FR2721036A1 - New products improving the crystallinity of polymeric materials. - Google Patents

Abstract

The subject of the invention is a polymer composition comprising at least one nucleating agent chosen from the group of imides and at least one organic polymer material. The invention also relates to a method for increasing the degree of crystallinity, the crystallization temperature and / or the mechanical properties of organic polymeric materials as well as the use of these imides as nucleating agents in organic polymeric materials. The invention also relates to agents which contain these particular imide compounds.

Description

The subject of the present invention is a polymer composition comprising at least

  at least one nucleating agent selected from the group of compounds

  having the general formulas I to VII and at least one polymeric material.

  The invention also relates to a process for increasing the degree of crystallinity of organic polymeric materials and the use of imides

  as nucleating agents in organic polymeric materials.

  The invention also relates to agents which contain these particular imide compounds. Polymers with a high degree of crystallinity are needed in many technical uses to meet the requirements

mechanical and thermomechanical.

  In general, a molten polymer crystallizes under cooling under

  form of spherulites, which include amorphous and crystalline domains.

  The quantity and size of the spherulites depend on the crystallization temperature, external influences (eg pressure or orientation) and

  the number of germs. By the artificial introduction of germinating agents,

  that is, nucleating agents, the amount of the resulting spherulite per unit volume can be substantially increased and thus their diameter reduced. A fine-crystalline material is formed which is, for example, less sensitive to

  stress crack formation as a large crystal structure.

  The Applicant has now found that certain compounds, because of their particular chemical structure are perfectly suitable as

nucleating agents.

  The invention thus relates to polymer compositions which comprise at least one organic polymeric material and a nucleating agent which is selected from the group consisting of the following formulas I to VIII R R '

(II) N-R

R 2 o n (II) $ NuR

(III) N R

R 2 - -n Ri R O

(IV) R

(v) N-R R2 1 3 R3 n

(V) N-R

  (RI) .o n Rs o (VI) Ri N-R RL n -R (VII) 4 L n o 0

R6 -R

(VIII)

  in which R 1 where n = 1, signifies hydrogen or a linear or branched C 1 -C 24 alkyl radical, a C 5 -C 2 cycloalkyl, C 6 -C 24 aryl, C 4 -C 24 heteroaryl or C 7 aralkyl radical; -C24, C7-C24 alkaryl or the group (C1-C24 alkylene) -R7; in particular hydrogen or a linear or branched C 1 -C 8 alkyl radical, a C 5 -C 8 cycloalkyl, C 6 -C 18 aryl, C 4 -C 8 heteroaryl, C 7 -C 8 aralkyl or alkaryl group; C7-C18 or a (C1-C18) alkylene-R7; preferably hydrogen or a linear or branched C1-C12 alkyl radical, a C5-C8 cycloalkyl, C6-C8 aryl, C4-C12 heteroaryl, C7-C8 aralkyl or C7 alkaryl radicals -CI8 or the group (C₁-C₁ alk alkylene) -R7; especially hydrogen or a linear or branched C1-C12 alkyl radical, a cyclohexyl, phenyl, biphenyl, C7-C12 aralkyl or alkaryl radical.

C7-C12;

  when n> 1, means a linear or branched C 1 -C 24 alkylene radical, a C 5 -C 12 cycloalkylene, C 6 -C 24 arylene, C 4 -C 24 heteroarylene, C 7 -C 24 aralkylene, or C 1 -C 24 alkarylene radical; in particular a linear or branched C 1 -C 18 alkylene radical, a C 1 -C 8 cycloalkylene, C 6 -C 8 arylene, C 4 -C 8 heteroarylene, C 7 -C 18 aralkylene or C 7 -C 18 alkarylene radicals; ; preferably a linear or branched C 1 -C 12 alkylene radical, a C 5 -C 8 cycloalkylene, C 6 -C 18 arylene, C 4 -C 2 heteroarylene, C 1 -C 8 aralkylene or C 7 alkarylene radicals; -C, 8; especially a linear or branched C 1 -C 8 alkylene radical, a cyclohexylene, phenylene, biphenylene, C 7 -C 12 aralkylene or C 7 -C 12 alkarylene radical; R ", R2, R3, independently of one another, means hydrogen or a linear or branched CC-C24 alkyl radical, a C5-C12 cycloalkyl radical, a C6-C24 aryl radical, a C4-C24 heteroaryl radical, aralkyl radical; C 7 -C 24, C 7 -C 24 alkaryl or the group -NHR 4, in particular hydrogen or a linear or branched C 1 -C 18 alkyl radical, a C 5 -C 8 cycloalkyl radical, a C 6 -C 18 aryl radical or a heteroaryl radical. C4-C18, C7-C8 aralkyl, C7-C8 alkaryl or the -NHR4 group, preferably hydrogen or a linear or branched C1-C12 alkyl radical, a C5-C8 cycloalkyl radical, C6-C18 aryl, C7-C18 aralkyl or C7-C18 alkaryl, especially hydrogen or a linear or halogenated C1-C12 alkyl radical, a cyclohexyl, phenyl, biphenyl or C7-C7 aralkyl radical, 2 or alkaryl in

C7-C12;

  R4 is hydrogen or straight or branched C1-C24 alkyl, C5-C12 cycloalkyl, C6-C4 aryl, C4-C24 heteroaryl, C7-C24 aralkyl, C7-C24 alkaryl; or the group (C1-C24 alkylene) -R7; in particular hydrogen or a linear or branched C 1 -C 18 alkyl radical, a C 5 -C 8 cycloalkyl, C 6 -C 8 aryl, C 4 -C 8 heteroaryl or C 7 -C 8 aralkyl radical, C 7 -C 8 alkaryl, or C 1 -C 8 alkylene-R 7; preferably hydrogen or a linear or branched C 1 -C 8 alkyl radical, a C 5 -C 8 cycloalkyl, C 6 -C 8 aryl, C 7 -C 8 aralkyl or C 7 -C 18 alkaryl radical; especially hydrogen or a linear or branched C 1 -C 8 alkyl radical, a cyclohexyl, phenyl, C 7 -C 12 aralkyl or C 7 -C 12 alkaryl radical; R5 is hydrogen or a linear or branched C1-C24 alkyl radical or the group -CH2OH, in particular hydrogen or a methyl radical; R6 is OH or -NHR4; R7 is O-N-R -NH X is a bridging group of formula -CH2-,> CH- (C1-C4) alkyl- or -O-; in particular -CH2-,> CH-CH3 or -O-; n is a number from 1 to 6, especially from 1 to 4;

  m is a number from 0 to 4, in particular from 0 to 2.

  Compounds of general formulas I to VIII are not

  limited to the isomers represented in these formulas.

  The compounds of the formulas I to VIII are known or can be

  prepared easily according to known methods.

  The polymer compositions of the invention contain a nucleating agent of the invention in an amount of between 0.01 and 5%, preferably between 0.02 and 0.5%, in particular between 0.02 and 0.3. % by weight, based on weight

  total of the organic polymeric material.

  The polymeric compositions of the invention may contain the nucleating agent of the invention, optionally in the form of mixtures with other

germination substances known.

  According to another aspect, the invention also relates to a process for increasing the degree of crystallinity, the crystallization temperature and / or the mechanical properties of the organic polymeric materials, in which process in a first step is added and mixed according to methods known, at least one nucleating agent selected from the group consisting of the imides of formulas I to VIII optionally in admixture with other germinating agents or other known additives to an unmelted organic polymeric material in a second step, the organic polymeric material containing the nucleating agent is melt-processed and in a third step the processing is carried out according to a known method; or else, in a first step, the nucleating agent according to the invention, optionally mixed with other known germination substances, is added and mixed according to known methods with an organic polymeric material in the molten state, and , in

  a second step, we continue the implementation according to a known method.

  The invention also relates to the use of the imides selected from the group consisting of the compounds of the general formulas I to VIII, as nucleating agents in organic polymeric materials. The imides of the invention can be used individually, in the form of mixtures and

  also in combination with other known germination substances.

  The nucleating agents corresponding to the general formula I and o R when n = 1, signifies hydrogen or a linear or branched C 1 -C 2 alkyl radical, a cyclohexyl, phenyl, biphenyl or C 7 -C 7 aralkyl radical. , 2 or C7-C alkaryl, 2; when n> 1, a linear or branched C1-C8 alkylene radical, a cyclohexylene, phenylene, biphenylene, C7-C12 aralkylene or C7-C12 alkarylene residue; R1, R2 independently of one another, hydrogen or a linear or branched C1-C12 alkyl radical, a cyclohexyl, phenyl, biphenyl, C7-C12 aralkyl or C7-C alkaryl radical; , 2; n means a number from 1 to 4, are particularly suitable because they are very effective as nucleating agents, are perfectly compatible with organic polymeric materials

  and particularly easy to prepare.

  The invention therefore also relates to auxiliaries, for example liquid concentrates or masterbatches which contain nucleating agents of the invention in a concentration of between 5 and 80%,

  preferably between 10 and 50% by weight.

  Examples of organic polymeric materials include the following homopolymers, copolymers and polymer blends: cellulose acetate; cellulose acetate butyrate; cellulose acetopropionate; cresol-formaldehyde resins; carboxymethylcellulose; cellulose nitrate; cellulose propionate; casein plastics; casein-formaldehyde; cellulose triacetate; ethylcellulose; epoxy resins; methylcellulose; melamine-formaldehyde resins; polyamides; polyamideimides; the

  polyacrylonitrile; polybutene-1; polybutylacrylate; poly (butylene

  terephthalate); poly (ethylene terephthalate); polycarbonates; the poly-

  (Chlorotrifluoroethylene); poly (diallylphthalate); polyethylene; chlorinated polyethylene; poly (ether ether ketone); polyetherimide; polyethylene oxide; polyethersulfone; polyethylene terephthalate; polytetrafluoroethylene; phenol-formaldehyde resins; polyimide; polyisobutene; polyisocyanurate; polymethacrylamide; polymethyl methacrylate; poly (4-methylpentene-1); poly (c-methylstyrene); polyoxymethylene; polyacetate; polypropylene; polyphenylene ether; polyphenylene sulfide; polyphenylenesulphone; polystyrene; polysulfones; polyurethane; polyvinyl acetate; polyvinyl alcohol; polyvinyl butyral; chlorinated polyvinyl chloride; polyvinylidene chloride; polyvinylidene fluoride; polyvinyl fluoride; polyvinylformaldehyde; polyvinylcarbazole; polyvinylpyrrolidone; silicone polymers; saturated polyester; urea-formaldehyde resins; unsaturated polyester; polyacrylate; polymethacrylate; polyacrylamide; maleic resins; phenolic resins; aniline resins; the resins

  furan; carbamidic resins; epoxy resins and silicone resins.

  Examples of suitable copolymers include the following: acrylonitrile / butadiene / acrylate; acrylonitrile / butadiene / styrene; acrylonitrile / methylmethacrylate; acrylonitrile / styrene / acrylic ester; acrylonitrile / ethylene-propylene; acrylonitrile / chlorinated polyethylene / styrene; ethylene / ethylacrylate; ethylene / methacrylate; ethylene / propylene copolymers; ethylene / propylene-diene; ethylene / vinyl acetate; ethylene / vinyl alcohol; ethylene / tetrafluoroethylene; tetrafluoroethylene / hexafluoropropylene; methacrylate / butadiene / styrene; melamine / phenol-formaldehyde; blockamide polyester; perfluoro-alkoxyalkane; styrene / acrylonitrile; styrene / butadiene; styrene / maleic anhydride; styrene / ct-methylstyrene; vinyl chloride / ethylene; vinyl chloride / ethylene / methacrylate; vinyl chloride / ethylene / vinyl acetate; vinyl chloride / methyl methacrylate; vinyl chloride / octyl acrylate; vinyl chloride / vinyl acetate; and chloride

vinyl / vinylidene chloride.

  The nucleating agents of the invention are particularly suitable for increasing the degree of crystallinity of polyolefins, that is to say in particular

  for polypropylene and all types of polyethylene (for example poly-

  high density ethylene, medium density polyethylene and low density polyethylene), polyisobutene, poly-4-methylpentene and their copolymers and blends as well as polyesters such as polyethylene terephthalate,

  poly (butylene terephthalate), polyamides and polyoxymethylene.

  The nucleating agents of the invention have proved to be particularly suitable, in particular for polyolefins prepared according to the new methods with catalysts of generations II to V ("Generation II to

  V-Catalysts "), which are not removed from the polymer after the polymerization.

  Said catalysts of generations II to V are in fact often deactivated after the polymerization by addition of a poison (for example by water vapor, aliphatic alcohols, ether or a ketone), the residues remain however in the polymer and, like water vapor and other materials / compounds used for their deactivation, promote the hydrolysis of phosphite and phosphonite stabilizers. Said catalysts and the products thus prepared are described for example by Rolf M llhaupt in "New Trends in Polyolefin Catalysts and Influence on Polymer Stability", pages 181 to 196 (Twelfth Annual International Conference on Advances in Stabilization and Controlled

  Degradation of Polymers, Lucerne, Switzerland, 21-23 May 1990).

  Table I on page 184 of this publication describes the catalysts.

  Metallocene catalysts belong for example to these new generations

catalysts.

  Table I: Evolution of polyolefin catalysts * Generation Example Cat. Act. % Act.Ti Stereo-reg. Process (gPP / g Ti hatmr) (% hept Ins) Technology I. TiCl 3 / AIR 3 40 0.01 45% Elimination. cat residues and Atactic PP TiCl 3 / AIEt 2 Cl. 0.1 92% / Elimination of catalyst residues

  I Mg (OEt 2) / TiCl 3 / AIR 3 40000 50% No elimination of residues

  SiO2Cp2Cr 40000 HDPE sidus cat. (essentially

HDPE / LLDPE)

  111I Mod.TiCI1cat. 5000 1 95% No purification MgC / TiCI, / AIE3 + 20000 92% / -ester donor IV MgC'TiCI, / AIR3 + 40000 18 99% Not. purification-donor-silane pa-extrusion V Bis.indenyl-TiR2 on40000 100 99% New PP, distribution of (AICHO) 2 narrow molecular weight o R means an organo group; HDPE stands for high density polyethylene;

  LLDPE means low density polyethylene; Cp means a cyclo-

  pentadienyl; And means ethyl; PP means polypropylene; MWD means the

  molecular weight distribution and x means an integer greater than 2.

  * (Twelfth Annual International Conference on Advances in Stabilization and

  Controlled Degradation of Polymers, Lucerne, 21-23 May 1990, page 184).

  The polymer compositions of the invention, besides the nucleating agents of the invention, may also contain additives and adjuvants in usual concentrations. Examples include, for example, dyes, pigments, antioxidants, UV absorbers, UV extinguishers, UV stabilizers, processing stabilizers, metal deactivators, radical scavengers, acids, peroxide reducing compounds, lubricants, flame retardants, anti-static agents, impact modifiers, blowing agents, optical brighteners, hardeners, crosslinking agents, plasticizers, extenders, emulsifiers, photoinitiators, release agents, anti-corrosion agents,

  reinforcement, fillers, and foils.

  The advantage of the nucleating agents of the invention lies in the fact that they improve the thermal and / or mechanical properties of the organic polymeric materials without impairing their properties of implementation. In addition, by addition of the nucleating agents of the invention, it is possible to obtain a

  increase of the crystallization temperature. This equates to solidification

  cation, for example of an injection molded or blown part and

  leads to an improvement in the profitability of the preparation process.

  Since all the properties of the polymers which depend on the degree of crystallinity are not influenced or improved in the same way by the class of nucleating agents of the invention, the choice of a suitable nucleating agent makes it possible to modify that the polymeric properties that

  need to be improved for a specific use.

  Another advantage of the nucleating agents of the invention is their

  good compatibility with organic polymeric materials.

  The following examples illustrate the invention without in any way limiting

the scope.

  1. Preparation of the nucleating agents of the invention

Example 1

  Synthesis of 1,3-phenylene-N, N-bis-succinimide: To a solution comprising 0.1 mole of anhydride of succinic acid in 100 ml of acetone, stirring is added at 50 ° C. and at room temperature. 30 minutes, a solution of 0.05 moles of 1,3-phenylenediamine in 60 ml of acetone. After 2 hours under reflux, the solid material obtained is filtered, dried and heated at 70 ° C. for 3 hours with a mixture of 2 g of sodium acetate and 0.21 mol of acetic anhydride. After addition of 100 ml of water, the reaction mixture is stirred for 1 hour. The product is then filtered,

  Wash thoroughly with hot water and dry. Mp = 203 ° C; yield: 72%.

Example 2

  Synthesis of 1,2-phenylene-N, N-bis-succinimide: To a solution comprising 0.1 mol of anhydride of succinic acid in 100 ml of acetone is added with stirring at 50 ° C. and at room temperature. 30 minutes, a solution of 0.05 moles of 1,2-phenylenediamine in 60 ml of acetone. After 2 hours under reflux, the solid material obtained is filtered, dried and heated at 70 ° C. for 2 hours with a mixture of 2 g of sodium acetate and 0.21 mol of acetic anhydride. After addition of 150 ml of water, the reaction mixture is stirred for 1 hour. The product is then filtered,

  recrystallize in hot water and dry. F> 250 C; yield: 32%.

Example 3

  Synthesis of 1,4-phenylene-N, N-bis-succinimide: To a solution comprising 0.2 mole of succinic acid anhydride in 150 ml of acetone is added with stirring and over a period of 30 minutes. minutes, a solution of 0.1 mole of 1,4-phenylenediamine in 50 ml of acetone. After 2 hours under reflux, the solvent is removed. 2 g of sodium acetate and 0.3 moles of acetic anhydride are then added. After stirring the reaction mixture for 3 hours at 70 ° C., the colorless crystals are collected on a Buchner funnel,

  Wash them in cold water, dry them and recrystallize them in water.

Mp 254-256 ° C; yield: 42%.

Example 4

  Synthesis of ethylene-N, N-bis-succinimide To a solution comprising 0.1 mole of succinic acid anhydride in 50 ml of acetone is added with stirring and within 30 minutes, a solution of 0.05 moles of ethylenediamine in 50 ml of acetone. After one hour at reflux, the solid material obtained is filtered off, dried and maintained for 2 hours at 70 ° C. with 2 g of sodium acetate and 0.21 mol of acetic anhydride. After addition of 110 ml of water, the reaction mixture is stirred for 1 hour, the product is then filtered, recrystallized in hot water and

  dry it. Mp = 255 ° C; yield: 62%.

Example 5

  Synthesis of (4,4'-diamino-diphenylmethane) -N, N-bis-succinimide: To a solution comprising 0.1 mole of succinic acid anhydride in 100 ml of acetone is added with stirring for 30 minutes, a solution of 0.05 mole of 4,4'-diaminodiphenylmethane in 50 ml of acetone. After one hour at reflux, the solid material obtained is filtered off, dried and, after addition of 2 g of sodium acetate and 0.2 mol of acetic anhydride, is maintained for 2 hours at 70 ° C. After addition of 200 ml of water, the reaction mixture is stirred for a further hour, then the product is filtered, recrystallized from DMF / water and dried. Mp = 165 ° C;

yield: 68%.

Example 6

  Synthesis of ethylene-N, N-bis- (bicyclo [2,2,2] dibenzo-octadienedicarboximide)

  To a solution of 0.1 mole of bicyclo [2,2,2] -dicarboxylic anhydride

  benzo-octadiene dicarboxylic acid in 200 ml of acetone, in the course of 30 minutes, a solution of 0.05 mol of ethylenediamine in ml of acetone is added with stirring. After refluxing for one hour, 2 g of sodium acetate and 0.21 moles of acetic anhydride are added and the reaction mixture is refluxed for 2.5 hours. After addition of 200 ml of water, the reaction mixture is stirred for a further hour, the product is filtered and recrystallized.

  in dioxane and dried. F => 250 C; yield: 10%.

Example 7

  Synthesis of ethylene-N, N-bis- (4-norbornene-dicarboximide)

  To a solution of 0.1 mole of norbornenedi

  In 100 ml of acetone, a solution of 0.05 mole of ethylenediamine in 10 ml of acetone is slowly added. After addition of 2 g of sodium acetate and 10 ml of acetic anhydride, the reaction mixture is stirred at 60 ° C. for 2 hours. After addition of 50 ml of water, the mixture is stirred for a further hour, then the product is filtered, dried and recrystallized from

  toluene. M.p. 244-248 ° C; yield: 43%.

Example 8

  Synthesis of phenyl-N-bis- (1- (hydroxymethyl) -7-oxo-4-norbornenedicarboximide To a solution of 0.1 mol of maleic anhydride in 150 ml of acetone is added 30 minutes, a solution of 0.1 mol of aniline in 50 ml of acetone, After 2 hours at reflux, 2 g of sodium acetate and 0.21 mol of acetic anhydride are added. The reaction mixture is kept under reflux for 2.5 hours and after the addition of 200 ml of water, the reaction mixture is kept under reflux for a further 1 hour, the resulting solid material is filtered off, recrystallized from cyclohexane, and the resulting mixture is heated to reflux. After drying at 700 ° C. for 12 hours, the resulting intermediate product is reacted with a solution of 0.075 mole of furfuryl alcohol in 100 ml of toluene, the product is then filtered and recrystallized from water. ethyl acetate: mp 154 ° C;

yield 58%.

Example 9

  Synthesis of 1,4-phenylene-N, N-bis (1-hydroxy-methyl) -7-oxo-4-norbornene

  dicarboximide To a solution of 0.2 mol of maleic anhydride in ml of acetone, over a period of 30 minutes, a solution of 0.1 mol of 1,4-phenylenediamine in 50 ml of 'acetone. After refluxing for one hour, 2 g of sodium acetate and 0.21 moles of acetic anhydride are added and the reaction mixture is kept at reflux for 5 hours. After addition of 200 ml of water, the reaction mixture is maintained at reflux for another hour. After cooling, the resulting solid material is filtered, recrystallized from

  DMF and dried. The product is reacted for 10 hours at 70 ° C.

  median obtained with a solution of 0.1 mole of furfuryl alcohol in 100 ml

  toluene. The product is then filtered and washed in methanol.

F => 2500C; yield: 27%.

Example 10

  Synthesis of trimellitimide-anilide To 0.1 mole of methyl ester of trimellitimide, 0.1 mole of aniline and 100 ml of decalin are added and the mixture is heated until the amount

  The theoretical amount of methanol is removed by distillation (12 hours). After cooling

  The precipitated product is filtered and dried. For subsequent purification, the product is recrystallized from dimethylacetamide. F => 250 ° C;

yield: 86%.

  Example 11: Comparison Example Synthesis of 1,3-phenylene-N, N-bisphthalimide To a solution of 0.2 mole of phthalic anhydride in 200 ml of acid

  during 30 minutes, a solution of 0.1 mol of

  phenylenediamine in 100 ml of acetic acid. After stirring for a further 2 hours, the off-white precipitate is collected on a Buchner funnel and washed.

  until neutral in water and acetone and dried.

F => 250 C; yield = 62%.

  H. Preparation of the Polymer Compositions of the Invention: Examples 12 to 17 Polymer compositions containing 0.01 parts of a polypropylene random copolymer prepared with a 3rd generation catalyst and having a melt index of 7.0 were prepared. Part of Irganox R 1010, 0.10 part of Sandostab R P-EPQ, 0.10 part of calcium stearate, 0.10 part of a nucleating agent of Table 1 in the following manner: From the components of the polymer compositions, a fluid dried mixture is prepared which is extruded at 210 ° C in a single-screw Handle extruder and granulated. At 245 ° C. in an Arburg type injection machine, these granules are converted into

x 100 x 1 mm3.

  Examples 18 to 22: Proceeding as described in Examples 12 to 17, polymer compositions similar to those of Examples 12 to 17 are prepared, but

  0.3 part nucleating agent instead of 0.1 part.

  Examples 23 to 26: Proceeding as described in Examples 12 to 17, polymer compositions are prepared containing 0.01 parts of a polypropylene random copolymer prepared with a 3rd generation catalyst and having a melt index of 6.0, 05 part of Irganox R 1010, 0.10 part of Sandostab R P-EPQ, 0.10 part of calcium stearate,

  0.10 part of a nucleating agent of Table 1.

  Examples 27 to 29: Proceeding as described in Examples 12 to 17, polymer compositions analogous to those of Examples 23 to 26 are prepared, but

  0.3 part nucleating agent instead of 0.1 part.

  The following properties are determined on samples of Examples 12 to 29: the melting index of the granules after the first extrusion according to the standard

ASTM D-1238-70 / L,

  - Yellowness index of injection molded plates according to ASTM D-1925-70 (Reflection), - Haze point (haze) of injection molded plates according to standard

ASTM D-1003-70,

  the initial crystallization temperature (TOC) on a differential scanning calorimetric analysis curve; In the middle of the injection-molded plates, 3 mg samples are cut and in a Mettler DSC 20 apparatus, measurements are made at a temperature of 200 to 50 ° C with a cooling rate of 10 ° C / min. tensile strength according to DIN 53455: on injection molded plates, samples are cut perpendicular to the

  injection direction and the average value of 5 samples is determined.

  The results of the tests are presented in Tables 1 and 2.

Table 1

  Test results for the polymeric compositions of the invention and for a polymer composition free of nucleating agent N of Ex. Nucleic acid agent Amount of agent Cloud point TOC Resistance to extion of ex. nucleation tensile [parts] [%] [C] [N / mm2]

12 I 0.1 33 109 26.1

13 2 0.1 27 110 27.6

14 3 0.1 65 122 27.2

4 0.1 27 109 25.8

16 6 0.1 43 119 25.5

17 - 27 108 24.9

18 1 0.3 55 109 25.5

19 2 0.3 40 110 24.6

3 0.3 79 118 27.4

21 4 0.3 32 109 26.5

22 6 0.3 57 108 24.6

Table 2

  Test results for the polymeric compositions of the invention and for a nucleating agent-free polymer composition COT No. Nucleic acid Agent quantity Cloud point TOC Resistance to ex. of nucleation traction I _____________________ [parts] [%] [C] [N / mm 2]

23 7 0.1 23 104 28.9

24 8 0.1 22 106 32.4

9 0.1 24 105 30.9

26 26 105 29.4

27 7 0.3 25 104 29.6

28 8 0.3 30 104 32.9

29 9 0.3 55 110 30.0

  Examples 30 and 31 and Comparative Examples 32 and 33: Efflorescence test From a polymer composition containing 00 parts of a polypropylene random copolymer prepared with a 3rd generation catalyst and having a melt index of 7, 0.05 part of Irganox R 1010, 0.10 part of Sandostab R P-EPQ, 0.10 part of calcium stearate, and 0.1 or 0.3 part of a nucleating agent of Table 3 injection molded plates are prepared, stored at room temperature

  ambient and the efflorescence is determined over a period of 2 months.

  While no efflorescence is observed after 2 months on the nucleating agent of the invention, there is already an efflorescence after

  one week for the nucleating agent according to the state of the art.

  Table 3: N4 Efflorescence Test of Ex. Nucleic acid Agent amount Efflorescence of ex. nucleation [parts] 1 0.1 no 31 I 0.3 no 32 11 * 0.1 yes 33 11 * 0.3 yes * nucleating agent according to the state of the art, e.g. DE 1 951 632

Claims (10)

  A polymeric composition comprising at least one organic polymeric material and at least one functional agent characterized in that the nucleating agent is selected from the group of compounds of the general formulas I to VIII (I) R R A1 R2 R2 on R1 (II) --R (III) N R R2 n RR0 \ N- Ri R 0 R2 N-R (IV) R2 R3 RO (v) L-R (V) N-R (Rl) m n R5 0 (VI) Ri OrNR R R2o - O R (VII) N_ n 0 o R 6 N-R   When n = 1, means hydrogen or a linear or branched C1-C24 alkyl radical, a C5-C12 cycloalkyl radical, a C6-C24 aryl radical, a C4-C24 heteroaryl aralkyl radical; C7-C24, C7-C24 alkaryl or the group (C1-C24alkylene) -R7, when n> 1, means a linear or branched C1-C24 alkylene radical, a C5-C2cycloalkylene radical, C 6 -C 24 arylene, C 4 -C 24 heteroarylene, C 7 -C 24 aralkylene, or C 7 -C 24 alkarylene; R 1, R 2, R 3 independently of one another means hydrogen or a linear C 1 -C 24 alkyl radical; or branched, a C 5 -C 12 cycloalkyl, C 6 -C 24 aryl, C 4 -C 24 heteroaryl, C 7 -C 24 aralkyl, C 7 -C 24 alkaryl or the -NHR 4 group; R 4 is hydrogen or an alkyl group C, -C24 linear or branched, a C4-C12 cycloalkyl, C6-C24 aryl, C4-C24 heteroaryl, C7-C24 aralkyl, C7-C24 alkaryl or the (C4-C24) alkylene group; C1-C24) -R7;   R5 is hydrogen or a linear or branched C1-C24 alkyl radical or the group -CH2OH; R6 is OH or -NHR4; R7 is N-R -NH O X is bridging of the formula -CH2-,> CH- (C1-C4) -alkyl- or -O-; n is a number from 1 to 6; m means a number from 0 to 4.   2. A composition according to claim 1, characterized in that in the formula IR when n = 1 means hydrogen or a linear or branched C 1 -C 8 alkyl radical, a C 5 -C 8 cycloalkyl radical, aryl C6-C18, C4-C8-heteroaryl, C7-C18 aralkyl, C7-C8-alkaryl, or (C1-C18) alkylene-R7; when n> 1 means a linear or branched C 1 -C 18 alkylene radical, a C 5 -C 8 cycloalkylene, C 6 -C 18 arylene, C 4 -C 8 heteroarylene, C 7 -C 8 aralkylene or C 7 alkarylene radicals -C, 8; R 1, R 2 and R 3 independently of one another are hydrogen or a linear or branched C 1 -C 8 alkyl radical, a C 6 -C 8 cycloalkyl, a C 6 -C 8 aryl or a C 4 -C 18 heteroaryl radical; C7-C18 aralkyl, C7-C8 alkaryl, or the -NHR4 group; R4 is hydrogen or straight or branched C1-C18 alkyl, C5-C8 cycloalkyl, C6-C8 aryl, C4-C8 heteroaryl, C7-C8 aralkyl, alkaryl; C7-C, 8 or the group (alkylene C1-C18) -R7;   3. A composition according to claim 1, characterized in that in the formula IR when n = 1, means hydrogen or a linear or branched C 1 -C 2 alkyl radical, a cyclohexyl, phenyl, biphenyl or aralkyl radical. C7-C, 2 or C7-C: 2 alkaryl; when n> 1, denotes a linear or branched C 1 -C 8 alkylene radical, a cyclohexylene, phenylene, biphenylene, C 7 -C 12 aralkylene or C 7 -C 12 alkarylene radical; R ", R2, independently of one another, means hydrogen or a linear or branched C1-C12 alkyl radical, a cyclohexyl, phenyl, biphenyl, C7-C7 aralkyl or C7-C12 alkaryl radical; ; n means a number from 1 to 4.   4. A composition according to any one of claims 1 to 3,   characterized in that the agent - ucl I e n represents from 0.01 to 5% by weight per   relative to the total weight of the organic polymeric material.   5. A composition according to any one of claims 1 to 4,   characterized in that the organic polymeric material is a polyolefin, a polyester, a polyamide, a polyoxymethylene or a copolymer thereof. 6. A process for increasing the degree of crystallinity, the crystallization temperature and / or the mechanical properties of the organic polymeric materials, characterized in that a) is added and mixed at least one agent selected from the group consisting of the imides of the formulas I to VIII according to claim 1 to an unmelted organic polymeric material, b) the organic polymeric material containing the nucleant is treated in the molten state, and c) the reaction is continued. implemented according to a known method; or a) adding and mixing the agent ha (jeanr selected from the group consisting of the imides of formulas I to VIII according to claim 1 to an organic polymeric material in the molten state and,   b) the method is continued using a known method.   7. A method according to claim 6, characterized in that at step   a), imides according to claim 2 or 3 are added.   8. A process according to claim 6 or 7, characterized in that the agent m <c-D ci '+ represents from 0.01 to 5% by weight relative to the total weight of the organic polymeric material.   9. The use of the imides selected from the group of compounds of formulas I to VIII as specified in claim 1, as agents   nucleating agent in organic polymeric materials.   10. Liquid concentrates and masterbatches comprising from 5 to% by weight of a nucleating agent of the formula I to VII as specified in claim 1.