacting for 6 hours while adding a mixed gas so as to keep the gas phase pressure at 50 kg / cm ² G , the autoclave was kept at 40 ° C.
It was cooled to below and depressurized to atmospheric pressure. Acetone was added to the content, the solid was filtered off, and dried under reduced pressure at room temperature to obtain a white powder. The viscosity of a 0.5 g / dlm-cresol solution of this powder was measured at 60 ° C. using an Ubbelohde viscometer to obtain a reduced viscosity ηsp / c value defined below.

Claims (7)

[Claims] 1. An ethylene-carbon monoxide copolymerization method comprising polymerizing ethylene and carbon monoxide in a carbonic acid ester in the presence of a radical initiator. 2. The copolymerization method according to claim 1, wherein the carbonic acid ester is a dialkyl carbonate. 3. The radical initiator is selected from peroxydicarbonate type, peroxyester type, diacyl peroxide type and azo type initiators.
The copolymerization method described. 4. The copolymerization method according to claim 3, wherein the radical initiator is polyperoxydicarbonate represented by the general formula (1). [Chemical 1] Here, n is a natural number of 3 to 200, R ₁ is an ether group,
It represents a hydrocarbon group which may contain a carbonate group, an ester bond, a saturated carbon ring or an aromatic ring and which has a carbon number of 3 to 50 and whose both ends are primary, secondary or tertiary carbon atoms. 5. The copolymerization method according to claim 3, wherein the radical initiator is a polyperoxy ester represented by the general formula (2). [Chemical 2] Here, n represents a natural number of 2 to 200, R ₂ and R ₃ represent an ether group, a hydrocarbon group having 2 to 50 carbon atoms which may contain a saturated carbon ring or an aromatic ring. 6. The copolymerization method according to claim 3, wherein the radical initiator is a diacyl type polymeric peroxide represented by the general formula (3). [Chemical 3] Here, n represents a natural number of 3 to 50, R ₄ represents a hydrocarbon group of 3 to 50 carbon atoms which may contain an ether group, an ester bond, a saturated carbon ring or an aromatic ring. 7. The copolymerization method according to claim 3, wherein the radical initiator is a macroazo initiator represented by the general formula (4). [Chemical 4] Here, n is a natural number of 3 to 50, and R ₅ is-(CH
₃₎ C (CN) - or - (CH ₃₎ C (COOC
H ₃₎ - a and represents a cyano group, an ether group or a hydrocarbon group of the ester bonds to carbon atoms which may contain 8 to 20.