Ultraviolet transmissive polyhedral silsesquioxane polymers

Abstract

Inorganic/organic hybrid polymers containing silsesquioxane cages are robust and exhibit desirable physical properties such as strength, hardness, and optical transparency at infrared and ultraviolet wavelengths. The polymers are prepared by polymerizing functionalized polyhedral silsesquioxane monomers such as polyhedral silsesquioxanes bearing two complementarily reactive functional groups bonded to cage silicon atoms by means of spacer moieties. The spacer moieties allow for steric mobility and more complete cure than polyhedral silsesquioxanes bearing reactive functional groups bound directly to cage silicon atoms.

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         19 . A process for preparing an organic-inorganic hybrid polymer UV transparent material, comprising:
 a) functionalizing a polyhedral silsesquioxane with a first functionalizing group to form a first reactive functionalized polyhedral silsesquioxane of the approximate formula [R 1 Me 2 SiOSiO 1.5 ] n  where n is 6, 8, 10, or 12, or a mixture thereof,   b) functionalizing a polyhedral silsesquioxane with a second functionalizing group to form a second reactive functionalized polyhedral silsesquioxane of the approximate formula [R 2 Me 2 SiOSiO 1.5 ] n  where n is 6, 8, 10, or 12, or a mixture thereof,   
       where R 1  and R 2  are reactive functional groups which react with each other to covalently bond said first reactive functional polyhedral silsesquioxane with said second reactive silsesquioxane, and wherein some of R 1  and R 2  may be replaced by R groups which are non-reactive with R 1  and R 2 , and
 c) curing said first and second reactive functionalized silsesquioxanes. 
 
     
     
         20 . The process of  claim 19 , wherein said first reactive functionalized polyhedral silsesquioxane bears on average at least 2 R 1  groups and said second reactive functionalized polyhedral silsesquioxane bears on average at least 2 R 2  groups. 
     
     
         21 . The process of  claim 19 , wherein said first reactive functionalized polyhedral silsesquioxane bears on average at least 4 R 1  groups and said second reactive functionalized polyhedral silsesquioxane bears on average at least 4 R 2  groups. 
     
     
         22 . The process of  claim 19 , wherein said first reactive functionalized polyhedral silsesquioxane bears on average at least 6 R 1  groups and said second reactive functionalized polyhedral silsesquioxane bears on average at least 6 R 2  groups. 
     
     
         23 . The process of  claim 19 , wherein reactive functional groups R 1  comprise two different reactive functional groups R 1 ′ and R 2 ″ and wherein reactive functional groups R 2  comprise two different reactive functional groups R 2 ′ and R 2 ″, R 1 ′ and R 2 ′ reactive with each other and R 1 ″ and R 2 ″ reactive with each other. 
     
     
         24 . The process of  claim 19 , wherein at least one reactive functional group is selected from the group consisting of Si-bonded hydrogen, alkenyl, alkynyl, and cycloalkenyl. 
     
     
         25 . The process of  claim 19 , wherein non-reactive R group are selected from the groups comprising of alkyl, cycloalkyl, trialkylsilyl, and trialkylsilyl-terminated (poly)siloxy. 
     
     
         26 . The process of  claim 23 , wherein at least one reactive functional group is selected from the group consisting of Si-bonded hydrogen, alkenyl, alkynyl, and cycloalkenyl. 
     
     
         27 . The process of  claim 19 , wherein at least one reactive functional group is derived from the reaction of a polyhedral silsesquioxane moiety with a functionalizing reagent selected from the group consisting of 4-vinyl-1-cyclohexene, dimethylvinylchlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dicyclopentadiene, bis[trimethylsilyl]acetylene, trimethylsilylacetylene and cyclohexadiene, dimethylallylchlorosilane, dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene. 
     
     
         28 . The process of  claim 19 , wherein the mol ratio of R 1  to R 2  is 0.20:1 to 1:1. 
     
     
         29 . The process of  claim 23 , wherein the mol ratio of R 1″  to R 2″  is 0.20:1 to 1:1. 
     
     
         30 . The process of  claim 19 , wherein in either or both steps of functionalizing, a catalyst which accelerates the reaction of a polyhedral silsesquioxane with a functionalizing reagent is added. 
     
     
         31 . The process of  claim 30 , wherein said catalyst comprises a transition metal. 
     
     
         32 . The process of  claim 31 , wherein said catalyst comprises at least one of Pt(dvs), Pt(dcp), or PtO 2 . 
     
     
         33 . The process of  claim 30 , wherein following reaching a targeted average content of reactive functional groups, functionalization is stopped without adding a deactivation agent. for the catalyst in either or both steps of functionalizing. 
     
     
         34 . The process of  claim 30 , wherein following reaching a targeted average content of reactive functional groups, functionalization is stopped by adding a catalyst deactivator in an amount less than that required to totally deactivate said catalyst in either or both steps of functionalizing. 
     
     
         35 . The process of  claim 34 , wherein the catalyst comprises a platinum compound and the catalyst deactivator comprises triphenylphosphine in a deactivating amount greater than 0 mol % and less than 0.09 mol % based on mols of functionalized polyhedral silsesquioxane. 
     
     
         36 . The process of  claim 19 , further comprising precipitating said functionalized silsesquioxane following step b) from solution in a solvent or solvent mixture, washing the precipitate with the same or a different solvent or solvent mixture to provide a solid, purified polyhedral silsesquioxane macromonomer, and optionally redissolving, precipitating, and washing, more than two times, to provide a further purified solid macromonomer in either or both steps of functionalizing. 
     
     
         37 . The process of  claim 36 , wherein at least one solvent is selected from the group consisting of alcohols, nitriles, ethers, sulfoxides, and amides. 
     
     
         38 . The process of  claim 19  or  23 , wherein a curing catalyst effective to accelerate the reaction of reactive functionalities is added prior to or during curing. 
     
     
         39 . The process of  claim 19  or  23 , wherein said curing is conducted in a liquid phase. 
     
     
         40 . The process of  claim 39 , wherein said liquid phase is a melt phase. 
     
     
         41 . The process of  claim 39 , wherein said liquid phase is a solution phase. 
     
     
         42 . The process of  claim 19 , wherein R 1  and R 2  are the same. 
     
     
         43 . The process of  claim 42 , wherein said first and said second functionalized silsesquioxanes are prepared by reacting a silsesquioxane of the approximate formula
   [H—Si(Me) 2 -O—SiO 1.5 ] n  
   
       where n is 6, 8, 10, or 12, or mixtures thereof, with at least one silane selected from the group consisting of dimethylvinylmethoxysilane and dimethylvinylethoxysilane. 
     
     
         44 . A process for preparing an organic-inorganic hybrid polymer encapsulating material, comprising:
 a) providing a polyhedral silsesquioxane;   b) functionalizing said polyhedral silsesquioxane with one or more types of reactive functional groups R 1  to provide functional polyhedral silsesquioxane of the formula
   [RMe 2 SiOSiO 1.5 ] n    
    where n is 6, 8, 10, 12, or mixtures thereof, and where R is a reactive or non-reactive organic group, with the proviso that at least one R is a reactive functional group R 1 , to form a macromonomer;   c) adding a crosslinking agent reactive with reactive functional group R 1 , to form a curable mixture; and   d) curing said curable mixture to form a hybrid organic-inorganic encapsulant having a light transmission at 215 nm of at least 60%.   
     
     
         45 . The process of  claim 44 , wherein said polyhedral silsesquioxane bears HMe 2 SiO-functionality, and said functionalizing comprises hydrosilylating at least one functionalizing reagent selected from the group consisting of 4-vinyl-1-cyclohexene, dimethylvinylchlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dicyclopentadiene, bis[trimethylsilyl]acetylene, trimethylsilylacetylene and dimethylallylsilane, 1,1,3,3-tetramethyl-1-allyldisiloxane 1,1,3,3-tetramethyl-1-vinyldisiloxane, dimethyloctenylsilane, dimethylsilane, 1,1,3,3-tetramethyl-1,3-disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,2-dimethylsilylethane, divinyldimethylsilane, 1,3-diallyltetramethyldisiloxane, 1,3-diallyltetraphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,2-bis(dimethylsilyl)ethane, dimethylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, 1,1,3,3-tetramethylvinylchlorosilane, 1,1,3,3-tetramethylvinylmethoxysilane, 1,1,3,3-tetramethylvinylethoxysilane, [(bicycloheptenyl)ethyl]dimethylchlorosilane, [(bicycloheptenyl)ethyl]dimethylmethoxysilane, [(bicycloheptenyl)ethyl]dimethylethoxysilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, 6-hexenyldimethylchlorosilane, 6-hexenyldimethylmethoxysilane, 6-hexenyldimethylethoxysilane, 10-undecenyldimethylchlorosilane, 10-undecenyldimethylmethoxysilane, 10-undecenyldimethylethoxysilane, [2-(3-cyclohexenyl)ethyl]dimethylchlorosilane, [2-(3-cyclohexenyl)ethyl]dimethylmethoxysilane, [2-(3-cyclohexenyl)ethyl]dimethylethoxysilane, 1,5-dichlorohexamethyltrisiloxane, 1,5-dimethoxyhexamethyltrisiloxane, 1,5-diethoxyhexamethyltrisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, 1,3-dichlorotetraphenyldisiloxane, 1,3-dimethoxytetraphenyldisiloxane, 1,3-diethoxytetraphenyldisiloxane, diallyldiphenylsilane, 1,4-Bis(hydroxydimethylsilyl)benzene, diisopropylchlorosilane, diisopropylmethoxysilane, diisopropylethoxysilane, diisopropyldichlorosilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, dimesityldichlorosilane, diphenylchlorosilane, diphenylvinylchlorosilane, diphenylvinylmethoxysilane, diphenylvinylethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, diphenylsilane, di(p-tolyl)dichlorosilane, di(p-tolyl)dimethoxysilane, di(p-tolyl)diethoxysilane, 1,5-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,5-divinyl-3-phenylpentamethyltrisiloxane, divinyltetraphenyldisiloxane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, phenylethyldichlorosilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethylsilane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, 1,1,3,3-tetraisopropyl-1,3-dichlorodisiloxane, 1,1,3,3-tetraisopropyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetraisopropyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraisopropyldisiloxane, vinylphenylmethylchlorosilane, vinylphenylmethylmethoxysilane, vinylphenylmethylethoxysilane, and vinylphenylmethylsilane. 
     
     
         46 . The process of  claim 44  or  45 , wherein a catalyst which accelerates said step of functionalizing is present during said step of functionalizing. 
     
     
         47 . The process of  claim 46 , wherein a catalyst deactivator is added when a targeted amount of functionalization has been reached, said catalyst deactivator added in a quantity less than that necessary to completely deactivate the catalyst. 
     
     
         48 . The process of  claim 44 , further comprising purifying said macromonomer at least twice by precipitating said macromonomer from a solvent or solvent mixture and washing the precipitate with the same or a different solvent or solvent mixture to obtain a purified macromonomer. 
     
     
         49 . The process of  claim 44 , wherein a curing catalyst which accelerates the reaction between reactive groups R 1  and the crosslinker are added prior to or during curing. 
     
     
         50 . The process of  claim 44 , wherein prior to curing said, macromonomer is dissolved in one or more solvents. 
     
     
         51 . A process for synthesizing a UV transparent organic-inorganic hybrid macromonomer, comprising:
 a) providing a polyhedral silsesquioxane having reactive sites thereon;   b) reacting at least a portion of said reactive sites with one or more functionalizing reagents to provide a macromonomer of the formula
   [RMe 2 SiOSiO 1.5 ] n    
    wherein n is 6, 8, 10, 12, or mixtures thereof, and R is a non-reactive or reactive group, with the proviso that at least one R is an R 1  reactive group and at least one R is an R 2  reactive group, where R 1  and R 2  are interreactive, and wherein all groups R are selected such that said macromonomer has a light transmission of at least 60% at 215 nm.   
     
     
         52 . The process of  claim 51 , wherein R 1  and R 2  are individually selected from the group consisting of silicon-bonded H, alkenyl, alkynyl, and cycloalkenyl. 
     
     
         53 . The process of  claim 51 , wherein non-reactive R are individually selected from the group consisting of alkyl, cycloalkyl, trimethylsilyl, and trimethylsilyl-terminated(poly)dimethylsiloxy. 
     
     
         54 . The process of  claim 51 , wherein said polyhedral silsesquioxane has the formula
   [HMe 2 SiOSiO 1.5 ] n      
       and functionalizing takes place with one or more functionalizing reagents selected from the group consisting of 4-vinyl-1-cyclohexene, dimethylvinylchlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dicyclopentadiene, bis[trimethylsilyl]acetylene, trimethylsilylacetylene, cyclohexadiene, dimethylallylchlorosilane, dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene. 
     
     
         55 . The process of  claim 51 , wherein the mol ratio of R 1  to R 2  is from 0.20:1 to 1:1. 
     
     
         56 . The process of  claim 51 , wherein a catalyst which accelerates functionalizing is present during said step of functionalizing. 
     
     
         57 . The process of  claim 56 , wherein said catalyst is a transition metal compound. 
     
     
         58 . The process of  claim 56 , wherein said catalyst is a platinum-containing catalyst. 
     
     
         59 . The process of  claim 56 , wherein at least one catalyst comprises Pt(dvs) or Pt(dcp), or PtO 2 . 
     
     
         60 . The process of  claim 56 , wherein when a targeted degree of functionalization with reactive groups has been attained, functionalization is stopped without deactivating said catalyst. 
     
     
         61 . The process of  claim 56 , wherein when a targeted degree of functionalization with reactive groups has been attained, functionalization is stopped by adding a catalyst deactivator in an amount less than that required to totally deactivate said catalyst. 
     
     
         62 . The process of  claim 61 , wherein the catalyst is a platinum-containing catalyst and the catalyst deactivator is triphenylphosphine added in an amount greater than 0 mol % and less than 0.09 mol % relative to mols of macromonomer. 
     
     
         63 . The process of  claim 51 , further comprising purifying said macromonomer at least twice by each time precipitating from a solution in a solvent or solvent mixture, washing the precipitate with the same or a different solvent or solvent mixture, to obtain a purified macromonomer. 
     
     
         64 . The process of  claim 63 , wherein at least one solvent is selected from the group consisting of alcohols, nitriles, ethers, sulfoxides, and amides. 
     
     
         65 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently bonded polyhedral silsesquioxane macromonomer-derived moieties of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     where n is a positive whole number, n′ is 0 or a positive whole number and the sum n+n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1  or R 2 , and   A is a divalent bridging group linking two polyhedral silsesquioxane moieties and   derived from the reaction of two interreactive groups R 1  and R 2  which are different from each other, each macromonomer possessing, on average, both R 1  and R 2  groups,   
       wherein one of said reactive functional groups is Si-bonded H, the other is derived from reaction of silicon-bonded H with one or more functionalizing reagents selected from the group consisting of dicyclopentadiene, bis[trimethylsilyl]acetylene, trimethylsilylacetylene, cyclohexadiene, and 5-vinyl-2-norbornene. 
     
     
         66 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently bonded polyhedral silsesquioxane macromonomer-derived moieties, of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     where n is a positive whole number, n′ is 0 or a positive whole number and the sum n+n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1  or R 2 ,   A is a divalent bridging group linking two polyhedral silsesquioxane moieties and   derived from the reaction of two different interreactive groups R 1  and R 2 , each macromonomer bearing at least two R 1  or R 2  groups, and not bearing both R 1  and R 2  groups,   
       wherein the reactive and non-reactive groups R and the bridging group A are selected such that the polymer material has a light transmission of at least 60% at 215 nm. 
     
     
         67 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently bonded polyhedral silsesquioxane macromonomer-derived moieties, of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [B 0.5 Me 2 SiOSiO 1.5 ] n″ [RMe 2 SiOSiO 1.5 ] n′     where n′ is 0 or a positive whole number, and n and n″ are positive whole numbers, and the sum of n, n′, and n″ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1 , R 2 , R 3 , or R 4 ,   A is a divalent bridging group linking two polyhedral silsesquioxane moieties and derived from the reaction of two interreactive groups R 1  and R 2 ,   B is a divalent bridging group linking two polyhedral silsesquioxane moieties and derived from the reaction of two interreactive groups R 3  and R 4 ,   
       wherein a first polyhedral silsesquioxane macromonomer bears R 1  and R 3  groups and a second polyhedral silsesquioxane macromonomer bears R 2  and R 4  groups, and 
       wherein non-reactive groups R, unreacted groups R, bridging groups A, and bridging groups B are such that said polymer material has a light transmission of at least 60% at 215 nm. 
     
     
         68 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently linked polyhedral silsesquioxane macromonomers, of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     wherein n is a positive whole number and n′ is 0 or a positive whole number and the sum n+n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive group R 1 , R 1  being the same or different;   A is a bridging group linking two polyhedral silsesquioxane moieties, formed from the reaction of two R 1 ,   
       wherein R, R 1 , and A are such that the polymer material has a light transmission of at least 60% at 215 nm. 
     
     
         69 . An organic-inorganic polymer material comprising a plurality of identical or different covalently bonded silsesquioxane macromonomer-derived moieties, of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     where n is a positive whole number and n′ is 0 or a positive whole number and the sum of n and n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1 ,   R 1  are the same or different reactive functional groups which are interreactive with a reactive functional group R 5  borne on a crosslinker molecule having at least two R 5  groups, R 5  being the same or different,   A is a divalent linking group derived from the reaction of a reactive R 1  group of a polyhedral silsesquioxane macromonomer and a reactive R 5  group of a crosslinker molecule,   
       wherein R, R 1 , R 5 , and A are such that the polymer has a light transmission of at least 60% at 215 nm. 
     
     
         70 . The polymer material of  claims 65  to  69 , wherein reactive functional groups are selected from the group consisting of silicon-bonded H, alkenyl, alkynyl, and cycloalkenyl groups, and mixtures thereof. 
     
     
         71 . The polymer material of  claims 65  to  69 , wherein said reactive functional groups are derived from reaction of silicon-bonded H with one or more functionalizing reagents selected from the group consisting of 4-vinyl-1-cyclohexene, dimethylvinylchlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dicyclopentadiene, bis[trimethylsilyl]acetylene, trimethylsilylacetylene, cyclohexadiene, dimethylallylchlorosilane, dimethylhexenylchlorosilane, and 5-vinyl-2-norbornene. 
     
     
         72 . The polymer material of  claims 65  to  69 , wherein at least two interreactive functional groups have reacted, these two interreactive functional groups present, prior to forming bridging moieties A or B, in a mol ratio of 0.25:1 to 1:1. 
     
     
         73 . The polymer material of  claim 68 , wherein said reactive functional groups R 1  are the same. 
     
     
         74 . The polymer material of  claim 68 , wherein said reactive functional groups are derived from the reaction of polyhedral silsesquioxane moiety with a functionalizing reagent selected from the group consisting of dimethylvinylmethoxysilane and dimethylvinylethoxysilane. 
     
     
         75 . The polymer material of  claim 69 , wherein at least one crosslinker is selected from the group consisting of alkenyl-functional di- or polysiloxanes Si—H-functional di- or polysiloxanes, and aliphatic di- and polyenes. 
     
     
         76 . The polymer material of  claim 69 , wherein at least one crosslinker is selected from the group consisting of vinyl-functional di- or polysiloxanes containing minimally three vinyl groups on average and Si—H-functional di- or polysiloxanes containing minimally three Si-bonded H atoms on average. 
     
     
         77 . A polymer exhibiting transmission below 380 nm, comprising the polymerized product of
 a) a monomer mixture comprising one or more polyhedral silsesquioxanes (A), the cage of which corresponds approximately to the formula Si n O 1.5n  where n is from 6 to 12, wherein silicon atoms of polyhedral silsesquioxane (A) are functionalized with complementarily reactive functional groups such that from about 20 to 80 mol percent of a first complementarily reactive group are present, and from about 80 to about 20 mol percent of a second complementarily reactive group are present, and not more than 80 mol percent of non-reactive groups are present, at least one of said first or said second complementarily reactive groups bonded to said silicon atoms of said polyhedral silsesquioxane (A) through a spacer moiety; or   b) a monomer mixture comprising
 b)i) one or more polyhedral silsesquioxane (B), the cage of which corresponds approximately to the formula Si n O 1.5n  where n is from 6 to 12, wherein from 20 to 100 mol percent of silicon atoms of said polyhedral silsesquioxane (B) are bonded to a first reactive group by means of a spacer moiety, and the remaining silicon atoms of said cages silsesquioxane (b) are bonded to non-functional groups; 
   b)ii) optionally one or more further polyhedral silsesquioxanes (C) of the approximate formula Si n O 1.5n  wherein cage silicon atoms of said polyhedral silsesquioxane (C) are bonded to reactive groups of the same reactive type as said first reactive group of polyhedral silsesquioxane (B), or to a complementarily reactive group with respect to the first reactive groups of said polyhedral silsesquioxane (B),    wherein when said first reactive groups of said polyhedral silsesquioxane (B) are not polymerizable without a complementarily reactive group being present; then polyhedral silsesquioxane (C) having a complementarily reactive group is present, the reactive groups of polyhedral silsesquioxane (C) optionally bonded to silicon atoms of polyhedral silsesquioxane (C) by spacer moieties; or   c) mixtures of a) and b).   
     
     
         78 . The polymer of  claim 77 , comprising the polymerized product of polyhedral silsesquioxane (A). 
     
     
         79 . The polymer of  claim 78 , wherein said mixture further comprises at least one of a hydrido-functional polyhedral silsesquioxane (D) having hydrogen bonded to silicon atoms of said polyhedral silsesquioxane (D) or a polyhedral silsesquioxane (E) having hydridosiloxy or dihydridosiloxy groups bonded to silicon atoms of said polyhedral silsesquioxane (D). 
     
     
         80 . The polymer of  claim 77 , wherein for said polyhedral silsesquioxane (A),
 a)i) said first reactive group comprises hydrogen bonded directly to silicon atoms of said polyhedral silsesquioxane (A) and said complementarily reactive groups comprise alkenyl or alkynyl groups bonded to said silicon atoms of said polyhedral silsesquioxane (A) through a spacer moiety;   a)ii) said first reactive group comprises silicon-bonded hydrogen bonded to silicon atoms of said polyhedral silsesquioxane (A) through a spacer moiety and said complementarily reactive groups comprise alkenyl or alkynyl groups bonded directly to silicon atoms of said polyhedral silsesquioxane (A) or bonded to silicon atoms of said polyhedral silsesquioxane through spacer moieties; or   a)iii) said first reactive group and said complementarily reactive group are both bonded to silicon atoms of said polyhedral silsesquioxane (A) by spacer moieties.   
     
     
         81 . A process for the preparation of the polyhedral silsesquioxane (A) of  claim 77 , comprising one of
 a) reacting a polyhedral silsesquioxane containing Si-bonded hydrogen with an amount of an unsaturated compound having two sites of ethylenic or ethylynic unsaturation in the presence of a hydrosilylation catalyst, the mol ratio of unsaturated compound and time of reaction such that a polyhedral silsesquioxane (A) containing spacer-linked unsaturated moieties and retaining unreacted Si-bonded hydrogen is obtained; or   b) reacting a polyhedral silsesquioxane containing alkenyl groups bonded to silicon atoms of said polyhedral silsesquioxane (A) with an SiH 2 -functional compound in the presence of a hydrosilylation catalyst in a mol ratio of SiH 2 -functional compound to alkenyl groups and for a time such that a polyhedral silsesquioxane (A) is obtained which contains SiH-functional groups bonded to said polyhedral silsesquioxane (A) by alkylene spacer moieties, and which also contains unreacted alkenyl groups bonded to silicon atoms of said polyhedral silsesquioxane (A); or   c) reacting, in any order or simultaneously, an anion of the approximate formula Si n O 1.5n   n+  with a chlorosilane bearing a first reactive functional group and with a chlorosilane bearing a complementarily reactive functional group.   
     
     
         82 . The process of  claim 81 , wherein an Si—H functional polyhedral silsesquioxane is reacted with an alkenyl- or alkynyl-functional compound containing at least two alkenyl, alkynyl, or alkenyl and alkynyl groups, wherein the hydrosilylation catalyst is a solid, heterogenous hydrosilylation catalyst, further comprising separating said solid, heterogenous catalyst from a hydrosilyated reaction product. 
     
     
         83 . The process of  claim 82 , wherein said hydrosilylation catalyst comprises PtO 2 . 
     
     
         84 . A process for the preparation of a transparent inorganic/organic hybrid polymer, comprising
 selecting as a monomer mixture one of the monomer mixtures a), b), or c) of  claim 77  and polymerizing said monomer mixture to form a rigid, non-elastomeric transparent polymer, wherein at least one of polyhedral silsesquioxanes (A), (B), or (C) have been purified following their synthesis to remove oligomers and polymers produced during their synthesis.   
     
     
         85 . A process for the preparation of a transparent inorganic/organic hybrid polymer, comprising polymerizing one or more polyhedral silsesquioxane monomers prepared by the process of  claim 82 . 
     
     
         86 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently bonded polyhedral silsesquioxane macromonomer-derived moieties of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     where n is a positive whole number, n′ is 0 or a positive whole number and the sum n+n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1  or R 2 , and   A is a divalent bridging group linking two polyhedral silsesquioxane moieties and derived from the reaction of two interreactive groups R 1  and R 2  which are different from each other, each macromonomer possessing, on average, both R 1  and R 2  groups,   wherein one of said reactive functional groups is Si-bonded H, the other is hexenyl.   
     
     
         87 . An organic-inorganic hybrid polymer material comprising a plurality of identical or different covalently bonded polyhedral silsesquioxane macromonomer-derived moieties of the formula
   [A 0.5 Me 2 SiOSiO 1.5 ] n [RMe 2 SiOSiO 1.5 ] n′     where n is a positive whole number, n′ is 0 or a positive whole number and the sum n+n′ is 6, 8, 10, or 12,   R is a non-reactive organic group or an unreacted reactive functional group R 1  or R 2 , and   A is a divalent bridging group linking two polyhedral silsesquioxane moieties and derived from the reaction of two interreactive groups R 1  and R 2  which are different from each other, each macromonomer possessing, on average, both R 1  and R 2  groups,   wherein both of said reactive functional groups are alkoxy groups, each of said alkoxy groups is derived from reaction of silicon-bonded H with one or more functionalizing reagents selected from the group consisting of dimethylvinylmethoxysilane and dimethylvinylethoxysilane.