WO2015022248A1 - Agents de nucléation pour polyesters et polyoléfines - Google Patents

Agents de nucléation pour polyesters et polyoléfines Download PDF

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WO2015022248A1
WO2015022248A1 PCT/EP2014/066897 EP2014066897W WO2015022248A1 WO 2015022248 A1 WO2015022248 A1 WO 2015022248A1 EP 2014066897 W EP2014066897 W EP 2014066897W WO 2015022248 A1 WO2015022248 A1 WO 2015022248A1
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ester
carbon atoms
hydrogen bonding
motif
polymer
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PCT/EP2014/066897
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English (en)
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Katrien Bernaerts
Jules Harings
Carolus WILSENS
Yogesh DESHMUKH
Dietmar AUHL
Sanjay Rastogi
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Maastricht University
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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates

Definitions

  • polystyrene resin polystyrene resin
  • polyolefins and polyesters are very popular materials.
  • the main factors responsible for the growth in consumption are the inherent versatility of these polymers and the ease with which they can be processed.
  • Such polymers can be used for a large variety of products, as e.g. packaging products, textiles, stationary, containers and automotive components.
  • the properties and the morphology of the semi-crystalline polymers mainly depend on the molecular structure, processing additives and the processing conditions.
  • lamellae organize from a primary nucleus to form complex macro-structures called spherulites. These spherulites continue to grow until they impinge on an adjacent spherulite at which point the growth ceases.
  • Properties of the polymers including optical and physical characteristics depend on the end size of the spherulite structures, i.e. the crystal structure of the polymer.
  • nucleation is basically the formation of a focal center around which the lamellae can organize themselves. These nucleation sites can either be imperfections or inconsistencies in a polymer chain or foreign particles in the melt. Nucleation involves the addition of a foreign phase presenting a new surface on which crystal growth can occur. Typically, this foreign phase takes the form of a nucleating agent.
  • nucleated polymers In nucleated polymers, crystallization occurs earlier in the cooling process and happens at a faster rate. This allows decreased cooling time of the polymer. Also, nucleation density is much higher and crystal spherulite size is much smaller. The crystallization status also influences other semi-crystalline polymer properties, as e.g. transparency.
  • US 2005209377A1 discloses the use of nucleants for the crystallization of thermoplastic polyester, especially polybutylene succinates, polycaprolactones, polyhydroxyalkanoates, polyglycolic acids, polylactic acids, and combinations thereof.
  • the nucleant includes compounds with a nitrogen-containing
  • heteroaromatic core e.g. pyridine, pyrimidine, pyrazine, pyridazine, triazine, or imidazole.
  • pyridine e.g. pyridine, pyrimidine, pyrazine, pyridazine, triazine, or imidazole.
  • it contains the triazine cyanuric acid.
  • CN101857715(A) achieves the quick crystallization of PLA with an organic compound comprising four amide motifs and modified benzyl side arms.
  • the use of dicarboxylic acid chlorides as starting compounds makes the synthesis of this model compound prone to side reactions resulting in multiple time consuming purification steps.
  • these nucleating agents use benzoic hydrazide as starting compound which is known to be highly toxic and is suspected to be carcinogenic.
  • EP1477526A1 describes the use of amide compounds in the crystallization of PLA resins. Potentially, also a compound with multiple amide motifs can be used. However, the nucleating agent has an aromatic side arm. Such side arms can cause yellowing of the final polymer product and compounds comprising them are often toxic.
  • amide motifs reside in one molecular plane because no linker is placed between the amide motifs or (e.g. in the case of ethylene bisstearamide) an unmodified ethyl linker.
  • Ethylene bisstearamide has also been described in WO2009/064851 A2.
  • EP2319882A1 pertains to nucleating agents comprising e.g. four carbamate (i.e. urethane) groups, or one hydrogen bonding motif (e.g. hydrazides) with e.g. cycloaliphatic side arms.
  • US201 1 13101330 discloses a polypropylene resin composition comprising a polypropylene polyethylene copolymer and an amide compound as nucleating agent.
  • the amide groups are substituents of an aromatic ring or in the form of a propane tricarboxylic acid triamide.
  • EP0557721 and EP1431335 describe bisamide compounds for the crystallization of polypropylene.
  • the side arms comprise aromatic or cyclic groups.
  • Aromatic arms have the disadvantage that they can cause yellowing of the final polymer product and compounds comprising them are often toxic.
  • the combination of nucleation efficiency, decrease in crystallization half-time, and desired transparency of the product in the presence of the nucleating agents in the prior art is not optimal.
  • the aim of present invention is to overcome at least in part the disadvantages that lie in the use of known nucleating agents and to provide alternative nucleating agents for polyesters and polyolefins.
  • the present invention describes using a class of compounds as nucleating agents for polyesters and polyolefins, which compounds have a high nucleation efficiency and a melting temperature which can be adjusted to the melting temperature of the specific polymer. Also, due to the use of the nucleating agents the half-time of crystallization of the polymer is decreased.
  • the nucleating agents of present invention allow for a high onset crystallization temperature and a high degree of crystallinity. Additionally, the inventive use of the nucleating agents results in good transparency, good structural order of the crystallized polymers and polymers which retain their molar mass.
  • Another objective of this invention is to provide a process for crystallization of polyester or polyolefins wherein the nucleating agent has a high nucleation efficiency. Furthermore, a composition of the polymer and nucleating agents with high nucleation efficiency is provided and films, moldings, composite materials, extrusion- or injection-molded products or elongated products comprising the composition.
  • the compound comprises a core and side arms R and FT flanking the core, which core consists of two hydrogen bonding motifs and a linker connecting said hydrogen bonding motifs, wherein the hydrogen bonding motifs are independently of each other chosen from an amide motif, an oxalamide motif, a hydrazide motif, an urethane motif or an urea motif;
  • linker does not comprise any of said hydrogen bonding motifs and is chosen from:
  • an alkanediyl group comprising 1 to 12 carbon atoms wherein at least one of the carbon atoms is substituted by a moiety comprising N, O, P or S;
  • side arms R and R' are independently of each other chosen from: (i) H;
  • X is a saturated aliphatic hydrocarbon group comprising 1 to 20 carbon atoms
  • Y is chosen from H or an alkyl group with a total number of carbon atoms between 1 and 20 and Ester is -C(0)-0- or -O-C(O)-.
  • nucleating agent according to the invention consists of said core and said flanking side arms R and R'.
  • the hydrogen bonding motifs present in the nucleating agent are the driving force for crystallization of the nucleating agent.
  • Two hydrogen bonding motifs are present in the nucleating agent.
  • the hydrogen bonding motif preferably is an amino carboxy motif.
  • the hydrogen bonding motifs preferably are chosen from an amide motif (-C(O)- NH- or inverted), an oxalamide motif (-NH-C(0)-C(0)-NH-), a hydrazide motif (- C(0)-NH-NH-C(0)-), an urethane motif (-O-C(O)-NH-, or inverted) or an urea motif (-NH-C(O)-NH-).
  • the hydrogen bonding motif is an oxalamide or hydrazide in fact four hydrogen bonding moieties are present. This is
  • different plane means non-parallel planes, such that at least one hydrogen bonding motif resides in a plane positioned at an angle compared to the plane of another hydrogen bonding motif.
  • the hydrogen bonding motifs are not planar, but anti planar or periplanar positioned to each other.
  • the angle a between the plane of one hydrogen bonding motif and the plane of another one is preferably chosen to be: 0° ⁇ a ⁇ 180°, more preferably 5° ⁇ a ⁇ 175° (or the corresponding 360°-a angle). The angle is determined by placing a fictional line in the plane of each hydrogen bonding motif.
  • the line runs along the main extension direction of the plane and can be defined as the line from the atom of the hydrogen bonding motif which is connected to the side arm R or R' to the atom which is connected to the linker moiety.
  • extended lines of two planes i.e. from two different hydrogen bonding motifs
  • the deviating planes of the hydrogen bonding motifs within one nucleating agent molecule disturb the formation of large three dimensional crystal aggregates.
  • smaller crystal aggregates are formed which can form fibrillar networks and improve the transparency of the crystallized polymer. Therefore, the nucleating agents of present invention differ from prior art nucleating agents where hydrogen bonding motifs reside in the same molecular plane.
  • Such prior art nucleating agent is e.g. ethylene bisstearamide, where two amide motifs are connected by an ethyl linker.
  • the angle between the planes of the hydrogen bonding motifs can be influenced by choosing the linker between the hydrogen bonding motifs carefully.
  • the linker is chosen from: (i) an alkanediyi group comprising 1 to 12 carbon atoms wherein at least one of the carbon atoms is substituted by a moiety comprising N, O, P or S;
  • linker doesn't comprise any of the hydrogen bonding motifs. That means that the linker does not contain an amide, oxalamide, hydrazide, urethane or urea motif.
  • the linker is the part of the molecule between any of these motifs, i.e.
  • the linker As part of the molecule of the nucleating agent the longest possible hydrogen bonding motifs should be defined (e.g. a hydrazide instead of two amide motifs) and the chain between those motifs is defined as the linker.
  • the linker comprises between 1 and 8 backbone atoms, more preferably between 1 and 6 backbone atoms and even more preferably between 1 and 4 backbone atoms.
  • the number of unsaturated carbon bonds preferably is uneven, for example 1 or 3.
  • alkanediyi group is chosen where at least one of the carbons is replaced by a moiety comprising N, P, S or O.
  • An alkanediyi is a series of divalent radicals of the general formula ⁇ ⁇ ⁇ 2 ⁇ derived from aliphatic
  • hydrocarbons hydrocarbons. It can be branched.
  • an alkanediyi chain is chosen as linker, however, at least one of the hydrogen atoms on the alkanediyi group is
  • Possible substituents are alkyl groups, halogens, oxygen (resulting in a keto group:-C(0)-), monovalent organic functional groups or alkyl groups where at least one of the carbon atoms is substituted by a divalent organic functional group, a heteroatom, a halogen or a monovalent organic functional group.
  • Monovalent organic functional groups are e.g. amino (-NH 2 ), thio (-SH) and hydroxyl (-OH) groups.
  • Divalent organic functional groups are e.g. ester (-C(O)-O- or O-C(O)-), ketone (-C(O)-) or amide groups (-C(O)-NH-).
  • a linker comprising substituted hydrocarbons an uneven number of substituents for carbon atoms or hydrogen atoms is present.
  • the linker length influences the peak melting and crystallization temperature of the compound in such a manner that a longer linker decreases the melting
  • the length and structure of the linker can also be used as a tool to design the optimal compound for a specific polymers matrix in terms of solubility and melting temperature. Control of the melting point is useful to use the compound (or combination of compounds) as efficient nucleating agent for different polymers which have different melting temperatures. High melting temperatures of nucleating agents are advantageous because they improve the nucleation efficiency of the nucleating agent.
  • the arms R and FT can be chosen in a way to improve the miscibility with the polymer.
  • a good miscibility of the nucleating agent with the polymer causes a homogenous distribution of the nucleating agent in the polymer matrix and leads to better crystallization. This is obtained by designing the arms to be similar to the molecular configuration of the polymer.
  • the side arms R and R' also influence the melting temperature of the compounds described in the invention.
  • the side arms R and R' are the same such that a compound with symmetric ends or side arms is obtained.
  • At least one of the side arms R and R' is chosen from an alkyl group with a total carbon number between 2 and 20, preferably with a total carbon number between 2 and 10 and more preferably with a total carbon number between 2 and 8, even more preferably with a total carbon number between 2 and 6 or 2 and 4.
  • hydrocarbon group and/or on the alkyl side arms R or R' are substituted by methyl, ethyl or alkyl groups of up to 8 carbon atoms, where the total number of all carbon atoms of the saturated aliphatic hydrocarbon group or the alkyl group is not higher than 20.
  • at least one of the arms R or R' comprises a branched alkyl group and/or a branched saturated aliphatic
  • the arms R and R' do not comprise cyclic or aromatic structures.
  • the nucleating agent does not comprise cyclic aliphatic or aromatic groups.
  • An ester is a group containing a carbonyl connected to an oxygen atom (-C(O)-O-) or an oxygen atom connected to a carbonyl group (-O-C(O)-).
  • the saturated aliphatic hydrocarbon group (referred to as X) of the side arms R and R' comprising 1 to 20 carbon atoms is part of an alkane chain and only consists of carbon and hydrogen atoms. All carbons are bound to each other by single carbon bonds.
  • X includes unbranched carbon chains and branched carbon chains, i.e. isomers where the total number of carbon atoms is limited to 20.
  • the saturated aliphatic hydrocarbon group is bound to the other moieties of the nucleating agent by two bonds.
  • Examples of the aliphatic hydrocarbon group are: -CH 2 -CH 2 -CH 2 - or -CH 2 (CH 3 )- CH 2 -.
  • the saturated aliphatic hydrocarbon group is bound to a methyl group or H (i.e. Y) on one side and to an ester group or the bisoxalamide motif, i.e. the core of the nucleating agent on the other side.
  • alkyl is a monovalent aliphatic moiety with a total number of carbon atoms between 1 and 20, i.e. a functional group comprising only carbon and hydrogen atoms derived from an alkane by removing one hydrogen atom.
  • This definition includes unbranched carbon chains and branched carbon chains, i.e. isomers. Examples are: methyl, ethyl, propyl or isopropyl.
  • a compound according to the invention has one of the following structural formula:
  • n is between 2 to 5 and any of the described linkers is chosen.
  • the nucleating agents described in present invention are used for the crystallization of polyesters and polyolefins. Preferably, they are used for the crystallization of thermoplastic and thermoelastomeric polymers, as e.g.
  • nucleating agents of the present invention are less suited and thus not preferred for the crystallization of polyimides.
  • the nucleating agents described in present invention are e.g. suitable for the crystallization of polyesters in general, preferably for bio-based polyesters, as e.g. PHA, PLA and furan-based polyesters, produced either conventionally or from natural resources.
  • polypropylene includes isotactic, syndiotactic and atactic polypropylene, where the tacticity can vary from approximately 60 to 100% in the case of isotactic and syndiotactic polypropylenes.
  • Polypropylene copolymers for the purpose of this invention include polypropylene- alpha-olefin copolymers and poly(propylene-styrene) copolymers.
  • suitable alpha-olefins include but are not limited to polyethylene (PE),
  • the polypropylene copolymers include polypropylene block copolymers and polypropylene random copolymers.
  • the polypropylene copolymers comprise at least 60% propylene units.
  • a preferred polypropylene copolymer is a propylene-ethylene copolymer, where e.g. the amount of ethylene monomers varies between 1 and 10 mole% based on the total amounts of monomers which are used to produce the polymer, preferably between 2 and 5 mole%.
  • Polyethylene copolymers comprise at least 60% of ethylene units.
  • hexyl, butyl or octyl monomers at an amount of 2-8mole% based on the total amount of monomers can be chosen.
  • the nucleating agents are preferably used for bio-based polyesters as polyhydroxy-alkanoates (PHAs) and poly(lactic) acid (PLA), and furan-based polyesters.
  • PHA is defined as a polymer comprising various possible PHA monomers known to the person skilled in the art, with varying possible pendant groups in the side chains, including homopolymers, copolymers, terpolymers and higher combinations of monomers, for example including the following polyhydroxybutyrates: poly-hydroxybutyrate-hydroxyvalerate (PHBHV) and poly-hydroxybutyrate-hydroxyhexanoate (PHBHH).
  • PHA monomers known to the person skilled in the art, with varying possible pendant groups in the side chains, including homopolymers, copolymers, terpolymers and higher combinations of monomers, for example including the following polyhydroxybutyrates: poly-hydroxybutyrate-hydroxyvalerate (PHBHV) and poly-hydroxybutyrate-hydroxyhexanoate (PHBHH).
  • PLA includes the stereo complexes P(L)LA, P(D)LA and all possible combinations thereof. Depending on the stereo-chemical purity of the monomer feed, the ratio L- LA versus D-LA, PLAs can be obtained with a variety of stereo-chemical purity, from pure P(L)LA and pure P(D)LA to P(D/L)LA copolymers and P(L)LA/P(D)LA stereocomplexes.
  • Furan-based polymers are obtained by using furan or furan-based aromatic units (e.g. Furan-2,5-dicarboxylic Acid) as building blocks for a esterification.
  • furan or furan-based aromatic units e.g. Furan-2,5-dicarboxylic Acid
  • the polymer to be crystallized is a combination of PHA and PLA.
  • PHA and PLA each can be present in varying percentages based on the total amount of polymer.
  • the compounds used according to the invention have a peak melting temperature ranging between 100 and 300 °C, preferably between 120 and 290 °C, more preferably 150 and 280 °C.
  • the compound or the combination of compounds are applied at a concentration of 0.05-2wt%, preferably 0.1 -1 wt%, more preferably 0.2-0.5wt% based on the weight of the polymer.
  • a combination of compounds is used to crystallize a polyolefin or polyester, said amounts refer to the combined amount of the different compounds.
  • the total amount of nucleating agent added to the polymer can either consist of one nucleating agent or a combination of different nucleating agents according to this invention. If a combination of nucleating agents is used, the total amount of nucleating agents is the same as if one nucleating agent is used. The amount is always based on the weight of the polymer. For example, 0.05wt% of nucleating agent A and 0.05wt% of nucleating agent B result in an amount of 0.1 wt% nucleating agent based on the weight of the polymer.
  • each compound of such a combination of compounds can vary depending on the polymer, copolymer or polymer mixture which is to be crystallized.
  • the invention relates to a process for crystallization of polyester or polyolefin polymers, comprising the steps of:
  • the compound comprises a core and side arms R and R' flanking the core, which core consists of two hydrogen bonding motifs and a linker connecting said hydrogen bonding motifs, wherein the hydrogen bonding motifs are independently of each other chosen from an amide motif, an oxalamide motif, a hydrazide motif, an urethane motif or an urea motif; wherein the linker does not comprise any of said hydrogen bonding motifs and is chosen from:
  • an alkanediyi chain comprising 1 to 12 carbon atoms wherein at least one of the carbon atoms is substituted by a moiety comprising N, O, P or S;
  • side arms R and R' are independently of each other chosen from: (i) H;
  • X is a saturated aliphatic hydrocarbon group comprising 1 to 20 carbon atoms
  • Y is chosen from H or an alkyl group with a total number of carbon atoms between 1 and 20 and Ester is -C(0)-0- or -O-C(O)-.
  • the compound has a peak melting temperature ranging between 100 and 300 °C, preferably between 120 and 290 °C, more preferably 150 and 280 °C.
  • the compound or a combination of compounds is applied at a concentration of 0.05-2wt%, preferably 0.1 -1wt%, more preferably 0.2-0.5wt% based on the weight of the polymer.
  • the first temperature at which the polymer and the nucleating agent(s) are mixed ranges between 10°C and 140°C, preferably between 20 °C and 120°C, more preferably between 40 °C and 120°C above the peak melting temperature of the polymer.
  • the second temperature, i.e. the cooling temperature preferably ranges from 140°C above the peak melting temperature of the polymer to 20 °C, preferably from 120°C above the peak melting temperature of the polymer to 20 °C.
  • a high crystallization temperature is beneficial for the polymer product and its production.
  • the cooling occurs at a rate ranging between 1 °C /min and 500 °C /min, preferably between 10°C /min and 300 °C /min, more preferably between 20 °C /min and 100°C /min. With an increased cooling rate the nucleation efficiency becomes more evident and it reduces production time.
  • the use of the nucleating agents according to this invention leads to the assembly of the nucleating agents in a fibrillar structure of small dimension.
  • the presence of the fine fibrillar or network morphology of the nucleating agent enhances the nucleation efficiency of the polymer in comparison with a polymer without nucleating agents or in comparison to a polymer which is nucleated with a nucleating agent that assembles in large three-dimensional aggregates.
  • the dimensions of the fibrillar crystals vary with the crystallization conditions and the chosen combinations of the nucleating agents. Usually, they cannot be observed by optical microscopy (at an enlargement of ca. 1 x10 to 1 x40).
  • the small, fibrillar dimensions probably increase the surface area and cause also an increase in the number of the nucleation sites. This is likely to lead to an increase in the surface- volume ratio compared to nucleating agents which cause larger, needle-like aggregates. Without being bound by theory this probably improves the
  • the crystal size of the nucleating agent in the polymer matrix can be determined by electron microscopy or atomic force microscopy.
  • the nucleating agents according to the invention show high nucleation
  • the nucleation efficiency is defined as the increase of the crystallization temperature of the polymer with the nucleating agent compared to the crystallization temperature without nucleating agent. This is calculated by using equation 1 :
  • T c i and T C 2max are the peak crystallization temperatures of the non- nucleated and self-nucleated polymer, respectively.
  • T c is the peak crystallization temperature of the polymer with the nucleating agents.
  • the material which can be obtained without nucleating agent is of lower crystallinity and has a lower dimensional stability.
  • the onset temperature for crystallization of the polymer is increased.
  • the here described nucleating agents or combinations thereof increase the onset crystallization temperature by at least 5°C, preferably by at least 10°C, more preferably by at least 15°C, or by at least 20 °C compared to the polymer or copolymer without any nucleating agent.
  • the specific temperature depends on the specific compound or combination of compounds according to this invention, the amount of nucleating agent and the polymer or copolymer. A higher onset temperature is better for the produced plastics because the mechanical properties of the material are better, the production time is shorter because less cooling has to take place and no or less shrinkage of the crystallized polymer occurs.
  • the high nucleation efficiency provides the desired dimensional stability.
  • the high onset crystallization temperature of the polymer or copolymer in the presence of the nucleating agents of present invention enables easier processability and a higher dimensional stability of the polymer product.
  • Present invention is also directed to a composition
  • a composition comprising polyester or polyolefin polymer and at least one compound, characterized in that the compound comprises a core and side arms R and FT flanking the core, which core consists of two hydrogen bonding motifs and a linker connecting said hydrogen bonding motifs, wherein the hydrogen bonding motifs are independently of each other chosen from an amide motif, an oxalamide motif, a hydrazide motif, an urethane motif or an urea motif;
  • linker does not comprise any of said hydrogen bonding motifs and is chosen from:
  • side arms R and R' are independently of each other chosen from: (i) H;
  • X is a saturated aliphatic hydrocarbon group comprising 1 to 20 carbon atoms
  • Y is chosen from H or an alkyl group with a total number of carbon atoms between 1 and 20 and Ester is -C(0)-0- or -O-C(O)-.
  • the composition comprises 0.05-2wt%, preferably 0.1 -1wt%, more preferably 0.2- 0.5wt% of the compound or a combination of compounds based on the weight of the polymer.
  • films, moldings, composite materials, injection- or extrusion- molded products or elongated products comprise a composition according to this invention.
  • Elongated products include fibers, as e.g. staple fiber, short fiber and continuous fiber, and tapes.
  • compositions i.e. polymers crystallized with nucleating agents or a combination of compounds according to the invention have a good transparency. Also, the obtained crystallized polymers retain a high molar mass. Both properties are advantageous for the production of articles made from polymeric materials.
  • polypropylene copolymer PP, RB206MO, from Borealis
  • poly lactic (L) acid PLLA, 1010, from Syntera
  • polyhydroxy butarate valerate copolymer PHBV, Mirel, MZ100, Metabolix Inc., comprising ca. 12 mole% of valerate monomers.
  • the polymers were processed at elevated temperatures, as indicated in the tables.
  • the onset melting temperature is defined as the start of the endothermic process, whereas the peak melting temperature or peak melting point is defined as the peak of the endothermic process recorded by DSC.
  • the onset crystallization temperature is defined as the start of the exothermic process, whereas the peak crystallization temperature is defined as the peak of the exothermic process recorded by DSC.
  • Crystallization measurements were conducted on a Zeiss Axioplan 2 Imaging optical microscope under crossed polarizers with a CD achorplan objective (Zoom) using a magnification of 20 times.
  • a Linkam hotstage (TMS 94) was used to heat the sample into the melt state at 230 °C for 5 minutes, after which the sample was cooled to 120°C with 40°C/min. As soon as the temperature of 120°C was reached, micrographs were taken every 10 seconds. 5.
  • the viscosity change was measured using isothermal crystallization experiments at the temperature of 120°C, which were carried out using a stress-controlled shear rheometer (TA Instruments, DHR-1 ) with 25 mm plate-plate setup at an angular frequency of 1 rad/second. In order to erase the thermal history the samples were heated with 5°C/min into the melt state at 200 °C, where the temperature was held for 5 minutes prior to cooling to 120°C.
  • Transparency measurements were performed on a Shimadzu UV-3102PC UV- VIS-NIR scanning spectrometer. Samples were scanned in the range between 800 to 300 nm "1 . The transparency values are shown for the wavelength of 500 nm "1 . Samples were prepared via compression molding (1 .5 mm x 50 mm x 12.5 mm) at 210 °C (PP-copolymer). Actual thickness of the samples after compression molding was 1 .57 mm. The value reflects the light which passes through the sample and therefore a higher value corresponds with better transparency.
  • T C /T C N Peak crystallization temperature of the polymer in the presence of the nucleating agent (T C N ) or of the pristine polymer (T c )
  • Tonset Onset of crystallization temperature of the polymer in the presence of the nucleating agent or of the pristine polymer
  • Tc2max peak crystallization temperature of the self-nucleated polymer
  • Visco time of polymer melt viscosity increase until onset of crystallization, under isothermal conditions
  • PLLA poly lactic (L) acid
  • NA1 N-hexyl-N'-[2-(hexylamino)-2-oxo-ethyl]oxamide
  • NA2 N,N'-Ethylenebis(stearamide)
  • NA3 Behenamide
  • NA4 [3-(octylcarbamoyloxy)-2,2-bis(octylcarbamoyloxymethyl)propyl] N- octylcarbamate
  • NA1 as nucleating agent was tested for three different polymers. More specifically, the crystallization behavior of the respective polymer with NA1 and without any nucleating agent was determined using differential scanning calorimetry (DSC) and viscosity measurements (for rheology analysis). For one example, also optical microscopy was carried out.
  • the polymers as indicated in table 2 were melt-mixed with NA1 or without any nucleating agent and subsequently cooled (as described above).
  • the nucleation efficiency was determined for NA1 in PP as 48%, calculated according to equation 1 , with Tc2max experimentally determined to be 1 13°C.
  • the enthalpy of crystallization is directly correlated to the crystallinity of the polymer, where a high enthalpy accounts for a high crystallinity. Accordingly, the use of the nucleating agent according to the invention increases the crystallinity for all polymers. The results also demonstrate the increased onset of crystallization upon cooling and the increased crystal growth rate upon cooling from the melt in the presence of the nucleating agent.
  • PP polypropylene ethylene copolymer sample
  • Fig. 1 shows optical micrographs of the polymer crystal growth and final dimensions of the spherulites for the polymer comprising the nucleating agent or without any nucleating agents. In regular intervals (each 10 seconds between 0 and 400 seconds, depicted in Fig. 1 is a selection of those) a picture was taken. In the top panel (NA a, i.e.
  • the spherulitic dimensions are significantly smaller, which promotes polymer properties such as transparency.
  • the spherulites grow on top of the fibrillar network provided by the nucleating agent.
  • the polymer growth is much slower and much larger spherulites occur.
  • Example 2 Comparison of a nucleating agent according to the invention and known nucleating agents for the crystallization of PHBV
  • the crystallization behavior of PHBV was analyzed after addition of either NA1 , NA2, NA3 or NA5. Additionally, the molar mass of the obtained polymer was
  • NA2 is a nucleating agent consisting of two amide motifs linked by an ethyl group and having alkyl side arms. The linker is not modified. NA2 has been described in EP1477526.
  • NA3 (behenamide) is a nucleating agent comprising one amide motif.
  • NA5 is a nucleating agent comprising one hydrazide motif and benzyl rings as side arms.
  • nucleating agents comprising ring structures are e.g. known from
  • NA2 neither decreases the molar mass polymer but the crystallization onset temperature is only increased marginally.
  • NA3 increases the crystallization onset temperature but the molar mass of the polymer is lower compared to the sample where the nucleating agent according to the invention (NA1 ) is used.
  • NA1 nucleating agent according to the invention
  • Example 3 Comparison of a nucleating agent according to the invention and known nucleating agents for the crystallization of PP
  • NA4 (known from EP2319882) comprises four urethane motifs and alkyl side arms. The results are shown in table 4.
  • nucleating agent of the invention effectively increases the onset crystallization temperature and also the crystallization enthalpy. While the known nucleating agents also increase the onset crystallization temperature and the enthalpy, these nucleating agents result in a much lower transparency of the obtained polymer. NA1 increases the transparency of the polymer, while the other nucleating agents decrease the transparency of the polymer.
  • NA1 shows a good combination of properties: the transparency of the polymer is improved and the crystallization behavior is also improved.
  • the results of the comparison experiments of examples 2 and 3 demonstrate that the nucleating agents of present invention combine attractive properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'au moins un composé pour la cristallisation de polymères de polyester ou de polyoléfine, caractérisée en ce que le composé comprend deux motifs de liaison d'hydrogène, un lieur reliant lesdits motifs de liaison d'hydrogène et des bras latéraux R et R' liés à l'opposé des motifs de liaison d'hydrogène, chaque motif de liaison d'hydrogène se trouvant dans un plan moléculaire et le lieur entre les motifs de liaison d'hydrogène étant choisi de manière telle qu'un des motifs de liaison d'hydrogène se trouve dans un plan moléculaire différent de celui de l'autre ou des autres motifs de liaison d'hydrogène. Ils fonctionnent efficacement pour favoriser la cristallisation d'une gamme de polymères et les polymères cristallisés obtenus présentent une bonne transparence et conservent une masse molaire élevée.
PCT/EP2014/066897 2013-08-14 2014-08-06 Agents de nucléation pour polyesters et polyoléfines WO2015022248A1 (fr)

Applications Claiming Priority (2)

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EP13180409 2013-08-14
EP13180409.8 2013-08-14

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WO2015022248A1 true WO2015022248A1 (fr) 2015-02-19

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1477526A1 (fr) * 2003-04-25 2004-11-17 Asahi Denka Co., Ltd. Composition et objets moulés à base d'une résine d'acide polylactique, et procédé de preparation des objets moulés
WO2007097953A1 (fr) * 2006-02-21 2007-08-30 Sabic Innovative Plastics Ip B.V. Agent anti-adherence pour melanges transparents de polyimide
WO2009064851A2 (fr) * 2007-11-15 2009-05-22 E. I. Du Pont De Nemours And Company Composition à base d'hydro-acide poly(alcanoïque) plastifiée
EP2199052A1 (fr) * 2007-09-12 2010-06-23 Kao Corporation Procédé de production d'article moulé par injection de résine d'acide polylactique
EP2319882A1 (fr) * 2008-08-28 2011-05-11 Adeka Corporation Composition de résine de polyoléfine
WO2013120793A1 (fr) * 2012-02-16 2013-08-22 Technische Universiteit Eindhoven Agents de nucléation pour biopolymères
WO2013156565A1 (fr) * 2012-04-19 2013-10-24 Technische Universiteit Eindhoven Agents de nucléation pour polypropylène et copolymères de propylène

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1477526A1 (fr) * 2003-04-25 2004-11-17 Asahi Denka Co., Ltd. Composition et objets moulés à base d'une résine d'acide polylactique, et procédé de preparation des objets moulés
WO2007097953A1 (fr) * 2006-02-21 2007-08-30 Sabic Innovative Plastics Ip B.V. Agent anti-adherence pour melanges transparents de polyimide
EP2199052A1 (fr) * 2007-09-12 2010-06-23 Kao Corporation Procédé de production d'article moulé par injection de résine d'acide polylactique
WO2009064851A2 (fr) * 2007-11-15 2009-05-22 E. I. Du Pont De Nemours And Company Composition à base d'hydro-acide poly(alcanoïque) plastifiée
EP2319882A1 (fr) * 2008-08-28 2011-05-11 Adeka Corporation Composition de résine de polyoléfine
WO2013120793A1 (fr) * 2012-02-16 2013-08-22 Technische Universiteit Eindhoven Agents de nucléation pour biopolymères
WO2013156565A1 (fr) * 2012-04-19 2013-10-24 Technische Universiteit Eindhoven Agents de nucléation pour polypropylène et copolymères de propylène

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