Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/14—Unsaturated ethers
  • C07C43/17—Unsaturated ethers containing halogen
• • 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
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
  • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
  • C08F216/1408—Monomers containing halogen

Definitions

• This invention relates to a novel class of fluorovinyl ether monomers which are useful as cure site monomers in fluoroelastomers, a process for the preparation of these fluorovinyl ether monomers and to curable fluoroelastomer copolymers having copolymerized units of these fluorovinyl ether monomers.
• Elastomeric fluoropolymers exhibit excellent resistance to the effects of heat, weather, oil, solvents and chemicals.
• Such materials are commercially available and are most commonly either dipolymers of vinylidene fluoride (VF 2 ) with hexafiuoropropylene (HFP) or terpolymers of VF 2 , HFP, and tetrafluoroethylene (TFE). While these di- and terpolymers have many desirable properties, including low compression set and excellent processability, their low temperature flexibility is not adequate for all applications, nor is their resistance to attack by alkaline solvents.
• fluoroelastomers include the copolymers of TFE with one or more hydrocarbon olefins such as ethylene or propylene, and, optionally VF 2 (for example U.S. Patent No. 4,758,618). These copolymers are generally more resistant to attack by alkaline solutions than other types of fluoroelastomers.
• the copolymers may also contain a perfluoro(alkyl vinyl) ether (PAVE) in order to impart good low temperature sealing properties (U.S. Patent No. 4,694,045).
• PAVE perfluoro(alkyl vinyl) ether
• fluoroelastomers listed above require incorporation of a cure site monomer into their polymer chains in order to crosslink efficiently. Without such a cure site monomer, the fluoroelastomer may not react at all with curing agents, it may only partially react, or reaction may be too slow for use on a commercial scale. Seals made from poorly crosslinked elastomers often fail sooner than might otherwise be expected. Unfortunately, disadvantages are associated with many of the cure site monomers in use today. For example, monomers which contain reactive bromine or iodine atoms can release byproducts during the curing reaction that are harmful to the environment. Other cure site monomers (e.g.
• those which contain double bonds at both ends of the molecule may be so reactive that they disrupt polymerization of the fluoroelastomer by altering the polymerization rate, terminating polymerization, or by causing undesirable chain branching, or even gelation to occur.
• incorporation of a cure site monomer into a fluoroelastomer polymer chain may negatively impact the properties of the fluoroelastomer (both physical properties and chemical resistance).
• the present invention is also directed to a process for the preparation of the above fluorovinyl ether.
• the process comprises the steps of
• B condensing said chlorinated hydroxy ether with hexafluoropropene to produce a chorinated ether of the formula CF 3 CHFCF 2 -(O) n -(CH 2 ) m -(CF 2 ) p -RrOCFCl-CF 2 Cl; and C.
• the present invention is also directed to a fluoroelastomer composition
• a fluoroelastomer composition comprising
• the present invention is also directed to a polyhydroxylic curable composition of the above fluoroelastomer.
• the fluoroelastomers utilized in the curable compositions of the present invention are copolymers capable of undergoing crosslinking reactions with polyhydroxylic compounds to form cured elastomeric compositions that exhibit excellent physical properties and chemical resistance. Furthermore, the cure site monomers employed in the fluoroelastomers of this invention do not adversely affect the polymerization process, nor do byproducts of the curing reaction pose an environmental concern.
• the fluoroelastomers of this invention may further comprise copolymerized units of at least one additional monomer, different from said first, second and cure site monomers.
• the additional monomer or monomers may be selected from the group consisting of perfluoro(alkyl vinyl) ethers, perfluoro(alkoxy vinyl) ethers, fluoroolefms and hydrocarbon olefins.
• the fluoroelastomer copolymers of this invention may optionally contain up to about 1 wt.% iodine bound to polymer chain ends, the iodine being introduced via use of an iodine-containing chain transfer agent during polymerization.
• fluoroolefin monomers useful as the second monomer and as the optional additional monomer in the fluoroelastomers of this invention include, but are not limited to vinylidene fluoride (VF 2 ), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), pentafluoropropylene, vinyl fluoride and the like.
• VF 2 vinylidene fluoride
• TFE tetrafluoroethylene
• CTFE chlorotrifluoroethylene
• HFP hexafluoropropylene
• pentafluoropropylene vinyl fluoride and the like.
• Hydrocarbon olefin monomers which may be employed as the second monomer and as the optional additional monomer in fluoroelastomers of this invention contain no fluorine atoms.
• hydrocarbon olefins include, but are not limited to ethylene (E), propylene (P), butylene -1 and isobutylene.
• Perfluoro(alkyl vinyl) ethers suitable for use as comonomers include those of the formula
• CF 2 CFO(R f O) friendship(R O) m Rf (I) where R f and R f , are different linear or branched perfluoroalkylene groups of 2-6 carbon atoms, m and n are independently 0-10, and R f is a perfluoroalkyl group of 1-6 carbon atoms.
• a most preferred class of PAVE includes those ethers wherein n is 0 or 1 and R f contains 1-3 carbon atoms.
• perfluorinated ethers include perfluoro(methyl vinyl) ether and perfluoro(propyl vinyl) ether.
• Additional perfluoro(alkyl vinyl) ether monomers include compounds of the formula
• fluoroelastomers of this invention include, but are not limited to polymers having copolymerized units of the fluorovinyl ether cure site monomers of this invention and units of VF 2 /HFP; VF 2 /HFP/TFE; VF 2 /PMVE; VF 2 /PMVE/TFE; TFE/P; TFE/P/VF 2 ; and E/TFE/PMVE.
• R f is - [OCF(CF 3 )CF 2 ] x - , wherein x is 1 or 2; n is 1, m is 1 and p is an integer from 1 to 4.
• cure site monomers polymerize into the fluoroelastomer polymer chain through their vinyl group, resulting in copolymerized units having pendant CF 3 CHFCF 2 -(O) n -(CH 2 ) m -(CF 2 )p-R f -O- side chains.
• the side chains may readily dehydrofluorinate to form carbon-carbon double bonds. These sites of unsaturation then act as cure sites for crosslinking.
• a particular characteristic of the cure site monomer of this invention is that it acts as an independent cure site monomer that takes part in crosslinking reactions with polyhydroxylic curing agents. That is, polymers that contain copolymerized units of this cure site monomer do not require the presence of copolymerized VF 2 monomer sequences flanlced by perfluoromonomers (e.g. HFP/VF 2 /HFP) for initiation of dehydrofluorination.
• perfluoromonomers e.g. HFP/VF 2 /HFP
• the copolymers need contain only low levels of cure site monomer, i.e. 0.3-5 wt.% (preferably 0.7-3 wt.%), to promote efficient polyhydroxylic cures. This permits adjustment of other comonomer levels to maximize particular physical properties.
• the polymers of the present invention exhibit excellent cure characteristics when only low levels of cure site monomer are present.
• a preferred means for dechlorinating is by reaction with a reducing agent (such as zinc) in an aprotic solvent at a temperature between 70 to 140°C.
• a reducing agent such as zinc
• the hydroxy vinyl ether starting material is known in the art. Some of these hydroxy vinyl ethers are available commercially from DuPont, or they may be synthesized by the process disclosed in U.S. Patent No. 4,982,009.
• the hydroxy vinyl ether may be chlorinated by a variety of means including by the reaction with neat chlorine at a temperature between -15 to 40°C, preferably 0 to 10°C.
• the chlorinated hydroxy ether may be condensed with hexafluoropropene by a variety of means, including by the reaction at a temperature between -15 to 70°C of hexafluoropropylene with the chlorinated vinyl ether contained in an anhydrous aprotic solvent and in the presence of a strong base.
• Suitable aprotic solvents include dimethylsufoxide and dimethylformamide.
• Suitable strong bases include potassium t-butoxide.
• the polymers of this invention may be prepared using free radical batch or semi-batch, or continuous free radical emulsion polymerization processes. They may also be prepared by free radical suspension polymerization processes.
• the polymers are generally prepared in a continuous stirred tank reactor.
• Polymerization temperatures may be in the range of 40° to 145°C, preferably 80° to 135°C at pressures of 1 to 8 MPa. Residence times of 20 to 360 minutes are preferred.
• Free radical generation may be effected through use of a water-soluble initiator such as ammonium persulfate, either by thermal decomposition or by reaction with a reducing agent such as sodium sulfite.
• An inert surface-active agent such as ammonium perfluorooctanoate may be utilized to stabilize the dispersion, usually in conjunction with addition of a base such as sodium hydroxide or a buffer such as disodium phosphate to control pH in the range 3 to 7.
• a base such as sodium hydroxide or a buffer such as disodium phosphate
• Unreacted monomer is removed from the reactor effluent latex by vaporization at reduced pressure.
• Polymer is recovered from the stripped latex by coagulation.
• coagulation may be effected by reducing latex pH to about 3 by addition of acid, then adding a salt solution, such as an aqueous solution of calcium nitrate, magnesium sulfate, or potassium aluminum sulfate, to the acidified latex.
• the polymer is separated from the serum, then washed with water and subsequently dried. After drying, the product may be cured.
• Chain transfer agents may be used in the polymerization in order to control the molecular weight distribution of the resulting polymers.
• chain transfer agents include isopropanol; methyl ethyl ketone; ethyl acetate; diethyl malonate; isopentane;l,3-diiodoperfluoropropane; 1,4-diiodoperfluorobutane; 1,6- diiodoperfluorohexane; 1,8-diiodoperfluorooctane; mefhylene iodide; trifluoromethyl iodide; perfluoro(isopropyl) iodide; and perfluoro(n-heptyl) iodide.
• Polymerization in the presence of iodine-containing chain transfer agents may result in a polymer with one or two iodine atoms per fluoroelastomer polymer chain, bound at the chain ends (see for example U.S. 4,243,770 and U.S. 4,361,678).
• Such polymers may have improved flow and processability compared to polymers made in the absence of a chain transfer agent.
• up to about 1 weight percent iodine chemically bound to fluoroelastomer chain ends will be incorporated into the polymer, preferably from 0.1-0.3 wt.%.
• An embodiment of the present invention is a curable composition that comprises the above-described copolymers and a polyhydroxylic curing agent.
• the polymers of the invention are also curable with amines and amine derivatives (e.g. carbamates).
• crosslinking agent is usually added in amounts of from about 0.5-4 parts by weight per hundred parts by weight fluoroelastomer (phr), usually 1-2.5 phr.
• Preferred crosslinking agents are di- tri-, tetrahydroxybenzenes, naphthalenes, anthracenes and bisphenols of the formula
• A is a stable divalent radical, such as a difunctional aliphatic, cycloaliphatic, or aromatic radical of 1-13 carbon atoms, or a thio, . oxy, carbonyl, sulf ⁇ nyl, or sulfonyl radical; A is optionally substituted with at least one chlorine or fluorine atom; x is 0 or 1; n is 1 or 2 and any aromatic ring of the polyhydroxylic compound is optionally substituted with at least one atom of chlorine, fluorine, or bromine, a -CHO group, or a carboxyl or acyl radical (e.g.
• R is OH or a C]-C 8 alkyl, aryl, or cycloalkyl group. It will be understood ftom the above formula describing bisphenols that the -OH groups can be attached in any position (other than number one) in either ring. Blends of two or more such compounds can also be used.
• A when A is alkylene, it can be, for example, methylene, ethylene, chloroethylene, fluoroethylene, difluoroethylene, 1,3-propylene, 1,2-propylene, tetramethylene, chlorotetramethylene, fluorotetramethylene, trifluorotetramethylene, 2-methyl- 1,3-propylene, 2-methyl-l,2-propylene, pentamethylene, and hexamethylene.
• A is alkylidene
• it can be for example ethylidene, dichloroethylidene, difluoroethylidene, propylidene, isopropylidene, trifluoroisopropylidene, hexafluoroisopropylidene, butylidene, heptachlorobutylidene, heptafluorobutylidene, pentylidene, hexylidene, and 1,1-cyclohexylidene.
• A is a cycloalkylene radical
• it can be for example 1,4-cyclohexylene, 2-chloro- 1 ,4-cyclohexylene, 2-fluoro- 1 ,4-cyclohexylene, 1 ,3 -cyclohexylene, cyclopentylene, chlorocyclopentylene, fluorocyclopentylene, and cycloheptylene.
• A can be an arylene radical such as m-phenylene, p-phenylene, 2-chloro- 1 ,4-phenylene, 2-fluoro-l,4-phenylene, o-phenylene, methylphenylene, dimethylphenylene, trimethylphenylene, tetramethylphenylene, 1,4-naphthylene, 3-fluoro-l,4-naphthylene, 5-chloro-l,4-naphthylene, 1,5-naphthylene, and 2,6- naphthylene.
• Bisphenol AF (4,4'-(hexafluoroisopropylidene)diphenol) is a preferred crosslinking agent.
• crosslinking agents include hydroquinone, dihydroxybenzenes such as catechol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2-methyl hydroquinone, 2,5-dimethyl hydroquinone; 2-t-butyl hydroquinone; and 1,5-dihydroxynaphthalene.
• Additional polyhydroxy curing agents include alkali metal salts of bisphenol anions, quaternary ammonium salts of bisphenol anions and quaternary phosphonium salts of bisphenol anions.
• the salts of bisphenol A and bisphenol AF include the disodium salt of bisphenol AF, the dipotassium salt of bisphenol AF, the monosodium monopotassium salt of bisphenol AF and the benzyltriphenylphosphonium salt of bisphenol AF.
• Quaternary ammonium and phosphonium salts of bisphenol anions and their preparation are discussed in U.S. Patents 4,957,975 and 5,648,429.
• derivatized polyhydroxy compounds such as diesters
• diesters are useful crosslinking agents.
• examples of such compositions include diesters of phenols, such as the diacetate of bisphenol AF, the diacetate of sulfonyl diphenol, and the diacetate of hydroquinone.
• the curable compositions When cured with polyhydroxy compounds, the curable compositions will also generally include a cure accelerator.
• the most useful accelerators are quaternary phosphonium salts, quaternary alkylammonium salts, or tertiary sulfonium salts. Particularly preferred accelerators are n-tetrabutylammonium hydrogen sulfate, tributylallylphosphonium chloride and benzyltriphenylphosphonium chloride.
• Other useful accelerators include those described in U.S.
• Patents 5,591,804; 4,912,171; 4,882,390; 4,259,463 and 4,250,278 such as tributylbenzylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl tris(dimethylamino)phosphonium chloride; 8-benzyl-l,8-diazabicyclo[5,4,0]-7-undecenonium chloride, [(C 6 H 5 ) 2 S + (C 6 H 13 )] [Cl] " , and [(C 6 H 13 ) 2 S(C 6 H 5 )] + [CH 3 CO 2 ] ⁇
• about 0.2 phr accelerator is an effective amount, and preferably about 0.35-1.5 phr is used.
• the polyhydroxy cure system will also contain a metal compound composed of a divalent metal oxide, such as magnesium oxide, zinc oxide, calcium oxide, or lead oxide, or a divalent metal hydroxide; or a mixture of the oxide and/or hydroxide with a metal salt of a weak acid, for example a mixture containing about 1-70 percent by weight of the metal salt.
• a metal compound composed of a divalent metal oxide such as magnesium oxide, zinc oxide, calcium oxide, or lead oxide, or a divalent metal hydroxide
• a metal salt of a weak acid for example a mixture containing about 1-70 percent by weight of the metal salt.
• useful metal salts of weak acids are barium, sodium, potassium, lead, and calcium stearates, benzoates, carbonates, oxalates, and phosphites.
• the amount of the metal compound added is generally about 1-15 phr, about 2-10 parts being preferred.
• additives may be compounded into the fluoroelastomer to optimize various physical properties.
• additives include carbon black, stabilizers, plasticizers, lubricants, pigments, fillers, and processing aids typically utilized in perfluoroelastomer compounding. Any of these additives can be incorporated into the compositions of the present invention, provided the additive has adequate stability for the intended service conditions.
• Carbon black is used in elastomers as a means to balance modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity, and processability of the compositions. Carbon black is generally useful in amounts of from 5-60 phr.
• fluoropolymer fillers may be present in the composition. Generally from 1 to 50 phr of a fluoropolymer filler is used, and preferably at least about 5 phr is present.
• the fluoropolymer filler can be any finely divided, easily dispersed plastic fluoropolymer that is solid at the highest temperature utilized in fabrication and curing of the perfluoroelastomer composition.
• solid it is meant that the fluoroplastic, if partially crystalline, will have a crystalline melting temperature above the processing temperature(s) of the perfiuoroelastomer(s).
• Such finely divided, easily dispersed fluoroplastics are commonly called micropowders or fluoro additives. Micropowders are ordinarily partially crystalline polymers.
• a preferred additive class includes molecular sieves, particularly zeolites.
• Molecular sieve zeolites are crystalline aluminosilicates of Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium. Chemically, they are represented by the empirical formula: M 2/n O.Al O . ySiO 2 .wH 2 O where y is 2 or greater, n is the cation valence, and w represents the water contained in the voids of the zeolite.
• Commercially available examples of such compositions include Molecular Sieve 3A, Molecular Sieve 4A, Molecular Sieve 5A, and Molecular Sieve 13X, all available from Aldrich Chemical Co., Inc. Milwaukee, Wisconsin.
• Use of this class of additives prevents sponging and improves heat aging of vulcanizates upon press curing in many instances. In general, use of about 1-5 phr is sufficient.
• modified silane coated mineral fillers include modified silane coated mineral fillers.
• modified silane is meant that the silane contains at least one reactive functional group such as an amino group, or an epoxy group.
• the mineral fillers used in this invention are preferably somewhat alkaline, such as calcium metasilicates (CaSiO 3 ), especially wollastonite. Wollastonite coated with either an aminosilane or an epoxysilane is especially preferred. These compounds are commercially available from Quarzwerke GmbH of Freschen, Germany as Tremin ® 283 EST (epoxysilane treated wollastonite) and Tremin ® 283 AST (aminosilane treated wollastonite). These modified silane coated mineral fillers prevent sponging of the fluoroelastomer composition during press cure and also accelerate the cure rate. Generally, about 5 to 80 phr modified silane coated mineral filler is useful in the compositions of this invention, about 10 to 60 phr being preferred.
• crosslinking agent accelerator, metal oxide, and other additives are generally incorporated into the polymer by means of an internal mixer or on a rubber mill.
• the resultant composition is then cured, generally by means of heat and pressure, for example by compression transfer or injection molding.
• the curable compositions of the present invention are useful in production of gaskets, tubing, seals and other molded components.
• Such articles are generally produced by molding a compounded formulation of the curable composition with various additives under pressure, curing the part, and then subjecting it to a post cure cycle.
• the cured compositions have excellent low temperature flexibility and processability as well as excellent thermal stability and chemical resistance. They are particularly useful in applications such as seals and gaskets requiring a good combination of oil resistance, fuel resistance and low temperature flexibility, for example in fuel injection systems, fuel line connector systems and in other seals for high and low temperature automotive uses.
• MDR moving disk rheometer
• the preparation of this hydroxy vinyl ether is disclosed in U.S. Patent No.
• the chlorinated hydroxy ether prepared in step 1 above was condensed with hexafluoropropene to produce the chlorinated ether intermediate l,2-dichloro-9,9,12-trihydro-perfluoro(3,6,10 ⁇ trioxa-5-methyl-tridecane [CF 2 Cl-CFCl-O-CF 2 CF(CF 3 )O-CF 2 CF 2 -CH 2 O-
• the chorinated ether intermediate produced in the second step was reduced to yield the fluorovinyl ether monomer of this invention.
• a reaction flask was charged with zinc-dust (23.5 g, 0.359 mol) in anhydrous dimethylformamide (DMF) solvent (180 ml). Bromine (1.5 ml) was then added to the flask in order to activate the zinc metal.
• the 1,2-dichloro- 9,9,12-trihydro-perfluoro-(3,6,10-trioxa-5-methyl-l-tridecene (87 g, 0.141 mol) (produced above in the second step) was added and the reaction mixture was heated to a temperature between 98 and 104°C for 4 hours.
• a 4-liter polymerization vessel was charged with de-ionized water (2000 ml), disodium phosphate heptahydrate (20 g), ammonium perfluorooctanoate (3.9 g), and 9,9,12-trihydro-perfluoro(3,6,10-trioxa-5-methyl-l-tridecene) [CF 2 -CF- O-CF 2 CF(CF 3 )O-CF 2 CF 2 -CH 2 O-CF 2 CFHCF 3 ] monomer (36 g).
• the reactor was sealed. Oxygen was removed from the reactor by evacuating it and then purging with nitrogen gas. The latter process was repeated three times.
• the reactor was then charged with a monomer gas mixture of TFE (10 g/hr), VF 2 (320 g/hr) and PMVE (670 g/hr) until the pressure had reached 200 psi (1.38 MPa) at 80°C.
• the reactor contents were stirred by a mechanical stirrer operating at 200 rpm.
• a solution of ammonium persulfate initiator (2.0 wt. % in water, 30 ml) was then added to the reactor at a rate of 10 ml/min.
• the monomer gas feed was switched to a mixture of TFE (37 g/hr), VF 2 (212 g/hr) and PMVE (140 g/hr).
• the monomer feed flow rate was controlled so as to maintain the total reactor vessel pressure at 200 psi (1.38 MPa) as additional ammonium persulfate initiator solution was co-fed to the reactor at a rate of 0.2 ml/min.
• the polymerization was terminated after a total of 728 grams of monomer had been fed to the reactor.
• the resulting fluoroelastomer latex was then coagulated by addition of a magnesium sulfate aqueous solution.
• the coagulated fluoroelastomer polymer was collected by filtration, and washed thoroughly with warm water (70 °C). Polymer was then dried in an air oven at 80°C.
• the resulting fluoroelastomer polymer had a T g of-30.5°C, as determined by Differential Scanning Calorimetry (DSC).
• the composition of the polymer was analyzed by infrared spectroscopy and 19 F-NMR (in hexafluorobenzene at 80°C) and was determined to be 75.17 mol% VF 2 , 6.30 mol% TFE, 18.44 mol% PMVE and
• Samples of polymer A from Example 2, and of a control polymer (a fluoroelastomer of the prior art containing 33.3 wt.% VF 2 , 39.4 wt.% PMVE and 27.3 wt.%) TFE) were compounded on a two-roll rubber mill with the components shown in Table I. Cure characteristics, measured according to the Test Method described above, are also reported in Table I.
• control polymer which contained no cure site monomer, exhibited essentially no cure response, whereas polymer A of this invention cured well.

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