USH521H - Thermosetting polysulfones - Google Patents
Thermosetting polysulfones Download PDFInfo
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- USH521H USH521H US07/004,721 US472187A USH521H US H521 H USH521 H US H521H US 472187 A US472187 A US 472187A US H521 H USH521 H US H521H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/20—Cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the invention relates to thermosetting end-capped polyarylene polyethers, including end-capped polyarylene polyethers, processes of preparing and using such resins, composites containing such resins, and homopoLymers and copolymers prepared from such resins.
- Thermoplastic polyarylene polyethers are known.
- Thermoplastic silane end-capped polyarylene polyethers and thermoplastic polysiloxane-polyarylene polyether copolymers are also known.
- An object of the invention is to provide a new and useful class of high performance end-capped polyarylene polyethers, particularly end-capped polysulfones. Another object of the invention is to provide compositions containing and copolymers produced from such polyarylene polyethers and comonomers. Another object of this invention is to provide homopolymers prepared from such polyarylene polyethers. A further object of the invention is to provide processes for preparing and using such polyarylene polyethers, compositions, homopolymers and copolymers. A still further object of the invention is to provide a composite of a substrate and such polyarylene polyethers, homopolymers and copolymers. Other objects and advantages of the invention are set out herein or are obvious herefrom to one ordinarily skilled in the art.
- thermosetting polyarylene polyethers and so forth of the invention.
- thermosetting, monovalent unsaturated organo end-capped polyarylene polyethers of the invention differ from the known thermoplastic polyarylene polyethers and the known silane end-capped polyarylene polyethers most significantly in that the compositions of the invention have reactive, monovalent, unsaturated organo end-capping groups.
- the polyarylene polyether chain can be substituted or unsubstituted.
- the end-capped resins of the invention are a class of organic resins having etheric oxygen valently connecting together aromatic nuclei or residue of aromatic compounds. These end-capped resins are appropriately termed end-capped polyarylene polyethers resins.
- thermosetting end-capped polyarylene polyether resins having the formula:
- thermosetting resins can be produced by reacting an alkali metal phenoxide end-capped polyarylene polyether with a monovalent, monohalo-substituted, unsaturated organo compound.
- n is 2 to 300; and preferably Z and Z' are each an alkylene, aralkylene or cycloalkylene moiety.
- thermosetting end-capped polyarylene polyether ogliomers or resins having the formula:
- thermosetting resins can be produced by reacting an alkali metal phenoxide end-capped polyarylene polyether with a monovalent, monohalo-substituted, unsaturated organo compound.
- n is 2 to 300; and preferably Z and Z' are each an alkylene, aralkylene or cycloalkylene moiety.
- the polyarylene polyether chain particularly the benzenoid constituents, can contain inert substituents such as halogens (e.g., chlorine, bromide and fluorine) alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having 1 to 4 carbon atoms.
- halogens e.g., chlorine, bromide and fluorine
- the end-capped polyarylene polyether resins of the invention have excellent strength and toughness properties as well as outstanding thermal oxidative and chemical stability. They find wide utility in the production of shaped and molded articles where such properties are necessary and are highly desirable and also in the preparation of film and fiber products which have excellent mechanical properties
- Heat-hardenable resins can be blended with thermosetting, end-capped polyarylene polyether resins of this invention to yield useful mixtures.
- thermosetting resins of the invention are those polysulfones where the thermosetting polyarylene polyether resin is composed of recurring units having the formula: ##STR1## wherein R is hydrogen, lower alkyl, lower aryl and halogen substituted lower alkyl and lower aryl groups. Most preferably R is methyl.
- the lower alkyl groups have from 1 to 4 carbon atoms.
- polysulfone-vinyl reactive resins or PSF-VR are the above end-capped resins when R is methyl and the end-capping moieties are alkylene, aralkylene or cycloalkylene moieties.
- PSF-VR polysulfone-vinyl reactive resins
- polysulfone-vinyl reactive resins to be cured by conventional techniques and their ability to copolymerize with a variety of commercially available, inexpensive comonomers, make them an important class of new thermoset resins.
- polysulfone-vinyl reactive styrene binder system which not only forms a true solution in any proportion but also yields a copolymer of uniform, well-defined properties. It can be formulated, processed and cured like an unsaturated polyester resin to impart higher use temperatures, better mechanical and electrical properties, and, above all, improved chemical resistance to strong alkaline environment.
- the polysulfone-vinyl reactive resins of the invention are particularly useful as (1) corrosion resistance matrix resins or additives, (2) powder coatings, (3) magnet wire coatings, (4) photocurable and radiation coatings and (5) in fiber reinforced structural composites.
- thermoset vinyl benzyloxy end-capped polysulfones in coating form on metal sheets and the like are highly resistant to the solvent action to acetone and chlorinated hydrocarbons, such as, methylene chloride. Such coatings are also highly resistant to hot alkali solutions.
- thermoset or baked coating of the allyl end-capped polysulfones on a metal or glass substrate is readily removable or strippable once subjected to hot detergent solutions.
- This property means strippable coating applications to protect glass substrates, particularly to hot alkali solutions for the thermoset allyl-terminated polysulfone coatings of the invention.
- metal protective coatings such as, metal strip and prime coatings, can coatings, wire magnet coatings and pipe liner coatings are also applications for the thermoset allyl-terminated polysulfones of the invention.
- thermoset vinylbenzyloxy end-capped polysulfone 10,000 molecular weight had significant resistance to the solvent action of trichloroethylene, which is important in some electrical applications.
- the end-capped polyarylene polyethers of the invention have the same advantages and uses as the subgroup end-capped polysulfones of the invention.
- the invention includes the homopolymers of the end-capped polyarylene polyether having the formula:
- Z and Z' are each a monovalent unsaturated organo moiety.
- the polyarylene polyether chain can be substituted or unsubstituted.
- the homopolymer can be prepared from any of the vinyl reactive end-capped polyarylene polyethers taught or described herein.
- a preferred class of homopolymers which are within the scope of the invention are the homopoIymers of the end-capped polyarylene polyethers having the formula:
- n 2 to 300
- Z and Z' are each a monovalent unsaturated organo moiety
- E is the residue after removal of the hydryoxyl groups of a dihydric phenol
- E' is the residue after removal of the two activated halo groups of an aromatic compound having two activated halo substituents.
- the residues represented by E and E' being unsubstituted or substituted beyond the already defined degree.
- copolymers which are within the scope of the invention are the homopolymers of an end-capped polyarylene polyethers having the formula:
- n 2 to 300
- Z and Z' are each a monovalent unsaturated organo moiety
- Ar is a divalent aromatic group that can be the same or different from one --O--Ar-- group to the next, and in which each Ar group is bonded to the connecting oxy groups through aromatic carbon atoms.
- the aromatic group represented by Ar being substituted or unsubstituted.
- monomer (B) can have one, two, three or more reactive vinyl groups, depending upon the type of copolymer wanted, speed and cost of curing, etc.
- the invention also includes the process of preparing such homopolymers by homopolymerizing the end-capped polyarylene polyether monomer of the invention.
- the polymerization is effectively conducted in the presence of a free radical initiator, with concurrent heat application being preferred.
- Polymerization can also be effected by means of actinic radiation, such as ultraviolet light.
- the invention further includes the copolymers comprised of:
- Z and Z' are each a monovalent unsaturated organo moiety, the polyarylene polyether chain being substituted or unsubstituted;
- (B) at least one monomer having at least one monovalent unsaturated organo moiety.
- the copolymer can be prepared using any of the vinyl reactive end-capped polyarylene polyethers taught or described herein.
- a preferred class of copolymers which are within the scope of the invention are those wherein on monomer (B) the monovalent unsaturated organo moiety is an alkylene, aralkylene or cycloalkylene moiety.
- monomer (B) contains at least one reactive vinyl group R 7 R 8 C ⁇ CR 9 --, reactive vinylidene group R 7 R 8 C ⁇ C ⁇ C--, and/or reactive vinylene group --CR 10 ⁇ CR 11 --.
- R 7 , R 8 , R 9 , R 10 and R 11 each is (a) hydrogen, (b) alkyl having 1 to 4 carbon atoms, (c) alkoxy having 1 to 4 carbon atoms, (d) alkylcarboxy having 2 to 12 carbon atoms, (e) aryl having 6 to 10 carbon atoms, (f) alkoxycarbonyl having 2 to 12 carbon atoms, (g) substituted aryl having 6 carbon atom and being substituted with at least one halogen, nitrile, alkyl having 1 to 4 carbon atoms, and/or alkoxy having 1 to 4 carbon atoms, (h) aralkyl wherein the alkyl has 1 to 4 carbon atoms and the aryl has 6 to
- the invention still further includes the process of preparing such copolymers by copolymerizing the end-capped polyarylene polyether monomer (A) of the invention and monomer (B) (described above).
- the polymerization is effectively conducted in the presence of a free radical initiator, with concurrent heat application being preferred.
- Polymerization can also be effected by means of actinic radiation, such as, ultraviolet light.
- monomer (A) and monomer (B) are present in approximately equal stoichiometric amounts, although effectively the molar ratio of monomer (A) to monomer (B) is between 4 to 1 and 0.8 to 1.
- FIG. 1 is a graph of methylene chloride solubility curves for certain plated substrates
- FIG. 2 is a graph of a methylene chloride solubility curve for certain plated substrates
- FIG. 3 is a graph of the charge ratio versus the reduced viscosity
- FIG. 4 is a graph of the glass transition temperature versus the reduced viscosity.
- the end-capped high molecular weight polyarylene polyether resins of the present invention are the linear thermosetting reaction products of an alkali metal double salt of a dihydric phenol and a dihalobenzenoid compound, the thermosetting resins then being end-capped with mnovalent unsaturated organo compounds.
- a residuum of a dihydric phenol and a residuum of a benzenoid compound are both valently bonded to the ether oxygen through aromatic carbon atoms.
- Dihydric phenol such as, 2,2-bis(4-hydroxyphenyl)propane (“bisphenol-A")
- bisphenol-A 2,2-bis(4-hydroxyphenyl)propane
- the dihydric phenol is converted to the alkali metal salt by adding an alkali metal hydroxide, such as, sodium hydroxide, an alkali metal hydride, an alkali metal hydroxide, an alkali metal alkoxide or an alkali metal alkyl compound, and removing the water of condensation by azeotropic distillation.
- An aromatic compound having two activated halo substituents is added to the alkali metal salt.
- 4,4'-Dichlorodiphenyl sulfone is illustrative of such aromatic compounds.
- the dihalo aromatic compound is used in a controlled proportion so that there will be a stoichiometric excess of the alkali metal salt.
- the dihalo aromatic compound and the alkali metal salt are reacted to form a linear polyarylene-polyether chain having alkali metal salt end groups.
- This compound is then reacted with an appropriate end-capping agent, such as, allyl chloride, to form a monovalent unsaturated organo end-capped polyarylene-polyether, which is recovered by coagulating the solution in anhydrous methanol or anhydrous isopropyl alcohol.
- the dihydric phenol used can be a mononuclear compound such as hydroquinone or resorcinol, which may be substituted with an inert substituent such as alkyl, alkoxy or halo (with the allyl having 1 to 4 carbon atoms).
- hydroquinone and the like a process using K 2 CO 3 in dimethylacetamide is used wherein the monomers (hydroquinone, 4,4'-dichlorodiphenyl sulfone and K 2 CO 3 ) are charged into the dimethylacetamide (sulfolane is also useful), and the water of reaction is removed azeotropically with toluene or the like.
- the dihydric phenol can also be a polynuclear phenol.
- polynuclear phenols are p,p-biphenol, naphthalene diol, alkane bisphenols such as bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl) propane, bisphenol sulfones such as bis(4-hydroxyphenyl) sulfone, the bisphenol sulfides such as bis(4-hydroxyphenyl) sulfide, the bisphenol ethers such as bis(4-hydroxyphenyl) ether, and the bisphenol ketones such as bis(4-hydroxyphenyl) ketone.
- the preferred dihydric phenols are hydroquinone, bisphenol-A, p,p'-biphenol and bis(4-hydroxyphenyl) sulfone.
- the second class of compounds used are aromatic compounds that have two activated halo substitutents.
- the halo substituents are activated so that, in the absence of a catalyst, the aromatic compound can react with alkali metal phenoxide to form an ether.
- one way to activate the halo substituents is to have an inert electron withdrawing group ortho or para to the two halo groups.
- the halo-substituted aromatic compound can be a mononuclear compound, such as, 1,2,4,5-tetrabromobenzene, 1,2,4,5-tetrachlorobenzene, 2,4- and 2,6-dichlorobenzonitrile, hexachlorobenzene and 1,4-dibromo2,3,5,6-tetrachlorobenzene, or a polynuclear compound, such as, 4,4'-dichlorodiphenyl sulfone, 4,4'-bis(4-chlorophenylsulfonyl) biphenyl, 4,4 '-dichlorodiphenyl ketone, 3,4,5,3', 4',5'-hexachlorobiphenyl and 4,4'-dibromo-3,5,3',5'-tetrachlorobiphenyl.
- a mononuclear compound such as, 1,2,4,5-tetrabromobenzene, 1,
- the dihydric phenol is preferably employed in a stoichiometric excess over the dihalo aromatic compound.
- the reduced viscosities in chloroform at 25° C. and at a concentration of 0.2 gram of polymer per 100 milliliters of solution, of the polyarylene polyethers and the end-capped polymers derived therefrom usually will be within the range of from about 0.1 to 0.5 dl/g.
- reaction step (2) can be carried out with an excess of the dihalo compound (the preferred proportion of stoichiometric excess being the same as that given above for the dihydric phenol), followed by an alkaline hydrolysis reaction to convert the halo substituent to alkali metal phenoxide. Then, after azeotropic removal of water, the product is subjected to reaction step (3).
- the "single salt process" can be employed (e.g. as described in British Pat. No.
- reaction step (1) the dihydric phenol is converted to the corresponding alkali metal salt.
- alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
- DMSO dimethyl sulfoxide
- DMAC dimethylacetamide
- azeotroping agents include chlorinated benzenes, benzene, toluene, and xylene.
- the condensation reaction to produce the alkali metal phenoxide normally is conducted from about 120 to about 240 minutes at a temperature of from about 110° to about 132° C. While a much broader temperature range can be used, the above one is the most convenient.
- reaction step (2) the dihalo aromatic compound is added to the reaction mixture to carry out reaction step (2).
- This reaction is carried out at an elevated temperature, for example, from about 150° C. to about 170° C., for a period of from about 60 to about 120 minutes.
- reaction step (2) Upon completion of reaction step (2), a polyarylene polyether having alkali metal phenoxide end groups is produced. This composition is reacted with a monovalent unsaturated organo compound to produce the end-capped polyarylene polyether resins of the invention.
- the monovalent unsaturated organo moiety is selected from the group consisting of: ##STR3## wherein R 1 , R 2 and R 3 each is hydrogen, an aliphatic hydrocarbon radical containing 1 to 20 carbon atoms, an alicyclic hydrocarbon radical containing 1 to 20 carbon atoms or an aromatic radical, and R 4 , R 5 and R 6 each is a divalent alkylene radical containing 1 to 20 carbon atoms, a divalent arylene radical containing 6 to 10 carbon atoms or a divalent cycloalkylene radical containing 3 to 8 carbon atoms.
- R 1 , R 2 and R 3 each is hydrogen, an alkyl radical having 1 to 8 carbon atoms, an aryl radical, an aralkyl radical, an alicyclic radical having 3 to 8 carbon atoms or a bicyclic radical.
- R 4 , R 5 and R 6 each is a divalent alkylene radical having 1 to 8 carbon atoms.
- Typical aromatic radicals are benzyl, phenyl and naphthyl.
- Typical alkyl radicals are methyl, ethyl, 2-propyl, 1-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 1-pentyl, 3-metyl-1-butyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 1-hexyl, 2-ethyl-1-butyl, 2-metyl-1pentyl, 3-methyl-1-pentyl, 2,3-dimethyl-1-butyl, 3-methyl-2pentyl, 4-methyl-2-pentyl, 2,3-dimethyl-2-butyl, 1-heptyl, 2,4-dimethyl-3-pentyl, 1-octyl, 2-octyl, 1-dodecyl, 1-octadecyl and 1-hexadecyl.
- aromatic radicals are benzyl, methyl benzyl, o-, m- and p-dimethylbenzyl, ethylbenzyl, trimethyl benzyl, n-propylbenzyl and isopropylbenzyl.
- alicyclic and bialicyclic radicals are cyclobutyl, cyclopropyl methyl, cyclopropyl, cyclopentyl, cyclopentyl methyl, cyclohexyl, cyclohexyl methyl and cyclooctyl.
- divalent alkylene radicals are --CH 2 --, --CH 2 CH 2 --, --(CH 2 ) 3 --, --(CH 2 ) 5- , ##STR4## and --(CH 2 ) 12 --.
- divalent arylene radicals are --C 6 H 4 -- (o, m and p), and --C 10 H 6 --.
- divalent cycloalkylene radicals are ##STR5##
- the preferred halide end-capping agents are allyl chloride, 2-chloroethylacrylate, 2-chloroethylmethacrylate, chloromethyldimethylvinylsilane, vinyl benzyl chloride and 2-chloroethyl vinyl ether.
- halides for end-capping are: allyl chloride (CH 2 ⁇ CH--CH 2 Cl), allyl fluoride, allyl bromide, 1-propenyl chloride (CH 3 CH ⁇ CHCl), 1-propenyl fluoride, 1-propenyl bromide, CH 3 CH ⁇ CHCH 2 Cl, CH 2 ⁇ CHCH 2 CH 2 Cl, CH 2 ⁇ CHCH 2 , CH 2 F, CH 2 ⁇ CH(CH 2 ) 3 Cl, CHhd 2 ⁇ CHCH 2 CH 2 CH 2 Cl, CH 3 CH ⁇ CHCH 2 CH 2 Cl, CH 2 ⁇ C(CH 3 )CH 2 CH 2 Cl, CH 2 ⁇ CHCH 2 CH 2 CH 2 CH 2 Cl, vinyl benzyl chloride, vinyl benzyl floride, vinyl benzyl bromide, 3-phenylpropenyl chloride, ##STR6##
- thermoplastic polyarylene polyethers are rendered "cross-linkable" through the incorporation of unsaturated moieties This is accomplished conveniently by replacing saturated agents, such as, methyl chloride, an end-capping reagent, with an unsatuxated reagent.
- saturated agents such as, methyl chloride, an end-capping reagent
- unsatuxated reagent an unsatuxated reagent.
- the resulting resins contain unsaturated group at the chain ends.
- the composition is cross-linkable in the presence of a suitable free radical initiator. Upon curing these end-capped polysulfone compositions have been shown to provide improved stress-cracking resistance and better adhesive properties. They are also useful for various polymer modification purposes particularly as a "rigid block” in forming block and graft copolymers.
- the end-capping reaction i.e., reaction step (3), is carried out by reacting the monovalent unsubstituted organo compound with the alkali metal phenoxide-capped polyarylene polyether resin produced by reaction step (2).
- the stoichiometric proportions are two moles of unsubstituted organo compound per mole of polyarylene polyether resin. It is preferred to employ about a 2 to 10 mole percent stoichiometric excess of the unsubstituted organo compound.
- the reaction mixture preferably should be substantially anhydrous.
- the reaction medium can be the same solvent system that was employed for reaction steps (1) and (2).
- the reaction is carried out at elevated temperatures, e.g., at from about 110° C. to about 165° C.
- the reaction will usually take from about 10 to about 90 minutes.
- the completion of the reaction can be detected by treating a sample of the reaction mixture with bromocresol purple indicator. When the alkali metal phenoxide has reacted, the treated sample will be greenish yellow in color.
- the reaction mixture can be cooled, filtered to remove salt by-product, and then the end-capped polyarylene polyether resin can be recovered by coagulation in a non-solvent for the resin, e.g., methanol or isopropyl alcohol.
- a non-solvent for the resin e.g., methanol or isopropyl alcohol.
- the reaction mixture and the resin is kept anhydrous until the resin has been recovered as a solid.
- the substantially equimolar one-step reaction of a double alkali metal salt of a dihydric phenol with a dihalobenzenoid compound is done in the presence, for example, of specific liquid organic sulfoxide or sulfone solvents under substantially anhydrous conditions. Catalysts are not necessary for this reaction.
- Another feature of the invention involves simultaneously contacting substantially equimolar amounts of an alkali metal double salt of a dihydric phenol and a dihalobenzenoid compound with a solvent mixture comprising an azeotrope former and a sulfoxide or sulfone reaction solvent in a weight ratio of from about 10:1 to about 1:1, preferably from about 4:1 to about 3:1, removing water from the reaction mass as an azeotrope with the azeotrope former until substantially anhydrous conditions are attained, adjusting the ratio of azeotrope former to reaction solvent from about 1:1 to about 1:10, preferably from about 1:3 to about 1:4, by removing excess azeotrope former, and reacting the alkali metal double salt with the dihalobenzenoid compound in the liquid phase of the sulfoxide or sulfone reaction solvent.
- the useful sulfoxide or sulfone solvents are those of the formula:
- each R represents a monovalent lower hydrocarbon group free of aliphatic unsaturation of the alpha carbon atom, and preferably contains less than about 8 carbon atoms or when connected together represents a divalent alkylene group with v being an integer from 1 to 2 inclusive.
- v being an integer from 1 to 2 inclusive.
- solvents as those having the formula: ##STR7## wherein the R groups are lower alkyl, such as methyl, ethyl, propyl, butyl and like groups and aryl groups such as phenyl and alkyl phenyl groups as well as those where the R groups are interconnected as in a divalent alkylene bridge, such as: ##STR8## as in thiophene oxides and dioxides.
- solvents Specifically mentionable of these solvents but by no means exhaustive of these solvents are dimethylsulfoxide, dimethylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene 1,1-dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene-1 monooxide.
- the dimethylsulfoxide has been found to be the most useful as the solvent for this reaction because it is a solvent for the widest variety of reactants as well as for the resulting polymer of the reaction.
- Aliphatic unsaturation on the alpha-carbon atom such as occurs in divinyl sulfone and sulfoxide, should not be present as such materials tend to be reactive and polymerize under the conditions of this reaction. However, unsaturation on a beta-carbon atom or one further removed from the sulfur atom can be tolerated and such solvents can be employed in this reaction.
- the dihydric phenol and an alkali metal hydroxide are admixed in essentially stoichiometric amounts and normal precautions taken to remove all the water of neutralization preferably by distillation of a water-containing azeotrope from the solvent-metal salt mixture.
- any other technique for removing essentially all of the water can be equally satisfactory.
- the azeotrope former can be one either miscible or immiscible with the sulfone or sulfoxide major solvent. If it is not miscible it should be one which will not cause precipitation of the polymer in the reaction mass. Heptane is such a solvent. When employed, it will merely remain inert and immiscible in the reaction mass. If the azeotrope former would cause precipitation of the polymer, it should be removed almost completely from the reaction mass before initiating polymerization. For such reasons, it is preferred to employ azeotrope formers which are miscible with the major solvents and which also act as co-solvents for polymer during polymerization.
- Chlorobenzene, dichlorobenzene and xylene are azeotrope formers of this class.
- the azeotrope former should be one boiling below the decomposition temperature of the major solvent and be perfectly stable and inert in the process, particularly inert to the alkali metal hydroxide when the alkali metal salt of the dihydric phenol is prepared in situ in the presence of the inert diluent or azeotrope former. It has been found that chlorobenzene and o-dichlorobenzene serve particularly well as the inert diluent and are able to significantly reduce the amount of the sulfone or sulfoxide solvent necessary.
- any of the alkali metal hydroxides can be employed in this technique, that is to say any alkali metal salt of the dihydric phenol can be used as the one reactant.
- Potassium and cesium salts have been found to react considerably faster than the sodium salts, but due to expense of the cesium salts, the potassium salts are preferred.
- the alkali metal salt should, of course, be the double metal salt, i.e., both aromatic hydroxyl groups being saponified, in order to prepare these products. Single metal salts ordinarily limit the molecular weight of the product.
- the initial reaction and the major portion thereof should be with the double alkali metal salt of the dihydric phenol.
- the alkali metal moieties of this compound however can be the same or different alkali metals.
- Substantially equimolar amounts of the alkali metal double salt of a dihydric phenol (or a dihydric phenol for in situ conversion to the salt) and a dihalobenzenoid compound are simultaneously contacted with a solvent mixture comprising an azeotrope former and a sulfoxide or sulfone reaction solvent in a ratio of from about 10:1 to about 1:1 by weight based on the combined weight of the azeotrope former and reaction solvent.
- a solvent mixture comprising an azeotrope former and a sulfoxide or sulfone reaction solvent in a ratio of from about 10:1 to about 1:1 by weight based on the combined weight of the azeotrope former and reaction solvent.
- the water and hydrated alkali metal double salt of a dihydric phenol are preferentially dissolved in the sulfoxide or sulfone reaction solvent phase and the dihalobenzenoid compound is preferentially dissolved in the azeotrope former phase.
- the initial ratio of azeotrope former to reaction solvent is critical in this respect because with lesser amounts of azeotrope former, two liquid phases are not formed and undesirable hydrolysis of the dihalobenzenoid compound occurs. Only when the ratios specified are used does a phase separation occur which isolates the dihalobenzenoid compound from hydrolysis by the water in the system.
- the water in the system be removed as quickly as possible, usually by refluxing the mixture at about the boiling point of the azeotrope former until substantially all of the water is removed.
- the dehydrated alkali metal double salt which is insoluble in the reaction solvent at the reflux temperatures, precipitates.
- the fact that all the water has been removed is usually signaled by no further precipitate formation, no further azeotrope formation, and the formation of one liquid phase when miscible liquids are used.
- excess azeotrope former is removed by distillation until the ratio of azeotrope former to sulfoxide or sulfone reaction solvent is about 1:1 to 1:10. Only when the amount of azeotrope former is reduced to within these ratios, does significant polymerization occur.
- the residuum of the dihydric phenol of these alkali metal salts is not narrowly critical. It can be, for instance, a mononuclear phenylene group as results from hydroquinone and resorcinol, or it may be a di- or polynuclear residuum. Likewise the residuum be substituted with other inert nuclear substituents such as halogen, alkyl, alkoxy and like inert substituents.
- the dihydric phenol should be a weakly acidic dinuclear phenol, such as, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, such as, the 2,2- bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)2-phenyl ethane, bis(4-hydroxyphenyl)methane, or the chlorinated derivatives containing one or two chlorines on each aromatic ring.
- the dihydric phenol should be a weakly acidic dinuclear phenol, such as, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, such as, the 2,2- bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)2-phenyl ethane, bis(4-hydroxyphenyl)methane, or the chlorinated derivatives containing one or two chlorines on each aromatic ring.
- These materials are the bisphenols of a symmetrical or unsymmetrical joining group, as, for example, ether oxygen (--O--), ##STR9## or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue such as, for example, the bisphenol of acetophenone, the bisphenol of benzophenone, the bisphenol of vinyl cyclohexene, the bisphenol of alpha-pinene, and the like bisphenols where the hydroxyphenyl groups are bound to the same or different carbon atoms of an organic linking group.
- Such dinuclear phenols can be characterized as having the structure: ##STR10## wherein Ar is an aromatic group and preferably is a phenylene group, Y and Y 1 can be the same or different inert substituent groups as alkyl groups having from 1 to 4 carbon atoms, halogen atoms, i.e., fluorine, chlorine, bromine or iodine, or alkoxy radicals having from 1 to 4 carbon atoms, m and z are integers having a value from 0 to 4, inclusive, and R is representative of a bond between aromatic carbon atoms as in dihydroxydiphenyl, or is a divalent radical, including for example, inorganic radicals as ##STR11## --O--, --S--, --S--S--, --SO 2 --, and divalent organic hydrocarbon radicals such as alkylene, alkylidene, cycloaliphatic, or the halogen, alkyl, aryl or like substituted alkylene,
- Examples of specific substituted dihydric polynuclear phenols include among others: the substituted bis-(hydroxylphenyl)alkanes, such as, 2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenyl methane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-2-chlorphenyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)propane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxypheny
- the --E-- or --E'-- residuum in the polymer structure can actually be the same or different aromatic residue.
- E or E' when defined as being the "residuum of the dihydric phenol" of course refers to the residue of the dihydric phenol after the removal of the two aromatic hydroxyl groups.
- these polyarylene polyethers contain recurrding groups of the residuum of the dihydric phenol and the residuum of the benzenoid compound bonded through aromatic ether oxygen atoms.
- any dihalobenzenoid compound or mixture of dihalobenzenoid compounds can be employed in the invention which compound or compounds has the two halogens bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho and para to the halogen group.
- the dihalobenzenoid compound can be either mononuclear where the halogens are attached to the same benzenoid ring or poly nuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.
- Any of the halogens may be the reactive halogen substituents on the benzenoid compounds.
- Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpensiveness. Fluorine substituted benzenoid compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about 1 percent and preferably below 0.5 percent for best results.
- any electron withdrawing group can be employed as the activator group in these compounds. It should be, of course, inert to the reaction, but otherwise its structure is not critical. Preferred are the strong activating groups such as the sulfone group ##STR12## bonding two halogen substituted benzenoid nuclei as in the 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, although such other strong withdrawing groups can also be used. The more powerful of the electron withdrawing groups give the fastest reactions and hence are preferred.
- the ring contain no electron supplying groups on the same benzenoid nucleus as the halogen; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated.
- all of the substituents on the benzenoid nucleus are either hydrogen (zero electron withdrawing), or other groups having a positive sigma value [as set forth in J. F. Bunnett, Chem. Rev. 49,273 (1951), and Quart. Rev., 12, 1 (1958)].
- the electron withdrawing group of the dihalobenzenoid compound can function either through the resonance of the aromatic ring, as indicated by those groups having a high sigma value, i.e., above about +0.7, or by induction as in perfluoro compounds and like electron sinks.
- the activating group should have a high sigma value, preferably above 1.0, although sufficient activity to promote the reaction is evidence in those groups having a sigma value above 0.7, although the reaction rate with such a low powered electron withdrawing group may be somewhat low.
- the activating group can be basically either of two types:
- (b) divalent group which can activate displacement of halogens on two different rings such as the sulfone group ##STR13## the carbonyl group ##STR14## the vinyl group ##STR15## the sulfoxide group ##STR16## the azo-group --N ⁇ N; the saturated fluorocarbon groups --CF 2 CF 2 --; organic phosphine oxides ##STR17## wherein R is a hydrocarbon group, and the ethylidene group ##STR18## where X can be hydrogen or halogen or which can activate halogens on the same ring such as with difluorobenzoquinone, 1,4- or 1,5- or 1,8-difluoroanthraquinone.
- a plurality of electron withdrawing groups can be employed if desired, including electron withdrawing groups having a sigma value below about +0.7, provided the cumulative sigma influence on each of the reactive halogen groups of the halobenzenoid compound is at least about +0.7.
- the polymers may be made with mixtures of two or more dihalobenzenoid compounds each of which has this structure, and which may have different electron withdrawing groups.
- E or E' when defined as being the "residuum of the benzenoid compound” refers to the aromatic or benzenoid residue of the compound after the removal of the halogen atoms on the benzenoid nucleus.
- Dimethylsulfoxide decomposes at its boiling point, i.e., about 189° C.; it is desirable to keep the reaction temperature below this to avoid such problems when employing this solvent.
- reaction temperature can be effectively increased even above the normal boiling point of the solvent or mixture of solvents by the use of pressure in the system.
- pressure in the system can be used for most practical reactions contemplated herein, atmospheric pressures are quite adequate, though if desired pressures as high as 1000 psig or more can be employed.
- the molecular weight of the polymer can be easily controlled in this process by the addition of a precipitating solvent to the reaction mixture when the desired reduced viscosity of the resin is secured or when the indicated viscosity of the polymerization mass is high enough to indicate the desired molecular weights are achieved. It is also possible to terminate the growing polymer chain by the addition of a monofunctional chain stopper, such as an alkyl halide or other suitable coreactant.
- a monofunctional chain stopper such as an alkyl halide or other suitable coreactant.
- the molecular weight of the end-capped resins is indicated by reduced viscosity in indicated solvents.
- the viscosity of a resin solution bears a direct relationship to the weight average molecular size of the resin chains, and can be used to characterize the degree of polymerization.
- the reduced viscosity values used herein are of significance only relative to each other rather than in any absolute sense, and for this reason other polyether-solvent systems can be employed as an indication of the relative molecular weight of these resins.
- solvents other than chloroform are employed, the required average molecular size relationship can readily be established by reference to the reduced viscosity values defined herein even though the numerical reduced viscosity values of the alternative system may be different.
- the preferred solvent is dimethylacetamide; the process uses K 2 CO 3 .
- thermosetting resins of the invention are those polysulfone where the thermosetting polyarylene polyether resin is composed of recurring units having the formula: ##STR19## wherein R is hydrogen, lower alkyl, lower aryl and halogen substituted lower alkyl and lower aryl groups. Most preferably R is methyl.
- the lower alkyl groups have from 1 to 4 carbon atoms.
- the polysulfone-vinyl reactive resins or PSF-VR are the above end-capped resins when R is methyl and the end-capping moieties are alkylene, aralkylene or cycloalkylene moieties.
- polysulfone-silane reactive resins or PSF-SR refer to silane end-capped polyarylene polyether polymers made from bisphenol-A and dihalodiphenylsulfone. (See U.S. Pat. No. 4,093,600 and 4,183,874.)
- the cured polysulfonevinyl reactive resins exhibit a markedly improved environmental stress-crack resistance and a better dimensional stability at elevated temperatures than those of the thermoplastic polysulfone.
- the polysulfone-vinyl reactive resin is prepared by a two step process, namely, polymerization followed by end-capping.
- bisphenol A and dihalodiphenylsulfone are polymerized in the presence of an alkali metal hydroxide, an alkali metal oxide and/or ammonium hydroxide.
- a deficient amount of sulfone monomer is used during the polymerization to produce the desired sodium phenate terminated oligomers.
- polysulfone-vinyl reactive resin of a wide range of molecular weights can be prepared.
- the preferred alkali metal hydroxide is sodium hydroxide.
- Useful alkali metal hydroxides include lithium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.
- Useful alkali metal oxides include sodium oxide, lithium oxide, potassium oxide, rubidium oxide and cesium hydroxide. Ammonium hydroxide is also useful in the polymerization step in place of the sodium hydroxide.
- the polymerization step is carried out at a temperature preferably between 163° and 165° C. in a mixed solvent composed of dimethyl sulfoxide (DMSO) and monochlorobenzene (MCB), although any other suitable solvent(s) such as dimethyl acetamide (DMAC) can also be employed.
- DMSO dimethyl sulfoxide
- MBC monochlorobenzene
- Any suitable polymerization temperature e.g., 120° to 185° C.
- Precautions which are normally observed during the preparation of standard polysulfone are equally important here to achieve quality products. Of particular importance is the caustic charge which affects both the "color” and "stability" of the finished polysulfone-vinyl reactive resin in addition to its anticipated effect on the molecular weight and composition of the latter.
- Useful polar solvents include: alcohols, such as, methanol, ethanol, n-propyl alcohol, n-butyl alcohol, amyl alcohol, isopropyl alcohol, sec-butyl alcohol, isobutyl alcohol and 4-methyl 2-pentanol; ethers, such as ethyl ether, diethyl Cellosolve and butyl ether; aldehydes, such as, benzaldehyde and furfural; triethyl phosphate; and amides, such as, N,N-dimethyl formamide, acetamide and butramide.
- alcohols such as, methanol, ethanol, n-propyl alcohol, n-butyl alcohol, amyl alcohol, isopropyl alcohol, sec-butyl alcohol, isobutyl alcohol and 4-methyl 2-pentanol
- ethers such as ethyl ether, diethyl Cellosolve and butyl ether
- the alkali oxy (e.g., NaO--) end groups of the polysulfone are reacted with a halo organo compound containing a terminal or near terminal unsaturated group.
- the compounds used for end-capping or terminating are halogenated, unsaturated compounds.
- the end-capping reagents are described by the generic formula:
- X is a halogen, preferably chlorine
- Z is an unsaturated organic radical. More specifically, Z is usually a reactive, unsaturated radical having an alkylene, aralkylene or cycloalkylene moiety (linked to the halogen). Most halophenyl compounds have limited reactivity.
- Examples of the preferred end-capping reagents are allyl chloride, 2-chloroethylacrylate, 2-chloroethylmethacrylate, chloromethyldimethylvinylsilane, vinyl benzyl chloride and 2-chloroethyl vinyl ether.
- the halo organo compound reacts like an alkyl halogen with the alkali oxy end groups.
- end-capping is preferably done at a temperature of 115° to 120° C., no deleterious effect was usually evident even when the end-capping was performed at the preferred polymerization temperature which is from 163° to 165° C. Because of a much greater reaction rate at the latter temperature, the required reaction time is shortened drastically. Apparently a more complete reaction also results at the high temperature levels due to lower viscosities. Any suitable temperature can be used in the end-capping step.
- anhydrous condition during the end-capping stage is used whereby premature gelation of the polysulfone-vinyl reactive resin is normally not a problem in the reactor.
- the reaction mixture should be neutral which can be readily diluted with dry monochlorobenzene (or other suitable solvent) and filtered without difficulty.
- the presence of residual alkalinity which may result from either a deficiency in end-capping reagent charged or an incompletion in reaction, can cause problems during subsequent filtering when the polymer solution is exposed to either atmospheric moisture and/or wet diluent. For this reason a speedy product recovery is recommended whenever the above circumstance is present or suspected.
- the preferred (average) molecular weight of the polysulfone-vinyl reactive resin is between 5,000 and 15,000, although higher and lower molecular weights are within the scope of the invention.
- the polysulfone-vinyl reactive resin can range in size from oligomer to polymer.
- the average molecular weight of the polysulfone-vinyl reactive resin can be determined by the NMR technique.
- the polysulfone-vinyl reactive resin can be separated or recovered from the reaction mixture by any appropriate method, but the coagulation method and the melt recovery process are preferred Recovery by coagulation is normally done in isopropanol (or methanol).
- the melt recovery production process involves removing the solvents by passing the polymer solution through a recovery system consisting of a concentrator, a devolatilizer and a Marshall mill.
- polysulfone-silane reactive resins are outside of the scope of the invention, they are frequently used herein for comparitive purposes.
- the polysulfone-silane reactive resins are structurally very similar to the polysulfone-vinyl reactive resins of the invention, except for the end-capping by reaction with silane groups such as 3-chloropropyltrimethoxysilane.
- the production process is very similar for the two types of end-capped polysulfones.
- the polysulfone-silane reactive resins have been prepared in a broad range of molecular weights by varying the monomer feed ratio in the synthesis of the oligomers.
- the polysulfone-silane reactive resins have excellent hydrolytic stability in bulk form below their glass transition temperature. They can even be suspended in water without premature gelation. Cross-linking occurs readily above the glass transition temperature, and the cure rate can be further increased by prehydrolysis of the silylalkoxy end groups or by the use of catalysts.
- Cross-linked polysulfone-silane reactive resins have mechanical and electrical properties comparable to those of standard polysulfone. Cured polysulfone-silane reactive may enable higher use temperature limits than thermoplastic polysulfone resins, and large improvements over such thermoplastic polysulfone resins are found in their solvent resistance (environmental stress crack resistance). Also, due to the silane end groups, a built-in bonding capability exists towards many inorganic and metallic surfaces
- the reaction temperature is kept below 125° C. during the end-capping step and the system is kept under positive nitrogen pressure throughout.
- the polysulfone-vinyl reactive resins are usually easier to handle than polysulfone-silane reactive resins during preparation. Once the end-capping reaction is complete, the polysulfone-vinyl reactive resins may be exposed to water or wet solvent without being affected. The only exceptions, however, are the polysulfone-vinyl reactive resins having methacryloxy or acryloxy end groups which are hydrolized readily by moisture. For this reason, the chloroalkyl esters of such are preferred.
- the end-groups of all of the polysulfone-vinyl reactive resins shown in Table I are monofunctional. This difference requires that a precise stoichiometry of the reactants be maintained in order to produce the desire curable product, that is, a completely end-capped resin. When there is either an excess amount of bisphenol A or a deficiency in caustic charge (NaOH), a lower end-capping efficiency will result.
- the molecular weights of the polysulfone-vinyl reactive resins are controlled by adjusting the stoichiometry cf mononers in the feed. Using reduced viscosity (R.V.) as a measure of the molecular weight, the sulfone bisphenol-A molar ratios used in the feed are plotted against the deduced viscosity values of a series of vinyl benzyloxy end-capping polysulfone-vinyl reactive resins in FIG. 3. The other polysulfone-vinyl reactive resins (not shown in FIG. 3) follow roughly the same relationship.
- R.V. reduced viscosity
- Polysulfone-vinyl reactive resins are compositionally identical to the polysulfone-silane reactive resins except the end-groups. Consequently, the physical properties of the two types of resins are quite similar even though they cure by two distinctively different mechanisms. A comparison of the properties of these two resins is illustrated in Table I below.
- the thermal stability of the polysulfone-vinyl reactive resins apparently is much influenced by the nature of the end groups. Resins end-capped with the methacryloxy ethoxy groups were found to retain their thermoplasticity upon repeated thermal abuses at elevated temperatures, while those having the vinyl benzyloxy end groups would advance under similar conditions. This difference in behavior is consistent in the fact that, while the methacrylates are known to be fairly stable (thermally) in the absence of an initiator, the styrene monomers will undergo thermal-initiated polymerization--see W. R. Sorenson and T. W. Campbell, "Preparative Methods of Polymer Chemistry", 2nd Edition, Interscience (1968), pp. 210 and 253.
- the polysulfone-vinyl reactive resins are not subject to hydrolysis under normal conditions. They are therefore more tolerant of water or alkaline contaminates than the polysulfone-silane reactive resins.
- the polysulfone-vinyl reactive resins share the common unique feature with the polysulfone-silane reactive resins in exhibiting excellent stability at ambient temperatures. This phenomenon has been attributed to the high glass transition temperature of the polysulfone backbone which severely restrictsthe mobility of the end groups. Curing of the polysulfone-vinyl reactive resins is effected, however, by heating above the glass transition temperature of polysulfone, usually in the presence of a free radical initiator.
- the preferred free radical initiators are the peroxides, and the preferred peroxide is dicumyl peroxide.
- useful peroxides are the dialkyl peroxides, such as, di-t-butyl peroxide, lauroyl peroxide, decanoyl peroxide, 2-methylpentanoyl peroxide, acetyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy-hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, the diaryl peroxides, such as, benzoyl peroxide, the alkaryl peroxides, such as, dicumyl peroxide, the sulfonyl peroxides, such as acetyl cyclohexysulfonyl peroxide and acetyl sec-heptylsulfonyl peroxide, the peresters, such as
- the organometallic peroxides such as, vinyl tris(t-butyl peroxy)silane
- the hydroperoxides such as, t-butyl hydroperoxide and cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and 2,5-dihydroperoxy-2,5-dimethylhexane
- the azo compounds such as, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile).
- a polysulfone-vinyl reactive resin will vary greatly, depending on the type of end groups employed. Those having alloxy or vinyl ether ethoxy end groups react with difficulty, those terminated with either methacryloxy ethoxy or acryloxy ethoxy end groups are reactive but the presence of an initiator is usually necessary, and those with vinyl benzyloxy end groups will react upon thermal initation.
- a neat (pure) polysulfone-vinyl reactive resin requires prolonged heating at temperatures above the glass transitional temperature of polysulfone to reach a high degree of cross-linking.
- the cure rate can be accelerated by the addition of a peroxide. This approach, however, is often hampered by the lack of a suitable peroxide which will endure the high process temperature necessary for these resins.
- a neat polysulfone-vinyl reactive resin is not curable by either electron beam or U. V. radiation due to a restricted molecular mobility.
- polysulfone-vinyl reactive (PSF-VR) resins are soluble in styrene monomer over the entire compositional range, and that the resultant polymer/comonomer binder system will polymerize and yield a true copolymer.
- the latter may be either a thermoset or thermoplastic depending on the polysulfone-vinyl reactive/styrene feed ratio, and the method of polymerization. Bulk polymerization usually leads to cross-linked products while solution polymerization at low polysulfone-vinyl reactive concentrations often produces soluble copolymers.
- a polysulfone-vinyl reactive resin/styrene binder system is not only peroxide curable, it also can be cured by exposure to electron beahm or U. V. radiation in the presence of a photo-sensitizer. In the latter cases, styrene also acts as a diluent for the polysulfone-vinyl reactive resin to provide the necessary mobility at ambient temperatures.
- polysulfone-vinyl reactive resins can be mixed and cured with a variety of other comonomers to produce copolymers having a broad range of thermal and mechanical properties.
- This approach not only permits the use of polysulfone-vinyl reactive resins for various polymer modification purposes but also provides an attractive may of reducing the cost of the resin through compounding with cheaper comonomers.
- polysulfone-vinyl reactive resins of various initial molecular weights, polysulfone-vinyl reactive resin/comonomer binder systems having different cross-linking densities as well as polysulfone block lengths can be prepared.
- polysulfone-vinyl reactive resins offer a number of advantages: (a) the formulation is rendered curable b conventional methods; (b) property modifications are permitted through a wide selection of comonomers; and (c) flexibility is allowed in meeting the cost/performance requirements for different end-use areas.
- polysulfone-vinyl reactive resins exhibit a marked improvement in environmental stress-crack resistance over the regular polysulfone, similar to that of the polysulfone-silane reactive resins. The degree of improvement is usually parallel to the increase in cross-linking density of the cured material.
- thermoplastic resins can be compression-molded to clear or slightly hazy plaques; they are usually brittle and resemble polystyrene.
- Polysulfone has exceptional chemical resistance, particularly in a strong alkaline environment. This quality makes the polysulfone-vinyl reactive resin a suitable matrix resin for fabricating corrosion-resistant composite materials. Polysulfone-vinyl reactive resins, while retaining most of the polysulfone's properties, exhibit a number of additional features which are highly desirable for the coating applications. Because of their oligomeric nature, they are characterized by high solubilities in polysulfone-soluble solvents, low melting points and good melt flow characteristics which make them suitable for a variety of fabrication processes, particularly the solution and power coating techniques.
- the reactive end-groups of the polysulfone-vinyl reactive resins permit curing by either heat, peroxide, U.V., electon-beam radiation or other suitable energy sources. Once cured, the coating is transformed to a clear, rigid, tough thermoset possessing excellent solvent, chemical and thermal resistance.
- polysulfone-vinyl reactive resins lack inherent bonding capabilities. Better adhesion, however, can be achieved by modifying with say unsaturated silane or silyl peroxide adhesion promoters or suitable polar comonomers.
- the polysulfone-vinyl reactive resins can be for a variety of coating applications including magnet wire coatings, photocurable coatings and and powder coatings.
- polysulfone-vinyl reactive resins can be modified to acquire improved properties over the parent polysulfone. This is exemplified by the broad spectrum of polysulfone-vinyl reactive comonomer binder systems shown in Tables VI to X below.
- the thermoplastic versions of the polysulfone-vinyl reactive resins are useful, for instance, to bring out compatibility between polysulfone and inexpensive polystyrene.
- the polysulfone-vinyl reactive resins are also useful as modifiers for other (reactive) polymers to impart certain desirable polysulfone properties.
- the resulting compositions can be either copolymers or interpenetrating polymeric networks (IPN's).
- IPN's interpenetrating polymeric networks
- the polysulfone-vinyl reactive resins can be used for formulating photocurable printing plates and for making membranes to take advantage of their mechanical rigidity, and chemical resistance; porosity in the membrane can be readily developed by solvent leaching upon curing.
- the polysulfone-vinyl reactive/comonomer binder system of the invention is often a cross-linked copolymer produced by chain extension with a suitable comonomer from the reactive end-groups of the polysulfone-vinyl reactive resin. So the polysulfone-vinyl reactive/comonomer binder systems should be handled like a thermoset. This behavior undoubtedly restricts its melt processability, but it also provides several useful properties being a thermoset. The broad spectrum of comonomers available provide a great deal of freedom to the formulation of such binder systems. Styrene, acrylonitrile and divinyl benzene are among the preferred comonomers for this purpose.
- Vinylbenzylchloride is the preferred end-capping compound because of its commercial ayailability, attractive economy and good reactivity.
- a drawback of this reagent is that polysulfone-vinyl reactive resins having the vinyl benzyloxy end-groups are subject to thermal-initiated polymerization. This behavior complicates the melt recovery process employed for the standard polysulfone as well as limits the operating altitude during melt fabrications. This difficulty can be resolvable by the addition of a suitable inhibitor.
- thermosetting composition with excellent solvent resistance. At 200 psi, this material did not rupture after twenty-five minutes of exposure of acetone, toluene, and trichloroethylene. Although compression molded plaques were brittle the high cure speed and good flow behavior should make this material of interest in coating applications (e.g., powder coating).
- thermosetting polysulfone-vinyl reactive resin The properties of the thermosetting polysulfone-vinyl reactive resin and their blends with some epoxy resins are listed in Table A below:
- the 5,000 MW polysulfone-vinyl reactive resin/epoxy system exhibited excellent flow characteristics, solvent resistance, a high glass transition temperature (Tg) and good tensile properties.
- the comonomer having at least one monovalent unsaturated organo radical should be one which is not gaseous at ambient conditions.
- Such comonomer preferably also is compatible with the polysulfone-vinyl reactive monomer.
- compatibility means that such comonomer has a reasonable degree of solubility in the polysulfone-vinyl reactive. For example, styrene is completely soluble in the polysulfone-vinyl reactive monomers, so styrene is very compatible with the polysulfone vinyl reactive monomers.
- Acrylates have some solubility in the polysulfone-vinyl reactive monomers, so acrylates have some compatibility with the polysulfone-vinyl reactive monomers. Acrylonitriles also have a good degree of compatibility.
- vinyl monomer broadly means a monomer containing at least one of the groups vinyl, vinylidene or vinylene. Vinyl is H 2 C ⁇ CH--; vinylidene is H 2 C ⁇ C ⁇ ; and vinylene is --CH ⁇ CH--. Each of such terms includes substituted groups. (Broadly monomers having at least one monovalent reactive unsaturated organo moiety are used as the comonomers.)
- the monovinyl monomer is a vinyl monomer having the formula:
- R is a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, an alkylcarboxyl group having from 2 to 12, preferably from 2 to 10 carbon atoms, a nitrile group, a halogen atom, preferably a chlorine atom, a phenyl group, or an alkoxycarbonyl group having from 2 to 12, preferably from 2 to 9 carbon atoms.
- a single vinyl monomer as well as mixtures of vinyl monomers can be used.
- the compatible monovinyl monomers include: styrene; ⁇ -substituted styrenes, i.e. ##STR21## wherein R 2 is alkyl and/or alkoxy having 1 to 6 carbon atoms; substituted styrene, i.e., R n C 6 H 5-n CH ⁇ CH 2 , wherein n is 1 to 5, R is chlorine, fluorine, bromine, iodine, alkyl having 1 to 6 carbom atoms, alkoxy having 1 to 6 carbon, --CN or --NO 2 ; alkylacrylates wherein the alkyl has 1 to 11 carbons, preferably 1 to 6 carbons; alkoxyacrylates, wherein the alkyl has 1 to 11 carbons, preferably 1 to 6 carbons; alkyl methacrylates, wherein the alkyl has 1 to 10 carbons, preferably 1 to 6 carbons; alkoxy methacrylates, wherein the alkyl has 1 to 10 carbons,
- Examples of useful monovinyl monomers include: vinyl esters of aliphatic monocarboxylic acids, such as, vinyl acetate, vinyl propionate, vinyl laurate, vinyl decanates, vinyl butyrate, vinyl isobutyrate, vinyl dimethylpropionate, vinyl ethylbutyrate, vinyl valerate, vinyl caproate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl ⁇ -phenylbutyrate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, and vinyl naphthoate; vinyl ethers, such as, n-butyl vinyl ether, isobutyl vinyl ether, vinyl propyl ether, vinyl 2-ethylhexyl ether, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhe
- Examples of further useful monovinyl monomers include: acrylic acid esters of monohydric alkanols, such as, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoetbyl acrylate, 2-nitroethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chloro cyclohexyl acrylate,
- the compatible divinyl monomers include conjugated dienes and substituted divinyl acryl monomers (preferably p-divinyl-benzene) and diallyl monomers.
- divinyl monomers examples include: o-, m- and p-divinylbenzene; divinyl ether or divinyl oxide [(CH 2 ⁇ CH) 2 O], 3,9-divinylspirobi-meta-dioxane, divinyl sulfone (CH 2 ⁇ CHSO 2 CH ⁇ CH 2 ); dienes or conjugated diolefins, such as, propadiene, 1,3-butadiene, 1,3-pentadiene (cis and trans), 1,5-hexadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-methylbutadiene; dicyclopentadiene; 2-chloro-1-3-butadiene; and diallyl monomers, such as, diallyl fumarate, diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl digylcollate, diallyl chlorendate, diallyl adipate and diallyl
- Comonomers having three vinyl or allyl reactive moieties are particularly useful in the crosslinking version of the invention.
- Such comonomers can be termed crosslinking boosters, as they speed up the crosslinking and give better results, but as they are usually expensive, cheaper difunctional comonomers are used as the main crosslinkers.
- the vinyl reactive moieties of the end-capped polyarylene polyether and the vinyl reactive moieties of the comonomers can be substituted, but the substituents (e.g., Cl) must not be directly on either of the double bond carbon atoms of the vinyl group (i.e., monovalent unsaturated organo group) unless the substituent is alkyl or alkoxy.
- additives can be used in the homopolymerization and copolymerization.
- Wetting and dispersing agents and thickening agents e.g., carboxymethyl cellulose
- Plasticizers e.g., dibutyl phthalate
- the amounts added will vary upon the desired results, but preferably each additive is used in the range of about 0.1 to 10 percent by weight.
- Polymerization can be achieved by the use of free radical initiators, with or without the aid of heat, or by the use of actinic radiation, such as, ultraviolet radiation.
- the free radical initiator is a peroxide
- the preferred peroxide is dicumyl peroxide.
- the polymerization temperature effectively is between 25° (ambient temperature) and 300° C. and preferably is between 100° and 250° C.
- the co- or homopolymerization can be effected using slurry suspension or emulsion type polymerization (with conventional aqueous and non-aqueous solvents and liquid carriers).
- the invention includes oligomers curable by the free radical mechanism. This is realized by terminating, for example, the polysulfone chains with reactive unsaturated end-groups.
- the polysulfone-vinyl reactive resins resemble the silane-reactive counterparts in many physical and mechanical properties, but they do not, however, possess adhesive property.
- the polysulfone-vinyl reactive resins are soluble in styrene, and will copolymerize to give a copolymer (usually thermoset) intermediate in Tg.
- Such polysulfone-vinyl reactive resin comonomer binder system greatly expands the flexibility in meeting the cost/performance requirements for different potential end-uses.
- the polysulfone-vinyl reactive resins uses include corrosion-resistance maxtrix resins or additives, photocurable coatings, powder coatings, magnet wire coatings, polysulfone modifications and fiber reinforced structural composites.
- corrosion-resistance maxtrix resins or additives include corrosion-resistance maxtrix resins or additives, photocurable coatings, powder coatings, magnet wire coatings, polysulfone modifications and fiber reinforced structural composites.
- the data, advantages, methods, etc., concerning the polysulfone-vinyl reactive resins of the invention set out herein is equally applicable to the generic end-capped polyarylene polyether resins of the invention.
- V HCl volume of HCl/DMSO used in ml
- P s purity of end-capping reagent.
- DMSO dimethyl sulfoxide
- This information is needed for determining the amount of reagent required for the end-capping reaction.
- a titration method is used for this purpose.
- a small sample (about 2 to 3 gm) of the reaction mixture is quickly taken from the vessel and placed in a 250 ml Erlenmeyer flask. The sample is weighed and a 50 ml solution of DMSO/MCB (1/1) is introduced (MCB is monochlorobenzene). The sample solution is heated gently on a hot plate until dissolution is complete. A drop of bromocresol purple indicator (0.5 percent in methanol) is added and the sample is titrated with a 0.1N HCL solution (in DMSO) to a yellow end point (pH 5.2 to 6.8). Duplicate tests should be made.
- a 1 to 2 gm sample of the reaction mixture is introduced into a 250 ml Erlenmeyer flask containing a 50 ml solution of DMSO/MCB (1/1). The sample solution is heated on a hot plate until dissolution is complete. Two drops of the bromocresol purple solution are added. The reaction is complete if the indicator turns greenish yellow or yellow. Otherwise, the color will be blue indicating the presence of unreacted phenolate end groups.
- T g glass transition temperature
- DCS Differential Scanning Calorimeter; the procedure for using it is described in A. Duswalt, "Industrial Research," July 1975, pp. 42-45.
- Comparable values can also be obtained from the temperature-modulus data measured with an Instron machine at a heating rate of 1.5° C. per minute.
- phase transition of a polysulfone-vinyl reactive resin can be visually observed. This test is useful for a rapid but rough identification of a polysulfone-vinyl reactive resin.
- the number average molecular weight (Mn) of the polysulfone-vinyl reactive resins is determined by NMR technique using a Varian 100 MHZ NMR Instrument. Assuming the polysulfone-vinyl reactive resins are completely endcapped, i.e., each molecule is terminated with two unsaturated organo end groups, and there is no hydrolysis of the end groups, they are represented by the following general formula: ##STR22## wherein n is the number average degree of polymerization.
- the peroxide usually DiCup
- DiCup was dissolved in the liquid comonomer, and was subsequently mixed with the polysulfone-vinyl reactive resin fluff.
- a common solvent of low boiling point such as acetone
- the solvent was removed by air drying. The latter method usually provides a more uniform mixture, but some comonomer may be lost due to evaporation.
- Sample Preparation--A 4" ⁇ 4"30 mil plaque was employed for the electron-beam curing.
- the plaque was prepared by compression molding of a thoroughly blended mixture of the polysulfone-vinyl reactive resin and comonomer. A mild molding temperature, usually around 160° C., was used to prevent premature gellation of the formulation.
- Irradiation--A two-million volt van de Graaf electron accelerator was used as the source of electron beam radiation. Different irradiation doses were achieved by varying the exposure time.
- Sample Preparation--A formulation usually containing a polysulfone-vinyl reactive (PSF-VR) resin, a comonomer and a photo-initiator, was thoroughly mixed and was compression-molded to a 10 mil thick film. By using a molding temperature at or below 160° C., the resulting film remained thermoplastic. The film was mounted on an 8" ⁇ 8" ⁇ 5 mil aluminum foil to facilitate handling.
- PSF-VR polysulfone-vinyl reactive
- U.V. Irradiation--Linde photocuring equipment having a flux density of 160 watts/ft 2 , was used as the U.V. source. Different irradiation doses were accomplished by varying the conveyor speed and the number of passes through the irradiation zones.
- the gel contents of the cured polysulfone-vinyl reactive resin samples were measured by solvent extraction in boiling chloroform.
- the data of percent extractables shown in Tables XVI and XVIII were determined in methylene chloride. The higher the cross-linking is,the greater the gel content and the lower the percent extractables.
- Swelling index may be related quantitatively to the cross-linking density of a given network structure.
- Table XVII and XVIII were values measured in methylene chloride and calculated according to the following equation: ##EQU2##
- Environmental stress-crack resistance data were measured at constant stress levels using an environment of solvent-saturated cotton swab attached to the specimen. Performance was rated on the basis of time elapsed before rupture at a given stress level.
- the desired amounts of polysulfone-vinyl reactive resin and freshly distilled styrene monomer were placed into a pyrex glass ampoule.
- a solution made of freshly distilled monochlorobenzene and benzoyl peroxide (1.67 mg. benzoyl peroxide/1 ml monochlorobenzene) was added so that the final solution contained 20 percent of reactants and 0.1 percent of benzoyl peroxide.
- the ampoule was degassed at liquid nitrogen temperature and was sealed under a nitrogen atmosphere. Polymerization was carried out at 80° C. for a period of 19 hrs. At the end of polymerization, the ampoule was opened and the polymer recovered by coagulation in isopropanol.
- the reduced viscosity is determined by the procedure of ASTM-D-2857 at a concentration of 0.2 grams of the resin in 100 milliliters of solution.
- Oxalic acid (10 g) was added to acidify the reaction, 2 liters of chlorobenzene was added to cut the viscosity and the solution was filtered to remove sodium chloride. The filtrate containing the product was washed seven times with 1.4 liters of water to remove the DMSO and the product was then recovered by processing through a vented extruder at 300° C. to afford 620 grams of pelletized, allyl-terminated polysulfone oligomer.
- a vinyl benzyl end-capped polysulfone (10,000 molecular weight) was prepared as in Example 2 above, except that in this preparation a hydroxy terminated polysulfone oligomer (10,000 molecular weight) was employed.
- the hydroxy terminated polysulfone oligomer was prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- the vinyl end-capped polymer was compression molded at 250° C. for 10 minutes.
- a 15 mil plaque exhibited a tensile modulus of 320,000 psi, a tensile strength of 11,000 psi, an elongation to break of 6 percent and a pendulum impact of 27 ft. lb./in. 3 .
- a significant resistance to trichloroethylene is useful in some electrical
- Allylic terminated polysulfone prepared as in Example 1 above was dissolved in methylene chloride solvent to provide a 10 percent solids-containing solution.
- methylene chloride solvent to provide a 10 percent solids-containing solution.
- Several steel "D" plates, 10 mils thick, were dip coated in this solution and dried at room temperature for 10 minutes which was followed first by, oven drying at 125° C. for 45 minutes and then by various high temperature oven time bake exposures at 315° to 320° C.
- the appropriate graph in FIG. 1 illustrates that the degree of solubility to methylene chloride is an inverse function of bake time exposure in an oven at 315° to 320° C. Similar extraction data following the identical procedure outlined above was obtained for glass and chrome substrates coated allylic terminated polysulfone (prepared as in Example 1 above) and for controls which had P-1700 polysulfone coatings.
- the appropriate graph in FIG. 1 illustrates the methylene chloride solubility curve for the glass-plated substrates; and the graph in FIG. 2 illustrates the methylene chloride solubility curve for the chrome-plated substrates.
- the contol P-1700 did not show chlorinated solvent resistance whereas the allyl terminated and baked coating provides solvent resistance (chlorinated and acetone) yet may be readily removed with hot detergent solutions.
- the reaction mixture was brought to a temperature of 115° C., and a solution of vinyl benzyl chloride (the end-capping reagent) in 30 ml dry monochlorobenzene was introduced.
- the reaction was kept at this temperature for 90 min. until the bromocresol purple test became yellowish in color. Thereafter, the reaction was stopped, and the reaction mixture was cooled down to room temperature.
- the hazy, viscous solution was diluted with 600 ml of monochlorobenzene and was filtered to remove the salt.
- the 0.22 RV, 2-chloroethyl methacrylate end-capped polysulfone-vinyl reactive resin shown in Table IV is an example of low end-capping efficiency. Its deficiency is reflected by the higher than expected number average molecular weight (M n ) value calculated on the assumption of 100 percent end-capping efficiency. Such a resin may contain up to 30 percent of non-curable fraction as evidenced by solvent extraction test. When the above mentioned precautions are observed during the preparation, however, this difficulty may be largely alleviated.
- glass transition temperature (Tg) of a polysulfone-vinyl reactive resin increases with increasing molecular weight and, eventually, approaches that of the standard polysulfone.
- FIG. 4 shows the above relationship for a series of vinyl benzyloxy end-capped polysulfone-vinyl reactive resins.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- the hollow circles indicate the Tg values of the virgin samples.
- the virgin sample was heated to a temperature of 217° C., cooled, and then measured again to study the effect of thermal history. The second reading was often found to be several degrees higher, which is a sign of resin advancement. Above the Tg, there is a rubbery polymer; below the Tg, there is a glassy polymer.
- Polysulfone-vinyl reactive resins containing (a) vinyl ether ethoxy end-groups, (b) methacryloxy ethoxy end-groups and (c) vinyl benzyloxy end-groups were subjected to thermal abuse at several temperatures.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- Table V illustrates the differences in reactivities of such resins.
- the true loading of a comonomer in a test specimen may vary significantly from the value indicated. This is thought to be reflected by some erratic glass transitional temperature values. Roughly speaking, however, the glass transitional temperature of the cured compositions varied according to those of homopolymers derived from the corresponding comonomers as well as the comonomer loadings.
- the cured resins exhibited a markedly improved environmental stress-crack resistance and a better dimensional stability at elevated temperatures than those of the thermoplastic polysulfone.
- polysulfone-vinyl reactive resins of various initial molecular weights
- polysulfone-vinyl reactive comononer binder systems having different cross-linking densities as well as polysulfone block lengths can be prepared.
- the effect on the properties three compositions which are otherwise identical except for the above-mentioned aspects, are set out in Table IX below.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- the mechanical properties of the cured materials are similar.
- the environmental stress-crack resistance and residual moduli at 200° C. improves with decreasing initial molecular weights of the polysulfone-vinyl reactive resins; which is consistent with the anticipated direction of increasing cross-linking densities. Since the polysulfone-vinyl reactive and the styrene monomer are miscible in all proportions, such a binder system can be a free-flowing powder, a dough, a paste or a solution depending on the relative amount of styrene incorporated. Preliminary data showed that in all instances a copolymer composition was obtained. The glass transitional temperature of the latter went down with increasing amount of polystyrene blocks in the cured resin.
- polysulfone-vinyl reactive bearing the end reactive groups is necessary for cross-linking. Polysulfone alone or with comonomer will not crosslink without the vinyl reactive end groups.
- polysulfone-vinyl reactive resins exhibit a marked improvement in environmental stress-crack resistance over the regular polysulfone, similar to that of the polysulfone-silane reactive resins.
- the degree of improvement is usually parallel to the increase in cross-linking density of the cured material.
- Table XIII below where the environmental stress crack resistance of a series of cured polysulfone-vinyl reactive styrene resins are related to their swelling indices.
- the cross-linking density is expected to increase with a decrease in the initial molecular weight of the polysulfone-vinyl reactive, which is reflected by a lowering in the swelling index.
- the environmental stress-crack resistance data was measured at constant stress levels using an environment of solvent-saturated cotton swab attached to the specimen.
- the environmental stress-crack reistance of a cured polysulfone-vinyl reactive comonomer composition aIso depended on the type and loading of comonomer employed.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4 'dichlorodiphenyl sulfone as described in Example 1.
- Table XIV below sets out the environmental stress-crack resistance performance, in decreasing order, of 20 different types of matrices in toluene and trichloroethylene. Three of the more effective comonomers among those studied were divinyl benzene, acrylonitrile and styrene.
- the neat polysulfone-vinyl reactive resin also performed well upon cross-linking and is comparable to cross-linked polysulfone-silane reactive resin.
- styrene was the comonomer used, the resistance of the cured material to solvent-induced stress-crack deteriorated with increasing comonomer loadings.
- the polysulfone-vinyl reactive was found to be richer in the copolymer than in the feed. They are soluble in methyl ethyl ketone or toluene, which are non-solvents for the polysulfone-vinyl reactive homopolymers. The molecular weights of the products increased rapidly with increasing polysulfone-vinyl reactive/styrene charge ratios. These thermoplastic resins can be compression-molded to clear or slightly hazy plaques; they are usually brittle and resemble polystyrene.
- Examples 21 and 22 involve the cross-linking of the polysulfone-vinyl reactive resins.
- a methacryloxy ethoxy end-capped polysulfone-vinyl reactive resin having a reduced viscosity (R.V.) of 0.22 dl/g (measured in chloroform at 25° C.) and a number average molecular weight of 11,590 was treated thermally in the presence of dicumyl peroxide to produce a higher molecular weight polymer of a cured polymer composition.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- Table XVIII sets out the data.
- a vinyl benzyloxy end-capped polysulfone-vinyl reactive resin having a R. V. of 0.37 dl/g was compression molded at elevated temperatures in the presence of a radical initiator to produce a cross-linked polyarylether composition.
- the hydroxy terminated polysulfones which were vinyl end-capped were prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- Table XIX sets out the data.
- Example 23 Using the same apparatus as described in Example 23 but employing the following starting materials and reagents.
- the hydroxy terminated polysulfone was prepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.
- the end-capping reaction and product isolation were carried out following the procedures used in Example 23. 38 g of a white fluffy polysulfone-vinyl reactive polymer was recovered. It showed a reduced viscosity of 0.58 dl/gm in chloroform at 25° C.
- Example 23 Ten grams of the alloxy end-capped polysulfone resin prepared in Example 23 was placed between two sheets of aluminum foil and the assembly was pressed at 240° C. for a period of 15 minutes. T-peel test showed the peel strength between the aluminum foil and polysulfone to be between 4 to 8 lbs./in.
- An aluminum-polysulfone-aluminum joint was prepared with the alloxy terminated polysulfone resin prepared in Example 23 and aluminum Q-panels.
- the polysulfone-vinyl reactive resin adhesive layer was cured by adding 2 percent of each of 2,5-dimethyl-2,5-bis-(trimethyl-silylperoxy) hexane and triallylcyanurate in a manner as described in Example 26.
- the finished joint was measured for T-peel strength with an Instron machine at a cross-head speed of 2 inches per minute. The value was 5 to 6 lbs./in. Under similar conditions, joints made of standard polysulfone showed less than 2 lbs./in. peel strength.
- Alloxy terminated polysulfone resin prepared from Example 23 was molded at 210° C. to a 25 mil thick plaque. A set of lap-shear joints was subsequently made with the above plaque and titanium bars (1" ⁇ 4" ⁇ 55 mil). A peroxide initiator, vinyl tris-(t-butylperoxy) silane, was used to prime the surface of both the polysulfone-vinyl reactive resin layer and the titanium substrates. Curing was effected at 230° C. for a ten minute cycle. Lap-shear strength of the above joints was measured to be 880 psi.
- the polymer had the following structural formula: ##STR25## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 32 The same apparatus and procedure as in Example 32 was used with 25.03 grams of 4,4'-dihydroxydiphenyl sulfone (0.1 mole), 60 milliliters of DMSO, 85 milliliters of toluene and 16.04 grams of 49.90 per cent NaOH (0.2 mole).
- the bisphenol disodium salt was dehydrated as before and most of the toluene was distilled. The mixture was cooled.
- the polymer derived from bisphenol S was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 32 Into an apparatus similar to that described in Example 32 were placed 25.03 grams of 4,4'-dihydroxydiphenyl sulfone (0.1 mole), 70 milliliters of DMSO and 100 milliliters of toluene. Air was displaced by N 2 and 16.03 grams of 49.90 percent NaOH (0.2 mole) was added. The mixture was refluxed, removing water until no more was evident, and then toluene was distilled off to a pot temperature of 160° C. A solution of 24.15 grams of 4,4'-difluorodiphenyl sulfone (0.095 mole) and 33 milliliters of dry chlorobenzene were added. The mixture was heated with stirring at 160° to 170° C.
- the polymer (Bisphenol S polyether) was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 32 Into an apparatus like that described in Example 32 were placed 22.83 grams of Bisphenol A (0.1 mole), 70 milliliters of DMSO and 80 milliliters of toluene. Air was displaced by nitrogen and 15 85 grams of 50.48 percent NaOH (0.2 mole) was added. The mixture was refluxed, removing water until no more was evident, and then toluene was distilled off to a pot temperature of 150° C. A solution of 20.51 grams of 4,4'-difluorobenzophenone (0.095 mole) in 20 milliliters of dry chlorobenzene was gradually added. On adding the last increment of the difluorobenzophenone, the polymer viscosity became very high, but on continued heating at about 160° C.
- the mixture was refluxed for 3 to 4 hours, continuously removing the water contained in the reaction mixture as an azeotrope with benzene and distilling off enough of the latter to give a refluxing mixture at 130° to 135° C., consisting of the dipotassium salt of the 2,2-bis(4-hydroxyphenyl)propane and dimethylsulfoxide essentially free of water.
- the mixture was cooled and 14.35 grams (0.05 mole) of 4,4'-dichlorodiphenylsulfone was added followed by 40 ml. of anhydrous dimethylsulfoxide, all under nitrogen pressure.
- the mixture was heated to 130° C. and held at 130° to 140° C. with good stirring for 4 to 5 hours.
- the viscous, orange solution was poured into 300 ml. water, and rapidly circulating in a Waring Blender.
- the resultant finely divided white polymer was filtered and then dried in a vacuum oven at 110° C. for 16 hours.
- the yield was 22.2 g (100 percent) and the reaction was 99 percent complete based on a titration for residual base.
- the polymer had the following structural formula: ##STR26##
- the polymer was end-capped with allyl groups via the potassium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except 1,1-bis-(4-hydroxyphenyl)-1-phenylethane (bisphenol of acetophenone) was used as the dihydric phenol.
- the reaction time was 10 hours at 130° to 140° C. and the reduced viscosity in chloroform was 0.54.
- a solution of 0.5 g methyl chloride in 6 ml of dimethylsulfoxide was added at 90° to 100° C. to convert unreacted aryloxide end-groups to the more stable aryl methyl ether end-groups.
- the polymer had the following structural formula: ##STR27##
- the polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except that the dihydric phenol employed was 4,4'-dihydroxydiphenylmethane and the reaction temperature and time were 130° to 135° C. and 7 hours, respectively.
- the polymer had the following structural formula: ##STR28## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 1 using vinyl benzyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except hydroquinone was used as the dihydric phenol and reaction conducted at 130° to 140° C. for 6 hours.
- the polymer had the following structural formula: ##STR29##
- the polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except that 1,3-bis(p-hydroxyphenyl)-1-ethylcyclohexane (the bisphenol prepared by acid catalyzed condensation of 2 moles of phenol with one mole vinylcyclohexene) was used as the dihydric phenol. The reaction was conducted for 7 hours at 130° to 140° C.
- the polymer had the following structural formula: ##STR30##
- the polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except that the dihydric phenol was 1,1-bis(4-hydroxyphenyl)-2,2-dimethylethane (i.e., the bisphenol of isobutyraldehyde). The reaction was conducted for 7 hours at 130° to 135° C.
- the polymer had the following structural formula: ##STR31## The polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except that the dihydric phenol was 4,4'-dihydroxybenzophenone. The reaction was conducted for 41/2 hours at 135° to 145° C.
- the polymer had the following structural formula: ##STR32## The polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 36 This example was conducted using the procedure of Example 36, except the dihydric phenol was 4,4'-(dihydroxyphenyl) diphenylmethane (bisphenol of benzophenone). The reaction was conducted for 20 minutes at 110°-127° C.
- the polymer had the following structural formula: ##STR33## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- the reaction mixture was then warmed to about 130° C. for 3.5 hours during which time it became quite viscous.
- the mixture was cooled to 110° to 120° C. and methyl chloride bubbled in for a short time to methylate any unreacted phenoxide groups.
- the polymer had the following structural formula: ##STR34##
- the polymer was end-capped with allyl groups via the potassium phenolate end groups following the procedure of Example 1 using allyl chloride.
- the polymer had the following structural formula: ##STR35## The polymer was end-capped with vinyl benzyl groups via the potassium phenolate end groups following the procedure of Example 5 using vinyl benzyl chloride.
- Example 29 This example was conducted using essentially the procedure of Example 29, employing as one reactant, the dipotassium salt of hexafluorobisphenol-A having the structural formula: ##STR36##
- the polymer was end-capped with vinyl benzyl groups via the potrassium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 46 This example was conducted using substantially the procedure of Example 46, except that 4,4'-difluorobenzophenone was substituted for the 4,4'-difluorodiphenylsulfone.
- the polymer had the following structural formula: ##STR37## The polymer was end-capped with vinyl benzyl groups via the potassium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- the temperature of the reaction mass was rapidly dropped to about 150° to 160° C. and held there with stirring for about one hour. Gaseous methyl chloride was introduced until no more was absorbed. The mixture was diluted to 10 to 15 percent solids by adding chlorobenzene.
- the polymer ha the structural formula: ##STR38## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 48 was repeated except that in place of 4,4'-dichlorodiphenylsulfone, 32.0 g (0.1314 mole) of 4,4'-dichloroazobenzene was used.
- the polymer had the following structural formula: ##STR39## The polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 48 was repeated except that in place of the 1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 25.5 g (0.05 mole) of tetramethylene dibisphenol-A (the bisphenol prepared by condensation of 2 moles of phenol with 1,4-bis(p-isopropenyl phenyl) butane and the corresponding molecular quantities of the 4,4'-dichlorodiphenyl sulfone (14 4 g, 0.05 mole) and caustic (8.1 g of 12.46 me/g., 0.10 mole) were used.
- the polymer had the following structure: ##STR40##
- the polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 48 was repeated except that instead of the 1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 22.5 g (0.0985 mole) of bisphenol A was used in addition to 16.8 g (0.0329 mole of tetramethylene dibisphenol A.
- the polymer had the structural formula: ##STR41## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 48 was repeated except that instead of the 1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 22.5 g (0.0985 mole) of bisphenol A was used in addition to 6.7 g (0.033 mole) of 4,4'-dihydroxydiphenyl ether.
- the polymer had the structural formula: ##STR42## The polymer was end-capped with vinyl benzyl groups via the sodium phenolate end groups following the procedure of Example 2 using vinyl benzyl chloride.
- Example 48 was repeated except that in place of 4,4'-dichlorodiphenylsolfone, 61.17 g of 1,4-bis(p-chloro-N-methyl-benzene sulfonamido)butane, having the structural formula: ##STR43## (melting point 179.5°-180.5° C.) and prepared by the reaction of potassium p-chloro-N-methyl-benzenesulfonamide with 1,4-dichlorobutane, was used. The reaction time was 2 hours at about 160° C.
- the polymer had the structural formula: ##STR44## The polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- Example 48 was repeated except that in place of 4,4'-dichlorodiphenylsulfone, 57.2 g of piperazine bis-p-chlorobenzenesulfonamide having the structural formula: ##STR45## (melting point 324° to 325° C.) and prepared by reacting p-chloro-benzenesulfonyl) chloride with piperazine, was used.
- the polymerization time was 1 hour at 160° to 170° C.
- the polymer crystallized out on cooling the reaction mixture.
- the polymer had the structural formula: ##STR46##
- the polymer was end-capped with allyl groups via the sodium phenolate end groups following the procedure of Example 1 using allyl chloride.
- a 50/50 blend of the polysulfone-vinyl reactive resin of Example 1 and a commercial polysulfone was extruded with a 1-foot single-screw extruder operating at a temperature between 260° to 310° C., and was pelletized to give a uniform composition.
- the pellets were injection molded using a Van Dorne Injection Machine at 358° C.
- the barrel residence time was about 3 minutes, and the mold temperature was maintained at 115° C.
- the injection-molded parts were post-cured using either an air oven or an acid (or base) bath. For instance, a 21/2" ⁇ 1/2" ⁇ 1/8" specimen was heated in an air oven at 275° C. for a period of 35 minutes.
- the polysulfone-vinyl reactive resin (of Example 3) was compression molded at 220° C. (200 psi, 30 min.) to form a 20 mil thick plaque.
- the latter was laminated with a 4" ⁇ 1" ⁇ 1/16" titanium panel at an initial temperature of 220° C. and a finish temperature of 270° C.
- the total heating time lasted for 55 min., and only contact pressure was used.
Abstract
Z--polyarylene polyether chain--Z'
Description
Z--polyarylene polyether chanin--Z'
Z--O--E'--O--E).sub.n OZ'
Z--O--Ar).sub.n OZ'
Z--polyarylene polyether chain--Z'
Z--O--E'--O--E).sub.n OZ'
Z--O--Ar).sub.n OZ'
Z--polyarylene polyether chain--Z'
Z--O--E'--O--E).sub.n OZ'
Z--O--Ar).sub.n OZ'
R--S(O).sub.v --R
XZ
TABLE I ______________________________________ A COMPARISON BETWEEN PSF-VR.sup. (a) AND PSF-SR.sup. (b) RESINS Property PSF-VR.sup. (a) PSF-SR.sup. (b) ______________________________________ Appearance White Fluff Same Solubility Soluble in chlorinated hydro- Same carbons, THF, Dioxane, DMSO, DMF, etc. Tg (uncured) Increases with increasing --Mn Same Tg (cured) Equivalent to that of standard Same polysulfone Thermal Will advance gradually above Same Stability Tg.sup.(c) Hydrolytic Good either in bulk or in Good in bulk Stability solution Curing Addition Polymerization Condensation Reaction Polymerization Curing Peroxide, radiation (UV Heat and Method Electron Beam, etc.) moisture By-product None.sup.(d) Methanol and evolved water during Adhesive None Excellent Capability ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive. .sup.(b) Polysulfonesilane reactive. .sup.(c) Depending on the reactivity of the end groups. .sup.(d) Not counting the decomposition products from the peroxide if used.
TABLE A ______________________________________ ELONGA- TENSILE TION Tg, STRENGTH, @ BREAK, COMPOSITE °C. PSI % ______________________________________ 5,000 MW polysulfone- 160° 12,000 5 vinyl reactive resin/ ERRE-0100 10,000 MW polysulfon- 166° 13,300 5 vinyl reactive resin/ ERRE-0100 Vinylbenzylchloride 166° 3,040 1.2 capped 5,000 MW polysulfone-vinyl reactive resin Vinylbenzylchloride -- 11,000 6 Capped 10,000 MW polysulfone-vinyl reactive resin ______________________________________
TABLE B __________________________________________________________________________ ENVIRONMENTAL STRESS AGING CHARACTERISTICS TIME TO FAILURE STRESS TRICHLORO- LEVEL ACETONE ETHYLENETOLUENE __________________________________________________________________________ Vinylbenzylchloride 200 psi >25 min. >25 min. >25 min. Capped 5,000MW PSF Vinylbenzylchloride 200 psi inst. 480 sec. inst. Capped 10,000 MW PSF __________________________________________________________________________
H.sub.2 C═CH--R
__________________________________________________________________________ Bisphenol A Union Carbide Corp., bisphenol A, 99.71 percent purity. Used without further purification. Sulfone Monomer ICI sulfone monomer, 100 percent purity assumed. Vinyl benzyl chloride Dow NC-1915, 98 plus percent purity, 40 percent para-/60 percent meta- isomer ratio. 2-chloroethyl acrylate Haven Chemical, 95 plus percent purity, inhibited with 0.5 percent of hydroquinone. 2-chloroethyl same as immediately above. methacrylate 2-chloroethyl vinyl Polysciences, P. p. 109° -110° C. ether Allyl Chloride Matheson Coleman and Bell B.p. 45° -46° C. Methacryloyl Chloride Polysciences, B.p. 95° -96° C. Dimethyl Sulfoxide Matheson Coleman and Bell. (DMSO) Monochlorobenzene (MCB) Matheson Coleman and Bell. Sodium Hydroxide Mallinckrokt Chemical Works, 98.5 percent purity. Lupersol-130 2,5-dimethyl-2,5-di(t-butyl peroxy) hexyne-3. Atlac 382-05A Commercial chemical-resistant corrosion-resistant grade of polyester (thermosetting), ICI, Wilmington, Del. Stypol-2995 Commercial polyester resin, Freeman Chemical Corp., Port Washington, Wisc. UDEL ® Polysulfone Commercial tough, rigid, high-strength, thermoplastic polysulfone end-terminated with methoxy moieties, Union Carbide, New York, New York. Polysulfone P-1700 is one of a line of UDEL ® polysulfones commercially available from Union Carbide. Polysulfone P-1700 is composed of the recurring units of formula I above (see page 5) with methoxy end-capping moieties. __________________________________________________________________________
TABLE II ______________________________________ POLY- SOLVENT SULFONE AND SUBSTRATE TYPE TREATMENT RESULTS ______________________________________ Steel "D" P-1700 Acetone, Stress cracked Plate 1 minute coating. immersion. Allyl Acetone, No effect. Terminated 1 minute immersion. P-1700 Methylene Coating dissolved. Chloride, 10 minute immersion. Allyl Methylene No effect. Terminated Chloride, 10 minute immersion. P-1700 Acetone, Coating dissolved. 10 minute immersion. Allyl Acetone, No effect. Terminated 10 minute immersion. ______________________________________
TABLE III ______________________________________ POLY- SOLVENT SUB- SULFONE AND STRATE.sup.1 TYPE TREATMENT RESULTS ______________________________________ Aluminum P-1700 1 minute in Aluminum attacked. Acetone followed by 15 sec. dip in 20% NaOH solution. Allyl 1 minute in No effect. Terminated Acetone followed by 15 sec. dip in 20% NaOH solution. P-1700 10 minutes in Coating removed; CH.sub.2 Cl.sub.2 all metal attacked. followed by hot NaOH solution.Allyl 10 minutes in No effect. Terminated CH.sub.2 Cl.sub.2 followed by hot NaOH solution. P-1700 10 minute Stress cracked immersion coating. in Acetone.Allyl 10 minute No effect. Terminated immersion in Acetone. ______________________________________ Note: .sup.1 All substrates were given at least one 90° bend in the test coupon prior to solvent resistance testing.
______________________________________ Reactor Charge Water-trap Material gm Discharge, gm ______________________________________ Bisphenol A 183.16 Sulfone monomer 208.86 NaOH solution 139.96 (mainly MCB + water) DMSO 589.60 MCB 1,050.70 Total 2,172.28 1,111.20 ______________________________________
______________________________________ Product recovered 311 gm (91 percent of theoretical) Reduced viscosity, R.V. 0.17 (chloroform, 25° C.)Melting point 160° C. ______________________________________
______________________________________ Bisphenol A 183.16 gm (0.8 mole) Sulfone monomer (4,4'-di- 220.34 gm (0.768 mole) chlorodiphenyl sulfone) Sodium hydroxide 64.96 gm (1.6 mole) 2-chloroethyl methacrylate 11 gm (0.0703 mole, 25 percent excess) ______________________________________
______________________________________ Product recovered 313 gm (90 percent of theoretical) R.V. (chloroform, 25° C.) 0.25Melting point 180° -183° C. ______________________________________
______________________________________ Bisphenol A 183.16 gm (0.8 mole) Sulfone monomer (4,4'-di- 208.86 gm (0.728 mole) chlorodiphenyl sulfone) Sodium hydroxide 64.96 gm (1.6 mole) Allyl chloride 21.37 gm (0.279 mole, 100 percent excess) ______________________________________
______________________________________ Product recovered 306 gm (90 percent of theoretical) R.V. (chloroform, 25° C.) 0.20 Number average molecular 6,540 weight (--M.sub.n ) Melting point 163-165° C. ______________________________________
______________________________________ Bisphenol A 183.16 gm (0.8 mole) Sulfone monomer (4,4-'di- 220.33 gm (0.768 mole) chlorodiphenyl sulfone) Sodium hydroxide 64.96 gm (1.6 mole) 2-chloroethyl acrylate 8.6 gm (0.0607 mole, 10 percent excess) ______________________________________
______________________________________ Product recovery 306 gm (88 percent of theoretical) R.V. (chloroform, 25° C.) 0.30 Melting point 170° -190° C. ______________________________________
TABLE IV __________________________________________________________________________ PREPARATION AND CHARACTERIZATION OF REPRESENTING LABORATORY-PREPARED PSF-VR.sup.(a) RESINS Sulfone/Bis A R.V. End-Capping Charge Ratio.sup.(d) Recovery Chloroform T.sub.m.sup.(b) Reagent Mole/Mole % 25° C. °C. --M.sub.n __________________________________________________________________________ 2-chloroethylmethacrylate 0.93 88 0.22 165°-175° 11,560.sup.(c) 0.93 92 0.21 163°-177° 0.944 96 0.21 180°-185° 0.944 92 0.21 180°-190° 0.96 89 0.25 177°-196° 0.96 92 0.25 180°-183° 0.98 93 0.35 210°-212° 2-chloroethylacrylate 0.93 89 0.23 160°-173° 0.96 88 0.30 170°-190° methacryloyl chloride 0.93 90 0.25 175°-190° 10,600 vinyl benzyl chloride 0.91 97 0.16 159°-160° 0.91 93 0.17 158°-162° 0.93 94 0.19 172°-174° 0.96 91 0.25 178°-182° vinyl benzyl chloride 0.96 92 0.25 191°-195° 0.98 88 0.37 206°-210° 0.98 91 0.35 198°-200° allyl chloride 0.91 90 0.20 163°-165° 6,540 2-chloroethyl vinylether 0.91 88 0.20 170°-173° __________________________________________________________________________ Notes: .sup.(a) Polysulfonevinyl reactive. .sup.(b) Polymer softens and melts gradually within the temperature range .sup.(c) Abnormally high value due to incomplete endcapping. .sup.(d) The hydroxy terminated polysulfones which were vinyl endcapped were prepared from bisphenol A and 4,4dichlorodiphenyl sulfone as described in Example 1.
TABLE V ______________________________________ EFFECT OF END-GROUP TYPE ON THE REACTIVITY OF POLYSULFONE-VINYL REACTIVE R.V..sup.(a) After 10 min. Initial Heating at (% Gel).sup.(b) Type of End-Group R.V. 160° C. 200° C. 220° C. ______________________________________ Vinyl Ether Ethoxy 0.17 0.173 0.176 0.174 Methacryloxy Ethoxy 0.193 0.197 0.206 0.207 Vinyl Benzyloxy 0.172 (5.1) (55.1) (76.2) ______________________________________ Notes: .sup.(a) Measured in chloroform at 25° C. .sup.(b) Gel content determined by extraction test with boiling chloroform.
TABLE VI __________________________________________________________________________ PEROXIDE (HEAT) CURING OF PSF-VR.sup. (a) /COMONOMER BINDER SYSTEMS Methacryloxy Methacryloxy Methacryloxy Vinyl Vinyl Vinyl Acryloxy PSF-VR.sup. (a), End-Gp. Type Ethoxy Ethoxy Ethoxy Benzyloxy Benzyloxy Benzyloxy Ethoxy __________________________________________________________________________ R. V. dl/g 0.35 0.25 0.25 0.25 0.25 0.25 0.23 Comonomer (% By wt) Styrene Styrene Styrene Styrene Styrene Diacetone Styrene (17) (17) (17) (39) (17) (17) Acryla- mide (20) CuringConditions 160° C. 160° C. 160° C. 160° C. 160° C. 210° C. 160° C. 15 min. 25 min. 25 min. 25 min. 15 min. 10 min. 30 min. Dicup.sup.(b) Dicup Dicup Dicup Dicup Lupersol t-Butyl 1.7% 1.7% 1.7% 1.7% 1.7% 130, 1% perbenzoate Gel Content, % 73 96 89 95 91 98 75 Appearance clear, clear, clear clear, clear, yellowish, clear transparent, transparent, transparent, transparent transparent fairly transparent, and tough and tough somewhat and tough and tough transparent tough brittle fairly tough Stress-crack good good fair-good good good good good Resistance to Acetone __________________________________________________________________________ Notes: .sup.(a) Polysulfonevinyl reactive .sup.(b) Dicumyl peroxide
TABLE VII __________________________________________________________________________ THERMAL AND MECHANICAL PROPERTIES OF REPRESENTING PSF-VR.sup.(a) /COMONOMER BINDER SYSTEMS.sup.(b) __________________________________________________________________________ (c) a-Methyl Methyl Ethyl Hydroxypropyl Comonomer Type Styrene Styrene Methacrylate Acrylonitrile Fumarate Methacrylate __________________________________________________________________________ PSF-VR.sup.(a), End-Gp. Type Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl benzyloxy benzyloxy benzyloxy benzyloxy benzyloxy benzyloxy R.V. dl/gm 0.17 0.17 0.17 0.17 0.16 0.16 Color colorless colorless colorless yellow colorless colorless Clarity.sup.(d) transparent transparent transparent transparent transparent transparent Tg °C. 140° 150° 160° 155° 105° 130° Modulus at 250° C., psi 310 360 310 730 105 400 Tensile Strength, psi 10,400 9,180 11,000 11,000 4,000 5,000 Tensile Mod- 2.99 3.29 3.25 3.14 3.23 3.00 ulus, psi × 10.sup.-6 Elongation at break, % 8 4 5.5 6 1.5 2.2 Pendulum Impact, ft-lb/in.sup.3 34 34 35 25 12 16 __________________________________________________________________________ 2-chloroethyl 2-Ethylhexyl Comonomer Type Methacrylate Diacetone Acrylamide Acrylate Ethyl Acrylate Vinyl Acetate __________________________________________________________________________ PSF-VR.sup.(a), End-Gp. Type Vinyl benzyloxy Vinyl benzyloxy Vinyl benzyloxy Vinyl benzyloxy Vinyl benzyloxy R.V. dl/gm 0.16 0.25 0.16 0.16 0.16 Color yellow colorless colorless colorless Clarity.sup.(d) transparent transparent transparent transparent Tg °C. 120° 155° 120° 130° 150° Modulus at 250° C., psi 1,000 150 300 400 570 Tensile Strength, psi 5,640 9,950 10,300 9,000 9,620 Tensile Mod- 3.13 2.60 3.26 2.78 3.06 ulus, psi × 10.sup.-6 Elongation at break, % 2.2 8 5.5 6 5 Pendulum Impact, ft-lb/in.sup.3 7 15 11 30 9 __________________________________________________________________________ Notes: .sup.(a) Polysulfonevinyl reactive .sup.(b) All specimens cured by compression molding at 160° C. .sup.(c) Each formulation contained 17.4 percent of comonomer. .sup.(d) The degree of transparency may vary considerably.
TABLE VIII __________________________________________________________________________ THERMAL AND MECHANICAL PROPERTIES OF REPRESENTATIVE PSF-VR.sup.(a) /MULTI-FUNCTIONAL CO-MONOMER BINDER SYSTEMS.sup.(b) (c) Trimethylol- Styrene/ Styrene/ Diallyl Ethylene propane Divinyl Polymeric Divinyl Divinyl Isophtha- Dimethacry- Trimethacry- Benzene Booster.sup.(f) Co-Monomer Type.sup.(d) Benzene (17.4).sup.(e) Benzene (17.4) late (17.4) late (17.4) late (17.4) (18.5/15.4) (14.4/13.4) __________________________________________________________________________ PSF-VR.sup.(a), End-Group Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Type benzyloxy benzyloxy benzyloxy benzyloxy benzyloxy benzyloxy benzyloxy R.V. dl/gm 0.17 0.17 0.17 0.16 0.16 0.17 0.17 Color colorless colorless colorless colorless colorless colorless colorless Clarity.sup.(g) transparent transparent transparent transparent transparent transparent transparent Tg °C. 170° 165° 115° 148° 160° 155° 165° Modulus at 250° C. 800 450 400 1,050 310 1,230 380 Tensile Strength, psi 11,300 4,690 11,400 5,530 4,560 12,100 8,120 Tensile Modulus, 3.15 3.25 3.55 3.10 3.13 3.42 3.15 psi × 10.sup.-6 Yield Elongation, % -- -- 5.5 -- -- -- -- Elongation at break, % 6.0 2.5 5.8 1.9 1.7 6.5 3.5 Pendulum Impact ft-lb/in.sup.3 44 5 14 20 6 24 28 __________________________________________________________________________ Notes: .sup.(a) Polysulfonevinyl reactive. .sup.(b) Peroxide cured. .sup.(c) All specimens cured by compression molding at 160° C. unless otherwise specified. .sup.(d) Percent by weight of comonomer added. .sup.(e) Post cured at 200° C. for 10 min. .sup.(f) A polymeric booster containing both pendant and terminal vinyl groups. .sup.(g) The degree of transparency may very considerably.
TABLE IX ______________________________________ EFFECT OF THE INITIAL MOLECULAR WEIGHT OF PSF-VR.sup.(a) TO THE PROPERTIES OF PSF-VR.sup.(b) /STYRENE.sup.(c) BINDER SYSTEM.sup.(d) ______________________________________ PSF-VR.sup.(a), R.V. dl/gm 0.17 0.25 0.37 Tg °C. 140° 155° 145° Modulus at 200° C. 340 200 90 Tensile Strength, psi 10,400 10,000 10,400 Tensile Modulus × 10.sup.-6 psi 2.99 2.84 2.76 Yield Elongation, % -- -- 5.5 Elongation at break, 8 5 7 Pendulum Impact, ft-lb/in.sup.3 34 15 15 ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive, all have vinyl benzyloxy end groups. .sup.(b) Polysulfonevinyl reactive. .sup.(c) All formulations contained 17.4 percent by wt. of styrene monomer. .sup.(d) Cured by compression molding at 160° C.
TABLE X ______________________________________ PSF-VR.sup.(a) /COMONOMER BINDER SYSTEMS CURED BY ELECTRON BEAM IRRADIATION ______________________________________ PSF-VR.sup.(a), R.V. 0.21 (60).sup.(b) 0.35 (60) 0.35 (60) 0.35 (60) Comonomer.sup.(c) NGD (30).sup.(b) DB (30) Styrene DB (10) (40) Styrene Styrene Styrene (10).sup.(b) (10) (30)Radiation 20 20 20 20 Dose, MRAD.sup.(d) Gel Content, % 59 57 60 53 Color Yellow Light Very Light Yellow Light Yellow Yellow Transparency Hazy Slightly Clear Slightly Hazy Hazy Mechanical Rigid, Rigid, Rigid, Rigid, Strength Brittle Fairly Fairly Fairly Brittle Tough Brittle ______________________________________ Notes: .sup.(a) Polysulfonevinyl radiation, endcapped with methacryloxy ethoxyl groups. .sup.(b) Percent by weight. .sup.(c) NGD = Neopentyl glycol diacrylate; DB = divinyl benzene. .sup.(d) Unit for radiation dose.
TABLE XI ______________________________________ EFFECT OF RADIATION DOSAGE ON THE CURING OF PSF--VR/COMONOMER BINDER SYSTEM.sup.(a) ______________________________________ Radiation Dosage, 5 10 15 20 MRad Gel Content, % 54 65 67 64 Swelling Index.sup.(b) 3.48 2.93 2.92 3.3 Tg °C. 145° 155° 145° 150° Modulus at 690 600 670 570 300° C., psi ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive, methacryloxy ethoxyl endgroups. 0.35 R.V. Comonomers, Neopentyl glycol diacrylate (30 percent); Styrene (10 percent). .sup.(b) Corrected for extractables.
TABLE XII ______________________________________ CURING OF PSF--VR/COMONOMER BINDER SYSTEMS.sup.(a) BY U.V.IRRADIATION ______________________________________ Irradiation 3 6 12 Dosage.sup.(b) Gel Content, % 18 27 50 Appearance clear, trans- clear, trans- clear, trans- parent parent parent Mechanical fairly tough fairly tough flexible, tough Strength Resistance to poor-fair fairly good good Acetone- Induced Stress Crack ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive, vinyl benzyloxy end groups, 0.37 R.V. (80%); ethyl acrylate (19 percent); benzophenone (1 percent). U.V. catalyst necessary when cured by U.V. .sup.(b) Expressed in number of passes at a conveyor speed of 100 ft/min.
Table XIII ______________________________________ ENVIRONMENTAL STRESS CRACK RESISTANCE VS. CROSS-LINKING DENSITY ______________________________________ PSF--VR.sup.(a), R.V. (82).sup.(b) 0.17 0.25 0.37 Comonomer (17).sup.(b) styrene styrene styrene Percent Extractables.sup.(c) 6.11 21.68 29.97 Swelling Index.sup.(d) 2.64 5.77 9.25 Time to Rupture: Toluene 1,000 psi 22 min. -- 10 sec. 500 psi -- 150 sec. 25 sec. Trichloroethylene 1,000psi 15 min. -- -- 500 psi -- 7 min. 5 min. Acetone 1,000 psi 25 min. -- -- 500 psi -- 75 sec. 20 sec. ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive, having vinyl benzyloxy end groups. .sup.(b) Percent by weight. .sup.(c) Equals 100 minus percent gel. .sup.(d) Corrected for extractables.
TABLE XIV __________________________________________________________________________ ENVIRONMENTAL STRESS CRACK RESISTANCE VS. COMONOMER TYPE Toluene Trichloroethylene Comonomer(s) Percent Swelling Time to Time to Type.sup.(a) Extractables Index.sup.(b) Stress (psi) Rupture (min) Stress (psi) Rupture (min) __________________________________________________________________________ Styrene (18.5) 3.9 1.70 2,000 >60 1,000 90 Divinyl benzene (15.4) 4,000 4 4,000 7 None.sup.(c) 8.3 3.53 2,000 25 2,000 80 Divinyl benzene (17.4) 13.5 2.78 1,000 >60 2,000 10 2,000 18 Divinyl benzene.sup.(d) (17.4) 3.5 1.96 2,000 5 2,000 14 4,000 1 Acrylonitrile (17.4) 3.5 2.38 1,000 >90 2,000 6 2,000 5 Ethylene dimeth- 4.9 1.92 1,000 30 1,000 20 acrylate (17.4) Styrene (9) 5.4 2.50 1,000 23 2,000 4 2,000 3 Styrene (13.4).sup.(e) 5.3 2.72 2,000 2 1,000 5 Vinyl acetate (17.4) 8.2 2.73 1,000 22 1,000 11 Ethyl acrylate (17.4) 8.1 2.79 1,000 10 1,000 16 2-chloroethyl meth- 11.6 2.83 1,000 7 1,000 5 acrylate (17.4) Methyl methacrylate 8.8 3.15 1,000 5 1,000 6 (17.4) 2-Ethyl hexyl 8.2 3.08 1,000 41/2 1,000 6 acrylate (17.4) 2-methyl Styrene 6.0 2.98 1,000 4 1,000 6 (17.4) Diallyl isophthal- 8.2 2.54 1,000 4 1,000 5 ate (17.4) Hydroxy propyl 11.0 2.96 1,000 31/2 1,000 5 Methacrylate (17.4) Styrene (29.4) 5.9 3.11 1,000 3 1,000 3 Ethyl Fumarate (17.4) 20.4 4.20 1,000 21/2 1,000 2 Trimethylol propane 8.2 2.15 1,000 1/2 1,000 3 trimethacrylate (17.4) PSF P-1700.sup.(f) Soluble -- 200 Instantaneous 200 1/6 __________________________________________________________________________ Notes: .sup.(a) Percent by weight present in the feed before curing. .sup.(b) Corrected for extractables. .sup.(c) Polysufonevinyl reactive, thermally cured at 275° C. .sup.(d) Cured at 200° C. .sup.(e) Also contained 14.5 percent of a crosslinking booster. .sup.(f) Polysulfone P1700 (union carbide)
TABLE XV ______________________________________ SOLUTION COPOLYMERIZATION OF PSF-VR.sup.(a) WITH STYRENE ______________________________________ PSF-VR.sup. (a) /styrene 0/100 5/95 7.5/ 10/90 12.5/ Wt. ratio in feed 92.5 87.5 PSF-VR.sup. (a) /polystyrene.sup.(b) 0/10 9.27/ 16.4/ 14.9/ 24.7/ Wt. ratio in copolymer 90.73 83.6 85.1 75.3 R.V., dl/gm.sup.(c) 0.51 0.58 0.61 0.70 1.06 Conversion, percent 48 49 48 55 50 ______________________________________ Notes: .sup.(a) Polysulfonevinyl reactive, acryloxy ethoxy endgroups, 0.23 R.V. .sup.(b) Copolymer composition determined by elemental analysis. .sup.(c) Measured in chloroform at 25° C.
TABLE XVI ______________________________________ MECHANICAL PROPERTIES OF GLASS MAT.sup.(a) REINFORCED LAMINATES PSF-VR.sup. (c) (Vinyl PSF-VR.sup. (c) benzyloxy (Methacryloxy Atlac Matrix Resin.sup.(b) 0.17) ethoxy 0.21) 382-05A ______________________________________ Percent Glass (plies) 29 30 28 Sp. gr. 1.82 1.85 1.81 Tensile Strength, psi 14,300 14,400 11,900 Tensile Modulus, × 1.01 0.89 0.83 10.sup.-6 psi Elongation, percent 1.69 1.79 1.81 Flexural Strength psi 24,700 28,700 27,600 Flexural Modulus, × 1.48 1.38 1.55 10.sup.-6 psi Izod Impact Strength 13.5 15.0 13.9 ft-lb/in. of notch Compressive Strength, 15,900 14,000 14,100 psi Compressive Modulus, 1.98 1.96 1.60 10.sup.-6 psi × HDT @ 264 psi, °C. 276°-305° 258° 258° (6 mil. def.) (2 mil. def.) ______________________________________ Notes: .sup.(a) VitroFlex 630D, 1 inch chopped strand mat. .sup.(b) Dissolved in styrene monomer. .sup.(c) Polysulfonevinyl reactive.
TABLE XVII ______________________________________ ELECTRICAL PROPERTIES OF GLASS MAT.sup.(a) REINFORCED LAMINATES PSF-VR.sup. (c) Methacryloxy Ethoxy (end groups, Freeman Matrix Resin.sup.(b) 0.20 R.V.) Stypol 2995 ______________________________________ Percent Glass (plies) 28 (4) 28 (4) Dielectric Strength, volts/mil 359 194 Volume Resistivity, 0.6 1.1 Ohm-cm × 10.sup.-16 Dissipation Factor, 60 cycles 0.00325 0.00599 10.sup.3 cycles 0.00283 0.00579 Dielectric Constant, 60 cycles 4.90 5.63 10.sup.3 cycles 4.88 5.56 Arc Resistance, sec. 167 182 ______________________________________ Notes: .sup.(a) VitroFlex 630D, 1 inch chopped strand mat. .sup.(b) Dissolved in styrene monomer. .sup.(c) Polysulfonevinyl reactive.
TABLE XVIII __________________________________________________________________________ Dicumyl Proxide.sup.(a) Method T °C. t.sub.min % of wt. Results __________________________________________________________________________ Compression molding 190° 30 2 R.V. advanced to 0.65 dl/g Compression molding 220° 10 2 Cross-linked no longer soluble in CHCl.sub.3 Compression molding 190° 30 2% plus Cross-linked, no 1% TAC.sup.(b) longer soluble in CHCl.sub.3 Compression molding (i)190° (i)30 2% plus Highly cross-lined (ii)220° (ii)12 1% TAC no longer soluble in CHCL.sub.3 __________________________________________________________________________ Notes: .sup.(a) Incorporated by imbibing from hexane solution and followed by vacuum drying to remove the hexane. .sup.(b) Triallylcyanurate, a crosslinking booster.
TABLE XIX __________________________________________________________________________ Initiator Loading Molding Initiator Type % by wt T ° C. t min Results __________________________________________________________________________ Dicumyl peroxide 1 220° 10 crosslinked, no longer soluble in CHCl.sub.3 Dicumyl peroxide 1 220° 10 crosslinked, improved TAC.sup.(a) 1 stress-cracking resistance to acetone Vinyltris (t-butyl-peroxy) 1 220° 10 crosslinked, good silane adhesion to aluminum substrate 2,5-Dimethyl-2,5-bis 1 220° 10 crosslinked, improved (t-butylperoxy)hexyne-3 stress-cracking resistance. __________________________________________________________________________ Notes: .sup.(a) Triallyl cyanurate
______________________________________ Hydroxy terminated polysulfone 39 gm (0.001 mole) (molecular wt. 39,000) KOH (in the form of a 11.2% 0.112 gm (0.002 mole) solution)Dimethyl Sulfoxide 200ml Benzene 80 ml Allyl Chloride 1.147 gm (0.015 mole) ______________________________________
Claims (10)
Z--O--(polyarylene polyether)--O--Z'
--E--(OE'--O--E)n--
Priority Applications (1)
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US07/004,721 USH521H (en) | 1982-06-30 | 1987-01-20 | Thermosetting polysulfones |
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US39376882A | 1982-06-20 | 1982-06-20 | |
US07/004,721 USH521H (en) | 1982-06-30 | 1987-01-20 | Thermosetting polysulfones |
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US06775713 Continuation | 1985-09-16 |
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US07/004,721 Abandoned USH521H (en) | 1982-06-30 | 1987-01-20 | Thermosetting polysulfones |
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-
1987
- 1987-01-20 US US07/004,721 patent/USH521H/en not_active Abandoned
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