EP2780407A1 - Additives for the hydrolytic stabilisation of polycondensates - Google Patents
Additives for the hydrolytic stabilisation of polycondensatesInfo
- Publication number
- EP2780407A1 EP2780407A1 EP12783627.8A EP12783627A EP2780407A1 EP 2780407 A1 EP2780407 A1 EP 2780407A1 EP 12783627 A EP12783627 A EP 12783627A EP 2780407 A1 EP2780407 A1 EP 2780407A1
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- EP
- European Patent Office
- Prior art keywords
- polymers
- alkyl
- mixture
- different
- independently
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Definitions
- the present invention relates to mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for polymers. Furthermore, the invention relates to mixtures of multifunctional chain extenders, mono- or difunctional hydrolysis stabilizers and polymers. Further objects of the invention are the use of the mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for stabilizing polymers and methods for stabilizing against molecular weight loss of polymers.
- Chain extenders were originally developed to obtain polycondensates with high molecular weights by reactive extrusion.
- WO 98/47940 A1 describes bifunctional caprolactam chain extenders for the preparation of high molecular weight polyesters and polyamides.
- Multifunctional chain extenders with three or more reactive groups lead to branched structures.
- the use of such additives in a polymer matrix therefore often leads, in addition to the chain extension, to branchings which, when processed in the melt, markedly increase the viscosity.
- Such additives are in the US
- 5,354,802 for use in, for example, polyesters or polyamides.
- WO 2004/067629 A1 describes the use of chain extenders in the form of a dilution in an inert carrier plastic.
- No. 6,984,694 B2 describes the use of copolymers containing epoxy-functionalized (meth) acrylic acid monomers, styrene and / or (meth) acrylic acid monomers as chain extenders.
- Carbodiimides are known as hydrolysis stabilizers, for example from US Pat. No. 5,439,952, EP 799843 A1 or EP 126251 1 A2. In their use, however, arise often toxic by-products such as phenyl isocyanates. To avoid problems with toxicity, oligomeric or polymeric carbodiimides are used.
- DE 3217440 A1 describes polyethylene terephthalates having improved hydrolysis resistance, containing polycarbodlimides.
- EP 0 507 407 A1 describes multifunctional water-dispersible crosslinking agents based on oligomeric substances containing carbodiimide and other reactive 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.
- JP 2007023100 A2 describes the use of alkyl ketene dimers in the stabilization of aliphatic polyesters.
- Polymers for example polycondensation polymers such as polyesters, are often degraded by hydrolysis at elevated temperatures. Such conditions occur, for example, when processing the polymers under heat with the simultaneous presence of moisture. Hydrolysis of the polymers leads to a reduction in the molecular weight and a decrease in the melt viscosity, while affecting the mechanical properties of the polymers. These effects severely limit the applicability of such hydrolyzable polymers and, moreover, require a great deal of drying before the polymers are processed.
- the object of the present invention was therefore to provide stabilizers for polymers which lead to a reduction in the degradation and a reduction in the hydrolysis.
- the chain extenders (K) and the hydrolysis stabilizers (H) react with the end groups of polymers (P) in the molten or solid state of the polymers (P) to form a chemical bond.
- the chain extenders (K) react with the end groups of polymers (P) in the molten state of the polymers (P) and the hydrolysis stabilizers (H) with the end groups of polymers (P) in the molten or solid state of the polymers (P).
- 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 C3-alkyl, such as methyl, ethyl, propyl, isopropyl, or C4-C6-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, 1,3
- 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-C6 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- prop
- C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-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 C10 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 chain extenders (K) are selected from the group of homopolymers and copolymers containing at least three epoxide groups, at least three aziridine groups, or at least three anhydride groups.
- Particularly preferred chain extenders (K) are homo- or copolymers containing at least three epoxy groups. Very particular preference is given to such chain extenders (K) are copolymers containing at least three epoxy groups, in particular copolymers functionalized with epoxy groups containing styrene, (meth) acrylic acid ester monomer in polymerized form.
- Preferred chain extenders (K) are copolymerization products of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer.
- these are epoxy group-functionalized (meth) acrylic acid ester monomers in combination with non-epoxy-functionalized styrene monomers and / or
- (meth) acrylic ester monomers refers to For the purposes of the present application, both acrylic ester monomers (acrylate monomers) and methacrylic acid ester monomers (methacrylate monomers) are included.
- epoxy group-functionalized (meth) acrylic ester monomers examples include those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate.
- Other monomers functionalized with epoxy groups include allyl glycidyl ether, glycidyl methacrylate, glycidyl titanate.
- Acrylate and methacrylate monomers that can be used in the invention include, independently of a functionalization with epoxy groups, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-hexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n Propyl methacrylate, methylcyclohexyl methacrylate, isobornyl methacrylate, butyl acrylate, butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures of these.
- Preferred non-functionalized acrylate and methacrylate include butyl acrylate, butyl methacrylate, methyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
- Styrenic monomers that can be used in the present invention include styrene, alpha-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, vinylpyridines and mixtures thereof.
- the monomers are selected from styrene or alpha-methylstyrene.
- Particularly preferred co-polymerization products contain at least one monomer selected from glycidyl acrylate and glycidyl methacrylate and at least one monomer selected from styrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl hexyl acrylate.
- (Meth) acrylic ester monomer an epoxy equivalent weight (EEW) of 180 to 2800 g / mol, preferably from 190 to 1400 g / mol and particularly preferably from 200 to 700 g / mol.
- Efn Mn / EEW
- Efn stands for the number average of the epoxy functionality and Efw for the weight average of the epoxy functionality.
- (Meth) acrylic acid ester monomer has a number average molecular weight (Mn) of less than 6000 g / mol, preferably from 1000 to 5000 g / mol and particularly preferably from 1500 to 4000 g / mol.
- these co-polymerization preferably have a weight average molecular weight (Mw) of less than 25,000 g / mol, preferably from 1500 to 18000 g / mol, more preferably from 3000 to 13000 g / mol and in particular from 4000 to 8500 g / mol
- Mw weight average molecular weight
- the EEW values correspond to the mass of co-polymerization product having one equivalent of epoxy functionality and are determined according to ASTM D 1652-90 (Standard Test Method for Epoxy Content of Epoxy Resins (1990) Test Method B) or as described, for example, in US 6,552,144 B1 determined from the mass balance of the monomers used with epoxy groups.
- Molecular weight distributions of the co-polymerization products are determined by gel permeation chromatography (GPC) measurements.
- the co-polymerization products are first dissolved in tetrahydrofuran (THF) and then injected into the GPC apparatus.
- THF tetrahydrofuran
- RI refractive index
- columns the PLGEL MIXED B columns can be used with a monitoring column and, among other things, determine the Mn and Mw values.
- Co-polymerization of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer are commercially available, for example as Joncryle® Fa. BASF SE.
- the hydrolysis stabilizers (H) are selected from the a. oligomeric carbodiimides of the general formula (I)
- a 1 , A 2 independently of one another, the same or different,
- C3-C14 cycloalkylene, arylene, B 1 , B 2 independently of one another, identical or different, heterocycles, C 1 -C 30 -alcohols, poletherols, polyesterols, amines, polyetheramines, polyesteramines, thioalcohols, polyether thiols, polyester thiols, n integer in the range from 2 to 100, preferably in the range of 2 to 50, more preferably in the range of 2 to 20,
- Halogen preferably C 1 -C 4 -alkyl, mono- or difunctional epoxy compounds of the general formulas (IIa) or (IIb)
- X 1 , X 2 , X 3 independently of one another, identical or different, CH 2 , O,
- Z 2 , Z 3 independently of one another, identical or different, single bond, SiR 1 R 2 , Si (OR 1 ) R 2 , Si (OR 1 ) (OR 2 ),
- R 1, R 2, R 3 independently of one another, identical or different, Ci-C2o-alkyl, preferably Ci-Cio-alkyl, particularly preferably Ci-C4-alkyl, in particular Ci-C2 alkyl, R 20 , R 21 , R 22 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
- R 20 together with R 21 or R 22 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system
- R 23 , R 24 , R 25 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
- R 23 together with R 24 or R 25 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system
- R 4 , R 42 are each, independently of one another or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
- R 51 R 52 independently of one another are identical or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
- R 6 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, NR 26 R 27 ,
- R 16 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, halogen,
- R 26 , R 27 independently of one another, the same or different, H,
- R 7 , R 8 , R 9 , R 10 are independently, the same or different, H,
- hydrolysis stabilizers (H) have no negative influence on the melt viscosity, color, turbidity or odor of polymers.
- the hydrolysis stabilizers (H) are preferably chosen such that the melt viscosity does not increase significantly during the extrusion, preferably by less than 20%, more preferably by less than 10%, so that an adjustment of the target viscosity essentially via the addition of the chain extender (K ) is regulated.
- Oligomeric carbodiimides c. of the general formula (I) can be as described for example in EP 0 507 407 A1 or our unpublished patent application EP
- a general preparation process for preparing oligomeric carbodiimides containing at least one heterocyclic end group includes, for example, the reaction of a diisocyanate with a polyetherol and a heterocycle.
- the substituents of the oligomeric carbodiimides of the general formula (I) A 1 , A 2 contain the hydrocarbon groups
- the substituents of the carbodiimides B 1 , B 2 are selected from the group of the three- to zwoifgliedrigen, preferably three- to nine-membered, more preferably five- to seven-membered, 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, pyrogen rolidine, tetrahydrofuran, tetrahydrothiophene, oxazolidine, dioxolane, oxathiolane, thiazolidine
- Epoxy compounds b. of the general formulas (IIa) and (IIb) and their preparation are known to the skilled person from his specialist knowledge, for example from US 4,385,144, US 4,393,156 or US 4,393,158. Epoxy compounds of the general formulas (IIa) and (IIb) are commercially available.
- Alkyl ketene dimers c. of the general formulas (III) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 5,028,236 or WO 92/15746 A1. Alkylketene dimers of the general formulas (III) are commercially available.
- Heterocycles (oxazolidinones and derivatives or isomers) d. of the general formulas (IV) and (IV) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 3,770,693 or US Pat. No. 4,123,419. Heterocycles of the general formulas (IV) and (V) are commercially available.
- the ratio between the at least one multifunctional chain extender (K) and the at least one mono- or difunctional hydrolysis stabilizer (H) in the mixture (M) can vary over a wide range, depending on the application. For example, in applications requiring a higher initial viscosity, eg PET recycling, higher amounts of chain extenders (K) are used.
- the proportion of hydrolysis stabilizers increases accordingly.
- the skilled person is able to set the appropriate ratio by appropriate experiments.
- the quantitative ratio (weight) of K to H is in the range from 1: 100 to 100: 1, preferably from 1:50 to 50: 1, more preferably from 1:20 to 20: 1 and especially from 1:10 to 10: 1.
- the polymers (P) 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), biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6 (polyamide 6).
- biodegradable aliphatic-aromatic copolyesters are poly (butylene adipate-co-terephthalates) and suitable biopolymers are in particular PLA (polylactic acid) and PHA (polyhydroxyalkanoates).
- PLA polylactic acid
- PHA polyhydroxyalkanoates
- the stabilized polymers also include recycled or recycled polymers.
- the polymers (P) comprise hydroxyl, amine, carboxy or carboxylic acid end groups, in particular carboxylic acid end groups.
- Another object of the present invention are mixtures (MP) containing a. at least one mixture (M) described above and
- At least one mixture (M) is added to the at least one polymer (P) in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.1 to 2
- the incorporation of the mixtures (M) in the polymers (P) is generally carried out by mixing the ingredients. 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 mixtures (M) in solid, liquid or dissolved form preferably used for the equipment of polyaddition or polycondensation polymers.
- the mixtures (M) 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. Mentioned here is, for example, the mixing of the mixtures (M) with the polymers (P) before or during an extrusion step, kneading, calendering, film, fiber extrusion or blow molding.
- the additized polymers can be present, for example, as granules, pellets, powders, films or fibers.
- polymer moldings containing the mixture (M) is carried out by methods known to the person skilled in the art.
- the polymer moldings can be produced 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 other, often commercially available, additive, preferably selected from colorants, antioxidants, other stabilizers, e.g. Hindered amine light stabilizers (HALS), UV absorbers, nickel quenchers, metal deactivators, reinforcing agents and fillers, anti-fogging 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 ⁇ 02, inorganic or organic reflectors (for example aluminum flakes). It is also possible to use other chain extenders or hydrolysis stabilizers not contained in the mixtures (M).
- HALS Hindered amine light stabilizers
- UV absorbers e.g. Hindered amine light stabilizers
- nickel quenchers e.g., nickel quenchers, metal deactivators, reinforcing agents and fillers
- anti-fogging agents e.g.,
- the invention relates to the use of mixtures (M) described above as stabilizers for polymers (P) described above, in particular the use for stabilizing against molecular weight loss and / or hydrolysis.
- Another object of the invention is a process for the stabilization of polymers (P), in particular against molecular weight loss and / or hydrolysis, wherein the polymer (P) an effective amount of mixture (M) is added.
- the amount of (M) from 0.01 to 10% by weight, based on the total amount of polymer (P) and mixture (M), is preferably added to the polymer (P).
- the polymer (P) in the context of the process according to the invention stabilization, the additives described in the foregoing added.
- the present invention provides stabilizing mixtures (M) for polymers which result in a reduction in degradation and a reduction in the hydrolysis of the polymers, particularly in their processing. The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
- PET Polyethylene terephthalate
- the PET had a low concentration of carboxylic end groups (about 21 mmol / kg).
- the acid numbers are obtained by titration of the respective PET solution in the solvent mixture of chloroform / cresol.
- the additives were coextruded with the PET in various concentrations at a temperature of 260 ° C.
- the resulting films were then exposed to elevated temperatures (1-10 ° C) and high humidity (100%) and stored for a period of two or five days.
- the degradation of the polymer was determined by measuring the viscosity number (VZ) and / or the acid end group concentration of the PET before and after storage.
- the VZ measurements (units in mg / l) were carried out with the aid of a micro Ubbelohde capillary viscometer using as solvent a 1: 1 mixture of phenol and o-dichlorobenzene.
- Ultradur® B4520 (BASF SE) with a viscosity number of 18 ml / g and an acid number of about 25 mmol / kg was used as the PBT matrix. Additives were added to the PBT by coextrusion and moldings were made for tensile tests. Viscosity numbers and acid end groups were determined on parts of the test specimens before and after storage at 110 ° C. and 100% atmospheric humidity.
- Table 1 .1 compares the viscosity numbers and acid end group concentrations in comparison to the reference (Ref.). Table 1.1
- the amount of Joncryl® is given based on the total amount of Joncryl® and polymer.
- the concentration of acid end groups refers to the total amount of Joncryl® and polymer.
- the Joncryle® causes a significant increase in the melt viscosity after the extrusion of the films.
- only low levels of Joncryl® can be used (for example, 0.2% by weight of Joncryl® 4300). At these concentrations, however, the increase in acid end groups during storage is not prevented.
- Table 1 .2 summarizes the course of the viscosity number during the storage of the films. The data are the same as in Table 1 .1. As reference (reference), however, the viscosity number of the respective sample before storage is now selected.
- VZ PBT test specimen [mL / g] 1 18 130 -
- Tables 2.1 and 2.2 show the stabilization of polymers such as PET and PBT against hydrolysis by the AKD of the form (III '):
- Table 2.1 shows the effect of the AKD alone as a comparison.
- the amount of AKD is given based on the total amount of AKD and polymer.
- the concentration of acid end groups refers to the total amount of AKD and polymer.
- the AKD prevents the increase in acid end groups during storage. However, the viscosity number does not increase significantly during the extrusion.
- Table 2.2 shows a comparison of the efficiency of using AKD alone and in conjunction with the Joncryl® ADR 4300 chain extender. It can be clearly seen that its combination of hydrolysis stabilizer (H) and chain extender (H) has a synergistic effect.
- the amount of AKD and Joncryl® ADR 4300 is given based on the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
- the acid end group concentration refers to the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
- the amount of oxazolidinone is based on the total amount of oxazolidinone and polymer.
- the concentration of acid end groups refers to the total amount of oxazolidinone and polymer.
- Tables 4.1 and 4.2 show the results of the extrusion of PET or PBT in the presence of an epoxysilane: 3-glycidoxypropyltriethoxysilane, which is available under the designation Geniosil® GF 82 (Wacker Chemie AG). Furthermore, the tables contain results for the use of 1, 2-epoxydecane as a hydrolysis stabilizer.
- the concentration of acid end groups refers to the total amount of additive and polymer.
- the concentration of additive is given based on the total amount of additive and polymer.
- the concentration of acid end groups refers to the total amount of additive and polymer.
- the additives in the form of a masterbatch and thereby to obtain the advantageous effect as a hydrolysis stabilizer in the end product.
- the amount of hydrolysis stabilizer which is necessary to completely stabilize 5 kg of extruded PBT by reaction with the acid end groups (about 30 mmol / kg) is extruded in about 800 g of PBT to prepare the masterbatch.
- the acid end group concentration of the masterbatch was determined before storage and after two days storage at 110 ° C and 100% humidity.
- the concentration of additive is given based on the total amount of additive and polymer.
- the concentration of acid end groups refers to the total amount of additive and polymer.
- the monoepoxy compounds hardly increase the initial viscosity during the extrusion and can therefore advantageously be combined synergistically with chain extenders as already described above in Examples 2 and 3.
- the concentration of additive is given based on the total amount of additive and polymer.
- the concentration of acid end groups refers to the total amount of additive and polymer.
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Abstract
The invention relates to a mixture containing at least one multi-functional chain extender with at least three reactive groups, as well as at least one monofunctional or difunctional hydrolytic stabiliser, said chain extender and hydrolytic stabilisers reacting with the end groups of polymers when the polymers are in a melted or solid state, with a chemical bond being formed. The invention also relates to the use of such mixtures as stabilisers for polymers, and to a method for the stabilisation of polymers against losses in molecular weight in which an effective amount of such a mixture is added to the polymer.
Description
Additive zur Hydrolysestabilisierung von Polykondensaten Beschreibung: Die vorliegende Erfindung betrifft Mischungen enthaltend multifunktionelle Kettenver- längerer und mono- oder difunktionelle Hydrolysestabilisatoren für Polymere. Weiterhin betrifft die Erfindung Mischungen von multifunktionellen Kettenverlängerern, mono- oder difunktionelle Hydrolysestabilisatoren und Polymeren. Weitere Gegenständ der Erfindung sind die Verwendung der Mischungen enthaltend multifunktionelle Kettenver- längerer und mono- oder difunktionelle Hydrolysestabilisatoren zur Stabilisierung von Polymeren und Verfahren zur Stabilisierung gegen Molekulargewichtsverlust von Polymeren. Description: The present invention relates to mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for polymers. Furthermore, the invention relates to mixtures of multifunctional chain extenders, mono- or difunctional hydrolysis stabilizers and polymers. Further objects of the invention are the use of the mixtures containing multifunctional chain extenders and mono- or difunctional hydrolysis stabilizers for stabilizing polymers and methods for stabilizing against molecular weight loss of polymers.
Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Be- Schreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils konkret angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen. Bevorzugt, beziehungsweise ganz bevorzugt, sind insbesondere auch die- jenigen Ausführungsformen der vorliegenden Erfindung, in denen alle Merkmale des erfindungsgemäßen Gegenstandes die bevorzugten, beziehungsweise ganz bevorzugten, Bedeutungen haben. Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. In particular, those embodiments of the present invention in which all features of the article according to the invention have the preferred, or very preferred, meanings are preferred or very particularly preferred.
Kettenverlängerer wurden ursprünglich entwickelt um Polykondensate mit hohen Mo- lekulargewichten durch reaktive Extrusion zu erhalten. Beispielsweise werden in der WO 98/47940 A1 bifunktionale Caprolactam-Kettenverlängerer zur Herstellung von hochmolekularen Polyestern und Polyamiden beschrieben. Chain extenders were originally developed to obtain polycondensates with high molecular weights by reactive extrusion. For example, WO 98/47940 A1 describes bifunctional caprolactam chain extenders for the preparation of high molecular weight polyesters and polyamides.
Multifunktionelle Kettenverlängerer mit drei oder mehr reaktiven Gruppen führen zu verzweigten Strukturen. Der Einsatz solcher Additive in einer Polymermatrix führt daher neben der Kettenverlängerung häufig zu Verzweigungen, die bei einer Verarbeitung in der Schmelze die Viskosität deutlich erhöhen. Solche Additive sind in der US Multifunctional chain extenders with three or more reactive groups lead to branched structures. The use of such additives in a polymer matrix therefore often leads, in addition to the chain extension, to branchings which, when processed in the melt, markedly increase the viscosity. Such additives are in the US
5,354,802 für den Einsatz in beispielsweise Polyestern oder Polyamiden beschrieben. Die WO 2004/067629 A1 beschreibt den Einsatz von Kettenverlängereren in Form einer Verdünnung in einem inerten Trägerkunststoff. 5,354,802 for use in, for example, polyesters or polyamides. WO 2004/067629 A1 describes the use of chain extenders in the form of a dilution in an inert carrier plastic.
In der US 6,984,694 B2 wird die Verwendung von Copolymeren enthaltend epoxy- funktionalisierte (Meth)acrylsäure Monomere, Styrol und/oder (Meth)acrylsäure Monomere als Kettenverlängerer beschrieben. No. 6,984,694 B2 describes the use of copolymers containing epoxy-functionalized (meth) acrylic acid monomers, styrene and / or (meth) acrylic acid monomers as chain extenders.
Carbodiimide sind als Hydrolysestabilisatoren beispielsweise aus der US 5,439,952, EP 799843 A1 oder EP 126251 1 A2 bekannt. Bei ihrer Verwendung entstehen jedoch
häufig toxische Nebenprodukte wie Phenylisocyanate. Um Probleme mit der Toxizität zu vermeiden werden oligomere oder polymere Carbodiimide eingesetzt. Carbodiimides are known as hydrolysis stabilizers, for example from US Pat. No. 5,439,952, EP 799843 A1 or EP 126251 1 A2. In their use, however, arise often toxic by-products such as phenyl isocyanates. To avoid problems with toxicity, oligomeric or polymeric carbodiimides are used.
Beispielsweise beschreibt die DE 3217440 A1 Polyethylenterephthalate mit verbesser- ter Hydrolysebeständigkeit, enthaltend Polycarbodlimide. For example, DE 3217440 A1 describes polyethylene terephthalates having improved hydrolysis resistance, containing polycarbodlimides.
Die DE 198 09 634 A1 beschreibt Verfahren zur Herstellung von Carbodiimiden und Mischungen enthaltend Carbodiimide und Polyester oder Polyurethane. Carbodiimide enthaltend über Harnstoffgruppen gebundene Silangruppen sowie deren Mischungen mit Polymeren sind in der WO 2005/1 1 1048 A1 beschrieben. 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 beschreibt multifunktionelle wasserdispergierbare Vernetzungsmittel auf der Basis oligomerer Substanzen, enthaltend Carbodiimid und andere reaktive funktionelle Gruppen, wie beispielsweise Heterocyclen. Weiterhin werden wässrige Dispersionen, Emulsionen oder Lösungen solcher Vernetzungsmittel sowie Verfahren zur Herstellung der Vernetzungsmittel beschrieben. EP 0 507 407 A1 describes multifunctional water-dispersible crosslinking agents based on oligomeric substances containing carbodiimide and other reactive 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.
Unsere unveröffentlichte Patentanmeldung EP 1 1 158914.9 beschreibt die Verwendung oligomerer Carbodiimide, enthaltend mindestens eine heterocyclische Endgruppe, als Stabilisatoren für Polymere. Our unpublished patent application EP 1 1 158914.9 describes the use of oligomeric carbodiimides containing at least one heterocyclic end group as stabilizers for polymers.
US 4,385,144 beschreibt Epoxyalkane mit zwischen 10 bis 50 Kohlenstoffatomen in PET zur Verbesserung der Verarbeitungseigenschaften des Polymers. US 4,385,144 describes epoxyalkanes having between 10 to 50 carbon atoms in PET for improving the processing properties of the polymer.
In der US 4,393,156 und US 4,393,158 werden die Verwendung von Epoxy-Silanen und Epoxy-Siloxanen zur Hydrolysestabilisierung von Polyestercarbonaten oder aromatischen Polycarbonaten beschrieben. Alkylketendimere werden häufig in der Hydrophobierung von Papier oder Fasern eingesetzt wie beispielsweise in US 5,028,236 oder WO 92/15746 A1 beschrieben. US 4,393,156 and US 4,393,158 describe the use of epoxy silanes and epoxy siloxanes for the hydrolysis stabilization of polyester carbonates or aromatic polycarbonates. Alkylketene dimers are frequently used in the hydrophobicization of paper or fibers, as described, for example, in US Pat. No. 5,028,236 or WO 92/15746 A1.
JP 2007023100 A2 beschreibt die Verwendung von Alkylketendimeren bei der Stabilisierung von aliphatischen Polyestern. JP 2007023100 A2 describes the use of alkyl ketene dimers in the stabilization of aliphatic polyesters.
US 3,770,693 und US 4,123,419 beschreiben die Verwendung von Oxazolidinen als Stabilisatoren von Ester-(Co)polymeren, insbesondere Polyesterurethanen. US 3,770,693 and US 4,123,419 describe the use of oxazolidines as stabilizers of ester (co) polymers, especially polyester urethanes.
Polymere, beispielsweise Polykondensationspolymer wie Polyester unterliegen bei erhöhten Temperaturen häufig einem Abbau durch Hydrolyse. Solche Bedingungen treten beispielsweise bei einer Verarbeitung der Polymere unter Wärmezufuhr bei gleichzeitigem Vorhandensein von Feuchtigkeit auf. Hydrolyse der Polymere führt zu
einer Herabsetzung des Molekulargewichts und zu einer Abnahme der Schmelzviskosität unter gleichzeitiger Beeinträchtigung der mechanischen Eigenschaften der Polymere. Diese Effekte schränken die Anwendbarkeit solcher hydrolysierbarer Polymere stark ein und bedingen außerdem einen großen Trocknungsaufwand vor der Verarbei- tung der Polymere. Polymers, for example polycondensation polymers such as polyesters, are often degraded by hydrolysis at elevated temperatures. Such conditions occur, for example, when processing the polymers under heat with the simultaneous presence of moisture. Hydrolysis of the polymers leads to a reduction in the molecular weight and a decrease in the melt viscosity, while affecting the mechanical properties of the polymers. These effects severely limit the applicability of such hydrolyzable polymers and, moreover, require a great deal of drying before the polymers are processed.
Aufgabe der vorliegenden Erfindung war es daher Stabilisatoren für Polymere zur Verfügung zu stellen, die zu einer Verringerung des Abbaus und einer Verminderung der Hydrolyse führen. Insbesondere war es eine Aufgabe der Erfindung eine Abnahme der Schmelzviskosität von Polymeren bei der Verarbeitung zu unterdrücken. The object of the present invention was therefore to provide stabilizers for polymers which lead to a reduction in the degradation and a reduction in the hydrolysis. In particular, it was an object of the invention to suppress a decrease in the melt viscosity of polymers during processing.
Diese Aufgaben wurden gelöst durch Mischungen (M) enthaltend a. mindestens einen multifunktionellen Kettenverlängererer (K) mit mindestens drei reaktiven Gruppen, und These objects have been achieved by mixtures (M) containing a. at least one multifunctional chain extender (K) having at least three reactive groups, and
b. mindestens einen mono- oder difunktionellen Hydrolysestabilisator (H), wobei, die Kettenverlängerer (K) und die Hydrolysestabilisatoren (H) mit den Endgruppen von Polymeren (P) im geschmolzenen oder festen Zustand der Polymere (P) unter Ausbildung einer chemischen Bindung reagieren. Bevorzugt reagieren die Kettenverlängerer (K) mit den Endgruppen von Polymeren (P) im geschmolzenen Zustand der Polymere (P) und die Hydrolysestabilisatoren (H) mit den Endgruppen von Polymeren (P) im geschmolzenen oder festen Zustand der Polymere (P). Ausdrücke der Form Ca-Cb bezeichnen im Rahmen dieser Erfindung chemische Verbindungen oder Substituenten mit einer bestimmten Anzahl von Kohlenstoffatomen. Die Anzahl an Kohlenstoffatomen kann aus dem gesamten Bereich von a bis b, einschließlich a und b gewählt werden, a ist mindestens 1 und b immer größer als a. Eine weitere Spezifizierung der chemischen Verbindungen oder der Substituenten erfolgt durch Ausdrücke der Form Ca-Cb-V. V steht hierbei für eine chemische Verbindungsklasse oder Substituentenklasse, beispielsweise für Alkylverbindungen oder Alkylsub- stituenten. b. at least one mono- or difunctional hydrolysis stabilizer (H), wherein the chain extenders (K) and the hydrolysis stabilizers (H) react with the end groups of polymers (P) in the molten or solid state of the polymers (P) to form a chemical bond. Preferably, the chain extenders (K) react with the end groups of polymers (P) in the molten state of the polymers (P) and the hydrolysis stabilizers (H) with the end groups of polymers (P) in the molten or solid state of the polymers (P). 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 steht für Fluor, Chlor, Brom, oder lod, vorzugsweise für Fluor, Chlor oder Brom, besonders bevorzugt für Fluor oder Chlor. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
Im Einzelnen haben die für die verschiedenen Substituenten angegebenen Sammelbegriffe folgende Bedeutung: Ci-C2o-Alkyl: geradkettige oder verzweigte Kohlenwasserstoffreste mit bis zu 20 Kohlenstoffatomen, beispielsweise Ci-Cio-Alkyl oder Cn-C2o-Alkyl, bevorzugt Ci-Cio-Alkyl beispielsweise Ci-C3-Alkyl, wie Methyl, Ethyl, Propyl, Isopropyl, oder C4-C6-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-Methyl-pentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 2-Ethylbutyl, 1,1,2- Trimethylpropyl, 1 ,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl, oder C7-C10-Alkyl, wie Heptyl, Octyl, 2-Ethyl-hexyl, 2,4,4-Trimethylpentyl, 1,1,3,3- Tetramethylbutyl, Nonyl oder Decyl sowie deren Isomere. In detail, the collective terms given for the various substituents have the following meaning: 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 C3-alkyl, such as methyl, ethyl, propyl, isopropyl, or C4-C6-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, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1.1 , 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C7-C10-alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2,4 , 4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers.
C2-C2o-Alkenyl: ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 20 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, beispielsweise C2-Cio-Alkenyl oder Cn-C2o-Alkenyl, bevorzugt C2-Cio-Alkenyl wie C2-C4- Alkenyl, wie 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, oder Cs-C6-Alkenyl, wie 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1- Methyl-1-butenyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl- 2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3- butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1- Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5- Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1- pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2- pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3- pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4- pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2- Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1-butenyl, 1,3-Dimethyl-2- butenyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3- Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2- butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2- Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Ethyl-1-methyl-2- propenyl, 1-Ethyl-2-methyl-1-propenyl oder 1-Ethyl-2-methyl-2-propenyl, sowie C7-C10- Alkenyl, wie die Isomere von Heptenyl, Octenyl, Nonenyl oder Decenyl. 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-C6 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-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3 Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2- propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl 2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4 pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2- Dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3- Dimethyl 3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3- Dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2- Ethyl 2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and C7-C10 alkenyl, such as the isomers of heptenyl, octenyl, nonenyl or decenyl.
C2-C2o-Alkinyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 20 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, beispielsweise C2-Cio-Alkinyl oder Cn-C2o-Alkinyl, bevorzugt C2-Cio-Alkinyl wie C2-C4-Alkinyl, wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Me-thyl-2-propinyl, oder C5-C7-Alkinyl, wie 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1 -Me-thyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1 -butinyl, 1,1-Dimethyl-2-propinyl, 1- Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1 -Methyl-2- pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4- pentinyl, 3-Methyl-1-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2- pentinyl, 1,1-Dimethyl-2-butinyl, 1,1-Dimethyl-3-butinyl, 1,2-Dimethyl-3-butinyl, 2,2- Dimethyl-3-butinyl, 3, 3-Dimethyl-1 -butinyl, 1 -Ethyl-2-butinyl, 1 -Ethyl-3-butinyl, 2-Ethyl-
3-butinyl oder 1 -Ethyl-1 -methyl-2-propinyl sowie C7-C10-Alkinyl, wie die Isomere von Heptinyl, Octinyl, Noninyl, Decinyl. 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- propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2- pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3-dimethyl-1 - butinyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl 3-butynyl or 1-ethyl-1-methyl-2-propynyl and C7-C10 alkynyl, such as the isomers of heptynyl, octynyl, nonynyl, decynyl.
C3-Ci5-Cycloalkyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis zu 15 Kohlenstoffringgliedern, bevorzugt Cs-Cs-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl sowie ein gesättigtes oder ungesättigtes cyclisches System wie z. B. Norbornyl oder Norbenyl. C3-C15-cycloalkyl: monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.
Aryl: ein ein- bis dreikerniges aromatisches Ringsystem enthaltend 6 bis 14 Kohlen- stoffringglieder, z. B. Phenyl, Naphthyl oder Anthracenyl, bevorzugt ein ein- bis zweikerniges, besonders bevorzugt ein einkerniges aromatisches Ringsystem. 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.
Ci-C2o-Alkoxy bedeutet eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 20 Kohlenstoffatomen (wie vorstehend genannt), welche über ein Sauerstoffatom (-0-) an gebunden sind, beispielsweise Ci-Cio-Alkoxy oder Cn-C2o-Alkoxy, bevorzugt C1-C10- Alkyloxy, insbesondere bevorzugt Ci-C3-Alkoxy, wie beispielweise Methoxy, Ethoxy, Propoxy. 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 C10 alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.
Heteroatome sind Phosphor, Sauerstoff, Stickstoff oder Schwefel bevorzugt Sauerstoff, Stickstoff oder Schwefel, deren freie Valenzen gegebenenfalls durch H-Atome abgesättigt sind. Heteroatoms are phosphorus, oxygen, nitrogen or sulfur, preferably oxygen, nitrogen or sulfur whose free valencies are optionally saturated by H atoms.
In einer bevorzugten Ausführungsform der Erfindung werden die Kettenverlängererer (K) gewählt werden aus der Gruppe der Homo- und Copolymere enthaltend mindes- tens drei Epoyxgruppen, mindestens drei Aziridin-Gruppen, oder mindestens drei anhydridische Gruppen. In a preferred embodiment of the invention, the chain extenders (K) are selected from the group of homopolymers and copolymers containing at least three epoxide groups, at least three aziridine groups, or at least three anhydride groups.
Besonders bevorzugt sind hierbei als Kettenverlängererer (K) Homo- oder Copolymere enthaltend mindestens drei Epoxygruppen. Ganz besonders bevorzugt handelt es sich bei solchen Kettenverlängererer (K) um Copolymere enthaltend mindestens drei Epoxygruppen, insbesondere um mit Epoxygruppen funktionalisierte Copolymere enthaltend Styrol, (Meth)acrylsäreestermonomer in polymerisierter Form. Particularly preferred chain extenders (K) are homo- or copolymers containing at least three epoxy groups. Very particular preference is given to such chain extenders (K) are copolymers containing at least three epoxy groups, in particular copolymers functionalized with epoxy groups containing styrene, (meth) acrylic acid ester monomer in polymerized form.
Beispiele für solche ganz bevorzugten Kettenverlängerer (K) und deren Herstellung sind in der US 6,984,694 B2 beschrieben. Examples of such very preferred chain extenders (K) and their preparation are described in US 6,984,694 B2.
Bevorzugt sind als Kettenverlängerer (K) Co-Polymerisationsprodukte von mindestens einem Monomer mit mindestens einer Epoxygruppe und mindestens einem Styrol und/oder (Meth)acrylsäreestermonomer. Beispielsweise handelt es sich hierbei um mit Epoxygruppen funktionalisierte (Meth)acrylsäreestermonomere in Kombination mit nicht epoxyfunktionalisierten Styrolmonomeren und/oder Preferred chain extenders (K) are copolymerization products of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer. For example, these are epoxy group-functionalized (meth) acrylic acid ester monomers in combination with non-epoxy-functionalized styrene monomers and / or
(Meth)acrylsäreestermonomeren. Der Ausdruck (Meth)acrylsäureestermonomere um-
fasst im Rahmen der vorliegenden Anmeldung sowohl Acrylsäureestermonomere (Ac- rylatmonomere) als auch Methacrylsäureestermonomere (Methacrylatmonomere). (Meth) acrylsäreestermonomeren. The term (meth) acrylic ester monomers refers to For the purposes of the present application, both acrylic ester monomers (acrylate monomers) and methacrylic acid ester monomers (methacrylate monomers) are included.
Beispiele der mit Epoxygruppen funktionalisierten (Meth)acrylsäreestermonomere um- fassen solche, die 1 ,2-Epoxygruppen enthalten, wie Glycidylacrylat und Glycidylme- thacrylat. Andere mit Epoxygruppen funktionalisierten Monomere umfassen Allyl- glycidylether, Glycidylethacrylat, Glycidylitoconat. Examples of the epoxy group-functionalized (meth) acrylic ester monomers include those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate. Other monomers functionalized with epoxy groups include allyl glycidyl ether, glycidyl methacrylate, glycidyl titanate.
Acrylat- und Methacrylatmonomere, die im Rahmen der Erfindung eingesetzt werden können, umfassen, unabhängig von einer Funktionalisierung mit Epoxygruppen, Me- thylacrylat, Ethylacrylat, n-Propylacrylat, n-Hexylacrylat, n-Octylacrylat, Methyl- methacrylat, Ethyl-methacrylat, n-Propylmethacrylat, Methylcyclohexyl-methacrylat, Isobornyl-methacrylat, Butylacrylat, Butylmethacrylat, Iso-butyl-methacrylat, Cyclohe- xylacrylat, Cyclohexylmethacrylat, Isobornylacrylat, Isobornylmethacrylat, und Mi- schungen aus diesen. Acrylate and methacrylate monomers that can be used in the invention include, independently of a functionalization with epoxy groups, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-hexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n Propyl methacrylate, methylcyclohexyl methacrylate, isobornyl methacrylate, butyl acrylate, butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures of these.
Bevorzugte Nichtfunktionalisierte Acrylate- und Methaycrylate umfassen Butylacrylat, Butylmethacrylat, Methyl-methacrylat, Iso-butyl-methacrylat, Cyclohexylacrylat, Cyclohexylmethacrylat, Isobornylacrylat, Isobornylmethacrylat, und Mischungen aus diesen. Preferred non-functionalized acrylate and methacrylate include butyl acrylate, butyl methacrylate, methyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
Styrolmonomere, die im Rahmen der vorliegenden Erfindung eingesetzt werden können, umfassen Styrol, alpha-Methylstyrol, Vinyltoluol, p-Methylstyrol, tert-Butylstyrol, o- Chlorstyrol, Vinylpyridine und Mischungen aus diesen. In speziellen Ausführungsfor- men sind die Monomere gewählt aus Styrol oder alpha-Methylstyrol. Styrenic monomers that can be used in the present invention include styrene, alpha-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, vinylpyridines and mixtures thereof. In specific embodiments, the monomers are selected from styrene or alpha-methylstyrene.
Besonders bevorzugte Co-Polymerisationsprodukte enthalten wenigstens ein Monomer gewählt aus Glycidylacrylat und Glycidyl-Methacrylat und wenigstens ein Monomer gewählt aus Styrol, Methyl-methacrylat, Methylacrylat, Butylacrylat und Ethyl-hexyl- acrylat. Particularly preferred co-polymerization products contain at least one monomer selected from glycidyl acrylate and glycidyl methacrylate and at least one monomer selected from styrene, methyl methacrylate, methyl acrylate, butyl acrylate and ethyl hexyl acrylate.
Bevorzugt haben die Co-Polymerisationsprodukte von mindestens einem Monomer mit mindestens einer Epoxygruppe und mindestens einem Styrol und/oder Preferably, the co-polymerization of at least one monomer having at least one epoxy group and at least one styrene and / or
(Meth)acrylsäreestermonomer ein Epoxy Äquivalent Gewicht (Epoxy Equivalent Weight, EEW) von 180 bis 2800 g/mol, bevorzugt von 190 bis 1400 g/mol und besonders bevorzugt von 200 bis 700 g/mol. Bevorzugt weisen diese Co- Polymerisationsprodukte einen Efn-Wert (Efn=Mn/EEW) von weniger als 30, bevorzugt von 2 bis 20 und besonders bevorzugt von 3 bis 10 auf. Bevorzugt weisen diese Co- Polymerisationsprodukte weiterhin einen Efw-Wert (Efw=Mw/EEW) von weniger als 140, bevorzugt von 3 bis 65 und besonders bevorzugt von 6 bis 45 auf. Efn steht für das Zahlenmittel der Epoxyfunktionalität und Efw für das Massenmittel der Epoxyfunk- tionalität.
Bevorzugt haben die Co-Polymerisationsprodukte von mindestens einem Monomer mit mindestens einer Epoxygruppe und mindestens einem Styrol und/oder (Meth) acrylic ester monomer an epoxy equivalent weight (EEW) of 180 to 2800 g / mol, preferably from 190 to 1400 g / mol and particularly preferably from 200 to 700 g / mol. These copolymerization products preferably have an Efn value (Efn = Mn / EEW) of less than 30, preferably from 2 to 20 and particularly preferably from 3 to 10. These copolymerization products furthermore preferably have an Efw value (Efw = Mw / EEW) of less than 140, preferably from 3 to 65 and particularly preferably from 6 to 45. Efn stands for the number average of the epoxy functionality and Efw for the weight average of the epoxy functionality. Preferably, the co-polymerization of at least one monomer having at least one epoxy group and at least one styrene and / or
(Meth)acrylsäreestermonomer ein Zahlenmittel der Molmasse (Mn) von weniger als 6000 g/mol, bevorzugt von 1000 bis 5000 g/mol und besonders bevorzugt von 1500 bis 4000 g/mol auf. Weiterhin weisen diese Co-Polymerisationsprodukte bevorzugt ein Massenmittel der Molmasse (Mw) von weniger als 25000 g/mol, bevorzugt von 1500 bis 18000 g/mol, besonders bevorzugt von 3000 bis 13000 g/mol und insbesondere von 4000 bis 8500 g/mol auf. Die EEW Werte entsprechen der Masse des Co-Polymerisationsproduktes, die ein Äquivalent der Epoxyfunktionalität aufweist und werden gemäß ASTM D 1652-90 (Standard Test Method for Epoxy Content of Epoxy Resins (1990) Test Method B) oder wie beispielsweise in der US 6,552,144 B1 aus der Massebilanz der eingesetzten Monomere mit Epoxygruppen bestimmt. (Meth) acrylic acid ester monomer has a number average molecular weight (Mn) of less than 6000 g / mol, preferably from 1000 to 5000 g / mol and particularly preferably from 1500 to 4000 g / mol. Furthermore, these co-polymerization preferably have a weight average molecular weight (Mw) of less than 25,000 g / mol, preferably from 1500 to 18000 g / mol, more preferably from 3000 to 13000 g / mol and in particular from 4000 to 8500 g / mol , The EEW values correspond to the mass of co-polymerization product having one equivalent of epoxy functionality and are determined according to ASTM D 1652-90 (Standard Test Method for Epoxy Content of Epoxy Resins (1990) Test Method B) or as described, for example, in US 6,552,144 B1 determined from the mass balance of the monomers used with epoxy groups.
Die Molkulargewichtsverteilungen der Co-Polymerisationsprodukte werden mit Hilfe von Gel-Permeations-Chromatographie (GPC) -Messungen bestimmt. Hierzu werden die Co-Polymerisationsprodukte zunächst in Tetrahydrofuran (THF) gelöst und danach in die GPC-Apparatur injiziert. Beispielsweise lässt sich als GPC-Apparatur eine Wa- ters 2695 Apparatur mit einem Waters 2410 Brechungsindex (Refractive Index, Rl)- Detektor einsetzen. Als Säulen lassen sich die PLGEL MIXED B Säulen mit einer Überwachungssäule einsetzen und unter anderem die Mn und Mw Werte bestimmen. Molecular weight distributions of the co-polymerization products are determined by gel permeation chromatography (GPC) measurements. For this purpose, the co-polymerization products are first dissolved in tetrahydrofuran (THF) and then injected into the GPC apparatus. For example, a Waters 2495 refractive index (RI) detector can be used as the GPC apparatus. As columns, the PLGEL MIXED B columns can be used with a monitoring column and, among other things, determine the Mn and Mw values.
Co-Polymerisationsprodukte von mindestens einem Monomer mit mindestens einer Epoxygruppe und mindestens einem Styrol und/oder (Meth)acrylsäreestermonomer sind kommerziell erhältlich, beispielsweise als Joncryle® der Fa. BASF SE. Co-polymerization of at least one monomer having at least one epoxy group and at least one styrene and / or (meth) acrylic acid ester monomer are commercially available, for example as Joncryle® Fa. BASF SE.
In einer weiteren bevorzugten Ausführungsform der erfindungsgemäßen Mischung werden die Hydrolysestabilisatoren (H) gewählt aus den a. oligomeren Carbodiimiden der allgemeinen Formel (I) In a further preferred embodiment of the mixture according to the invention, the hydrolysis stabilizers (H) are selected from the a. oligomeric carbodiimides of the general formula (I)
A1, A2 unabhängig voneinander, gleich oder verschieden, A 1 , A 2 independently of one another, the same or different,
Kohlenwasserstoffgruppen mit 3 bis 20 Kohlenstoffatomen, Hydrocarbon groups having 3 to 20 carbon atoms,
bevorzugt enthaltend cyclische Kohlenwassersroffreste, preferably containing cyclic hydrocarbons,
insbesondere C3-C14 Cycloalkylen, Arylen,
B1, B2 unabhängig voneinander, gleich oder verschieden, Heterocyclen, Ci-C3o-Alkohole, Poletherole, Polyesterole, Amine, Polyetheramine, Polyesteramine, Thioalkohole, Polyetherthiole, Polyesterthiole, n ganze Zahl im Bereich von 2 bis 100, bevorzugt im Bereich von 2 bis 50, besonders bevorzugt im Bereich von 2 bis 20, in particular C3-C14 cycloalkylene, arylene, B 1 , B 2 independently of one another, identical or different, heterocycles, C 1 -C 30 -alcohols, poletherols, polyesterols, amines, polyetheramines, polyesteramines, thioalcohols, polyether thiols, polyester thiols, n integer in the range from 2 to 100, preferably in the range of 2 to 50, more preferably in the range of 2 to 20,
insbesondere im Bereich von 2 bis 10 sind, und wobei A1, A2, B1 und B2 jeweils an beliebiger Position durch Ci-C2o-Alkyl, C2-C2o-Alkenyl, C2-C2o-Alkinyl, Ci-C20-Alkoxy, Carbonyl-Sauerstoff (=0) oderin particular in the range of 2 to 10, and wherein A 1 , A 2 , B 1 and B 2 are each at any position by C 1 -C 20 -alkyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl , Ci-C 20 alkoxy, carbonyl oxygen (= 0) or
Halogen, bevorzugt Ci-C4-Alkyl substituiert sein können, mono- oder difunktionellen Epoxyverbindungen der allgemeinen Formeln (IIa) oder (IIb) Halogen, preferably C 1 -C 4 -alkyl, mono- or difunctional epoxy compounds of the general formulas (IIa) or (IIb)
(IIa) (IIa)
(IIb) (IIb)
mit With
X1, X2, X3 unabhängig voneinander, gleich oder verschieden, CH2, O, X 1 , X 2 , X 3 independently of one another, identical or different, CH 2 , O,
C(=0), OC(=0), C(=0)NH, bevorzugt O, CH2, besonders bevorzugt O, C (= O), OC (= O), C (= O) NH, preferably O, CH 2 , particularly preferably O,
Y1, Y2, Y3 unabhängig voneinander, gleich oder verschieden, Y 1 , Y 2 , Y 3 independently of one another, the same or different,
Einfachbindung, Ci-C2o-Alkylen, Ci-C2o-Alkylenyl, Arylen, bevorzugt Einfachbindung, Ci-C2o-Alkylen, besonders bevorzugt Ci-C2o-Alkylen, Single bond, C 1 -C 20 -alkylene, C 1 -C 20 -alkylenyl, arylene, preferably single bond, C 1 -C 20 -alkylene, particularly preferably C 1 -C 20 -alkylene,
Z H, SiR1R2R3, Si(OR1)R2R3, ZH, SiR 1 R 2 R 3 , Si (OR 1 ) R 2 R 3 ,
Si(OR1)(OR2)R3, Si(OR1)(OR2)(OR3), Si (OR 1 ) (OR 2 ) R 3 , Si (OR 1 ) (OR 2 ) (OR 3 ),
bevorzugt Si(OR1)(OR2)(OR3) preferably Si (OR 1 ) (OR 2 ) (OR 3 )
Z2, Z3 unabhängig voneinander, gleich oder verschieden, Einfachbindung, SiR1R2, Si(OR1)R2, Si(OR1)(OR2), Z 2 , Z 3 independently of one another, identical or different, single bond, SiR 1 R 2 , Si (OR 1 ) R 2 , Si (OR 1 ) (OR 2 ),
L1 Einfachbindung, O, CH2, L 1 single bond, O, CH 2 ,
R1, R2, R3 unabhängig voneinander, gleich oder verschieden, Ci-C2o-Alkyl, bevorzugt Ci-Cio-Alkyl, besonders bevorzugt Ci-C4-Alkyl, insbesondere Ci-C2-Alkyl,
R20, R21, R22 unahängig voneinander, gleich oder verschieden, H, C1-C20- Alkyl, bevorzugt H, oder R 1, R 2, R 3 independently of one another, identical or different, Ci-C2o-alkyl, preferably Ci-Cio-alkyl, particularly preferably Ci-C4-alkyl, in particular Ci-C2 alkyl, R 20 , R 21 , R 22 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
R20 gemeinsam mit R21 oder R22 Dimethylen, Trimethylen, Tetramethylen unter Ausbildung eines fünf-, sechs-, oder sieben- gliedrigen Ringsystems, R 20 together with R 21 or R 22 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system,
R23, R24, R25 unahängig voneinander, gleich oder verschieden, H, C1-C20- Alkyl, bevorzugt H, oder R 23 , R 24 , R 25 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, preferably H, or
R23 gemeinsam mit R24 oder R25 Dimethylen, Trimethylen, Tetramethylen unter Ausbildung eines fünf-, sechs-, oder sieben- gliedrigen Ringsystems, R 23 together with R 24 or R 25 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system,
Alkylketendimeren der allgemeinen Formel Alkylketene dimers of the general formula
mit With
R4 , R42 unabhängig voneinander gleich oder verschieden, H , Ci-C3o-Alkyl, bevorzugt H, C4-C2o-Alkyl, besonders bevorzugt H, C6-Ci8-Alkyl,R 4 , R 42 are each, independently of one another or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
R51 R52 unabhängig voneinander gleich oder verschieden, H , Ci-C3o-Alkyl, bevorzugt H, C4-C2o-Alkyl, besonders bevorzugt H, C6-Ci8-Alkyl, R 51 R 52 independently of one another are identical or different, H, C 1 -C 30 -alkyl, preferably H, C 4 -C 20 -alkyl, particularly preferably H, C 6 -C 18 -alkyl,
Heterozyklen der allgemeinen Formeln (IV) oder (V) IV) Heterocycles of the general formulas (IV) or (V) IV)
mit With
A O, NR16, AO, NR 16 ,
R6 H, Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, NR26R27, R 6 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, NR 26 R 27 ,
bevorzugt H, Ci-Cio-Alkyl, Propionyl, Acetyl, Crotonyl, besonders bevorzugt H, Ci-C4-Alkyl, preferably H, C 1 -C 10 -alkyl, propionyl, acetyl, crotonyl, particularly preferably H, C 1 -C 4 -alkyl,
insbesondere H, Ci-C2-Alkyl,
R16 H, Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, Halogen, in particular H, C 1 -C 2 -alkyl, R 16 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, halogen,
bevorzugt H, Ci-Cio-Alkyl, Aryl, preferably H, C 1 -C 10 -alkyl, aryl,
besonders bevorzugt H, Ci-C4-Alkyl, Phenyl, Toloyl, particularly preferably H, C 1 -C 4 -alkyl, phenyl, tobolyl,
R26, R27 unabhängig voneinander, gleich oder verschieden, H, R 26 , R 27 independently of one another, the same or different, H,
Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl,
bevorzugt H, Ci-Cio-Alkyl, Aryl, preferably H, C 1 -C 10 -alkyl, aryl,
besonders bevorzugt H, Ci-C4-Alkyl, Phenyl, Toloyl, particularly preferably H, C 1 -C 4 -alkyl, phenyl, tobolyl,
R7, R8, R9, R10 unabhängig voneinander, gleich oder verschieden, H, R 7 , R 8 , R 9 , R 10 are independently, the same or different, H,
Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl,
bevorzugt H, Ci-Ci8-Alkyl, Aryl, C5-C8-Cycloalkyl, besonders bevorzugt H, Ci-C4-Alkyl, preferably H, C 1 -C 8 -alkyl, aryl, C 5 -C 8 -cycloalkyl, particularly preferably H, C 1 -C 4 -alkyl,
insbesondere H, Ci-C2-Alkyl, wobei R6, R16 jeweils an beliebiger Position durch Ci-C2o-Alkyl, C2-C2o-Alkenyl, C2-C2o-Alkinyl, Ci-C2o-Alkoxy, Carbonyl-Sauerstoff (=0) oder Halogen, in particular H, C 1 -C 2 -alkyl, where R 6 , R 16 are each at any position by C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 1 -C 20 -alkoxy, carbonyl oxygen (= O) ) or halogen,
bevorzugt Ci-C4-Alkyl, C2-Cio-Alkenyl, Carbonyl-Sauerstoff (=0) preferably C 1 -C 4 -alkyl, C 2 -C 10 -alkenyl, carbonyl oxygen (= 0)
substituiert sein können. may be substituted.
Weitere Vorteile dieser Hydrolysestabilisatoren (H) sind, dass sie keinen negativen Einfluß auf die Schmelzviskosität, Farbe, Trübung oder den Geruch von Polymeren haben. Further advantages of these hydrolysis stabilizers (H) are that they have no negative influence on the melt viscosity, color, turbidity or odor of polymers.
Bevorzugt werden die Hydrolysestabilisatoren (H) so gewählt, dass die Schmelzviskosität während der Extrusion nicht wesentlich zunimmt, bevorzugt um weniger als 20%, besonders bevorzugt um weniger als 10%, so dass eine Einstellung der Zielviskosität im Wesentlichen über die Zugabe des Kettenverlängererers (K) geregelt wird. The hydrolysis stabilizers (H) are preferably chosen such that the melt viscosity does not increase significantly during the extrusion, preferably by less than 20%, more preferably by less than 10%, so that an adjustment of the target viscosity essentially via the addition of the chain extender (K ) is regulated.
Oligomere Carbodiimide c. der allgemeinen Formel (I) lassen sich, wie beispielsweise in der EP 0 507 407 A1 oder unserer unveröffentlichten Patentanmeldung EP Oligomeric carbodiimides c. of the general formula (I) can be as described for example in EP 0 507 407 A1 or our unpublished patent application EP
1 1 158914 beschrieben, nach dem Fachmann bekannten Verfahren herstellen. Ein allgemeines Herstellungsverfahren zur Herstellung oligomerer Carbodiimide, enthaltend mindestens eine heterocyclische Endgruppe, umfasst beispielsweise die Reaktion eines Diisocyanats mit einem Polyetherol und einem Heterocyclus. 1 1 158914, according to methods known in the art. A general preparation process for preparing oligomeric carbodiimides containing at least one heterocyclic end group includes, for example, the reaction of a diisocyanate with a polyetherol and a heterocycle.
In einer weiteren bevorzugten Ausführungsform enthalten die Substituenten der oligo- meren Carbodiimide der allgemeinen Formel (I) A1, A2 die Kohlenwasserstoffgruppen
In a further preferred embodiment, the substituents of the oligomeric carbodiimides of the general formula (I) A 1 , A 2 contain the hydrocarbon groups
In einer weiteren bevorzugten Ausführungsform der erfindungsgemäßen Mischung werden die Substituenten der Carbodiimide B1, B2 gewählt aus der Gruppe der drei- bis zwoifgliedrigen, bevorzugt drei- bis neungliedrigen, besonders bevorzugt fünf- bis sie- bengliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome und ein oder mehrere Ringe aufweisenden Ringsysteme (Heterocyclen, heterocyclische Endgruppen), wie Aziridin, Epoxid, Thiiran, Azirin, Oxiren, Thiiren, Azetidin, Oxetan, Thietan, beta- Lactam, beta-Lacton, Thiethanon, Furan, Pyrrolin, Dihydrofuran, Dihydrothiophen, Py-
rolidin, Tetrahydrofuran, Tetrahydrothiophen, Oxazolidin, Dioxolan, Oxathiolan, Thiazo- lidin, Imidazolin, Dithiolan, Pyrazolidin, Pyrazolin, Oxazolin, Thiazolin, Imidazolin, Dio- xol, Oxazolon, Pyrrolidon, Butyrolacton, Thiobutyrolacton, Butyrothiolacton, Thiobuty- rothiolacton, Oxazolidon, Dioxolan-2-οη, Thiazolidinon, Dihydropyridin, Tetrahydropyri- din, Pyran, Dihydropyran, Tetrahydropyran, Bernsteinsaureanhydrid, Succinimid, Thio- pyran, Dihydrothiopyran, Tetrahydrothiopyran, Dihydropyrimidin, Tetrahydropyrimidin, Hexahydropyrimidin, Dioxan, Morpholin, Thiamorpholin, Dithian, Triazin, wobei diese in beliebiger weise chemisch in der allgemeinen Formel (I) angebunden sind, beispielsweise über eine Bindung zu einem Kohlenstoffatom des Heterocyclus oder eine Bin- dung zu einem der Heteroatome. In a further preferred embodiment of the mixture according to the invention, the substituents of the carbodiimides B 1 , B 2 are selected from the group of the three- to zwoifgliedrigen, preferably three- to nine-membered, more preferably five- to seven-membered, 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, pyrogen rolidine, tetrahydrofuran, tetrahydrothiophene, oxazolidine, dioxolane, oxathiolane, thiazolidine, imidazoline, dithiolane, pyrazolidine, pyrazoline, oxazoline, thiazoline, imidazoline, dioxol, oxazolone, pyrrolidone, butyrolactone, thiobutyrolactone, butyrothiolactone, thiobutyrothiolactone, oxazolidone, Dioxolan-2-one, thiazolidinone, dihydropyridine, tetrahydropyridine, pyran, dihydropyran, tetrahydropyran, succinic anhydride, succinimide, thiopyran, dihydrothiopyran, tetrahydrothiopyran, dihydropyrimidine, tetrahydropyrimidine, hexahydropyrimidine, dioxane, morpholine, thiamorpholine, dithiane, triazine, these being in any way chemically bound in the general formula (I), for example via a bond to a carbon atom of the heterocycle or a bond to one of the heteroatoms.
Insbesondere bevorzugt sind fünf-, sechs- oder siebengliedrige gesättigte stickstoffhaltige Ringsysteme, die über ein Ringstickstoffatom oder Ringkohlenstoffatom angebunden sind und die noch ein oder zwei weitere Stickstoffatome oder Sauerstoffatome enthalten können. Diese werden hierbei ganz bevorzugt gewählt aus der Gruppe der Particular preference is given to five-, six- or seven-membered saturated nitrogen-containing ring systems which are attached via a ring nitrogen atom or ring carbon atom and which may contain one or two further nitrogen atoms or oxygen atoms. These are very preferably selected from the group of
In einer besonders bevorzugten Ausführungsform gilt für die Substituenten der Car- bodiimide: A1 = A2 und B1 = B2. In a particularly preferred embodiment, the substituents of the carbodiimides are: A 1 = A 2 and B 1 = B 2 .
Epoxyverbindungen b. der allgemeinen Formeln (IIa) und (IIb) und deren Herstellung sind dem Fachmann aus seinem Fachwissen, beispielsweise aus US 4,385,144, US 4,393,156 oder US 4,393,158, bekannt. Epoxyverbindungen der allgemeinen Formeln (IIa) und (IIb) sind kommerziell erhältlich. Epoxy compounds b. of the general formulas (IIa) and (IIb) and their preparation are known to the skilled person from his specialist knowledge, for example from US 4,385,144, US 4,393,156 or US 4,393,158. Epoxy compounds of the general formulas (IIa) and (IIb) are commercially available.
Alkylketendimere c. der allgemeinen Formeln (III) und ihre Herstellung sind dem Fachmann aus seinem Fachwissen, beispielsweise aus US 5,028,236 oder WO 92/15746 A1 , bekannt. Alkylketendimere der allgemeinen Formeln (III) sind kommerziell erhältlich. Alkyl ketene dimers c. of the general formulas (III) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 5,028,236 or WO 92/15746 A1. Alkylketene dimers of the general formulas (III) are commercially available.
Heterozyklen (Oxazolidinone und Derivate bzw. Isomere) d. der allgemeinen Formeln (IV) und (IV) und deren Herstellung sind dem Fachmann aus seinem Fachwissen, bei- spielsweise aus US 3,770,693 oder US 4,123,419, bekannt. Heterozyklen der allgemeinen Formeln (IV) und (V) sind kommerziell erhältlich.
Das Mengenverhältnis zwischen dem mindestens einem multifunktionellen Kettenver- längerer (K) und dem mindestens einen mono- oder difunktionellen Hydrolysestabilisator (H) in der Mischung (M) kann je nach Anwendung über einen weiten Bereich variieren. Beispielsweise werden in Anwendungen, die eine höhere Anfangsviskosität benö- tigen, z.B. PET-Recycling, höhere Mengen an Kettenverlängerern (K) eingesetzt. Bei Anwendungen, bei denen die Polymere höheren Temperaturen und erhöhter Luftfeuchtigkeit ausgesetzt sind, erhöht sich entsprechend der Anteil der Hydrolysestabilisatoren. Der Fachmann ist in der Lage durch entsprechende Experimente das geeignete Verhältnis einzustellen. Im allgemeinen liegt das Mengenverhältnis (Gewicht) von K zu H im Bereich von 1 : 100 bis 100 : 1 , bevorzugt von 1 : 50 bis 50 : 1 , ganz bevorzugt von 1 : 20 bis 20 : 1 und insbesondere von 1 : 10 bis 10 : 1 . Heterocycles (oxazolidinones and derivatives or isomers) d. of the general formulas (IV) and (IV) and their preparation are known to the person skilled in the art from his specialist knowledge, for example from US Pat. No. 3,770,693 or US Pat. No. 4,123,419. Heterocycles of the general formulas (IV) and (V) are commercially available. The ratio between the at least one multifunctional chain extender (K) and the at least one mono- or difunctional hydrolysis stabilizer (H) in the mixture (M) can vary over a wide range, depending on the application. For example, in applications requiring a higher initial viscosity, eg PET recycling, higher amounts of chain extenders (K) are used. In applications in which the polymers are exposed to higher temperatures and higher atmospheric humidity, the proportion of hydrolysis stabilizers increases accordingly. The skilled person is able to set the appropriate ratio by appropriate experiments. In general, the quantitative ratio (weight) of K to H is in the range from 1: 100 to 100: 1, preferably from 1:50 to 50: 1, more preferably from 1:20 to 20: 1 and especially from 1:10 to 10: 1.
In einer weiteren Ausführungsform der erfindungsgemäßen Mischung sind die Polymere (P) Polykondensate oder Polyadditionsprodukte. Bevorzugt werden die Polymere gewählt werden aus der Gruppe der Polyester, Polyamide, Polyurethane, Polycarbona- te, ihrer Copolymere und/oder Gemische. Insbesondere sind die zu stabilisierenden Polymere gewählt aus PET (Polyethylenterephthalat), PBT (Polybutylenterephthalat), PEN (polyethylennaphthalat), PC (Polycarbonat), bioabbaubare aliphatisch- aromatische Copolyester, Biopolymere oder PA6 (Polyamid 6). Als bioabbaubare aliphatisch-aromatische Copolyester sind insbesondere Poly(butylen adipate -co- terephthalate) geeignet und als Biopolymere kommen vor allem PLA (Polymilchsäure) und PHA (Polyhydroxylalkanoate) in Frage. Als Mischungen sind insbesondere In a further embodiment of the mixture according to the invention, the polymers (P) are polycondensates or polyaddition products. The polymers are preferably selected from the group of polyesters, polyamides, polyurethanes, polycarbonates, their copolymers and / or mixtures. In particular, the polymers to be stabilized are selected from PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6 (polyamide 6). Particularly suitable as biodegradable aliphatic-aromatic copolyesters are poly (butylene adipate-co-terephthalates) and suitable biopolymers are in particular PLA (polylactic acid) and PHA (polyhydroxyalkanoates). As mixtures are in particular
PC/ABS (Acrylnitril-Butadien-Styrol-Copolymer) Mischungen geeignet. Die stabilisierten Polymere umfassen selbstverständlich auch recyclierte oder wiederaufbereitete Polymere. Weiterhin enthalten in einer bevorzugten Ausführungsform der erfindungsgemäßen Mischung die Polymere (P) Hydroxy, Amin, Carboxy- oder Carbonsäure- Endgruppen, insbesondere Carbonsäure-Endgruppen. PC / ABS (acrylonitrile-butadiene-styrene copolymer) mixtures suitable. Of course, the stabilized polymers also include recycled or recycled polymers. Furthermore, in a preferred embodiment of the mixture according to the invention, the polymers (P) comprise hydroxyl, amine, carboxy or carboxylic acid end groups, in particular carboxylic acid end groups.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Mischungen (MP) enthaltend a. mindestens eine im Vorangegangenen beschriebene Mischung (M) und Another object of the present invention are mixtures (MP) containing a. at least one mixture (M) described above and
b. zusätzlich mindestens ein im Vorangegangenen beschriebenes Polymer (P). b. additionally at least one polymer (P) described above.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Mischung (MP) werden mindestens eine Mischung (M) dem mindestens einem Polymer (P) in einer Menge von 0,01 bis 10 Gew.-%, bevorzugt von 0,1 bis 5 Gew.-%, insbesondere von 0,1 bis 2In a preferred embodiment of the mixture (MP) according to the invention, at least one mixture (M) is added to the at least one polymer (P) in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.1 to 2
Gew.-% bezogen auf die Gesamtmenge an Polymer (P) und Mischung (M) dem Polymeren zugegeben. Wt .-% based on the total amount of polymer (P) and mixture (M) added to the polymer.
Die Einarbeitung der Mischungen (M) in die Polymere (P) erfolgt im Allgemeinen durch das Mischen der Bestandteile. Beispielsweise erfolgt das Mischen durch dem Fachmann bekannte Verfahren wie sie bei der Additivierung von Polymeren allgemein eingesetzt werden. Die Mischungen (M) in fester, flüssiger oder gelöster Form werden
bevorzugt zur Ausrüstung von Polyadditions- oder Polykondensationspolymeren eingesetzt. Die Mischungen (M) lassen sich zu diesem Zweck sowohl als feste oder flüssige Formulierung, als auch als Pulver nach den üblichen Methoden in die Polymere einarbeiten. Zu nennen ist hier beispielsweise das Vermischen der Mischungen (M) mit den Polymeren (P) vor oder während eines Extrusionsschrittes, Kneten, Kalandrieren, Folien-, Faserextrusion oder Blasformen. Das Mischen der Bestandteile vor der Einarbeitung, mit oder ohne Hilfe eines Lösungsmittels, ist möglich. Das Lösungsmittel lässt sich gegebennenfalls vor der Einarbeitung entfernen. Weitere Beispiele für die Ausrüstung oder Stabilisierung von Polymeren mit Additiven können dem Plastics Additives Handbook, 5. Auflage, Hanser Verlag, ISBN 1 -56990-295-X entnommen werden. Die additivierten Polymere können beispielsweise als Granulate, Pellets, Pulver, Folien oder Fasern vorliegen. The incorporation of the mixtures (M) in the polymers (P) is generally carried out by mixing the ingredients. 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 mixtures (M) in solid, liquid or dissolved form preferably used for the equipment of polyaddition or polycondensation polymers. The mixtures (M) 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. Mentioned here is, for example, the mixing of the mixtures (M) with the polymers (P) before or during an extrusion step, kneading, calendering, film, fiber extrusion or blow molding. The mixing of the ingredients before incorporation, with or without the aid of a solvent, is possible. If necessary, the solvent can be removed before incorporation. Further examples of the equipment or stabilization of polymers with additives can be found in the Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1 -56990-295-X. The additized polymers can be present, for example, as granules, pellets, powders, films or fibers.
Die Herstellung von Polymer-Formkörpern, die die Mischung (M) enthalten erfolgt durch dem Fachmann bekannte Verfahren. Insbesondere lassen sich die Polymer- Formkörper durch Extrusion oder Coextrusion, Compoundierung, Verarbeitung von Granulaten oder Pellets, Spritzguss, Blasformung oder Knetung herstellen. Bevorzugt erfolgt die Verarbeitung durch Extrusion oder Coextrusion zu Folien (vgl. Saechtling Kunststoff Taschenbuch, 28. Auflage, Karl Oberbach, 2001 ). The preparation of polymer moldings containing the mixture (M) is carried out by methods known to the person skilled in the art. In particular, the polymer moldings can be produced 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).
Die Polymere oder Polymer-Formkörper können zusätzlich wenigstens ein weiteres, häufig kommerziell erhältliches, Additiv enthalten, dass vorzugsweise ausgewählt ist unter Farbmitteln, Antioxidantien, anderen Stabilisatoren, z.B. Hindered Amine Light Stabilisatoren (HALS), UV-Absorbern, Nickelquenchern, Metalldesaktivatoren, Verstär- kungs- und Füllstoffen, Beschlagverhinderungsmittel (Antifog), Bioziden, Säurefängern, Antistatika, IR-Absorbern für langwellige IR Strahlung, Antiblockmittel wie Si02, Lichtstreuern wie MgO oder ΤΊ02, anorganischen oder organischen Reflektoren (beispielsweise Aluminium-Flakes). Möglich ist ebenfalls der Einsatz von weiteren nicht in den Mischungen (M) enthaltenen Kettenverlängerern oder Hydrolysestabilisatoren. The polymers or polymer moldings may additionally contain at least one other, often commercially available, additive, preferably selected from colorants, antioxidants, other stabilizers, e.g. Hindered amine light stabilizers (HALS), UV absorbers, nickel quenchers, metal deactivators, reinforcing agents and fillers, anti-fogging 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 ΤΊ02, inorganic or organic reflectors (for example aluminum flakes). It is also possible to use other chain extenders or hydrolysis stabilizers not contained in the mixtures (M).
Weiterhin betrifft die Erfindung die Verwendung von im Vorangegangenen beschriebenen Mischungen (M) als Stabilisatoren für im Vorangegangenen beschriebenen Polymere (P), insbesondere die Verwendung zur Stabilisierung gegen Molekulargewichtsverlust und/oder Hydrolyse. Furthermore, the invention relates to the use of mixtures (M) described above as stabilizers for polymers (P) described above, in particular the use for stabilizing against molecular weight loss and / or hydrolysis.
Eine weiterer Gegenstand der Erfindung ist ein Verfahren zur Stabilisierung von Polymeren (P), insbesondere gegen Molekulargewichtsverlust und/oder Hydrolyse, wobei dem Polymeren (P) eine effektive Menge an Mischung (M) zugegeben wird. Bevorzugt wird dem Polymeren (P) eine Menge (M) von 0,01 bis 10 Gew.-% bezogen auf die Ge- samtmenge an Polymer (P) und Mischung (M) zugegeben. Weiterhin werden dem Polymeren (P) im Rahmen des erfindungsgemäßen Verfahrens tur Stabilisierung, die im Vorangehenden beschriebenen Additive zugegeben.
Die vorliegende Erfindung stellt stabilisierend wirkende Mischungen (M) für Polymere zur Verfügung, die zu einer Verringerung des Abbaus und einer Verminderung der Hydrolyse der Polymere, insbesondere bei ihrer Verarbeitung, führen. Die Erfindung wird durch die Beispiele näher erläutert ohne dass die Beispiele den Gegenstand der Erfindung einschränken. Another object of the invention is a process for the stabilization of polymers (P), in particular against molecular weight loss and / or hydrolysis, wherein the polymer (P) an effective amount of mixture (M) is added. The amount of (M) from 0.01 to 10% by weight, based on the total amount of polymer (P) and mixture (M), is preferably added to the polymer (P). Furthermore, the polymer (P) in the context of the process according to the invention stabilization, the additives described in the foregoing added. The present invention provides stabilizing mixtures (M) for polymers which result in a reduction in degradation and a reduction in the hydrolysis of the polymers, particularly in their processing. The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
Beispiele: Polyethylenterephthalat (PET) mit einer Viskositätszahl von 69 ml/g für die Herstellung von biaxial orientierten Folien wurde von der Fa. Mitsubishi Polyester Film GmbH, Wiesbaden bezogen. Das PET wies eine geringe Konzentration an carboxylischen Endgruppen auf (ca. 21 mmol/kg). Die Säurezahlen werden durch Titration der jeweiligen PET-Lösung im Lösungsmittelgemisch aus Chloroform/Kresol erhalten. Examples: Polyethylene terephthalate (PET) having a viscosity number of 69 ml / g for the production of biaxially oriented films was purchased from Mitsubishi Polyester Film GmbH, Wiesbaden. The PET had a low concentration of carboxylic end groups (about 21 mmol / kg). The acid numbers are obtained by titration of the respective PET solution in the solvent mixture of chloroform / cresol.
Die Additive wurden in verschiedenen Konzentrationen bei einer Temperatur von 260°C mit dem PET gemeinsam extrudiert. Die so entstandenen Folien wurden dann erhöhten Temperaturen (1 10°C) und hoher Luftfeuchtigkeit (100 %) ausgesetzt und für einen Zeitraum von zwei oder fünf Tagen gelagert. Der Abbau des Polymers wurde durch Messung der Viskositätszahl (VZ) und/oder der Säure-Endgruppenkonzentration des PET vor und nach der Lagerung bestimmt. Die VZ Messungen (Einheiten in mg/l) wurden mit Hilfe eines Mikro-Ubbelohde Kapillarviskosimeters durchgeführt wobei als Lösungsmittel eine 1 :1 Mischung von Phenol und o-Dichlorbenzol eingesetzt wurde. Als PBT-Matrix kam Ultradur® B4520 (BASF SE) mit einer Viskositätszahl von 1 18 ml/g und einer Säurezahl von ca. 25 mmol/kg zum Einsatz. Additive wurden dem PBT durch Coextrusion hinzugefügt und Formkörper für Zugprüfungen hergestellt. Viskositätszahlen und Säureendgruppen wurden an Teilen der Prüfkörper vor und nach der Lagerung bei 1 10°C und 100% Luftfeuchtigkeit bestimmt. The additives were coextruded with the PET in various concentrations at a temperature of 260 ° C. The resulting films were then exposed to elevated temperatures (1-10 ° C) and high humidity (100%) and stored for a period of two or five days. The degradation of the polymer was determined by measuring the viscosity number (VZ) and / or the acid end group concentration of the PET before and after storage. The VZ measurements (units in mg / l) were carried out with the aid of a micro Ubbelohde capillary viscometer using as solvent a 1: 1 mixture of phenol and o-dichlorobenzene. Ultradur® B4520 (BASF SE) with a viscosity number of 18 ml / g and an acid number of about 25 mmol / kg was used as the PBT matrix. Additives were added to the PBT by coextrusion and moldings were made for tensile tests. Viscosity numbers and acid end groups were determined on parts of the test specimens before and after storage at 110 ° C. and 100% atmospheric humidity.
Als Referenz (Ref.) dienen, soweit nichts anderes angegeben ist, jeweils die Polymere, wie PET oder PBT, die ohne Hydrolysestabilisator oder Kettenverlängerer extrudiert wurden. Vergleichsbeispiel 1 : Joncryle The reference (ref.), Unless stated otherwise, is in each case the polymers, such as PET or PBT, which have been extruded without hydrolysis stabilizer or chain extender. Comparative Example 1: Joncryle
In diesem Beispiel kamen zwei Joncryl-Klassen zum Einsatz: In this example, two Joncryl classes were used:
Joncryl® ADR 4368 (Styrol/Acrylat copolymer, Mw = 6,800 g/mol, EEW = 285 g/mol) Joncryl® ADR 4368 (styrene / acrylate copolymer, Mw = 6.800 g / mol, EEW = 285 g / mol)
Joncryl® ADR 4300 (Styrol/Acrylate copolymer, Mw = 5,500 g/mol, EEW = 445 g/mol) Joncryl® ADR 4300 (styrene / acrylate copolymer, Mw = 5,500 g / mol, EEW = 445 g / mol)
In Tabelle 1 .1 findet sich der Vergleich der Viskositätszahlen und Säureendgruppen- konzentrationen im Vergleich zur Referenz (Ref.).
Tabelle 1.1 Table 1 .1 compares the viscosity numbers and acid end group concentrations in comparison to the reference (Ref.). Table 1.1
Die Menge an Joncryl® ist bezogen auf die Gesamtmenge an Joncryl® und Polymer angegeben. Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Joncryl® und Polymer. The amount of Joncryl® is given based on the total amount of Joncryl® and polymer. The concentration of acid end groups refers to the total amount of Joncryl® and polymer.
Die Joncryle® bewirken eine deutliche Erhöhung der Schmelzviskosität nach der Extrusion der Folien. Um jedoch einen unerwünschten Anstieg der Viskosität während der Verarbeitung zu vermeiden, können nur geringe Konzentrationen von Joncryl® eingesetzt warden (beispielsweise 0,2 Gew.-% Joncryl® 4300). Bei diesen Konzenrati- onen wird jedoch der Anstieg der Säureendgruppen während der Lagerung nicht verhindert. The Joncryle® causes a significant increase in the melt viscosity after the extrusion of the films. However, to avoid an undesirable increase in viscosity during processing, only low levels of Joncryl® can be used (for example, 0.2% by weight of Joncryl® 4300). At these concentrations, however, the increase in acid end groups during storage is not prevented.
Tabelle 1 .2 fasst den Verlauf der Viskositätszahl während der Lagerung der Filme zusammen. Die Daten sind die gleichen wie in Tabelle 1 .1 . Als Referenz (Bezugsgröße) wird nun jedoch die Viskositätszahl der jeweiligen Probe vor der Lagerung gewählt. Table 1 .2 summarizes the course of the viscosity number during the storage of the films. The data are the same as in Table 1 .1. As reference (reference), however, the viscosity number of the respective sample before storage is now selected.
Tabelle 1.2 Table 1.2
PET ADR 4300 ADR 4368 PET ADR 4300 ADR 4368
VZ extrudierte PET Folie [mL/g] 69 78 78 VZ extruded PET film [mL / g] 69 78 78
Delta VZ nach 2 Tagen Lagerung bei 1 10 °C/ 100% Luft- 23 - 21 - 26 Delta VZ after 2 days storage at 1 10 ° C / 100% air 23-21-26
feuchtigkeit [%] humidity [%]
VZ PBT Prüfkörper [mL/g] 1 18 130 - VZ PBT test specimen [mL / g] 1 18 130 -
Delta VZ nach 2 Tagen Lagerung bei 1 10 °C/ 100% Luft- 22 - 20 - feuchtigkeit [%]
Es ist offensichtlich, dass das Joncryl® währen der Lagerung alleine nicht in der Lage war den Abbau des Polymers effektiv zu unterbinden. Nach zweitägiger Lagerung hat die Viskositätszahl in allen Fällen bereits um 20 bis 25 % abgenommen, ohne Unterschied zum Polymer ohne den Zusatz von Joncryl®. Delta VZ after 2 days storage at 1 10 ° C / 100% air 22 - 20 - humidity [%] It is obvious that during storage, the Joncryl® alone was unable to effectively inhibit degradation of the polymer. After two days of storage, the viscosity number has already decreased by 20 to 25% in all cases, without any difference to the polymer without the addition of Joncryl®.
Beispiel 2: Alkylketendimer (AKD) Verbindungen Example 2: Alkyl ketene dimer (AKD) compounds
Die Tabellen 2.1 und 2.2 zeigen die Stabilisierung von Polymeren, wie PET und PBT, gegen Hydrolyse durch das AKD mit der Forme (III'): Tables 2.1 and 2.2 show the stabilization of polymers such as PET and PBT against hydrolysis by the AKD of the form (III '):
mit
With
wobei die Formel (III') eine Mischung der Isomere darstellt bei denen R41 und R42 bzw. R51 und R52 nicht gleichzeitig H oder (CH2)i5-CH3 sind. wherein the formula (III ') represents a mixture of the isomers in which R 41 and R 42 or R 51 and R 52 are not simultaneously H or (CH 2 ) i5-CH 3 .
Tabelle 2.1 zeigt als Vergleich die Wirkung des AKD alleine. Tabelle 2.1 Table 2.1 shows the effect of the AKD alone as a comparison. Table 2.1
Die Menge an AKD ist bezogen auf die Gesamtmenge an AKD und Polymer angegeben. The amount of AKD is given based on the total amount of AKD and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an AKD und Polymer.
Das AKD verhindert den Anstieg an Säureendgruppen während der Lagerung. Die Viskositätszahl steigt jedoch während der Extrusion nicht signifikant an. The concentration of acid end groups refers to the total amount of AKD and polymer. The AKD prevents the increase in acid end groups during storage. However, the viscosity number does not increase significantly during the extrusion.
Tabelle 2.2 zeigt einen Vergleich der Effizienz des Einsatzes von AKD alleine und in Verbindung mit dem Kettenverlängerer Joncryl® ADR 4300. Es ist deutlich zu erkennen, dass seine Kombination von Hydrolysestabilsator (H) und Kettenverlängerer (H) eine synergistische Wirkung aufweist. Table 2.2 shows a comparison of the efficiency of using AKD alone and in conjunction with the Joncryl® ADR 4300 chain extender. It can be clearly seen that its combination of hydrolysis stabilizer (H) and chain extender (H) has a synergistic effect.
Tabelle 2.2 Table 2.2
Die Menge an AKD und Joncryl® ADR 4300 ist jeweils bezogen auf die Gesamtmenge an AKD und/oder Joncryl® ADR 4300 und Polymer angegeben. The amount of AKD and Joncryl® ADR 4300 is given based on the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an AKD und/oder Joncryl® ADR 4300 und Polymer. The acid end group concentration refers to the total amount of AKD and / or Joncryl® ADR 4300 and polymer.
Beispiel 3: Oxazolidinone Example 3: Oxazolidinones
Tabelle 3.1 zeigt Ergebnisse, die mit dem Oxazolidinon der Formel (IV) in PBT erzielt wurden: Table 3.1 shows results obtained with the oxazolidinone of formula (IV) in PBT:
(iv) (Iv)
mit A = O, R6 Tabelle 3.1 with A = O, R 6 Table 3.1
2- VZ [mL/g] COOH [mmol/kg] 2-VZ [mL / g] COOH [mmol / kg]
Oxazolidinon nach nach Nach nach fünf Oxazolidinone gradually after five
(IV) 0 zwei 0 zwei fünf (Iv) 0 two 0 two five
Tagen meet
[Gew.-%] Tagen Tagen Tagen [Weight%] days days days
Ref. 1 18 92 57 29 47 1 10Ref. 1 18 92 57 29 47 1 10
0,4 1 17 98 64 27 45 890.4 1 17 98 64 27 45 89
1 ,0 - - - 29 42 80
Die Menge an Oxazolidinon ist bezogen auf die Gesamtmenge an Oxazolidinon und Polymer angegeben. 1, 0 - - - 29 42 80 The amount of oxazolidinone is based on the total amount of oxazolidinone and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Oxazolidinon und Polymer. The concentration of acid end groups refers to the total amount of oxazolidinone and polymer.
Die in Tabelle 3.1 gezeigte Wirkung des Oxazolidionons in PBT, nämlich sein geringer Einfluss auf die anfängliche Viskosität und die Verringerung der Säureendgruppenkon- zentration im Verlauf der Lagerung, lässt sich ebenfalls wie im Falle des AKD in Beispiel 2 mit dem Effekt eines Kettenverlängereres (Joncryl® ADR 4300) synergistisch kombinieren. The effect of the oxazolidionone in PBT shown in Table 3.1, namely its slight influence on the initial viscosity and the reduction in the acid end group concentration during the course of storage, can also be achieved with the effect of a chain extender (Joncryl® ADR 4300) combine synergistically.
Beispiel 4: Mono-epoxy und Mono-epoxy-silan Verbindungen Example 4: mono-epoxy and mono-epoxy-silane compounds
Die Tabellen 4.1 und 4.2 zeigen die Ergebnisse der Extrusion von PET oder PBT in Gegenwart eines Epoxysilans: 3-Glycidoxypropyltriethoxysilane, dass unter der Be- Zeichnung Geniosil® GF 82 (Wacker Chemie AG) erhältlich ist. Weiterhin enthalten die Tabellen Resultate zum Einsatz von 1 ,2-Epoxydecan als Hydrolysestabilisator. Tables 4.1 and 4.2 show the results of the extrusion of PET or PBT in the presence of an epoxysilane: 3-glycidoxypropyltriethoxysilane, which is available under the designation Geniosil® GF 82 (Wacker Chemie AG). Furthermore, the tables contain results for the use of 1, 2-epoxydecane as a hydrolysis stabilizer.
Beide Additive (Hydrolysestabilisatoren) verringern signifikant den Abbau des Polyesters während der Lagerung ohne die anfängliche Viskositätszahl zu erhöhen. Both additives (hydrolysis stabilizers) significantly reduce the degradation of the polyester during storage without increasing the initial viscosity number.
Tabelle 4.1 (PET) Table 4.1 (PET)
COOH [mmol/kg] COOH [mmol / kg]
Konzentration concentration
Additiv vor der Lagenach zwei nach fünf Ta[Gew.-%] Additive before layer after two to five Ta [% by weight]
rung Tagen gen days ago
Ref. - 24 45 107Ref. - 24 45 107
3-Glycidoxy- 0,2 23 36 74 propyltriethoxy- 1 ,0 14 22 46 3-glycidoxy-0.2 23 36 74 propyltriethoxy-1, 0 14 22 46
silan 2,0 12 10 40 silane 2.0 12 10 40
Ref. - 26 46 1 14Ref. - 26 46 1 14
3-Glycidoxy- propyltriethoxy- silan (Wiederho1 ,0 13 23 59 lung wg. Reproduzierbarkeit) 3-glycidoxypropyltriethoxysilane (repeat, reproducibility)
Ref. - 24 54 147 Ref. - 24 54 147
1 ,2-epoxy deca-1, 2-epoxy deca
0,8 22 39 98 ne 0.8 22 39 98 ne
Ref. - 24 43 95 Ref. - 24 43 95
0,2 25 41 91 0,2 25 41 91
1 ,2-epoxy deca-1, 2-epoxy deca
1 ,0 22 37 82 ne 1, 0 22 37 82 ne
2,0 20 34 75
Die Konzentration an Additiv ist bezogen auf die Gesamtmenge an Additiv und Polymer angegeben. 2,0 20 34 75 The concentration of additive is given based on the total amount of additive and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Additiv und Polymer. The concentration of acid end groups refers to the total amount of additive and polymer.
Tabelle 4.2 (PBT) Table 4.2 (PBT)
Die Konzentration an Additiv ist bezogen auf die Gesamtmenge an Additiv und Polymer angegeben. The concentration of additive is given based on the total amount of additive and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Additiv und Polymer. The concentration of acid end groups refers to the total amount of additive and polymer.
Es war auch möglich die Additive in Form eines Masterbatches zuzusetzen und dabei die vorteilhafte Wirkung als Hydrolysestabilisator im Endprodukt zu erhalten. Hierzu wurde in einem ersten Schritt die Menge an Hydrolysestabilisator, der notwendig ist um 5 kg extrudiertes PBT vollständig durch Reaktion mit den Säureendgruppen zu stabilisieren (ca. 30 mmol/kg), in ca. 800g PBT extrudiert, um den Masterbatch herzustellen. It was also possible to add the additives in the form of a masterbatch and thereby to obtain the advantageous effect as a hydrolysis stabilizer in the end product. For this purpose, in a first step, the amount of hydrolysis stabilizer which is necessary to completely stabilize 5 kg of extruded PBT by reaction with the acid end groups (about 30 mmol / kg) is extruded in about 800 g of PBT to prepare the masterbatch.
Die Konzentration an Säureendgruppen des Masterbatches wurde vor der Lagerung und nach zwei Tagen Lagerung bei 1 10°C und 100% Luftfeuchtigkeit bestimmt. The acid end group concentration of the masterbatch was determined before storage and after two days storage at 110 ° C and 100% humidity.
In einem zweiten Schritt wurde dann der Masterbatch in PBT re-extrudiert (Gesamtmenge Einsatzsoffe war 5 kg). Die Konzentration an Säureendgruppen im Endprodukt wurden ebenfalls vor der Lagerung und nach zwei Tagen Lagerung bei 1 10°C und 100% Luftfeuchtigkeit bestimmt. Die Resultate sind in Tabelle 4.3 zusammengefasst:
Tabelle 4.3 (PBT Masterbatch und Endprodukt) In a second step, the masterbatch was re-extruded in PBT (total feed was 5 kg). The concentration of acid end groups in the final product were also determined before storage and after two days of storage at 1 10 ° C and 100% humidity. The results are summarized in Table 4.3: Table 4.3 (PBT masterbatch and final product)
Die Konzentration an Additiv ist bezogen auf die Gesamtmenge an Additiv und Polymer angegeben. The concentration of additive is given based on the total amount of additive and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Additiv und Polymer. The concentration of acid end groups refers to the total amount of additive and polymer.
Insbesondere die Monoepoxyverbindunge erhöhen die Anfangsviskosität während der Extrusion kaum und können daher wie oben bei den Beispielen 2 und 3 bereits beschrieben vorteilhaft synergistisch mit Kettenverlängereren kombiniert werden. In particular, the monoepoxy compounds hardly increase the initial viscosity during the extrusion and can therefore advantageously be combined synergistically with chain extenders as already described above in Examples 2 and 3.
Ein Vergleich der der Wirkung von 1 ,2-Epoxydecan alleine und in Kombination mit Joncryl® ADR 4300 ist inTabelle 4.4 gegeben. A comparison of the effect of 1, 2-epoxydecane alone and in combination with Joncryl® ADR 4300 is given in Table 4.4.
Tabelle 4.4 Table 4.4
Die Konzentration an Additiv ist bezogen auf die Gesamtmenge an Additiv und Polymer angegeben. The concentration of additive is given based on the total amount of additive and polymer.
Die Konzentration an Säureendgruppen bezieht sich auf die Gesamtmenge an Additiv und Polymer.
The concentration of acid end groups refers to the total amount of additive and polymer.
Claims
Patentansprüche: claims:
1 . Mischung (M) enthaltend 1 . Containing mixture (M)
a. mindestens einen multifunktionellen Kettenverlangererer (K) mit mindestens drei reaktiven Gruppen, und a. at least one multifunctional chain extender (K) having at least three reactive groups, and
b. mindestens einen mono- oder difunktionellen Hydrolysestabilisator (H), wobei, b. at least one mono- or difunctional hydrolysis stabilizer (H), wherein
die Kettenverlängerer (K) und die Hydrolysestabilisatoren (H) mit den Endgruppen von Polymeren (P) im geschmolzenen oder festen Zustand der Polymere (P) unter Ausbildung einer chemischen Bindung reagieren. the chain extenders (K) and the hydrolysis stabilizers (H) react with the end groups of polymers (P) in the molten or solid state of the polymers (P) to form a chemical bond.
2. Mischung nach Anspruch 1 , wobei die Kettenverlangererer (K) gewählt werden aus der Gruppe der Homo- und Copolymere enthaltend mindestens drei Epoyxgruppen, mindestens drei Aziridin-Gruppen oder mindestens drei anhydridische Gruppen. 2. Mixture according to claim 1, wherein the chain extenders (K) are selected from the group of homopolymers and copolymers containing at least three Epoyxgruppen, at least three aziridine groups or at least three anhydridische groups.
3. Mischung nach Anspruch 2, wobei es sich bei den Copolymeren enthaltend mindestens drei Epoxygruppen um mit Epoxygruppen funktionalisierte Copolymere enthaltend Styrol und (Meth)acrylsäuremonomer in polymerisierter Form handelt. 4. Mischung nach den Ansprüchen 1 bis 3, wobei die Hydrolysestabilisatoren (H) gewählt werden aus den a. oligomeren Carbodiimiden der allgemeinen Formel (I) 3. Mixture according to claim 2, wherein the copolymers containing at least three epoxy groups are functionalized with epoxy groups copolymers containing styrene and (meth) acrylic acid monomer in polymerized form. 4. Mixture according to claims 1 to 3, wherein the hydrolysis stabilizers (H) are selected from the a. oligomeric carbodiimides of the general formula (I)
A1, A2 unabhängig voneinander, gleich oder verschieden, A 1 , A 2 independently of one another, the same or different,
Kohlenwasserstoffgruppen mit 3 bis 20 Kohlenstoffatomen, Hydrocarbon groups having 3 to 20 carbon atoms,
B1, B2 unabhängig voneinander, gleich oder verschieden, Heterocyclen, Ci-C3o-Alkohole, Poletherole, Polyesterole, Amine, Polyetheramine,B 1 , B 2, independently of one another, identical or different, heterocycles, C 1 -C 30 -alcohols, poletherols, polyesterols, amines, polyetheramines,
Polyesteramine, Thioalkohole, Polyetherthiole, Polyesterthiole, n ganze Zahl im Bereich von 2 bis 100, und wobei A1, A2, B1 und B2 jeweils an beliebiger Position durch Ci-C2o-Alkyl,Polyesteramines, thioalcohols, polyether thiols, polyester thiols, n integer in the range from 2 to 100, and where A 1 , A 2 , B 1 and B 2 are in each case at any position by C 1 -C 20 -alkyl,
C2-C2o-Alkenyl, C2-C2o-Alkinyl, Ci-C20-Alkoxy, Carbonyl-Sauerstoff (=0) oder Halogen substituiert sein können,
b. mono- oder difunktionellen Epoxyverbindungen der allgemeinen Formeln (I- la) oder (IIb) C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl, C 1 -C 20 -alkoxy, carbonyl-oxygen (= O) or halogen may be substituted, b. mono- or difunctional epoxy compounds of the general formulas (I-la) or (IIb)
(IIa) (IIa)
(IIb) (IIb)
mit With
X1, X2, X3 unabhängig voneinander, gleich oder verschieden, Ch , O, X 1 , X 2 , X 3 are independently, the same or different, Ch, O,
C(=0), OC(=0), C(=0)NH, C (= 0), OC (= 0), C (= 0) NH,
Y1, Y2, Y3 unabhängig voneinander, gleich oder verschieden, Y 1 , Y 2 , Y 3 independently of one another, the same or different,
Einfachbindung, Ci-C2o-Alkylen, Ci-C2o-Alkylenyl, Arylen, Z H, SiR1R2R3, Si(OR1)R2R3, Single bond, C 1 -C 20 -alkylene, C 1 -C 20 -alkylenyl, arylene, ZH, SiR 1 R 2 R 3 , Si (OR 1 ) R 2 R 3 ,
Si(OR1)(OR2)R3, Si(OR1)(OR2)(OR3), Si (OR 1 ) (OR 2 ) R 3 , Si (OR 1 ) (OR 2 ) (OR 3 ),
Z2, Z3 unabhängig voneinander, gleich oder verschieden, Einfachbindung, SiR1R2, Si(OR1)R2, Si(OR1)(OR2), Z 2 , Z 3 independently of one another, identical or different, single bond, SiR 1 R 2 , Si (OR 1 ) R 2 , Si (OR 1 ) (OR 2 ),
L1 Einfachbindung, O, CH2, L 1 single bond, O, CH 2,
R1, R2, R3 unabhängig voneinander, gleich oder verschieden, Ci-C2o-Alkyl,R 1 , R 2 , R 3 independently of one another, identical or different, C 1 -C 20 -alkyl,
R20, R21, R22 unahängig voneinander, gleich oder verschieden, H, C1-C20- Alkyl, oder R 20 , R 21 , R 22 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, or
R20 gemeinsam mit R21 oder R22 Dimethylen, Trimethylen, Tetramethylen unter Ausbildung eines fünf-, sechs-, oder sieben- gliedrigen Ringsystems, R 20 together with R 21 or R 22 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system,
R23, R24, R25 unahängig voneinander, gleich oder verschieden, H, C1-C20- Alkyl, oder R 23 , R 24 , R 25 are independent of each other, identical or different, H, C 1 -C 20 -alkyl, or
R23 gemeinsam mit R24 oder R25 Dimethylen, Trimethylen, Tetramethylen unter Ausbildung eines fünf-, sechs-, oder sieben- gliedrigen Ringsystems, R 23 together with R 24 or R 25 dimethylene, trimethylene, tetramethylene to form a five-, six- or seven-membered ring system,
c. Alkylketendimeren der allgemeinen Formel (III)
c. Alkylketene dimers of the general formula (III)
mit With
R41, R42, unabhängig voneinander gleich oder verschieden, H, Ci-C3o-Alkyl, R51, R52, unabhängig voneinander gleich oder verschieden, H, Ci-C3o-Alkyl, R 41 , R 42 , independently of one another, are identical or different, H, C 1 -C 30 -alkyl, R 51 , R 52 , independently of one another the same or different, H, C 1 -C 30 -alkyl,
Heterozyklen der allgemeinen Formeln (IV) oder (V) Heterocycles of the general formulas (IV) or (V)
(IV) (IV)
mit With
A O, NR16, AO, NR 16 ,
R6 H, Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, NR26R27,R 6 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, NR 26 R 27 ,
R16 H, Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, Halogen,R 16 is H, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl, halogen,
R26, R27 unabhängig voneinander, gleich oder verschieden, H, R 26 , R 27 independently of one another, the same or different, H,
Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl, C 1 -C 20 -alkyl, aryl, C 3 -C 5 -cycloalkyl,
bevorzugt H, Ci-Cio-Alkyl, Aryl, preferably H, C 1 -C 10 -alkyl, aryl,
besonders bevorzugt H, Ci-C4-Alkyl, Phenyl, Toloyl, R7, R8, R9, R10 unabhängig voneinander, gleich oder verschieden, H, particularly preferably H, C 1 -C 4 -alkyl, phenyl, tobolyl, R 7 , R 8 , R 9 , R 10 independently of one another, identical or different, H,
Ci-C20-Alkyl, Aryl, C3-Ci5-Cycloalkyl wobei R6, R16 jeweils an beliebiger Position durch Ci-C2o-Alkyl, C2-C2o-Alkenyl, C2-C2o-Alkinyl, Ci-C2o-Alkoxy, Carbonyl-Sauerstoff (=0) oder Halogen substituiert sein können. Ci-C 20 alkyl, aryl, C 3 -C 5 -cycloalkyl wherein R 6, R 16 are each at an arbitrary position by Ci-C 2 -alkyl, C 2 -C 2 -alkenyl, C 2 -C 2 o Alkynyl, Ci-C 2 o-alkoxy, carbonyl-oxygen (= 0) or halogen may be substituted.
Mischung nach den Ansprüchen 1 bis 4, wobei die Polymere (P) Polykondensate oder Polyadditionsprodukte sind. Mixture according to claims 1 to 4, wherein the polymers (P) are polycondensates or polyaddition products.
Mischung nach Anspruch 5, wobei die Polymere (P) gewählt werden aus der Gruppe der Polyester, Polyamide, Polyurethane, Polycarbonate und ihrer Copolymere sowie Mischungen dieser Polymere.
Mixture according to claim 5, wherein the polymers (P) are selected from the group of polyesters, polyamides, polyurethanes, polycarbonates and their copolymers and mixtures of these polymers.
7. Mischung nach Anspruch 5, wobei die Polymere (P) PET, PBT, PEN, PC, bioab- baubare aliphatisch-aromatische Copolyester, Biopolymere oder PA6 sind. 7. Mixture according to claim 5, wherein the polymers (P) are PET, PBT, PEN, PC, biodegradable aliphatic-aromatic copolyesters, biopolymers or PA6.
8. Mischung nach den Ansprüchen 1 bis 7, wobei die Polymere (P) Hydroxy, Amin, Carboxy- oder Carbonsäure-Engruppen enthalten. 8. Mixture according to claims 1 to 7, wherein the polymers (P) hydroxy, amine, carboxy or carboxylic acid engroups.
9. Mischung (MP) enthaltend a. Mindestens eine Mischung (M) gemäß den Ansprüchen 1 bis 8 und b. zusätzlich Polymere (P) gemäß den Ansprüchen 1 bis 8. 9. Mixture (MP) containing a. At least one mixture (M) according to claims 1 to 8 and b. additionally polymers (P) according to claims 1 to 8.
10. Verwendung von Mischungen (M) gemäß den Ansprüchen 1 bis 8 als Stabilisatoren für Polymere (P). 1 1 . Verwendung nach Anspruch 10 zur Stabilisierung gegen Molekulargewichtsverlust oder Hydrolyse. 10. Use of mixtures (M) according to claims 1 to 8 as stabilizers for polymers (P). 1 1. Use according to claim 10 for stabilization against molecular weight loss or hydrolysis.
12. Verfahren zur Stabilisierung von Polymeren (P) gegen Molekulargewichtsverlust, dadurch gekennzeichnet, dass dem Polymeren (P) eine effektive Menge an Mi- schung (M) gemäß den Ansprüchen 1 bis 8 zugegeben wird. 12. A process for the stabilization of polymers (P) against molecular weight loss, characterized in that the polymer (P) is added an effective amount of mixture (M) according to claims 1 to 8.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet dass der Mischung (M) Polymere (P) in einer Menge von 0,01 bis 10 Gew.-%, bezogen auf die Gesamtmenge an Polymeren (P) und Mischung (M), zugegeben werden. 13. The method according to claim 12, characterized in that the mixture (M) polymers (P) in an amount of 0.01 to 10 wt .-%, based on the total amount of polymer (P) and mixture (M) are added ,
14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass dem Polymeren (P) zusätzlich eine effektive Menge an einem Additiv gewählt aus der Gruppe der Farbmittel, Antioxidantien, anderer Stabilisatoren, UV-Absorber, Nickelquen- cher, Metalldesaktivatoren, Verstärkungs- und Füllstoffe, Beschlagverhinderungs- mittel, Biozide, Säurefänger, Antistatika, IR-Absorbern für langwellige IR Strahlung,14. The method according to claim 12 or 13, characterized in that the polymer (P) additionally an effective amount of an additive selected from the group of colorants, antioxidants, other stabilizers, UV absorbers, nickel quenchers, metal deactivators, reinforcing and Fillers, antifogging agents, biocides, acid scavengers, antistatic agents, IR absorbers for long-wave IR radiation,
Antiblockmittel, Lichtstreuer, anorganische und organische Reflektoren zugegebn wird.
Antiblocking, light scatterers, inorganic and organic reflectors is zugegebn.
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WO2017110917A1 (en) | 2015-12-25 | 2017-06-29 | 東洋紡株式会社 | Polyester resin composition, light reflector and component for light reflector that include said composition, and method for producing polyester resin composition |
US11001706B2 (en) | 2017-02-02 | 2021-05-11 | Toyobo Co., Ltd. | Polyester resin composition, and light reflector component and light reflector including polyester resin composition |
WO2018143099A1 (en) | 2017-02-02 | 2018-08-09 | 東洋紡株式会社 | Polyester resin composition, and light reflector component and light reflector including same |
US11795298B2 (en) | 2018-03-26 | 2023-10-24 | Toyobo Mc Corporation | Polyester resin composition, light-reflector component containing same, and light reflector |
EP3670180A1 (en) * | 2018-12-17 | 2020-06-24 | LANXESS Deutschland GmbH | Multi-layer system made from at least 3 polyester layers, its preparation and use |
CN109971007B (en) * | 2019-04-01 | 2021-05-28 | 江南大学 | Normal-temperature curing polyurethane anti-fog film and preparation method thereof |
JP7282124B2 (en) | 2020-05-28 | 2023-05-26 | エコバンス カンパニー・リミテッド | Biodegradable polyester resin composition, nonwoven fabric and film, and method for producing the same |
KR102421034B1 (en) | 2020-05-28 | 2022-07-14 | 에코밴스 주식회사 | Method for preparing biodegradable polyester resin and bioderadable polyester resin therefrom |
WO2023229214A1 (en) * | 2022-05-21 | 2023-11-30 | 에코밴스 주식회사 | Biodegradable polyester resin composition and biodegradable molded article comprising same |
KR20230162745A (en) * | 2022-05-21 | 2023-11-28 | 에코밴스 주식회사 | Biodegradable polyester resin composition and preperation method thereof |
WO2023229216A1 (en) | 2022-05-21 | 2023-11-30 | 에코밴스 주식회사 | Biodegradable molded article and biodegradable polyester resin composition |
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