阅读说明：本技术 稳定的滚塑聚烯烃 (Stabilized rotomoulding polyolefins ) 是由 J·西格莱尔 于 2019-08-19 设计创作，主要内容包括：经由滚塑方法制备的聚烯烃中空制品通过在其中掺入受阻胺光稳定剂、紫外光吸收剂和硫醚添加剂而具备了针对热、光和氧的有害影响的稳定性。(Polyolefin hollow articles prepared via the rotomolding process are provided with stability against the deleterious effects of heat, light and oxygen by incorporating therein hindered amine light stabilizers, ultraviolet light absorbers and thioether additives.)

1. A plastic article stabilized against the deleterious effects of heat, light, and oxygen comprising a polyolefin substrate and an additive incorporated into the polyolefin substrate, the additive comprising

i) A hindered amine light stabilizer;

ii) an ultraviolet light absorber; and

iii) a thioether additive,

wherein the plastic product contains a hollow part.

2. The plastic article of claim 1, wherein the hindered amine light stabilizer is selected from the group consisting of:

(1) 1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-octadecylaminopiperidine,

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(3) bis (1-acetoxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(4) bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate,

(5) bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(6) bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate;

(7) bis (1-acyl-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(8) bis (1,2,2,6, 6-pentamethyl-4-piperidyl) n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonic acid ester

(9)2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -6- (2-hydroxyethylamino-s-triazine,

(10) bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate,

(11)2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine,

(12)1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine,

(13)1- (2-hydroxy-2-methylpropoxy) -4-oxo-2, 2,6, 6-tetramethylpiperidine,

(14)1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2, 2,6, 6-tetramethylpiperidine,

(15) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(16) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl) adipate,

(17)2, 4-bis { N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl ] -N-butylamino } -6- (2-hydroxyethylamino) s-triazine,

(18) 4-benzoyl-2, 2,6, 6-tetramethylpiperidine,

(19) bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) p-methoxyphenylmethylmalonate,

(20)2,2,6, 6-tetramethylpiperidin-4-yl octadecanoate,

(21) bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) succinate,

(22)1,2,2,6, 6-pentamethyl-4-aminopiperidine,

(23) 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxo-spiro [4,5] decane,

(24) tris (2,2,6, 6-tetramethyl-4-piperidyl) nitrilotriacetate,

(25) tris (2-hydroxy-3- (amino- (2,2,6, 6-tetramethylpiperidin-4-yl) propyl) nitrilotriacetate,

(26) tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane-tetracarboxylate,

(27) tetrakis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -1,2,3, 4-butane-tetracarboxylate,

(28)1,1' - (1, 2-ethanediyl) -bis (3,3,5, 5-tetramethylpiperazinone),

(29) 3-n-octyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione,

(30) 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione,

(31) 3-dodecyl-1- (2,2,6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione,

(32) 3-dodecyl-1- (1,2,2,6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione,

(33) n, N '-biscarboxyl-N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexanediamine,

(33a) bis (1-undecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate,

(34) reaction product of 2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine with N, N' -bis (3-aminopropyl) ethylenediamine),

(35) a condensate of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid,

(36) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine,

(37) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine,

(38) a condensate of N, N' -bis- (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(39) a condensate of N, N' -bis- (1,2,2,6, 6-pentamethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(40) condensate of 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6, 6-tetramethylpiperidyl) -1,3, 5-triazine with 1, 2-bis (3-aminopropylamino) ethane

(41) Condensate of 2-chloro-4, 6-bis (4-n-butylamino-1, 2,2,6, 6-pentamethylpiperidyl) -1,3, 5-triazine with 1, 2-bis- (3-aminopropylamino) ethane

(42) A reaction product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4,5] decane and epichlorohydrin,

(43) poly [ methyl, (3-oxy- (2,2,6, 6-tetramethylpiperidin-4-yl) propyl) ] siloxane, CAS #182635-99-0,

(44) maleic anhydride-C₁₈-C₂₂Reaction product of alpha-olefin copolymer with 2,2,6, 6-tetramethyl-4-aminopiperidine

(45) Oligomeric condensates of 4,4' -hexamethylenebis (amino-2, 2,6, 6-tetramethylpiperidine) with 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine),

(46) oligomeric condensates of 4,4' -hexamethylenebis (amino-1, 2,2,6, 6-pentamethylpiperidine) with 2, 4-dichloro-6- [ (1,2,2,6, 6-pentamethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) -s-triazine),

(47) an oligomeric condensate of 4,4' -hexamethylenebis (amino-1-propoxy-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (1-propoxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine),

(48) oligomeric condensates of 4,4' -hexamethylenebis (amino-1-acyloxy-2, 2,6, 6-tetramethylpiperidine) with 2, 4-dichloro-6- [ (1-acyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) -s-triazine)

(49) A product obtained by reacting (a) a product obtained by reacting 1, 2-bis (3-aminopropylamino) ethane with cyanuric chloride, and (b) a (2,2,6, 6-tetramethylpiperidin-4-yl) butylamine.

3. The plastic article of claim 1 or 2, wherein the ultraviolet light stabilizer is selected from the group consisting of: oxamides, hydroxyphenyl benzotriazoles, tris-aryl-s-triazines, hydroxybenzoates, 2-hydroxybenzophenones and cyanoacrylate ultraviolet light absorbers.

4. The plastic article of any of the preceding claims, wherein the thioether additive comprises a thiol-containing compound comprising one or more moieties of the formula

5. The plastic article of any of the preceding claims, wherein the thioether additive comprises a thiol-containing compound comprising one or more moieties of the formula

Wherein R is a hydrocarbyl group.

6. The plastic article of any of the preceding claims, wherein the thioether additive has the formula:

wherein each R is independently a hydrocarbyl group.

7. The plastic article of any of the preceding claims, wherein the thioether additive comprises a disulfide-containing compound having the formula R-S-R, wherein each R is independently a hydrocarbyl group.

8. The plastic article of any one of the preceding claims, wherein the polyolefin substrate comprises polyethylene.

9. The plastic article of any of the preceding claims, wherein the article comprises from about 50 wt% to about 95 wt% of the polyolefin, based on the total weight of the article.

10. The plastic article of any one of the preceding claims, wherein the article comprises from about 50ppm to about 2000ppm of the hindered amine light stabilizer, based on the total weight of the article.

11. The plastic article of any one of the preceding claims, wherein the article comprises from about 50ppm to about 2000ppm of the ultraviolet light absorber, based on the total weight of the article.

12. The plastic article of any of the preceding claims, wherein the article comprises from about 50ppm to about 2000ppm of the thioether additive, based on the total weight of the article.

13. The plastic article of any one of the preceding claims, wherein the weight/weight ratio of the hindered amine light stabilizer to the thioether additive is from about 7/1 to about 1/1.

14. The plastic article of any of the preceding claims, wherein the weight/weight ratio of the ultraviolet light absorber to the thioether additive is from about 3/1 to about 1/3.

15. The plastic article of any of the preceding claims, wherein the article further comprises one or more additives selected from the group consisting of: phenolic antioxidants, hydroxylamine stabilizers, organophosphorus stabilizers and acid scavengers.

16. The plastic article of any one of the preceding claims, wherein the article comprises from about 0.1 wt% to about 50 wt% of one or more fillers, based on the total weight of the article.

17. The plastic article of any of the preceding claims, wherein the article has an average wall thickness of about 1.50mm to about 6.00 mm.

18. The plastic article of any one of the preceding claims, wherein a 125 mil thick, 5 inch by 5 inch test sample of the article exhibits an impact strength of ≧ 21 f/lbs.

19. The plastic article of any of the preceding claims, wherein a 125 mil thick, 5 inch by 5 inch test sample of the article exhibits a ductility of ≧ 50%.

20. The plastic article of any one of the preceding claims, wherein a 125 mil thick, 5 inch by 5 inch test sample of the article exhibits a Yellowness Index (YI) of ≦ 2.0.

21. A method for manufacturing a hollow plastic article, the method comprising

Incorporating into a polyolefin substrate an additive comprising: i) a hindered amine light stabilizer; ii) an ultraviolet light absorber; and iii) a thioether additive to provide a fully formulated polyolefin blend,

adding the mixture to a mold, heating the mold to a temperature greater than 280 ℃, rotating the mold about at least 2 axes, wherein the molten polyolefin mixture coats the interior of the mold, cooling the mold while still rotating, opening the mold and removing the formed hollow article.

Background

Rotational molding (rotational molding) is a manufacturing process for making hollow plastic articles. Generally, a plastic material is filled into one half of a mold, which is then closed with the other half. The closed mold is heated and rotated about different axes, with the molten polymer coating the interior of the mold-a process known as "sintering". The mold is then cooled and the molded article is removed. The process may require temperatures greater than about 300 ℃ or even greater than about 400 ℃.

The rotomolding process can be used to prepare articles such as storage tanks for water, oil, etc.; kayaks, toys, trash cans, equipment enclosures, and the like. Typically, rotomoulding processes employ a polyolefin substrate, such as polyethylene.

In the rotomoulding process, there are generally higher processing temperatures and longer heating times. Even during the cooling cycle (crystallization) of the polymer, it may be adversely affected by heat. Rotomoulded parts are typically cooled slowly to avoid distortion and warpage, and depending on the size and thickness of the part, the part may be exposed to a significant amount of heat during the cooling stage. Even after removal from the mold, the plastic part may still cool and crystallize. Prolonged exposure to heat and oxygen can negatively impact the mechanical properties of rotomoulded plastic parts. Current process stable packages do not provide the desired mechanical properties, such as impact strength or ductility, to the rotomoulded part.

Disclosure of Invention

Accordingly, a hollow plastic article stabilized against the deleterious effects of heat, light, and oxygen is disclosed, the article comprising a polyolefin substrate having incorporated therein a hindered amine light stabilizer, an ultraviolet light absorber, and a thioether additive.

Also disclosed is a process for making a hollow plastic article comprising incorporating a hindered amine light stabilizer, an ultraviolet light absorber, and a thioether additive into a polyolefin substrate to provide a fully formulated polyolefin mixture, adding the mixture to a mold, heating the mold to a temperature greater than 280 ℃, rotating the mold about at least 2 axes, wherein the molten polyolefin mixture coats the interior of the mold, cooling the mold while still rotating, opening the mold, and removing the formed hollow article.

Detailed Description

In certain embodiments, the polyolefin substrate comprises polyethylene. Polyethylenes include, for example, High Density Polyethylene (HDPE), high molecular weight high density polyethylene (HMW HDPE), ultra high molecular weight high density polyethylene (UHMW HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Branched Low Density Polyethylene (BLDPE), or polyethylene and ethylene copolymers prepared using Phillips catalysts and polyethylene blends. The ethylene copolymers may contain different proportions of comonomers. In some embodiments, the comonomer comprises a 1-olefin, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or isobutylene; styrene; cyclic olefins, such as cyclopentene, cyclohexene or norbornene; or dienes such as butadiene, isoprene, 1, 4-hexadiene, cyclopentadiene, dicyclopentadiene, norbornadiene or ethylidene norbornene.

The polyolefin substrate also includes a blend of polyethylene and polyolefin. Examples include mixtures of polyethylene with polypropylene (PP) and mixtures of various PE types, for example mixtures comprising two or more High Density Polyethylenes (HDPE), high molecular weight high density polyethylene (HMW HDPE), ultra high molecular weight high density polyethylene (UHMW HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Branched Low Density Polyethylene (BLDPE) or ethylene-propylene-diene terpolymers (EPDM) containing a high proportion of dienes. Certain embodiments of the polymer blend include, for example, PP/HDPE, PP/LLDPE and LLDPE/HDPE and ternary blends such as PP/HDPE/LLDPE. In certain embodiments, the polymers may be linear or branched, and may be formulated with or without crosslinking (e.g., chemical crosslinking).

The polyolefin substrate may have incorporated therein other polymers such as polystyrene, polyamide, polyester, polycarbonate, epoxy, polyurethane, copolymers thereof (e.g., random or block copolymers), or mixtures thereof. In some embodiments, such "other" polymers may be present in the final article in any of about 1 wt% (weight percent), about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, or about 7 wt% to any of about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt%, based on the total weight of the final article.

In some embodiments, the hollow articles of the present disclosure may comprise the hindered amine light stabilizer in an amount of any one of about 50ppm (parts per million), about 100ppm, about 200ppm, about 300ppm, about 400ppm, about 500ppm, or about 600ppm to about 700ppm, about 800ppm, about 900ppm, about 1000ppm, about 1100ppm, about 1200ppm, about 1300ppm, about 1400ppm, about 1500ppm, about 1600ppm, about 1700ppm, about 1800ppm, about 1900ppm, or about 2000ppm by weight based on the total weight of the article.

In other embodiments, the article may comprise any of about 0.1 wt% (weight percent), about 0.2 wt%, about 0.5 wt%, about 1.0 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, or about 3.0 wt% to any of about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt%, about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, or about 7.5 wt% of the hindered amine light stabilizer, based on the total weight of the article.

In some embodiments, the hollow articles of the present disclosure may comprise the ultraviolet light absorber in an amount of any of about 50ppm (parts per million), about 100ppm, about 200ppm, about 300ppm, about 400ppm, about 500ppm, or about 600ppm to any of about 700ppm, about 800ppm, about 900ppm, about 1000ppm, about 1100ppm, about 1200ppm, about 1300ppm, about 1400ppm, about 1500ppm, about 1600ppm, about 1700ppm, about 1800ppm, about 1900ppm, or about 2000ppm by weight, based on the total weight of the article.

In other embodiments, the article may comprise any of about 0.1 wt% (weight percent), about 0.2 wt%, about 0.5 wt%, about 1.0 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, or about 3.0 wt% to any of about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt%, about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, or about 7.5 wt% of the ultraviolet light absorber, based on the total weight of the article.

In some embodiments, the hollow articles of the present invention may comprise the thioether additive in an amount of from any one of about 50ppm (parts per million), about 100ppm, about 200ppm, about 300ppm, about 400ppm, about 500ppm, or about 600ppm to any one of about 700ppm, about 800ppm, about 900ppm, about 1000ppm, about 1100ppm, about 1200ppm, about 1300ppm, about 1400ppm, about 1500ppm, about 1600ppm, about 1700ppm, about 1800ppm, about 1900ppm, or about 2000ppm by weight, based on the total weight of the article.

In other embodiments, the article may comprise any of about 0.1 wt% (weight percent), about 0.2 wt%, about 0.5 wt%, about 1.0 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, or about 3.0 wt% to any of about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt%, about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, or about 7.5 wt% of the thioether additive, based on the total weight of the article.

In certain embodiments, the weight/weight ratio of the hindered amine light stabilizer to the thioether additive is any one of about 7/1, about 6/1, about 5/1, or about 4/1 to any one of about 3/1, about 2/1, or about 1/1.

In some embodiments, the weight/weight ratio of the ultraviolet light absorber to the thioether additive is any one of about 3/1, about 2/1, about 1.5/1, or about 1/1 to any one of about 1/1.5, about 1/2, or about 1/3.

In some embodiments, the hollow article comprises any of about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 73 wt%, about 76 wt%, about 79 wt%, or about 82 wt% to any of about 85 wt%, about 88 wt%, about 90 wt%, about 93 wt%, or about 95 wt% of the polyolefin substrate, based on the total weight of the article.

Hindered Amine Light Stabilizers (HALS) are disclosed, for example, in US2015/0284535 and U.S. patent nos. 5,004,770, 5,204,473, 5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156, 5,844,026, 5,980,783, 6,046,304, 6,117,995, 6,271,377, 6,297,299, 6,392,041, 6,376,584 and 6,472,456.

Hindered amine light stabilizers include, for example:

(1) 1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-octadecylaminopiperidine,

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(3) bis (1-acetoxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(4) bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate,

(5) bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(6) bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate;

(7) bis (1-acyl-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(8) bis (1,2,2,6, 6-pentamethyl-4-piperidyl) n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonic acid ester

(9)2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -6- (2-hydroxyethylamino-s-triazine,

(10) bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) adipate,

(11)2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine,

(12)1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine,

(13)1- (2-hydroxy-2-methylpropoxy) -4-oxo-2, 2,6, 6-tetramethylpiperidine,

(14)1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2, 2,6, 6-tetramethylpiperidine,

(15) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(16) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl) adipate,

(17)2, 4-bis { N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl ] -N-butylamino } -6- (2-hydroxyethylamino) s-triazine,

(18) 4-benzoyl-2, 2,6, 6-tetramethylpiperidine,

(19) bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) p-methoxyphenylmethylmalonate,

(20)2,2,6, 6-tetramethylpiperidin-4-yl octadecanoate,

(21) bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) succinate,

(22)1,2,2,6, 6-pentamethyl-4-aminopiperidine,

(23) 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxo-spiro [4,5] decane,

(24) tris (2,2,6, 6-tetramethyl-4-piperidyl) nitrilotriacetate,

(25) tris (2-hydroxy-3- (amino- (2,2,6, 6-tetramethylpiperidin-4-yl) propyl) nitrilotriacetate,

(26) tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane-tetracarboxylate,

(27) tetrakis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -1,2,3, 4-butane-tetracarboxylate,

(28)1,1' - (1, 2-ethanediyl) -bis (3,3,5, 5-tetramethylpiperazinone),

(29) 3-n-octyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione,

(30) 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione,

(31) 3-dodecyl-1- (2,2,6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione,

(32) 3-dodecyl-1- (1,2,2,6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione,

(33) n, N '-biscarboxyl-N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexanediamine,

(33a) bis (1-undecyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate,

(34) reaction product of 2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine with N, N' -bis (3-aminopropyl) ethylenediamine),

(35) a condensate of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid,

(36) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine,

(37) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine,

(38) a condensate of N, N' -bis- (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(39) a condensate of N, N' -bis- (1,2,2,6, 6-pentamethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(40) condensate of 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6, 6-tetramethylpiperidyl) -1,3, 5-triazine with 1, 2-bis (3-aminopropylamino) ethane

(41) Condensate of 2-chloro-4, 6-bis (4-n-butylamino-1, 2,2,6, 6-pentamethylpiperidyl) -1,3, 5-triazine with 1, 2-bis- (3-aminopropylamino) ethane

(42) A reaction product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4,5] decane and epichlorohydrin,

(43) poly [ methyl, (3-oxy- (2,2,6, 6-tetramethylpiperidin-4-yl) propyl) ] siloxane, CAS #182635-99-0,

(44) maleic anhydride-C₁₈-C₂₂Reaction product of alpha-olefin copolymer with 2,2,6, 6-tetramethyl-4-aminopiperidine

(45) Oligomeric condensates of 4,4' -hexamethylenebis (amino-2, 2,6, 6-tetramethylpiperidine) with 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine),

(46) oligomeric condensates of 4,4' -hexamethylenebis (amino-1, 2,2,6, 6-pentamethylpiperidine) with 2, 4-dichloro-6- [ (1,2,2,6, 6-pentamethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) -s-triazine),

(47) an oligomeric condensate of 4,4' -hexamethylenebis (amino-1-propoxy-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (1-propoxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine),

(48) oligomeric condensates of 4,4' -hexamethylenebis (amino-1-acyloxy-2, 2,6, 6-tetramethylpiperidine) with 2, 4-dichloro-6- [ (1-acyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) -s-triazine)

(49) A product obtained by reacting (a) a product obtained by reacting 1, 2-bis (3-aminopropylamino) ethane with cyanuric chloride, and (b) a (2,2,6, 6-tetramethylpiperidin-4-yl) butylamine.

Also included are the sterically hindered N-H, N-methyl, N-hydroxy and N-acyloxy analogs of any of the compounds mentioned above. For example, replacing an N-H hindered amine with an N-methyl hindered amine would employ an N-methyl analog in place of N-H.

For illustrative purposes, some structures of the above compounds are shown below.

(6)

(8)

(9)

(12)

(19)

(23)

(25)

(26)

(28)

(29)

(31)

(33)

(34)

(35)

(36)

(38)

(41)

(42)

(43)

(44)

(45)

(49)

In some embodiments, the hindered amine light stabilizer may be selected from the group consisting of:

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(20)2,2,6, 6-tetramethylpiperidin-4-yl octadecanoate,

(14)1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2, 2,6, 6-tetramethylpiperidine,

(33) n, N '-biscarboxyl-N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexanediamine,

(36) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine,

(38) a condensate of N, N' -bis- (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(39) a condensate of N, N' -bis- (1,2,2,6, 6-pentamethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine,

(44) maleic anhydride-C₁₈-C₂₂Reaction product of alpha-olefin copolymer with 2,2,6, 6-tetramethyl-4-aminopiperidine

(45) Oligomeric compounds of 4,4' -hexamethylenebis (amino-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine),

(47) oligomeric compounds of 4,4' -hexamethylenebis (amino-1-propoxy-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (1-propoxy-2, 2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine) and

binary or ternary combinations thereof.

Certain binary or ternary combinations of hindered amine light stabilizers may be advantageous. For example, binary or ternary combinations:

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate and

(36) the condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine;

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate and

(45)4,4' -Hexamethylenebis (amino-2, 2,6, 6-tetramethyl)

Piperidine) and 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine);

(20)2,2,6, 6-tetramethylpiperidin-4-yl octadecanoate and

(45) an oligomeric condensate of 4,4' -hexamethylenebis (amino-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino ] -s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) s-triazine);

(2) bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate and

(20)2,2,6, 6-tetramethylpiperidin-4-yloctadecanoate; or

(2) Bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate,

(14)1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2, 2,6, 6-tetramethylpiperidine and

(36) condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine.

In some embodiments, HALS (38) or (39) may be substituted with HALS (36) in binary and ternary combinations.

Many hindered amine stabilizers are currently commercially available, such as TINUVIN 770, CHIMASSORB 944, CHIMASSORB 2020, CYASORB UV 3853, CYASORB UV 3529, TINUVIN NOR 371, UVINUL 4050, UVINUL 5050, and the like.

In the binary HALS combination, the weight/weight ratio is any one of about 1/19, about 1/18, about 1/17, about 1/16, about 1/15, about 1/14, about 1/13, about 1/12, about 1/11, about 1/10, about 1/9, about 1/8, about 1/7, about 1/6, about 1/5, about 1/4, about 1/3, about 1/2 or about 1/1 to about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8, about 1/9, about 1/10, about 1/11, about 1/12, about 1/13, about 1/14, about 1/15, about 1/16, Any one of about 1/17, about 1/18, about 1/19, or about 1/20.

In a ternary HALS combination, the weight/weight ratio of any two of the HALS is as for a binary combination.

In some embodiments, a combination of low molecular weight and high molecular weight HALS may be employed. The low molecular weight stabilizer has a molecular weight of about 200g/mol to about 1000 g/mol. The high molecular weight stabilizer has a molecular weight of about 1200g/mol to about 10,000 g/mol.

Some low molecular weight hindered amines are (1) - (33 a). Some high molecular weight hindered amines are (34) - (49). In oligomeric or polymeric hindered amines, the repeating unit "n" is such that the average molecular weight is from about 1200g/mol to about 10,000 g/mol.

The Ultraviolet (UV) light absorber may be selected from the group consisting of: oxamides, hydroxyphenyl benzotriazoles, tris-aryl-s-triazines, hydroxybenzoates, 2-hydroxybenzophenones and cyanoacrylate ultraviolet light absorbers (UVAs).

Oxamide UVAs include, for example, 4 '-dioctyloxyoxanilide, 2' -diethoxyoxanilide, 2 '-dioctyloxy-5, 5' -di-tert-butoxanilide, 2 '-didecyloxy-5, 5' -di-tert-butoxanilide, 2-ethoxy-2 '-ethyloxanilide (N' - (2-ethoxyphenyl) -N- (2-ethylphenyl) oxamide), N '-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2' -ethoxanilide and mixtures thereof with 2-ethoxy-2 '-ethyl-5, 4' -di-tert-butoxanilide, Mixtures of o-and p-methoxy disubstituted oxanilides and mixtures of o-and p-ethoxy disubstituted oxanilides.

Hydroxyphenylbenzotriazole UVA is disclosed in, for example, U.S. Pat. Nos. 3,004,896, 3,055,896, 3,072,585, 3,074,910, 3,189,615, 3,218,332, 3,230,194, 4,127,586, 4,226,763, 4,275,004, 4,278,589, 4,315,848, 4,347,180, 4,383,863, 4,675,352, 4,681,905, 4,853,471, 5,268,450, 5,278,314, 5,280,124, 5,319,091, 5,410,071, 5,436,349, 5,516,914, 5,554,760, 5,563,242, 5,574,166, 5,607,987, 5,977,219 and 6,166,218, such as 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-octylphenyl) -2-tert-butylphenyl) -2-octylphenyl-2H-benzotriazole Oxazole, 5-chloro-2- (3, 5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-sec-butyl-5-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3, 5-bis-alpha-cumyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2-methyl-ethyl-phenyl) -2H-benzotriazole, and mixtures thereof, 2- (3-tert-butyl-2-hydroxy-5- (2- (. omega. -hydroxy-octa- (ethyleneoxy) carbonyl-ethyl) -, phenyl) -2H-benzotriazole, 2- (3-dodecyl-2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-octyloxycarbonyl) ethylphenyl) -2H-benzotriazole, dodecylated 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-octyloxycarbonylethyl) phenyl) -5-chloro-2H- Benzotriazole, 2- (3-tert-butyl-5- (2- (2-ethylhexyloxy) -carbonylethyl) -2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-methoxycarbonylethyl) phenyl) -2H-benzotriazole, 2- (3-tert-butyl-5- (2- (2-ethylhexyloxy) carbonylethyl) -2-hydroxyphenyl) -2H-benzotriazole, and mixtures thereof, 2- (3-tert-butyl-2-hydroxy-5- (2-isooctyloxycarbonylethyl) phenyl-2H-benzotriazole, 2' -methylene-bis (4-tert-octyl- (6-2H-benzotriazol-2-yl) phenol), 2- (2-hydroxy-3-. alpha. -cumyl-5-tert-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-tert-octyl-5-. alpha. -cumylphenyl) -2H-benzotriazole, 5-fluoro-2- (2-hydroxy-3, 5-di-. alpha. -cumylphenyl) -2H-benzotriazole, 2-hydroxy-5-cumylphenyl-2H-benzotriazole, 2-methyl-ethyl-2-hydroxy-5-cumylphenyl-2, 5-chloro-2- (2-hydroxy-3, 5-di-alpha-cumylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-isooctyloxycarbonylethyl) phenyl) -5-chloro-2H-benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) -2H-benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole 5-trifluoromethyl-2- (2-hydroxy-3, 5-di-tert-octylphenyl) -2H-benzotriazole, methyl 3- (5-trifluoromethyl-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate, 5-butylsulfonyl-2- (2-hydroxy-3-. alpha. -cumyl-5-tert-octylphenyl) -2H-benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3-. alpha. -cumyl-5-tert-butylphenyl) -2H-benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3, 5-di-tert-butylphenyl) -2H-benzotriazole, 5-trifluoromethyl-2- (2-hydroxy-3, 5-di-alpha-cumylphenyl) -2H-benzotriazole, 5-butylsulfonyl-2- (2-hydroxy-3, 5-di-tert-butylphenyl) -2H-benzotriazole and 5-phenylsulfonyl-2- (2-hydroxy-3, 5-di-tert-butylphenyl) -2H-benzotriazole.

Tri-aryl-s-triazine UVAs are, for example, those disclosed in U.S. Pat. Nos. 3,843,371, 4,619,956, 4,740,542, 5,096,489, 5,106,891, 5,298,067, 5,300,414, 5,354,794, 5,461,151, 5,476,937, 5,489,503, 5,543,518, 5,556,973, 5,597,854, 5,681,955, 5,726,309, 5,736,597, 5,942,626, 5,959,008, 5,998,116, 6,013,704, 6,060,543, 6,242,598 and 6,255,483, for example, 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4-octyloxyphenyl) -s-triazine, CYASORB 1164, 4, 6-bis- (2, 4-dimethylphenyl) -2- (2, 4-dihydroxyphenyl) -s-triazine, 2, 4-bis (2, 4-chlorophenyls) -6- (4-chlorophenyls) -s-triazine, 2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (4-chlorophenyl) -s-triazine, 2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (2, 4-dimethylphenyl) -s-triazine, 2, 4-bis [ 2-hydroxy-4- (2-hydroxyethoxy) phenyl ] -6- (4-bromophenyl) -s-triazine, 2, 4-bis [ 2-hydroxy-4- (2-acetoxyethoxy) phenyl ] -6- (4-chlorophenyl) -s-triazine, 2, 4-bis (2, 4-dihydroxyphenyl) -6- (2, 4-dimethylphenyl) -s-triazine, 2, 4-bis (4-biphenyl) -6- (2-hydroxy-4-octyloxycarbonylphenyleneethoxyphenyl) -s-triazine, 2-phenyl-4- [ 2-hydroxy-4- (3-sec-butoxy-2-hydroxypropoxy) phenyl ] -6- [ 2-hydroxy-4- (3-sec-pentyloxy-2-hydroxypropoxy) phenyl ] -s-triazine, 2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- (3-benzyloxy-2-hydroxypropoxy) phenyl ] -s-triazine, 2, 4-bis (2-hydroxy-4-n-butoxyphenyl) -6- (2, 4-di-n-butoxyphenyl) -s-triazine, 2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- (3-nonanyloxy-2-hydroxypropoxy) -5- α -cumylphenyl ] -s-triazine ([ sic ] represents a mixture of octyloxy, nonanyloxy and decyloxy), methylenebis- {2, 4-bis (2, 4-dimethylphenyl) -6- [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -s-triazine }, in a ratio of 3: 5'; 1: 5 }, in a ratio of 5:4:1, Mixtures of methylene bridged dimers bridged in the 5:5 'and 3:3' positions, 2,4, 6-tris (2-hydroxy-4-isooctyloxycarbonylisopropoxyphenyl) -s-triazine, 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-hexyloxy-5-. alpha. -cumylphenyl) -s-triazine, 2- (2,4, 6-trimethylphenyl) -4, 6-bis [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -s-triazine, 2,4, 6-tris [ 2-hydroxy-4- (3-sec-butoxy-2-hydroxypropoxy) phenyl ] -s-triazine, mixtures of 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-dodecyloxy-2-hydroxypropoxy) -phenyl) -s-triazine and 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3-tridecyloxy-2-hydroxypropoxy) -phenyl) -s-triazine, TINUVIN 400, 4, 6-bis- (2, 4-dimethylphenyl) -2- (2-hydroxy-4- (3- (2-ethylhexyloxy) -2-hydroxypropoxy) -phenyl) -s-triazine and 4, 6-diphenyl-2- (4-hexyloxy-2-hydroxyphenyl) -s-triazine ) -s-triazine.

Hydroxybenzoate UV absorbers are, for example, esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

2-hydroxybenzophenone UV absorbers are, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4' -trihydroxy and 2 '-hydroxy-4, 4' -dimethoxy derivatives.

Cyanoacrylate UV absorbers are, for example, pentaerythritol tetrakis (2-cyano-3, 3-diphenylacrylate), ethyl or isooctyl alpha-cyano-beta, beta-diphenylacrylate and methyl or butyl alpha-cyano-beta-methyl-p-methoxy-cinnamate.

Many UVAs are commercially available, such as TINUVIN 326, TINUVIN 234, TINUVIN 1577, TINUVIN 1600, CYASORB UV 1164, CYASORB THT, CYASORB UV 2908, CHIMASSORB 81, UVINUL 3030, and the like.

Thioether additives include, for example, thiol-containing compounds or disulfide-containing compounds. In some embodiments, the thiol-containing compound contains one or more, e.g., 1,2,3, or 4 moieties of the formula

In some embodiments, the thiol-containing compound contains one or more, e.g., 1,2,3, or 4 moieties of the formula

Or

Wherein R is a hydrocarbyl group.

For example, in some embodiments, the thioether additive comprises a compound of the formula

Or

Wherein each R is independently a hydrocarbyl group.

The disulfide-containing compound has the formula R-S-S-R, wherein each R is independently a hydrocarbyl group.

The phrase "each R is independently a hydrocarbyl group" means that each R can be the same or different from any other R group.

In some embodiments, the thioether additive comprises dilauryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (. beta. -lauryl thiopropionate), distearyl disulfide, or dilauryl disulfide.

In some embodiments, the hydrocarbyl group may be C₂-C₄₀Hydrocarbyl radical, C₂-C₂₄Hydrocarbyl or C₂-C₅A hydrocarbyl group. The hydrocarbyl group is any hydrocarbon-containing group, for example a linear or branched alkyl or alkenyl group, which may be interrupted or substituted by one or more heteroatom-containing groups or aryl groups, for example interrupted by one or more-O-, -NH-, or-c (O) O-groups and/or substituted by one or more hydroxyl, carboxyl, amino, thiol, phosphonate or aryl groups. Aryl includes phenyl.

In some embodiments, the hydrocarbyl group can be nonyl, decyl, undecyl, 1-methylundecyl, lauryl (dodecyl), tridecyl, or stearyl (octadecyl).

Alkyl groups may be straight or branched chain and may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl, 1, 3-trimethylhexyl, 1,3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl and octadecyl. Alkenyl is an alkyl group containing an ethylenically unsaturated group.

In some embodiments, one or more other additives may be incorporated into the hollow articles of the present invention. The other additives may be selected from the group consisting of antioxidants and acid scavengers.

The antioxidant may be selected from the group consisting of: hindered phenolic antioxidants, organic phosphorus stabilizers, dialkyl hydroxylamine stabilizers, amine oxide stabilizers and tocopherols. In some embodiments, the antioxidant comprises a combination of an organophosphorus stabilizer and a hindered phenolic antioxidant, a dialkylhydroxylamine stabilizer, a combination of an organophosphorus stabilizer and a dialkylhydroxylamine stabilizer, an amine oxide stabilizer, or a combination of an organophosphorus stabilizer and an amine oxide stabilizer.

Antioxidants also include vitamin E and vitamin E acetate (tocopherol). Each of which may be used alone, in combination with each other, or in combination with one or more antioxidants selected from the group consisting of hindered phenolic antioxidants, dialkylhydroxylamine stabilizers, organophosphorus stabilizers, and amine oxide stabilizers.

Organic phosphorus stabilizers are, for example, known phosphite and phosphonite stabilizers and include triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-alpha-cumylphenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (D), bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (E), diisodecyl-pentaerythritol diphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, tris (N-phenyl) phosphite, tris (N-phenyl), Bis (2,4, 6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) 4,4' -biphenylene-diphosphonite (H), 6-isooctyloxy-2, 4,8, 10-tetra-tert-butyl-dibenzo [ d, f ] [1,3,2] dioxaphosphepin (C), 6-fluoro-2, 4,8, 10-tetra-tert-butyl-12-methyl-dibenz [ d, G ] [1,3,2] dioxaphosphepin (A), bis (2, 4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite (G), 2,2',2 "-nitrilo [ triethyltris (3,3', 5-tetra-tert-butyl-1, 1 '-biphenyl-2, 2' -diyl) phosphite ] (B), bis (2, 4-di-tert-butylphenyl) octylphosphite, poly (4,4'- {2,2' -dimethyl-5, 5 '-di-tert-butylphenyl-thio } octylphosphite), poly (4,4' - { -isopropylidenediphenol } -octylphosphite), poly (4,4'- { isopropylidenebis [2, 6-dibromophenol ] } -octylphosphite), poly (4,4' - {2,2 '-dimethyl-5, 5' -di-tert-butylphenyl-thio } -pentaerythritol diphosphite ],

Suitable organophosphorus stabilizers are also liquid stabilizers as disclosed in U.S. publication No. 2010/048782 and U.S. patent No. 7,888,414, such as the liquid phosphites P-2, P-3 and P-4, among others. Suitable liquid organophosphorus stabilizers are also disclosed in U.S. publication nos. 2013/0225736 and 2010/0029844 and in U.S. patent nos. 7,468,410 and 8,304,477.

Hindered phenolic antioxidants include, for example, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, the calcium salt of the monoethyl ester of 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.

The combination of the organophosphorus stabilizer and the hindered phenol type antioxidant may be tris (2, 4-di-t-butylphenyl) phosphite and pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] or octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate.

The weight/weight ratio of the organophosphorus stabilizer to hindered phenolic antioxidant can be any one of about 9/1, about 8/1, about 7/1, about 6/1, about 5/1, about 4/1, about 3/1, about 2/1, or about 1/1 to any one of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8, or about 1/9.

Hydroxylamine stabilizers are, for example, N-benzhydrylhydroxylamine, N-diethylhydroxylamine, N-dioctylhydroxylamine, N-dilaurylhydroxylamine, N-didodecylhydroxylamine, N-ditetradecylhydroxylamine, N-dihexadecylhydroxylamine, N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N-heptadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine or N, N-di (C) dihydroxyhydroxylamine₁₆-C₁₈Alkyl) hydroxylamine.

Amine oxide stabilizers are, for example, di (C)₁₆-C₁₈) Alkylmethyl amine oxide, CAS # 204933-93-7.

Combinations of organophosphorus stabilizers and dialkylhydroxylamines are, for example, tris (2, 4-di-tert-butylphenyl) phosphite and N, N-bis (C)₁₆-C₁₈Alkyl) hydroxylamine.

Combinations of organophosphorus stabilizers and amine oxide stabilizers are, for example, tris (2, 4-di-tert-butylphenyl) phosphite and bis (C)₁₆-C₁₈) Alkyl methyl amine oxide.

The weight/weight ratio of these combinations may be any of about 9/1, about 8/1, about 7/1, about 6/1, about 5/1, about 4/1, about 3/1, about 2/1, or about 1/1 to any of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8, or about 1/9.

The antioxidants can be present in a total of any of about 0.05 wt%, about 0.10 wt%, about 0.20 wt%, about 0.30 wt%, about 0.40 wt%, about 0.50 wt%, or about 0.60 wt% to any of about 0.70 wt%, about 0.80 wt%, about 0.90 wt%, about 1.0 wt%, about 1.5 wt%, or about 2.0 wt%, based on the total weight of the hollow article.

Acid scavengers include hydrotalcite and amorphous basic aluminum magnesium carbonates such as those described in U.S. patent nos. 4,427,816, 5,106,898 and 5,234,981. Hydrotalcite (hydrotalcite)Also known as hydrotalcite (hycite), DHT4A, DHT4V, DHT4Z, DHT4a2, or DHT 4C. Hydrotalcites are natural or synthetic and may include a coating. Retaining natural hydrotalcite to have the structure Mg₆Al₂(OH)₁₆CO_3.4 H₂And O. A typical empirical formula for the synthetic hydrotalcite is Al₂Mg_4.35OH_11.36CO_3(1.67).x H₂And O. Examples of synthetic products include Mg_0.7Al_0.3(OH)₂(CO₃)_0.15.0.54H₂O、Mg_4.5Al₂(OH)₁₃CO₃.3.5H₂O and Mg_4.2Al(OH)_12.4CO₃。

In some embodiments, the acid scavenger comprises a metal salt of a fatty acid, such as an alkali metal or alkaline earth metal salt of a fatty acid. In some embodiments, the acid scavenger comprises a calcium, magnesium, zinc, sodium, potassium, or aluminum salt of a fatty acid. In some embodiments, the acid scavenger comprises stearic acid, behenic acid, ricinoleic acid, or calcium palmitate, magnesium, zinc, sodium, potassium, or aluminum. In certain embodiments, the acid scavengers include calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate. In other embodiments, the acid scavenger comprises zinc oxide.

In some embodiments, a combination of one or more acid scavengers may be employed.

The acid scavenger may be present in a total of from any of about 50ppm (parts per million), about 100ppm, about 200ppm, about 300ppm, about 400ppm, about 500ppm, or about 600ppm to any of about 700ppm, about 800ppm, about 900ppm, about 1000ppm, about 1100ppm, about 1200ppm, about 1300ppm, about 1400ppm, about 1500ppm, about 1600ppm, about 1700ppm, about 1800ppm, about 1900ppm, or about 2000ppm, based on the total weight of the article.

In other embodiments, the hollow article may comprise any of about 0.1 wt% (weight percent), about 0.2 wt%, or about 0.5 wt% to any of about 1.0 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, or about 3.0 wt% acid scavenger, based on the total weight of the article.

Colorants, pigments or fillers may also be added to the present polyolefin substrates.

Pigments include inorganic pigments such as titanium dioxide in the form of rutile, anatase or brookite crystals, ultramarine, iron oxide, bismuth vanadate, carbon black; effect pigments including metallic pigments (e.g., aluminum flake powder) and pearlescent pigments (e.g., mica); and organic pigments such as phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones, dioxazines and indanthrones. The amount of pigment that can be included, alone or in any combination, is generally up to about 5 weight percent, based on the total weight of the article. Dyes are any colorants which are completely soluble in the plastic used or are present in molecularly dispersed form and can therefore be used to provide high transparency, non-diffusing colorations of the polymer. Other dyes are organic compounds that fluoresce in the visible portion of the electromagnetic spectrum, such as fluorescent dyes. The amount of dye that may be included, alone or in any combination, is generally up to about 5 weight percent based on the total weight of the article.

The particulate filler may be present in an amount of any of about 0.01 wt%, about 0.1 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, or about 20 wt% to about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt%, based on the total weight of the article. Fillers include, but are not limited to, titanium dioxide, silicon carbide, silica (and other oxides of precipitated or non-precipitated silica), antimony oxide, lead carbonate, zinc white, lithopone, zirconium, emery, spinel, apatite, barite powder, barium sulfate, carbon black, dolomite, calcium carbonate, talc, and the ions Mg, Ca or Zn with Al, Cr or Fe and CO₃And/or HPO₄The hydrotalcite compound containing or not containing water; quartz powder, magnesium carbonate hydrochloride acid, glass fibers, clay, alumina and other metal oxides and carbonates, metal hydroxides, chromium, phosphorus, antimony trioxide, silica, silicones, and blends thereof. These fillers may include any other fillers and porous fillers known in the art as well as carriers.

Other Additives may also be incorporated into the polyolefin substrate, for example Additives such as antistatic agents (antistatic agents), anti-scratch Additives, slip agents, polymer processing aids, etc. (see plastics Additives Handbook; 6 th edition). Including metal salts of fatty acids such as calcium stearate, magnesium stearate, zinc stearate or aluminum stearate. Other additives also include thioether additives, such as dilauryl thiodipropionate or distearyl thiodipropionate.

Other additives also include benzofuranone stabilizers such as those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, 5,369,159, 5,356,966, 5,367,008, 5,428,177, or 5,428,162 or in U.S. patent application publication 2012/0238677, including 3- [4- (2-acetoxyethoxy) phenyl ] -5, 7-di-t-butyl-benzofuran-2-one, 5, 7-di-t-butyl-3- [4- (2-stearoyloxyethoxy) phenyl ] benzofuran-2-one, 3' -bis [5, 7-di-t-butyl-3- (4- [ 2-hydroxyethoxy ] phenyl) benzofuran-2-one ], (a) a mixture of, 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butyl-benzofuran-2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5, 7-di-tert-butyl-benzofuran-2-one, 3- (3, 4-dimethylphenyl) -5, 7-di-tert-butyl-benzofuran-2-one, 3- (2-acetyl-5-isooctylphenyl) -5-isooctylbenzofuran-2-one and 3- (2, 3-dimethylphenyl) -5, 7-di-tert-butyl-benzofuran-2-one. Other additives also include compatibilizers or dispersing aids, such as maleic anhydride grafted PE or PP, poly (ethylene-co-vinyl acetate), poly (ethylene-acrylic acid), and the like. The other additives may be present in any of about 0.05 wt%, about 0.1 wt%, about 0.2 wt%, about 0.5 wt%, about 0.7 wt%, or about 1.0 wt% to any of about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, or about 5.0 wt%, based on the total weight of the article.

Rotational moulding (rotational moulding) is used to manufacture relatively large plastic hollow articles which can be reinforced with glass fibres. The method comprises filling one half of the mould with a plastics material. The mold is then closed with the other half and heated in an oven and rotated so that the molten plastic spreads onto the walls of the mold while rotating about a different axis. After cooling, a hollow article is obtained. In this way it is possible to manufacture tanks made of HD polyethylene, for example. In some embodiments, the process entails heating the polyolefin mixture to a temperature in the range of any of about 170 ℃, about 190 ℃, about 210 ℃, about 215 ℃, about 220 ℃, about 230 ℃, about 240 ℃, about 260 ℃, or about 280 ℃ to any of about 300 ℃, about 340 ℃ to about 370 ℃, or about 400 ℃ or higher. These temperatures represent the Peak Internal Air Temperature (PIAT) of the oven.

In some embodiments, a 125 mil thick, 5 inch by 5 inch test sample of a hollow article of the present invention can exhibit an impact strength of greater than or equal to 21ft/lbs (ft/lb), greater than or equal to 23ft/lbs, greater than or equal to 25ft/lbs, greater than or equal to 27ft/lbs, greater than or equal to 29ft/lbs, greater than or equal to 31ft/lbs, greater than or equal to 33ft/lbs, greater than or equal to 35ft/lbs, greater than or equal to 37ft/lbs, greater than or equal to 39ft/lbs, greater than or equal to 40ft/lbs, greater than or equal to 41ft/lbs, greater than or equal to 42ft/lbs, or greater than or equal to 43 ft/lbs.

In certain embodiments, a 125 mil thick, 5 inch by 5 inch test sample of a hollow article of the present invention can exhibit a ductility of 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

In certain other embodiments, a 125 mil thick, 5 inch by 5 inch test sample of a hollow article of the present invention can exhibit a thickness of 0.0 or less, 0.5 or less, 0.7 or less, 1.0 or less, 1.2 or less, 1.4 or less, or a combination thereof,

A Yellowness Index (YI) of not more than-1.6, not more than-1.8, not more than-2.0, not more than-2.2, not more than-2.4, not more than-2.6, not more than-2.7, not more than-2.8 or not more than-2.9.

In some embodiments, a 125 mil thick, 5 inch by 5 inch test sample of a hollow article of the present invention can exhibit ≦ -3.0, ≦ -3.3, ≦ -3.5, ≦ -3.7, ≦ -3.9, ≦ -4.0, ≦ -4.1, or ≦ 4.1,

A Yellowness Index (YI) of not more than-4.2, not more than-4.3, not more than-4.4 or not more than-4.5.

In certain embodiments, a 125 mil thick, 5 inch by 5 inch test sample of a hollow article of the present invention can exhibit an impact strength of greater than or equal to 40ft/lbs, a ductility of greater than or equal to 90%, and a YI of less than or equal to 0.0 or less than or equal to-1.0 or less than or equal to-1.5 or less than or equal to-2.0.

Mechanical properties can be determined according to the rotary molder Association (ARM) impact test. The above examples regarding impact strength, ductility, and color can be determined on test samples of rotomolded hollow articles, where the peak internal air temperature is about 380 ° f, about 400 ° f, or about 420 ° f.

The incorporation of the phosphonate, the N-alkoxy hindered amine, the melamine cyanurate (additive of the invention) and optionally further additives into the polyolefin substrate can be carried out by known methods, for example before or after moulding, or also by applying the dissolved or dispersed additive mixture to the polyolefin with or without subsequent evaporation of the solvent. The additives of the present invention may also be added to the polyolefin in the form of a masterbatch containing the additives in a concentration of, for example, about 2.5 to about 40 weight percent, based on the total weight of the masterbatch. In the form of a masterbatch, the polymer of the masterbatch need not be the same as the polyolefin substrate.

The molding is carried out using known mixing machines, such as mixers, kneaders or extruders. The additives of the present invention and optional other additives may be premixed or added separately. The additives of the present invention and optionally further additives may also be added before or during polymerization or before crosslinking. The additives of the invention and optionally further additives can be incorporated in pure form into the polymer intended for preparing the flame retardant or encapsulated in wax, oil or polymer.

The additives of the present invention and optionally other additives may also be sprayed onto the polyolefin substrate. It is capable of diluting other additives or their melts so that they can also be sprayed onto the polyolefin together with these additives. The addition is suitably carried out by spraying during the deactivation of the polymerization catalyst, it being possible to spray using, for example, steam for deactivation.

In some embodiments, the present methods comprise measuring the raw materials by weight, followed by dry blending the ingredients. In certain embodiments, the additives of the present invention and optional other additives are incorporated into the thermoplastic polyolefin substrate by melt blending in an extruder. The additives of the present invention and optional additives may be added together or separately. In some embodiments, the term "incorporated into the polyolefin" means melt blended, that is, the mixture is subjected to melting conditions at elevated temperatures.

The mixture may be fed at a constant feed rate to a melt mixing device, such as an extruder, to extrude the material into a desired form, such as pellets. Pellets are "fully formulated polyolefin substrates". The pellets may be ground to a generally uniform small particle size, for example to an average particle size of about 150 microns to about 500 microns prior to rotomolding.

The fully formulated polyolefin particles are filled into one half of the mold, which is then closed with the other half. The mold is typically made of aluminum or steel. The closed mold is heated and rotated about different axes, with the molten polymer coating the interior of the mold-a process known as "sintering". The mold is then cooled and the molded article is removed.

In addition to storage tanks, many other articles can be made by rotomoulding processes, such as kayaks, toys, trash cans, equipment enclosures, and the like. Rotomoulded articles may in many cases have a relatively large average wall thickness. In some embodiments, the rotomoulded articles of the present invention have an average wall thickness of no less than about 1.50mm, no less than about 1.75mm, no less than about 2.00mm, no less than about 2.25mm, no less than about 2.50mm, no less than about 2.75mm, no less than about 3.00mm, no less than about 3.25mm, no less than about 3.50mm, no less than about 3.75mm, no less than about 4.00mm, no less than about 4.25mm, no less than about 4.50mm or no less than about 4.75 mm. In some embodiments, the rotomolded article has an average wall thickness of any one of about 1.50mm, about 1.75mm, about 2.00mm, about 2.25mm, about 2.50mm, about 2.75mm, or about 3.00mm to any one of about 3.25mm, about 3.50mm, about 3.75mm, about 4.00mm, about 4.25mm, about 4.50mm, about 4.75mm, about 5.00mm, about 5.25mm, about 5.50mm, about 5.75mm, or about 6.00 mm.

The articles "a" and "an" are used herein to refer to one or to more than one (e.g., to at least one) of the grammatical object. Any ranges recited herein are inclusive of the endpoints. The term "about" is used throughout to describe and account for small fluctuations. For example, "about" may mean that the index value may vary by 5%, ± 4%, ± 3%, ± 2%, ± 1%, ± 0.5%, ± 0.4%, ± 0.3%, ± 0.2%, ± 0.1% or ± 0.05%. All numerical values are modified by the term "about," whether or not explicitly indicated. A value modified by the term "about" includes a specific stated value. For example, "about 5.0" includes 5.0.

The U.S. patents, U.S. patent applications, and published U.S. patent applications discussed herein are incorporated by reference.

All parts and percentages are by weight unless otherwise indicated. Weight percent (wt%) is based on the entire composition without any volatiles, if not otherwise indicated.

Example 1

Mixing the additive with low density polyethylene (LDPE, 0.935 g/cm)³) Dry blended to provide the formulation. The content of additives is reported in ppm by weight (parts per million) based on the weight of the polyethylene. The dried mixture was melt extruded into pellets, which were ground to 35 mesh and then placed into a laboratory scale FST M20 "shell flip top" aluminum die. The mold was rotated biaxially in a gas oven. Hot air is circulated in the chamber by the blower while the temperature is increased to provide a Peak Internal Air Temperature (PIAT) of 400 ° f or 420 ° f. The temperature was maintained for 20 minutes. The oven was opened and cooled over 24 minutes while still rotating. The mold is opened and the hollow article is removed.

The control formulation contained no additives. Each of the formulations 1-4 contained 400ppm of tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (phenolic antioxidant), 600ppm of N, N-bis (C)₁₆-C₁₈Alkyl) hydroxylamine (hydroxylamine stabilizer), 1200ppm of tris (2, 4-di-tert-butylphenyl) phosphite (organophosphorus stabilizer), 1200ppm of 4,4' -hexamethylenebis (amino-2, 2,6, 6-tetramethylpiperidine) and 2, 4-dichloro-6- [ (2,2,6, 6-tetramethylpiperidin-4-yl) butylamino]Oligomeric condensates of s-triazine (end-capped with 2-chloro-4, 6-bis (dibutylamino) -s-triazine) (hindered amine light stabilizer), 400ppm of N' - (2-ethoxyphenyl) -N- (2-ethylphenyl) oxamide (oxamide UV absorber), 400ppm of waterTalc (acid scavenger) and 200ppm zinc stearate (acid scavenger). Formulations 2-4 also contained 500ppm of a thioether additive as outlined below. Mercaptan 1 is distearyl thiodipropionate. Thiol 2 is pentaerythritol tetrakis (. beta. -lauryl thiopropionate). Thiol 3 is distearyl disulfide. The weight of the additive is ppm (parts per million) based on the weight of the polyethylene.

The samples tested were 125 mils thick (3.175mm) according to the impact test of the rotary molder Association (ARM). The samples were tested for impact strength, ductility and color formation. Impact strength is reported in feet per pound (ft/lbs). Ductility is reported in percent (%). The color is reported as YI. The results for samples of hollow articles prepared at peak internal air temperatures of 400 ° f and 420 ° f are as follows.

PIAT＝400℉

PIAT＝420℉