Radical polymerizable compositions containing polycyclic olefins

Abstract

In accordance with the present invention, there are provided free-radical polymerizable compositions comprising polycyclic olefins, wherein the polycyclic olefins contain little, if any, cyclopentenyl unsaturation. As a result, these olefins are sufficiently reactive with the propagating free-radicals during cure to provide a highly crosslinked thermoset resin. Moreover, invention compositions comprise high molecular weight polycyclic olefins having low volatility. Accordingly, the observed undesirable weight loss upon cure of prior art thermosetting compositions is considerably reduced. Further provided by the present invention are compositions comprising functionalized polycyclic olefin monomers. These functionalized olefin monomers provide additional benefits such as increased adhesion to a variety of surfaces and greater control over glass transition temperatures.

What is claimed is:  
     
         1 . A free-radical polymerizable thermoset resin composition comprising: 
 (A) at least one polycyclic olefin monomer, the monomer having at least one terminal norbornenyl functional group,    (B) one or more free-radical curing monomers, and    (C) at least one thermally activated free-radical curing catalyst.    
     
     
         2 . A composition of  claim 1 , wherein the polycyclic olefin monomer contains little, if any, cyclopentenyl unsaturation.  
     
     
         3 . A composition according to  claim 1 , wherein the polycyclic olefin monomer comprises the structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 each R 1  is 
 (a) independently hydrogen, alkyl or substituted alkyl, or  
 (b) —X—Y, wherein: 
 X is an optional bridging group,  
 Y is a reactive heterocyclic group or a reactive substituted aryl group;  
 
 
 each x is independently 0, 1 or 2, and n=0 to about 8.  
 
     
     
         4 . A composition according to  claim 3 , wherein bridging group X is an alkylene or oxyalkylene comprising up to about 20 atoms.  
     
     
         5 . A composition according to  claim 3 , wherein bridging group X is a siloxane.  
     
     
         6 . A composition according to  claim 3 , wherein Y is optionally substituted and is selected from the group consisting of a maleimide, a succinimide, an itaconimide, an epoxy group, an oxazoline, a cyanate ester-substituted aryl, and an oxazine.  
     
     
         7 . A composition according to  claim 3 , wherein Y is an optionally substituted maleimide or oxazine.  
     
     
         8 . A composition according to  claim 7 , wherein Y is an oxazine.  
     
     
         9 . A composition according to  claim 8 , wherein the oxazine is a benzoxazine.  
     
     
         10 . A composition according to  claim 1 , wherein the polycyclic olefin monomer comprises the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 R 1 , x, and n are as defined above, and  
 Q is a bridging group.  
 
       
     
     
         11 . A composition according to  claim 10 , wherein Q comprises a siloxane or —K 0,1 —R′—K 0,1 —, wherein 
 R′ is optionally substituted and is an alkylene, an arylene or a polycyclic hydrocarbylene, and  
 each K is independently —O—, —C(O)—, —NH—, —C(O)—NH—, —O—C(O)—NH—, —C(O)—O—, —NH—C(O)—NH—, or —O—C(O)—O—.  
 
     
     
         12 . A composition according to  claim 10 , wherein Q comprises siloxane.  
     
     
         13 . A composition according to  claim 11 , wherein the siloxane is a tetramethyldisiloxane.  
     
     
         14 . A composition according to  claim 11 , wherein the siloxane is 1,3-bis-bicyclo[2.2.1]hept-5-en-2-yl-1,1,3,3-tetramethyl-disiloxane or 1,3-bis-(2-bicyclo[2.2.1]hept-5-en-2-yl-ethyl)-1,1,3,3-tetramethyl-disiloxane.  
     
     
         15 . A composition according to  claim 1  wherein the one or more free-radical curing monomers are selected from the group consisting of a maleimide, succinimide, itaconimide, unsaturated anhydride, (meth)acrylate, styrene, cyanate ester, vinyl ester, vinyl ether, divinyl compound, and allyl amide.  
     
     
         16 . A composition according to  claim 15 , wherein the maleimide, succinimide, and itaconimide comprise, respectively, the structures I, II and III:  
       
         
           
           
               
               
           
         
         wherein: 
 each R 2  is independently selected from hydrogen or lower alkyl, and  
 J is a monovalent or a polyvalent moiety comprising organic or organosiloxane radicals, and combinations of two or more thereof.  
 
       
     
     
         17 . A composition according to  claim 16 , wherein: 
 J is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from the group consisting of a covalent bond, —O—, —S—, —NR—, —O—C(O)—, —O—C(O)—O—, —O—C(O)—NR—, —NR—C(O)—, —NR—C(O)—O—, —NR—C(O)—NR—, —S—C(O)—, —S—C(O)—O—, —S—C(O)—NR—, —O—S(O) 2 —, —O—S(O) 2 —O—, —O—S(O) 2 —NR—, —O—S(O)—, —O—S(O)—O—, —O—S(O)—NR—, —O—NR—C(O)—, —O—NR—C(O)—O—, —O—NR—C(O)—NR—, —NR—O—C(O)—, —NR—O—C(O)—O—, —NR—O—C(O)—NR—, —O—NR—C(S)—, —O—NR—C(S)—O—, —O—NR—C(S)—NR—, —NR—O—C(S)—, —NR—O—C(S)—O—, —NR—O—C(S)—NR—, —O—C(S)—, —O—C(S)—O—, —O—C(S)—NR—, —NR—C(S)—, —NR—C(S)—O—, —NR—C(S)—NR—, —S—S(O) 2 —, —S—S(O) 2 —O—, —S—S(O) 2 —NR—, —NR—O—S(O)—, —NR—O—S(O)—O—, —NR—O—S(O)—NR—, —NR—O—S(O) 2 —, —NR—O—S(O) 2 —O—, —NR—O—S(O) 2 —NR—, —O—NR—S(O)—, —O—NR—S(O)—O—, —O—NR—S(O)—NR—, —O—NR—S(O) 2 —O—, —O—NR—S(O) 2 —NR—, —O—NR—S(O) 2 —, —O—P(O)R 2 —, —S—P(O)R 2 —, —NR—P(O)R 2 —, wherein each R is independently hydrogen, alkyl or substituted alkyl, and combinations of any two or more thereof.    
     
     
         18 . A composition according to  claim 16 , wherein: 
 m=1-6,    p=0-6, and    J is 
 (a) saturated straight chain alkyl or branched chain alkyl, optionally containing optionally substituted aryl moieties as substituents on the alkyl chain or as part of the backbone of the alkyl chain, and wherein the alkyl chains have up to about 20 carbon atoms;  
 (b) a siloxane having the structure: —(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —, —(C(R 3 ) 2 ) d —C(R 3 )—C(O)O—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —O(O)C—(C(R 3 ) 2 ) e —, or —(C(R 3 ) 2 ) d —C(R 3 )—O(O)C—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —C(O)O—(C(R 3 ) 2 ) e — wherein: 
 each R 3  is independently hydrogen, alkyl or substituted alkyl,  
 each R 4  is independently hydrogen, lower alkyl or aryl,  
 d=1-10,  
 e=1-10, and  
 f=1-50;  
 
   (c) a polyalkylene oxide having the structure:    —[(CR 2 ) r —O—] f —(CR 2 ) s — wherein: 
 each R is independently hydrogen, alkyl or substituted alkyl,  
 r=1-10,  
 s=1-10, and  
 f is as defined above;  
     (d) aromatic groups having the structure:                        wherein each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and Z is: 
 (i) saturated straight chain alkylene or branched chain alkylene, optionally containing saturated cyclic moieties as substituents on the alkylene chain or as part of the backbone of the alkylene chain, or  
 (ii) polyalkylene oxides having the structure:  
 —[(CR 2 ) r —O—] q —(CR 2 ) s — wherein each R is independently defined as above, r and s are each defined as above, and q falls in the range of 1 up to 50;    
     (e) di- or tri-substituted aromatic moieties having the structure:                        wherein each R is independently defined as above, t falls in the range of 2 up to 10, u falls in the range of 2 up to 10, and Ar is as defined above;      (f) aromatic groups having the structure:                        wherein: 
 each R is independently defined as above,  
 t=2-10,  
 k=1, 2 or 3,  
 g=1 up to about 50, each Ar is as defined above,  
 E is —O— or —NR 5 —, wherein R 5  is hydrogen or lower alkyl; and  
 W is 
 (i) straight or branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene, oxyalkenylene, ester, or polyester,  
 (ii) a siloxane having the structure —(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —, —(C(R 3 ) 2 ) d —C(R 3 )—C(O)O—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —O(O)C—(C(R 3 ) 2 ) e —, or —(C(R 3 ) 2 ) d —C(R 3 )—O(O)C—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —C(O)O—(C(R 3 ) 2 ) e — wherein,  
  each R 3  is independently hydrogen, alkyl or substituted alkyl,  
  each R 4  is independently hydrogen, lower alkyl or aryl,  
  d=1-10,  
  e=1-10, and  
  f=1-50; or  
 (iii) a polyalkylene oxide having the structure:  
 —[(CR 2 ) r —O—] f —(CR 2 ) s — 
  wherein:  
  each R is independently hydrogen, alkyl or substituted alkyl,  
  r=1-10,  
  s=1-10, and  
  f is as defined above;  
 optionally containing substituents selected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl;  
 
     (g) a urethane group having the structure:    R 7 —U—C(O)—NR 6 —R 8 —NR 6 —C(O)—(O—R 8 —O—C(O)—NR 6 —R 8 —NR 6 —C(O)) v —U—R 8 — wherein: 
 each R 6  is independently hydrogen or lower alkyl;  
 each R 7  is independently an alkyl, aryl, or arylalkyl group having 1 to 18 carbon atoms;  
 each R 8  is an alkyl or alkyloxy chain having up to about 100 atoms in the chain, optionally substituted with Ar;  
 U is —O—, —S—, —N(R)—, or —P(L) 1,2 — wherein R as defined above, and wherein each L is independently ═O, ═S, —OR or —R; and  
 v=0-50;  
     (h) polycyclic alkenyl; or    (i) mixtures of any two or more thereof.    
     
     
         19 . A composition according to  claim 16 , wherein J is of sufficient length to render liquid at ambient temperature the maleimide, succinimide, itaconimide or combinations of two or more thereof.  
     
     
         20 . A composition according to  claim 16 , wherein, 
 m=1, 2 or 3, and    J is a branched chain alkyl, alkylene or alkylene oxide of sufficient length and branching to render liquid at ambient temperature the maleimide, succinimide, itaconimide or combinations of two or more thereof.    
     
     
         21 . A composition according to  claim 16 , wherein the maleimide is selected from the group consisting of N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-t-butylmaleimide, N-hexylmaleimide, N-2-ethylhexylmaleimide, N-cyclohexylmaleimide, N-octylmaleimide, N-decylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, 2-methyl-N-phenylmaleimide, 4-methyl-N-phenylmaleimide, 2-ethyl-N-phenylmaleimide, 4-ethyl-N-phenylmaleimide, 2,6-diethyl-N-phenylmaleimide, and a mixture of any two or more thereof.  
     
     
         22 . A composition according to  claim 15 , wherein the free-radical curing comonomer is unsaturated anhydride.  
     
     
         23 . A composition according to  claim 22 , wherein the unsaturated anhydride is selected from the group consisting of maleic anhydride, citraconic anhydride, itaconic anhydride, and cyclopentadiene Diels-Alder adducts thereof.  
     
     
         24 . A composition according to  claim 23 , wherein the Diels-Alder adducts comprise the structure:  
       
         
           
           
               
               
           
         
         wherein: 
 each V is independently an alkyl or substituted alkyl,  
 each x is independently 0, 1 or 2, and  
 m=0-9.  
 
       
     
     
         25 . A composition according to  claim 15 , wherein the monomer is a (meth)acrylate.  
     
     
         26 . A composition according to  claim 25 , wherein the (meth)acrylate is selected from the group consisting of 
 (a) the formula:                        wherein: 
 G is hydrogen, halogen, or an alkyl having from 1 to 4 carbon atoms, R 10  has from 1 to 16 carbon atoms and is an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl group, optionally substituted or interrupted with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulfur, sulfonate, or sulfone;  
     (b) urethane acrylates or ureide acrylates represented by the formula:                        wherein: 
 G is hydrogen, halogen, or an alkyl having from 1 to 4 carbon atoms;  
 R 11  is a divalent alkyl, cycloalkyl, aromatic, or arylalkyl group, bound through a carbon atom or carbon atoms thereof indicated at the —O— atom and —X— atom or group;  
 X is —O—, —NH—, or —N(alkyl)-, in which the alkyl radical has from 1 to 8 carbon atoms;  
 z is 2 to 6; and  
 R 12  is a z-valent cycloalkyl, aromatic, or arylalkyl group bound through a carbon atom or carbon atoms thereof to the one or more NH groups; or  
     (c) a di- or tri-(meth)acrylate selected from polyethylene glycol di(meth)acrylates, bisphenol-A di(meth)acrylates, tetrahydrofurane di(meth)acrylates, hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, and combinations of any two or more thereof.    
     
     
         27 . A composition according to  claim 26 , wherein the (meth)acrylate is selected from the group consisting of triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, di-pentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, bisphenol-A-ethoxylate dimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, bisphenol-A-diepoxide dimethacrylate, and combinations of any two or more thereof.  
     
     
         28 . A composition according to  claim 26 , wherein the (meth)acrylate is selected from the group consisting of polyethylene glycol di(meth)acrylates, bisphenol-A di(meth)acrylates, tetrahydrofurane (meth)acrylates and di(meth)acrylates, citronellyl acrylate and citronellyl methacrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, ethoxylated trimethylol propane triacrylate, triethylene glycol acrylate, triethylene glycol methacrylate, and combinations of any two or more thereof.  
     
     
         29 . A composition according to  claim 15 , wherein the monomer is a divinyl compound.  
     
     
         30 . A composition according to  claim 29 , wherein the divinyl compound comprises the structure:  
       CHR 9 ═CR 9 -M 0,1 -D-M 0,1 -D-M 0,1 -CR 9 ═CHR 9    wherein: 
 each R 9  is independently hydrogen, lower alkyl or aryl,  
 each M is independently —O—, —O—C(O)—, —C(O)— or —C(O)O—, and  
 D is a monovalent or a polyvalent moiety comprising organic or organosiloxane radicals, and combinations of any two or more thereof.  
   
     
     
         31 . A composition according to  claim 30 , wherein D is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from the group consisting of a covalent bond, —O—, —S—, —NR—, —O—C(O)—, —O—C(O)—O—, —O—C(O)—NR—, —NR—C(O)—, —NR—C(O)—O—, —NR—C(O)—NR—, —S—C(O)—, —S—C(O)—O—, —S—C(O)—NR—, —O—S(O) 2 —, —O—S(O) 2 —O—, —O—S(O) 2 —NR—, —O—S(O)—, —O—S(O)—O—, —O—S(O)—NR—, —O—NR—C(O)—, —O—NR—C(O)—O—, —O—NR—C(O)—NR—, —NR—O—C(O)—, —NR—O—C(O)—O—, —NR—O—C(O)—NR—, —O—NR—C(S)—, —O—NR—C(S)—O—, —O—NR—C(S)—NR—, —NR—O—C(S)—, —NR—O—C(S)—O—, —NR—O—C(S)—NR—, —O—C(S)—, —O—C(S)—O—, —O—C(S)—NR—, —NR—C(S)—, —NR—C(S)—O—, —NR—C(S)—NR—, —S—S(O) 2 —, —S—S(O) 2 —O—, —S—S(O) 2 —NR—, —NR—O—S(O)—, —NR—O—S(O)—O—, —NR—O—S(O)—NR—, —NR—O—S(O) 2 —, —NR—O—S(O) 2 —O—, —NR—O—S(O) 2 —NR—, —O—NR—S(O)—, —O—NR—S(O)—O—, —O—NR—S(O)—NR—, —O—NR—S(O) 2 —O—, —O—NR—S(O) 2 —NR—, —O—NR—S(O) 2 —, —O—P(O)R 2 —, —S—P(O)R 2 —, —NR—P(O)R 2 —, wherein each R is independently hydrogen, alkyl or substituted alkyl, and combinations of any two or more thereof.  
     
     
         32 . A composition according to  claim 31 , wherein D is 
 (a) saturated straight chain alkyl or branched chain alkyl, optionally containing optionally substituted aryl moieties as substituents on the alkyl chain or as part of the backbone of the alkyl chain, and wherein the alkyl chains have up to about 20 carbon atoms;    (b) a siloxane having the structure —(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —, —(C(R 3 ) 2 ) d —C(R 3 )—C(O)O—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —O(O)C—(C(R 3 ) 2 ) e —, or —(C(R 3 ) 2 ) d —C(R 3 )—O(O)C—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —C(O)O—(C(R 3 ) 2 ) e — wherein, 
 each R 3  is independently hydrogen, alkyl or substituted alkyl,  
 each R 4  is independently hydrogen, lower alkyl or aryl,  
 d=1-10,  
 e=1-10, and  
 f=1-50;  
   (c) a polyalkylene oxide having the structure:    —[(CR 2 ) r —O—] f —(CR 2 ) s — wherein: 
 each R is independently hydrogen, alkyl or substituted alkyl,  
 r=1-10,  
 s=1-10, and  
 f is as defined above;  
     (d) aromatic groups having the structure:                        wherein each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to 10 carbon atoms, and Z is: 
 (i) saturated straight chain alkylene or branched chain alkylene, optionally containing saturated cyclic moieties as substituents on the alkylene chain or as part of the backbone of the alkylene chain, or  
 (ii) polyalkylene oxides having the structure:  
 —[(CR 2 ) r —O—] q —(CR 2 ) s — wherein each R is independently defined as above, r and s are each defined as above, and q falls in the range of 1 up to 50;    
     (e) di- or tri-substituted aromatic moieties having the structure:                        wherein each R is independently defined as above, t falls in the range of 2 up to 10, u falls in the range of 2 up to 10, and Ar is as defined above;      (f) aromatic groups having the structure:                        wherein: 
 each R is independently defined as above,  
 t=2-10,  
 k=1, 2 or 3,  
 g=1 up to about 50,  
 each Ar is as defined above,  
 E is —O— or —NR 5 —, wherein R 5  is hydrogen or lower alkyl; and  
 W is 
 (i) straight or branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene, oxyalkenylene, ester, or polyester,  
 (ii) a siloxane having the structure —(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —, —(C(R 3 ) 2 ) d —C(R 3 )—C(O)O—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —O(O)C—(C(R 3 ) 2 ) e —, or —(C(R 3 ) 2 ) d —C(R 3 )—O(O)C—(C(R 3 ) 2 ) d —[Si(R 4 ) 2 —O] f —Si(R 4 ) 2 —(C(R 3 ) 2 ) e —C(O)O—(C(R 3 ) 2 ) e — wherein, 
 each R 3  is independently hydrogen, alkyl or substituted alkyl,  
 each R 4  is independently hydrogen, lower alkyl or aryl,  
 d=1-10,  
 e=1-10, and  
 f=1-50; or  
 
 
 (iii) a polyalkylene oxide having the structure:  
 —[(CR 2 ) r —O—] f —(CR 2 ) s — wherein:     each R is independently hydrogen, alkyl or substituted alkyl,     r=1-10,     s=1-10, and     f is as defined above;    optionally containing substituents selected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl;    
     (g) a urethane group having the structure:    —R 7 —U—C(O)—NR 6 —R 8 —NR 6 —C(O)—(O—R 8 —O—C(O)—NR 6 —R 8 —NR 6 —C(O)) v —U—R 8 — wherein: 
 each R 6  is independently hydrogen or lower alkyl;  
 each R 7  is independently an alkyl, aryl, or arylalkyl group having 1 to 18 carbon atoms;  
 each R 8  is an alkyl or alkyloxy chain having up to about 100 atoms in the chain, optionally substituted with Ar;  
 U is —O—, —S—, —N(R)—, or —P(L) 1,2 — wherein R as defined above, and wherein each L is independently ═O, ═S, —OR or —R; and  
 v=0-50;  
     (h) polycyclic alkenyl; or    (i) mixtures of any two or more thereof.    
     
     
         33 . A composition according to  claim 1 , wherein the curing catalyst is selected from the group consisting of peroxy ester, peroxy carbonate, hydroperoxide, alkylperoxide, arylperoxide, and an azo compound.  
     
     
         34 . A die-attach formulation comprising: 
 (A) a thermoset resin composition according to  claim 1 , and    (B) a conductive filler.    
     
     
         35 . A die-attach formulation according to  claim 34  wherein the filler is electrically conductive.  
     
     
         36 . A die-attach formulation according to  claim 34  wherein the filler is thermally conductive.  
     
     
         37 . In a die-attach formulation, the improvement comprising incorporating into the die-attach formulation an effective amount of a composition according to  claim 1 .  
     
     
         38 . An assembly comprising a first article adhered to a second article by a cured aliquot of a die-attach formulation according to  claim 34 .  
     
     
         39 . An assembly comprising a first article adhered to a second article by a cured aliquot of a die-attach formulation according to  claim 35 .  
     
     
         40 . An assembly comprising a first article adhered to a second article by a cured aliquot of a die-attach formulation according to  claim 36 .  
     
     
         41 . A method for adhesively attaching a device to a substrate, the method comprising curing a die-attach formulation according to  claim 34  positioned between the substrate and the device.  
     
     
         42 . A method according to  claim 41 , wherein the device is a semiconductor die and the substrate is a lead frame.  
     
     
         43 . A method according to  claim 41 , wherein the lead frame is a copper lead frame.  
     
     
         44 . An adhesive film formulation comprising: 
 (A) a thermoset resin composition according to  claim 1 , and    (B) a thermoplastic elastomer that is a block copolymer having at least one unit of the general formula (A-B) or (A-B-A), wherein A is a non-elastomeric polymer block and B is an elastomeric polymer block that is the polymerization product of optionally substituted olefin monomers and/or optionally substituted conjugated diene monomers.    
     
     
         45 . A method for adhesively attaching a device to a substrate, the method comprising curing an adhesive film formulation according to  claim 44  positioned between the substrate and the device.  
     
     
         46 . A method according to  claim 45 , wherein the device is a semiconductor die and the substrate is a lead frame.  
     
     
         47 . An assembly comprising a first article adhered to a second article by a cured aliquot of an adhesive film formulation according to  claim 44 .  
     
     
         48 . In a free radical-polymerizable thermoset resin composition, the improvement comprising incorporating into the composition an effective amount of at least one polycyclic olefin monomer, the monomer having at least one terminal norbornenyl functional group.