Novel fluorinated and alkylated alditol derivatives and compositions and polyolefin articles containing same

Abstract

Plastic additives which are useful as nucleating agents and which are especially useful for improving the optical properties of polymeric materials are provided. More particularly, this invention relates to certain alkyl (or alkoxy) substituted fluorobenzylidene sorbitol acetals and polymer compositions thereof which may be utilized within, as merely examples, food or cosmetic containers and packaging. These inventive fluorinated and alkylated benzylidene sorbitol acetals are also useful as gelling agents for water and organic solvents, particularly those used in the preparation of antiperspirant gel sticks.

What is claimed is:  
     
         1 . A benzylidene alditol acetal comprising at least one substituted benzylidene component wherein said at least one substituted benzylidene component possesses at least one fluorine pendant group and at least one other pendant group, wherein said at least one other pendant group is not hydrogen, and wherein if said at least one other pendant group is fluorine, at least one other non-hydrogen pendant group is present on said benzylidene component.  
     
     
         2 . A compound of Structure (I) or Structure (II):  
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from the group consisting of hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; R 1 , R 2 , R 3 , and R 4  are independently selected from the group consisting of lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; with the proviso that only one of R 1  and R 2  is fluorine, only one of R 3  and R 4  is fluorine, and wherein at least one of R 1 , R 2 , R 3 , and R 4  is a lower alkyl group.  
     
     
         3 . The compound of  claim 2  wherein said compound is selected from the group consisting of bis(4-fluoro-3-methylbenzylidene)sorbitol; bis(3-fluoro-4-methylbenzylidene)-sorbitol; bis(4-fluoro-2,3-dimethylbenzylidene)sorbitol; bis(3-fluoro-2,4-dimethylbenzyl-idene)sorbitol; bis(3-fluoro-4-methoxy-benzylidene)sorbitol; and bis(2,4-difluoro-3-methylbenzylidene)sorbitol.  
     
     
         4 . A compound of the structure (III)  
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; R 1  and R 2  are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; with the proviso that one and only one of R 1  and R 2  is fluorine.  
     
     
         5 . A polyolefin plastic composition having improved transparency and nucleation, which comprises a polymer selected from aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated aliphatic comonomers and at least one di-acetal of an alditol; said di-acetal of the alditol having the structures (I) and (II)  
       
         
           
           
               
               
           
         
       
       wherein R is selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; R 1 , R 2 , R 3 , and R 4  are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; with the proviso that only one of R 1  and R 2  is fluorine, only one of R 3  and R 4  is fluorine, and wherein at least one of R 1 , R 2 , R 3 , and R 4  is a lower alkyl group.  
     
     
         6 . The composition of  claim 5 , wherein said di-acetal is selected from bis(4-fluoro-3-methylbenzylidene)sorbitol; bis(3-fluoro-4-methylbenzylidene)-sorbitol; bis(4-fluoro-2,3-dimethylbenzylidene)sorbitol; bis(3-fluoro-2,4-dimethylbenzylidene)sorbitol; bis(3-fluoro-4-methoxy-benzylidene)sorbitol; and bis(2,4-difluoro-3-methylbenzylidene)sorbitol.  
     
     
         7 . The composition of  claim 5 , wherein said aliphatic monoolefin is selected from the group consisting of ethylene, propylene, copolymers of ethylene and propylene, and 1-butene.  
     
     
         8 . The composition of  claim 5 , wherein said di-acetal is provided in said polymer in substantially pure form.  
     
     
         9 . The composition of  claim 5 , wherein said diacetal is provided in th e form of an admixture with dibenzylidene sorbitol.  
     
     
         10 . The composition of  claim 5 , wherein said aliphatic monoolefin is selected from the group consisting of ethylene, propylene, copolymers of ethylene and propylene, and 1-butene.  
     
     
         11 . The composition of claim, wherein said di-acetal is provided in said polymer in substantially pure form.  
     
     
         12 . The composition of  claim 6 , wherein said diacetal is provided in the form of an admixture with dibenzylidene sorbitol.  
     
     
         13 . The composition of  claim 5 , which further includes at least one plasticizer selected from the group consisting of dioctyl phthalate, dibutyl phathalate, dioctyl sebacate, mineral oil, and dioctyl adipate.  
     
     
         14 . A polyolefin plastic composition having improved transparency, which comprises at least one homopolymer of an aliphatic monoolefin or a copolymer containing an aliphatic monoolefin, said monoolefin containing from 2 to about 6 carbon atoms having an average molecular weight of from about 10,000 to about 500,000 and one or more ethylenically unsaturated aliphatic comonomers, said copolymer having been made by polymerizing said monoolefin with said comonomer; and at least one di-acetal of sorbitol selected from bis(4-fluoro-3-methylbenzylidene)sorbitol; bis(3-fluoro-4-methylbenzylidene)sorbitol; bis(4-fluoro-2,3-dimethylbenzylidene)sorbitol; bis(3-fluoro-2,4-dimethylbenzylidene )sorbitol; bis(3-fluoro-4-methoxy-benzylidene)sorbitol; and bis(2,4-difluoro-3-methylbenzylidene)sorbitol; the proportion of the di-acetal being from about 0.01 to about 2 percent by weight based upon the total weight of the composition.  
     
     
         15 . The composition of  claim 14 , wherein the aliphatic monoolefin is selected from the group consisting of ethylene, propylene, 1-butene, vinyl cyclohexane, and methylpentene.  
     
     
         16 . A solid gelled composition comprising: 
 (a) about 0.25% to about 10% of a gelling agent selected from at least one di-acetal of an alditol (such as sorbitol, xylitol, and ribitol) and mixtures thereof; said di-acetal of the alditol having the structure (I) or (II)                          wherein R is selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; R 1 , R 2 , R 3 , and R 4  are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; with the proviso that only one of R 1  and R 2  is fluorine, only one of R 3  and R 4  is fluorine, and wherein at least one of R 1 , R 2 , R 3 , and R 4  is a lower alkyl group; and    (b) from about 10% to about 98% of a solvent for said gelling agent.    
     
     
         17 . A solid gel according to  claim 16  wherein the solvent is selected from the group consisting of monohydric alcohols, polyhydric alcohols, propylene carbonate, propylene glycol, dipropylene glycol, DMSO, DMF, NMP, water, and mixtures thereof.  
     
     
         18 . A solid gel according to  claim 17  wherein the solvent is selected from the group consisting of propylene carbonate, methanol, ethanol, n-propanol, n-butanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,2-butylene glycol, diethylene glycol, isopropanol, isobutanol, monomethyl ether, diethylene glycol monoethyl ether, 1,3-butylene glycol, 2,3-butylene glycol, dipropylene glycol, 2,4-dihydroxy-2-methylpentane, and mixtures thereof.  
     
     
         19 . A solid gel according to  claim 17  wherein the solvent is selected from aromatics, halogenated aromatics, nitrated aromatics, ketones, amines, nitriles, esters, aldehydes, and mixtures thereof.  
     
     
         20 . A polyolefin plastic composition having improved transparency and nucleation, which comprises a polymer selected from aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated aliphatic comonomers and at least one monoacetal of alditol of the structure (III) of the structure (III)  
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; R 1  and R 2  are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; with the proviso that one and only one of R 1  and R 2  is fluorine.  
     
     
         21 . A polyolefin additive composition comprising at least one compound conforming to the formula of either Structure (I) or Structure (II):  
       
         
           
           
               
               
           
         
       
       wherein R is independently selected from the group consisting of hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, and fluorine; R 1 , R 2 , R 3 , and R 4  are independently selected from the group consisting of lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; with the proviso that only one of R 1  and R 2  is fluorine, only one of R 3  and R 4  is fluorine, and wherein at least one of R 1 , R 2 , R 3 , and R 4  is a lower alkyl group, and at least one other clarifying agent.  
     
     
         22 . The composition of  claim 21  wherein said compound is selected from the group consisting of bis(4-fluoro-3-methylbenzylidene)sorbitol; bis(3-fluoro-4-methylbenzylidene)-sorbitol; bis(4-fluoro-2,3-dimethylbenzylidene)sorbitol; bis(3-fluoro-2,4-dimethylbenzyl-idene)sorbitol; bis(3-fluoro-4-methoxybenzylidene)sorbitol; and bis(2,4-difluoro-3-methylbenzylidene)sorbitol.  
     
     
         23 . The composition of  claim 22  wherein said other clarifying agent is selected from at least one dibenzylidene sorbitol derivative.  
     
     
         24 . The composition of  claim 23  wherein said at least one dibenzylidene sorbitol derivative is selected from the group consisting of bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS), bis(3,4-dichlorobenzylidene) sorbitol, bis(3,4-difluorobenzylidene) sorbitol, bis(3-chloro-4-fluorobenzylidene) sorbitol, and bis(4-chloro-3-fluorobenzylidene) sorbitol.  
     
     
         25 . A polyolefin plastic composition having improved transparency and nucleation, which comprises a polymer selected from aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated aliphatic comonomers and at least one di-acetal of an alditol; said di-acetal of the alditol having the structures (I) and (II)  
       
         
           
           
               
               
           
         
       
       wherein R is selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; R 1 , R 2 , R 3 , and R 4  are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine; with the proviso that only one of R 1  and R 2  is fluorine, only one of R 3  and R 4  is fluorine, and wherein at least one of R 1 , R 2 , R 3 , and R 4  is a lower alkyl group, wherein said polyolefin also comprises at least one other clarifying agent.  
     
     
         26 . The composition of  claim 25 , wherein said di-acetal is selected from bis(4-fluoro-3-methylbenzylidene)sorbitol; bis(3-fluoro-4-methylbenzylidene)-sorbitol; bis(4-fluoro-2,3-dimethylbenzylidene)sorbitol; bis(3-fluoro-2,4-dimethylbenzylidene)sorbitol; bis(3-fluoro-4-methoxy-benzylidene)sorbitol; and bis(2,4-difluoro-3-methylbenzylidene)sorbitol.  
     
     
         27 . The composition of  claim 26  wherein said other clarifying agent is selected from at least one dibenzylidene sorbitol derivative.  
     
     
         28 . The composition of  claim 27  wherein said at least one dibenzylidene sorbitol derivative is selected from the group consisting of bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS), bis(3,4-dichlorobenzylidene) sorbitol, bis(3,4-difluorobenzylidene) sorbitol, bis(3-chloro-4-fluorobenzylidene) sorbitol, and bis(4-chloro-3-fluorobenzylidene) sorbitol.