JP2003238689A - Method for purifying organosilicon polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To remove metallic impurities from an organosilicon polymer because it contains metallic impurities, such as Cu, Mg, Fe, and Cr, originating in the raw materials and the catalyst and the apparatuses used in its production process. <P>SOLUTION: The method for purifying an organosilicon polymer comprises the step of dissolving the organosilicon polymer in a water-insoluble solvent and adding a solution containing an aqueous polybasic (at least dibasic) organic acid solution to the solution; the step of settling the resultant mixture after agitation to separate it into a water phase and an oil phase; and the step of removing the water phase. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for purifying organosilicon polymers which are useful as precursors for heat and flame resistant polymers and insulating polymers.

[0002]

2. Description of the Related Art Organosilicon polymers include Cu, Mg and F depending on raw materials, catalysts used in the manufacturing process, and equipment origin.
Metallic impurities such as e and Cr are included. In order to remove this metal impurity, the organosilicon polymer is treated with hydrochloric acid, iodo acid,
Washing has been performed with a volatile aqueous acid solution such as acetic acid.

[0003]

However, after washing with these acids, metal impurities cannot be completely removed even after repeated heating and washing with pure water. Although a slight amount, there was a problem that the halogen component remained. It is known that not only the metal but also the halogen component remaining in the polymer has conductivity and causes a decrease in insulation. In particular, when an aqueous hydrochloric acid solution is used, the Cl ion, which is a component thereof, forms a hydrogen bond with a part of the polymer, and it is difficult to completely remove it. Further, when the acid concentration is increased, the cleaning ability is improved, but there are problems that the acid component remains in the polymer, or a part of the polymer is decomposed or deteriorated.

[0004]

Means for Solving the Problems As a result of earnest studies, the present inventors have removed metal impurities from an organosilicon polymer by using a polyvalent organic acid aqueous solution without using a halogen-based acid. The inventors have found that it is possible to complete the present invention.
That is, the present invention includes (1) a step of dissolving an organosilicon polymer in a non-water-soluble solvent and adding a solution containing a polyvalent (divalent or higher) organic acid aqueous solution, and stirring the mixed solution. A method for purifying an organosilicon polymer, which comprises a step of separating the aqueous phase and an oil phase by allowing to stand, and a step of removing the aqueous phase. (2) The organosilicon polymer has at least the general formula (1)

[0005]

[Chemical 2]

(In the formula, R1 and R2 may independently have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and a substituent, or a substituent having 1 to 30 carbon atoms. An alkenyl group, an alkynyl group having 1 to 30 carbon atoms which may have a substituent, or an aromatic group which may have a substituent, and R3 represents -C≡C-, and at least one -C≡. C-
Linked may have a substituent -CH ₂ and - at least one -C≡C- and linked alkylene group which may have a substituent group having 2 to 30, at least one -C
Alkenylene group which may have a substituent having 2 to 30 carbon atoms linked to ≡C-, and alkynylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one -C≡C-. , A divalent aromatic group which may have a substituent linked to at least one —C≡C—) and has a weight average molecular weight measured by gel filtration chromatography. 100 to 1 in terms of styrene
The purification method according to claim 1, which is 0,000. Regarding

DETAILED DESCRIPTION OF THE INVENTION The organosilicon polymer used in the present invention has at least the general formula (1).

[0008]

[Chemical 3]

(In the formula, R1 and R2 may independently have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and a substituent, or a substituent having 1 to 30 carbon atoms. An alkenyl group, an alkynyl group having 1 to 30 carbon atoms which may have a substituent, or an aromatic group which may have a substituent, and R3 represents -C≡C-, and at least one -C≡. C-
Linked may have a substituent -CH ₂ and - at least one -C≡C- and linked alkylene group which may have a substituent group having 2 to 30, at least one -C
Alkenylene group which may have a substituent having 2 to 30 carbon atoms linked to ≡C-, and alkynylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one -C≡C-. , A silicon-containing resin having a repeating unit represented by at least one —C≡C— and a divalent aromatic group which may have a substituent).

The alkyl group of R1 and R2 which may have a substituent having 1 to 30 carbon atoms includes a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecanyl group and a trifluoromethyl group. 3,3,3-
Examples thereof include a trifluoropropyl group, a chloromethyl group, an aminomethyl group, a hydroxymethyl group, a silylmethyl group, and a 2-methoxyethyl group, and the alkenyl group which may have a substituent having 1 to 30 carbon atoms is a vinyl group. , 2-propenyl group, isopropenyl group, 3-butenyl group, 5-
A hexenyl group, a 1,3-butadienyl group, a 3,3,3-trifluoro-1-propenyl group, etc., and a carbon number of 1
To 30 alkynyl groups which may have a substituent include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a trimethylsilylethynyl group, a phenylethynyl group, or the like. Examples of the aromatic group that may also be a phenyl group, a naphthyl group, a pyrazinyl group,
4-methylphenyl group, 4-vinylphenyl group, 4-ethynylphenyl group, 4-aminophenyl group, 4-chlorophenyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, 4-methoxyphenyl group, 4-silyl Phenyl group and the like, at least one of R3 --C≡
Examples of -CH2-, which may have a substituent linked to C-, include a group in which 1 or 2 -C≡C- are bonded to a methylene group, a fluoromethylene group or the like, and at least one -C
Examples of the alkylene group which may have a substituent having 2 to 30 carbon atoms and which is linked to ≡C- are an ethylene group, a propylene group,
-C for tetramethylene group, tetrafluoroethylene group, etc.
Examples of the alkenylene group that may have a substituent having 2 to 30 carbon atoms, which is linked to at least one -C≡C-, include a group in which 1 or 2 of ≡C- is bonded, and a vinylene group.
A group in which one or two —C≡C— are bonded to a propenylene group, a butadienylene group or the like can be mentioned, and at least one —C
Examples of the alkynylene group which may have a substituent having 2 to 30 carbon atoms and which is linked to ≡C− include a group in which 1 or 2 —C≡C— is bonded to an ethynylene group, a propynylene group, a butynylene group or the like. As the divalent aromatic group which may have a substituent linked to at least one —C≡C—, a phenylene group, a naphthylene group, a biphenylene group, an anthracenedyl group, a pyridinedyl group, a thiophenedylyl group. ,
Fluorophenylene group, chlorophenylene group, methylphenylene group, silylphenylene group, hydroxyphenylene group, aminophenylene group, phenylenemethylenephenylene group, phenyleneoxyphenylene group, phenylenepropylidenephenylene group, phenylene (hexafluoropropylidene) phenylene group, etc. -C≡C- is 1 or 2
Examples include individually bonded groups. The silicon-containing resin represented by the general formula (1) used in the present invention specifically has repeating units of silyleneethynylene, methylsilyleneethynylene, phenylsilyleneethynylene, silyleneethynylene-1,3-phenyleneethene. Nylene (chemical formula (2))

[0011]

[Chemical 4]

Silyleneethynylene-1,4-phenyleneethynylene, silyleneethynylene-1,2-phenyleneethynylene, methylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (3))

[0013]

[Chemical 5]

Methylsilyleneethynylene-1,4-phenyleneethynylene, methylsilyleneethynylene-1,2
-Phenyleneethynylene, dimethylsilyleneethynylene-1,3-phenyleneethynylene, dimethylsilyleneethynylene-1,4-phenyleneethynylene, dimethylsilyleneethynylene-1,2-phenyleneethynylene, diethylsilyleneethynylene-1 , 3-phenyleneethynylene, phenylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (4))

[0015]

[Chemical 6]

Phenylsilyleneethynylene-1,4-phenyleneethynylene, phenylsilyleneethynylene-
1,2-phenyleneethynylene, diphenylsilyleneethynylene-1,3-phenyleneethynylene, hexylsilyleneethynylene-1,3-phenyleneethynylene, vinylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (5 ))

[0017]

[Chemical 7]

Ethynylsilyleneethynylene-1,3-phenyleneethynylene, 2-propenylsilyleneethynylene-1,3-phenyleneethynylene, 2-propynylsilyleneethynylene-1,3-phenyleneethynylene, trifluoromethylrosyrylene Ethynylene-1,3-phenyleneethynylene, 3,3,3-trifluoropropylsilyleneethynylene-1,3-phenyleneethynylene, 4-
Methylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-vinylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-ethynylphenylsilyleneethynylene-1,3-phenyleneethynylene, phenylethynylsilyleneethylene Nylene-1,3-phenyleneethynylene, silyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5- Cyril-1,
3-phenylene) ethynylene, phenylsilyleneethynylene (5-hydroxy-1,3-phenylene) ethynylene, phenylsilyleneethynylene-2,7-naphthyleneethynylene, silyleneethynylene-5,10-anthracenediylethynylene , Phenylsilyleneethynylene-
4,4'-biphenyleneethynylene (chemical formula (6))

[0019]

[Chemical 8]

Phenylsilyleneethynylene-1,4-phenylenemethylene-1 ', 4'-phenyleneethynylene,
Phenylsilylene-ethynylene-1,4-phenylene-2,
2-propylidene-1 ', 4'-phenyleneethynylene,
Phenylsilylene-ethynylene-1,4-phenylene-2,
2- (1,1,1,1,3,3,3-hexafluoropropylidene) -1 ', 4'-phenyleneethynylene, (chemical formula (7))

[0021]

[Chemical 9]

Phenylsilyleneethynylene-1,4-phenyleneoxy-1 ', 4'-phenyleneethynylene (chemical formula (8))

[0023]

[Chemical 10]

Phenylsilyleneethynylene-2,5-pyridynediylethynylene, phenylsilyleneethynylene-2,5-thiophenedylylethynylene, methylsilyleneethynylenemethyleneethynylene, phenylsilylene-1,4-phenylene (Phenylsilylene) ethynylene-1 ', 3'-phenyleneethynylene (chemical formula (9))

[0025]

[Chemical 11]

Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ', 3'-phenyleneethynylene (chemical formula (10))

[0027]

[Chemical 12]

Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ', 4'-phenyleneethynylene,
Phenylsilyleneimino (phenylsilylene) ethynylene-1 ', 3'-phenyleneethynylene (Chemical formula (1
1))

[0029]

[Chemical 13]

Phenylsilyleneimino (phenylsilylene) ethynylene-1 ', 4'-phenyleneethynylene, chemical formula (12)

[0031]

[Chemical 14]

Chemical formula (13)

[0033]

[Chemical 15]

Chemical formula (14)

[0035]

[Chemical 16]

Chemical formula (15)

[0037]

[Chemical 17]

Chemical formula (16)

[0039]

[Chemical 18]

Chemical formula (17)

[0041]

[Chemical 19]

Chemical formula (18)

[0043]

[Chemical 20]

Silylene-1,3-phenyleneethynylene (chemical formula (19))

[0045]

[Chemical 21]

Silylene-1,4-phenyleneethynylene, silylene-1,2-phenyleneethynylene, phenylsilylene-1,3-phenyleneethynylene (chemical formula (20))

[0047]

[Chemical 22]

Phenylsilylene-1,4-phenyleneethynylene, phenylsilylene-1,2-phenyleneethynylene, diphenylsilylene-1,3-phenyleneethynylene, methylsilylene-1,3-phenyleneethynylene (chemical formula (21 ))

[0049]

[Chemical 23]

Methylsilylene-1,4-phenyleneethynylene, methylsilylene-1,2-phenyleneethynylene, dimethylsilylene-1,3-phenyleneethynylene, diethylsilylene-1,3-phenyleneethynylene, phenylsilylene- 1,3-butadiynylene, diphenylsilylene-1,3-butadiynylene, phenylsilylenemethyleneethynylene, diphenylsilylenemethyleneethynylenemethylene, phenylsilylenemethyleneethynylenemethylene, silylene-1,4-phenyleneethynylene-1 ′, 4 ′ -Phenylene, methylsilylene-1,4-
Phenyleneethynylene-1 ', 4'-phenylene, dimethylsilylene-1,4-phenyleneethynylene-1', 4'-
Examples thereof include phenylene and phenylsilylene-1,4-phenyleneethynylene-1 ′, 4′-phenylene. The weight average molecular weight is not particularly limited, but the weight average molecular weight in terms of styrene measured by gel filtration chromatography is 1
00-100,000, preferably 500-500,0
00. The form of these silicon-containing resins is solid or liquid at room temperature.

As the method for producing the silicon-containing resin represented by the general formula (1), a dehydrogenative copolymerization of a diethynyl compound and a silane compound is carried out using a basic oxide, a metal hydride or a metal compound as a catalyst. (JP-A-7-90085, JP-A-10-120689, JP-A-11-158187)
Alternatively, a method for dehydrogenative polymerization of an ethynylsilane compound using a basic oxide as a catalyst (JP-A-9-143721), a method of reacting an organomagnesium reagent with dichlorosilanes (JP-A-7-102069, JP-A-11-02957).
9), a method of performing dehydrogenative copolymerization of a diethynyl compound and a silane compound using cuprous chloride and a tertiary amine as a catalyst (Hua
Qin Liu and John F. Harrod, The Canadian Journal o
Chemistry, Vol. 68, 1100-1105 (1990)) and the like can be used, but the method is not particularly limited to these.

Next, the polyvalent organic acid shown in the present invention is a divalent or higher valent acid, examples of which include oxalic acid, citric acid, and
Malic acid, maleic acid, malonic acid, ethylenediamine 4
Examples thereof include acetic acid (EDTA) and pyridinedicarboxylic acid. These acids may be used alone or in a mixture of two or more kinds. These acids are used in a state of being dissolved in pure water. The concentration is not particularly limited, but is preferably in the range of 0.1 to 5M. And
This purification method will be described. First, the above organosilicon polymer is dissolved in an organic solvent. Examples of the organic solvent used include non-aqueous aromatic hydrocarbon solvents such as benzene, toluene, xylene, and mesitylene. These solvents may be used alone or as a mixture of two or more kinds. The concentration of the above-mentioned organosilicon polymer is not particularly limited, but 1 to 50 wt% is preferable.

An aqueous solution of a polyvalent organic acid is mixed with the organic silicon polymer solution in a separating funnel to form a suspension.
The ratio of the organosilicon polymer solution and the polyvalent organic acid aqueous solution is not particularly limited, but the ratio of the polyvalent organic acid aqueous solution to the organosilicon polymer solution is in the range of 0.05 to 20 volume times. preferable. Then, after this suspension is completely separated into an oil phase and an aqueous phase, the oil phase is separated. At this time, the water phase portion contains water and an organic acid, as well as a metal and its oxide, and the oil phase portion contains an organic silicon compound and an organic solvent. Next, how to remove the solvent contained in the oil phase is not particularly limited, and it is removed by a method such as distillation, reprecipitation, and vacuum drying.
The method for molding the organosilicon polymer and the method for producing a cured product will be briefly described. The powder or liquid thus obtained is dissolved in a solvent, or the liquid as it is is formed into various shapes, and then air, nitrogen or an inert gas atmosphere such as argon or helium is formed. 50-70
A cured product is obtained by heating in the range of 0 ° C for 1 minute to 100 hours. The heating temperature of this organosilicon polymer,
The time depends on the type of organosilicon polymer and the purpose of use of the cured product.

[0054]

EXAMPLES The present invention will be described below with reference to synthesis examples, examples and comparative examples.

(Synthesis Example 1) Poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) was synthesized based on the methods described in JP-A-7-90085 and JP-A-10-204181. In a 50 liter stainless steel reaction vessel, Mg (OH) 2 was calcined at 400 ° C. for 7 hours in a nitrogen stream, 3.39 kg of MgO, 2.16 kg of phenylsilane and 2.82 of m-diethynylbenzene.
kg and 27.4 liters of toluene as a solvent were charged. Next, in a nitrogen atmosphere, at 30 ℃ for 1 hour, 40 ℃
1 hour, 50 ° C for 1 hour, 60 ° C for 1 hour, then 8
The reaction was carried out at 0 ° C. for 2 hours, for a total of 6 hours. The reaction solution was filtered to separate and remove MgO. The filtered reaction solution was concentrated under reduced pressure to 9.44 kg (polymer concentration 43% by weight). The concentrate has a weight average molecular weight of 3,400 and a number average molecular weight of 150.
It was 0. To this concentrated solution, 9.45 kg of n-heptane was added, stirred at room temperature for 30 minutes, and allowed to stand for 2 hours. An upper phase containing a cloudy low molecular weight component and a brown lower phase containing a high molecular weight component were separated. Take out 3.91 kg of the lower phase from the bottom,
Next, 4.42 kg of the upper phase was taken out. The solvent of the upper phase was distilled off under reduced pressure to obtain a weight average molecular weight of 1460 and a number average molecular weight of 85.
1.32 kg of an orange viscous liquid of 0 (yield 2
7%). The lower phase was concentrated under reduced pressure and dried under reduced pressure at 60 ° C. for 23 hours to obtain a weight average molecular weight of 4890 and a number average molecular weight of 213.
2.74 kg of a pale yellow powder of 0 was obtained (yield 56%).
The structures of liquid and powdery poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) are IR and N.
Confirmed by MR spectrum.

Example 1 To 9 g of the powdery poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) obtained in Synthesis Example 1 was added 51 g of toluene, and the mixture was stirred for about 1 hour to obtain a solid content concentration of 15% by weight. % Yellow homogeneous solution was obtained. This solution and 50 g of a 2.0 N oxalic acid solution were added to a separating funnel and mixed well, and then waited until the oil layer and the aqueous layer were completely separated. After completely removing this water layer, the oil layer was taken out, and 150 g of hexane was gradually added,
A precipitate was deposited. Remove the supernatant layer by filtration,
The precipitate layer was dried under reduced pressure at room temperature to obtain about 7 g of pale yellow powder. Regarding this powder and the powder of Synthesis Example 1, ICP-
Metal analysis by MS was performed. In addition, in the metal analysis by ICP, after performing qualitative analysis for all elements,
Quantitative analysis was carried out for elements whose presence was confirmed to be 0.1 ppm or more. The results are shown in Table 1.

(Example 2) The same procedure was carried out except that maleic acid was used instead of oxalic acid in Example 1.

Comparative Example 1 The oxalic acid of Example 1 was treated with HCl.
The same method was used except that the above was replaced.

(Comparative Example 2) The same procedure was carried out except that oxalic acid in Example 1 was replaced with acetic acid.

[0060]

[Table 1]

[0061]

The organosilicon polymer purified by the method of the present invention contains almost no metal impurities, and since it is a purification method that does not use a halogen-based acid, it may not contain halogen. Therefore, the insulating property does not deteriorate due to the influence of impurities, and it can be used as an excellent electric and electronic material.

Continued front page    (72) Inventor Makoto Aizuka             32 Mitsui Chemicals, 580 Nagaura, Sodegaura City, Chiba Prefecture             Within the corporation F term (reference) 4J035 HA01 HA06 HB01 JA02 JB01                       LB20

Claims (2)

[Claims] 1. A step of dissolving an organosilicon polymer in a non-water-soluble solvent, adding a solution containing a polyvalent (divalent or higher) organic acid aqueous solution, and stirring the mixed solution and then leaving it standing. A method for purifying an organosilicon polymer, which comprises a step of separating an aqueous phase and an oil phase by doing so, and a step of removing the aqueous phase. 2. The organosilicon polymer has at least the general formula (1): (In the formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 1 to 30 carbon atoms which may have a substituent, An alkynyl group which may have a substituent having 1 to 30 carbon atoms, or an aromatic group which may have a substituent, and R3 represents-
C≡C-, optionally substituted with at least one -C≡C-, -CH _2- , at least one -C≡
An alkylene group which may have a substituent having 2 to 30 carbon atoms linked to C-, an alkenylene group which may have a substituent having 2 to 30 carbon atoms linked to at least one -C≡C-, 2 carbon atoms linked to at least one -C≡C-
To 30 alkynylene group which may have a substituent, a divalent aromatic group which may have a substituent linked to at least one -C≡C-) and have a repeating unit represented by The purification method according to claim 1, wherein the weight average molecular weight measured by gel filtration chromatography is 100 to 100,000 in terms of styrene.