EP2686297A2 - Utilisation de carbodiimides oligomères comme stabilisateurs - Google Patents

Utilisation de carbodiimides oligomères comme stabilisateurs

Info

Publication number
EP2686297A2
EP2686297A2 EP12710204.4A EP12710204A EP2686297A2 EP 2686297 A2 EP2686297 A2 EP 2686297A2 EP 12710204 A EP12710204 A EP 12710204A EP 2686297 A2 EP2686297 A2 EP 2686297A2
Authority
EP
European Patent Office
Prior art keywords
polymers
oligomeric
carbodiimides
independently
oligomeric carbodiimides
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.)
Withdrawn
Application number
EP12710204.4A
Other languages
German (de)
English (en)
Inventor
Theo SMIT
Laurence Pottie
Simone Schillo
Volker Frenz
Roelof Van Der Meer
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 SE
Original Assignee
BASF SE
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
Application filed by BASF SE filed Critical BASF SE
Priority to EP12710204.4A priority Critical patent/EP2686297A2/fr
Publication of EP2686297A2 publication Critical patent/EP2686297A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C267/00—Carbodiimides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms

Definitions

  • the present invention relates to the use of oligomeric carbodiimides containing at least one heterocyclic end group as stabilizers for polymers. Furthermore, the invention relates to methods for stabilizing polymers against hydrolysis by adding oligomeric carbodiimides. Further objects of the invention are selected carbodiimides and mixtures containing oligomeric carbodiimides, further additives and / or polymers.
  • Monomeric carbodiimides are known as hydrolysis stabilizers (US 5,439,952). When used, however, toxic by-products such as phenyl isocyanate often arise. To avoid problems with toxicity, oligomeric or polymeric carbodiimides are used.
  • DE 3217440 describes polyethylene terephthalates having improved hydrolysis resistance, containing polycarbodlimides.
  • DE 198 09 634 A1 describes processes for the preparation of carbodiimides and mixtures comprising carbodiimides and polyesters or polyurethanes.
  • Carbodiimides containing bonded via urea groups silane groups and their mixtures with polymers are described in WO 2005/1 1 1048 A1.
  • EP 0 507 407 A1 describes multifunctional water-dispersible crosslinking agents based on oligomeric substances containing carbodiimide and other reactive ones functional groups, such as heterocycles. Furthermore, aqueous dispersions, emulsions or solutions of such crosslinking agents as well as processes for the preparation of the crosslinking agents are described.
  • the toxicity of oligomeric or polymeric carbodiimides is reduced over the monomeric carbodiimides, presumably due to the lower volatility of the by-products.
  • the higher molecular weight compounds, compared to the monomeric carbodiimides also often have a reduced stabilizing effect.
  • the object of the present invention was therefore to provide stabilizers based on carbodiimides which do not have the abovementioned problems.
  • oligomeric carbodiimides containing at least one heterocyclic end group as stabilizers for polymers.
  • Expressions of the form C a -Cb designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by expressions of the form C a -Cb-V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl, isopropyl, or C 4 -C 6 -alkyl, n- Butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1 - dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl , 3-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl
  • C 2 -C 20 -alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and one double bond in any position, for example C 2 -C 10 -alkenyl or C 2 -C 20 -alkenyl, preferably C 2 -C 10 -alkenyl, such as C 2 -C 4 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2- propenyl, 2-methyl-2-propenyl, or Cs-C0-alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-buteny
  • C 2 -C 20 -alkynyl straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, for example C 2 -C 10 -alkynyl or C 2 -C 20 -alkynyl, preferably C 2 -C 10 -alkynyl, such as C 2 -C 4 -alkynyl, such as Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, or C 5 -C 7 -alkynyl, such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2- propy
  • C 3 -C 15 -cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Ca-Ce-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, eg. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy, preferably C 1 -C 10 - Alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.
  • Heteroatoms are phosphorus, oxygen, nitrogen or sulfur, preferably oxygen, nitrogen or sulfur whose free valencies are optionally saturated by H atoms.
  • the oligomeric carbodiimides containing at least one heterocyclic end group are used as hydrolysis stabilizers or acid scavengers for polymers.
  • Oligomeric carbodiimides containing at least one heterocyclic end group can be prepared by processes known to those skilled in the art. For example, the production of such carbodiimides is described in the abovementioned EP 0 507 407 A1.
  • a general preparation process for preparing the oligomeric carbodiimides containing at least one heterocyclic end group includes, for example, the reaction of a diisocyanate with a polyetherol and a heterocycle.
  • oligomeric carbodiimides which are used in the context of the invention are preferably compounds of the general formula (I) (I)
  • a 1 , A 2 independently of one another, the same or different,
  • Hydrocarbon groups having 2 to 20 carbon atoms are and preferably cyclic Kohlenwassersrrissaste,
  • R 1 , R 2 are independently, the same or different
  • n is an integer in the range from 2 to 100, preferably in the range from 2 to 50, particularly preferably in the range from 2 to 20,
  • the substituents of carbodiimides A 1 , A 2 contain the hydrocarbon group
  • the substituents of the carbodiimides A1, A2 preferably contain the hydrocarbon groups
  • the substituents of the carbodiimides B 1 , B 2 are selected from the group of the three- to twelve-membered, preferably three- to nine-membered, particularly preferably five- to bengliedrigen, oxygen, nitrogen and / or sulfur atoms and one or more ring-containing ring systems (heterocycles, heterocyclic end groups), such as aziridine, epoxide, thiirane, azirine, oxirene, thiirene, azetidine, oxetane, thietane, beta-lactam, beta Lactone, thiethanone, furan, pyrroline, dihydrofuran, dihydrothiophene, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, oxazolidine, dioxolane, oxathiolane, thiazolidine, imidazoline, dithi
  • the stabilized polymers are polycondensates or polyaddition products.
  • the polymers are preferably selected from the group of polyesters, polyamides, polyurethanes,
  • polycarbonates their copolymers and / or mixtures.
  • the polymers to be stabilized are selected from PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene copolymer), biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6 (Polyamide 6).
  • biodegradable aliphatic-aromatic copolyesters are poly (butylene adipate-co-terephthalates) and biopolymers Especially PLA (polylactic acid) and PHA (Polyhydroxylalkanoate) come into question.
  • PLA polylactic acid
  • PHA Polyhydroxylalkanoate
  • the stabilized polymers also include recycled or recycled polymers.
  • Another object of the present invention is a method for stabilizing polymers against hydrolysis, wherein the polymer is an effective amount of the above-mentioned oligomeric carbodiimides, preferably the carbodiimides of the general formula (I) is added.
  • the oligomeric carbodiimides in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, in particular from 0.1 to 2 wt .-% based on the total amount of polymer and oligomeric carbodiimide added to the polymer.
  • the incorporation of the oligomeric carbodiimides, containing at least one heterocyclic end group, into the polymers generally takes place by mixing the constituents. For example, mixing is carried out by methods known to those skilled in the art, such as those generally used in the addition of polymers.
  • the oligomeric carbodiimides in solid, liquid or dissolved form are preferably used for finishing polyaddition or polycondensation polymers.
  • the oligomeric carbodiimides can be incorporated for this purpose both as a solid or liquid formulation, as well as a powder by the usual methods in the polymers.
  • polymer moldings which contain oligomeric carbodiimides containing at least one heterocyclic end group are carried out by methods known to the person skilled in the art.
  • the polymer moldings can be prepared by extrusion or coextrusion, compounding, processing of granules or pellets, injection molding, blow molding or kneading.
  • the processing preferably takes place by extrusion or coextrusion into films (see Saechtling Kunststoff Taschenbuch, 28th Edition, Karl Oberbach, 2001).
  • the polymers or polymer moldings may additionally contain at least one further, frequently commercially available, additive, which is preferably selected from chain extenders, colorants, antioxidants, other stabilizers, for example Heated Amine Light Stabilizers (HALS), UV absorbers, nickel quenchers, Metal deactivators, reinforcing and filling agents, antifogging agents, biocides, acid scavengers, antistatic agents, IR absorbers for long-wave IR radiation, antiblocking agents such as SiO 2, light scatterers such as MgO or TiO 2, inorganic or organic reflectors (for example aluminum flakes).
  • additive is preferably selected from chain extenders, colorants, antioxidants, other stabilizers, for example Heated Amine Light Stabilizers (HALS), UV absorbers, nickel quenchers, Metal deactivators, reinforcing and filling agents, antifogging agents, biocides, acid scavengers, antistatic agents, IR absorbers for long-wave IR radiation, antiblocking agents such
  • Preferred additional additives are chain extenders, especially epoxy group-containing functionalized styrene- (meth) acrylic acid ester copolymers based on epoxy group-containing (meth) acrylic acid monomers in combination with styrene and / or (meth) acrylic acid esters, as used, for example, in US Pat US 6,984,694 are described.
  • a preferred use according to the invention of the oligomeric carbodiimides containing at least one heterocyclic end group as stabilizers for polymers therefore takes place in combination with chain extenders, in particular epoxy-functionalized styrene (meth) acrylate copolymers.
  • the invention relates to methods for stabilizing polymers against hydrolysis by adding oligomeric carbodiimides.
  • a further preferred embodiment of the invention is a process for stabilizing polymers, in particular against hydrolysis, wherein the polymer in addition to the oligomeric carbodiimides containing at least one heterocyclic end group, an effective amount of epoxy groups functionalized styrene (meth) acrylic acid copolymers added becomes.
  • the epoxy groups-containing functionalized styrene- (meth) acrylic acid ester copolymers in an amount of 0.01 to 5 wt .-%, preferably from 0, 1 to 3 wt .-%, in particular from 0 , 2 to 2% by weight based on the total amount of polymer and oligomeric carbodiimide added to the polymer.
  • the oligomeric carbodiimides containing at least one heterocyclic end group and the functionalized styrene- (meth) acrylic acid ester copolymers containing epoxy groups can in this case be added to the polymer separately from one another or as a mixture.
  • the addition to the polymer can be carried out successively or simultaneously.
  • Another object of the invention are mixtures containing oligomeric carbodiimides, containing at least one heterocyclic end group, especially those according to the general formula (II) and chain extenders, wherein as chain extenders epoxy groups functionalized styrene (meth) acrylic acid ester copolymers are preferred.
  • the ratio of oligomeric carbodiimides containing at least one heterocyclic end group to chain extenders may vary depending on the application vary over a wide range.
  • Such mixtures preferably contain the oligomeric carbodiimides containing at least one heterocyclic end group and the epoxy groups-containing functionalized styrene- (meth) acrylic acid ester copolymers in a ratio of 99.9: 0.01 to 0.01: 99.9, preferably 90 : 10 to 10:90, more preferably from 80:10 to 10:80.
  • a further preferred subject matter of the invention are mixtures comprising oligomeric carbodiimides containing at least one heterocyclic end group, in particular those corresponding to the general formula (II), chain extenders, where the chain extender contains epoxy groups containing functionalized styrene
  • (Meth) acrylic acid ester copolymers are preferred and polymers.
  • Such mixtures preferably contain from 0.01 to 15, preferably from 0.2 to 15,% by weight of oligomeric carbodiimides containing at least one heterocyclic end group, from 0.01 to 30, preferably from 0.2 to 30,% by weight of epoxy Groups containing functionalized styrene- (meth) acrylic ester copolymers and from 55 to 99.98 preferably from 55 to 99.6 wt .-% polymers, each based on the total amount of oligomeric carbodiimide, containing at least one heterocyclic end group, chain extenders and Polymer.
  • the polymers are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates, their copolymers and / or mixtures see.
  • the polymers to be stabilized are selected from PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene copolymer), biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6 (polyamide 6).
  • Suitable biodegradable aliphatic-aromatic copolyesters are, in particular, poly (butylene adipate-co-terephthalates), and suitable biopolymers are in particular PLA (polylactic acid) and PHA (polyhydroxyalkanoates). As mixtures are in particular
  • Another object of the invention are selected oligomeric carbodiimides of general formula (II),
  • a 1 , A 2 are independently, the same or different, the groups
  • R 1 , R 2 are independently, the same or different
  • R 3 is C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, preferably C 1 -C 4 -alkyl,
  • R 4 is H, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, preferably H, C 1 -C 4 -alkyl, and
  • n is an integer in the range of 1 to 500, preferably 1 to 100, 1 to 50
  • Another object of the invention are mixtures containing oligomeric carbodiimides according to the general formula (II) and polymers, wherein the polymers are preferably polycondensates or polyaddition products.
  • the polymers also include recycled or recycled polymers.
  • the polymers are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers, and in particular the polymers are PET, PBT, PEN, PC, ABS, biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6.
  • biodegradable aliphatic-aromatic copolyesters in particular poly (butylene adipate-co-terephthalate) are suitable and as biopolymers are especially PLA and PHA in question.
  • biopolymers are especially PLA and PHA in question.
  • PC / ABS mixtures are suitable.
  • the oligomeric carbodiimides in the mixture in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, in particular from 0.1 to 2 wt .-% based to the total amount of polymer and oligomeric carbodiimide.
  • the present invention provides oligomeric carbodiimides for the stabilization of polymers which, owing to their oligomeric structure, are less toxic during handling, incorporation and use as stabilizer, in particular as hydrolysis stabilizer or acid scavenger.
  • the oligomeric carbodiimides owing to their functionalization with at least one heterocyclic end group, enable an efficient and effective stabilization of the polymer.
  • the oligomeric carbodiimides used in the present invention show excellent properties. The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
  • the oligomeric carbodiimides of Table 1 were compounded in PET by means of a mini-extruder at 280 ° C in an amount of 0.3% by weight based on the total amount of PET and oligomeric carbodiimide.
  • the acid numbers are measured after a period of 2 to 5 minutes residence time in the extruder and compared with the values that result for an extruded PET without additives at the same times.
  • the acid numbers are obtained by titration of the respective PET solution in the solvent mixture of chloroform / cresol.
  • the non-inventively functionalized oligomeric carbodiimides of Table 2 were used for comparative experiments.
  • n is on average at the oligomeric carbodiimide groups 10th
  • Table 3 shows the results of the measurement of the acid numbers after 2 and 5 min for different amounts of CDI.
  • Table 4 shows the results of viscosity measurements (VZ: viscosity number) on a number of PBT (Ultradur® B4520) samples extruded with various additives in a mini extruder for two minutes at 280 ° C.
  • the measurement of VZ was carried out before and after storage at 1 10 ° C and a relative humidity of 100%.
  • the VZ measurements (units in mg / l) were carried out with the aid of a microbubble capillary viscometer using, as solvent, a 1: 1 mixture of phenol and o-dichlorobenzene.
  • CDU based on the total amount of PBT and CDU.
  • the other samples contain an equivalent to these 1 wt .-% CDU molar amount of caprolactam or carbodiimide groups.
  • Oligomeric carbodiimides containing at least one heterocyclic end group show an improved stabilizing effect compared with the oligomeric carbodiimide without a heterocyclic end group (CDI8).
  • CDU oligomeric carbodiimide without a heterocyclic end group
  • CDI8 oligomeric carbodiimide without a heterocyclic end group
  • the amounts of chain extender and oligomeric carbodiimide are based on the total amount of PET, chain extender and oligomeric carbodiimide.
  • the change in the acid number refers to the acid number of PET without chain extender and oligomeric carbodiimides, measured 2 min. after extrusion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Utilisation de carbodiimides oligomères présentant au moins un groupe terminal hétérocyclique, comme stabilisateurs pour des polymères. Les composés carbodiimides oligomères peuvent être de formule (I),dans laquelle A1, A2 représentent indépendamment l'un de l'autre, de manière identique ou différente, des groupes hydrocarbure comportant 2 à 20 atomes de carbone, B1, B2 représentent indépendamment l'un de l'autre, de manière identique ou différente, des hétérocycles, des alcools C1-C30, des polyétherols, des polyesterols, des amines, des polyétheramines, des polyesteramines, des thioalcools, des polyétherthiols, des polyesterthiols, R1, R2 représentent indépendamment l'un de l'autre, de manière identique ou différente [], n est un nombre entier de 2 à 100, et A1, A2, B1 et B2 peuvent être chacun substitués en position quelconque par alkyle C1-C20, alcényle C2-C20, alkinyle C2-C20, alcoxy C1-C20, oxygène carbonyle (=O) ou halogène, dans la mesure où au moins un substituant B1 ou B2 est un groupe terminal hétérocyclique. L'invention porte également sur des procédés de stabilisation de polymères contre l'hydrolyse au moyen de carbodiimides oligomères.
EP12710204.4A 2011-03-18 2012-03-15 Utilisation de carbodiimides oligomères comme stabilisateurs Withdrawn EP2686297A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12710204.4A EP2686297A2 (fr) 2011-03-18 2012-03-15 Utilisation de carbodiimides oligomères comme stabilisateurs

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11158914 2011-03-18
PCT/EP2012/054550 WO2012126797A2 (fr) 2011-03-18 2012-03-15 Utilisation de carbodiimides oligomères comme stabilisateurs
EP12710204.4A EP2686297A2 (fr) 2011-03-18 2012-03-15 Utilisation de carbodiimides oligomères comme stabilisateurs

Publications (1)

Publication Number Publication Date
EP2686297A2 true EP2686297A2 (fr) 2014-01-22

Family

ID=45876723

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12710204.4A Withdrawn EP2686297A2 (fr) 2011-03-18 2012-03-15 Utilisation de carbodiimides oligomères comme stabilisateurs

Country Status (2)

Country Link
EP (1) EP2686297A2 (fr)
WO (1) WO2012126797A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013072310A1 (fr) * 2011-11-17 2013-05-23 Basf Se Additifs pour la stabilisation à l'hydrolyse de polycondensats

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3217440A1 (de) 1982-05-08 1983-11-10 Basf Ag, 6700 Ludwigshafen Polyethylenterephthalat mit verbesserter hydrolysebestaendigkeit sowie dessen verwendung
NL9100578A (nl) 1991-04-03 1992-11-02 Stahl Holland Bv Multifunctionele waterdispergeerbare verknopingsmiddelen.
DE4318979A1 (de) * 1993-06-08 1994-12-15 Basf Ag Carbodiimide und/oder oligomere Polycarbodiimide auf Basis von 1,3-Bis-(1-methyl-1-isocyanato-ethyl)-benzol, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisator
US5439952A (en) 1993-12-21 1995-08-08 The Thompson Minwax Company Self-curing coating composition exhibiting reduced discoloration upon storage
DE19809634A1 (de) 1998-03-06 1999-09-09 Basf Ag Carbodiimide und Verfahren zu deren Herstellung
CA2474251C (fr) 2002-02-01 2009-05-12 Johnson Polymer, Llc Allongeurs de chaine oligomeres destines au traitement, au post-traitement et au recyclage de polymeres de condensation, synthese, compositions et applications associees
DE102004024196A1 (de) 2004-05-13 2005-12-01 Basf Ag Carbodiimide enthaltend Harnstoffgruppen und Silangruppen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012126797A2 *

Also Published As

Publication number Publication date
WO2012126797A3 (fr) 2013-01-10
WO2012126797A2 (fr) 2012-09-27

Similar Documents

Publication Publication Date Title
EP2780407A1 (fr) Additifs pour la stabilisation à l'hydrolyse de polycondensats
US20130131255A1 (en) Additives for stabilizing polycondensates with respect to hydrolysis
CH626109A5 (fr)
DE202017007332U1 (de) Biologisch abbaubare Polyesterzusammensetzung
EP2418251A1 (fr) Matières synthétiques bio à longue durée de vie à base de polyhydroxyalcanoate, leur procédé de fabrication et d'utilisation
DE3750887T2 (de) Verfahren zur Herstellung von Oxymethylencopolymeren und Harzzusammensetzung.
DE4033096A1 (de) Feuchtigkeitshaertende einkomponenten-polysiloxanmasse
US8623945B2 (en) Use of oligomeric carbodiimides as stabilizers
EP2705083A1 (fr) Nouveaux plastiques biosourcés durables, stables à l'hydrolyse, à base de polyhydroxyalcanoate (pha), procédé pour la fabrication desdits plastiques et utilisation de ces derniers
DE202011110977U1 (de) Polylactidharz mit ausgezeichneter Wärmebeständigkeit
DE69620575T2 (de) Härtbare polymethylsilsesquioxanzusammensetzung
EP2418248B1 (fr) Matières synthétiques bio à longue durée de vie, leur procédé de fabrication et d'utilisation
DE102019200596A1 (de) Verwendung einer additivzusammensetzung zum kontrollierten beschleunigten abbau von kondensationspolymeren
EP2686297A2 (fr) Utilisation de carbodiimides oligomères comme stabilisateurs
CH632746A5 (de) Verfahren zur herstellung von 2.2.6.6-tetramethyl-piperidin-verbindungen.
WO2012168324A1 (fr) Mélange polyester biodégradable
DE102018201018A1 (de) Verwendung von Terephthaloyl-bis-N,N'-naphthalimidestern als Nukleierungsmittel für thermoplastische Formmassen, Verfahren zur Kristallisation von thermoplastischen Kunststoffen sowie kristalline thermoplastische Kunststoffzusammensetzungen
DE3508531A1 (de) Hydrophobierte, leichtfliessende thermoplastische polyamide
EP3891208B1 (fr) Procédé de purification d'un (co)polyester
EP3686240B1 (fr) Compositions contenant le polyéthylène téréphtalate (pet) stabilisé par hydrolyse
DE2911301C2 (de) Bei Raumtemperatur zu Elastomeren vernetzbare Formmassen
DE3233953A1 (de) Carbonamidgruppenhaltige formmassen oder formkoerper mit verbesserter bestaendigkeit gegen die einwirkung von licht
DE102018005741B4 (de) Polyesterharzzusammensetzung und unter Verwendung derselben hergestellter Gegenstand
DE102011005630A1 (de) Hydrophobes ABS Kunststoffmaterial für Gehäuse
EP2217635B1 (fr) Système composite biodégradable, et son utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131018

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20161001