Polymeric compositions and components thereof

Abstract: Polymer compositions comprising phenol/formaldehyde systems and polyarylsulphones having epoxy pendent or end groups are disclosed together with novel epoxy-ended polyarylsulphones and novel cross-linked epoxy-ended polyarylsulphones. The compositions can be both unreinforced and reinforced with fibres and/or other fillers.

Description: This invention relates to thermosettable and thermoset compositions derived from aromatic polymers having reactive groups and to processes for making such polymers. US-A-4448948 discloses polyethersulphones and polyetherketones of relatively low molecular weight which are terminated by glycidyloxy end groups and a method of making such polymers. The polymers are described as being cross-linkable using a conventional epoxy cross-linking reagent such as diaminodiphenyl sulphone. EP-A-311349 discloses inter alia polymer compositions which have a polyarylsulphone component and a thermoset resin component. The thermosetting component can be selected from a epoxy resin, a bismaleimide resin or a phenol-formaldehyde resin and preferred polyarylsulphone polymers are of specified formula and preferably have reactive end groups, -OH and -NH 2 end groups particularly being exemplified. In accordance with the invention, polymer compositions comprising a phenol/formaldehyde (PF) thermosetting system and a polyarylsulphone comprising reactive epoxy end groups exhibit exceptional and surprising increases in certain physical properties, especially when containing reinforcing fillers such as glass or carbon fibres. Suitable PF systems include both Novolac and resoles types of PF. Accordingly the present invention provides a curable polymer composition comprising a phenol formaldehyde thermosetting system and a polyarylsulphone comprising units E and E 1 connected by ether and/or thioether linkages, E being a divalent aromatic radical containing a sulphone group and E 1 being a divalent aromatic radical optionally containing a sulphone group and having reactive epoxy groups formula I:- where k is an integer from 1 to 3 selected in dependence upon G; and G is a direct link or is of formula II:- where J is a residue selected from at least one a dihydric phenol residue, an aminophenol residue or an aromatic diamine residue, said residues preferably being of formula III:- -PhAPh- where Ph is phenylene, especially 1,4-phenylene; and A is a direct link, -O-, -S-, -SO-, -SO 2 -, -CO-, -CO 2 - or a C 1 to C 6 hydrocarbon and wherein the epoxy groups are end-groups, the number of such end groups per polymer chain is preferably in the range 1.5 to 2.5 and very suitably is 1 ± 0.2 at each end of each chain on average in a given sample of polymer. In preferred polymer compositions according to the invention, the polysulphone units E and E 1 are independently selected from radicals of formula IV:- -(PhSO 2 Ph) n - where Ph is phenylene, especially 1,4-phenylene, and optionally carrying up to four non-interfering substituents such as halogen, alkyl or alkoxy; and n = 1 to 2 and can be fractional; and optionally, in a minor proportion, from radicals of formula V:- (Ph) a where a is 1 to 3 and can be fractional, and such phenylenes are linked linearly through a single chemical bond or a divalent group other than SO 2 or are fused together. By "fractional" reference is made to the average value for a given polymer chain containing units having various values of n or a. In a preferred polymer composition according to the invention, the relative proportions of the repeating units of the polyarylsulphone is such that on average at least two units (PhSO 2 Ph) n are in immediate mutual succession in each polymer chain present and is preferably in the range 1:99 to 99:1, especially 10:90 to 90:10, respectively. Typically, the ratio is in the range 25-50 (Ph) a , balance (Ph SO 2 Ph) n . In preferred polyarylsulphones for use in polymer compositions according to the invention, the units are of formula VI:- X Ph SO 2 Ph X Ph SO 2 Ph ("PES") alone or together with units of formula VII:- X (Ph) a X Ph SO 2 Ph ("PEES") where X is O or S and may differ from unit to unit; and the ratio of VI to VII is preferably between 10:90 and 80:20 especially between 10:90 and 55:45. The preferred relative proportions of the repeating units of the polyarylsulphone may be expressed in terms of the weight percent SO 2 content, defined as 100 times (weight of SO 2 )/(weight of average repeat unit). The preferred SO 2 content is at least 22%, preferably 23% to 30%. When a = 1, this corresponds to PES/PEES ratios of at least 20:80, preferably in the range 35:65 to 65:35. The above proportions refer only to the units mentioned. In addition to such units the polyarylsulphone may contain up to 50Z especially up to 25% molar of other repeating units; the preferred SO 2 content ranges (if used) then apply to the whole polymer. Such units may be for example of the formula:- in which A 1 is a direct link, O, S, CO or a divalent hydrocarbon radical. When the polyarylsulphone is the product of nucleophilic synthesis, its units may have been derived for example from one or more the following bisphenols and/or corresponding bisthiols or phenol-thiols:- hydroquinone 4,4'-dihydroxybiphenyl resorcinol dihydroxynaphthalene (2,6 and other isomers) 4,4'-dihydroxydiphenylether or thioether 4,4'-dihydroxybenzophenone 2,2'-bis(4-hydroxyphenyl)propane or methane. If a bisthiol is used, it may be formed in situ, that is a dihalide as described for example below may be reacted with an alkali sulphide or polysulphide or thiosulphate. Other examples of such additional units are of the formula:- where X is independently CO or SO 2 ; Ar 1 is a divalent aromatic radical; and m is an integer from 0 to 3, provided that m is not zero where X is SO 2 . Ar 1 is preferably at least one divalent aromatic radical selected from phenylene, biphenylene or terphenylene. Particular units have the formula:- where m>0. When the polymer is the product of nucleophilic synthesis, such units may have been derived from one or more dihalides, for example:- 4,4'-dihalobenzophenone 4,4'-bis(4-chlorophenylsulphonyl)biphenyl 1,4 bis(4-halobenzoyl)benzene 4,4'-bis(4-halobenzoyl)biphenyl They may of course have been derived partly from the corresponding bisphenols. The polyarylsulphone may be the product of nucleophilic synthesis from halophenols and/or halothiophenols. In any nucleophilic synthesis, the halogen, if chlorine or bromine, may be activated by the presence of a copper catalyst. Such activation is often unnecessary if the halogen is activated by an electron withdrawing group. In any event fluoride is usually more active than chloride. Any nucleophilic synthesis of the polyarylsulphone is carried out, preferably in presence of one or more alkali metal carbonates in up to 10% molar excess over the stoichiometric and of an aromatic sulphone solvent, at a temperature in the range 150-350°C. If desired, the polyarylsulphone may be the product of electrophilic synthesis. The polyarylsulphone before epoxidation preferably contains end groups and/or pendant groups of formula -R 1 -Z where R 1 is a divalent hydrocarbon group, preferably aromatic, and Z is a residue of a group having an active hydrogen reactive with an appropriate epoxy-containing compound which will form an epoxy group as hereinbefore defined, Z especially being the residue of -OH, -NH 2 , -NHR 2 or -SH, where R 2 is a hydrocarbon group containing up to 8 carbon atoms. The number average molecular weight of the polyarylsulphone is suitably in the range 2000 to 60000. Preferably it is over 9000 especially over 10000 for example 11000 to 25000. However, if desired, polymers having a lower molecular weight, eg 3000 to 9000, may be utilised in some applications, for example to control the final molecular weight of extended polymers described in more detail below. It is convenient to use reduced viscosity (RV), measured on a solution of 1g of polymer in 100 ml of solution in dimethyl formamide at 25°C as an indication of molecular weight, the correlation being as follows:- RV 0.15 0.25 0.45 0.92 MW (number average) 5000 13000 20000 60000 (Such molecular weights were in fact measured by vapour phase osmometry and are of course subject to the usual error range of about 10 %). The epoxy groups on the polyarylsulphones according to the invention can typically be derived from epoxide-containing compounds which are the mono or poly-glycidyl derivative of one or more of:- aromatic diamines aromatic monoprimary amines aminophenols polyhydric phenols polyhydric alcohols polycarboxylic acids. Examples are the following, which are liquids at ambient temperature:- tetraglycidyl diamino diphenylmethane eg "MY 720" or "MY 721" sold by Ciba-Geigy, viscosity 10-20 Pa s at 50°C; (MY 721 is a lower viscosity version of MY720 and is designed for higher use temperatures); triglycidyl derivative of p-aminophenol (eg "MY 0510" sold by CibaGeigy), viscosity 0.55 - 0.85 Pa s at 25°C; or diglycidyl ether of 2,2-bis(4,4'-dihydroxy phenyl) propane (eg "Epikote 828" sold by Shell), preferably of viscosity 8-20 25 Pa at 25°C. The invention also includes a polymer composition containing a polyarylsulphone as hereinbefore described and which has epoxy end-groups, said epoxy end-groups being of formula IIA:- where k is an integer from 1 to 3 selected in dependence upon J; and J is a residue selected from at least one of the following:- a dihydric phenol residue, an aminophenol residue or an aromatic diamine residue, said residues preferably being of formula III:- -PhAPh- where Ph is phenylene, especially 1,4-phenylene; and A is a direct link, -O-, -S-, -SO-, -SO 2 -, -CO-, -CO 2 - or a C 1 to C 6 hydrocarbon. The polyarylsulphones containing epoxy group can be made by reacting at least one starting polymer of units E and E 1 connected by ether and/or thioether linkages which has terminal groups of formula -R 1 ZH, as hereinbefore defined, with:- (a) when G is to be a direct link, at least one epihalohydrin; and (b) when G is to be of formula II, at least one compound of formula IIB:- The curable polymer composition may also contain a second polyarylsulphone chain having units E and E 1 connected by ether and/or thioether linkages and which has at least one pendent or terminal group of formula -R 1 ZH. The starting molecular weights and the relative proportions of the two polyarylsulphones are chosen according to the final molecular weight required. Preferably, the ratio of groups of formula -R 1 Z- to which is connected an epoxy group of formula I to groups of formula -R 1 ZH is in the range 10:90 to 90:10, more preferably in the range 20:80 to 80:20 and, more especially in the range 70:30 to 60:40. Such polymers exhibit surprising and significantly improved properties relative to polymers having end groups of formula -R 1 ZH, especially when containing reinforcing fillers such as glass or carbon fibres. The polyarylsulphones having epoxy groups in accordance with the invention are cured in the presence of a phenol/formaldehyde condensate and possibly also a catalyst. Additional curing agents include an amino compound having a molecular weight up to 500 per amino group, for example an aromatic amine or a guanidine derivative. Particular examples are 3,3'- and 4,4'-diaminodiphenylsulphone, methylenedianiline and dicyandiamide. The total amine content of the curing agent is in the range 70-110% of the stoichiometric requirement of the polyarylsulphone. Other standard epoxy curing agents such as aliphatic diamines, amides, carboxylic acid anhydrides, carboxylic acids, phenols can be used if desired. If a catalyst is used, it is typically a Lewis acid, for example boron trifluoride, conveniently as a derivative with an amine such as piperidine or methyl ethylamine. Alternatively it can be basic, for example an imidazole or amine. The polymer compositions of the invention are particularly suitable for the fabrication of structures, including load-bearing or impact resisting structures. For this purpose it may contain a reinforcing agent such as fibres. In composites according to the invention, the fibres can be added short or chopped typically of mean fibre length not more than 20 mm, for example about 3-6mm, typically at a concentration of 5% to 70%, more especially 20% to 60%, by weight. However, for structural applications, it is preferred to use continuous fibre for example glass or carbon, especially at 30% to 70%, more especially 50% to 70%, by volume. The fibre can be organic, especially of stiff polymers such as poly paraphenylene terephthalamide, or inorganic. Among inorganic fibres glass fibres such as "E" or "S" can be used, or alumina, zirconia, silicon carbide, other compound ceramics or metals. A very suitable reinforcing fibre is carbon, especially as graphite. Organic or carbon fibre is preferably unsized or is sized with a material that is compatible with the composition according to the invention, in the sense of being soluble in the liquid precursor composition without adverse reaction or of bonding both to the fibre and to the thermoset/thermoplast composition according to the invention. In particular carbon or graphite fibres that are unsized or are sized with epoxy resin precursor or thermoplast such as polyarylsulphone are preferred. Inorganic fibre preferably is sized with a material that bonds both to the fibre and to the polymer composition; examples are the organo-silane coupling agents applied to glass fibre. The composition may contain for example conventional toughening agents such as liquid rubbers having reactive groups, aggregates such as glass beads, rubber particles and rubber-coated glass beads, fillers such as polytetrafluoroethylene, graphite, boron nitride, mica, talc and vermiculite, pigments, nucleating agents, and stabilisers such as phosphates. The total of such materials and any fibrous reinforcing agent should be such that the composition contains at least 20% by volume of the polymer composition. The percentages of fibres and such other materials are calculated on the total composition once the composition is in its final usable state, eg cured or cross-linked. For composites according to the invention, short fibres may be added to a solution of the polyarylsulphone according to the invention or to polymer compositions containing said polyarylsulphone prior to evaporation of the solvent. However, preferred composites comprise continuous fibres, the composites being made by passing essentially continuous fibre into contact the solution of the polyarylsulphone and, when present, other ingredients. The resulting impregnated fibrous reinforcing agent may be used alone or together with other materials, for example a further quantity of the same or a different polymer or resin precursor or mixture, to form a shaped article. A further procedure comprises forming incompletely cured composition into film by for example compression moulding, extrusion, melt-casting or belt-casting, laminating such films to fibrous reinforcing agent in the form of for example a non-woven mat of relatively short fibres, a woven cloth or essentially continuous fibre in conditions of temperature and pressure sufficient to cause the mixture to flow and impregnate the fibres and curing the resulting laminate. Composites according to the invention can be comprised by plies of impregnated fibrous reinforcing agent laminated together by heat and pressure, for example by compression moulding or by heated rollers, at a temperature above the curing temperature of the thermoset component or, if cure has already taken place, above the glass transition temperature of the mixture, conveniently at least 150°C and typically about 190°C, and at a pressure in particular at least 0.1 MN/m 2 , preferably at least 5 MN/m 2 , followed by a free-standing post cure period, typically at about 240°C. The resulting multi-ply laminate may be anisotropic in which the fibres are oriented essentially parallel to one another or quasi-isotropic in each ply of which the fibres are oriented at an angle, conveniently 45° as in most quasi-isotropic laminates but possibly for example 30° or 60° or 90° or intermediately, to those in the plies above and below. Orientations intermediate between anisotropic and quasi-isotropic, and combination laminates, may be used. Suitable laminates contain at least four, preferably at least eight, plies. The number of plies is dependent on the application for the laminate, for example the strength required, and laminates containing thirty-two or even more, for example several hundred, plies may be desirable. There may be aggregates, as mentioned above, in interlaminar regions. The invention will now be illustrated by reference to the following Examples. In the Examples, the properties of flexural modulus, compressive yield stress (yield strength) and resin fracture strength and toughness, K 1c and G 1c , were determined as follows. Flexural modulus was measured using a three point bend uniform specimen on an "Instron" model 1122 testing machine, at a cross-head speed of 5mm/min, and is determined in accordance with the following formula:- E = ¼.F/ .L 3 /BW 3 where F is the force required to cause central deflection of the specimen; F/ was evaluated at small deflection; is less than W/2; W is the thickness of the specimen; B is the breadth of the specimen; and L is the separation of the supports. Typically, L = 50mm, B = 3mm and W = 10mm. The compressive yield stress, σ y , was measured on the "Instron" machine with a cross-head speed of 5mm/min using samples of various dimensions. To characterise fracture strength and toughness, a three point bend, single edge-notched, linear elastic fracture mechanics test was used, the data being generated using an impact instrument. The fracture toughness, the critical value of the strain energy release rate in crack opening mode, is given by:- G 1c = U c /BW.Φ where Φ is a function of geometry and U c is the energy absorbed in the impact test. The specimens were tested at -65°C using a machined notch and a test speed of 1ms -1 . Example 1 A sample of 40:60 PES:PEES polyarylsulphone was made by reacting 4,4'-dichlorodiphenylsulphone (50 molar parts) with hydroquinone (30 molar parts) and dihydroxydiphenylsulphone (20 molar parts) in the presence of potassium carbonate (50 molar parts) and in diphenylsulphone solvent at a temperature rising to 280°C. A slight excess 4,4'-dichlorodiphenylsulphone was used resulting in -Cl end groups on the polymer. During the reaction, m-aminophenol was added to the reaction mixture as an end-capping agent. Following cooling, the polymer sample was ground, washed with acetone, methanol and water until essentially free from potassium salts and dried. The polymer, Sample A, had an RV of 0.28 (1% solution in dimethylformamide - DMF), a Tg of 195°C and a structure as follows:- A part of Sample A was mixed with diglycidyl ether of 2,2-bis (4,4'-dihydroxy phenyl)propane ("Epikote 828" sold by Shell) (2 molar parts). The mixture was warmed until the polymer dissolved, heated at 180°C for 2 hours. After cooling, the reactants were dissolved in dichloroethane (virtually colourless in solution) and then poured into methanol to precipitate the polymer. Examination of the polymer (hereinafter Sample B) by infra red (IR) and nuclear magnetic resonance (nmr) techniques showed the polymer to be of formula:- Example 2 A 50:50 mixture of Sample A and Sample B, both in powder form, was compression-moulded at 300°C, 4 tonnes pressure for 15 minutes to give a film of 2mm thickness. The resultant film was very tough and stiff particularly when compared to a similar film moulded from Sample A (which is brittle at these molecular weights). In dichloromethane at ambient temperatures, a portion of the film exhibited only slight swelling after 7 days (polyarylsulphones are usually soluble or swell extensively in dichloromethane). The film was also thermoplastic in that it is meltable. Sample B, when moulded at 300°C, did not appear to homopolymerise. Example 3 At room temperature, samples of PF precondensate (Novolak SFP 118 ex Schenectady Chemicals Inc) (68g) and hexamethylenetetramine (12g) were mixed in 90:10 v/v methylene chloride:methanol with various amounts of the polymers of Samples A and B. A control sample not containing any polymer was also prepared. The mixtures were poured into trays lined with mould release paper and the solvent allowed to evaporate. The residual solvent was then removed in a vacuum oven at 60°C/0mm Hg. The resultant materials were then ground into powder and moulded into test plaques as follows. The press and the matched metal mould used for forming the plaques was heated to 150°C g for 1 hour. Vacuum bags were prepared using a nylon bagging film stable up to 260°C. Three sides of the bags were sealed using mastic tape. The pre-heated mould parts with the powdered moulding compound therebetween were placed in the bag which was then sealed and evacuated. The bag containing the mould was then placed in the press and increasing pressure was applied until "flashings" appeared to decrease with increasing pressure at which point maximum moulding pressure (eg 15 tonnes for a 150mm x 100mm mould) was applied. The mould was held under vacuum at 150°C for 15 minutes and then was removed from the press and allowed to cool to 50°C before de-moulding the plaque. The mechanical properties of two of the samples are given in Table 1. The ductility factors (DF) of all of the samples are shown in Table 2. SAMPLE 5 9 1 Flexural Modulus GPa 5.15 5.00 6 Yield Strength σ y MPa 226 241 343 Fracture Strength K 1c MNm -1.5 0.63 1.9 0.52 Fracture Toughness G 1c KJm -2 0.17 0.88 0.07 Ductility Factor (K 1c /σ y ) 2 µm 7.8 62 2.2 SAMPLE % OF A DF SAMPLE % OF B DF 1 0 2.2 1 0 2.2 2 10 3.3 5 10 10 3 15 12 6 15 14 4 20 13 7 20 23 - - 8 30 55 5 35 7.8 9 35 62 - - - 10 40 102 It is evident that polymer compositions consisting of PF and polyarylsulphones according to the invention have greatly increased toughness as shown by the ductility factor results. Examination of the morphologies of the moulded samples revealed that the morphologies appeared to change from homogeneous to ribbon-like and then co-continuous as the level of polyarylsulphone increased, the co-continuous morphologies being present at above about 20% by weight of polyarylsulphone. Example 4 Further compositions were prepared according to the method of Example 3 using various amounts of polymers of Samples A and B and including chopped glass fibre (3.2mm long, aminosilane sized, ex Certaineed, USA) and the resultant plaques were tested for fracture strength and yield strength to enable the ductility factors (DF) to be determined for the samples. Two of the compositions (25% polymer, 40% glass) are set out in Table 3 (proportions by weight) together with the results relating thereto, the full set of samples and their ductility factors being listed in Table 4, the figures in brackets after "DF" being the weight % of glass fibre in the composition. Example 5 Prepreg was fabricated by pumping 25-35% by weight solutions of polymer onto a spread 12K tow of Hercules IM7 carbon fibre as it was wound onto a drum, the prepreg being cut off the drum and laid flat to dry at room temperature. The resultant composite plaques consisted of 24 unidirectional layers of prepreg which were moulded at 320°C and 2.4MPa pressure for 5 minutes following a 15 minute preheat period during which no pressure was applied. The test plaques were used to determine fracture toughness (G 1c ). The samples and results are summarised in Table 5. Chopped glass fibre 40 32.18 32.2 Z of glass 40 40 40 SFP 118 38.13 30.4 40.5 Hexamethylenetetramine 6.73 5.36 7.16 Sample A 15.14 - - Sample B - 12.06 - % of polymer 25 25 - Flexural Modulus GPa 13.8 12.6 12.6 Yield Strength σ y MPa 441 450 473 Fracture Strength K 1c MNm -1.5 5.63 8.45 4.23 Fracture Toughness G 1c KJm -2 4.48 8.18 2.95 Ductility Factor (K 1c /σ y ) 2 µm 163 353 80 % OF A DF(20) DF(40) DF(60) % OF B DF(20) DF(40) DF(60) 0 55 80 95 0 55 80 95 15 49 182 99 15 175 285 293 25 138 151 97 25 178 353 725 35 200 210 144 35 190 321 665 POLYMER FIBRE VOLUME FRACTION (%) G 1c (Average of 2) (KJm -2 ) 100%A1 65.2 1.09 100%A 57.9 1.37 100%A 57.3 0.86 67%A/33%B 60.3 2.30 50%A/50%B 60.6 1.64 50%A/50%B 63.1 1.95 50%A/50%B 62.8 1.91 33%A/67%B 54.8 2.87 20%A/80%B 57.3 2.65

Claims: A curable polymer composition comprising a phenol/formaldehyde thermosetting system and a polyarylsulphone comprising repeating units E and E 1 connected by ether and/or thioether linkages, E being a divalent aromatic radical containing a sulphone group and E 1 being a divalent aromatic radical optionally containing a sulphone group and having reactive epoxy groups of formula I :- where k is an integer from 1 to 3 selected in dependence upon G; and G is a direct link or is of formula II :- where J is a residue selected from at least one dihydric phenol residue, an aminophenol residue or an aromatic diamine residue, said residues preferably being of formula III :- -Ph-A-Ph- where Ph is phenylene, especially 1,4 phenylene; and A is a direct link, -O-, -S-, -SO-, -SO 2 -, -CO-, -CO 2 -, or a C 1 to C 6 hydrocarbon and wherein the epoxy groups are end groups and the number of such end groups per polymer chain is in the range 1.5 to 2.5 and is, preferably, 1 ± 0.2 at each end of each chain on average in a given sample of polymer. A curable polymer composition according to claim 1 wherein the units E and E1 are radicals of formula IV :- -(Ph-SO 2 -Ph) n - where Ph is phenylene, especially 1,4 phenylene and optionally carrying up to four non-interfering substituents such as halogen, alkyl, or alkoxy; and n = 1 to 2 and can be fractional; and optionally, in a minor proportion, from radicals of formula V :- (Ph) a where a = 1 to 3 and can be fractional, and such phenylenes are linked linearly through a single chemical bond or a divalent group other than SO 2 or are fused together. A curable polymer composition as claimed in either claim 1 or claim 2 comprising a reinforcing filler.

Inventors: CARTER JEFFREY THOMAS, MCGRAIL PATRICK TERENCE, CARTER, JEFFREY THOMAS, MCGRAIL, PATRICK TERENCE
Applicants: FIBERITE INC, ICI PLC, FIBERITE INC., IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1990
Main classification: C08L63
IPC codes: C08G75, C08G65, C08L81, C08G59, C08L61, C08L63