Novel polyester resins

Abstract

A polymerizable vinylester composition is described which comprises at least three monomers and oligomers, said composition comprising: 2-95% by weight of: diaryl compounds comprising at least two aryl groups linked directly together or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, 2-65% by weight of: a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and 1-35% by weight of: dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or their counterparts where aromatic rings are linked together directly, and 2-95% by weight of: unsaturated oligomers, and said reactive composition has less than 1% mol basis of monoaryl phenolic compounds. Another preferred polymerizable divinylaromatic composition comprises at least a divinylaromatic monomer and its oligomerization products, said composition comprising: 5-99% by weight of: aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic rings, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, and 1-75% by weight of: unsaturated dimer of said divinylaromatic monomer having the structure CH 2 ═CH-AR—CH(CH 3 )—CH═CH-Ar-CH═CH 2 , 0.1-40% by weight of: unsaturated trimer of said divinylaromatic monomer having the structure  wherein n=1, 0.1-30% by weight of: unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer having the structure  wherein n=2-30, and said reactive composition has less than 1% mol basis of monoaryl phenolic compounds. A method of synthesizing polymerizable divinylaromatic compositions of the invention is described comprising the steps of dehydrating a diol by heating wherein heating said diols is performed in the presence of a sulfonic acid at a concentration of 0.5-10.0 mmole/L in aromatic solvent at the boiling temperature of the reaction mixture in the range of 100-160° C., and then removing at least some water produced by the dehydration reaction.

What is claimed is:  
     
         1 . A polymerizable vinylester composition comprising at least three monomers and oligomers, said composition comprising: 
 2-95% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
   2-65% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
   1-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or their counterparts where aromatic rings are linked together directly, and  
   2-95% by weight of: 
 unsaturated oligomers, and  
   said reactive composition having less than 1% mol basis of monoaryl phenolic compounds.    
     
     
         2 . A composition according to  claim 1  comprising less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         3 . A composition according to  claim 1  comprising less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         4 . The polymerizable vinyl ester composition of  claim 1  wherein said polymerizable composition has a viscosity of from 80 to 600 cps at 20° C., a content of ester endgroups so that there is an ester number of greater than or equal to 160 mg KOH/g, comprising: 
 5-45% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
 
 10-65% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
 
 5-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or its counterparts where aromatic rings are linked together directly, and  
 
 2-35% by weight of: 
 unsaturated oligomers, and  
 
 said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         5 . A composition according to  claim 4  wherein said reactive composition comprises less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         6 . A composition according to  claim 4  wherein said reactive composition comprises less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         7 . The polymerizable vinyl ester composition of  claim 1  wherein said polymerizable composition comprises: 
 5-30% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
 
 10-20% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
 
 1-30% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or its counterparts where aromatic rings are linked together directly, and  
 
 40-95% by weight of: 
 unsaturated oligomers, and  
 
 said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         8 . A composition according to  claim 7  wherein said reactive composition comprises less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         9 . A composition according to  claim 7  wherein said reactive composition comprises less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         10 . A polymerizable vinyl ester composition according to  claim 1  comprising at least three monomers and oligomers wherein said polymerizable composition has unsaturated oligomers of molecular weight between about 200 and 500, a viscosity at 25 degrees Centigrade of between about 600 and 1000 cps, and having ether units comprising: 
 10-25% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
 
 10-25% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
 
 20-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or its counterparts where aromatic rings are linked together directly, and  
 
 20-35% by weight of: 
 unsaturated oligomers with ether units, and  
 
 said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         11 . The composition of  claim 10  which comprises less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         12 . The composition of  claim 10  which comprises less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         13 . A polymerizable divinylaromatic composition comprising at least a divinylaromatic monomer and its oligomerization products, said composition comprising: 
 5-99% by weight of: 
 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic rings, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, and  
   1-75% by weight of: 
 unsaturated dimer of said divinylaromatic monomer having the structure CH 2 ═CH-AR-CH(CH 3 )—CH═CH-Ar-CH═CH 2 ,  
   0.1-40% by weight of: 
 unsaturated trimer of said divinylaromatic monomer having the structure  
                     
   0.1-30% by weight of: 
 unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer having the structure  
                     
 and  
   said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.    
     
     
         14 . The composition of  claim 13  which comprises less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         15 . The composition of  claim 13  which comprises less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         16 . A polymerizable divinylaromatic composition according to  claim 13  comprisi ng enriched with divinylaromatic monomer said composition comprising at least the following components: 
 75-99% by weight of: 
 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic rings, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, and  
 
 0.2-24% by weight of: 
 unsaturated dimer of said divinylaromatic monomer having the structure CH 2 ═CH-Ar-CH(CH 3 )—CH═CH-Ar-CH═CH 2 ,  
 
 0.1-10% by weight of: 
 unsaturated trimer of said divinylaromatic monomer having the structure  
                     
 
 0.1-1% by weight of: 
 unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer having the structure  
                     
 and  
 
 said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         17 . A method of synthesizing the polymerizable divinylaromatic composition of  claim 13  comprising the steps of dehydrating a diol by heating wherein heating said diol is performed in the presence of a sulfonic acid at a concentration of 0.5-10.0 mmole/L in aromatic solvent at the boiling temperature of the reaction mixture in the range of 100-160° C., and then removing at least some water produced by the dehydration reaction.  
     
     
         18 . The method of  claim 17  wherein separation and purification of said divinylaromatic monomer is performed by recrystallization from a solvent, and/or sublimation of said monomer by heating said composition at 80 to 150° C. under vacuum.  
     
     
         19 . The polymerizable divinylaromatic composition of  claim 13  wherein said composition has its increased molecular weight increased by the presence of oligomeric composition of higher molecular weight than the average molecular weight of the polymerizable divinylaromatic composition, said oligomeric composition comprising at least the following components: 
 5-75% by weight of: 
 aryl compounds comprising at least one non-alkylated or alkylated aryl group and two vinyl groups attached directly to aromatic rings, such as diaryl compounds comprising at least two aryl groups linked together directly as in biphenyl or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto, and  
 
 20-75% by weight of: 
 unsaturated dimer of said divinylaromatic monomer having the structure CH 2 ═CH-Ar-CH(CH 3 )—CH═CH-Ar-CH═CH 2 ,  
 
 1-40% by weight of: 
 unsaturated trimer of said divinylaromatic monomer having the structure  
                     
 
 0.5-30% by weight of: 
 unsaturated tetramer and higher oligomer homologs of said divinylaromatic monomer having the structure  
                     
 and  
 
 said polymerizable divinylaromatic composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         20 . The method of synthesizing the polymerizable divinylaromatic composition of  claim 19  comprising the steps of heating a diol reaction mixture of diol and 5-15 mmole/L sulfonic acid in aromatic solvent at the boiling temperature of the reaction mixture and removing reaction water evolving during a condensation process in the formation of said composition and keeping and stirring the reaction mixture at a temperature above 80° C. for more than 0.5 hours, with or without the addition of an additional amount of acidic catalyst.  
     
     
         21 . The method of  claim 17  wherein heating said diol is performed in aromatic solvents with high boiling temperature selected from the group consisting of toluene or xylene, in the presence of a concentration of acidic catalyst in the range of 1 to 10 mMole/L, such as p-tolunesulfonic acid, during removing said reaction water and with successive decreasing in temperature down to 70-80° C. and keeping and stirring said mixture at said temperature in the presence of extra amounts of acidic catalyst.  
     
     
         22 . The method of  claim 21  wherein said acid comprises p-toluene sulfonic acid.  
     
     
         23 . A polymerizable composition comprising styrene and the polymerizable divinylaromatic composition of  claim 10  as crosslinking agents comprising: 
 80-99.8% by weight of: 
 styrene, and  
 
 0.2-19% by weight of: 
 the polymerizable divinylaromatic composition.  
 
 
     
     
         24 . A method for prolonging shelf life of the compositions of  claim 10  comprising the steps of reducing the concentration acidic catalyst released during storage of the composition by adding a basic compound to the composition in concentrations of at least 0.2 wt. percent to 1 wt-%.  
     
     
         25 . The method of  claim 20  wherein said basic compound is selected from the group consisting of dimethylformamide, dimethylacetamide, compounds capable of generating organic base during storage at room temperature, organic bases, and basic solvents.  
     
     
         26 . The method of  claim 20  wherein said basic compound is selected from the group consisting of alkylamines, dialkyl, or trialkyl amines, amidines, aliphatic polyamines, polyethylenepolyamines, pyridines, thiodiphenylamine, and amine-hardeners for epoxy resins, and n-methylpyrrolidone.  
     
     
         27 . A polymerizable formulation for producing composites comprising: 
 45-65 wt-% of: 
 unsaturated polyester resin or vinylester resin, and  
   0.3-10 wt-% of: 
 epoxy resin comprising 2-25 wt-% of epoxy groups, and  
   3-15 wt-% of: 
 amide of unsaturated carboxylic acid, and  
   20-40 wt-% of: 
 divinylaromatic composition of  claim 13 ,  
   0.1-2 wt-% of: 
 thermoinitiator, and  
   optionally 0.05-2 wt-% of: 
 antioxidant, and  
   optionally 0.1-2 wt-% of: 
 silica.  
   
     
     
         28 . The composition of  claim 23  wherein said antioxidant comprises such as (N-(1,3-dimethyl-butyl)-N′-phenylphenylene-diamine-1,4, and said unsaturated carboxylic acid comprises an amide selected from the group consisting of acrylamides and methacrylamides.  
     
     
         29 . A method for forming a high temperature resistant composite comprising combining the composition of  claim 23  with a reinforcing material and then curing said composition with said reinforcing material therein.  
     
     
         30 . The method of  claim 25  wherein said reinforcing materials are selected from the group consisting of fibers, filaments or fabrics comprising glass, carbon, ceramics, metals, polymers, or composites.  
     
     
         31 . A polymerizable formulation for producing composites comprising fibrous material comprising: 
 10-50 wt-% of a divinylaromatic monomer comprising: 
 5-95% by weight of divinylaromatic monomer selected from the group consisting of p-(CH 2 ═CH—C 6 H 4 ) 2 O, p-(CH 2 ═CH—C 6 H 4 ) 2 S, p-(CH 2 ═CH—C 6 H 4 ) 2 CH 2  and p-(CH 2 ═CH—C 6 H 4 ) 2  and  
 35-75 wt-% of: 
 the polymerizable vinylester composition of  claim 1 ,  
 
 0.3-10 wt-% of: 
 epoxy resin comprising 2-25 wt-% of epoxy groups, and  
 
 3-15 wt-% of: 
 at least one amide of an unsaturated carboxylic acid, and  
 
 0.1-5 wt-% of initiator, and  
 optionally 0.05-2 wt-% of antioxidant, and  
 optionally 0.1-2 wt-% of filler.  
   
     
     
         32 . A polymerizable formulation for producing composites comprising fibrous material comprising: 
 10-50 wt-% of a divinylaromatic monomer comprising: 
 5-95% by weight of divinylaromatic monomer selected from the group consisting of p-(CH 2 ═CH—C 6 H 4 ) 2 O, p-(CH 2 ═CH—C 6 H 4 ) 2 S, p-(CH 2 ═CH—C 6 H 4 ) 2 CH 2  and p-(CH 2 ═CH—C 6 H 4 ) 2  and  
 30-80 wt-% of: 
 vinylesters or unsaturated polyester resin,  
 
 0.3-10 wt-% of: 
 epoxy resin comprising 2-25 wt-% of epoxy groups, and  
 
 3-15 wt-% of: 
 amide of unsaturated carboxylic acid, and  
 
 0.1-5 wt-% of initiator, and  
 optionally 0.05-2 wt-% of antioxidant, and  
 optionally 0.1-2 wt-% of filler.  
   
     
     
         33 . A method for forming a polymer comprising the steps of providing a reactive composition comprising: 
 2-95% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together or bridged by a linking group selected from the group consisting of oxygen, sulfur and methine, each of said at least two aryl groups having a vinyl group attached thereto,  
   2-65% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
   1-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or counterparts where the ether linkage is replaced with sulfur or methine group, or aromatic rings are linked together directly, and  
   2-95% by weight of: 
 unsaturated oligomers which can be described by formulae (I) or (II):  
                     
  wherein Ar is an aromatic group  
   and said reactive composition having less than 1% mol basis of monoaryl phenolic compounds, and    polymerizing said at least three monomers and oligomers to form a polymer.    
     
     
         34 . The method of  claim 29  wherein said Ar is selected from the group consisting of biphenyl, diphenyl methane, 1,1-diphenyl ethane, naphthalene, diphenyl ether, diphenyl sulfide, diphenyl sulfone, 2,2-diphenyl propane, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, bis-(4-phenoxyphenyl) ether, bis-(3-phenoxyphenyl) sulfide, 4-phenoxy biphenyl, 1,4-dibenzyl benzene, 1,3-dibenzyl benzene, 3-phenyl biphenyl, and alkylated aryl species comprising one, two, three or more alkyl groups comprising C 1  to C 15 , and X=CH(CH 3 )-Ar-CH, X′=CH═CH-Ar-CH(CH 3 ), Y=Y′=CH 2 ═CH, CH 2 ═CR—COO—CH(CH 3 ), or Y=CH 2 ═CH, Y′=CH 2 ═CR—COO—CH(CH 3 ), R=H, CH 3 , alkyl (C 1  to C 15 ), n=0-3, m=k=0, or m=1 and k=0, or m=0 and k=1, or m=k=1.  
     
     
         35 . The method of  claim 29  wherein said reactive composition has less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         36 . The method of  claim 29  wherein said aryl groups are selected from the group consisting of alkyl(of 1 to 20 carbon atoms)-O-phenyl, —O-phenyl, alkyl(of 1 to 20 carbon atoms)phenyl, and phenyl.  
     
     
         38 . The method of  claim 30  wherein said reactive composition has less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         39 . The method of  claim 29  wherein said reactive composition has less than 0.7% mol basis of monoaryl phenolic compounds and less than 1% mol basis of hydroxy-substituted monoaryl non-phenolic compounds.  
     
     
         40 . The method of  claim 29  wherein said polymerizing is performed at temperatures less than 40° C., and a hydrogen pressure of less than 10 atmospheres.  
     
     
         41 . The method of  claim 29  wherein said polymerizing is performed at temperatures less than 40° C.  
     
     
         40 . The method of  claim 33  wherein said polymerizing is done by free radical polymerization.  
     
     
         41 . The method of  claim 33  wherein said polymerizing is effected by photoinitiation of said polymerizable composition.  
     
     
         42 . A polymer comprising the reaction product of a polymerizable composition comprising at least three monomers, said monomers comprising: 
 2-95% by weight of: 
 diaryl compounds comprising at least two aryl groups linked together directly (as in biphenyl) or bridged by a linking group selected from the group consisting of oxygen, sulfur and methine, each of said at least two aryl groups having a vinyl group attached thereto,  
   2-65% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
   1-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or counterparts where the ether linkage is replaced with sulfur or methine group, or aromatic rings are linked together directly, and  
   2-95% by weight of: 
 unsaturated oligomers comprising oligomers which can be described by formulae (I) and/or (II):  
                     
  wherein Ar is an aromatic group.  
   
     
     
         43 . The polymer of  claim 42  wherein Ar comprises a diaryl species selected from the group consisting of biphenyl, diphenyl methane, 1,1-diphenyl ethane, naphthalene, diphenyl ether, diphenyl sulfide, diphenyl sulfone, 2,2-diphenyl propane, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, bis-(4-phenoxyphenyl) ether, bis-(3-phenoxyphenyl) sulfide, 4-phenoxy biphenyl, 1,4-dibenzyl benzene, 1,3-dibenzyl benzene, 3-phenyl biphenyl, or Ar comprises alkylated aryl species comprising one, two, three or more alkyl groups comprising C 1  to C 15  alkyl groups and X=CH(CH 3 )-Ar′-CH, X′=CH═CH-Ar′-CH(CH 3 ), Y=Y′=CH 2 ═CH , CH 2 ═CR—COO—CH(CH 3 ), or Y=CH 2 ═CH, Y′=CH 2 ═CR—COO—CH(CH 3 ), R=H, CH 3 , alkyl (C 1  to C 15 ), n=0-3, m=k=0, or m=1 and k=0, or m=0 and k=1, or m=k=1, where Ar′ comprises a monoring aromatic group, 
 and said reactive composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         44 . The polymer of  claim 43  wherein said composition has less than 0.7% mol basis of monoaryl phenolic compounds and less than 1% mol basis of hydroxy-substituted monoaryl non-phenolic compounds.  
     
     
         46 . The polymer of  claim 44  wherein said aryl groups are selected from the group consisting of alkyl(of 1 to 20 carbon atoms)-O-phenyl, —O-phenyl, alkyl(of 1 to 20 carbon atoms)phenyl, and phenyl.  
     
     
         47 . A polymerizable composition comprising at least three monomers, said monomers and oligomers comprising: 
 2-95% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together (as in biphenyl) or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
   2-65% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
   1-35% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or counterparts where the ether linkage is replaced with sulfur or methine group, or aromatic rings are linked together directly, and  
   2-95% by weight of: 
 unsaturated oligomers which comprise oligomers of the formulae:  
                     
  wherein Ar is an aromatic group,  
   and said reactive composition having less than 1% mol basis of monoaryl phenolic compounds.    
     
     
         48 . The polymerizable composition of  claim 47  wherein Ar comprises a diaryl species selected from the group consisting of biphenyl, diphenyl methane, 1,1-diphenyl ethane, naphthalene, diphenyl ether, diphenyl sulfide, diphenyl sulfone, 2,2-diphenyl propane, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, bis-(4-phenoxyphenyl) ether, bis-(3-phenoxyphenyl) sulfide, 4-phenoxy biphenyl, 1,4-dibenzyl benzene, 1,3-dibenzyl benzene, 3-phenyl biphenyl, or Ar comprises alkylated aryl species comprising one, two, three or more alkyl groups comprising C 1  to C 15  alkyl groups and X=CH(CH 3 )-Ar′-CH, X′=CH═CH-Ar′-CH(CH 3 ), Y=Y′=CH 2 ═CH, CH 2 ═CR—COO—CH(CH 3 ), or Y=CH 2 ═CH, Y′=CH 2 ═CR—COO—CH(CH 3 ), R=H, CH 3 , alkyl (C 1  to C 15 ), n=0-3, m=k=0, or m=1 and k=0, or m=0 and k=1, or m=k=1, where Ar′ comprises a monoring aromatic group.  
     
     
         49 . The polymerizable composition of  claim 47  of  claim 1  wherein said polymerizable composition has less than 1% mol basis of monoaryl phenolic compounds and less than 1% mol basis of hydroxy-substituted monoaryl non-phenolic compounds.  
     
     
         50 . The polymerizable composition of  claim 47  wherein said aryl group is selected from the group consisting of alkyl (of 1 to 20 carbon atoms)-O-phenyl, —O-phenyl, alkyl(of 1 to 20 carbon atoms)phenyl, and phenyl.  
     
     
         51 . The polymerizable composition of  claim 49  wherein said polymerizable composition has less than 0.5% mol basis of monoaryl phenolic compounds.  
     
     
         52 . The polymerizable composition of  claim 49  wherein said polymerizable composition has less than 0.7% mol basis of monoaryl phenolic compounds.  
     
     
         53 . The polymerizable composition of  claim 47  further comprising a photoinitiator capable of initiating polymerization of said polymerizable composition.  
     
     
         54 . The polymerizable composition of  claim 47  further comprising a photoinitiator capable of initiating polymerization of said polymerizable composition.  
     
     
         55 . The polymerizable composition of  claim 48  further comprising a photoinitiator capable of initiating polymerization of said polymerizable composition.  
     
     
         56 . The polymerizable composition of  claim 49  further comprising a photoinitiator capable of initiating polymerization of said polymerizable composition.  
     
     
         57 . The polymerizable composition of  claim 50  further comprising a photoinitiator capable of initiating polymerization of said polymerizable composition.  
     
     
         58 . The polymerizable vinyl ester composition of  claim 1  wherein said polymerizable composition has low melt viscosity between 550 and 1050 cps at 25 degrees Centigrade, a content of vinyl endgroups ≧20 weight %, and ≧20 weight % of ester endgroups, said composition comprising: 
 15-60% by weight of: 
 diaryl compounds comprising at least two aryl groups linked directly together or bridged by a linking group, each of said at least two aryl groups having a vinyl group attached thereto,  
 
 10-20% by weight of: 
 a methacrylic acid ester of a vinyl-substituted sec-ethylol-diaryl oxide or its thioether or methine or biphenyl counterpart, and  
 
 2-30% by weight of: 
 dimethacrylic acid esters of bis-[4-(1-hydroxyethyl)aryl] ether, thioether or methine, or its counterparts where aromatic rings are linked together directly, and  
 
 10-40% by weight of: 
 unsaturated oligomers, and  
 
 said reaction composition has less than 1% mol basis of monoaryl phenolic compounds.  
 
     
     
         59 . A method for altering the physical properties of the composition of  claim 1  comprising adding a sufficient amount of monoaryl phenolic compounds to said composition to alter its viscosity at 25 degrees Centigrade.  
     
     
         60 . The method of  claim 59  wherein said amount of monoaryl phenolic compounds added to said composition comprises at least 0.1% by weight of said composition.  
     
     
         61 . A method for prolonging shelf life of the compositions of  claim 13  comprising the steps of reducing the concentration acidic catalyst released during storage of the composition by adding a basic compound to the composition in concentrations of at least 0.2 wt. percent to 1 wt-%.  
     
     
         62 . The method of  claim 61  wherein said basic compound is selected from the group consisting of dimethylformamide, dimethylacetamide, compounds capable of generating organic base during storage at room temperature, organic bases, and basic solvents.  
     
     
         63 . A polymerizable composition comprising styrene and said divinylaromatic composition of  claim 13  as crosslinking agents comprising: 
 80-99.5% by weight of: 
 styrene, and  
 
 0.2-19% by weight of the divinylaromatic composition.  
 
     
     
         64 . A polymerizable composition comprising styrene and the divinylester composition of  claim 1  as crosslinking agents comprising: 
 80-99.5% by weight of: 
 styrene, and  
 
 0.2-19% by weight of the polymerizable vinylester composition.  
 
     
     
         65 . A method of preparing a polymerizable composition comprising the steps of heating a reaction mixture comprising: 
 a) a diol of comprising HO—(H 3 C)R 4 C-Q-CR 5 (CH 3 )—OH 
 wherein Q is a diaryl group comprising two aryl groups bridged by a bond, an oxygen atom, sulfur atom or methine group,  
 and R 4  and R 5  are independently selected from the group consisting of hydrogen and lower alkyl groups of 1 to 4 carbon atoms,  
 said diol comprising less than 1% mol basis of monoaryl phenolic compounds with a carboxylic acid, and  
   b) a carboxylic acid.    
     
     
         66 . The method of  claim 63  wherein said carboxylic acid comprises methacrylic acid and is performed at mole ratio of diol:methacrylic acid of not less than 1:0.1.  
     
     
         67 . The method of  claim 64  wherein said mole ratio comprises 1:1.5-2.5, and said heating is performed in the presence of a sulfonic acid.  
     
     
         68 . The method of  claim 65  wherein said concentration of a sulfonic acid is 0.9-14.0 mmole/L.  
     
     
         69 . The method of  claim 66  wherein said sulfonic acid comprises p-toluenesulfonic acid.  
     
     
         70 . The method of  claim 67  wherein p-toluene sulfonic acid is present in a reaction mixture with said diol and an aromatic solvent at a temperature of 80-160° C. of the reaction mixture.  
     
     
         71 . The method of  claim 68  wherein reaction water evolving during the heating is at least removed in part from the reaction mixture.  
     
     
         72 . The method of  claim 68  wherein there is stirring at 70-80° C.  
     
     
         73 . The method of  claim 68  wherein additional acid catalyst is added to said reaction mixture during an oligomerization stage in the reaction to increase the molecular weight of ethylenically unsaturated oligomers that are formed during the process.  
     
     
         74 . The method of  claim 63  comprising heating at least one diol (D) with a carboxylic acids (CA) is performed at mole ratio D:CA not less than 1:1.1 in the presence of from 0.5 to 14.0 mmole/L of a sulfonic acid.  
     
     
         75 . The method of  claim 68  wherein the ratio D:CA is between 1:1.5-2.5.  
     
     
         76 . The method of  claim 69  wherein said sulfonic acid comprises p-toluenesulfonic acid in an aromatic solvent.  
     
     
         77 . The method of  claim 76  wherein said organic solvent comprises toluene.  
     
     
         78 . The method of  claim 77  wherein water is removed from said reaction mixture during heating.  
     
     
         79 . The method of  claim 74  comprising heating at least one diol (D) with carboxylic acids (CA) in the presence of mainly 10-15 mmole/L sulfonic acid in an aromatic solvent.  
     
     
         80 . The method of  claim 76  wherein said organic solvent comprises benzene and said method is performed at the boiling temperature of the reaction mixture.  
     
     
         81 . The method of  claim 77  which is performed at 70-80° C. with additional stirring after removing reaction water.  
     
     
         82 . The method of  claim 72  wherein heating is performed in aromatic solvents having boiling points over 75° C.  
     
     
         83 . The method of  claim 79  wherein said aromatic solvents comprise at least on solvent in the group consisting of toluene and o-xylene.  
     
     
         84 . The method of  claim 81  wherein there is a second addition of acidic catalyst to the reaction mixture after heating has begun.