Reinforcement promoters for filled thermoplastic polymers

Abstract

A reinforced, filled thermoplastic polymer composition, having increased strength and ductility, contains a reinforcement promoter having at least two reactive olefinic double bonds and a positive promoter index, based on the double bond resonance and polarity, and the promoter adsorptivity.

What is claimed is: 
     
       1. A polymer composition substantially free of a free radical initiator or its residue comprising a thermoplastic polymer, selected from the groups consisting .Iadd.of .Iaddend.normally .[.of.]. solid hydrocarbon polymers, polyamides and polyvinyl chlorides including the copolymers of the latter with vinyl acetate and an inorganic filler having an average particle size <100 μm wherein the improvement comprises providing about 0.1 to 5 weight % based on the weight of the total composition of a reinforcement promoter having at least two reactive olefinic double bonds, said promoter being characterized by having a promoter index, P, being greater than zero, which is defined by the formula:   P=n(n--1)Q(e+2)(1--2R°.sub.f)--2.5     wherein n is the number of olefinic double bonds in the promoter, having .[.values ≧.]. .Iadd.a value of at least .Iaddend.2, Q and e are the Alfrey-Price resonance and polarity parameters, respectively, of at least one of the olefinic double bonds in the compound, wherein Q.[.≧2.]..Iadd.>0 .Iaddend.and e.[.≧2 but <4,.]..Iadd.>0 .Iaddend.and R° f , having .[.values≧0 to ≦.]. .Iadd.a value <.Iaddend.0.5, is the relative flow ratio of the promoter measured by thin layer chromatography on a neutral silica gel using xylene as the eluant and di-n-butyl fumarate as the standard.   
     
     
       2. The composition of claim 1 wherein the thermoplastic polymer is a hydrocarbon homopolymer or copolymer. 
     
     
       3. The composition of claim 2 wherein the hydrocarbon polymer is a polyolefin homopolymer or copolymer, or a natural or synthetic rubber. 
     
     
       4. The composition of claim 1 wherein the reinforcement promoter has the structure: ##STR18## wherein R 1  is an organic group free of olefinic or acetylenic unsaturation having a valence of n; R 2 , and R 3  and R 4  are hydrogen, carboxy or monovalent organic groups free of olefinic or acetylenic unsaturation; X is: ##STR19## m has a value of 0 or 1; and n has a value of at least two. 
     
     
       5. The composition of claim 4 wherein the reinforcement promoter has an .[.R'.]. .Iadd.R 1  .Iaddend.or X group, for when m is 1 or 0, respectively, which contains a double or triple bond which is in conjugation with the olefinic bond and which is electron withdrawing. 
     
     
       6. The composition of claim 1 wherein the reinforcement promoter is a condensation product of an acrylic or maleamic acid with an aliphatic, aromatic or heterocyclic polyol; or an acrylamide, maleimide or maleamic acid of an aliphatic, aromatic or heterocyclic polyamine. 
     
     
       7. The composition of claim 6 wherein the reinforcement promoter compound is an imide, maleate, acrylate, or acryloyl heterocyclic compound. 
     
     
       8. The composition of claim 7 wherein the reinforcement promoter is epoxidized linseed oil/acrylate, 1,3,5-triacryloylhexahydro-s-triazine, melamine triacrylate or maleamic acid derivatives of methylene-aniline oligomers. 
     
     
       9. The composition of claim 1 wherein the inorganic filler is aluminum trihydrate, clay, talc or calcium carbonate. 
     
     
       10. The composition of claim 1 wherein the reinforcement promoter is present in an amount of from about 0.1 to 5.0 weight percent, the filler is from about 10 to 90 weight percent and the thermoplastic polymer is from about 10 to 90 weight percent, based on the total weight of promoter, filler and polymer in the composition. 
     
     
       11. A reinforced polymer composition substantially free of a free radical initiator or its residue comprising a thermoplastic polymer .Iadd.selected from the group consisting of normally solid hydrocarbon polymers, polyamides and polyvinyl chlorides including the copolymers of the latter with vinyl acetate .Iaddend.and an inorganic filler .Iadd.having an average particle size <100 μm .Iaddend.wherein the improvement comprises providing .Iadd.about 0.1 to 5 weight % based on the weight of the total composition of .Iaddend.a reinforcement promoter at the boundary between the filler and polymer, for increasing the strength and ductility of the filled thermoplastic polymer, wherein the promoter has at least two reactive olefinic double bonds, and wherein said promoter is characterized by having a promoter index, P, being greater than zero, and which is defined by the formula:   P=n(n--1)Q(e+2) (1-2R.sub.f °)--2.5     wherein n is the number of olefinic bonds in the promoter, .Iadd.having a value of at least 2, .Iaddend.Q and e are the Alfrey-Price resonance and polarity parameters, respectively, for at least one of the olefinic double bonds in the promoter, .Iadd.wherein Q>0 and e>0, .Iaddend.and R f  °.Iadd., having a value <0.5, .Iaddend.is the relative flow ratio of the promoter measured by thin layer chromatography on a neutral silica gel using xylene as the eluant and di-n-butyl fumarate as the standard.   
     
     
       12. A process for making a reinforced, filled polymeric composition comprising: (a) admixing a filler .Iadd.having an average particle size <100 μm .Iaddend.with a reinforcement promoter having at least two reactive olefinic double bonds, wherein said promoter is characterized by having a promoter index, P, being greater than zero, and which is defined by the formula:   P=n(n-1)Q(e+2)(1-2R.sub.f °)--2.5     wherein n is the number of olefinic double bonds in the promoter, .Iadd.having a value of at least 2, .Iaddend.Q and e are the Alfrey-Price resonance and polarity parameters, respectively, of at least one of the olefinic double bonds in the promotor, .Iadd.wherein Q>0 and e>0, .Iaddend.and R f  °, .Iadd.having a value <0.5, .Iaddend.is the relative flow ratio of the promotor measured by thin layer chromatography on a neutral silica gel using xylene as the eluant and di-n-butyl fumarate as the standard;     (b) compounding the filler and promoter mixture with a thermoplastic polymer .Iadd.selected from the group consisting of normally solid hydrocarbon polymers, polyamides and polyvinyl chlorides including the copolymers of the latter with vinyl acetate .Iaddend.for a time sufficient to generate a reinforced, filled thermoplastic polymer having increased strength and ductility;   (c) wherein said admixing and compounding is carried out in the substantial absence of any free radical initiator.   
     
     
       13. The process of claim 12 wherein the filler and promoter are admixed simultaneously to the compounding with the thermoplastic polymer. 
     
     
       14. The process of claim 12 wherein the reinforcement promoter is formed in situ during mixing with the filler or during compounding with the polymer. 
     
     
       15. The use of a reinforcement promoter in a filled thermoplastic polymer.Iadd., selected from the group consisting of normally solid hydrocarbon polymers, polyamides and polyvinyl chlorides including the copolymers of the latter with vinyl acetate, .Iaddend.composition substantially free of a free radical initiator or its residue wherein the improvement comprises providing a reinforcement promoter having at least two reactive olefinic double bonds, said promoter being characterized by having a promoter index, P, being greater than zero, and which is defined by the formula:   P=n(n-1)Q(e+2)(1-2R.sub.f °)--2.5     wherein n is the number of olefinic double bonds in the promoter, .Iadd.having a value of at least 2, .Iaddend.Q and e are the Alfrey-Price resonance and polarity parameters, respectively, of at least one of the olefinic double bonds in the promoter, .Iadd.wherein Q>0 and e>0, .Iaddend.and R f  °.Iadd., having a value <0.5, .Iaddend.is the relative flow ratio of the promoter measured by thin layer chromatography on a neutral silica gel using xylene as the eluant and di-n-butyl fumarate as the standard. .Iadd.   
     
     
       16.  The composition of claim 1 wherein the Alfrey-Price resonance parameter, Q, is ≧0.4..Iaddend. .Iadd.17. The composition of claim 16 wherein the number of olefinic bonds, n, is at least 3 and the relative flow ratio, R° f , is <0.05..Iaddend. .Iadd.18. The composition of claim 11 wherein the Alfrey-Price resonance parameter, Q, is ≧0.4..Iaddend. .Iadd.19. The composition of claim 18 wherein the number of olefinic bonds, n, is at least 3 and the relative flow ratio, R° f , is <0.05..Iaddend. .Iadd.20. The process of claim 12 wherein the Alfrey-Price resonance parameter, Q, is ≧0.4..Iaddend. .Iadd.21. The process of claim 20 wherein the number of olefinic bonds, n, is at least 3 and the relative flow ratio, R° f , is <0.05..Iaddend. .Iadd.22. The process of claim 15 wherein the Alfrey-Price resonance parameter, Q, is ≧0.4..Iaddend. .Iadd.23. The process of claim 22 wherein the number of olefinic bonds, n, is at least 3 and the relative flow rate, R° f , is <0.05..Iaddend.