MX2008009692A - Use of secondary sterically hindered amines as processing additives in rotomolding processes - Google Patents

Abstract

The instant invention pertains to the use of secondary sterically hindered amines as processing additives in rotational molding processes. These additives increase process stability, since they provide a broader temperature range towards higher temperatures during the melt processing step.

Description

USE OF SECONDARY AMINES, ESTRICALLY OBSTRUCTED, AS PROCESS ADDITIVES IN MOLDING PROCESSES ROTATORY The present invention pertains to the use of secondary amines, sterically clogged, as process additives, in rotary molding processes. These additives! they increase the stability of the process, since they provide a wider range of temperature towards the higher temperatures, during the process stage of the sundried mass.

Rotary molding is a highly versatile manufacturing option that allows for unlimited design possibilities with the added benefit of low production costs. i The rotary molding process (rotomolding process) starts with a good quality mold, which is placed inside a molding machine, which has a loading, heating and cooling area. ! Several molds can be placed on the machine at the same time. Plastic resins previously measured, are loaded into each mold, and then the molds move inside the furnace, where they are slowly rotated in both the vertical and horizontal axis. The molten resin st to the mold Warm and coat each surface evenly. Mold continues to rotate during the cooling cycle, so the pairs retain a uniform wall thess.

Once the parts cool, they are released from the mold. The rotation speed, and the heating and cooling times can be controlled during the process.

Rotary molds offer design advantages over others Molding processes, With the appropriate design, the parts that are assembled from different pieces, can be molded as One part, eliminating costly manufacturing costs.

The process also has a number of inherent resistances of the design, such as the consistent wall thess and strong external corners, which are virtually exempt from tensions If additional strength is required, reinforcement ribs can be designed in that part.

Rotary molding delivers the product as imagined by the designer. Designers can select the best material for its application., which include the materials that comply with the requirements of the FDA. Additives for help make the part resistant to the environment, "which slows down the flame, or free of static, can be specified. And because the parts are formed with heat and rotation, more Well that pressure, the molds do not need to be | engineered to withstand the high pressure of the injection molding.

Production costs for product conversions are reduced because light weight plastics replace the heavier ones, often more expensive materials, which make the rotational molding effective in cost for a class of prototypes such as for operations of large production.

The rotational molding is versatile and capable of handling a wide variety of configurations and sizes.

Many parts can not be easily produced by any other method. Typical examples are especially tanks and containers for fuel, water and chemical processes, livestock feeders, systems! drainage, food service containers, instrument housings, vending machines, road barriers and road markers. Other areas of application are consumer products, toys and transport. Many aspects of the rotational molding process are, for example, described in R. J. Crawford and J. L. Throne in Rotational Molding Technology, Plastics Design Library, illiam Andrew i Publishing, 2001..

As mentioned before, the rotational speed, heating and cooling times, can all be completely controlled through the process. The maximum temperature of the air, which is reached inside the hollow molded article, depends strongly on the heating time. This temperature is also called the internal air peak temperature (PIAT). It correlates with the temperature of the molten resin.

The concept of internal air peak temperature (PIAT) and consequences, if a < PIAT is too low or too high, it is applied, as described, by; example, by M. C. Cramez et al. in Proc. Instn Mech. Engrs. Vol. 217 Part B: J. of Engineering Manufacture, 2003.

The peak temperature of the internal air can influence the final properties of the molded product. For example, if the temperature becomes too high, strong yellowing may occur and also the mechanical properties are negatively affected, by. example, the impact resistance decreases significantly. If the temperature remains too low, the final properties may also be adversely affected because the resins have not melted properly. In other words, there is only a small temperature range to achieve the desired final properties. It is therefore of high interest to widen this temperature range I or process window, within which almost constant mechanical properties are obtained. ! Botkin et al., In "An additive approach for the reduction of cycle time in rotary molding", Rotational Molding by Design Conference, Society of Plastics engineers, 2004, have shown that by, the use of a process stabilizer patented, PIAT can move to lower temperatures, maintaining good impact resistance. This corresponds to the amplification of the process window to lower temperatures.

Surprisingly, it has now been found that, when a secondary clogged amine compound is added to the resin formulation, a significantly wider window of process toward higher temperatures is achieved without adversely affecting the color and mechanical properties of the product. molded article.

Accordingly, one aspect of the invention is | the use of an amine composed of spherically clogged amine, secujndaria, as additive of the process to enlarge the window! of the process towards higher peak temperatures of the internal air, in the rotational molding processes of thermoplastic polymers.

Under the process window, which is understood to be the temperature range, as measured by the internal air peak temperature (PIAT) method, within which the mechanical properties and / or the color of the molded article remain essentially the same. A particularly suitable mechanical property to measure is the impact resistance, for example, at low temperatures. The low temperature means, in this context, from 0 to 50 ° C, particularly from 20 ° C to 40 ° C.

For example, the sterically clogged amine is a compound that contains at least one group of the formula (I) or (II): in which * indicates a link G is hydrogen or methyl, and Gi and G2. independently of one another, they are hydrogen, methyl or together represent a substituent = 0.

For example, the sterically clogged amine is a compound that contains at least one group of the formula (la): The sterically clogged amine compounds are known and widely used as thermal or light stabilizers for polymers. They are commercially available or can be prepared as described, for example, in the publications: US-A-5, 679, 733, US-A-3, 640, 928, US-A-4, 198, 334, US -A- 5, 204, 473, US-A-4, 619, 958, US-A-4, 110, 306, US-A-4, 110, 33, US-A-4, 689, 416, US -A-4, 408, 051, SU-A-768,175 (Derwent 88-138,751 / 20), US-A-5, 049, 604, US-A-4, 769, 457, US-A-4, 356 , 307, US-A-4, 619, 956, US-A-5, 182, 390, GB-A-2, 269, 819, US-A-4, 292.2 0, US-A-5, 026, 849, US-A-5, 071, 981, US-A-4, 547, 538 , US-A-, 976, 889, US-A-, 086, 20, US-A-6, 046, 304, US-A-4, 331, 586, US-A-4, 108, 829, US -A-5, 051, 458, WO-A-94 / 12,544 (Derwent 94-177,274 / 22), DD-A-262,439 (Derwent 89-122,983 / 17), US-A-4, 857, 595, US -A-4, 529, 760, US-A-4, 77, 615, CAS 136,504-96-6, US-A-4, 233, 12, US-A-4, 340, 534, WO-A- 98/51, 690 and EP-A-1,803, the descriptions of which are incorporated herein by reference.

Preferred are the following commercial compounds.

Chimassorb 2020®, Chimassorb 944®, Tinuvin 770® and Tinuvin 783®, Cyasorb UV 3346®, Cyasorb UV 3581®, Dastib 845®, Dastib 1082®, Diacetam 5, Fero 806-X®, Goodrite 3034®, Goodrite 3150® , HALS IC-TAM, Hostavin N 20®, Hostavin N 24®, Hostavin N 30®, Hüls S-95®, ICI PA 500®, Lichtschutzstoff UV 31, Luchem HA-B 18®, Mark LA 55®, Mark LA 57®, Mark LA 67®, Mark LA 68®, Sanduvor 3050®, Sumilizer 61®, Sumilizer 70®, Suimisorb TM 61®, UVASORB HA 88®, Uvinul 4049®, Uvinul 5050®, Uvasil 299®, Uvasil 125® .

These compounds are commercially available and are described in the publications: US-A-5, 679, 733, US-A-3,640,928, US-A-5, 204, 473, US-A-4, 619, 958, US -A-4, 110, 306, US-A-4, 110, 334, US-A-, 689, 16, US-A-, 408, 051, SU-A-768,175 (Derwent 88-138,751 / 20) , US-A-5, 049, 604, US-A-4, 769, 457, US-A-4, 356, 307, US-A-4, 619, 956, US-A-5, 182, 390 , GB-A-2, 269, 819, US-A-4, 292, 240, US-A-5, 026, 849, US-A-5, 071, 981, US-A-4,547,538, US-A -4, 976, 889, US-A-4, 086, 204, US-A-6, 046, 304, US-A-4, 331, 586, US-A-, 108, 829, US-A- 5, 051, 458, OA-94 / 12,544 (Derwent 94-177,274 / 22), DD-A-262,439 (Derwent 89-122,983 / 17), US-A-, 857, 595, US-A-4, 529 , 760, US-A-4, 77, 615 (CAS 136,504-96-6), US-A-4, 3 0, 53, WO-A-98/51, 690, EP-A-1,803, whose descriptions they are incorporated here as a reference.

The sterically clogged amine compound, according to the invention, is preferably added in an amount of 0.01 to 5%, more preferably 0.05 to 2% and even more preferably 0.1 to 1% by weight, based on the weight of the thermoplastic polymer.

For example, the thermoplastic polymer is a polyolefin, a polyvinyl chloride or a polyamide. Examples are given below. 1. Polymers of monoolefins and diolefins, for example, polypropylene, polyisobutylene, polybut-l-ene, poly-4-methylpent-l-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as cycloolefin polymers, for example, cyclopentene or norbornene , polyethylene (which may optionally be interlaced), for example high density polyethylene (HDPE), high molecular weight high density polyethylene (HDPE-H; W), high density polyethylene and ultra-high molecular weight (HDPW-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), VLDPE) and (ULDPE).

Polyolefins, ie, the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially by the following methods: a) Radial polymerization (usually under high pressure and high temperature); b) catalytic polymerization using a catalyst, which normally contains one or more than one metal of the groups (IVb, Vb, VIb or VII of the Periodic Table.) These metals usually have one or more than one ligation, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be a- or ß-coordinated. These metal complexes may be in free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators can be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkoxanes, said metals being elements of the groups la, lia and / or Illa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), methocene or single site catalysts ( SSC). 2. Mixtures of the polymers mentioned under 1), for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE). 3. or polymers of monoolefins and diolefins with each other or with other vinyl monomers, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-l-copolymers ene, propylene / isobutylene copolymers, ethylene-but-l-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers, copolymers ( for example of ethylene / norbornene, as COD), erylene / 1-olefin copolymers, where the 1-olefin is generated in situ; propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers, and its salts (ionomers), like the terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylene-norbornyl; and mixtures of such copolymers with each other and with the polymers mentioned in 1) above, for example, copolymers of polypropylene / ethylene-ptopylene LDPE copolymers / ethylene-vinyl acetate (EVA) LDPE / ethylene-acrylic acid (EA) copolymers, LLDOA / EVA, LLDP / EA and alternatively or randomly polyalkylene / carbon monoxide copolymers, and their mixtures with other polymers, for example polyamides. 4. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12 / 12, polyamide 11, polyamide | 1, aromatic polyamides that split m-xylen-diamine and adipic acid; polyamides, prepared from hexamethylenedimine and isophthalic or / and terephthalic acid and with or without an elastomer as a modifier, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the polyamides mentioned above, with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPD or ABS and polyamides condensed during the process (RIM polyamide systems).

Particular preference is given to polyethylene, preferably linear low density polyethylene (LLDPE).

For example, the peak air temperature range in the rotational molding processes is enlarged to 10 to 50 ° C, preferably up to 15 to 40 ° C to higher temperatures. The reference being without the addition of a spherically clogged amine.

Preferably, the peak air temperature range is 210 to 250 ° C, more preferably 215 to 250 ° C and even more preferably 110 to 250 ° C.

The above temperature range corresponds to the preferred process window, within which the mechanical properties and / or the color of the article are not adversely affected.

In a specific embodiment of the invention, an additional stabilizer, selected from the group consisting of a UV light absorber, a spherically clogged amine, different from those of the formulas (i) or (II), a phenolic antioxidant, a phosphite, or phosphonite and a benzofuranone or indolinone, is present.

Examples of the aforementioned additives are provided in the following. 1. Antioxidants 1.1 Alkylated onophenols, for example, 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4, 6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or branched nonylphenols in the side chain, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (11-methylundec-1'-yl) -phenol, 2, -dimethyl-6- (1'-methylheptadec-1'-yl) - phenol, 2,4-dimethyl-6- (11-methyltridec-11-yl) -phenol and its mixtures. 1. 2. Alkyltiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2, -dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol. 1. 3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquininone, 2,6- diphenyl-4-octadecyloxy-phenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy anisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 1. 4. Tocopherols, for example α-tocopherol, β-tocopherol, β-tocopherol, d-tocopherol and their mixtures (Vitamin E). 1. 5. Hydroxylated thiodiphenyl ethers, for example, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octyl-phenol), 4,4'-thiobis ( 6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), disulfide 4 , 4'-bis (2,6-dimethyl-4-hydroxy-phenyl). 1. 6. Bisphenols of allylidene, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 ' -methylenebis [4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol) , 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,21-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4) isobutylphenol), 2,2'-methylene-bis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6- (a, -dimethylbenzyl) -4 nonylphenol], 4, 4'-methylene-2,6-di-tert-butylphenol), 4,4 ' methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-bis (3-tert-butyl-5-) methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis (5-tert-butyl- 4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3, 3-bis (3'-tert-butyl- '-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-) hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (31-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy-phenyl) propane, 2,2-bis (5-tert-butyl-4) -hydroxy-2-methylphenyl) -4-n-dodecylmercapto-butane, 1, 1, 5, 5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane. 1. 7. Compounds of O-, N- and S-benzyl, for example 3, 5, 3 ', 51 -tetra-tert-butyl-4,41-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3-mercaptoacetate, 5-dimethylbenzyl, tridecyl-4-hydroxy-3, 5-di-tert-butyl-benzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl) dithioterephthalate butyl-3-hydroxy-2,6-dimethylbenzyl), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3, 5-di-tert-butyl-4-mercaptoacetate hydroxybenzyl. 1. 8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-) methyl-benzyl) -malonate, didodecyl-mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate, di- [4- (1,1,3,3-tetramethylbutyl) -phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) malonate. 1. 9. Hydroxybenzyl aromatic compounds, for example 1, 3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5) -di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol. 1. 10. Triazine compounds, for example 2,4-bis-octylmercapto-6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6 -bis (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 2,3-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxyphenyl-ethyl) -1,3,5-triazine, 1, 3, 5-tris (3,5-di-tert-butyl-4-hydroxy) phenylpropionyl) hexahydro-1,3,5-triazine, 1, 3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate. 1. 11. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-di butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-ethenylbenzylphosphonate, calcium salt of the 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester. 1. 12. Acylaminophenols, for example 4-hydroxylauranylide, 4-hydroxysteatenylidene, octyl-N- (3,5-di-tert-butyl-4-hydroxy-phenyl) carbamate. 1. 13. Esters of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, acid diamide ?,? '- bis (hydroxyethyl) oxalic, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l- phospha-2, 6, 7-trioxa-bicyclo [2.2.2] octane. 1. 14. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols for example with methanol, methanol, ethanol, n-octanol, isooctanol, octadecanol, , 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) -isocyanurate,?,? bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 1. 15. Esters of ß- (3,5-dicyclohexyl-4-hydroxy-phenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, -bis (hydroxyethyl) oxalic acid diamide. , 3-tiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 1. 16. Esters of 3,5-di-tert-butyl-4-hydroxy-phenylacetic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, diamine of N, N'-bis (hydroxyethyl) acid -oxalic, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 1. 17 Amides of ß- (3,5-di-tert-butyl-4-hydroxy-phenyl) ropionic acid, for example N, 1-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hexamethylene -diamide, N, '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene-diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazide ), N, '-bis [2- (3- [3, 5-di-tert-butyl-4-hydroxy-phenyl] -propionyloxy) ethyl] oxamide (Naugard®XL-1 from Uniroyal). 1. 18. Ascorbic acid (Vitamin C). 1. 19. Amine antioxidants, for example, α, β '- diisopropyl-p-phenylenediamine, N, 1-di-sec-butyl-p-phenylenediamine, N,' -bis (1,4-dimethylpentyl) -p-phenylenediamine,?,? '- bis { l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (l-methylheptyl) -p-phenylenediamine, N, 1-dicyclohexyl-p-phenylenediamine, N, N 1 -diphenyl-p-phenylenediamine, N, N'-di (2-naphthyl) -p-phenylenediamine, N-isopropyl- '-phenyl-p-phenylene-diamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N - (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl- '-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) -diphenylamine, N, N 1 -dimethyl-N, '-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2 -naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino-phenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,?,?,? ',?' - tetramethyl-4,4'-diaminodiphenylmethane , 1,2-bis [(2-methylphenyl) -amino-malene, 1,2-di (phenylamino) propane, (o-tolyl) -biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, tere mixtures. mono- and di-alkylated butyldiphenylamines, mixtures of mono- and dialkylated nonildiphenylamines, mixtures of mono- and dialkylated dodecyldienylamines a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and tert-butyldiphenylamines and di-alkylated, 2, 3-dihydro-3, 3-dimethyl-4H-l, 4-benzothiazine, phenothiazine, mixture of tert-butyl- / tert-octyl-phenothiazines mono- and di-alkylated, mixtures of ter- octylphenothiazines mono- and di-alkylated, N-allylphenothiazine or?,?,? ',?' - tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2, 2, 6, 6-tetramethyl) -piperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidine -4-ol. 2. Absorbents of UV radiation and light stabilizers 2. 1. 2- (2'-Hydroxyphenyl) -benzotriazoles, for example 2- (2 '-hydroxy-5' -methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2' - hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) -phenyl) -benzotriazole , 2- (3 ', 51-di-tert-butyl-2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3 '-sec-butyl 5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -benzotriazole, 2- (3', 51 -di-tert. -amil-2'-hydroxyphenyl) -benzotriazole, 2- (31, 5'-bis (a, a-dimethylbenzyl) 2'-hydroxyphenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy 5 ' - (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 'tert -butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2 '- hydroxyphenyl) -5-chlorobenzo-triazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl-ethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl) -21-hydroxy-51 - (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3') -tert -butyl-51 - [2- (2-ethylhexyloxy) carbonylethyl] -21-hydroxyphenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-isooctyloxycarbonylethyl) -phenyl-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2 -yl-phenol], the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -21-hydroxyphenyl] -benzotriazole with polyethylene glycol 300; [R - CH2CH2- COO - CH2CH2 - ^ - where R = 3'-tert-butyl- '-hydroxy-51 -2H-benzotriazol-2-yl-phenyl; 2- [2 '-hydroxy-3' - (, α-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) -phenyl] -benzotriazole; 2- [2'-Hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (a, a-dimethylbenzyl) -phenyl] -benzotriazole. 2. 2. 2-Hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 2 ', 4' -trihydroxy or 2'-hydroxy-4 derivative , '-dimetoxi. 2. 3. Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butyl-phenyl 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 ester, octadecyl-3,5-di-tert-butyl-4 -hydroxybenzoate, 2-methyl-4,6-di-tert. -butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. 2. 4 Acrylates, for example the ethyl ester or isooctyl ester of a-cyano-β, β-diphenylacrylic acid the methyl ester of a-methoxycarbonyl cinnamic acid, the methyl ester or the butyl ester of the α-cyano-p-acid -methyl-p-methoxycinnamic acid, the methyl ester of a-methoxycarbonyl-p-methoxycinnamic acid, and N- (p-methoxycarbonyl-p-cyanovinyl) -2-methyl-indoline. 2. 5. Nickel compounds, for example 2, 2'-thio-bis [4- (1, 1, 3, 3-tetramethylbutyl) phenol] nickel complexes, such as the 1: 1 or 1: 2 complex, optionally with additional ligatures, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutyl-nickel dithiocarbamate, nickel salts of 4-alkyl monoalkyl esters hydroxy-3, 5-di-tert-butylbenzylphosphonic acid, such as methyl or ethyl ester, ketoximes nickel complexes, such as 2-hydroxy-4-methylphenylundecyl-ketoxime, nickel complexes of 1-phenyl-4- lauroyl-5-hydroxypyrazole, optionally with additional ligatures. 2. 6. Clogged amines are, for example, bis (2, 2, 6,6-tetramethylpiperid-4-yl) sebacate, bis (2,6,6,6-tetramethylpiperid-4-yl) succinate, bis (1). , 2, 2, 6, 6-pentamethylpiperid-4-yl) sebacate, bis (l-octyloxy-2, 2,6,6-tetramethylpiperid-4-yl) sebacate, bis (1, 2, 2, 6, 6 - pentamethylpiperidyl) -ester of n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid, the condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and the succinic acid, linear or cyclic condensation products of N, * -bis (2, 2, 6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-l, 3 , 5- s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) -nitrile-triacetate, tetrakis (2,2,6,6-tetramet-il-4-piperidyl) - 1,2 , 3, -butanetetraate, 1,11- (1, 2-ethanediyl) bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2, 6, 6-tet.ramethyl-piperidine, bis (1,2,2 , 6, 6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) -malonate, 3-n-octyl- 7,7,9,9-tetramethyl-l, 3,8-triazaspiro [4.5] decane-2,4-dione, bis (l-octyloxy-2,6,6,6-tetramethylpiperidyl) -sebacate, bis (1) -octyloxy-2, 2,6,6,6-tetramethylpiperidyl) -succinate, linear or cyclic condensation products of N, N'-bis (2, 2, 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino -2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro-, 6-di (4-n-butylamino-2, 2,6,6-tetramethyl-piperidyl) -1 , 3, 5-triazine and 1,2-bis (3-aminopropylamino) -ethane, the condensation product of 2-chloro-, 6-di (4-n-butylamino-1, 2, 2, 6, 6 -pentamethylpiperidyl) -1, 3, 5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidin-2, 5-dione, 3-dodecyl-1- (1,2 , 2,6,6-pentamethyl-4-piperidyl) -pyrrolidine-2, 5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine , the condensation product of 1,2-bis (3-aminopropylamino) ethane and 2, 6-trichloro-l, 3, 5-triazine and 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); the condensation product of 1,6-diaminohexane and 2,4,6-trichloro-1,3,5-triazine and also the, -dibutylamine and the 4-butylamino-2, 2,6,6-tetramethylpiperidine (CAS No. of Reg. [192268-64-7]); N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl -7, 7, 9, 9-tetramethyl-l-oxa-3, 8-diaza-4-oxo-spiro [.5] decane, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl -l-oxa-3, 8-diaza-4-oxospiro [4.5] decane and epichlorohydrin, 1,1-bis (1,2,2,6, 6-pentamethyl-4-piperidyloxycarbonyl) -2- (4 -methoxyphenyl) ethene, N, '-bis-formyl-N,' -bis (2,6,6,6-tetramethyl-4-piperidyl) hexamethylene diamine, diester of 4-methoxymethylenemalonic acid with 1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2, 2, 6, 6-tetramethyl-4-piperidyl)] -siloxane, the reaction product of the copolymer of ot -maleic anhydride olefin and 2, 2, 6, 6-tetramethyl-4-aminopiperidine or 1, 2, 2, 6, 6-pentamethyl-4-aminopiperidine. 2. 7. Oxamides, for example 4,4'-dioctyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'- didodecyloxy-5, 51-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide and their mixtures with the 2-ethoxy- 2'-ethyl-5, 41-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and also of o- and p-ethoxy-oxanilides di-substituted. 2. 8. 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example the 2, 4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2, -dimethylphenyl) -1 , 3, 5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-) propyl ifenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1, 3, 5 -triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6 bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2, 4) -dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2, -dimethylphenyl) -1, 3, 5 -triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy] -4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) ) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2, 4, 6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1, 3 , 5-triazine, 2-. { 2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. 3. Metal deactivators, for example N, N-diphenyloxamide, N-salicylal-1-salicyloylhydrazine,?,? '-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-buty1-4) -hydroxyphenylpropionyl) hydrazine, 3-salicylamino-l, 2,4-triazole, bis (benzylien) oxalyl-dihydrazide, oxanilide, isophthaloyl-dihydrazide, sebacoyl-bis-phenylhydrazide,?,? '- diacetyl-dipoyl-dihydrazide N, 1-bis -salicyloyloxalyl-dihydrazide,, N 1 -bis- (salicyloyl) thiopropionyl dihydrazide. 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpenta-erythritol-diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4- di-cumylphenyl) -pentaerythritol diphosphite, bis (2,6-di-tert-butyl) 4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2, -di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,, 6-t-tert-butylphenyl) pentaerythritol -diphosphite, tristearyl sorbitol-triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,8-tetra-tert-butyl-12H- dibenzo [d, g] -1, 3, 2-dioxaphosphocin, bis (2,4-di-tert- butyl-6-methylphenyl) -methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -ethyl phosphite, 6-fluoro-2,, 8, 10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1, 3, 2-dioxaphosphocin, 2, 21, 2"-nitrile [triethyl-tris (3, 3 ', 5, 5' -tetra-tert-butyl-1,1 '-biphenyl) -2, 2'-diyl) -phosphite], 2-ethylhexyl- (3, 3 ', 5, 5' -tetra-tert-butyl-1,1'-biphenyl-2, 2'-diyl) -phosphite, 5-Butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1, 3, 2-dioxaphosphirane.

The following phosphites are especially preferred: Tris- (2,4-di-tert.-butylphenyl) phosphite (Irgafos® 169, Geigy), and tris (nonylphenyl) phosphite, . Hydroxylamines, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, -dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine hydrogenated tallow amines. 6. Nitrones, for example N-benzyl-alpha-phenylnitrona, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl -alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrona, N-hexadecyl-alpha-heptadecylnitrona, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrona, N-octadecyl-alpha-hexadecylnitrone, nitrones derived from the N , -dialkylhydroxylamines, prepared from hydrogenated tallow amines. 7. Thio-synergistic, for example dilauryl thiopropionate or distearyl thiodipropionate 8. Peroxide scavengers, for example ß-thio-dipropionic acid esters, such as lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol-tetrakis (ß- dodecilmercapto) propionate. 9. Polamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.

. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl-cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metals of higher fatty acids, for example calcium stearate , zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatechol or zinc pyrocatechol. 11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably alkaline earth metals, organic compounds, such as mono- or polyhydric acids carboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example ionic copolymers ("ionomers"). Special preference is given to 1, 3: 2, 4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4-di (benzylidene ) sorbitol. 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass beads, talc, kaolin, mica, barium sulfate sulfate, metal oxides and hydroxides, carbon black, graphite, wood dust and powders of fibers of other natural products, and synthetic fibers 13. Other additives, for example, plasticizing agents, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-improving agents, optical brighteners, flame retardants, antistatic agents and blowing agents. 14. Benzofuranones and indolinones, for example as described in U.S. Pat. 4 325 863; U.S. 4 338 244; U.S. 5 175 312, U.S. 5 216 052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5, 7-di- tert -butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4 - [2-hydroxyethoxy]] phenyl) -benzofuran-2-one], 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-pivaloyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3, -dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

The above additives are, in general, applied in an amount between 0.01 and 2% by weight, based on the weight of the thermoplastic polymer.

Another aspect of the invention relates to a method for enlarging the optimum peak temperature range in rotational molding processes of thermoplastic polymers, by the use of a secondary, sterically clogged amine compound, as a process additive.

Therefore, a method is described for enlarging the process window towards higher crest temperatures of the internal air, in rotational molding processes of thermoplastic polymers.

This method comprises incorporating a sterically clogged amine into a thermoplastic polymer and subjecting the polymer to a rotary raleo process.

Still another embodiment of the invention, refers to a process for the production of thermoplastic hollow articles, this process comprises: mixing a thermoplastic polymer with a sterically clogged amine; Y subjecting this mixture to a rotating mole process, where the internal peak temperature range is approximately 215 to 250 ° C. in that, when the thermoplastic polymer is polyethylene, the clogged amine is not a linear or cyclic condensate of the?,? bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholin-2,6-dichloro-1,3,5-triazine.

Definitions and preferences, given above, also apply to the other aspect of the invention.

The following examples illustrate the invention.

Example 1: Preparation of hollow polyolefin articles by a rotational molding process 100 parts of medium density polyethylene, copolymerized with hexene (nominal melt x of 3.3 g / 10 minutes, density of 0.938 g / cm3) were mixed dry with 0.050 parts of zinc stearate and a combination of additional stabilizers, as are given in Table 1. The mixtures were compounded pelletized at 190 ° C, in a Superior Extruder / MPM, using a 24: 1 L / D screw with addock mixing head at 100 rpm. The composite pellets were milled to a uniform particle size (150-500 μ) before the rotational molding process. This milling step increased the surface area of the particles, leading to a faster absorption of heat and thus reducing the overall energy consumption. The rotational molding process was performed in a MPS "Clamshell" MIO team at laboratory scale. The ground resin was placed in an aluminum mold, which rotated biaxially in a gas-fired oven. The outgoing air was circulated by blowers in the chamber, while the temperature was increased to 274 ° C. This temperature was maintained for a specific time, which gave a certain temperature of the internal air ridge (PIAT) as given in Table 2. Subsequently, the furnace was opened and while still rotating, the mold was forced air cooled circulating for 7.3 minutes, followed by water mist spraying for 1.5 minutes, air cooled for 2 minutes, sprayed with are for 2.9 minutes and air cooled for 4.4 minutes. Through all the heating and cooling cycles the velocity of the major axis was maintained at 6 rpm, with a ratio of 4: 1 rotation. After the cooling cycles, the mold was opened and the hollow object was removed.

The process interval was defined as the peak internal air temperature interval (PIAT), in which a part with high impact resistance can be produced. Impact resistance is measured with the Dynatup Falling (25 lb / 20"") weight method in accordance with ASTM D-3763 at -40 ° C.

Table 2: Results The data clearly cates that the useful process range can be significantly displaced toward higher temperatures by the use of sterically secondary, amine-blocked compounds without sacrificing impact strength.

Example 2: Preparation of Polyolefin Hollow Articulations by the rotational molding process The process given in Example 1 was repeated with other additives, as delineated in Table 3. The results are presented in Table 4.

Table 3 Table 4 As long as the process temperature, as measured by the peak air temperature (PIAT), should not exceed 190 ° C if a tertiary amine is not present sterically obstructed, 210 ° C are acceptable when a sterically clogged tertiary amine is present. However, this temperature can also be extended to 221 ° C when, according to the invention, a secondary, sterically clogged amine has been added.

Ogargafos 168 is a phenolic antioxidant Ciba Specialty Chemicals, © Irgastab FS042, is N, N-di (tallow alkyl) hydroxylamine from Ciba Specialty Chemicals © Irgafos 168 is a trisaryl phosphite from Ciba Specialty Chemicals © Tinuvin 622 is a sterically clogged tertiary amine, from Ciba Specialty Chemicals, © Cyasorb UV 3346 is a secondary amine, sterically clogged, from Dytech Industries, © Chimassorb 944 is a secondary amine, sterically clogged, from Ciba Specialty Chemicals, © Chimassorb 2020 is a secondary amine, sterically clogged, from Ciba Specialty Chemicals, © Chimassorb 119 is a sterically clogged tertiary amine from Ciba Specialty Chemicals, © Hostavin N 30 is a sterically clogged tertiary amine from Clariant, © Tinuvin 770 is a secondary amine, sterically clogged, from Ciba Specialty Chemicals, © Tinuvin 783 is a mixture of a secondary amine and a tertiary amine, sterically clogged, from Ciba Specialty Chemicals.

Claims (3)

1. Use of a secondary amine compound, sterically clogged, as a process additive to enlarge the process window towards higher peak temperatures of the internal air, in rotational molding processes of thermoplastic polymers.
2. Use, according to claim 1, wherein the sterically clogged amine is a compound containing at least one group of the formula (I) or) II): in which * indicates a bond G is hydrogen or methyl, and Gi and G2. independently of one another, they are hydrogen, methyl or together represent a substituent = 0.
3. 3. Use, according to claim 2, in which the sterically clogged amine is a compound containing at least one group of the formula (Ia): Use, according to claim 1, in which the sterically clogged amine compound is added in an amount of 0.01 to 5% by weight, based on the weight of the thermoplastic polymer. Use, according to claim 1, in which the thermoplastic polymer is a polyolefin, polyvinylchloride or polyamide. Use according to claim 1, in which the thermoplastic polymer is polyethylene. Use, according to claim 1, wherein the temperature range of the internal air peak in the rotational molar processes is enlarged to 10 to 50 ° C towards higher temperatures. Use, according to claim 1, wherein the internal air peak temperature range is from 215 to 250 ° C. Use according to claim 1, wherein in the rotational molding process an additional stabilizer, selected from the group consisting of a UV light absorber, a sterically clogged amine, different from that of the formula (I) or the formula (II), a phenolic antioxidant, a phosphite or a phosphonite and a benzofuranone or indolinone, is present. A method for enlarging the process window towards higher peak temperatures of the internal air in rotational molding processes of thermoplastic polymers, said method comprises incorporating a secondary amine, sterically clogged, into a thermoplastic polymer and subjecting the polymer to a rotational molding process. A method for using a secondary amine compound, sterically clogged, as a process additive, to enlarge the process window toward higher peak temperatures of the internal air, in rotational molding processes of thermoplastic polymers.