JP2875550B2 - Method for producing aromatic polysulfone copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel aromatic polysulfone copolymer and a method for producing the same, and more particularly, to a heat-resistant mechanical strength, excellent transparency, and excellent moldability. A novel aromatic polysulfone copolymer and a method for producing the same.

(Prior art) The following equation (A) Polysulfone having a structural unit represented by is known by Amoco under the trademark Udel, and this resin is 2,2-
It can be produced by a nucleophilic substitution reaction between an alkali metal salt of bis (4-hydroxyphenyl) propane [bisphenol A] and 4,4'-dichlorodiphenyl sulfone [DCDPS].

Also, the following equation (B) Polyether sulfone having a structural unit represented by
Known by the company I under the trademark Victicx PES, this resin can be prepared by a nucleophilic substitution reaction of DCDPS with an alkali metal salt of 4,4'-dihydroxydiphenylsulfone [bisphenol S].

(Problems to be Solved by the Invention) The above-mentioned polysulfone has extremely low water absorption, but does not have sufficient heat resistance when a printed circuit board or the like is formed.

On the other hand, the above-mentioned polyether sulfone has sufficient heat resistance, but has high water absorption, and is also unsuitable for uses such as printed circuit boards.

Polysulfone and polyethersulfone blends show a proportional relationship between mixing ratio and water absorption, but polysulfone has an adverse effect on heat moldability. Furthermore, molded articles made from this blend are opaque due to the incompatibility of both components and have inherent disadvantages.

U.S. Pat. No. 4,175,175 describes a method for producing a copolymer obtained by polycondensation of bisphenol A and bisphenol S with DCDPS, but the reaction between bisphenol S and DCDPS is actually based on The reaction temperature of bisphenol A and DCDPS is higher than 200 ° C because bisphenol A is decomposed by alkali present in the system. No polycondensate is obtained.

JP-A-62-273228 discloses an example of a copolycondensate comprising a polysulfone block and a polyethersulfone block, which is essentially a copolycondensate having a high blocking property.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that aromatic polysulfone copolymer in which polysulfone structural units and polyether sulfone structural units are randomly distributed. Then, it has been found that a molding resin which is thermally stable, has a small water absorption, is excellent in mechanical properties and chemical resistance, and is transparent can be obtained, and has completed the present invention.

That is, the present invention provides compounds of the formulas (V) and (VI) (R, l is an integer of 0 or more and one of them is not 0.
X and Y are such that when X is H, Y is an alkali metal atom;
Y is H when is an alkali metal atom. A) 25 g of a 1 g / dl solution in N, N-dimethylformamide characterized by reacting in a polar solvent in the presence of an alkali metal carbonate.
It is a method for producing an aromatic polysulfone copolymer having a reduced viscosity (ηred) at 0.1 ° C. of 0.1 dl / g or more. Preferably, X is H, and Y is an alkali metal atom. A production method, which is an aromatic polysulfone copolymer which can be obtained by the method described above and in which repeating units are randomly arranged.

The novel aromatic polysulfone copolymer of the present invention has the following formula: Is a unit represented by the following formula, or a linked body formed by linking a plurality of the units, and the following formula: Are connected to each other in a random and linear manner. Number of units of formula (I) in copolymer and (II)
The ratio with the number of units in the formula is not particularly limited.

Terminal of the novel aromatic polysulfone copolymer of the present invention,
It is a phenolic hydroxyl group or an alkali metal salt of a phenolic hydroxyl group, or is CH ₃ O—, C ₂ H ₅ O—, C ₃ H ₇ O—, i
-Pr-O-, m-BuO-, t-Bu-O-, i-BuO-, Aec-BuO
−, CH ₂ = CH-CH ₂ -O- may be blocked, etc..

The novel aromatic polysulfone copolymer of the present invention has a reduced viscosity (ηred) of this resin solution at 25 ° C. when the copolymer is dissolved in N, N-dimethylformamide to a concentration of 1.0 g / dl. Is a copolymer having a molecular weight of 0.1 dl / g or more. When the polymerization degree is such that ηred is less than 0.1 dl / g, the mechanical strength and heat resistance of the copolymer are inferior and the practicality is poor.

The copolymer of the present invention is produced as follows.
It can be obtained by reacting the compound represented by the formula (V) with the compound represented by the formula (VI) in the presence of an alkali metal carbonate in a polar solvent.

In the compounds represented by the formulas (V) and (VI), X and Y represent a hydrogen atom or an alkali metal atom, and the alkali metal atom is a sodium atom or a potassium atom. preferable.

The polar solvent used for producing the copolymer of the present invention is an aprotic polar solvent, and is not particularly limited as long as it does not inhibit the reaction at the reaction temperature and in the presence of an alkali. It is preferable that the solvent is a solvent that can sufficiently dissolve the compounds of formulas (V) and (VI) and the resulting copolymer. Specific examples of such solvents include N, N-
Examples thereof include dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, sulfolane, and chlorobenzene.

The amount of the polar solvent used to produce the copolymer of the present invention is preferably an amount sufficient to dissolve the compounds of the formulas (V) and (VI) and the resulting copolymer.

When the copolymer of the present invention is reacted in the presence of an alkali metal carbonate, sodium carbonate or potassium carbonate is preferable as the alkali metal carbonate to be used, and sodium hydrogen carbonate or potassium hydrogen carbonate may also be used. They can be used in combination. The amount of the alkali metal carbonate to be used is not particularly limited as long as it is an amount sufficient to convert the terminal phenolic hydroxyl group contained in the compounds (V) and (VI) into a terminal phenolate.

The reaction temperature for producing the copolymer of the present invention is 100 ° C.
It is carried out in the range of -300 ° C, preferably in the range of 120 ° C-240.

The copolymer of the present invention can be produced, for example, by the method described in Example 1 or 2 below.

The copolymer of the present invention can be synthesized by the following reaction mechanism. That is, the terminal phenoxide anion of the compound of the formula (V) or the formula (VI) attacks an ether bond in the main chain of the compound of the formula (V) or the formula (VI),
By producing a transesterification reaction, an aromatic polysulfone copolymer having a disordered arrangement is produced. Accordingly, the number average molecular weight of the resulting polymer is obtained as the average of the molecular weights of the compounds of (V) and (VI).

The terminal group of the copolymer of the present invention is present in the form of an alkali metal phenolate after the completion of the reaction. Therefore, it can be changed into a thermally stable form or a compound having various functional groups by an appropriate terminal treatment agent. Such a terminal treating agent is not particularly limited as long as it reacts with the terminal phenolate, but from the viewpoint of imparting thermal stability to the resulting copolymer, methyl chloride, methyl iodide, chloride, etc. Benzyl, 4-chlorophenylsulfonylbenzene and the like are preferred.

After completion of the reaction, known methods can be applied to the separation and purification of the copolymer. For example, if a precipitated salt (alkali halide) or an excess alkali metal carbonate is present in the reaction solvent, it is filtered off, and then the copolymer solution as the filtrate is usually mixed with the copolymer. The desired copolymer can be precipitated by dropping it into a solvent or conversely adding a non-solvent of the copolymer to the polymer solution.
Representative examples of non-solvents commonly used for the copolymer include methanol, ethanol, imepropanol, acetone, methyl ethyl ketone, and water. These may be used alone or as a mixture of two or more. Is also good.

(Effect of the Invention) The copolymer obtained by the present invention has excellent heat resistance, thermal stability, high mechanical strength, transparency and moldability, and thus is suitable for printed circuit boards, electric insulation applications, heat-resistant components, cooking utensils,
It can be used for coating materials and the like.

(Examples) The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

The molecular weight of the produced polymer was measured by gel permeation chromatography. (Equipment Shimadzu LC
-5A, column Shodex AD-805 + AD-803 + AD-802,
Eluent N, N-dimethylformamide (including LiBr), flow rate 1ml
/ min, column temperature 40 ° C, detector RI (40 ° C), molecular weight is polyethylene oxide-converted molecular weight) Example 1 Equipped with a stirrer, nitrogen inlet tube, thermometer, and condenser with a receiver at the tip. 2,2-bis-
(4-hydroxyphenyl) propane 45.66 g (0.2 mol), 4,4'-dichlorodiphenyl sulfone 45.94 g (0.16 g)
0 mol), 55.28 g (0.4 mol) of anhydrous potassium carbonate and N, N
-300 g of dimethylacetamide (DMAC) was charged, nitrogen gas was introduced for 30 minutes, and the system was replaced with nitrogen. The temperature was raised to the boiling point of the reaction and about 60 g of DMAC was distilled off over 2 hours. At the same time, about 3.6 g of H ₂ O was distilled off. Thereafter, the mixture was further reacted under reflux for 4 hours (0K-terminal polysulfone oligomer was obtained at this stage), and then VICTREX (ICI); 60 g of PES5003p (OH-terminal polyethersulfone) was dissolved in 170 g of DMAC and added. And then 4 hours DMA
The reaction was performed at the boiling point of C. During this time, about 20 g of DMAC was distilled off. The molecular weight change during this time was followed by GPC. The results are shown in FIG.

As can be seen from FIG. 1, after 1-2 hours of the reaction,
The peak of the -OK terminal polysulfone oligomer and the peak of the -OH terminal polyethersulfone become one, indicating that the copolymer of the present invention has been obtained.

After the completion of the reaction, the temperature was returned to room temperature, and the salt was precipitated and the excess potassium carbonate was separated by filtration. The filtrate was poured into a large amount of methanol to precipitate the produced polymer. The resulting polymer was isolated, washed several times with methanol, and dried under reduced pressure at 150 ° C. for 3 hours.

The yield of the obtained polymer was 92% and 1.0% wt / vol of N, N
-Reduced viscosity (ηred) at 25 ° C in a dimethylformamide solution was 0.20 dl / g.

Example 2 In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser having a receiver at the tip, 2,2-bis-
(4-hydroxyphenyl) propane 45.66 g (0.2 mol), 4,4'-dichlorodiphenyl sulfone 56.39 g (0.19
64 mol), 55.28 g (0.4 mol) of anhydrous potassium carbonate and N, N
-300 g of dimethylacetamide (DMAC) was charged, and nitrogen gas was introduced for 30 minutes to replace the inside of the system with nitrogen. The temperature was raised to the boiling point of the reaction and about 60 g of DMAC was distilled off over 2 hours. At the same time, about 3.6 g of H ₂ O was distilled off. afterwards,
After a further 4 hours of reaction under reflux (OK at this stage, polysulfone at the end was obtained), 60 g of Victrex; PES5003p (OH-terminated polyethersulfone) manufactured by ICI.
It was dissolved in 170 g of DMAC and added, and the reaction was further performed at the boiling point of DMAC for 4 hours. During this time, about 20 g of DMAC was distilled off. 100 ℃
Then, methyl chloride gas was blown at 300 ml / min for 30 minutes. The temperature was returned to room temperature, the precipitated salt and excess potassium carbonate were filtered off, and the filtrate was poured into a large amount of methanol to precipitate the produced polymer. The resulting polymer was isolated, washed several times with methanol, and dried under reduced pressure at 150 ° C. for 3 hours.

The yield of the obtained polymer is 97% and 1.0% wt / vol of N, N
-Reduced viscosity (ηred) at 25 ° C. in dimethylformamide solution was 0.39 dl / g; The number average molecular weight (n) determined by GPC was 16,500, and the chromatograms of the polymer before and after the reaction are shown in FIG. 285 ° C
When pressed at 5 cm × 5 cm × 1 mm, the molded product was transparent. The glass transition temperature of this polymer is 193 ℃
And 215 ° C., showing different values from each of the homopolymers. When the solubility of the obtained polymer in chloroform was examined, it was found that most of the polymer was soluble. On the other hand, the blend of polysulfone and polyethersulfone was insoluble in chloroform.

From the above, it is understood that the obtained polymer is not a mere blend of polysulfone and polyethersulfone, but a copolymer having polysulfone units and polyethersulfone units in a random arrangement.

Comparative Example 1 2,2-bis- was placed in a 1 SUS flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser with a receiver at the end.
(4-hydroxyphenyl) propane 22.83 g (0.100 mol), 4,4'-dihydroxydiphenyl sulfone 25.03 g
(0.100 mol), 4,4'-dichlorodiphenyl sulfone 56.
27 g (0.196 mol), 55.28 g (0.400 mol) of anhydrous potassium carbonate and 300 g of DMAC were charged, and nitrogen gas was introduced for 30 minutes.
The system was replaced with nitrogen. The temperature was raised to the boiling point of the reaction solution, and the reaction was performed for 18 hours. During this time, about 80 g of DMAC was distilled off. At the same time, about 3.6 g of H ₂ O was distilled off.

Changes in molecular weight during this time were sampled as needed and tracked by GPC. The result is shown in FIG. From Fig. 3
Even after the reaction for 18 hours, the number average molecular weight (n) was at most only about 9,000.

Comparative Example 2 2,2-bis- was placed in a 1 SUS flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser with a receiver at the tip.
(4-hydroxyphenyl) propane 22.83 g (0.100 mol), 4,4'-dihydroxydiphenyl sulfone 25.03 g
(0.100 mol), 4,4'-dichlorodiphenyl sulfone 56.
27 g (0.196 mol), 55.28 g (0.400 mol) of anhydrous potassium carbonate and 200 g of sulfolane were charged, and nitrogen gas was introduced for 30 minutes to replace the inside of the system with nitrogen. The temperature was raised to 235 ° C. and reacted for 12 hours. At the same time, about 3.6 g of H ₂ O was distilled off.

Changes in molecular weight during this time were sampled as needed and tracked by GPC. The results are shown in FIG. As can be seen from FIG. 4, at most a number average molecular weight (n) of about 5,000 is obtained at first, but thereafter the molecular weight decreases.

Comparative Examples 1 and 2 show that it is difficult to directly synthesize the copolymer of the present invention from monomers.

[Brief description of the drawings]

FIG. 1 is a GPC chromatogram showing the situation in the reaction of Example 1. FIG. 2 is a GPC chromatogram showing the situation in the reaction of Example 2. FIG. 3 shows Comparative Example 1.
5 is a graph showing a change in molecular weight in the reaction of FIG. FIG. 4 is a graph showing a change in molecular weight in the reaction of Comparative Example 2.

Claims (2)

(57) [Claims] 1. A compound of the formula (V) or (VI) (R, l is an integer of 0 or more and one of them is not 0.
X and Y are such that when X is H, Y is an alkali metal atom;
Y is H when is an alkali metal atom. A) 25 g of a 1 g / dl solution in N, N-dimethylformamide characterized by reacting in a polar solvent in the presence of an alkali metal carbonate.
A method for producing an aromatic polysulfone copolymer having a reduced viscosity (ηred) at 0.1 ° C. of 0.1 dl / g or more. 2. The method for producing an aromatic polysulfone copolymer according to claim 1, wherein X is H and Y is an alkali metal atom.