Thermoset composition, method, and article

Abstract

A curable composition includes a functionalized poly(arylene ether), an alkenyl aromatic monomer, an acryloyl monomer, and a polymeric additive effective selected from polystyrene, poly(styrene-maleic anhydride), poly(styrene-methyl methacrylate), polybutene, poly(ethylene-butylene), poly(vinyl ether), poly(vinyl acetate), and combinations thereof. The composition exhibits low shrinkage on curing and improved surface smoothness. It is useful, for example, in the manufacture of automotive body panels.

1 . A curable composition, comprising: 
 a functionalized poly(arylene ether);    an alkenyl aromatic monomer;    an acryloyl monomer; and    a polymeric additive selected from the group consisting of a polystyrene, a poly(styrene-maleic anhydride), a poly(styrene-methyl methacrylate), a polybutene, a poly(ethylene-butylene), a poly(vinyl ether), a poly(vinyl alkanoate) wherein the alkanoate group has at least three carbons, and combinations comprising at least one of the foregoing polymeric additives.    
     
     
         2 . The composition of  claim 1 , wherein the polymeric additive comprises the polystyrene.  
     
     
         3 . The composition of  claim 2 , wherein the polystyrene comprises comprising at least about 80 weight percent of repeating structural units having the formula  
       
         
           
           
               
               
           
         
       
       wherein R 34  is hydrogen, C 1 -C 8  alkyl, or halogen; Z is vinyl, halogen, or C 1 -C 8  alkyl; and p is 0 to 5.  
     
     
         4 . The composition of  claim 1 , wherein the polymeric additive comprises the poly(styrene-maleic anhydride).  
     
     
         5 . The composition of  claim 1 , wherein the polymeric additive comprises the poly(styrene-methyl methacrylate).  
     
     
         6 . The composition of  claim 1 , wherein the polymeric additive comprises the polybutene.  
     
     
         7 . The composition of  claim 1 , wherein the polymeric additive comprises the poly(ethylene-butylene).  
     
     
         8 . The composition of  claim 7 , wherein the polymeric additive further comprises a polybutadiene.  
     
     
         9 . The composition of  claim 8 , wherein the polybutadiene has a number average molecular weight of about 1,000 to about 10,000 atomic mass units.  
     
     
         10 . The composition of  claim 1 , wherein the polymeric additive comprises a poly(vinyl ether).  
     
     
         11 . The composition of  claim 10 , wherein the poly(vinyl ether) comprises at least about 80 weight percent of repeating structural units having the formula  
       
         
           
           
               
               
           
         
       
       wherein R 39  is C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 6 -C 18  aryl, C 7 -C 18  alkylaryl, or C 7 -C 18  aralkyl.  
     
     
         12 . The composition of  claim 10 , wherein the poly(vinyl ether) comprises poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(cyclohexyl vinyl ether), or a mixture thereof.  
     
     
         13 . The composition of  claim 1 , wherein the polymeric additive comprises the poly(vinyl alkanoate) wherein the alkanoate group has at least three carbons.  
     
     
         14 . The composition of  claim 13 , wherein the alkanoate group has about four to about twelve carbons.  
     
     
         15 . The composition of  claim 1 , comprising about 0.1 to about 30 parts by weight of the polymeric additive, based on 100 parts by weight total of the functionalized poly(arylene ether), the alkenyl aromatic monomer, the acryloyl monomer, and the polymeric additive.  
     
     
         16 . The composition of  claim 1 , further comprising a second polymeric additive selected from the group consisting of styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-styrene triblock copolymers, styrene-isoprene-styrene triblock copolymers, polybutadienes, polyacrylates, ethylene-propylene-diene terpolymers, and combinations comprising at least one of the foregoing second polymeric additives.  
     
     
         17 . The composition of  claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure  
       Q(J-K) y    
       wherein Q is the residuum of a monohydric, dihydric, or polyhydric phenol; y is 1 to 100; J comprises repeating structural units having the formula  
       
         
           
           
               
               
           
         
       
       wherein R 1 -R 4  are each independently selected from the group consisting of hydrogen, halogen, primary or secondary C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 2 -C 12  alkynyl, C 1 -C 12  amino alkyl, C 1 -C 12  hydroxyalkyl, phenyl, C 1 -C 12  halo alkyl, C 1 -C 12  hydrocarbonoxy, and C 2 -C 12  halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; m is 1 to about 200; and K is a capping group selected from the group consisting of  
       
         
           
           
               
               
           
         
       
       wherein R 5  is C 1 -C 2  alkyl; R 6 -R 8  are each independently selected from the group consisting of hydrogen, C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 6 -C 18  aryl, C 7 -C 18  alkyl-substituted aryl, C 7 -C 18  aryl-substituted alkyl, C 2 -C 12  alkoxycarbonyl, C 7 -C 18  aryloxycarbonyl, C 8 -C 18  alkyl-substituted aryloxycarbonyl, C 8 -C 18  aryl-substituted alkoxycarbonyl, nitrile, formyl, carboxylate, imidate, and thiocarboxylate; R 9 -R 13  are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 12  alkyl, hydroxy, and amino; and wherein Y is a divalent group selected from the group consisting of  
       
         
           
           
               
               
           
         
       
       wherein R 14  and R 15  are each independently selected from the group consisting of hydrogen and C 1 -C 12  alkyl.  
     
     
         18 . The composition of  claim 17 , wherein Q is the residuum of a monohydric phenol.  
     
     
         19 . The composition of  claim 17 , wherein the capped poly(arylene ether) comprises at least one capping group having the structure  
       
         
           
           
               
               
           
         
       
       wherein R 6 -R 8  are each independently selected from the group consisting of hydrogen, C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 6 -C 18  aryl, C 7 -C 18  alkyl-substituted aryl, C 7 -C 18  aryl-substituted alkyl, C 2 -C 12  alkoxycarbonyl, C 7 -C 18  aryloxycarbonyl, C 8 -C 18  alkyl-substituted aryloxycarbonyl, C 8 -C 18  aryl-substituted alkoxycarbonyl, nitrile, formyl, carboxylate, imidate, and thiocarboxylate.  
     
     
         20 . The composition of  claim 1 , wherein the functionalized poly(arylene ether) is a ring-functionalized poly(arylene ether) comprising repeating structural units having the formula  
       
         
           
           
               
               
           
         
       
       wherein each L 1 -L 4  is independently hydrogen, an alkenyl group, or an alkynyl group; wherein the alkenyl group is represented by  
       
         
           
           
               
               
           
         
       
       wherein L 5 -L 7  are independently hydrogen or methyl, and a is an integer from 1 to 4; wherein the alkenyl group is represented by  
       
         
           
           
               
               
           
         
       
       wherein L 8  is hydrogen, methyl, or ethyl, and b is an integer from 1 to 4; and wherein about 0.02 mole percent to about 25 mole percent of the total L 1 -L 4  substituents in the ring-functionalized poly(arylene ether) are alkenyl and/or alkynyl groups.  
     
     
         21 . The composition of  claim 1 , comprising about 10 to about 90 parts by weight of the functionalized poly(arylene ether) per 100 parts by weight total of the functionalized poly(arylene ether), the alkenyl aromatic monomer, the acryloyl monomer, and the polymeric additive.  
     
     
         22 . The composition of  claim 1 , wherein the alkenyl aromatic monomer has the structure  
       
         
           
           
               
               
           
         
       
       wherein each R 16  is independently selected from the group consisting of hydrogen, C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 2 -C 12  alkynyl, and C 6 -C 18  aryl; each R 17  is independently selected from the group consisting of halogen, C 1 -C 12  alkyl, C 1 -C 12  alkoxyl, and C 6 -C 18  aryl; p is 1 to 4; and q is 0 to 5.  
     
     
         23 . The composition of  claim 1 , wherein the alkenyl aromatic monomer comprises at least one alkenyl aromatic monomer selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, styrenes having from 1 to 5 halogen substituents on the aromatic ring, and mixtures comprising at least one of the foregoing alkenyl aromatic monomers.  
     
     
         24 . The composition of  claim 1 , comprising about 10 to about 90 parts by weight of the alkenyl aromatic monomer per 100 parts by weight total of the functionalized poly(arylene ether), the alkenyl aromatic monomer, the acryloyl monomer, and the polymeric additive.  
     
     
         25 . The composition of  claim 1 , wherein the acryloyl monomer comprises at least one acryloyl moiety having the structure  
       
         
           
           
               
               
           
         
       
       wherein R 18  and R 19  are each independently selected from the group consisting of hydrogen and C 1 -C 12  alkyl, and wherein R 18  and R 19  may be disposed either cis or trans about the carbon-carbon double bond.  
     
     
         26 . The composition of  claim 1 , wherein the acryloyl monomer comprises at least one acryloyl moiety having the structure  
       
         
           
           
               
               
           
         
       
       wherein R 20 -R 22  are each independently selected from the group consisting of hydrogen, C 1 -C 12  alkyl, C 2 -C 12  alkenyl, C 6 -C 18  aryl, C 7 -C 18  alkyl-substituted aryl, C 7 -C 18  aryl-substituted alkyl, C 2 -C 12  alkoxycarbonyl, C 7 -C 18  aryloxycarbonyl, C 8 -C 18  alkyl-substituted aryloxycarbonyl, C 8 -C 18  aryl-substituted alkoxycarbonyl, nitrile, formyl, carboxylate, imidate, and thiocarboxylate.  
     
     
         27 . The composition of  claim 26 , wherein the acryloyl monomer comprises at least two acryloyl moieties.  
     
     
         28 . The composition of  claim 1 , wherein the acryloyl monomer comprises at least one acryloyl monomer selected from the group consisting of trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, isobornyl (meth)acrylate, methyl (meth)acrylate, and mixtures comprising at least one of the foregoing acryloyl monomers.  
     
     
         29 . The composition of  claim 1 , comprising about 1 to about 50 parts by weight of the acryloyl monomer per 100 parts by weight total of the functionalized poly(arylene ether), the alkenyl aromatic monomer, the acryloyl monomer, and the polymeric additive.  
     
     
         30 . The composition of  claim 1 , further comprising a curing catalyst.  
     
     
         31 . The composition of  claim 30 , wherein the curing catalyst comprises at least one curing catalyst selected from the group consisting of benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, alpha,alpha′-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumylperoxide, di(t-butylperoxy isophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, 2,3-trimethylsilyloxy-2,3-diphenylbutane, and mixtures comprising at least one of the foregoing curing catalysts.  
     
     
         32 . The composition of  claim 1 , further comprising a particulate filler.  
     
     
         33 . The composition of  claim 32 , wherein the particulate filler is calcium carbonate.  
     
     
         34 . The composition of  claim 32 , comprising about 5 to about 80 weight percent of the particulate filler, based on the total weight of the composition.  
     
     
         35 . The composition of  claim 1 , further comprising a fibrous filler.  
     
     
         36 . The composition of  claim 35 , wherein the fibrous filler is glass fibers.  
     
     
         37 . The composition of  claim 35 , comprising about 2 to about 80 weight percent of the fibrous filler, based on the total weight of the composition.  
     
     
         38 . The composition of  claim 1 , further comprising an additive selected from the group consisting of flame retardants, mold release agents and other comprising at least one of the foregoing additives.  
     
     
         39 . The composition of  claim 1 , wherein the composition after molding exhibits a shrinkage at least 10% less than the shrinkage exhibited by a corresponding composition without the polymeric additive.  
     
     
         40 . The composition of  claim 1 , wherein the composition after molding in a Class A surface mold exhibits an orange peel value less than 40.  
     
     
         41 . The composition of  claim 1 , wherein the composition after molding in a Class A surface mold exhibits an orange peel value less than 300. lubricants, antioxidants, thermal stabilizers, ultraviolet stabilizers, pigments, dyes, colorants, anti-static agents, conductive agents, curing promoters, and combinations  
     
     
         42 . A curable composition, comprising: 
 about 10 to about 90 parts by weight of a functionalized poly(arylene ether);    about 10 to about 90 parts by weight of an alkenyl aromatic monomer;    about 1 to about 50 parts by weight of an acryloyl monomer; and    about 0.1 to about 30 parts by weight of a poly(vinyl ether).    
     
     
         43 . A curable composition, comprising: 
 about 20 to about 60 parts by weight of a methacrylate-capped poly(arylene ether);    about 20 to about 60 parts by weight of styrene;    about 5 to about 20 parts by weight of an acryloyl monomer; and    about 5 to about 20 parts by weight of a poly(vinyl ether);    about 100 to about 500 parts by weight of calcium carbonate; and    about 50 to about 200 parts by weight of glass fibers.    
     
     
         44 . A curable composition, comprising: 
 about 10 to about 90 parts by weight of a functionalized poly(arylene ether);    about 10 to about 90 parts by weight of an alkenyl aromatic monomer;    about 1 to about 50 parts by weight of an acryloyl monomer; and    about 0.1 to about 30 parts by weight of a polymeric additive comprising a polybutadiene and a poly(ethylene-butylene).    
     
     
         45 . The curable composition of  claim 44 , wherein the composition after curing has a first dispersed phase having an average particle size of about 0.5 to about 2 micrometers and a second dispersed phase having a particle size of about 5 to about 25 micrometers.  
     
     
         46 . A curable composition, comprising: 
 about 20 to about 60 parts by weight of a methacrylate-capped poly(arylene ether);    about 20 to about 60 parts by weight of styrene;    about 5 to about 20 parts by weight of an acryloyl monomer;    about 5 to about 20 parts by weight of a polymeric additive comprising a polybutadiene and a poly(ethylene-butylene);    about 100 to about 500 parts by weight of calcium carbonate; and    about 50 to about 200 parts by weight of glass fibers.    
     
     
         47 . A method of forming a curable composition, comprising: 
 blending 
 a functionalized poly(arylene ether);  
 an alkenyl aromatic monomer;  
 an acryloyl monomer; and  
 a polymeric additive selected from the group consisting of a polystyrene, a poly(styrene-maleic anhydride), a poly(styrene-methyl methacrylate), a polybutene, a poly(ethylene-butylene), a poly(vinyl ether), a poly(vinyl alkanoate) wherein the alkanoate group has at least three carbons, and combinations comprising at least one of the foregoing polymeric additives.  
   
     
     
         48 . A cured composition, comprising the reaction product of: 
 a functionalized poly(arylene ether);    an alkenyl aromatic monomer;    an acryloyl monomer; and    a polymeric additive selected from the group consisting of a polystyrene, a poly(styrene-maleic anhydride), a poly(styrene-methyl methacrylate), a polybutene, a poly(ethylene-butylene), a poly(vinyl ether), a poly(vinyl alkanoate) wherein the alkanoate group has at least three carbons, and combinations comprising at least one of the foregoing polymeric additives.    
     
     
         49 . An article comprising the composition of  claim 48 .  
     
     
         50 . An article comprising the composition of  claim 48  and selected from the group consisting of acid bath containers, neutralization tanks, electrorefining tanks, water softener tanks, fuel tanks, filament-wound tanks, filament-wound tank linings, electrolytic cells, exhaust stacks, scrubbers, automotive exterior panels, automotive floor pans, automotive air scoops, truck bed liners, drive shafts, drive shaft couplings, tractor parts, transverse leaf springs, crankcase heaters, heat shields, railroad tank cars, hopper car covers, boat hulls, submarine hulls, boat decks, marine terminal fenders, aircraft components, propeller blades, missile components, rocket motor cases, wing sections, sucker rods, fuselage sections, wing skins, wing flairings, engine narcelles, cargo doors, aircraft stretch block and hammer forms, bridge beams, bridge deckings, stair cases, railings, walkways, pipes, ducts, fan housings, tiles, building panels, scrubbing towers, flooring, expansion joints for bridges, injectable mortars for patch and repair of cracks in structural concrete, grouting for tile, machinery rails, metal dowels, bolts, posts, electrical encapsulants, electrical panels, printed circuit boards, electrical components, wire windings, seals for electromechanical devices, battery cases, resistors, fuses, thermal cut-off devices, coatings for printed wiring boards, capacitors, transformers, electrically conductive components for antistatic applications, tennis racquets, golf club shafts, fishing rods, skis, ski poles, bicycle parts, swimming pools, swimming pool slides, hot tubs, saunas, mixers, business machine housings, trays, dishwasher parts, refrigerator parts, furniture, garage doors, gratings, protective body gear, luggage, optical waveguides, radomes, satellite dishes, signs, solar energy panels, telephone switchgear housings, transformer covers, insulation for rotating machines, commutators, core insulation, dry toner resins, bonding jigs, inspection fixtures, industrial metal forming dies, and vacuum molding tools.  
     
     
         51 . An automotive part comprising the composition of  claim 48.