WO2000052089A1 - Agents de nucléation pour polymères thermoplastiques cristallisables - Google Patents

Agents de nucléation pour polymères thermoplastiques cristallisables Download PDF

Info

Publication number
WO2000052089A1
WO2000052089A1 PCT/EP1999/001429 EP9901429W WO0052089A1 WO 2000052089 A1 WO2000052089 A1 WO 2000052089A1 EP 9901429 W EP9901429 W EP 9901429W WO 0052089 A1 WO0052089 A1 WO 0052089A1
Authority
WO
WIPO (PCT)
Prior art keywords
moieties
integer
nucleators
thermoplastic polymer
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/001429
Other languages
English (en)
Inventor
Hans-Werner Schmidt
Thomas Schildbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Universitaet Bayreuth
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Universitaet Bayreuth
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BR9917195-3A priority Critical patent/BR9917195A/pt
Priority to AU33285/99A priority patent/AU3328599A/en
Priority to MXPA01008864A priority patent/MXPA01008864A/es
Priority to CN99816408A priority patent/CN1350565A/zh
Priority to EP99914479A priority patent/EP1179032A1/fr
Priority to KR1020017011217A priority patent/KR20020010578A/ko
Priority to CA002364504A priority patent/CA2364504A1/fr
Priority to PCT/EP1999/001429 priority patent/WO2000052089A1/fr
Priority to JP2000602710A priority patent/JP2002538255A/ja
Application filed by Ciba Spezialitaetenchemie Holding AG, Universitaet Bayreuth filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of WO2000052089A1 publication Critical patent/WO2000052089A1/fr
Priority to NO20014294A priority patent/NO20014294L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/80—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/56—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • compositions comprising nucleators for crystallizable thermoplastic polymers and in particular to nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds and that are thermally stable, and to the use thereof.
  • nucleating agents and clarifiers are commonly used in industrial practice in combination with crystallizable thermoplastic polymers to reduce processing cycle times or to impart improved physico-chemical characteristics, such as various optical and mechanical properties, as well as to reduce mold shrinkage. Elaborate lists of nucleating agents and clarifiers can be found in, for example, US Pat. No. 3,367,926, Plastics Additives Handbook (4th Ed. Hanser, Kunststoff, 1990, p. 863) .
  • Typical nucleating agents known in the art are metallic salts of aliphatic or aromatic carboxylic acids, aromatic salts, metallic salts of aromatic phosphorus compounds, quinacridones, pigments, polymers having melting points, highly branched polymers containing dendritic branches
  • German Offenlegungsschrift 1951 632 discloses the use of solid, crystalline aromatic carboxilicimide-diphthalimides and N-substituted aromatic carboxylic imide-diphthalimides .
  • nucleating agents and clarifiers dissolve in the polymer melt (R. Schlotmann and R. Walker, Kunststoffe, vol. 86, p. 1002 (1996)), which was found to be effective for improving dispersion of these additives.
  • Most popular have become compounds that are based on D-sorbitol, which belongs to the general chemical family of carbohydrates, that is defined as polyhydroxy aldehydes, polyhydroxy ketones, or compounds that can be hydrolyzed to them (R. T. Morrion and Robert Neilson Boyd, Organic Chemistry, 2nd. Ed. , (Allyn and Bacon, Inc., Boston), 1966, p. 983).
  • compositions which comprise: (i) one or more nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds ;
  • thermoplastic polymers which may optionally include common additives and fillers.
  • present invention relates to A composition comprising (i) a crystallizable thermoplastic polymer and (ii) one or more nucleators of the formula
  • (B ' )z (1) wherein: x is an integer from two to seven; y is an integer from zero to four; z is an integer from zero to four; the sum x + y + z equals an integer from three to seven; m is an integer from one to three; and wherein A is a center that is covalently bonded with moieties B, B' or X' , or combinations thereof; wherein said moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; wherein moieties X and X' are compatible with said crystallizable thermoplastic polymer; and wherein X is covalently bonded to B.
  • compositions of a crystallizable thermoplastic polymer and a nucleator that comprises moieties that are capable of forming intermolecular hydrogen bonds and moieties that are compatible with the crystallizable thermoplastic polymer are also useful as nucleator.
  • compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, upon cooling from the melt, their peak temperature of crystallization is at least about 3 °C higher than the peak temperature of crystallization of the neat -that is nucleating agent free- thermoplastic polymer.
  • compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, after cooling from the melt, the size of the spherulites in the crystallized polymer is less than 50 % of the size of the spherulites in the neat crystallized thermoplastic polymer.
  • Still yet another aspect of the present invention relates to compositions of a crystallizable thermoplastic polymer and one or more nucleators that are of reduced haze when compared to the neat crystallized thermoplastic polymer.
  • compositions of a crystallizable thermoplastic polymer and one or more nucleators that are of enhanced thermal stability.
  • Still other aspects of the present invention relate to a novel process for enhancing the rate of crystallization of a melt of a crystallizable thermoplastic polymer, which comprises adding to said melt an effective amount of the nucleators of this invention, and to products made according to that novel process .
  • Still yet another object of the present invention is to provide products made from crystallizable thermoplastic polymers that comprise an effective amount of the nucleators of this invention.
  • FIG. 1 is an optical photomicrograph of a film of isotactic polypropylene which does not contain a nucleating agent. The film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C. Magnification 120 times.
  • FIG. 2 is an optical photomicrograph of a film of isotactic polypropylene which contains 0.75 % by weight of the nucleating agent tris[3,4- bis (decyloxy)phenylene-carbonylimino-l, 4-phenylene] amine,
  • compound 1-1 of Table 1 (hereinafter also referred to as compound 1-1 of Table 1) .
  • the film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C . Magnification 120 times.
  • FIG. 3 depicts Thermo-Gravimetric -Analysis (TGA) records carried out under nitrogen on compounds 1-5 (3) and 1-7 (2) in Table 1 and Millad 3988 (1) showing the enhanced thermal stability of the compounds according to the present invention.
  • TGA Thermo-Gravimetric -Analysis
  • the nucleators for crystallizable thermoplastic polymers according to this invention are of the following general schematic formula:
  • A is a center that is covalently bonded to moieties B, B' or X' , or combinations thereof, wherein the moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; and wherein the moieties X and X' are compatible with the crystallizable thermoplastic polymer, and wherein X is covalently bonded to B.
  • the role of the center moiety A is to provide a means to connect a plurality of moieties B, B' , or X' and combinations thereof that are beneficial for the formation of structures that induce nucleation of the crystallizable thermoplastic polymer.
  • Preferred nucleators for crystallizable thermoplastic polymers according to this invention are those of the schematic formula (1) , wherein: x is an integer from three to six; y is an integer from zero to three; z is an integer from zero to two; the sum x + y + z equals an integer from three to seven; m is the integer one or two .
  • nucleators are those of the formula (1) wherein : x is the integer three or four; y is an integer from zero to two; z is the integer zero or one; the sum x + y + z equals an integer from three to six; m is the integer one or two.
  • nucleators for crystallizable thermoplastic polymers are of the general schematic formula (1) , wherein: x is three; y is an integer from zero to two; z is the integer zero or one; the sum x + y + z equals an integer from three to six; m is the integer one or two.
  • moieties that are useful as the center A of the nucleators according to the present invention are carbon, nitrogen, phosphorus, boron and silicon, without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 4, 5, 6 or 7 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, and without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them.
  • Preferred moieties are carbon and nitrogen, without and with one or more aromatic, cycloaliphatic or -
  • more preferred moieties are carbon and nitrogen, with one or more aromatic or cycloaliphatic links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 6 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more nitrogen atoms, without and with one or more aromatic, cycloaliphatic or -(CH 2 ) P - links, and combinations thereof, connected to them, where p is 1 or 2.
  • the moieties B and B' of the nucleators according to the present invention are those moieties that are capable of forming one or more intermolecular hydrogen bonds between the nucleator molecules of which they are part.
  • a hydrogen bond is defined as that bond that is due to the electrostatic interaction between a hydrogen atom and a strong electronegative element of small atomic radius, such as fluor, oxygen and nitrogen, and to a lesser extend, chlorine and sulfur (Lehrbuch der Organischen Chemie, H. Beyer; Hirzel, Stuttgart, 1976, p. 105, 106) .
  • the function of the moieties B and B' is to induce and guide and stabilize the formation of the structures that are beneficial for nucleation of the crystallizable thermoplastic polymer.
  • moieties B which may be the same or different at each occurrence, are those that comprise esters, thioester, ethers, thioethers, ketones, secondary and tertiary amines, amides, imides , imines, azo, azoxy, ureas, urethanes, thiourethanes, sulfonamides and the like.
  • Preferred moieties B which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides, imines, ureas, urethanes, thiourethanes, sulfonamides and the like.
  • more preferred moieties B which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides and sulfonamides.
  • Especially preferred are those that comprise amide units.
  • moieties B' which may be the same or different at each occurrence, are those moieties that comprise acids such as carboxylic acids, sulfonic acids, alcohols, phenols, thiols, amines, acetamides, cyano groups, hydrazine, and the like.
  • the nucleators for crystallizable thermoplastic polymers according to the present invention comprise moieties X and X' , the function of which is to compatibilize with, and assist in dispersing of the nucleators within the crystallizable thermoplastic polymers. Hence, selection of the particular chemical nature of the moieties X and X' is dependent on the choice of the crystallizable thermoplastic polymer. In general, nucleators comprising moieties X and X' that are of a polar nature are used in combination with the more polar thermoplastic polymers comprising polar groups. Nucleators comprising less polar moieties X and X' are used in combination with less polar thermoplastic polymers comprising few or no polar groups.
  • the moieties X and X' which may or may not be chiral are the same or different at each occurrence and are selected from the group consisting of: H, linear and branched alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, alkylthioalkyl, each having from 1 to about 20 carbon atoms; linear and branched alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl , alkylsulfonyl, alkoxycarbonyl , carboxylic acid, where the alkyl or alkoxy each has from 1 to about 20 carbon atoms; alkyl having from 1 to about 20 carbon atoms substituted with one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano, diazo, or epoxy moieties; one or more substituted and unsubstituted single and fused 3, 4, 5, 6 or 7 membered aromatic and ali
  • the above structures are also given according the notation of the schematic formula (1) .
  • the above nucleators are used in combination with weakly, or non- polar, crystallizable thermoplastic polymers, such as isotactic polypropylene, and copolymers thereof.
  • the nucleators according to the present invention have thermal properties, such as melting temperatures, that may vary widely, depending on the roome structure of the nucleator.
  • the nucleators preferably have a solidification temperature, i.e. that temperature or temperature range in which the molten or dissolved nucleator forms an molecular aggregate or solid, is equal to, or exceeds the temperature at which the crystallizable thermoplastic polymer crystallizes in the absence of the nucleator of the present invention.
  • Particularly excluded from the present invention are those structures that are based on carbohydrates, or comprise carbohydrate units, such as, for example, sorbitol and its derivatives. Such structures generally are well-known, and suffer from limited thermal stability, and, hence, are of restricted use as nucleating agents or clarifiers, especially for crystallizable thermoplastic polymers that have high melting temperatures or softening points, which generally require high processing temperatures.
  • the compositions according to the present invention have high decomposition temperatures, typically above 230 °C.
  • the amount of the nucleator according to the present invention added to a crystallizable thermoplastic polymer is an "effective amount” .
  • an “effective amount” is an amount which is sufficient to increase the crystallization peak temperature of the polymer by at least 3 °C.
  • Such amounts will normally correspond to amounts of conventional nucleating agents .
  • the amount of the nucleator employed is in the range from about 0.005 weight percent to about 20 weight percent based on the total weight of the polymer in the composition, and in the particularly preferred embodiments of this invention is from about 0.005 weight percent to about 10 weight percent, on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments where the amount of nucleator employed is from about 0.005 weight percent to about 5 weight percent based on the total weight of the polymer in the composition according to the present invention.
  • composition according to the present inventions are characterized in that the size of polymer spherulites in the thermoplastic polymer composition typically is less than 50 % of the size of spherulites in neat crystallized thermoplastic polymer that is void of the present nucleators; and, as a result, the former are of lower haze in comparison with the latter.
  • the crystallizable thermoplastic polymers for use in the practice of this invention may vary widely, and are selected for the particular end uses of the product comprising the compositions of the present invention.
  • the crystallizable thermoplastic polymers useful in the present invention include all thermoplastic polymers and copolymers commonly used in plastic products .
  • polyolefins such as polyethylenes, stereoregular polypropylenes, ethylene-propylene copolymers, stereoregular polystyrenes, polynorbonene, polyisobutylene, poly (1-butene) , poly (3 -methyl-1-butene) , poly (1-pentene) , poly ( 4-methyl-1-pentene) , poly (1-hexene) , poly (5-methyl-1-hexene) , poly (2-methylstyrene) , poly(4- methoxy styrene) and the like, and copolymers thereof, aromatic or aliphatic polyoxides such as polyoxymethylene, poly (ethylene oxide), poly ( tetra-methyloxide) , polypropylene oxide) , polyphenylene oxides, polysulfides such as poly (propylene sulfide) , poly (phenylene sulfide) , poly (phenylene sulfide
  • compositions according to the present invention may optionally include one or more other components which are additives commonly employed with thermoplastic resins.
  • Such optional components include fillers, reinforcing components, plasticizers, dispersion aids, impact modifiers, chain extenders, colorants, mold release agents, metal deactivators, antioxidants, light stabilizers, lubricants, antistatic agents, fire retardants, fluorescent whitening agents, biostabilizers, chemical blowing agents, cross-linking agents and other nucleating agents .
  • These optional components are well known to those skilled in the art, and are described in standard texts and handbooks such as Plastics Additives Handbook (4th Ed. Hanser, Kunststoff, 1990) .
  • compositions according to the present invention can be prepared by blending or mixing the essential ingredients, and other optional components as uniformly as possible employing conventional compounding means.
  • Appropriate compounding means such as extrusion, batch blending and the like, are well known in the art and will not be described here in detail.
  • all or a portion of the various components can be masterbatched or preblended in the melt or in an appropriately selected solvent .
  • compositions according to the present invention are outstandingly suitable for the production of films, fibers, containers, coatings, parts, membranes, rods, tubes, fabrics, and foams and the like that are of improved clarity and mechanical properties, and that are manufactured at reduced cycling times.
  • the present invention further relates to a process for enhancing the rate of crystallization of a crystallizable thermoplastic polymer that comprises the addition of an amount between about 0.001 percent by weight and about 20 percent by weight of one or more nucleators to yield the above shaped objects .
  • the composition of the present invention comprises the following combinations : one or more polyolefins, such as polyethylenes, stereoregular polypropylenes and ethylene-propylene copolymers and one or more of the following nucleators of formula (1) , wherein: i) the center A is a single atom selected from the group consisting of nitrogen and phosphorus; or A is an unsubstituted or substituted, single or fused 5 or 6 membered heterocyclic aromatic or nonaromatic ring, which ring includes carbon and one or more atoms such as nitrogen, sulfur or oxygen, or combinations thereof; and ii) moieties B that are the same at each occurrence and comprise amides or ureas; or moieties B that are not the same at each occurrence and comprise at least 2 amides and at least 1 moiety selected from the group consisting of esters and ureas; or moieties B that are not the same at each occurrence and that comprise at least 2 ureas and at least 1
  • the compounds of the formula (1) can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry] , published by Georg Thie e, Stuttgart) , under reaction conditions which are known. In carrying out these reactions, it is also possible to take advantage of variants known per se which are not specifically mentioned here.
  • the starting substances can, if so desired also be formed in situ, by not isolating them out of the reaction mixture but immediately reacting them further to the compounds of the formula (1) .
  • Example G 1.40 g (5.8 mmol) 3 , 5-diaminobenzoic acid-4- methylphenyl ester was added under inert atmosphere to 30 ml of dry NMP and 1.3 ml of dry pyridine and cooled to 5 °C. 2.16 g (14.0 mmol) phenylacetyl chloride was added. The reaction mixture was heated to 90 °C . After 2 hours the reaction mixture was added to 400 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives 3 , 5-bis [benzylcarbonylimino]benzoic acid-4- methylphenyl ester. (Table I, No. VII). m.p.: 212 °C.
  • powdered additive About 50 mg (1 % by weight) of powdered additive was added to about 4.95 g of the powdered isotactic polypropylene (Aldrich Chemical Co . ) , tumble mixed and ground in a mortar. Portions of this mixture were heated to 220 °C, unless indicated otherwise, for a period of about 5 to 10 min, and subsequently cooled down to room temperature. Polypropylene alone was similarly treated to produce a blank control sample. The loading of the additives was 1 % by weight unless otherwise noted.
  • a Perkin-Elmer DSC instrument (Model DSC 7), operated in a dry nitrogen atmosphere, was used for the analysis of the crystallization behavior of the various mixtures and control samples, according to standard procedures. About 5 to 10 mg of sample was sealed into an aluminium cup, heated from 130 °C to 230 °C at a rate of 10 °C/min, held at 220 °C for 5 min, and then subsequently cooled at a rate of 10 °C/min to 50 °C.
  • the data represented as crystallization peak temperatures (T c ) are the peak temperatures of the exotherms in the thermograms that were recorded upon cooling.
  • Selected samples were produced by forming a film from the melt by compression molding at 210 °C and subsequent cooling at a rate of 10 °C/min. These samples were examined in a polarizing optical microscope (Leitz Laborlux 12-Pol) under crossed Nicols in transmitted light.
  • Tris [3 , 4-bis (decyloxy)phenylene-carbonylimino- 1, 4-phenylene] amine, (compound 1-1 in Table 1) (1 % by weight) was mixed with polypropylene, using the mixing procedure A. Both the neat polypropylene reference sample and the mixture were analyzed by Differential Scanning Calorimetry. The crystallization peak temperature of the mixture is 12.4 °C higher than that of the neat control sample .
  • this difference between the crystallization temperatures of a mixture according to the present invention and that of the control sample is designated ⁇ T, which equals 12.4 °C in the present example .
  • Examples 1 and 2 were repeated with various compounds that were mixed with polypropylene, using either mixing method A (compounds 1-1 and 1-2) or method B (Bl: compounds 1-3, 1-6, 1-8, 1-9, II-l, III-l, III-2, III-3, III-4 and III-5; B2 : compounds 1-4, 1-5, 1-7, IV-1, IV-2, V-l, V-2, VI, VII and VIII) .
  • Table 1 collects results that were measured using DSC. Table 1:
  • FIG. 1 is an optical photomicrograph of polypropylene which does not contain a nucleating agent.
  • FIG. 2 is an optical photomicrograph of isotactic polypropylene which contains 1 % by weight of compound 1-1.
  • FIG. 3 depicts their respective TGA-curves showing the enhanced thermal stability of the compounds according to the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des compositions renfermant des agents de nucléation pour des polymères thermoplastiques cristallisables, et en particulier des composés chimiques utilisés comme agents de nucléation qui renferment des fragments thermiquement stables capables de former des liaisons hydrogènes intermoléculaires. Cette invention concerne également l'utilisation de ces compositions.
PCT/EP1999/001429 1999-03-05 1999-03-05 Agents de nucléation pour polymères thermoplastiques cristallisables Ceased WO2000052089A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PCT/EP1999/001429 WO2000052089A1 (fr) 1999-03-05 1999-03-05 Agents de nucléation pour polymères thermoplastiques cristallisables
AU33285/99A AU3328599A (en) 1999-03-05 1999-03-05 Nucleators for crystallizable thermoplastic polymers
MXPA01008864A MXPA01008864A (es) 1999-03-05 1999-03-05 Agentes de nucleacion para polimeros termoplasticos.
CN99816408A CN1350565A (zh) 1999-03-05 1999-03-05 可结晶热塑性聚合物用成核剂
EP99914479A EP1179032A1 (fr) 1999-03-05 1999-03-05 Agents de nucl ation pour polym res thermoplastiques cristallisables
BR9917195-3A BR9917195A (pt) 1999-03-05 1999-03-05 Nucleadores para polìmeros termoplásticoscristalizáveis
CA002364504A CA2364504A1 (fr) 1999-03-05 1999-03-05 Agents de nucleation pour polymeres thermoplastiques cristallisables
KR1020017011217A KR20020010578A (ko) 1999-03-05 1999-03-05 결정성 열가소성 중합체용 핵생성제
JP2000602710A JP2002538255A (ja) 1999-03-05 1999-03-05 結晶性熱可塑性ポリマーのための核剤
NO20014294A NO20014294L (no) 1999-03-05 2001-09-04 Nukleatorer for krystalliserbare termoplastiske polymerer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1999/001429 WO2000052089A1 (fr) 1999-03-05 1999-03-05 Agents de nucléation pour polymères thermoplastiques cristallisables

Publications (1)

Publication Number Publication Date
WO2000052089A1 true WO2000052089A1 (fr) 2000-09-08

Family

ID=8167233

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/001429 Ceased WO2000052089A1 (fr) 1999-03-05 1999-03-05 Agents de nucléation pour polymères thermoplastiques cristallisables

Country Status (10)

Country Link
EP (1) EP1179032A1 (fr)
JP (1) JP2002538255A (fr)
KR (1) KR20020010578A (fr)
CN (1) CN1350565A (fr)
AU (1) AU3328599A (fr)
BR (1) BR9917195A (fr)
CA (1) CA2364504A1 (fr)
MX (1) MXPA01008864A (fr)
NO (1) NO20014294L (fr)
WO (1) WO2000052089A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005528498A (ja) * 2002-05-30 2005-09-22 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド β−結晶ポリプロピレン
CN100336853C (zh) * 2001-05-17 2007-09-12 美利肯公司 低收缩聚丙烯纤维、由其制得的织物及它们的制备方法
JP2008050617A (ja) * 2000-12-06 2008-03-06 Ciba Specialty Chem Holding Inc ポリプロピレン樹脂組成物
US7696380B2 (en) 2003-10-17 2010-04-13 New Japan Chemical Co., Ltd. Amide-based compound, polyolefin resin composition and molded product
US7745661B2 (en) 2005-04-07 2010-06-29 New Japan Chemical Co., Ltd. Process for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide)
WO2010104628A1 (fr) * 2009-03-12 2010-09-16 Exxonmobil Chemical Patents Inc. Mélanges maîtres et films de polyoléfine
US8492468B2 (en) 2010-06-04 2013-07-23 Sumitomo Chemical Company, Limited Polypropylene resin composition

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0711647B1 (pt) * 2006-05-16 2018-06-05 Basf Schweiz Ag Películas sopradas por mono e múltiplas camadas
US9580575B2 (en) * 2013-09-23 2017-02-28 Milliken & Company Polyethylene articles
KR102182908B1 (ko) * 2016-03-09 2020-11-25 밀리켄 앤드 캄파니 트리스아미드 화합물 및 이를 포함하는 조성물
JP7260271B2 (ja) * 2018-09-21 2023-04-18 保土谷化学工業株式会社 核剤、該核剤を含有する樹脂組成物、および該樹脂組成物を含有する成形体
CN113861058B (zh) * 2021-09-18 2023-07-25 北京理工大学 一种三酰胺基甲苯类成核剂、制备方法及使用方法
CN113979888A (zh) * 2021-09-18 2022-01-28 北京理工大学 一种制备n,n,n-三特戊酰化-1,3,5-三氨基苯的方法
CN119039172A (zh) * 2024-08-22 2024-11-29 北京理工大学 一种n,n’,n’’-三酰基-1,3,5-三（对-氨基苯基）苯化合物、制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367926A (en) * 1964-03-25 1968-02-06 Dow Chemical Co Modification of crystalline structure of crystallizable high polymers
US4294747A (en) * 1979-09-24 1981-10-13 Milliken Research Corporation Shapeable thermoplastic resin composition containing cyclic acetal
JPS60252655A (ja) * 1984-05-28 1985-12-13 Mitsubishi Petrochem Co Ltd 成形性を改良したポリフエニレンエ−テル組成物
EP0278409A2 (fr) * 1987-02-07 1988-08-17 Idemitsu Petrochemical Co. Ltd. Composition de polyoléfine renforcée de fibres de verre
US5278216A (en) * 1989-04-18 1994-01-11 Mitsui Toatsu Chemicals, Incorporated Syndiotactic polypropylene resin composition
EP0780428A1 (fr) * 1995-12-21 1997-06-25 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation d'une pièce moulée en polyester aliphatique ainsi qu'une pièce moulée à partir de ce procédé
GB2310860A (en) * 1996-03-08 1997-09-10 Eastman Kodak Co Stable release agents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367926A (en) * 1964-03-25 1968-02-06 Dow Chemical Co Modification of crystalline structure of crystallizable high polymers
US4294747A (en) * 1979-09-24 1981-10-13 Milliken Research Corporation Shapeable thermoplastic resin composition containing cyclic acetal
JPS60252655A (ja) * 1984-05-28 1985-12-13 Mitsubishi Petrochem Co Ltd 成形性を改良したポリフエニレンエ−テル組成物
EP0278409A2 (fr) * 1987-02-07 1988-08-17 Idemitsu Petrochemical Co. Ltd. Composition de polyoléfine renforcée de fibres de verre
US5278216A (en) * 1989-04-18 1994-01-11 Mitsui Toatsu Chemicals, Incorporated Syndiotactic polypropylene resin composition
EP0780428A1 (fr) * 1995-12-21 1997-06-25 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation d'une pièce moulée en polyester aliphatique ainsi qu'une pièce moulée à partir de ce procédé
GB2310860A (en) * 1996-03-08 1997-09-10 Eastman Kodak Co Stable release agents

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 125, no. 24, 9 December 1996, Columbus, Ohio, US; abstract no. 309830, XP002073173 *
DATABASE BEILSTEIN XP002073174 *
DATABASE BEILSTEIN XP002073175 *
DATABASE BEILSTEIN XP002073176 *
DATABASE BEILSTEIN XP002073177 *
DATABASE BEILSTEIN XP002073178 *
DATABASE BEILSTEIN XP002073179 *
DATABASE BEILSTEIN XP002073180 *
YASUDA,Y. ET AL.: "4,4',4'',", ADV.MATER., vol. 8, no. 9, 1996, pages 740 - 741 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008050617A (ja) * 2000-12-06 2008-03-06 Ciba Specialty Chem Holding Inc ポリプロピレン樹脂組成物
US7479515B2 (en) 2000-12-06 2009-01-20 Ciba Specialty Chemicals Corp. Polypropylene resin compositions
CN100336853C (zh) * 2001-05-17 2007-09-12 美利肯公司 低收缩聚丙烯纤维、由其制得的织物及它们的制备方法
JP2005528498A (ja) * 2002-05-30 2005-09-22 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド β−結晶ポリプロピレン
US7696380B2 (en) 2003-10-17 2010-04-13 New Japan Chemical Co., Ltd. Amide-based compound, polyolefin resin composition and molded product
US7745661B2 (en) 2005-04-07 2010-06-29 New Japan Chemical Co., Ltd. Process for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide)
WO2010104628A1 (fr) * 2009-03-12 2010-09-16 Exxonmobil Chemical Patents Inc. Mélanges maîtres et films de polyoléfine
US8492468B2 (en) 2010-06-04 2013-07-23 Sumitomo Chemical Company, Limited Polypropylene resin composition

Also Published As

Publication number Publication date
MXPA01008864A (es) 2002-10-23
BR9917195A (pt) 2001-12-26
NO20014294L (no) 2001-10-25
CN1350565A (zh) 2002-05-22
JP2002538255A (ja) 2002-11-12
EP1179032A1 (fr) 2002-02-13
NO20014294D0 (no) 2001-09-04
KR20020010578A (ko) 2002-02-04
AU3328599A (en) 2000-09-21
CA2364504A1 (fr) 2000-09-08

Similar Documents

Publication Publication Date Title
EP0940431A1 (fr) Agents de nucléation de polymères cristallisables et thermoplastiques
EP1179032A1 (fr) Agents de nucl ation pour polym res thermoplastiques cristallisables
JP3826187B2 (ja) ポリオレフィン用改質剤
US7750113B2 (en) Supramolecular polymers
US4142029A (en) Bis-tetrazoles as chemical blowing agents for foaming thermoplastic resins
KR910009274B1 (ko) 향상된 투명성과 내산화성을 지닌 폴리올레핀 조성물
US8680186B2 (en) Semi-crystalline polyolefin composition, method of producing the same, and articles made therefrom
FR2479216A1 (fr) Derives amidiques de polyalkyl-piperidines, leur application comme stabilisants a la lumiere pour des matieres organiques, et leur utilisation comme corps intermediaires pour la preparation de stabilisants a la lumiere oligomeres
JP2001507730A (ja) ポリオレフィン用改質剤
US6043303A (en) Hexagonal crystals of diacetals, nucleating agent comprising said hexagonal crystal, polyolefin resin composition and molding containing said hexagonal crystals, and method for molding said composition
US6642290B1 (en) Highly nucleated syndiotactic polypropylene
JPS6243449A (ja) フタルイミドエステルを含有するポリエステル組成物
US6703434B2 (en) Methods of producing highly nucleated syndiotactic polypropylene
KR970001483B1 (ko) 트리아진게 화합물
WO1993009121A1 (fr) Agents de nucleation a base de polyol contenant des polyolefines et articles composes de ces substances
US6887963B2 (en) Highly nucleated syndiotactic polypropylene
US4728685A (en) Rapid-crystallizing polyphenylene sulphide compositions
JPH04211452A (ja) 加工性の改良されたポリアミド成型材料
US5283275A (en) Clarifiers for polyolefins and polyolefin compositions containing same
JPH07188246A (ja) テトラオキサスピロ化合物およびその利用
US5659064A (en) Hydrazone intermediates
JPH03140366A (ja) ビスフエノール類を含む高ガラス転移温度ポリアミド成型配合物
US20070112105A1 (en) Substituted thiophenylidene alditol derivatives and compositions
US4125536A (en) Pyrolysis product of N-substituted-1-cyclohexene-1,2-dicarboximides
KR100418564B1 (ko) 메타파라디메틸벤질리덴 파라메틸벤질리덴 솔비톨을 함유하는 플라스틱 핵제 및 그의 제조방법

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99816408.9

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1999914479

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2364504

Country of ref document: CA

Ref document number: 2364504

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/008864

Country of ref document: MX

Ref document number: 1020017011217

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2000 602710

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 33285/99

Country of ref document: AU

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 09914700

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1020017011217

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1999914479

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999914479

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020017011217

Country of ref document: KR