JPH10120630A - Production of bisalkycarbonic ester dimer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a lubricant for forming a polymer pellet, by using a bisalkylcarbonic ester of an aromatic dihydroxy compound as a raw material and subjecting it to self-condensation by using a catalyst. SOLUTION: A compound of the formal (R<1> and R<2> are each a 1-10C alkyl or cycloalkyl; Z is a bifunctional aromatic residue) as a raw material is subjected to self-condensation by using a phosphorus compound such as an alkyl-substituted phosphoric acid to produce a bisalkylcarbonic ester dimer. The amount of the catalyst used is generally 1×10<-5> to 1×10<-1> mol based on 1mol of the compound of the formula. The reaction conditions are different depending upon the kind of the raw material and that of the catalyst, etc., and the reaction is carried out usually at 100-350 deg.C, preferably 150-340 deg.C for 20 minutes to 10 hours, preferably 1-8 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing a bisalkyl dimer suitable as a lubricant used for molding polycarbonate, polyarylene, polyester and the like.

[0002]

2. Description of the Related Art Conventionally, as a self-condensing method of bisalkyl carbonate, a method of self-condensing bisphenol A bismethyl carbonate as a raw material has been proposed. Specifically, a method using an organotin compound as a catalyst ( German Patent No. 2736063, Japanese Patent Laid-Open No.
No. 2334), IIB, IIIB, IVA, IV of the periodic table
There are a method using a metal element belonging to Group B and its compound (JP-A-63-205318), a method using various metals as catalysts (JP-A-2-251522), and the like. For example, when used as a lubricant in resin molding, there is a problem that decomposition of the base resin produces low-molecular-weight products such as monomers and causes discoloration of molded products.

[0003]

SUMMARY OF THE INVENTION The present invention is particularly useful as a lubricant for molding pellets obtained by kneading a resin alone such as polycarbonate, polyarylene, polyester or the like, or other polymers and fillers. An object of the present invention is to provide a method for producing a bisalkyl carbonate dimer which can be suitably used without causing inconvenience such as loss of stability.

[0004]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have completed the present invention having the following contents. (1) A method for producing a bisalkyl carbonate dimer, which is obtained by using a bisalkyl carbonate of an aromatic dihydroxy compound represented by the formula (A) as a raw material and self-condensing using a phosphorus compound as a catalyst.

[0005]

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(Wherein R ¹ and R ^{2 each} have 1 to 10 carbon atoms)
And these may be the same or different from each other. Z is a divalent aromatic residue. (2) The method for producing a bisalkyl carbonate dimer according to the above (1), wherein the phosphorus compound is an oxide. (3) The method for producing a bisalkyl carbonate dimer according to the above (1), wherein the phosphorus compound is a compound having two phosphorus atoms in a molecule. (4) As the bisalkyl carbonate of the aromatic dihydroxy compound represented by the formula (A), a raw material in which R ¹ and R ² are each a methyl group or an ethyl group and the aromatic hydroxy compound is bisphenol A is used. ) ~
The method for producing a bisalkyl carbonate dimer according to any one of (3).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a method for producing a bisalkyl carbonate dimer by self-condensation using a bisalkyl carbonate of an aromatic dihydroxy compound represented by the formula (A) as a raw material and a phosphorus compound as a catalyst.

[0008]

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(In the formula, R ¹ , R ² and Z have the same meanings as described above.) In the bisalkyl carbonate of the aromatic dihydroxy compound represented by the formula (A) used for this raw material, R
¹ and R ² is preferably methyl, ethyl, propyl, iso - propyl, butyl, amyl, alkyl group having 1 to 10 carbon atoms such as hexyl, cyclopropyl, cyclobutyl, cyclopentyl, a cycloalkyl group such as cyclohexyl. Further, each of these alkyl groups or cycloalkyl groups may have a substituent such as an alkoxy group, an ester group, or a nitrile group. R ¹ , R ²
May be the same or different. Preferably,
R ¹ and R ² are preferably methyl groups.

Z is a divalent aromatic residue of an aromatic dihydroxy compound. Examples of such an aromatic residue include a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic residue represented by the general formula (B).

[0011]

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In the formula (B), Z ¹ and Z ² are divalent aromatic groups, for example, a phenylene group, a naphthylene group,
It is a biphenylene group or the like, which may be the same or different. T is a single bond or -O-, -CO-,-
_{S -, - SO 2 -,} - CO 2 -, - CON (R 3) -,

[0013]

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And a divalent group such as (Where R ³ , R
⁴ , R ⁵ and R ⁶ may be the same or different. Represents a hydrogen, an alkyl group, an alkoxy group, or a cycloalkyl group, and k represents an integer of 3 to 11. It preferably has 1 carbon atom
To 10 alkyl groups or cycloalkyl groups. Further, in Z, Z ¹ and Z ² , a hydrogen atom may be substituted with an alkoxy group, an ester group, a nitrile group or the like.

Typical examples of such bisalkyl carbonates of aromatic dihydroxy compounds include those obtained from the reaction of an alkyl chloroformate with a dialkali metal salt of bisphenol A (Japanese Patent Publication No. 37-3296). As specific compound names, for example, bis (methyl carbonate) of 4-hydroxyphenol, bis (methyl carbonate) of 3-hydroxyphenol, 1,1-bis (4-hydroxyphenyl) -butane as bismethyl carbonate Bis (methyl carbonate), bis (4-hydroxyphenyl) -methane bis (methyl carbonate), 2-methyl-1,1-bis (4-hydroxyphenyl) -propane bis (methyl carbonate), 2,2 -Bis (3,5-dimethyl-4
-Hydroxyphenyl) -propane bis (methyl carbonate), bis (3,5-dimethyl-4-hydroxyphenyl) -sulfone bis (methyl carbonate), bis (3,5-dimethyl-4-hydroxyphenyl) -ether Bis (methyl carbonate), 4,
Bis (methyl carbonate) of 4'-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl)
-Bis (methyl carbonate) of ethane, 1-ethyl-
Bis (methyl carbonate) of 1,1-bis (4-hydroxyphenyl) -propane, bis (methyl carbonate) of 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis (4-hydroxyphenyl) )
Bis (methyl carbonate) of cyclododecane, bis (methyl carbonate) of bis (4-hydroxyphenyl) -phenylmethane, bis (methyl carbonate) of bis (4-hydroxyphenyl) -naphthylmethane,
Bis (4-hydroxyphenyl)-(4-isopropylphenyl) -methane bis (methyl carbonate),
Bis (methyl carbonate) of 2,2-bis (4-hydroxyphenyl) -propane, bis (methyl carbonate) of 2,2-bis (4-hydroxyphenyl) -butane, 2,2-bis (4-hydroxyphenyl) ) -Hexane bis (methyl carbonate), 2,2-bis (3,5-dicyclolo-4-hydroxyphenyl) -propane bis (methyl carbonate), 2,2-bis (4-hydroxyphenyl) -pentane Bis (methyl carbonate), bis (methyl carbonate) of 2,2-bis (4-hydroxyphenyl) -nonane, bis (methyl carbonate) of diphenyl-bis (4-hydroxyphenyl) -methane, 4-methyl-2, Bis (methyl carbonate) of 2-bis (4-hydroxyphenyl) -pentane, 4,4-bis 4-hydroxyphenyl) - heptane bis (methyl carbonate), 1-naphthyl-1,1-bis (4-hydroxyphenyl) - bis ethane (methyl carbonate), 1-phenyl -
Bis (methyl carbonate) of 1,1-bis (4-hydroxyphenyl) -ethane, 2-cyclohexyl-4-
Bis (methyl carbonate) of (4-hydroxyphenyl) isopropylphenol, 2-methoxy-4- (4
Bis (methyl carbonate) of -hydroxyphenyl) isopropylphenol, bis (methyl carbonate) of 1,2-bis (4-hydroxyphenyl) -ethane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Bis (methyl carbonate) of propane, bis (methyl carbonate) of 2-isopropyl-4- (4-hydroxyphenyl) isopropylphenol, bis (methyl carbonate) of 2,2-bis (3-methyl-4-hydroxyphenyl) -propane Methyl carbonate), bis (methyl carbonate) of 2,2-bis (3-fluoro-4-hydroxyphenyl) -propane, bis (methyl carbonate) of 1,10-bis (4-hydroxyphenyl) -decane, bis ( Bis (methyl carbonate) of 3,5-dichloro-4-hydroxyphenyl) -methane, 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl)-
Bis (methyl carbonate) of propane, bis (methyl carbonate) of 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -cyclohexane, bis (4-
Bis (methyl carbonate) of hydroxyphenyl) -sulfide, bis (methyl carbonate) of bis (3-methyl-4-hydroxyphenyl) -sulfide, bis (methyl carbonate) of bis (4-hydroxyphenyl) -sulfoxide, bis ( 4-hydroxyphenyl)
Bis (methyl carbonate), bis (3-
Bis (methyl carbonate) of chloro-4-hydroxyphenyl) -sulfone, bis (methyl carbonate) of ethylene glycol-bis (4-hydroxyphenyl) ether, bis (methyl carbonate) of 1,4-bis (4-hydroxyphenyl) -butane Methyl carbonate), 1,4-
Bis (4-hydroxyphenylisopropyl) -bis (methyl carbonate) of benzene, 1,4-bis (3-
Bis (methyl carbonate) of chloro-4-hydroxyphenyl) -benzene, bis (methyl carbonate) of bis (4-hydroxyphenyl) ether, 1,4-
Bis (4-hydroxyphenoxy) -benzene bis (methyl carbonate), 1,4-bis (4-hydroxyphenylmethyl) -benzene bis (methyl carbonate), 1,4-bis (4-hydroxyphenylsulfonyl)- Bis (methyl carbonate) of benzene, bis (methyl carbonate) of bis (3,5-dimethyl-4-hydroxyphenyl) -methane, bis (methyl carbonate) of bis (3,5-dimethyl-4-hydroxyphenyl) -sulfide ), 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone bis (methyl carbonate), and the like.

Bisethyl carbonates wherein the methyl group of the bismethyl carbonate is replaced with an ethyl group,
Bispropyl carbonate substituted for various propyl groups, bisbutyl carbonate substituted for various butyl groups, bisamyl carbonate substituted for various amyl groups, bishexyl carbonate substituted for various hexyl groups, replaced with cyclopropyl group Biscyclopropyl carbonate can also be used.

Further, in the dialkyl carbonates having different alkyl groups, for example, the above-mentioned bismethyl carbonates, one of the methyl groups is replaced with an alkyl group having 2 to 10 carbon atoms such as an ethyl group, a propyl group or a butyl group, or a cycloalkyl group. And dialkyl carbonates can also be used. These bisalkyl carbonates may be used alone or in combination of two or more.

The reaction conditions vary depending on the type of raw materials, the type of catalyst used, the amount used, and the like.
° C, preferably in the temperature range of 150 to 340 ° C, for 20 minutes to 10 hours, preferably in the range of 1 hour to 8 hours. Further, in this reaction, the reaction can be promoted by discharging dialkyl carbonate, which is a by-product, to the outside of the system, so that a stirring operation, and further, an operation of replacing and removing with an inert gas such as nitrogen gas or carbon dioxide gas may be used in combination. It is effective.

In the present invention, the target compound can be effectively produced by using a phosphorus compound as a catalyst in the above reaction. Specific examples include phosphine oxides such as alkyl-substituted phosphine oxides, aryl-substituted phosphine oxides, and piperidine-substituted phosphine oxides, such as n-butylphosphine oxide, diphenylphosphine oxide, piperidinophosphine oxide, and triphenylphosphine oxide. Is mentioned. In addition, bis (diphenylphosphino) alkane having two phosphorus atoms in one molecule, such as bis (diphenylphosphino) methane and bis (diphenylphosphino) propane, may be mentioned. Furthermore, compounds having a phosphorus-carbon or nitrogen double bond include, for example, 1-triphenylphosphoranylidene-2-propane and N- (triphenylphosphoranylidene) aniline.

These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is usually 1 × 10 4 mol per mol of the starting bisalkyl carbonate.
^-5 to 1 × 10 ^-1 mol can be selected. Among these catalysts, tri-n-butylphosphine oxide can be suitably used.

According to the manufacturing method of the present invention, for example,
By reacting for 2 hours, a bisalkyl carbonate dimer can be obtained with a yield of about 30%. The dimer obtained in the present invention is a white solid at room temperature, has low toxicity, is used as a lubricant for resin molding, and is used as a powder coating raw material, a thermal adhesive,
It can be used as various modifiers for thermosetting resin beads for casting molds.

[0022]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. Example 1 Bisphenol A bismethyl carbonate 2 was placed in a 100 ml glass autoclave equipped with a stirrer.
0.0 g (58 mmol) was taken. To this, 0.58 mmol of tri-n-butylphosphine oxide dissolved in anhydrous methylene chloride was added using a syringe. After the argon substitution was repeated 5 times, the mixture was set in an oil bath at 200 ° C. so that the lower half was immersed, and heated for 2 hours while stirring. After heating for 2 hours, the product was taken out of the oil bath, cooled, opened, and the contents were discharged under a nitrogen atmosphere at 200 ° C., 10 torr and 30 minutes under the conditions of dimethyl carbonate as a by-product. Dissolve the remaining viscous material in methylene chloride and take it out.
The contents were analyzed using high performance liquid chromatography, and the concentration of the generated dimer (shown by the formula (C)) was determined.

Further, the obtained viscous material is placed in a nitrogen atmosphere,
After performing a retention burn test at 20 ° C. for 45 minutes, this was dissolved in methylene chloride to a concentration of 8% by weight, and YI (yellow index) was measured. Table 1 shows the results.

[0024]

[Table 1]

Examples 2-7 Example 1 except that the catalyst was used in place of the compounds shown in Table 1.
And the product was evaluated. Table 1 shows the results. Comparative Example 1 The same as Example 1 except that nothing was added as a catalyst. Table 1 shows the results.

Comparative Example 2 Dibutyltin dimethoxide was used as a catalyst at 5.8 × 10 ⁻³ m
The same as Example 1 except that mol was used.

[0027]

According to the present invention, the catalytic activity is not so different from the conventionally known organotin-based catalysts, but has a unique effect with little residual burning, which is considered to be caused by the residual catalyst contained in the product. Can be that's all

Claims (4)

[Claims] 1. A process for producing a bisalkyl carbonate dimer, which comprises using a bisalkyl carbonate of an aromatic dihydroxy compound represented by the formula (A) as a raw material and self-condensing using a phosphorus compound as a catalyst. Embedded image (In the formula, R ¹ and R ² are an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, which may be the same or different from each other. Z is a divalent aromatic residue. ) 2. The process for producing a bisalkyl carbonate dimer according to claim 1, wherein the phosphorus compound is an oxide. 3. The process for producing a bisalkyl carbonate dimer according to claim 1, wherein the phosphorus compound is a compound having two phosphorus atoms in the molecule. As the bis-alkyl carbonates wherein the aromatic dihydroxy compound represented by formula (A), R ¹ and R
^The method for producing a bisalkyl carbonate dimer according to any one of claims 1 to 3, wherein ^{2 comprises a} methyl group or an ethyl group and a raw material in which the aromatic hydroxy compound is bisphenol A.