AROMATIC SULPHIDE AMIDE POLYMERS AND A PROCESS FOR THE PRODUCTION THEREOF

Abstract: An aromatic sulphide amide polymer comprised of a repeating unit having the formula (I) and a repeating unit having the formula (II) below, having an inherent viscosity ranging from 0.02 to 10 dl/g, wherein, Ar¹, Ar², Ar³ and Ar⁴ are same or different aromatic rings and R¹, R², R³ and R⁴ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms, or aralkyl groups having 7 - 20 carbon atoms, and R¹, R², R³, and R⁴ may be the same or different from each other, and a, b, c and d each stand for integers 0, 1, 2, 3 or 4 and may be the same or different from each other. A process for producing an aromatic sulphide amide polymer or copolymer comprises a sulphide forming reaction of an amide group containing dihalogenide expressed by the general formula (III) with an aromatic dihalogenide expressed by the general formula (IV) under the action of a sulphide forming reagent,

Description: The present invention relates to a novel aromatic sulphide amide polymer and a process for the production thereof. This invention relates to a novel polymer in the chemical structure of which phenylene groups are bound with amide and thioether groups in between, and which are useful as raw materials for producing moulded matters with improved heat resistance, solvent resistance and mechanical properties, and a process for producing such a polymer. So far, a number of polymers, thermosetting and thermoplastic, are known as raw material for producing moulded matters of heat resistant resins. Particularly, whole aromatic heat resistant resins are being developed in many places. Typical polymers include polyphenyleneterephthalic amides, polyimides polyether etherketones, and polyphenylene sulphides. However, these heat resistant polymers generally hold troubles in the moulding operation. In addition, their properties do not suffice for the applications where improved heat resistance is required. Further defects of these heat resistant polymers are that their monomers are difficult to synthesise, they require special solvents to conduct the polymerisation process and their moulding is accompanied by a low degree of productivity. It is desirable to produce novel aromatic sulphide amide polymers having improved heat resistance, solvent resistance and mechanical properties, and a process for the production thereof. According to a first aspect of the present invention there is provided an aromatic sulphide amide polymer of which 1 - 100% by mole of the composing units consists of the repeating unit having Formula (I) below and 99 - 0% by mole of the composing units consists of a repeating unit having the Formula (II) below. In the formulae above, Ar¹, Ar², Ar³ and Ar⁴ are same or different aromatic rings and R¹, R², R³ and R⁴ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, aryl groups having 6 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms, or aralkyl groups having 7 - 20 carbon atoms, and R¹, R², R³ and R⁴ may be the same or different from each other. The subscripts a, b, c and d stand for the integers 0, 1, 2, 3 or 4 and may be the same or different from each other. Preferably, 20 - 80% by mole of the composing units consists of the repeating unit having Formula (I) and 20 - 80% by mole of the composing units consists of a repeating unit having the Formula (II). More preferably, 35 - 65% by mole of the composing units consists of the repeating unit having Formula (I) and 35 - 65% by mole of the composing units consists of a repeating unit having the Formula (II). Preferably Ar¹, Ar², Ar³ are same or different aromatic rings selected from wherein Z stands for -O-, -S-, -SO₂-, -CO-, -CH₂- or Preferably, the aromatic sulphide polymer has an inherent viscosity in the range from 0.02 to 10 dl/g when measured in a N-methyl-2-pyrrolidone/lithium chloride (in a ratio of 95/5 by weight) solvent in a concentration of 0.1 g/dl at 30°C or when measured in a chloronaphthalene solvent in a concentration of 0.1 g/dl at 210°C. According to a second aspect of the present invention there is provided a process for producing an aromatic sulphide amide polymer or copolymer described above by the reaction of a dihalogenide (III) containing amide group with an aromatic dihalogenide (IV) to form sulphide bonds with the aid of a sulphide forming reagent. In the formulae above, Ar¹, Ar², Ar³ and Ar⁴ are aromatic rings and R¹, R₂, R³ and R₄ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, aryl groups having 6 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms, or aralkyl groups having 7 - 20 carbon atoms, and the R¹, R², R³ and R⁴ may be the same or different from each other. The subscripts a, b, c and d each stand for the integers O, 1, 2, 3 or 4 and may be the same or different from each other. X and Y are halogens which may be the same or different from each other. Preferably, the ratio of p/q is in the range from 100/0 to 1/99. A more preferred range of the ratio of p/q is 80/20 to 20/80. more preferably the range of the ratio of p/q is 65/35 to 35/65. Preferably, the aromatic sulphide polymer or copolymer is composed of the repeating units expressed by the general formula (V): The process according to a second aspect of the present invention for synthesising an aromatic polysulphide amide polymer may include any of the processes for synthesising polyphenylene sulphide. Among them, however, those processes are particularly preferable in which an amide group containing aromatic dihalogen compound expressed by a general formula (III) is reacted with an aromatic dihalogen compound expressed by a general formula (IV) under the action of a sulphide forming reagent in an organic polar solvent. The amide group containing aromatic dihalogen compounds to be used in the process according to the second aspect of the present invention are expressed by the general formula (III). Preferably, Formula (III) is These amide group containing aromatic compounds should preferably have linkage at the para-positions for the sake of high heat resistance, but linkages at the meta-and/or the ortho-positions are also allowed to improve solubility and processability of the aromatic polysulphide amide polymers. The amide group containing aromatic compounds above may be synthesised by any amide bond forming reaction. For example, the synthesis may be performed by the reaction of an aromatic diamine with a halogen containing aromatic carboxylic acid chloride. The aromatic dihalogenides (IV) to be employed in this invention include all the aromatic dihalogenides described in Japanese Patent Publication No. Sho 45-3368. Preferable among them are dichlorobenzene, dichlorobenzophenone and dichlorodiphenylsulphone. Organic polar solvents are preferably selected from those solvents which are aprotic and stable to alkalis at higher temperature. Suitable organic polar solvents include N,N-dimethylacetamide, N-ethyl-2-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethylimidazolidinone. The sulphide forming reagents to be used in this invention preferably include an alkali metal sulphide, an alkali metal hydrosulphide and an alkali metal base, or hydrogen sulphide and an alkali metal base. The sulphides and hydrosulphides of alkali metals may be used in the form of a hydrate. The sulphide forming reagent may be either prepared in the reaction vessel or added from outside before adding the dihalogenide of the general formulae (III) and (IV) to the polymerisation system. Prior to the addition of the dihalogenide (III) and (IV) for polymerisation, the water content of the system should be preferably reduced, for instance by distillation, to less than 2.5 equivalents per mole of the sulphide forming reagent. The reagent for the sulphide formation are preferably sodium sulphide, a combination of hydrosulphide with sodium hydroxide or hydrogen sulphide with sodium hydroxide. Preferably, various compounds known to effectively improve molecular weight of the polymer obtained when they are added in the polymerisation stage, such as a crown ether compound known as a phase transfer catalyst, a phosphorous salt, an ammonium salt, or a alkali metal carboxylate, should be added at the polymerisation stage. The polymerisation is carried out under stirring at a temperature 150 - 300°C, preferably 180 - 280°C, for 0.5 - 24 hours, preferably 1 - 12 hours. The ratio of the amide group containing compound expressed by the general formula (III) to a sulphide forming reagent is preferably (0.9 - 1.1) : 1. The amount of solvent should be adjusted so that the polymer produced by the polymerisation process amounts to 7 - 50%, preferably 10 - 40 %, by weight of the total system. Conventional methods of recovery may be applied to the polymer obtained. Thus, the polymer may be isolated by distillation at a reduced pressure, flashing, and reprecipitation with water or an organic solvent, and purified by washing with water or an organic solvent, followed by drying. The aromatic sulphide amide polymer of the invention, when dissolved in NMP/LiCl (in a ratio of 95/5 by weight) at a concentration of 0.1 g/dl, preferably shows an inherent viscosity of about 0.02 -10 dl/g at 30°C, and preferably the value of the inherent viscosity ranges from about 0.05 to 10 dl/g. In case of a copolymer which is composed of a less amount of the amide group containing unit (I) and does not completely dissolve in said solvent, a solution in chloronaphthalene at 210°C to a concentration of 0.1 g/dl shows an inherent viscosity of about 0.02 - 10 dl/g, where, however, an inherent viscosity of about 0.05 - 10 dl/g is preferable. The molecular chain of the aromatic polysulphide amide polymers of the invention may favourably be changed to result in an elongated chain, cross linkage or branching by being heated in an oxidative atmosphere such as in air. The polymers of the invention may be mixed with various known filler components when they are treated for moulding operations. Preferable filler components include: (a) fibrous fillers; glass fibre, carbon fibre, boron fibre, Aramid fibre, and alumina fibre. (b) inorganic fillers: mica, talc, clay, graphite, carbon black, silica, asbestos, molybdenum sulphide, magnesium oxide, and calcium oxide. The aromatic polysulphide amide polymer of the invention shows improved heat resistance and moulding processability and is therefore useful as a raw material for making a variety of moulded parts, films, fibres and coating materials. Further objects and features of the present invention will become apparent from the following detailed description of preferred embodiments thereof with reference to the accompanying diagrams in which, Fig. 1 is a diagram for an infrared absorption spectrum of the polymer obtained in Example 1. Fig. 2 is an X-ray diffraction of the polymer obtained in Example 1. Example 1 In an autoclave of 2 litre capacity were placed 0.6 mole of Na₂S 2.9H₂O and 600 ml of N-methyl-2-pyrrolidone (NMP) and the mixture was agitated under a stream of nitrogen. The temperature was elevated up to 210°C for dehydration and 24.2g of a distilled liquid comprising mainly of water was obtained. The reaction system was then cooled to 120°C and 0.6 mole of was added together with 80 ml of N-methyl-2-pyrrolidone, and the whole was sealed in an atmosphere of nitrogen and the temperature was elevated. Thus, the polymerisation was conducted for 6 hours at 240°C. When the reaction was complete, the reaction system was cooled, the content was poured into water, repeatedly washed with water and filtered. After final washing with methanol and drying 190 g of a light grey powdery polymer according to the present invention was obtained with a yield of 92%. The polymer shown an inherent viscosity of 0.37 dl/g (NMP/LiCl; 95/5 by weight, 0.1 g/dl at 30°C). It was found that the polymer could not be melt-moulded, but it was soluble in concentrated sulphide acid and NMP/LiCl and lustrous films of amber colour were produced by casting the solutions. An infrared absorption (IR) spectrum of this polymer manifested an absorption assigned to a thioether bond at 1070 cm⁻¹ and absorptions assigned to an amide group at 3270, 1640 and 1505 cm⁻¹. In addition, the elemental analysis agreed will with the calculated values as shown below. Further the sulphide amide polymers decomposed at 489°C. Melting was not observed. Example 2 Using the starting materials of the following formulation polymerisation was conducted with the same apparatus and the same process as in Example 1. A polymer according to the present invention was obtained in an amount of 162 g with a yield of 94 %. The inherent viscosity was 0.45 dl/g (NMP/LiCl; 95/5 by weight 0.1 g/dl at 30°C). The polymer decomposed at 472°C and a small endothermic peak was observed at 246°C. Lustrous films of amber colour were produced by the compression moulding of this polymer at 380°C. An IR spectrum of the polymer of Example 2 manifested the following absorption peaks, 3270, 1640, 1505 cm⁻¹ (assigned to amide group) 1070 cm⁻¹ (assigned to thioether) Example 3 Polymerization was conducted with the following formulation of starting materials using the same apparatus and the same process as in Example 1. A polymer according to the present invention in an amount of 127 g was obtained with a yield of 94 %. The inherent viscosity was 0.43 dl/g (NMP/LiCl; 95/5 by weight, 0.1 g/dl at 30°C). The polymer decomposed at 493°C and a small endothermic peak was observed at 267°C. An IR spectrum of the polymer of Example 3 manifested the following absorption peaks, 3250, 1635, 1505 cm⁻¹ (assigned to amide group) 1070 cm⁻¹ (assigned to thioether) Example 4 Polymerisation was conducted using the following formulation of starting materials with the same apparatus and the same process as in Example 1. A polymer according to the present invention was obtained and amounted to 82 g with a yield of 92 %. The inherent viscosity was 0.19 dl/g (0.1 g/dl of chloronaphthalene at 210°C). This substance decomposed at 488°C and the melting point was 272°C. An IR spectrum of the polymer of Example 3 manifested the following absorption peaks, 3260, 1640, 1505 cm⁻¹ (assigned to amide group) 1070 cm⁻¹ (assigned to thioether) Example 5 Polymerisation was conducted with the following starting materials using the same apparatus and the same process as in Example 1. Since the polymer thus provided according to the present invention dissolved moderately well in NMP, the NMP was distilled off under a reduced pressure after completion of the reaction. The residue was repeatedly washed with hot water and filtered, then washed with methanol and dried, to obtain 146 g of the polymer with a yield of 85 %. The inherent viscosity was 0.24 dl/g (NMP/LiCl; 95/5 by weight, 0.1 g/dl at 30°C). The polymer thermally decomposed at 443°C and a small endothermic peak was observed at 217°C. An IR Spectrum of the polymer of Example 5 manifested the following absorption peaks, 3270, 1640, 1510 cm⁻¹ (assigned to amide group) 1070 cm⁻¹ (assigned to thioether) The polymer obtained was more soluble than the copolymer in Example 2 which contained dihalogenides comprising para-combined amide groups. Thus, the present invention provides novel aromatic sulphide amide polymers having amide groups in which the heat resistance and the mould property are improved and well balanced. Examples 6 to 9 Polymerisation was conducted using the same materials shown in Table 6 with the same apparatus and method as in Example 1, to provide polymers according to the present invention. Polymerisation results and properties of the resultant polymers are shown in Table 7.

Claims: An aromatic sulphide amide polymer, of which 1 - 100% by mole of the composing units consists of a repeating unit having the formula (I) and 99 - 0% by mole of the composing units consist of a repeating unit having the formula (II) below, having an inherent viscosity ranging from 0.02 to 10 dl/g when measured in a N-methyl-2-pyrrolidone/lithium chloride (in a ratio of 95/5 by weight) solvent in a concentration of 0.1 g/dl at 30°C or when measured in a dichloronaphthalene solvent in a concentration of 0.1 g/dl at 210°c, wherein, Ar¹, Ar², Ar³ and Ar⁴ are same or different aromatic rings and R¹, R², R³ and R⁴ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, aryl groups having 6 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms or aralkyl groups having 7 - 20 carbon atoms, and R¹, R², R³ and R⁴ may be the same of different from each other, and a, b, c and d each stand for the integers 0, 1, 2, 3 or 4 and may be the same or different from each other. An aromatic sulphide amide polymer according to claim 1, wherein Ar¹, Ar², Ar³ are same or different aromatic rings selected from wherein Z stands for -O-, -S-, -SO₂-, -CO-, -CH₂- or An aromatic sulphide amide polymer according to claim 1 or claim 2 wherein 20-80% by mole of the composing units consists of the repeating unit having formula (I) and 20-80% by mole of the composing units consists of a repeating unit having the formula (II). An aromatic sulphide amide polymer according to any one of the preceding claims wherein 35-65% by mole of the composing units consists of the repeating unit having formula (I) and 35-65% by mole of the composing units consists of a repeating unit having the formula (II). A process for the production of an aromatic sulphide amide polymer or copolymer according to claim 1 comprising the reaction of an amide group containing di-halogenide having the general formula (III) with an aromatic dihalogenide having the general formula (IV) to form sulphide bonds with the aid of a sulphide forming reagent, wherein Ar¹, Ar², Ar³ and Ar⁴ are aromatic rings and R¹, R₂, R³ and R₄ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms, or aralkyl groups having 7 - 20 carbon atoms, and the R¹, R², R³ and R⁴ may be the same or different from each other. The subscripts a, b, c and d each stand for the integers O, 1, 2, 3 or 4 and may be the same or different from each other. X and Y are halogens which may be the same or different from each other. A process according to claim 5 for producing an aromatic sulphide amide polymer or copolymer composed of the repeating units expressed by the general formula (V); comprising the reaction of an amide group containing dihalogenide expressed by the general formula (III) with an aromatic dihalogenide expressed by the general formula (IV) to form sulphide bonds with the aid of a sulphide forming reagent, where, in the formulae above Ar¹, Ar², Ar³ and Ar⁴ are aromatic rings and R¹, R², R³ and R⁴ are alkyl groups having 1 - 20 carbon atoms, cycloalkyl groups having 3 - 20 carbon atoms, aryl groups having 6 - 20 carbon atoms, alkoxyl groups having 1 - 20 carbon atoms, acyl groups having 2 - 20 carbon atoms, or aralkyl groups having 7 - 20 carbon atoms, and R¹, R², R³, and R⁴ may be the same or different from each other, a, b, c and d each stand for the integers 0, 1, 2, 3 or 4 and may be the same or different from each other, X and Y are halogens which may be the same or different atoms from each other, and the ratio of p/q is in the range from 100/0 to 1/99. A process for the production of an aromatic sulphide amide polymer or copolymer according to claim 5 or claim 6 wherein the reaction of the amide group containing dihalogenide having the general formula (IV) to form sulphide bonds with the aid of a sulphide forming reagent is carried out in an organic polar solvent. A process for the production of an aromatic sulphate amide polymer or copolymer according to claim 5, 6 or 7 where Ar¹, Ar², Ar³ are same or different aromatic rings selected from wherein Z stands for -O-, -S-, -SO₂-, -CO-, -CH₂- or A process according to claim 5, 6, 7 or 8 wherein the aromatic dihalogenide (IV) is selected from the group consisting of dichlorobenzene, dichlorobenzophenone and dichlorodiphenylsulphone. A process according to claim 5, 6, 7, 8 or 9 wherein the ratio of the amide group containing dihalogenide expressed by the general formula (III) to the sulphide forming reagent is 0.9:1 to 1.1:1.

Inventors: ISHIKAWA, TOMOHIRO, KONDO, YOZO
Applicants: TOSOH CORPORATION
Application year: 1987
Main classification: C08G75
IPC codes: C08G75