Thermally stabilized PVC compositions

Abstract: The present invention relates to PVC compositions, and in particular to flexible PVC compositions, containing oligomeric and/or polymeric aminouracyls and exhibiting high thermal stability.

Description: The present invention relates to PVC compositions and in particular to flexible PVC compositions containing oligomeric and/or polymeric aminouracyls and exhibiting high thermal stability It is a fundamental object of the present invention a new class of oligomeric and/or polymeric aminouracyls capable of imparting an improved stability against thermal and oxidative decomposition of chlorine-containing polymers and in particular of PVC. Said oligomers and/or polymers are useful when used as stabilizers in flexible PVC compositions allowing the preparation of fully transparent stabilized system, without staining or blistering. In the present text with the expression "flexible PVC" we mean a composition containing PVC (PVC-S, PVC-E, PVC-M) and at least 5 phc of a plasticizer chosen among those commonly used. The behaviour of the compositions of flexible PVC containing the oligomeric and/or polymeric aminouracyls of the present invention is unexpected, because the known compounds with similar structure do not exhibit the same behaviour and are suitable only for the stabilization of rigid and/or semi-rigid PVC. In prior art, i.e. in patents DE 1694873, US 4,656,209, US 5,925,696, GB (A) 2,318,188A, EP (A1) 967 209, EP (A1) 967 245, EP (A1) 967208 monomeric aminouracyls and aminothiouracyls are described as well as their use as PVC stabilizers; these patents neither describe the use of dimeric or polymeric aminouracyls and aminothiouracyls nor describe the new products of the present invention. According to the present invention, flexible PVC compositions with high thermal stability contain oligomeric and/or polymeric aminouracyls consisting of: a repetitive group of formula (I): wherein: R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, aryl substituted with -OH or C 1 -C 8 alkoxy (=substituted aryl), arylalkyl, alkylaryl; R 1 is H, -(C=O)-C 1 -C 12 linear o branched alkyl, -(C=O)-O- C 1 -C 12 linear o branched alkyl, -(C=O) phenyl, not substituted or substituted with -OH, C 1 -C 8 linear o branched alkyl, C 1 -C 8 alkoxy; Z is O or S; linking groups between the repetitive groups of formula (I) equal or different as: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is -H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl) alias 4,4'-methylenebis(cyclohexyl), methylenebis(3-cyclohexyl) alias 3,3'-methylenebis(cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; terminal groups as: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. Preferred stabilizers in flexible PVC compositions with a high thermal stability are oligomeric and/or polymeric aminouracyls consisting of repetitive groups of formula (I) wherein: R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, substituted aryl, R 1 is H, Z is O or S; linking groups between the repetitive groups of formula (I) equal or different as: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is -H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl) alias 4,4'-methylenebis(cyclohexyl), methylenebis(3-cyclohexyl) alias 3,3'-methylenebis(cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; terminal groups as: H , C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, C 1 -C 18 alkylamine, disubstituted with C 1 -C 18 linear or branched alkyl. Oligomeric and/or polymeric aminouracyls according to the present invention have a mean molecular weight of from 280 and 5.000. Oligomeric and/or polymeric aminouracyls according to the present invention are normally obtained by cyclization of an oligomeric and /or polymeric urea using cyanacetic acid or its derivatives. The product thus obtained can be further derivatized to give compounds where R and R 1 are different from H . Particularly the cyclization is carried out on a polyurea prepared by oligomerization and/or polymerization using suitable combinations of: 1. a diisocyanate of formula OCN-Y-NCO (DD) , where Y can be: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is H , C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl) alias 4,4'-methylenebis(cyclohexyl), methylenebis(3-cyclohexyl) alias 3,3'-methylenebis(cyclohexyl),1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; 2. an amine (A) of formula X-NH 2 where X can be: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. 3. A di-amine (AA) of formula H 2 N-K-NH 2 where K can be: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is - H , C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcydohexan-1-yl, methylenebis(4-cyclohexyl) alias 4,4'-methylenebis(cyclohexyl), methylenebis(3-cyclohexyl) alias 3,3'-methylenebis(cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; 4. An isocyanate (D) of formula W-NCO, where W can be: C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. According to the present invention in the preparation of the polyurea A, AA, D, DD can be used in all possible ratios. In the preferred embodiments, when AA and D are both equal to zero, the molar ratio DD/A is comprised between 0.3 and 0.6; when DD and A are both equal to zero, the molar ratio AA/D is comprised between 0.3 and 0.6. Obviously, the above description which was done assuming that Z is O in the repetitive group of formula (I) can be similarly repeated when Z is S by using the corresponding sulphurated compounds; in this case D and DD mean the corresponding isothiocyanate and diisothiocyanate. According to the present invention, in flexible PVC compositions with a high thermal stability, the oligomeric and/or polymeric aminouracyls may be incorporated in an amount of from 0.01 to 10% by weight, preferably of from 0.05 to 5% and especially of from 0.1 to 3% based on the entire composition. According to the present invention, stabilized PVC compositions can further contain customary additives such as, but not exclusively: stabilizers, auxiliaries and processing aids, compounds containing alkali metal compounds and alkaline earth metal compounds, lubricants, plasticizers, pigments, fillers, phosphites, thiophosphites, thiophosphates, mercaptocarboxylates, epoxidized fatty acid esters, antioxidants, UV absorbers and light stabilizers, fluorescent whitening agents, impact modifiers, gelling agents and antistatic agents, metals deactivators, flame retardants, blowing agents and antifogging agents. Examples of plasticizers that can be used according to the present invention are: esters of C 4 -C 20 alcohols ( adipates, phthalates, trimellitates, azelates, sebacates, benzoates, phosphates), epoxidized compounds ( typically epoxidized soy-bean oil), polymeric plasticizers such as polyester, polyadipates, polyphosphates, ... The compounds of the present invention are useful as stabilizers of polymers of vinyl chloride, vinyl resins containing vinyl chloride units in the structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, preferably vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic acid anhydride, post-chlorinated polymers and copolymers of vinyl chloride and vinyliden chloride with unsaturated aldehydes and ketones, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinylmethylether, vinyl isobuthylether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chlorides or other polymerizable compounds; polymers of vinyl chloroacetate and dichlorovinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and of α-substituted acrylic acid; polymers of chlorinated styrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated rubber; mixtures of the cited polymers alone or with other polymerizable compounds. These materials also include graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of above homo and copolymers, preferably homopolymers of vinyl chloride with other thermoplastic or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones. Suitable stabilizable compositions within the scope of this invention, are preferably recycled chlorine containing polymers; these polymers are the above mentioned polymers which have suffered damage through use, storage or production process. Particularly preferred is recycled PVC. Recycled products may also contain minor amounts of foreign material difficult to remove, such as paper, pigments, adhesives. The compositions of PVC containing the stabilizers of the present invention, show as their fundamental characteristic a high thermal stability together with a good transparency of the stabilized system, without staining and blistering. These properties of the compositions of PVC according to the invention, are very different from those described in the known art. This is demonstrated by the applicative results obtained on compositions of PVC containing the oligomeric and/or polymeric aminouracyls of the present invention. Example 1 The preparation of a diuracyl is reported. A solution of 19.2 g (150 mmol) of di n-octylamine in 22 ml of THF are added dropwise into10 g (60 mmol) of 1,6-hexamethylene diisocyanate dissolved in 100 ml of THF under stirring at a temperature not exceeding 15°C. After the addition the reaction mixture is stirred for 30 min and allowed to reach room temperature. The reaction mixture is then poured into 400 ml of acetone. The obtained precipitate is filtered, washed with acetone and dried under vacuum. 25.2 g of a white solid are obtained. (IR: (cm -1 ): 3333, 2955, 2929, 2853, 1616, 1577). 5 g (11.7 mmol) of the solid are reacted under stirring with 2.87 g (28.1 mmol) of acetic anhydride and 2.2 g (25.9 mmol) of cyanacetic acid. The mixture is heated at 90°C and then the temperature is maintained for 2 hours at 80-90°C. 10 ml of water and a 15% sodium hydroxide are added to the reaction mixture solution to obtain pH >9, then the reaction mixture is refluxed for 1 hour. The reaction mixture is then cooled down to room temperature and it is diluted with methylene chloride. After phase separation the organic layer is washed with water to neutral pH. The organic layer is dried on anhydrous sodium sulphate, then the solvent is evaporated under vacuum. 4.87 g of a brown solid are obtained. IR: (cm -1 ): 3349, 3207, 2926, 2855, 1623. MS: 561 (M+1) 13 CNMR: (DMSO d 6 ): δ (ppm): 13.5, 21.6, 25.4, 26.0, 27.2, 28.5, 31.0, 41.4, 75.0, 151.0, 154.0, 161.0. 1 HNMR.(CDCl 3 ): δ (ppm): 0.85 (t, 6H); 1.25 (m, 24 H); 1.61 (m,8H); 3.88 (m, 8H); 5.02 (bs, 2H). Example 2 The preparation of a polyuracyl is reported. A solution of 2.3 g (19.8 mmol) of 1,6-hexamethylendiamine in 30 ml of THF are added dropwise to 5 g (29.8 mmol) of 1,6-hexamethylene diisocyanate dissolved in 50 ml of THF under stirring at 5°C. After the addition the reaction mixture is allowed to reach room temperature and a solution of 2.9 g (22.5 mmol) of n-octylamine in 30 ml of THF are added dropwise. After stirring for 30 min at room temperature, the reaction mixture is poured into acetone, then it is dried under vacuum. 9.5 g of solid are obtained. (IR: (cm -1 ): 3329, 2929, 2854, 1616, 1579. 4 g of the solid are reacted under stirring with 10 g (98 mmol) of acetic anhydride and 5 g (58.8 mmol) of cyanacetic acid. The mixture is heated at 90°C under stirring for 4.5 hours. 10 ml of water and a 20% sodium hydroxide solution are added to the reaction mixture to obtain pH >9 then the reaction mixture is refluxed for 1.5 hours. The reaction mixture is cooled down to room temperature and a solid compound is obtained by decantation. The solid is dissolved in methylene chloride/methanol (1/1) and the insoluble residue is discarded. The organic layer is evaporated under vacuum. 5.14 g of a brown solid are obtained. IR (cm -1 ): 3419, 3252, 2927, 2855, 1628, 1575. 13 CNMR: (DMSO d 6 ): δ (ppm): 13.5, 21.5, 25.5, 26.0, 27.0, 27.2, 28.5, 29.6, 31.0, 41.5, 75.0, 151.0, 154.0, 161.0. 1 HNMR: (DMSO d 6 ): δ (ppm): 0.82 (m, 6H); 1.20 (m,37 H); 1.44 (m,17 H); 3.50 - 3.90 (m, 23H); 4.66 (bs, 3.75 H). Example 3 The preparation of a lipophylic diuracyl is reported. A solution of 1.96 g (16.9 mmol) of 1,6-hexamethylenediamine in 50 ml of THF are added dropwise to10 g (33.84 mmol) of octadecyl isocyanate dissolved in 100 ml of THF under stirring and at a temperature not exceeding 10°C. After the addition the reaction mixture is allowed to reach room temperature and then stirred for 30 min. The precipitate thus obtained is filtered. 10.97 g of a white solid are obtained. (IR: (cm -1 ): 3336, 2920, 2849, 1615, 1575). 5 g (7.08 mmol) of the solid are reacted under stirring with 1.73 g (17 mmol) of acetic anhydride and 1.32 g (15.58 mmol) of cyanacetic acid. The mixture is stirred and heated at 95°C for 3 hours. 10 ml of water and a 20% sodium hydroxide solution are added to the reaction mixture to obtain pH >9 then the reaction mixture is refluxed for 1 hour. The reaction mixture is cooled down to room temperature, the insoluble residue is filtered off and the remaining part is redissolved with ethyl acetate. The organic layer is washed with water and is dried on anhydrous sodium sulphate, then the solvent is evaporated under vacuum. 4.45 g of a brown solid are obtained. IR (cm -1 ): 3353, 3206, 2921, 2851,1623. 13 CNMR: (DMSO d 6 ): δ (ppm): 13.4, 21.8,25.7, 27.2, 28.7, 31.0, 41.3, 75.0, 151.0, 153.9, 161.0. 1 HNMR: δ (ppm): 0.87 (m, 6H); 1.25 (m, 64 H); 1.63 (m, 8 H); 3.76 (m, 8 H); 5.00 (bs, 2 H). Example 4 The preparation of a polyuracyl is reported. A solution of 2.42 g (20.86 mmol) of 1,6-hexamethylenediamine in 30 ml of THF are added dropwise to 7 g (41.67 mmol) of hexamethylene diisocyanate dissolved in 100 ml of THF under stirring and at 5°C. After the addition the reaction mixture is allowed to reach spontaneously 15°C, then a solution of 6.38 g (49.46 mmol) of n-octylamine in 40 ml of THF are added dropwise. The reaction mixture is stirred for 30 min at room temperature then it is filtered and the obtained precipitate is washed with acetone. 13.72 g of crude product are obtained. (IR: (cm -1 ): 3337, 2928, 2854, 1620, 1576). 5 g of the solid are reacted under stirring with 3.23 g (31.69 mmol) of acetic anhydride and 2.51 g (29.58 mmol) of cyanacetic acid. The mixture is heated at 100°C under stirring for 3.5 hours. 10 ml of water and a 15% sodium hydroxide solution are added to the reaction mixture to obtain pH 9 then the reaction mixture is refluxed for 2.5 hours. The reaction mixture is cooled down to room temperature and a solid compound is obtained by decantation. The solid is dissolved in methylene chloride/methanol (1/1) and the insoluble residue is discarded. The organic layer is evaporated under vacuum. 6.74 g of a yellow solid are obtained. IR (cm -1 ): 3414, 2927, 2854, 1631, 1574. 13 CNMR: (DMSO d 6 ): δ (ppm): 13.4, 21.8, 25.8, 27.3, 28.4, 29.8, 31.0, 41.5, 75.0, 151.0, 154.1, 161.2 1 HNMR: δ (ppm): 0.86 (m, 6H); 1.27 (m, 32 H); 1.47 (m, 16 H); 3.25 (m, 16 H); 4.67 (bs, 4 H). Example 5 The preparation of a diuracyl with unsaturated side chains is reported. According to the procedure described in Example 1, starting from 2 g (11.9 mmol) of hexamethylenediisocyanate in 50 ml of THF and 7.64 g (28.57 mmol) of oleylamine in 30 ml of THF, 8.38 g of a white solid are obtained. 5 g (7.12 mmol) of the solid are reacted with 1.33 g (15.6 mmol) of cyanacetic acid and 1.67 g (16.4 mmol) of acetic anhydride; the reaction mixture is treated as reported in Example 1 to obtain 4.06 g of a light yellow solid. IR (cm -1 ): 3386, 3214, 2924, 2853, 1620, 966. 13 CNMR: (DMSO d6): δ (ppm): 13.8, 21.9, 25.5, 26.6, 27.6, 28.5, 29.0, 31.1, 41.6, 75.0, 129.2, 151.0, 154.0, 161.0. 1 HNMR: (DMSO d6): δ (ppm): 0.84 (t, 6H); 1.24 (m, 48H); 1.50 (m,8H); 1.96 (m,8H); 3.63-3.83 (m, 8H); 4.65 (s, 2H); 5.32 (m, 4H). Example 6 The preparation of a diuracyl is reported. According to the procedure described in Example 1, starting from 10 g (45 mmol) of 3-methylen-3,5,5-trimethylcyclohexan-1-yl diisocyanate into 200 ml of THF and 12.77 g (99 mmol) of octylamine into 100 ml of THF, 16.35 g of a white solid are obtained. 5 g (10.42 mmol) of the solid are reacted with 1.96 g (23.06 mmol) of cyanacetic acid and 2.45 g (24.10 mmol) of acetic anhydride; the reaction mixture is treated as reported in Example 1 to obtain 5.51 g of a light yellow solid. IR (cm -1 ): 3359, 3261, 3213, 2955, 2926, 2855, 1623. 13 CNMR: (DMSO d6): δ (ppm): 13.5, 21.7, 26.0, 27.2, 28.4, 29.7, 30.9, 35.0, 42.1, 46.4, 52.3, 75.2, 151.9, 154.6, 155.0, 160.9. 1 HNMR: (DMSO d6): δ (ppm): 0.75 - 1.70 (m, 45H); 3.50 - 3.90 (m, 7H); 4.60 - 4.85 (m, 2H). Example 7 The preparation of a diuracyl is reported. According to the procedure described in Example 1, starting from 10 g (38.12 mmol) of methylene-bis(4-cyclohexylisocyanate), alias 4,4'-methylene-bis(cyclohexylisocyanate, into 200 ml of THF and 10.82 g (83.86 mmol) of octylamine into 100 ml of THF, 16.30 g of a white solid are obtained. 5 g (19.62 mmol) of the solid are reacted with 1.80 g (21.15 mmol) of cyanacetic acid and 2 26 g (22.11 mmol) of acetic anhydride; the reaction mixture is treated as reported in Example 1 to obtain 5.97 g of a yellow solid. IR (cm -1 ) 3384, 3212, 2925, 2853, 1631, 1560. CNMR: (DMSO d6): δ (ppm): 13.5, 21.7, 26.1, 28.3, 29.7, 30.9, 33.1, 44.5, 48 3, 55.2, 76.2, 150.7, 154.6, 157.3, 161.1. 1 HNMR (DMSO d6): δ (ppm): 0.70 - 1.95 (m, 50H); 3.50 - 3.82 (m, 4H); 3.85 - 4.15 (m, 2H); 4.60 -4.75 ( m,2H). The relevant data of Examples from 1 to 7 are summarized in Table I. 11 Example 8 The preparation of a dithiouracyl is reported. A solution of 11 g (80 mmol) of thiophenylisocyanate in 50 ml of THF are added dropwise to 4.22 g (36 mmol) of hexamethylenediamine dissolved in 100 ml of THF under stirring and at a temperature not exceeding 10°C. After the addition the reaction mixture is allowed to reach room temperature and then stirred for 2 hours. Then the solvent is evaporated under vacuum and 14 g of a white solid are obtained. IR: (cm -1 ): 3172, 3010, 2926, 1594, 1534, 1452. 1 HNMR (DMSO d 6 ): δ (ppm): 1.25-1.45 (m, 4H); 1.50-1.70 (m, 4 H); 3.45-3.55 (m, 4H); 7.07 (m, 2 H); 7.3 (m, 4 H); 7.45 (m, 4H); 7.6 (m, 2H). MS: 387 (M+1) 1.5 g (3.88 mmol) of the white solid are reacted under stirring with 0.84 g (8.23 mmol) of acetic anhydride and 0.7 g (8.23 mmol) of cyanacetic acid. The mixture is stirred and heated at 60°C for 3 hours. 10 ml of water and a 5% sodium hydroxide solution are added to the reaction mixture to obtain pH 9-10, then the reaction mixture is refluxed for 2 hours. The reaction mixture is cooled down to room temperature and methylene chloride is added. The organic layer is separated, washed with water, dried on anhydrous sodium sulphate and then the solvent is evaporated under vacuum. 1.13 g of a solid are obtained. The solid is purified by chromatography (silica gel, eluent: petroleum etherethylacetate 70:30 to 60:40). A fraction of 0.12 g of dithiouracyl is obtained. 1 HNMR (DMSO d 6 ) δ (ppm): 1.25-1.50 (m, 4H); 1.50-1.80 (m, 4 H); 3.45-3.65 (m, 4 H); 5.70 (3, 2 H); 7.25-7.50 (m, 10H). MS: 521 (M+1) Example 9 The preparation of a diuracyl with diphenylaliphatic internal chain and aliphatic side chain is reported. A solution of 11.36 g (87.9 mmol) of n-octylamine in 100 ml of THF are added dropwise to 10 g (40 mmol) of methylene bis(4-phenylisocyanate) dissolved in 200 ml of THF under stirring and at a temperature not exceeding 10°C. After the addition the reaction mixture is allowed to reach room temperature and then stirred for 30 min. ; the precipitate is then filtered, washed with acetone and dried under vacuum. 20 g of a white solid are obtained. IR: (cm -1 ): 3441, 3326, 2955, 2925, 2852, 1632, 1599, 1561. 5 g (98 mmol) of the white solid are reacted under stirring with 2.4 g (23.6mmol) of acetic anhydride and 1.84 g (21.6 mmol) of cyanacetic acid. The mixture is stirred and heated at 105°C and the temperature is set at 90-100° for 3 hours. 20 ml of water and a 15% sodium hydroxide solution are added to the reaction mixture to obtain pH >9, then the reaction mixture is refluxed for 2 hour. The reaction mixture is cooled down to room temperature and a solid compound is obtained by decantation. The solid is dissolved in methylene chloride. The organic layer obtained is washed with water and with a saturated solution of NaCI, then dried with sodium sulphate and evaporated under vacuum to obtain 6.1 g of a light yellow solid. IR (cm -1 ): 3473, 3319, 3247, 3191, 2954, 2925, 2854, 1635, 1547, 1510, 1473. 1 HNMR (DMSO d 6 ) δ (ppm): 0.75-0.95 (m, 6H); 1.1-1.35 (m, 20H); 1.35-1.60 (m, 4H); 3.60-4.05 (m, 4H); 4.83 (bs, 2H); 6.0 (m, 2H); 6.90-7.57 (m, 8H) 13 CNMR: (DMSO d6): δ (ppm): 13.4, 21.8, 26.0, 27.0, 28.5, 31.0, 74.8, 128.5, 129.5, 132.3, 141.2, 150.9, 154.0, 161.2. Example 10 The preparation of a diuracyl with cycloaliphatic side chain is reported. A solution of 14.5 g (146 mmol) of cyclohexylamine in 50 ml of THF are added dropwise to 12 g (71.4 mmol) of 1,6-hexamethylene diisocyanate dissolved in 150 ml of THF under stirring and at a temperature not exceeding 15°C. After the addition the reaction mixture is allowed to reach room temperature and then stirred for 30 min. then the precipitate is filtered, washed with THF and dried under vacuum. 24.5 g of a white solid are obtained. IR: (cm -1 ): 3346, 3314, 2929, 2854, 1624, 1574. 10 g (27 mmol) of the white solid are reacted under stirring with 6.1 g (60 mmol) of acetic anhydride and 5.1 g (60 mmol) of cyanacetic acid. The mixture is stirred and heated at 105°C and the temperature is set at 90-100° for 3 hours. 20 ml of water and a 15% sodium hydroxide solution are added to the reaction mixture to obtain pH >9, then the reaction mixture is refluxed for 2 hours. The reaction mixture is cooled down to room temperature and a solid compound is obtained by decantation. The solid is dissolved in methylene chloride-methanol (1:1) and the insoluble residue is discarded. The organic layer is evaporated under vacuum to obtain 13.2 g of a brown solid. 5 g of the brown solid are purified by chromatography (silica gel, eluent: methylene chloride-methanol 95:5 to 80:20). A fraction of 1 g of diuracyl is obtained. IR (cm -1 ): 3362, 3210, 2930, 2855, 1620, 1478. 1 HNMR (DMSO d 6 ) δ (ppm): 0.95-1.95 (m, 24H); 2.2-2.4 (m, 4H); 3.6-3.8 (m, 4H); 3.85-4.15 (m, 2 H); 4.7 (bs, 2H). MS: 501 (M+1). Example 11 The preparation of a diuracyl with hydroxyaromatic side chain is reported. A solution of 7.71 g (45.9 mmol) of 1,6-hexamethylene diisocyanate in 100 ml of THF are added dropwise to 10 g (91.7 mmol) of 3-amino-phenol dissolved in 150 ml of THF under stirring and at a temperature not exceeding 15°C. After the addition the reaction mixture is allowed to reach room temperature and then stirred for 1 hour; then the precipitate is filtered, washed with slightly acidic water and dried under vacuum. 12.3 g of a white solid are obtained. IR: (cm -1 ): 3322, 2930, 2857, 1630, 1605, 1566, 1442. 2 g (5.2 mmol) of the white solid are reacted under stirring with 2.22 g (21.8 mmol) of acetic anhydride and 1.85 g (21.8 mmol) of cyanacetic acid. The mixture is stirred and heated at 90°C and the temperature is set at 90-95° for 3 hours. 20 ml of water and a 15% sodium hydroxide solution are added to the reaction mixture to obtain pH >9, then the reaction mixture is refluxed for 2.5 hour. The reaction mixture is cooled down to room temperature and a solid compound is obtained by decantation. The solid is dissolved in methanol under reflux. The obtained solution is cooled, filtered and evaporated under vacuum to obtain 2.08 g of a crude solid. 2 g of the crude solid are purified by chromatography (silica gel, eluent: methylene chloride-methanol 95:5 to 90:10). A fraction of 0.34 g of diuracyl is obtained. 1 HNMR (DMSO d 6 ) δ (ppm): 1.25 (m, 4H); 1.50 (m, 4H); 3.67 (t, 4H); 4.77 (s, 2 H); 6.65 (m, 2H); 6.70 (m, 2H); 6.87 (m, 2H); 7.30 (m, 2H). MS: 521 (M+1). The relevant data of Examples from 8 to 11 are summarized in Table I (a). APPLICATION TESTS - STATIC HEAT TESTS. The thermal stability of PVC compositions stabilized with the products of the present invention is measured as reported below. A dry mixture of the ingredients reported in the following table, is laminated using a two cylinder apparatus for 1 min at 190°C. From the obtained rolled sheet, 20 x 220 mm samples are prepared. The test sample is subject to thermal stress in a Wherner Mathis oven equipped with a thermotester device. The oven temperature is set at 190°C and the thermotester device is set so that 20 mm of test sample are removed from the oven at regular intervals. In the reported conditions the sample is under a static heat stress. At the end of the experiment the evaluation is carried out measuring the Yellow Index according to ASTM D-1925-70. The results on rigid PVC (Compositions 1 and 2 - Tab. II) and on flexible PVC (Compositions 3 and 4 - Tab. III) are reported below. Low values of Yellow Index signify a good stabilisation. Compositions 1 and 2 (numbers refer to parts by weight): Composition 1 Composition 2 S-PVC (k value 64) 100 100 Epoxidized soy-bean oil 2 2 Compound of Example 1 - 0.4 Static heat test Thermal stress duration (min.) Y.L Composition 1 Y.I. Composition 2 3' 11.5 5.1 6' 29.3 5.9 9' 41.3 13 12' > 100 (burning) 22.4 15' 38.5 18' 55.6 21' 73.3 24' > 100 (burning) Compositions 3 and 4 (numbers refer to parts by weight): Composition 3 Composition 4 S-PVC (k value 70) 100 100 Dioctyl phtalate 60 60 Stearic acid 0.2 0.2 Epoxidized soy-bean oil 2 2 Compound of Example 1 - 0.4 Static heat test Thermal stress duration (min.) Y.I. Composition 3 Y.I. Composition 3 4' 5,5 3 8' 8,3 4,9 12' 25,8 10,9 16' 44,7 20,7 20' 62,5 33,5 24' 70,7 45,5 28' 74,1 59,7 32' > 100 (burning) 70,8 36' 77,3 40' > 100 (burning) In Table II (a) and in Tables from III (a) to III (e) the thermal stability of some other PVC compositions (Compositions 6-22) is reported. Compositions 6 and 7 (numbers refer to parts by weight): Composition 6 Composition 7 S-PVC (k value 64) 100 100 Epoxidized soy-bean oil 2 2 Compound of Example 4 0.4 0 Compound of Example 6 0 0.4 Compositions 8 and 9 (numbers refer to parts by weight): Composition 8 Composition 9 S-PVC (k value 70) 100 100 Dioctyl phtalate 60 60 Stearic Acid 0.5 0.5 Epoxidized soy-bean oil 2 2 Compound of Example 4 0.4 0 Compound of Example 6 0 0.4 Compositions 10, 11, 12, 13 (numbers refer to parts by weight): Composition 10 Composition 11 Composition 12 Composition 13 S-PVC (k value 70) 100 100 100 100 Dioctyl phtalate 40 40 40 40 Ca/Zn liquid stabilizer 2 2 2 2 Epoxidized soy-bean oil 2 2 0 0 Compound of Example 4 0 0.2 0 0.2 Compositions 14, 15, 16 (numbers refer to parts by weight): Composition 14 Composition 15 Composition 16 S-PVC (k value 70) 100 100 100 Dioctyl phtalate 60 60 60 Stearic Acid 0.5 0.5 0.5 Epoxidized soy-bean oil 2 2 2 Compound of Example 1 0.1 0.3 1 Compositions 17, 18, 19 (numbers refer to parts by weight): Composition 17 Composition 18 Composition 19 S-PVC (k value 70) 100 100 100 Dioctyl phtalate 60 60 60 Stearic Acid 0.5 0.5 0.5 Epoxidized soy-bean oil 2 2 2 Compound of Example 4 0.1 0.3 1 Compositions 20, 21, 22 (numbers refer to parts by weight): Composition 20 Composition 21 Composition 22 S-PVC (k value 70) 100 100 100 Dioctyl phtalate 60 60 60 Stearic Acid 0.5 0.5 0.5 Epoxidized soy-bean oil 2 2 2 Compound of Example 6 0.1 0.3 1 Static heat test Thermal stress duration (min.) Y.I. Composition 6 Y.I. Composition 7 4 9,85 7,56 8 15,25 10,64 12 33,39 20,11 16 52,91 33,61 20 67,73 52,23 24 79,15 67,84 28 > 100 (burning) 77,47 32 > 100 (burning) Static heat test Thermal stress duration (min.) Y.I. Composition 8 Y.I. Composition 9 4' 7,14 6,04 8' 11,47 12,45 12' 18,83 19,37 16' 27,55 30,59 20' 38,04 40,01 24' 52,30 50,71 28' 67,12 60,53 32' 74,29 70,00 36 75,59 76,58 40' 78,55 77,31 44' 81,85 79,58 48' > 100 (burning) 84,56 52' > 100 (burning) Static heat test Thermal stress duration (min.) Y.I. Composition 10 Y.I. Composition 11 Y.I. Composition 12 Y.I. Composition 13 4' 0.85 5.07 1.23 4.32 8' 0.90 4.53 1.25 6.00 12' 2.17 7.24 2.46 8.99 16' 3.92 11.44 3.28 10.86 20' 6.96 13.62 3.61 12.78 24' 18.18 17.90 29.94 13.94 28' 36.77 39.16 > 100 (burning) 14.58 32' > 100 (burning) 59.68 17.37 36 75.81 27.34 40' 83.79 70.59 44' > 100 (burning) > 100 (burning) Static heat test Thermal stress duration (min.) Y.I. Composition 14 Y.I. Composition 15 Y.I. Composition 16 3' 4.41 4.39 7.39 6' 12.31 5.70 10.67 9' 30.84 12.79 18.22 12' 45.36 24.22 24.65 15' 75.59 40.23 31.61 18' > 100 (burning) 61.69 40.97 21' 74.18 50.15 24' 78.33 58.80 27' > 100 (burning) 69.03 30' 74.67 33' > 100 (burning) Static heat test Thermal stress duration (min.) Y.I. Composition 17 Y.I. Composition 18 Y.I. Composition 19 3' 5.85 3.50 11.73 6' 18.78 6.53 11.55 9' 38.96 15.98 17.22 12' 63.53 28.64 25.62 15' 69.84 53.01 34.92 18' > 100 (burning) 71.06 48.58 21' 76.41 61.37 24' > 100 (burning) 70.89 27' 77.10 30' > 100 (burning) Static heat test Thermal stress duration (min.) Y.I. Composition 20 Y.I. Composition 21 Y.I. Composition 22 3' 3.39 3.58 3.73 6' 13.28 7.54 9.50 9' 29.32 19.82 17.03 12' 58.24 32.04 24.70 15' 74.91 52.44 34.79 18' > 100 (burning) 66.97 46.37 21' 78.94 55.40 24' 72.82 65.34 27' > 100 (burning) 73.99 30' 78.73 33' > 100 (burning) APPLICATION TESTS - EVALUATION OF STAINING AND BLISTERING. The appraisal of staining and blistering is carried out by the evaluation, respectively, of exudation and transparency on test samples obtained from lamination using a two cylinder apparatus for 1 min at 190°C. The exudation is evaluated by an organoleptic test. An exudated sample is tacky. An empirical evaluation has been set up with scores from 0 to 3, according to the definitions of Table IV. Degree of exudation tacky of the test sample 0 Tack free 1 Lightly tacky 2 Moderately tacky 3 Strongly tacky Transparency is measured by a BYK Colour Guide 45/0 colorimeter using the setting to measure opacity. The test sample is placed on a white and black cardboard and two different measurements are carried out: one against the black background and the other against the white background: opacity is the ratio % between the evaluation against the black background and the white background. The higher is the %, the higher is opacity and the lower is transparency. In table V the results of the application tests for the evaluation of exudation and transparency on flexible PVC are reported. The comparison is made among compositions 3 and 4, that are again reported below for better understanding, and a similar composition of flexible PVC containing the monomeric 1,3-dimethylamino uracyl (Composition 5). Compositions 3, 4, 5 (numbers refer to parts in weight): Composition 3 Composition 4 Composition 5 S-PVC (k value 70) 100 100 100 Dioctyl phtalate 60 60 60 Stearic acid 0,2 0,2 0,2 Epoxidised soy-bean oil 2 2 2 Compound of Example 1 - 0,4 - 1,3-dimethyl-6-amino uracyl - - 0,4 Exudation and transparency Composition Exudation value Transparency % 3 0 16,0 4 0 16,9 5 3 21,2 In Table V (a) the results of the application tests for the evaluation of exudation and transparency on some other flexible PVC compositions (Compositions 8, 9, 16, 19, 22, 23) are reported. Comp. 8 Comp. 9 Comp. 16 Comp. 19 Comp. 22 Com p. 23 S-PVC k value 70 100 100 100 100 100 100 Dioctyl phtalate 60 60 60 60 60 60 Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 Epoxidized soy-bean oil 2 2 2 2 2 2 Compound of Example 1 0 0 1 0 0 0 Compound of Example 4 0.4 0 0 1 0 0 Compound of Example 6 0 0.4 0 0 1 0 1,3-dimethyl-6-amino uracyl 0 0 0 0 0 1 Exudation and Trasparency Composition Degree of Exudation Transparency % 8 0 16.6 9 0 16.3 16 0 16.7 19 0 18.4 22 0 15.7 23 3 24.6

Claims: Flexible PVC compositions exhibiting high thermal and oxidative stability, containing oligomeric and/or polymeric aminouracyls, characterised by the fact that the oligomeric and/or polymeric aminouracyls consist of: a repetitive group of formula (I): wherein: R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, aryl substituted with -OH or C 1 -C 8 alkoxy ( = substituted aryl), arylalkyl, alkylaryl; R 1 is H, -(C = O)-C 1 -C 12 linear o branched alkyl, -(C = O)-O- C 1 -C 12 linear o branched alkyl, -(C=O) phenyl, not substituted or substituted with -OH, C 1 -C 8 linear o branched alkyl, C 1 -C 8 alkoxy; Z is O or S; linking groups between the repetitive groups of formula (I) equal or different as: - (CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1 -yl, methylenebis(4-cyclohexyl), methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; terminal groups as: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. Flexible PVC compositions according to Claim 1, wherein R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, substituted aryl, R 1 is H, Z is O or S; the linking groups between the repetitive groups of formula (I) are equal or different and are: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is -H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl, methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; the terminal groups are: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, C 1 -C 18 alkylamine, disubstituted with C 1 -C 18 linear or branched alkyl. Flexible PVC compositions according to Claim 1, wherein the oligomeric and/or polymeric aminouracyls are incorporated in an amount of from 0.01 to 10% by weight. Flexible PVC compositions according to Claim 3, wherein the oligomeric and/or polymeric aminouracyls are incorporated in an amount of from 0.05 to 5% by weight. Flexible PVC compositions according to Claim 3, wherein the oligomeric and/or polymeric aminouracyls are incorporated in an amount from 0.1 to 3% by weight. Oligomeric and/or polymeric aminouracyls suitable for the stabilization of flexible PVC consisting of: a repetitive group of formula (I): wherein: R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, aryl substituted with -OH or C 1 -C 8 alkoxy (=substituted aryl), arylalkyl, alkylaryl; R 1 is H, -(C=O)-C 1 -C 12 linear o branched alkyl, -(C=O)-O- C 1 -C 12 linear o branched alkyl, -(C = O) phenyl, not substituted or substituted with -OH, C 1 -C 8 linear o branched alkyl, C 1 -C 8 alkoxy; Z is O or S; linking groups between the repetitive groups of formula (I) equal or different as: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl), methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; terminal groups as: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. Oligomeric and/or polymeric aminouracyls according to Claim 6, wherein R is H, C 1 -C 18 linear o branched alkyl, C 5 -C 8 cycloalkyl, aryl, substituted aryl, R 1 is H, Z is O or S; the linking groups between the repetitive groups of formula (I) are equal or different and are: -(CR 2 R 3 ) n - where R 2 , R 3 can be equal or different and each independently of the other is -H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl), methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; the terminal groups are: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, C 1 -C 18 alkylamine, disubstituted with C 1 -C 18 linear or branched alkyl. Oligomeric and polymeric aminouracyls according to claim 6, characterized by the fact that they can be obtained by cyclization using cyanacetic acid or its derivatives of an oligomeric and/or polymeric urea obtained by oligomerization and/or polymerization using suitable combinations of: a diisocyanate (DD) of formula OCN-Y-NCO where Y can be: -(CR 2 R 3 ) n -where R 2 , R 3 are equal or different and each independently of the other is -H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl), methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; an amine (A) of formula X-NH 2 where X can be: H, C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl; a di-amine (AA) of formula H 2 N-K-NH 2 where K can be: -(CR 2 R 3 ) n - where R 2 , R 3 are equal or different and each independently of the other is H, C 1 -C 12 linear or branched or cyclic alkyl and n is an integer equal or greater than 2; or 3-methylen-3,5,5-trimethylcyclohexan-1-yl, methylenebis(4-cyclohexyl), methylenebis(3-cyclohexyl), 1,4-phenylene, 1-methyl-2,4-phenylene, 4,4'-diphenylenmethane; an isocyanate of formula W-NCO (D), where W can be: C 1 -C 18 linear or branched alkyl, C 5 -C 8 cycloalkyl, C 3 -C 18 alkenyl, aryl, substituted aryl, arylalkyl, alkylaryl, C 1 -C 18 hydroxyalkyl, C 2 -C 18 alkoxy alkyl, C 6 -C 10 cycloalkoxyalkyl, C 7 -C 14 alkoxyaryl, C 7 -C 14 aryloxyalkyl, C 2 -C 8 alkylthioalkyl, C 6 -C 10 cycloalkylthioalkyl, C 7 -C 14 alkylthioaryl, C 7 -C 14 arylthioalkyl, C 1 -C 18 alkylammine, disubstituted with C 1 -C 18 linear or branched alkyl. Oligomeric and/or polymeric aminouracyls according to Claim 8, wherein in the preparation of the polyurea, when AA and D are both equal to zero, the molar ratio DD/A is comprised between 0.3 and 0.6; when DD and A are both equal to zero, the molar ratio AA/D is comprised between 0.3 and 0.6.

Inventors: ALLIERI GUIDO, CASIRAGHI ANGELO ROBERTO, FERRACINI MAURO, LI BASSI GIUSEPPE, NORCINI GABRIELE PIETRO, VISCONTI MARCO, ALLIERI, GUIDO, CASIRAGHI, ANGELO ROBERTO, FERRACINI, MAURO, LI BASSI, GIUSEPPE, NORCINI, GABRIELE PIETRO, VISCONTI, MARCO
Applicants: LAMBERTI SPA, LAMBERTI S.P.A.
Application year: 2001
Main classification: C08K5
IPC codes: C08K5, C08L27, C07D239, C08L79