Coordination-polymeric triethanolamineperchlorato(triflato)metal inner complexes as additives for synthetic polymers

Abstract

Stabilizer system for chlorinated polymers, especially PVC, comprising at least one coordination-polymeric triethanolamineperchlorato(triflato)metal inner complex comprising the monomer unit of the formula (A) The stabilizer system may additionally comprise substituted cyanoacetylureas or/and 6-aminouracils or/and 3-aminocrotonic esters or/and hydantoins or/and monomeric or polymeric dihydropyridines or alkaline earth metal hydroxides or/and hydrotalcites or/and dawsonites or/and zeolites or/and glycidyl compounds or/and cyanamides or/and cyanoguanidines or/and melamines. In addition, phosphites or/and sterically hindered amines or/and NOR-HALS compounds may be present.

1 . Composition comprising at least one synthetic polymer and at least one coordination-polymeric triethanolamineperchlorato(triflato)metal inner complex comprising the monomer unit of the formula (A): 
     
       
         
         
             
             
         
       
     
     where
 Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; 
 An=OClO 3  or OS(O 2 )CF 3 ; 
 q=1 or 2. 
 
   
   
       2 . Composition according to  claim 1 , characterized in that the synthetic polymer is a halogenated polymer, preferably PVC. 
   
   
       3 . Stabilizer system for synthetic polymers, comprising a coordination-polymeric triethanolamineperchlorato(triflato)metal inner complex comprising the monomer unit of the formula (A): 
     
       
         
         
             
             
         
       
     
     where
 Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; 
 An=OClO 3  or OS(O 2 )CF 3 ; 
 q=1 or 2. 
 
   
   
       4 . Stabilizer system according to  claim 3 , characterized in that additionally present is a linear and cyclic ureide (substituted cyanoacetylurea, substituted iminobarbituric acid, substituted aminouracil, hydantoin) and/or a 3-aminocrotonic ester and/or a dihydropyridinedicarboxylic ester of the formula (B-1), (B-2), (C-1) and (C-2) 
     
       
         
         
             
             
         
       
       where 
       X═O or S; Y═CH 2 CN, Z=H, or Y and Z form the bridging member CH 2 —C═NH, CR 5 ═C—NHR 6  or R 1 R 2 C. 
       R 1 , R 2  are each independently H, C 1 -C 22 -alkyl, cyclohexyl, (meth)allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro)naphthyl, meth(or eth)oxypropyl(or ethyl), CH 2 —CHOH—R 1a , CH 2 —CHOH—CH 2 X′R 1a ; 
       X′═O or S; 
       R 1a ═H, C 1-22 -alkyl, cyclohexyl, (meth)allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro)naphthyl or meth(or eth)oxypropyl(or ethyl); 
       R 3 =unbranched or branched C 2 -C 20 -alkylene which may be interrupted by 1 to 4 oxygen or sulphur atoms and/or may be substituted by 1 to 4 OH groups, or dimethylolcyclohexane-1,4-diyl, polyethylene(or -propylene) glycol-α,ω-diyl (preferably, poly=tetra to deca), polyglyceryl-α,ω-diyl (preferably, poly=tetra to deca) or glyceroltriyl, trimethylolethane(or -propane)triyl, pentaerythritoltri(or -tetra)yl, bis(trimethylolethane(or -propane)tri(or -tetra)yl), diglyceroltri(or -tetra)yl, tetritoltetrayl, triglyceroltri(or -tetra, -penta)yl, pentitolpentayl, dipentaerythritolpenta(or -hexa)yl and hexitolhexayl; 
       n=2, 3, 4, 5 or 6; 
       R 5 ═H or (C 3 -C 10 -alkylidene) 1/2 ; where this alkylidene may be interrupted by up to 2 oxygen atoms or may have up to 2 substituents selected independently from the group consisting of OH, phenyl and hydroxyphenyl; 
       R 6 ═H, hydroxy-C 2 -C 4 -alkyl, 3-C 1 -C 10 -alkoxy-2-hydroxypropyl, or mono- to trihydroxy-, mono- to tri-C 1 -C 4 -alkyl- or/and mono- to tri-C 1 -C 4 -alkoxyphenyl, allyl, mono- to trisubstituted phenyl; 
       R 7 , R 7′  are each independently branched and unbranched C 1 -C 4 -alkyl, phenyl, cyclohexyl; 
       W═CO 2 CH 3 , CO 2 C 2 H 5 , CO 2   n C 12 H 25  or CO 2 C 2 H 4 —S— n C 12 H 25 ; 
       L, T=unsubstituted C 1-12 -alkyl; 
       and 
       m and n′ are each integers of 0 to 20, 
       k is 0 or 1 and 
       R and R′ are each independently ethylene, propylene, butylene or an alkylene- or cycloalkylenebismethylene group of the —(C p H 2p —X″—) t C p H 2p — type where p is an integer of 2 to 8, t is an integer of 0 to 10 and X″ is oxygen or sulphur. 
     
   
   
       5 . Stabilizer system according to  claim 3  or  4 , characterized in that additionally added is magnesium oxide or calcium oxide or magnesium hydroxide or calcium hydroxide and/or a magnesium soap or calcium soap and/or a Ca/Zn stabilizer and/or an (optionally Li- or titanium-containing) hydrotalcite and/or dawsonite and/or sodium zeolite A and/or a calcium aluminium hydroxo hydrogenphosphite and/or a glycidyl compound and/or an epoxidized fatty acid ester and/or a melamine and/or a phosphorous ester and/or 2-naphthol and/or a cyanamide of the formula (E) 
     
       
         
         
             
             
         
       
     
     where each R 4  is independently H, nitrile, carbamoyl, R 1 , R 2 , R 1 CO, R 2 CO, Na, K, Mg 1/2  and Ca 1/2 , or R 2   4 =tetra-, penta- or hexamethylene, and o=1, 2 or 3. 
   
   
       6 . Stabilizer system according to one of  claims 3  to  5 , characterized in that a sterically hindered amine (HALS) and/or an antioxidant and/or a UV absorber (benzotriazole derivative) and/or titanium dioxide and/or chalk is added. 
   
   
       7 . Stabilizer system according to  claim 6 , characterized in that the sterically hindered amine (HALS) is an NOR-HALS compound. 
   
   
       8 . Stabilizer system according to  claim 7 , characterized in that the NOR-HALS compound is a triazine-based NOR-HALS compound. 
   
   
       9 . Stabilizer system according to any of  claims 3  to  8 , characterized in that it further comprises a glyceryl ether and/or ester, R 8 CH 2 CH(OH)CH 2 OH or R 8 CO 2 CH 2 CH(OH)CH 2 OH and/or a DEA derivative R 9 —[C(O)] d —N(C 2 H 4 OH) 2  or R 8 OCH 2 CH(OH)CH 2 —[C(O)] d —N(C 2 H 4 OH) 2  or R 9 —N(OH)(CH 2 ) 2 (CH 2 ) 3 —[C(O)] d —N(C 2 H 4 OH) 2  and/or a paraffinsulphate(or -sulphonate) salt C 12 -C 18 -alkyl-(O) d′ —SO 3  Na, Li, K and/or a polyoxyalkylene of the formula (F)
   R 8 —O—[CH(R 10 )—CH 2 —O—] a —[CH 2 —[CH(OH)] b —CH 2 —O] c [C(O)] d″ —R 9   (F)   where   each R 8  is independently H, C 1 -C 24 -alkyl, C 2 -C 24 -alkenyl, CH 2 ═CH—C(O) or CH 2 ═CCH 3 —C(O);   each R 9  is independently C 1 -C 24 -alkyl, C 2 -C 24 -alkenyl, (CH 2 ) 2 OH, CH 2 —COOH or N(C 1 -C 8 -alkyl) 3 Hal,   R 10 ═H or CH 3 ,   Hal=Cl, Br or I;   a=an integer greater than or equal to 2,   b=an integer of 1 to 6, and   c, d, d′, d″ are each independently 0 or 1.   
   
   
       10 . Composition comprising a synthetic polymer and a stabilizer system according to any of  claims 4  to  9 . 
   
   
       11 . Composition according to  claim 10 , characterized in that the synthetic polymer is a chlorinated polymer, preferably PVC. 
   
   
       12 . Composition according to  claim 11 , characterized in that the chlorinated polymer is rigid PVC, flexible PVC, suspension PVC or emulsion PVC. 
   
   
       13 . Composition according to any of  claims 10  to  12 , characterized in that, based on 100 parts by weight of synthetic polymer, 0.001-1.0 part by weight of the inner complex (A) is present. 
   
   
       14 . Composition according to any of  claims 10  to  13 , characterized in that 0.01-10 parts by weight of sterically hindered amine and/or NOR-HALS compound and/or UV absorber and/or titanium dioxide are present. 
   
   
       15 . Composition according to any of  claims 10  to  14 , characterized in that the synthetic polymer is flexible PVC and the stabilizer system comprises 1,4-cyclohexanedimethanol diglycidyl ether. 
   
   
       16 . Process for stabilizing synthetic polymers by adding a stabilizer system according to any of  claims 5  to  10  to a synthetic polymer. 
   
   
       17 . Process for stabilizing synthetic polymers according to  claim 16 , characterized in that the synthetic polymer is a chlorinated polymer, preferably flexible PVC or PVC paste. 
   
   
       18 . Process for stabilizing chlorinated polymers according to  claim 17 , characterized in that the flexible PVC is suitable for the manufacture of floors, motor vehicle parts, wallpaper, flexible films, pipes, injection mouldings or preferably for wire sheathing (cables). 
   
   
       19 . Process for stabilizing synthetic polymers according to  claim 17 , characterized in that the chlorinated polymer is rigid PVC. 
   
   
       20 . Process for stabilizing chlorinated polymers according to  claim 19 , characterized in that the rigid PVC is suitable for the production of films (including Luvitherm), PVC pipes or profiles, preferably of window profiles. 
   
   
       21 . Useful articles comprising PVC, which also comprise a stabilizer system according to any of  claims 5  to  10 . 
   
   
       22 . Antistat or antistat component for synthetic polymers, comprising a triethanolamineperchlorato(triflato)metal inner complex of the formula (A) as specified in  claim 1 . 
   
   
       23 . Inner complex of the formula (A) as specified in  claim 1 , characterized in that Mt=Ca or Zn and q=2. 
   
   
       24 . Inner complex of the formula (A) as specified in  claim 1 , where Mt=Li, Na or Ca and q=1 or 2. 
   
   
       25 . Inner complexes according to  claim 24 , characterized in that Mt=Li or Na, q=1 and An=OClO 3 . 
   
   
       26 . Process for preparing an inner complex of the formula (A) as specified in  claim 1 , characterized in that the synthesis is effected in methanol, ethanol, propanol, triethanolamine or water, and the solvent and any water of reaction are removed by distillation. 
   
   
       27 . Process according to  claim 26 , characterized in that the distillation residue is digested in a nonpolar solvent. 
   
   
       28 . Process for preparing inner complexes of the formula (A) as specified in  claim 1 , characterized in that the synthesis is effected in an alcohol and the reaction product is removed by precipitation with a nonpolar solvent.