GB2290296A - Imide nucleating agents for polymers - Google Patents

Imide nucleating agents for polymers Download PDF

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GB2290296A
GB2290296A GB9511702A GB9511702A GB2290296A GB 2290296 A GB2290296 A GB 2290296A GB 9511702 A GB9511702 A GB 9511702A GB 9511702 A GB9511702 A GB 9511702A GB 2290296 A GB2290296 A GB 2290296A
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linear
hydrogen
nucleating agent
polymeric
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Peter Staniek
Klaus Stoll
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Sandoz AG
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Sandoz AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083Nucleating agents promoting the crystallisation of the polymer matrix

Description

1 2290296 NUCLEATING AGENTS The invention relates to a polymeric
composition comprising at least one polymeric material and at least one nucleating agent selected from the group consisting of compounds of formulae I to VHI.
More particularly the invention relates to a process to enhance the degree of crystallinity, the crystallization onset temperature, and the mechanical properties of polymeric materials. The invention relates further to the use of special in-dde compounds according to formulae I to VW as nucleating agents for polymeric materials as well as to compositions, e. g. masterbatches and liquid concentrates comprising said imide compounds.
The physical properties which are improved by these nucleating agents (hereinafter called NA), are for example, crystallization temperature andler mechanical properties like tensile strength or elongation at break.
According to the invention, there is provided a polymeric composition comprising a polymeric material and a nucleating agent of formulae I to VHI R1 R 1 N 1 R 2 R2 0 (I) n R1 1 N.
R 2 L 10 (11) -R n 2 0 RI NR 2 (III) (IV) (V) (VI) -R n RI RI 0 ---1 "' R2 1 Np R 2 R3 R 0 L 3 1 o- N- /0 p (R.' 1 0 )M RS X 0 RI-- N RS Z2 0 -R n R - n -R n 3 0 N--- --,R (VII) (VIII) in which R if n=l, is hydrogen,C1-24alkyl (linear or branched), C5- 12CYCloalkyl, C6-24aryl, C4-24heteroaryl, C7-24aralkyl, C7-24alkaryl, -Cl- 24alkylen-R7; 00 5>1 1 1 1 ex 1115 0 0 6"C N 1 - n R n particularly hydrogen, C,_1.alkyl (linear or branched), C,-,cycloalkyl, C6.,,aryl, C4-jeteroaryl, C7-1,aralkyl, C7-1,alkaryl, -Cl-,,alkylen-R7; preferably hydrogen,C1-12alkyl (linear or branched), C,-,cycloalkyl, C6- Haryl, C4-12heteroaryl,C7-18aralkyl,C7-18alkaryl, -C,-1,alkylen-R7; more preferably hydrogen, C,-12alkyl (linear or branched), cyclohexyl, phenyl, biphenyl, CM2aralkyl, C7A2alkaryl; 4 if n>l CP24alkylen (linear or branched), CS-12CYCloalkylen,C6-24arylen, C4-24heteroarylen,C7-24aralkylen, C7-24alkarylen; particularly C,-18alkylen. (linear or branched), C,-,cycloalkylen, C6-,, arylen, C4-,,heteroarylen, C7-1.aralkylen, C7.1.alkarylen; preferably CM2alkylen (linear or branched), C5.8cycloalkylen, C6-12arYlen, C4-12heteroarylen, C7-,.aralkylen, C7-Aalkarylen; more preferably C,-8alkylen (linear or branched), cyclohexylen, phenylen, biphenylen, C7-1,aralkylen, C7 -1.alkarylen; R,, R2, R3 are independently selected from hydrogen, C,-24alkyl (linear or branched), C,-12cycloalkyl, C6-24aryl, C4-24heteroaryl, C7-24aralkyl, C7-24alkaryl, -NHR4; particularly hydrogen, C,-,,alkyl (linear or branched), C,.,cycloalkyl, C6-1,aryl, C4-1.heteroaryl, C74,aralkyl, C7-1.alkaryl, -NHR4; preferably hydrogen, Cl-12alkyl (linear or branched), C5-scycloalkyl, C6- 18arYl, C7-18aralkyl, C74salkaryl; more preferably hydrogen, C,-,.alkyl (linear or branched), cyclohexyl, phenyl, biphenyl, C7-12aralkyl, C7.12alkaryl; R4 hydrogen, Cl-24alkyl (linear or branched), CS-12CYCloalkyl, C,-24aryl, C4-24heteroaryl, C7-24aralkyLC7-24alkaryl, -C,-24alkylen-R7; particularly hydrogen, C,-1,alkyl (linear or branched), C5-8cycloalkyl, C6-,,aryl, C4-18heteroaryl, C748aralkyl, C7-18alkaryl, -Cl-1,alkylen-R7; preferably hydrogen, C,_salkyl (linear or branched), C,_,cycloalkyl, C6.,, aryl, C7-2aralkyl, C7.1,Aaryl; more preferably hydrogen, C,_galkyl (linear or branched), cyclohexyl, phenyl, C7-12aralkyl, C7.12alkaryl; R5 hydrogen, C,_24alkyl (linear or branched), -CH2-OH; particularly hydrogen, methyl; R6 -OH, -NHR4; R7 0 I N-R - NH 0 X -CH.-, >CH-C,-4alkyl- oder -0-; particularly -CH2-, >CH-CH31 -0_; n is an integer selected from 1 to 6, particularly 1 to 4; m is an integer selected from 0 to 4, particularly 0 to 2; The structures are not limited to the isomers drawn in formulae I to VM.
Compounds of formulae I to VIII are known and can be produced according to well known processes.
Polymeric compositions according to the invention comprise the nucleating agent in an amount of from 0,01 to 5% by weight, preferably from 0,02 to 0,5% by weight, more preferably 0,02 to 0,3% by weight based on the polymeric material.
Another object of the invention is a process to enhance the degree of crystallinity, the 6 crystallization onset temperature andlor mechanical properties of polymeric materials characterized in that in a first step at least one nucleating agent selected from the group consisting of compounds of formulae I to V1H - optionally mixed with other nucleating agents according to the prior art - is added to the unmolten polymeric material and mixed according to known methods forming a mixture, in a second step said mixture is melted forming a polymeric composition and in a third step said polymeric composition is processed according to known methods or in a first step at least one nucleating agent selected from the group consisting of compounds of formulae I to VIII - optionally mixed with other nucleating agents according to the prior art - is added to the molten polymeric material and mixed according to known methods forming a polymeric composition and in a second step said polymeric composition is processed according to known methods.
The invention further relates to the use of special imides according to the above-mentioned formulae I to VHI as nucleating agents for polymeric materials.
Especially suitable as nucleating agents are those of formula I in which R if n=l, is hydrogen,C,-12alkyl (linear or branched), cyclohexyl, phenyl, biphenyl, C7-Uaralkyl, C7-12alkaryl; if n>l C,_,alkylen (linear or branched), cyclohexylen, phenylen, biphenylen, 4 7 C7-Uaralkylen, CM2alkarylen; R,, R2 are independently selected from hydrogen, CM2alkyl (linear or branched), cyclohexyl, phenyl, biphenyl, C,-Uaralkyl,C7-12alkaryl; R4 hydrogen, C1.8alkyl (linear or branched), cyclohexyl, phenyl, C7- 12aralkyl, C7-12alkaryl; R6 -OH, -NHR4; R7 0 N-R NH 0 n is an integer selected from 1 to 4.
The amount of nucleating agent applied is of from 0,01 to 5%, preferably 0,02 to 0,5%, more preferably 0,02 to 0,3% based on the weight of polymeric material present in the composition.
The use of such nucleating agents leads to enhanced physical properties of polymeric compositions, especially for polyolefins, such properties including improved haze, crystallization temperature and mechanical properties.
Further additives that can be added to a polymeric composition according to the invention include antioxidants, such as sterically hindered phenols, secondary aromatic amines or thioethers, such as described in "Kunststoff-Additive"- G5chter/Mfiller, 3rd Ed., 1990, pp 42-50, the contents of which is incorporated herein by reference; acid scavengers such as sodium-, magnesium- or calcium stearates or -lactates, hydrotalcite, alkoxylated or hydroxylated amines; U.V. stabilizers such as sterically hindered amine (e.g. N-unsubstituted, N-acyl-substituted or N-alkylated 2,2,6,6-tetra-methyl-piperidinyl compounds, also known as hindered amine light stabilizers HALS); U. V. absorbers (e.g.
2-(2'-hydroxy-phenyl)-benztdazoles, 2-hydroxy-benzophenones, 1,3-bis-(2'hydroxybenzoyl) benzene-salicylates, cinnamates or oxalic acid diamides); U.V. quenchers (e.g. benzoates or substituted benzoates), antistatic agents, flameproofing agents, softeners, plasticizers, lubricants, guard agents, metal deactivators, complexants, biocides, fungicides, other nucleating agents, fillers, pigments and other impact modifiers.
Polymeric materials whose properties can be enhanced by the nucleating agent according to the invention, include homopolymers, copolymers and polymer blends of:
cellulose acetate; cellulose acetatobutyrate; cellulose acetopropionate; cresol-formaldehyde resins; carboxyinethylcellulose; cellulose nitrate; cellulose propionate; casein plastics; casein-formaldehyde resins; cellulose triacetate; ethyl cellulose; epoxy resins; methyl cellulose; melamine-formaldehyde resins; polyamide; polyamidimide; polyacrylonitrile; polybut- 1 -ene; polybut-2-ene; polybutylacrylate; poly(butyleneterephthalate); poly(ethyleneterephthalate); polycarbonate;poly(chlorotrifluoro-ethylene);poly(diallylphthalate);polyeth ylene;chlorinated polyethylene; polyether ketone; polyetherimide; polyethyleneoxide; polyethersulfone; polytetrafluoroethylene; phenol- formaldehyde resins; polyimide; polyisobutylene; polyisocyanurate; polymethacrylimide; polymethyImethacrylate; poly(4-methylpent-l-ene); poly((x-methylstyrene); polyoxy-methylene; polyacetal, polypropylene; polyphenylene-ether; polyphenylenesulphide; polyphenylenesulfone; polystyrene; polysulfone; polyurethane; polyvinylacetate; polyvinylalcohol; polyvinylbutyral; chlorinated polyvinylchloride; polyvinylidenefluoride; polyvinylidenechloride; polyvinylfiuoride; polyvinylchloride; polyvinylforinaldehyd; polyvinylcarbazole., polyvinylpyrrolidone; silicon polymers; saturated polyesters., urea-formaldehyde resins; unsaturated polyesters; polyacrylates; polymethacrylate; polyacrylamide; maleinate resins; phenolic resins; aniline resins; furane resins; carbamide resins; epoxide resins and silicon resins.
Examples of suitable copolymers include:
acrylonitrilelbutadienelacrylate; acrylonitrilelbutadienelstyrene; acrylonitrilelmethylmethacrylate; acrylonitrilelstyrenelacrylic ester; acrylonitrilelethylene-propylene-dienelstyrene; acrylonitrilelchlorinated polyethylenelstyrene; ethylenelpropylene; ethylenelpropylene-diene; 9 ethylenelvinylacetate; ethylenelvinylalcohol; ethyleneltetrafluoroethylene; tetrafluoroethylenelhexafiuoropropylene; methacrylatelbutadienelstyrene; melamine/phenolformaldehyde; polyester blockamide; perfluoro-alkoxy-alkane; styrenelbutadiene; styrene/ maleic acid anhydride; styrenela-methylstyrene; vinylchloridelethylenelmethacry late; vinylchloridelethylenelvinylacetate; vinylchloridelmethylmethacrylate; vinylchloridel octylacetate; vinylchloride/vinylacetate and vinylchloridelvinylidenechloride.
Preferred polymeric materials whose properties can be improved by the nucleating agents according to the invention are polyolefins such as polyethylene (e.g. high density polyethylene, low density polyethylene, linear low density polyethylene, or medium density polyethylene), polybutylene, poly-4-methylpentene and copolymers and mixtures/blends thereof as well as polyesters [e. g.poly-(ethylenterephthalate), poly(butylenterephthalate)l,polyamides and polyoxymethylen.
The nucleating agents are especially suitable for the use in polyolefins and their copolymers prepared by using processing catalysts known as Generation H to Generation V catalysts and which may or may have not (preferably have not) been subjected to a catalyst removal step.
By the term "catalyst removal step" used herein is meant a step which comprises, for the purpose of actively removing the catalyst residue contained in the polymerized polyolefins, treating the polyolefins with the compounds which can react with the catalyst residue and inactivate or solubilize the residue, such as e.g. alcohols or water and then removing the inactivated or solubilized catalyst residue by physical means such as filtration, washing, and centrifuging.
Thus, in the case of suspension polymerization, the step of separating the resulting polymer from a dispersion medium such as a solvent or a liquified monomer does not fall under the above-mentioned definition of the catalyst residue-removal step, although the catalyst dissolved in the dispersion medium may be removed at the separation step. The step of adding a small amount of catalyst poisons such as ethers, alcohols, ketones, esters and water to the resulting polymer suspension with a gas such as steam or nitrogen to remove the dispersion medium also does not fall under the above-mentioned definition of the catalyst residue-removal step.
What is meant by Generation I catalysts are titanium halide catalysts and an organo aluminium compound or an organo aluminium halide.
What is meant by Generation H catalysts are Generation I catalysts supported on an organo magnesium compound or based on an organo chromium compound supported on S'02.
What is meant by a Generation M catalyst is a Ziegler type complex catalyst supported on a halogen containing magnesium compound.
What is meant by a Generation IV catalyst is a Generation III catalyst with a silane donor.
What is meant by a Generation V catalyst is a bis-indenyl organo titanium compound supported on alumoxane polymers or are bis-cyclopentadienyltitanium halides activated by aluminium alkyl compounds.
Further generations of highly specific catalysts, especially useful for manufacturing highly stereoregular poly-a-olefins, which are presently under development, belong in the sense of the present invention also to the aforementioned generations of supported catalyst systems. Examples for the microstructure of such highly stereoregular polyolefins are given by syndiotactic polypropylene, isotactic stereoblock polymers, isotactic polypropylene containing steric defects distributed along the polymer chain (so called anisotactic polypropylene) or stereoirregular stereoblock polymers.
Due to the rapid progress in the development of supported newer generation catalyst systems (eg the metallocene catalysts) the commercial significance of these polymers with novel, highly interesting properties increases more and more. However, residues of such further catalyst generations, as long as they contain metals of the 3d, 4d and 5d series of the periodic system supported analogously to the earlier catalyst generations, can also cause disadvantageous properties in the polymer, as long as such residues are not removed physically and are still present in the polymer even in a disactivated form.
These Generations of Catalysts are described in the Twelfth Annual International Conference 1 11 on Advances in the Stabilization and Controlled Degradation of Polymers held in Luzem, Switzerland, 21-23 May 1990 in an article on pages 181 to 196 inclusive by Rolf Millhaupt entitled "New Trends in Polyolefin Catalysts and Influence on Polymer Stability". The contents of this article is incorporated herein by reference and especially Table 1 on page 184 describing the Generation of Catalysts:
TABLE I Polyolerin Catalyst Evolution Generation Example Cat. Act. % Act. Ti Stereoreg. Process Technology (gPP/gTi h atm) (%hept.ins) I TiCI4/AIR3 40 0.01 45% removal of cat. residues and atactic PP TiCYAlEt2C1 30 0.1 92% removal of catalyst residues H Mg(OR2)/TiCI4/AIR3 40000 50% no removal of cat. residues S'02/CP2Cr 40000 HDPE (mainly 14PDEILLDPE) Ill Mod.TiChcat. 5000 1 95% no purification MgC12/TiCI4/AIR3 20000 10 92% + ester donor V M9C12/TiC4/AIR3 40000 18 99% no purification + silane donor no extrusion V Bis-indenyl-TR2on 40000 100 99% novel PPs, narrow MWD (A1CH30)2 in which R is an organo group; HDPE is high density polyethylene, LLDPEislinearlow density polyethyene,Cp is cyclopentadieny],Et is ethyl, PP is polypropylene, MWD is molecular weight distribution and x is an integer above 2.
12 Nucleating agents according to theinvention ffidy h W8d tO thg P81YWhQ ffifit@fial WOM during or after the polymerization step and may be added in solid or molten form, in solution preferably as a liquid concentrate or as a solid masterbatch composition containing 5 to 80% (preferably 10 to 50%) by weight of the nucleating agents and 95 to 20% (preferably 90 to 50%) by weight of a solvent or a solid polymeric material which is identical or compatible with the material to be stabilized.
Nucleating agents according to the invention may be incorporated by known methods into the polymeric material. Of importance is dry-blending of the compositions according to the invention with the polymer fluff or coating shaped polymer particles, e.g. polymers spheres, with the nucleating agents in the form of a molten liquid, a solution or suspension/dispersion. Of particular importance is blending of the compounds with thermoplastic polymers in the melt, for example in a melt blender or during the formation of shaped articles, including films, tubes, fibres and foams by extrusion, injection molding, blow molding, roto-molding, spinning or wire coating. The nucleating agents according to the invention are particularly useful for polypropylene and polyethylene, polyester, polyamide and polyoxymethylene articles of every type.
For avoidance of doubt, where a symbol appears more than once in a formula or once in two different formulae, its significances are independent unless indicated to the contrary. Any group capable of being linear or branched is linear or branched unless indicated to the contrary. Further, where a range is given, the figures defining the range are included therein. The abbreviation t-butyl means tertiary butyl, -C(CH3)3.
Nucleating agents according to the invention improve the thermal andlor mechanical properties of the polymer material without influencing negatively the processing properties of the said polymeric material. But not all properties may be influenced or improved at the same time. This offers the opportunity to modify exactly the properties needed for a certain application by choosing the right nucleating agent. Furthermore the compounds claimed show advantages concerning polymer compatibility over nucleating agents according to the prior art, e. g. the phthalimides claimed in DE 1951632.
13 The invention will now be illustrated by the following examples.
1, Pronaralin of thú jgu ents acc[lrdini, to the i v Example I
Synthesis of 1.3-12henylen-N.N-bis-succinimide To a stirred solution of 0. 1 mol succinic anhydride in 100 mI acetone at WC a solution of 0.05 mol 1,3-phenylenediamine in 60 nil acetone is added during 30 min. After 2 h of additional refluxing the solid is filtered off and dried. It is heated with 2 g sodium acetate and 0.21 moles acetic anhydride for 3 h at 7WC. 100 mI water are added, stirred for 1 h, filtered, washed intensively with hot water and dried. Yield: 72%, mp. 203C Example 2
Synthesis of 1.2-phenylen-N.N-bis-succinimide To a stirred solution of 0. 1 mol succinic anhydride in 100 nil acetone at WC a solution of 0.05 mol 1,2-phenylenediamine in 60 mI acetone is added during 30 min. After 2 h of additional refluxing the solid is filtered off and dried. It is heated with 2 g sodium acetate and 0.21 moles acetic anhydride for 2 h at 7WC. 150 nil water are added, stirred for 1 h, filtered and recrystallized from hot water and dried. Yield: 32%, mp. >25WC.
Example 3
Synthesis of 1.4-12henylene-N.N-bis-suceinimide To a stirred solution of 0.2 mol succinic anhydride in 150 mI acetone a solution of 0. 1 mol 1,4-phenylenediamine in 50 nil acetone is added during 30 min. After 2 h of additional refluxing the solvent is stripped in vacuo and 2 g sodium acetate and 0.3 moles acetic anhydride are added. The reaction mixture is stirred for 3 h at 70Q then the separated colorless crystals are collected 14 on a BUchner funnel, washed with cold water and dried. The raw product is recrystallized from water. Yield: 42%, mp.: 254 - 256'C.
Example 4 -A Synthesis of ethAene-N.N-bis-succinimide To a stirred solution of 0.1 mol succinic anhydride in 50 m]. acetone a solution of 0.05 mol ethylenediamine in 50 mI acetone is added during 30 min. After 1 h of refluxing the solid is filtered off and dried. It is heated with 2 g sodium acetate and 0.21 moles acetic anhydride for 2 h at 7WC. 110 mI water are added, stirred for 1 h, filtered and recrystallized from hot water and dried. Yield: 62%, mp. 255'C.
Example 5
Synthesis of (4.4'-diamino-diphenyl-methane)-N.N-bis-succinimide To a stirred solution of 0.1 mol succinic anhydride in 100 mI acetone a solution of 0.05 mol 4,4'-diamino-diphenyl-methane in 50 mI acetone is added during 30 min. After 1 h of refluxing the solid is filtered off and dried. It is heated with 2 g sodium acetate and 0.21 moles acetic anhydride for 2 h at 7WC. 200 m], water are added, stirred for 1 h, filtered and recrystallized from DMF/water and dried. Yield: 68%, mp. 165C Example 6
Synthesis of ethylene-N.N-bis-(bicyclo[2.2.2]dibenzo-octadiendicarboximide) To a stirred solution of 0.1 mol bicyclo[2.2.2]dibenzo-octadien- dicarboxylic anhydride in 200 ml acetone a solution of 0.05 mol ethylendiamine in 50 mI acetone is added during 30 min. After 1 h of reflux 2 g sodium acetate and 0.21 moles acetic anhydride are added and refluxed for 2.5 h. 200 mI water are added, refluxed for 1 h, filtered, recrystallized from dioxane and dried. Yield: 10%, mp. >250'C.
is Example 7
Synthesi of ethylene-N.N-bis-(norbon-4-en-dicarboximide) To a stirred solution of 0. 1 mol of norbonendicarboxylic anhydride in 100 nil acetone, a solution of 0.05 mols ethylendiamine in 100 nil acetone is slowly added. After refluxing the mixture for 2 h, it is cooled, filtered and dried. This substance is stirred for 2 h at WC with a mixture of 2 g sodium acetate and 10 mI acetic anhydride. 50 ml water are added, stirred for 1 h, filtered and dried. The raw product is recrystallized from toluene. Yield: 43%, mp. 244 - 24PC.
Example 8
Synthesis of 12heny]-N-bis-(1-(hydroxy-methyl)-7-oxo-norbon-4-endicarboximide) To a stirred solution of 0. 1 mol maleic anhydride in 150 mJ, acetone a solution of 0. 1 mol aniline in 50 nil acetone is added during 30 min. After 2 h of reflux 2 g sodium acetate and 0.21 moles acetic anhydride are added and refluxed for 2.5 h. 200 mI water are added, refluxed for 1 h, filtered and recrystallized from cyclohexane and dried. This substance is reacted with 0.075 mols furfurylalcohol in 100 nil toluene at WC for 12 h. The product is filtered off and recrystallized from ethyl acetate. Yield: 58%, mp. 154C Example 9
Synthesis of 1,4-phenylene-N.N-bis-(1-(hydroxy-methyl)-7-oxo-norbon-4-endicarboximide) To a stirred solution of 0.2 mol maleic anhydride in 150 nil acetone a solution of 0.1 mol 1,4-phenylenediamine in 50 nil acetone is added during 30 min. After 1 h of reflux 2 g sodium acetate and 0.21 moles acetic anhydride are added and refluxed for 5 h. 200 mI water are added, refluxed for 1 h., filtered after cooling and recrystallized from DMF and dried. This substance is reacted with 0. 1 mol furfurylalcohol in 100 nil toluene at 7WC for 10 h. The product is filtered off and washed with methanol. Yield: 27%, mp. >2SO'C.
16 Example 10
Synthesis of trimellitic acid imide-anilide To 0,1 mol of the methyl ester of trimellitic acid imide 0,1 mol aniline and 100 mI decalin is added. The mixture is heated until the theoretical amount of methanol is distilled off (12 h). After cooling the precipitated product is filtered off and dried. For further purification the raw product is recrystallized from dimethylacetamide. Yield: 86%, mp. >2500C.
Example 11 = Comparative example according to the prior art
Synthesis of 1,3-12henylen-N,N-bis-12hthalimide To a stirred refluxing solution of 0.2 mol phthalic anhydride in 200 mI acetic acid a solution of 0.1 mol 1,3-phenylenediamine in 100 mI acetic acid is added during 30 min. After 2 h of additional stirring the off white precipitate is collected on a Bilchner funnel, washed neutral with water, acetone and dried. Yield: 62%, mp.: >2SO'C.
II. Production of the nolymeric comDositions accordinLy to the invention Examples 12 - 17 Polymeric compositions containing 100.0 parts 0.05 parts 0.1 parts 0. 1 parts 0. 1 parts 3 rd generation random polypropylene copolymer (MFI 7) Irganox'r 1010 Sandostab'g P-EPQ calcium stearate nucleating agent according to table 1 below are prepared by dry blending the components and extruding this mixture at 21 WC on a Hlindle single screw extruder. The resulting pellets are then injection molded on an Arburg injection 17 molding machine at 245C to form plaques of 100 x 100 x 1 mm3.
Examnles 18 to 22 Polymeric compositions containing 100.0 parts 3 rd generation random polypropylene copolymer (MFI 7) 0.05 parts Irganox2' 10 10 0. 1 parts SandostaW' P-EPQ 0. 1 parts calcium stearate 0.3 parts nucleating agent according to table 1 below are prepared according to the procedure given in the examples 12 to Examples 23 to 26 Polymeric compositions containing 17.
100.0 parts 3 rd generation random polypropylene copolymer (MFI 6) 0.05 parts Irganoxl, 1010 0. 1 parts SandostaW' P-EPQ 0. 1 parts calcium stearate 0.1 parts nucleating agent according to table 1 below are prepared according to the procedure given in the examples 12 to 17.
Examples 7 to 29 Polymeric compositions containing 100.0 parts 3 rd generation random polypropylene copolymer (MFI 6) 0.05 parts Irganox'' 10 10 18 0. 1 parts SandostaW' P-WQ 0. 1 parts calcium stearate 0.3 parts nucleating agent according to table 1 below are prepared according to the procedure given in the examples 12 to 17.
The following properties are determined:
the melt flow index of the granules of the polymeric composition after the first extrusion according to ASTM D - 1238-70/L the yellowness index of the injection molded plaques according to ASTM D - 1925-70 (reflection) the haze values of the injection molded plaques according to ASTM D 1003no the crystallisation onset temperature (COT). For this purpose samples of about 3 mg are punched out of the middle of the plaques and the COT is determined with a Mettler DSC 20 (2000C to 500C, - 1 OOC min-1).
The textile strength (TS) according to DIN 53 455:
From the injection molded plaques samples are cut perpendicular to the injection direction. The values for TS given in the tables below are the averages of 5 measurements.
All test results are summarized in the tables 1 and 2.
19 Table 1
Results of polymeric compositions according to the invention and of a polymeric composition without a nucleating agent Example No. Nucleating agent of Amount of Haze COT TS Example nucleating agent [parts] loci [NImm21 12 1 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
Results of polymeric compositions according to the invention and of a polymeric composition without a nucleating agent Example No. Nucleating agent of Amount of Haze COT TS Example nucleating agent [parts] loci [NImmI 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 1 21 Examples 30 to 31 as well as Comjoarative Examples 32 and 33 Plaques were prepared according to the procedure above, containing 100.0 parts 0.05 parts 0. 1 parts 0. 1 parts 3 rd generation random polypropylene copolymer (MFI 7) Irganox' 1010 Sandostabo P-EPQ calcium stearate 0. 1 or 0.3 parts nucleating agent according to table 1 below The plaques were stored at ambient temperature. Both samples containing the nucleating agents according to the prior art showed significant blooming out of the nucleating agent already after one week, whereas the plaques containing the nucleating agent according to the invention showed no plate out even after two months.
Table 3 Bloomine out - test Example No. Nucleating agent of Amount of Blooming out example nucleating agent [parts] 1 0.1 no 31 1 0.3 no 32 11 0.1 yes 33 11 0.3 yes Nucleating agent according to the prior art, e. g. DE 1951632
22

Claims (8)

Claims
1. A polymeric composition comprising at least one polymeric material and at least one nucleating agent, characterized in that the nucleating agent is selected from the group consisting of compounds of formulae 1 to VIR 1 RI R 1 N-R R 2R 2 0 (1) n RI 1 N.
2 1 0 (H) -R - n 0 RI N- R 2 L _n (III) -R R, RI R 2 NRI R 3 R 3 0 -R (M i n 23 (V) (VI) (VII) (VIII) in which R if n=l, is hydrogen, Cl-24alkyl (linear or branched), C,-12cycloalkyl, C6-24aryl, 0- N p (RP 0 )M R - n R5 X 0 RI N R R5 2 0 N----- 0 0 0 R6 1 N p L_ 0 -R n 1 n R n R 24 C4-24heteroaryl,C7-24aralkyl,C7-24alkaryl, -Cl-24alkylen-R7; particularly hydrogen, Cl-1,alkyl (linear or branched), C,-,cycloalkyl, C6-1,aryl, C4-1.heteroaryl, C7-1.aralkyl, C7-1,alkaryl, -Cl-1.alkylen-R7; preferably hydrogen, Cl-12alkyl (linear or branched), C,-,cycloalkyl, C6-, ,aryl, C4-12heteroaryl, C7-1,aralkyl, C7-1galkaryl, -C,_lgalkylen-R7; more preferably hydrogen, CM2alkyl (linear or branched), cyclohexyl, phenyl, biphenyl,C7-12aralkyl,C7-12alkaryl; if n>l C,-24alkylen (linearorbranched),C5-12Cycloalkylen, C6-24arylen, C4- 24heteroarylen, C7-24aralkylen, C7-24alkarylen; particularly C1.1,alkylen (linear or branched), C,.,cycloalkylen, C64, arylen, C4-1.heteroarylen, C7-1,aralkylen, C7.1,alkarylen; preferably CM2alkylen (linear or branched), C,.,cycloalkylen, C6-1,arylen, C4-12heteroarylen, C7-1.aralkylen, C7-,,alkarylen; more preferably Cl-8alkylen (linear or branched), cyclohexylen, phenylen, biphenylen, C7-12aralkylen,C7-12alkarylen; R,, R2, R3 are independently selected from hydrogen, Cl-24alkyl (linear or branched), CS-12CYcloalkyl, C6-24aryl, C4-24heteroaryl, C7-24aralkyl, C7-24alkaryl, -NHR4; particularly hydrogen, Cl-,8alkyl (linear or branched), C,-,cycloalkyl, C6-1,aryl, C4-Mheteroaryl, C7-Maralkyl, C7-1,alkaryl, -NHR4; preferably hydrogen, Cl-12alkyl (linear or branched), C,.,cycloalkyl, 1 C6.,,aryl, C7-18aralkyl, C7-Malkaryl; more preferably hydrogen, Cl-12alkyl (linear or branched), cyclohexyl, phenyl, biphenyl,C7-,2aralkyl,C7-12alkaryl; R, hydrogen, Cl-24alkyl (linear or branched), C,-,2cycloalkyl, C.,24aryll C4-24heteroaryl, C7-24aralkyl, C7-24alkaryl, -CI.24alkylen-R7; particularly hydrogen, C -,8alkyl (linear or branched), C5-,cycloalkyl, C6-,8aryl, C4-,,heteroaryl, C7A,aralkyl, C7-18alkaryl, -C,-1,alkylen-R7; preferably hydrogen, Cl-8alkyl (linear or branched), C,-,cycloalkyl, C6-1, aryl, C7-1,aralkyl, C7-18alkaryl; more preferably hydrogen, C,-,alkyl (linear or branched), cyclohexyl, phenyl, C7A2aralkyl,C7A2alkaryl; R5 hydrogen, Cl-24alkyl (linear or branched), -CH2-OH; particularly hydrogen, methyl; R6 -OH, -NHR4; R7 0 N-R N H141 0 X -CH2-1 >CH-C,-4alkyl- oder -0-; particularly -CH2-, >CH-CH31 -0_; n is an integer selected from 1 to 6, particularly 1 to 4; m is an integer selected from 0 to 4, particularly 0 to 2; 26 2. A polymeric composition according to claim 1 characterized in that the the nucleating agent is of formula I in which R if n=l, is hydrogen, Cl-12alkYl (linear or branched), cyclohexyl, phenyl, biphenyl, C7-12aralkyl,C7-12alkaryl; if n>l Cl-,alkylen (linear or branched), cyclohexylen, phenylen, biphenylen, C7-,2aralkylen,C7-,2alkarylen; R,, R2 are independently selected from hydrogen, Cl-12alkyl (linear or branched), cyclohexyl, phenyl, biphenyl, C7-12aralkyl, C7-1.alkaryl; n is an integer selected from 1 to 4.
3. A polymeric composition according to any preceding claim in which the amount of nucleating agent applied is of from 0,0 1 to 5%, preferably 0,02 to 0,5 %, more preferably 0,02 to 0,3% by weight based on the polymeric material.
A polymeric composition according to any preceding claim in which the polymeric material is a polyolefin, a polyester, a polyamide, polyoxymethylene, copolymers or blends/mixtures thereof.
5. Process to enhance the degree of crystallinity, the crystallization temperature andlor the mechanical properties of polymeric materials characterized in that a) at least one nucleating agent selected from the group consisting of compounds of formulae I to VUl according to claim 1 is added to the unmolten polymeric material and mixed according to known methods forming a mixture b) said mixture is melted forming a polymeric composition and 27 c) said polymeric composition is processed according to known methods or a) at least one nucleating agent selected from the group consisting of compounds of formulae 1 to VIII according to claim 1 is added to the molten polymeric material and mixed according to known methods forming a polymeric composition and b) said polymeric composition is processed according to known methods.
6. Process according to claim 5 characterized in that the nucleating agent according to claim 2 is added in step a).
Process according to any preceding claim 5 or 6 characterized in that the nucleating agent is added in an amount of from 0,01 to 5%, preferably 0, 02 to 0,5%, more preferably 0,02 to 0,3% by weight based on the polymeric material.
8. Use of a compound of formulae 1 to V1H according to claim 1 as nucleating agent for polymeric material.
GB9511702A 1994-06-13 1995-06-09 Imide nucleating agents for polymers Withdrawn GB2290296A (en)

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US5922793A (en) * 1996-12-27 1999-07-13 Minnesota Mining And Manufacturing Company Modifying agents for polyolefins
US5981636A (en) * 1996-12-27 1999-11-09 3M Innovative Properties Company Modifying agents for polyolefins
US6794433B2 (en) 2001-03-29 2004-09-21 Milliken & Company Metal salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics
US6844382B2 (en) 2001-03-23 2005-01-18 Milliken & Company Gels comprising asymmetric dipolar multi-substituted alditol derivatives
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US6891058B2 (en) 2001-08-21 2005-05-10 Milliken & Company Low-color ultraviolet absorber compounds and compositions thereof
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US7094918B2 (en) 2003-04-28 2006-08-22 Milliken & Company Low-color ultraviolet absorbers for thermoplastic and thermoset high UV wavelength protection applications
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1224721A (en) * 1968-01-16 1971-03-10 Hoechst Ag Thermoplastic moulding compositions based on saturated polyesters
DE1935239B2 (en) * 1969-07-11 1976-02-12 Siemens AG, 1000 Berlin und 8000 München THERMOPLASTIC MOLDING COMPOUNDS BASED ON STABLE, FINE CRYSTALLINE STRUCTURES OF POLYOLEFINS
US4311636A (en) * 1978-12-14 1982-01-19 Basf Aktiengesellschaft Flame-retardant thermoplastic materials and molded parts therefrom
EP0295103A2 (en) * 1987-06-10 1988-12-14 Sumitomo Chemical Company, Limited Thermoplastic resin composition
EP0337814A2 (en) * 1988-04-14 1989-10-18 Sumitomo Chemical Company, Limited Thermoplastic resin composition
EP0373900A2 (en) * 1988-12-12 1990-06-20 Mitsubishi Petrochemical Co., Ltd. Polyphenylene ether resin composition
EP0410514A1 (en) * 1989-07-28 1991-01-30 Dsm N.V. Polyetherimide-polyamide blend
EP0574804A2 (en) * 1992-06-17 1993-12-22 BASF Aktiengesellschaft Maleic acid bisimide cured, soft polyolefin blends

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3386795A (en) * 1964-10-05 1968-06-04 Eastman Kodak Co Polyesters having improved dyeing properties
DE1288787B (en) * 1966-09-08 1969-02-06 Bayer Ag Polyamide molding compounds with compounds containing imide groups as mold release agents
GB1239651A (en) * 1968-02-16 1971-07-21
AT312922B (en) * 1969-07-11 1974-01-25 Siemens Ag Process for producing stable, finely crystalline structures in solid, partially crystalline polyolefins
DE3616431A1 (en) * 1986-05-15 1987-11-19 Hoechst Ag POLYESTER MOLDING MATERIAL AND METHOD FOR THE PRODUCTION THEREOF

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1224721A (en) * 1968-01-16 1971-03-10 Hoechst Ag Thermoplastic moulding compositions based on saturated polyesters
DE1935239B2 (en) * 1969-07-11 1976-02-12 Siemens AG, 1000 Berlin und 8000 München THERMOPLASTIC MOLDING COMPOUNDS BASED ON STABLE, FINE CRYSTALLINE STRUCTURES OF POLYOLEFINS
US4311636A (en) * 1978-12-14 1982-01-19 Basf Aktiengesellschaft Flame-retardant thermoplastic materials and molded parts therefrom
EP0295103A2 (en) * 1987-06-10 1988-12-14 Sumitomo Chemical Company, Limited Thermoplastic resin composition
EP0337814A2 (en) * 1988-04-14 1989-10-18 Sumitomo Chemical Company, Limited Thermoplastic resin composition
EP0373900A2 (en) * 1988-12-12 1990-06-20 Mitsubishi Petrochemical Co., Ltd. Polyphenylene ether resin composition
EP0410514A1 (en) * 1989-07-28 1991-01-30 Dsm N.V. Polyetherimide-polyamide blend
EP0574804A2 (en) * 1992-06-17 1993-12-22 BASF Aktiengesellschaft Maleic acid bisimide cured, soft polyolefin blends
US5362808A (en) * 1992-06-17 1994-11-08 Basf Aktiengesellschaft Bismaleimide-crosslinked, flexible polyolefin blends

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI Abstract Accession No:71-04536S/03 & DE 1935239 B2 *

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US5922793A (en) * 1996-12-27 1999-07-13 Minnesota Mining And Manufacturing Company Modifying agents for polyolefins
US5929146A (en) * 1996-12-27 1999-07-27 Minnesota Mining And Manufacturing Company Modifying agents for polyolefins
US5981636A (en) * 1996-12-27 1999-11-09 3M Innovative Properties Company Modifying agents for polyolefins
US6096811A (en) * 1996-12-27 2000-08-01 3M Innovative Properties Company Modifying agents for polyolefins
WO1998029495A1 (en) * 1996-12-27 1998-07-09 Minnesota Mining And Manufacturing Company Modifying agents for polyolefins
US7655689B2 (en) 2000-06-28 2010-02-02 Bristol-Myers Squibb Company Fused heterocyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function
US6906207B2 (en) 2000-09-01 2005-06-14 Milliken & Company Polymer additive compositions and articles comprising novel fluorinated and alkylated alditol derivatives
US7655688B2 (en) 2001-02-27 2010-02-02 Bristol-Myers Squibb Company Fused cyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function
US6972306B2 (en) 2001-03-23 2005-12-06 Milliken & Company Compositions and articles comprising asymmetric dipolar multi-substituted alditol derivatives
US6844382B2 (en) 2001-03-23 2005-01-18 Milliken & Company Gels comprising asymmetric dipolar multi-substituted alditol derivatives
US6894176B2 (en) 2001-03-23 2005-05-17 Milliken & Company Reaction product mixtures including both symmetric compounds and asymmetric dipolar multi-substituted alditol derivatives
US7144939B2 (en) 2001-03-29 2006-12-05 Milliken & Company Organic nucleating agents that impart very high impact resistance and other beneficial physical properties within polypropylene articles at very low effective amounts
US7332536B2 (en) 2001-03-29 2008-02-19 Milliken & Company Metal salts of hexahydrophthalic acid as nucleating additives for crystalline thermoplastics
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US7094820B2 (en) 2001-05-23 2006-08-22 Milliken & Company Polymer additive compositions comprising highly versatile thermoplastic nucleators
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US6891058B2 (en) 2001-08-21 2005-05-10 Milliken & Company Low-color ultraviolet absorber compounds and compositions thereof
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US6887963B2 (en) 2002-04-12 2005-05-03 Milliken & Company Highly nucleated syndiotactic polypropylene
US7094918B2 (en) 2003-04-28 2006-08-22 Milliken & Company Low-color ultraviolet absorbers for thermoplastic and thermoset high UV wavelength protection applications
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CN114031544B (en) * 2021-10-08 2023-10-20 中山大学 Substituted maleimide fluorescent compound, and preparation and application thereof

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FR2721036A1 (en) 1995-12-15
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GB9411800D0 (en) 1994-08-03
JPH0812809A (en) 1996-01-16
DE19520262A1 (en) 1995-12-14
GB9511702D0 (en) 1995-08-02

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