JPH0341120A - Aromatic polysulfone copolymer and its production - Google Patents

Abstract

PURPOSE:To produce an aromatic polysulfone copolymer which can form a molding which is thermally stable, has a low water absorptivity and excellent mechanical properties and chemical resistance, and is transparent by forming a copolymer composed of randomly arranged polysulfone units and polyether sulfone units. CONSTITUTION:An aromatic polysulfone copolymer composed of repeating units of formulas I and II and having a reduced viscosity (etared) >=0.1dl/g when measured in a 1g/dl solution in N,N-dimethylformamide at 25 deg.C. It can be obtained by reacting compounds of formulas III and IV (wherein R and (l) are each an integer >=0 and one of them is not 0; and M is an alkali metal atom) in a polar solvent or by reacting compounds of formulas V and VI (wherein R and (l) are each an integer >=0 and one of them is not 0; and Y is H or an alkali metal atom) in a polar solvent in the presence of an alkali metal carbonate.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel aromatic polysulfone copolymer and a method for producing the same, and more specifically, to a novel aromatic polysulfone copolymer that has excellent heat resistance, mechanical strength, transparency, and moldability. The present invention relates to a novel aromatic polysulfone copolymer and a method for producing the same.

(Prior Art) Polysulfone having a structural unit represented by the following formula (A) is known by Amoco under the trademark Udel, and this resin is
, 2-bis(4-hydroxyphenyl)propane [bisphenol A] and 4,4'-dichlorodiphenylsulfone [DCDPS] through a water displacement reaction.

In addition, polyether sulfone having a structural unit represented by the following formula (B) is I
Known under the trademark Victicx PES by CI Corporation, this resin can be produced by a water displacement reaction between an alkali metal salt of 4,4'-dihydroxydiphenylsulfone [bisphenol S] and DCDPS.

(Problems to be Solved by the Invention) The above-mentioned polysulfone has extremely low water absorption, but does not have sufficient heat resistance when used to form printed circuit boards and the like.

On the other hand, the above-mentioned polyether sulfone has sufficient heat resistance but high water absorption, making it unsuitable for applications such as printed circuit boards.

Blends of polysulfone and polyethersulfone show a proportional relationship between mixing ratio and water absorption, but thermoformability is adversely affected by polysulfone. Furthermore, molded articles made from this blend are opaque due to the incompatibility of the two components, which is an essential drawback.

Although the specification of US Pat. No. 4,175,175 describes a method for producing a copolymer obtained by polycondensation of bisphenol A and bisphenol S with DCDPS, in reality, the reaction between bisphenol S and DCDPS is due to the nucleophilic nature of bisphenol S. Since the reaction temperature is small, a reaction temperature of 200°C or higher is required. On the other hand, if the reaction temperature between bisphenol A and DCDPS is raised to 200°C or higher, bisphenol A will be decomposed by the alkali present in the system, resulting in high polymerization. No copolycondensate can be obtained.

JP-A-62-273228 discloses an example of a copolycondensate consisting of a polysulfone block and a polyethersulfone block, which is essentially a copolycondensate with high blocking properties.

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

That is, the novel aromatic polysulfone copolymer of the present invention is
It has a loosely repeating unit represented by the following formula: and a repeating unit represented by the following formula, and the reduced viscosity (rlred) at 25 °C of a 1 g 7 dl solution in N,N-dimethylformamide is 01 dl/g or more The manufacturing method is characterized by the following formulas (III) and (I
V) (R and l are integers of 0 or more and either one is not 0. M represents an alkali metal atom) in a polar solvent, or by reacting the compound of the following formulas (V) and (V
Reacting the compound of I) (R and l are integers of 0 or more and one of them is not O. Y represents H or an alkali metal atom) in the presence of an alkali metal carbonate in a polar solvent. It is characterized by:

The novel aromatic polysulfone copolymer ° of the present invention is (I)
A connected body formed by connecting one or more units represented by the formula (II) and a connected body formed by connecting one or more units represented by the formula (II) are disordered with each other. They are connected in a straight chain. The ratio of the number of units of formula (I) to the number of units of formula (II) in the copolymer is not particularly limited.

The terminal of the novel aromatic polysulfone copolymer of the present invention is a phenolic hydroxyl group, an alkali metal salt of a phenolic hydroxyl group, or CH30-C2H3O-, C3
H70-, i-Pr-0-, m-BuO-t-B
u O-, 1-BuO-, Aec-BuO-1so2
+o, coma c+2o-, CH2=CH-CH2-0-
It may be blocked.

The novel aromatic polysulfone copolymer of the present invention can be obtained by dissolving this copolymer in N,N-dimethylformamide to a concentration of 1.0 g/dl, at 25°C of this resin solution.
The reduced viscosity (rlred) in is 0.1 dl/g
It is a copolymer having a molecular weight as above. rl
If the degree of polymerization is such that red is less than 0.1 dl/g, the copolymer will have poor mechanical strength and heat resistance, and will be impractical.

The copolymer of the present invention is produced as follows. That is, the compound represented by the formula (III) and the compound represented by the formula (IV) are reacted in a polar solvent, or the compound represented by the formula (V) and the compound represented by the formula (Vl) are reacted. It can be obtained by reaction in a polar solvent in the presence of an alkali metal carbonate.

In the compounds represented by formulas (III) and (IV), M represents an alkali metal atom, and specifically, sodium atom and potassium atom are preferred because they have high reactivity despite their low cost. In the compounds represented by formulas (V) and (VI), Y represents a hydrogen atom or an alkali metal atom, and the alkali metal atom is preferably a sodium atom or a potassium atom because of their high reactivity despite their low cost.

The polar solvent used to produce 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 or in the presence of an alkali. At (III).

The solvent is preferably a solvent that can sufficiently dissolve the compound of the formula (IV) or the formulas (V) and (VI) and the bioactive copolymer. Specific examples of such solvents include N, N
-dimethylformamide, dimethylsulfoxide, N,
Examples include 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 expressed by formula (II), (IV), or (V).

(It is preferable that the amount is sufficient to dissolve the compound of formula V and the resulting copolymer.

When the copolymer of the present invention is reacted in the presence of an alkali metal carbonate, the alkali metal carbonate used is preferably sodium carbonate or potassium carbonate, and sodium hydrogen carbonate or potassium hydrogen carbonate may also be used. Yes, and these may be used together. The amount of alkali metal carbonate to be used is not particularly limited as long as it is sufficient to convert the terminal phenolic hydroxyl groups contained in compounds (V) and (VI) into terminal phenolates.

The reaction temperature for producing the copolymer of the present invention is 100°
C to 300°C, preferably 120°C.
It is within the range of °C to 240 °C.

The reaction for producing the copolymer of the present invention is carried out under substantially anhydrous conditions. If the compounds of formulas (III) and (IV) are sufficiently anhydrous, they may be used in the reaction as they are; however, if they are not, or if the reaction is carried out in the presence of an alkali metal carbonate, the system should be kept in an anhydrous state. In order to maintain the temperature, the reaction may be carried out under azeotropic dehydration conditions using an azeotropic dehydration solvent, or the reaction may be carried out while water is distilled off at the boiling point of the reaction solvent, or water may be removed under a N2 stream. A method of reacting while distilling off, etc. can be used.

The copolymer of the present invention can be synthesized by the following reaction mechanism. That is, the terminal phenoxide anion of the compound of formula (III) [(V)] or formula (IV) [(Vl)] is the compound of formula (ITI) [(V)] or formula (IV) [(VI)]. It attacks the ether bonds in the main chain of the compound and causes an ether exchange reaction to produce an aromatic polysulfone copolymer with a disordered arrangement. Therefore, the number average molecular weight of the produced polymer is (
III) [(V)] and the average molecular weight of the compounds of formulas (IV) and [(VI)].

The terminal group of the copolymer of the present invention exists in the form of an alkali metal ferulate after the reaction is completed.

Therefore, it can be changed into a thermally stable form or one having various functional groups by using an appropriate terminal treatment agent. There are no particular restrictions on such a terminal treatment agent as long as it reacts with the terminal ferulate, but for the purpose of imparting thermal stability to the resulting copolymer, methyl chloride and methyl iodide are preferred.

Benzyl chloride, 4. Chlorophenylsulfonylbenzene and the like are preferred.

After the reaction is completed, known methods can be applied to separate and purify the copolymer. For example, if precipitated salts (alkali halides) or excess alkali metal carbonates are present in the reaction solvent, they are filtered out and the copolymer solution, which is the filtrate, is usually filtered. dropwise into the solvent or
Conversely, the desired copolymer can be precipitated by adding a copolymer nonsolvent to the polymer solution. Typical examples of nonsolvents commonly used for copolymers include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, and water, but these can be used alone or as a mixture of two or more. You can.

(Effects of the Invention) The production method of the present invention is a method in which an aromatic polysulfone copolymer having a stable molecular weight can be easily obtained by mixing and reacting O-alkali-terminated polysulfone polymers. In addition, the copolymer obtained by the present invention has excellent heat resistance.

Due to its thermal stability, high mechanical strength, transparency, and formability, it can be used in printed circuit boards, electrical insulation applications, heat-resistant parts, cooking utensils, coating materials, etc.

(Example) The present invention will be explained in detail using 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 5hodex AD -805+ A
D-803+ AD-802 ligation, eluate N, N-
Dimethylformamide (including LiBr), flow rate 1ml/
min, column temperature 40°C2 detector RI (40
°C) 9 Molecular weight is the molecular weight in terms of polyethylene oxide) Example 1 A 2.2° bis- (
4, hydroxyphenyl) propane 45.66 g (0,
2 mol), 45.94 g (0,160 mol) of 4,4'-dichlorodiphenylsulfone, 5 mol of anhydrous potassium carbonate
5.28 g (0.4 mol) and 300 g of N,N-dimethylacetamide (DMAC) were 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 solution, and about 60 g of DMAC was distilled out over 2 hours. At the same time, about 3.6 g of H2O was distilled off. After that, the reaction was continued for another 4 hours under reflux (at this stage it was OK.
A terminal polysulfone oligomer is obtained. ) after I
60 g of PES 5003p (OH-terminated polyether sulfone) manufactured by CI Corporation was dissolved in 170 g of DMA, and the mixture was further reacted for 4 hours at the boiling point of DMAC. During this time, about 20 g of DMAC was distilled out. Changes in molecular weight during this time were tracked by GPC.

The results are shown in Figure 1.

As can be seen from Figure 1, after 1 to 2 hours of reaction,
It can be seen that the peak of the -OK-terminated polysulfone oligomer and the peak of the -OH-terminated polyether sulfone are combined into one, resulting in the copolymer of the present invention.

After the reaction was completed, the temperature was returned to room temperature, precipitated salts and excess potassium carbonate were filtered off, and the filtrate was poured into a large amount of methanol to precipitate the produced polymer.

After isolating the produced polymer and washing it with methanol several times,
It was dried under reduced pressure at 150°C for 3 hours.

The yield of the obtained polymer was 92% and 1.0%wt/
2 in vol of N,N-dimethylformamide solution
Reduced viscosity (rlred) at 5°C is 0.20 dl/
It was g.

Example 2 2,2-bis-(
4-hydroxyphenyl)propane 45.66g (0,
2 mol), 56.39 g (0.1964 mol) of 4,4'-dichlorodiphenylsulfone, 55.28 g (0.4 mol) of anhydrous potassium carbonate, and 300 g of N,N-dimethylacetamide (DMAC) were prepared and heated for 30 minutes. Nitrogen gas was introduced to replace the inside of the system with nitrogen. The temperature was raised to the boiling point of the reaction solution, and about 60 g of DMAC was distilled out over 2 hours. At the same time, about 3.6 g of H2O was distilled off.

After that, the reaction was further carried out under reflux for 4 hours (at this stage, OK-terminated polysulfone was obtained), and then ICI
60 g of PES 5003p (OH-terminated polyether sulfone) was dissolved in 70 g of DMACl and added thereto, and the reaction was further carried out for 4 hours at the boiling point of DMAC. During this time, about 20 g of DMAC was distilled out.

The temperature was lowered to 100°C, and 300ml/ml of methyl chloride gas was added.
It was blown for 30 minutes at min. 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. After the produced polymer was isolated and washed several times with methanol, 1
It was dried under reduced pressure at 50°C for 3 hours.

The yield of the obtained polymer was 97% and 1.0%wt/
2 in vol of N,N-dimethylformamide solution
Reduced viscosity (rlred) at 5°C is 0.39 dl/
It was g. Number average molecular weight (Wn) by GPC measurement
was 16,500, and the chromatograms of the polymer before and after the reaction are shown in Figure 2. When this polymer was pressed into a shape of 5 cm x 5 cm x 1 mm at 285°C, the molded product was transparent.

Moreover, the glass transition temperature of this polymer is 193°C and 21°C.
Two samples at 5°C were shown, and the values were different from those of each individual polymer. Furthermore, when the solubility of the obtained polymer in chloroform was examined, most of it was found to be soluble. On the other hand, a blend of polysulfone and polyethersulfone was insoluble in chloroform.

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

Comparative Example 1 22-83 g of 2.2-bis-(4-hydroxyphenyl)propane was placed in an 11SUS flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser with a receiver attached to the tip.
(0,100 mol), 25.03 g (0,100 mol) of 4,4'-dihydroxydiphenylsulfone,
4.4'-dichlorodiphenylsulfone 56.27g (
(L196 mol), anhydrous potassium carbonate 55.28 g (0
, 400 mol) and 300 g of DMAC were 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 solution and the reaction was continued for 18 hours. During this time, about 80 g of DMAC was distilled off. Approximately 3.6g at the same time
of H2O was distilled off.

During this period, the changes in molecular weight are sampled at any time and analyzed by GPC.
It was tracked by The results are shown in Figure 3. From Figure 3, even after 18 hours of reaction, the number average molecular weight (Mn) is at most 9,
Only a molecular weight of about 0.000 was obtained.

Comparative Example 2 2.2-
Bis-(4-hydroxyphenyl)propane 22.83
g (0,100 mol), 4.4'-dihydroxydiphenylsulfone 25.03 g (0,100 mol),
4.4'-dichlorodiphenylsulfone 56.27g
(0,196 mol), anhydrous potassium carbonate 55.28 g (
0,400 mol) and 200 g of sulfolane,
Nitrogen gas was introduced for 0 minutes to replace the inside of the system with nitrogen. The temperature was raised to 2356C and the reaction was carried out for 12 hours. Approximately 3.6 g of H2O was distilled off during this time.

During this period, changes in molecular weight were sampled at any time and tracked by GPC. The results are shown in Figure 4. As can be seen from Figure 4, the number average molecular weight (Mn) is at most 5,000.
Initially, a certain degree of molecular weight is obtained, but thereafter the molecular weight begins to decrease.

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

[Brief explanation of drawings]

Figure 1 is a GPC diagram showing the situation in the reaction of Example 1.
chromatogram. FIG. 2 is a GPC chromatogram showing the situation in the reaction of Example 2. FIG. 3 is a graph showing molecular weight changes in the reaction of Comparative Example 1. FIG. 4 is a graph showing molecular weight changes in the reaction of Comparative Example 2.

Claims (3)

[Claims] (1) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...The repeating unit indicated by (I) and the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...It is indicated by (II) A novel aromatic polysulfone copolymer having a repeating unit and having a reduced viscosity (ηred) of 0.1 dl/g or more at 25°C in a solution of 1 g/dl in N,N-dimethylformamide. (2) Compounds of the following formulas (III) and (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (IV) (R, l is an integer greater than or equal to 0, and either one is not 0; M represents an alkali metal atom) The reaction is carried out in a polar solvent. Reduced viscosity (ηre
d) is 0.1 dl/g or more, a method for producing an aromatic polysulfone copolymer. (3) Compounds of formula (V) and formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(VI) (R, l is an integer greater than or equal to 0, and either one is not 0; Y represents H or an alkali metal atom) The reduced viscosity (ηred) of a 1 g/dl solution in dimethylformamide at 25°C is 0.1 dl/
A method for producing an aromatic polysulfone copolymer having a polysulfone copolymer of at least 100 g.