JPH03215524A - Polyetherketone copolymer and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare a polyetherketone copolymer having a relatively low crystalline melting point while retaining its high glass transition point and thus having an improved moldability by incorporating two specific repeating units into the copolymer. CONSTITUTION:A polyetherketone copolymer contg. repeating units of formulas VI and VII in a mol ratio of formula VI to (formulas VI+VII) of 0.05-0.5 and having a reduced viscosity (in conc. sulfuric acid, 0.2g/dl concn., 30 deg.C) of 3.3dl/g or higher is prepd. by copolymerizing a dihydric phenol of formula I (wherein Ar is a group selected from the group consisting of formulas II to V) (A), 4,4'- biphenol (B) in a mol ratio to the sum of components A and B of 0.5-0.95, and 1,4-bis(4-halogenobenzoyl)benzene (C) in a mol ratio to the sum of components A and B of 0.98-1.02 in the presence of an alkali metal compd. in an amt. of 1.0-4.0 equivalents based on component A in a neutral polar solvent in such an amt. that the total monomer concn. in the solvent is 0.1-10mol/l.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyetherketone copolymer and a method for producing the same, and more particularly, to a polyetherketone copolymer and a method for producing the same. This article relates to etherketone copolymers and production methods for efficiently obtaining them. [Conventional techniques and problems to be solved by inventions] In recent years, engineering plastics have been widely used in various industrial fields. As the range of applications expands in this way, the required properties become increasingly strict, and new materials that satisfy these requirements are required to be developed. As an example, polyetherketones having the following repeating units are known (British Patent No. 220344). This resin has a high glass transition temperature (Tg) (184℃
), but its crystal melting point (Tm) is too high at 411"C, so it is extremely difficult to mold it.The object of the present invention is to have a relatively low crystal melting point while having a high glass transition temperature, and to have moldability. An object of the present invention is to provide a polyetherketone copolymer with excellent properties and a method for producing the same. [Means for solving the above-mentioned problems] A first aspect of the present invention for achieving the above-mentioned object (invention of claim 1) represents at least one of the following formulas (1) and . The content ratio of the repeating unit represented by I) is the molar ratio [(I)/{
(I) + (II))] 0.05 to 45,! The reduced viscosity at 30°C of a solution prepared by dissolving in sulfuric acid at a concentration of 0.2 g/d is 0. : ldu/g or more, and the second aspect of the present invention (the invention according to claim 2) is a polyetherketone copolymer characterized by having a Biphenol and HO-Ar Ichino [Tashi. Ar has the same meaning as above. 2. The method for producing a bosoetherketone octapolymer according to claim 1, characterized in that a dihydric phenol represented by the following formula is reacted in a neutral polar solvent in the presence of an alkali metal compound. The present invention will be explained in detail below. - Polyether ketone copolymer The polyether ketone copolymer of the present invention has the formula (I
) and (II). Among the various repeating units represented by the above formula (I), repeating units in which ^r has one of the following structures are preferred. O What is important in the present invention is the content ratio or molar ratio of the repeating unit represented by the general formula (I) [(I)/{
(I) + (II))] is in the range of 0.05 to 0.5. ” When the content ratio is within this range, the polyetherketone copolymer exhibits good moldability and heat resistance. ] If the above-mentioned content ratio is less than 0.05, the crystal melting point of the polyetherketone copolymer becomes high, resulting in poor moldability. On the other hand, when it exceeds 0.5, the polyetherketone octapolymer becomes of poor quality and its heat resistance decreases. What is important about the polyetherketone copolymer is that when it is dissolved in concentrated sulfuric acid at a concentration of 0.2 g/d, the reduced viscosity of the solution at 30°C is 0.2 g/d. :ldM/
Sometimes it is more than g. This reduced viscosity is 0.3 dl/
The thermal decomposition temperature of polyetherketone copolymers with a molecular weight of less than Although the polyetherketone copolymer of the present invention has a relatively low crystal melting point of about 330 to 400°C, it has a high glass transition temperature of, for example, 180 to 200°C. In other words, it exhibits good formability and excellent heat resistance. Therefore, it can be suitably used as a new material in the electrical/electronic equipment field, mechanical field, etc. -Production method of polyetherketone copolymer 1 The polyetherketone copolymer of the present invention can be produced by the production method of claim 2, that is, 1,4-bis(4-octalobenzoyl)benzene and 4,4° -Biphenol and HO-Ar-OH [Tashi. Ar has the same meaning as above. ] can be efficiently produced by copolymerizing dihydric phenol represented by the following in the presence of an alkali metal compound in a neutral polar solvent. The l,4'-bis(4-yakuchibenzoyl)benzene is a compound represented by the following general formula. (In the formula, X is a halogen atom which may be the same or different from each other.) Specific examples of 1,4-bis(4-octalobenzoyl)benzene suitably used in the present invention include those shown below. be. The dihydric phenol mentioned above can be represented by the following general formula. HO-Ar 0■ Specific examples of this dihydric phenol include: The alkali metal compound may be any compound that can convert the 4,4°-biphenol into an alkali metal salt, and there are no particular restrictions. Preferred are alkali metal salts and alkali metal hydrogen carbonates. Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate. Among these, preferred are sodium carbonate and potassium carbonate. Examples of alkali metal hydrogen carbonates include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Among these, sodium hydrogen carbonate and potassium hydrogen carbonate are preferred. Among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used. The various alkali metal compounds mentioned above can be used alone or in combination of two or more. Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide. N,
N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolitone, N
Mono-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-
Proyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolitone, N-methyl-3-methyl-2-pyrrolitone, N-ethyl-3-
Methyl-2-pyrrolidone, N-methyl:l,4.5-
Trimethyl-2-pyrrolidone, N-methyl-2-piberitone, N-ethyl-2-piberitone, N-isobrovir-
2-piveridone, N-methyl-6-methyl-2-piberitone, N-methyl-3-ethylpiberitone, dimethyl sulfoxide, diethyl sulfoxide, l-methyl-1-
Oxosulfolane, l-ethyl-1-oxosulfolane, l-phenyl-1-oxosulfolane. Examples include N,N--simethylimidazolidinone and cyphenylsulfone. Among the various neutral polar solvents mentioned above, N-methyl 2-pyrrolidone and diphenylsulfone are preferred. The proportion of the alkali metal compound used is usually 1.0 to 4.0 equivalents, preferably 1.05 to 2.5 equivalents, based on the total amount of the dihydric phenol. The molar ratio of 1.4-bis(4-halogenobenzoyl)benzene to the total amount of 4.4°-biphenol and dihydric phenol is usually 0.98 to 1.02, preferably 1. 0
It is between 0 and 1.01. The molar ratio of 4,4°-biphenol to the total amount of 4,4°-biphenol and dihydric phenol is usually 0.5 to 0.95. The total amount (moles) of 1,000 mols relative to the amount (mole) of the neutral polar solvent is usually 0.1 to 10 mol/l. The reaction is usually carried out at 150-380°C, preferably at 180-380°C.
The test is carried out at a temperature in the range of 50°C. Reaction temperature or I
If the temperature is less than SO''C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur.The reaction time is usually 0.1 to IO hours, and is preferably The reaction time is from 1 hour to 5 hours.The reaction is usually carried out under a stream of nitrogen or inert gas under reduced pressure to around normal pressure.The order of addition of the above raw materials is not particularly limited.After the reaction is completed. Since the neutral polar solvent solution contains a polyether ketone copolymer, the polyether ketone copolymer is recovered from the neutral polar solvent solution according to a known method.The obtained polyether Since ketone copolymers generally contain solvents, salts, unreacted polymers, etc., it is necessary to wash them appropriately using a known method. [Example] Next, the present invention will be described as an example. A more specific explanation will be given based on a comparative example. (Example 1) In a separable flask with an internal volume of 32 and equipped with an argon gas blowing tube, a stirring device, a Dean-Starck trap filled with toluene, and a thermocouple, 1. .4-bis(4-fluorobenzoyl)benzene 162.77 g (0.5 mol), phenolphthalene 32.03 g (0.1 mol), potassium carbonate 72.56 g (0.53 mol) and N- 1.2 grams of methyl-2-virolitone was charged, and the temperature was raised from room temperature to 200°C over 40 minutes while stirring. After raising the temperature, a small amount of toluene was added, and dehydration was carried out by azeotropy over 30 minutes. Next, 74.48 g of 4,4゛-biphenol (0
．． A solution of 4 mol) dissolved in 0.82 tomethyl-2- and Loliton was added, and the reaction was carried out at 0°C for 2 hours. After the reaction was completed, the reaction product was cooled and solid components were precipitated in methanol. This solid component was pulverized using a Warning blender and washed with a large amount of water and methanol to remove the solvent and salt. Thereafter, it was vacuum dried to obtain a powdery solid. The yield of this powdered solid is 242 g
(yield 98%). As a result of infrared absorption spectroscopy and elemental analysis of this powdery solid, it was confirmed to be a polyether catone copolymer having the repeating units shown below. Furthermore, the yield of this polyetherketone copolymer is 98%.
Met. (m) (II) Molar ratio (m) / { (III) + (II) } = 0.2 Next, the physical properties of the above bosoetherketone yarn copolymer were measured as follows. The results are shown in Table 1. Glass transition temperature (Tg): Seiko Electronics T Gyoichi D S
Using C 220, heating rate in nitrogen gas] 0'C
/min, and the peak top temperature of the Tg differential curve was taken as the glass transition temperature. Crystal melting point (Tm): The peak temperature of the melting peak when measured under the same conditions as above was defined as the crystal melting point. Thermal decomposition onset temperature (Td): The 5% weight loss temperature when measured under the same conditions as above was taken as the thermal decomposition onset temperature. Reduced viscosity (ηsp/c): I. A polyetherketone copolymer was dissolved in 84 g/m of concentrated sulfuric acid to a concentration of 0.2 g/41, and the viscosity of this solution was measured at 30°C. (Examples 2 to 5 and Comparative Example 1) A polyetherketone copolymer was produced in the same manner as in Example 1 except that the amount and type of dihydric phenol used were changed as shown in Table 1. We measured its physical properties. The results are shown in Table 1. The polyetherketone copolymer obtained in Example 2 is a polyetherketone copolymer consisting of the same repeating units as that obtained in Example I, and is represented by the general formula (m). The molar ratio of repeating units is 0.4. The copolymer obtained in Example 3 is a polyetherketone copolymer consisting of repeating units represented by the following general formula (TV) and the above general formula (■), and a repeating unit represented by the general formula (IV). The molar ratio of was 0.3.・ ・ ・ (rV) The copolymer obtained in Example 4 is a polyetherketone copolymer consisting of a repeating intermediate represented by the following general formula (V) and the above general formula (ri), and has the general formula ( The molar ratio of the repeating unit represented by V) is b. It was 4.・ ・ ・ (V) The copolymer obtained in Example 5 is a polyetherketone copolymer consisting of repeating units represented by the following general formula (Vl) and the above general formula (II), and has the general formula ( The molar ratio of the repeating units represented by VI) was 0.4. 1) (Example 6) In a separable flask equipped with the same device as in Example 1,
1.4-bis(4-chlorobenzoyl)benzene: I5
8.77g (1 mol), 4.4''-biphenol + 11.7:Ig (0.5 mol).4.4'-Dihydroxydiphenylsulfone I00.1Ig (0.4
), 145.1 g (1.05 mol) of potassium carbonate, and 2 kg of diphenylsulfone, and heated to 190°C.
The reaction was carried out for 1 hour at 270°C for 30 minutes and at 320°C for 30 minutes. After the reaction was completed, the solution was poured into a stainless steel vat and allowed to cool and solidify. Thereafter, this solidified material was pulverized using a Warning blender, washed sequentially with acetone and water, and dried to form a solid powder of 47.
I got 8g. When this solid powder was analyzed in the same manner as in Example 1, it was found to be a polyetherketone copolymer consisting of repeating units represented by the general formula f (■) and the general formula (II), and the formula ( The molar ratio of the repeating width expressed as (ii) was 0.4. The yield of this polyetherketone copolymer was 98%. (■) The physical properties of this polyetherketone copolymer are shown in Table 1. (Hereinafter, blank) [Effects of the Invention] According to the present invention, there is provided a polyetherketone-based octapolymer that has a high glass transition temperature and good moldability, and a manufacturing method that can efficiently produce the same. and can be provided.

[Brief explanation of drawings]

Claims (2)

[Claims] (1) The following formula (I) and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(I) [However, in the above formula, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas , chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Represents at least one of the following: There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] The following formula (II) and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (II) It has a repeating unit represented by, and the general formula (I)
The content ratio of repeating units expressed as molar ratio [(I)
/{(I)+(II)}] is 0.05 to 0.5,
3 of a solution dissolved in concentrated sulfuric acid at a concentration of 0.2 g/dl.
A polyetherketone copolymer having a reduced viscosity of 0.3 dl/g or more at 0°C. (2) 1,4-bis(4-halogenobenzoyl)benzene, biphenol, and HO-Ar-OH [However, Ar represents the same meaning as in Claim 1 above. 2. The method for producing a polyetherketone copolymer according to claim 1, wherein the dihydric phenol represented by the following formula is reacted in a neutral polar solvent in the presence of an alkali metal compound.