WO2018087158A1 - Polyesters réticulables par irradiation et leur utilisation - Google Patents

Polyesters réticulables par irradiation et leur utilisation Download PDF

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Publication number
WO2018087158A1
WO2018087158A1 PCT/EP2017/078632 EP2017078632W WO2018087158A1 WO 2018087158 A1 WO2018087158 A1 WO 2018087158A1 EP 2017078632 W EP2017078632 W EP 2017078632W WO 2018087158 A1 WO2018087158 A1 WO 2018087158A1
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Prior art keywords
polyester
cooh
functionalized
polyols
polyol
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PCT/EP2017/078632
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German (de)
English (en)
Inventor
Nicolai KOLB
Gabriele Brenner
Original Assignee
Evonik Degussa Gmbh
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Publication of WO2018087158A1 publication Critical patent/WO2018087158A1/fr

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Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to polyesters based on a polyester-polyol based on di- or polycarboxylic acids and di- or polyols, wherein at least 0, 1 wt .-% of OH and / or COOH-functionalized polyolefins as di- or polycarboxylic acids and / or Di- or polyols based on the total amount of di- or polycarboxylic acids and diols or polyols in the polyester polyol, characterized in that the polyester is at least one structural unit of the formula (I)
  • Polyester polyols are widely used today as raw materials, including for the production of adhesives and sealants.
  • adhesives and sealants may be, for example, thermoplastic or reactive hot melt adhesives, 1K or 2K liquid adhesives, or epoxy systems.
  • polyester polyols as raw materials in adhesives and sealants is their high formulation flexibility and a wide range of applications. For example, wood, textiles or metals can be bonded very well.
  • Polyester-based systems are compatible or miscible and the curing of such polyolefin-based adhesives usually takes longer.
  • a combination of polyester-based materials is compatible or miscible and the curing of such polyolefin-based adhesives usually takes longer.
  • Adhesives with polyolefin adhesives for combining the advantages of both systems is therefore currently not feasible, since the formulation of the polyolefins is not possible due to the lack of compatibility. Such systems would segregate due to incompatibility.
  • the present invention therefore relates to polyesters, preferably (meth) acryl-terminated polyesters, based on a polyester polyol based on di- or polycarboxylic acids and diesters of polyols, where at least 0, 1 wt .-% of OH and / or COOH functionalized
  • polyester-polyol Total sum of di- or polycarboxylic acids and diols or polyols in the polyester-polyol are contained, characterized in that the polyester at least one, preferably terminal, structural unit of the formula (I)
  • the present invention relates to corresponding adhesives or sealants or formulations and corresponding coating compositions and their
  • the disadvantages of the prior art namely the low adhesion of polyester-based adhesive systems to low-energy surfaces
  • the polyesters used according to the invention can be overcome by the incorporation of the polyesters used according to the invention.
  • the joining of polar and non-polar materials can be improved.
  • the polyesters of the invention combine materials of different polarity, which can be attributed to the presence of the polyolefin components.
  • the polyesters according to the invention have the advantage that the non-polar polyolefin structures are made compatible by the reactive incorporation into the polyester and are arbitrarily and versatile modifiable by means of the polyester, for example in terms of molecular weight, thermal properties and the
  • polyesters according to the invention and the use according to the invention of the polyesters are described below by way of example, without the invention being restricted to these exemplary embodiments.
  • ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the matters referred to, should form part of the disclosure content of the present invention. If the following information is given as a percentage, it is, unless stated otherwise, in% by weight. If mean values, for example molecular weight averages, are given below, this is the number average, unless stated otherwise.
  • the indicated indices may represent both absolute numbers and averages.
  • the indices are preferably average values.
  • the preferred (meth) acryl-terminated polyesters of the invention are based on a polyester polyol based on di- or polycarboxylic acids and di- or polyols, wherein at least 0.1% by weight of OH- and / or COOH-functionalized polyolefins are as di- or polycarboxylic acids and / or di- or polyols based on the total amount of di- or polycarboxylic acids and diols or polyols in the polyester polyol, are characterized in that the polyesters at least one, preferably terminal, structural unit, preferably two or more than two structural units of the formula (I)
  • polyester polyols may carry OH and / or COOH end groups, preferably OH groups, and preferably have a functionality in the range from 1.0 to 10.0, preferably in the range from 1.5 to 5.0, particularly preferably in the range of 1, 9 to 3.0.
  • Polyester polyols are used. In the context of the present invention, preference is given to
  • OH- or COOH-functionalized polyolefins in the context of the present invention are those polymers which are based on alkenes and / or polyenes as monomers.
  • the repeating units of the polyolefins consist exclusively of the elements carbon and hydrogen and have no aromatic structures.
  • the polyolefins may contain any proportion of double bonds.
  • suitable OH- and / or COOH-functionalized polyolefins are selected from OH- and / or COOH-functionalized polybutadiene, OH- and / or COOH-functionalized
  • the OH- and / or COOH-functionalized polyolefins are preferably OH-functionalized polyolefins, in particular OH-terminated polybutadiene.
  • the OH-functionalized polyolefin is partially or completely, preferably completely hydrogenated, OH-terminated polybutadiene.
  • the degree of hydrogenation is determined in the context of the present invention on the iodine number.
  • the measurement of the iodine number is carried out in the context of the present invention according to the DGF unit method C-V 11 b.
  • the iodine number of the OH- and / or COOH-functionalized polyolefins used according to the invention is a maximum of 260 g of iodine / 100 g of polymer, preferably a maximum of 100 g of iodine / 100 g of polymer, more preferably a maximum of 30 g of iodine / 100 g of polymer.
  • the OH and / or COOH-functionalized polyolefins used according to the invention generally have a molecular weight of 200 to 20,000 g / mol, preferably 500 to 15,000 g / mol, more preferably 1 to 10,000 to 10,000 g / mol.
  • the determination of the molecular weight of the OH- and / or COOH-functionalized polyolefins is carried out according to DIN 55672-1 by means of gel permeation chromatography in tetrahydrofuran as eluent and polystyrene for calibration.
  • polyolefins preferably usable in the context of the present invention are commercially available, for example POLYVEST® HT from Evonik Resource Efficiency GmbH or the products NISSO GI-1000, NISSO GI-2000 or NISSO GI-3000 from NIPPON SODA CO., LTD.
  • the functionality of the OH and / or COOH-functionalized polyolefins used is preferably in the range from 1.9 to 2.2.
  • Essential in the context of the present invention is the presence of OH and / or COOH groups to form the hybrid polyesters. These groups are usually present at the chain end of the polyolefin, moreover, further functional groups can be present along the chain.
  • the functionality is determined by the correlation of molecular weight to OH number (OH number) or acid number (SZ), according to the following formula: (OHZ + SZM ⁇ ⁇ Mn ⁇ ]
  • the above-described OH and / or COOH-functionalized polyolefins are polyols or
  • polyester polyols which are preferably synthesized by melt condensation with additional diols or polyols and di- or polycarboxylic acids or their derivatives.
  • diols or polyols and di- or polycarboxylic acids there are basically no restrictions and basically all mixing ratios can occur.
  • the selection depends on the desired physical properties of the polyester. These may be solid at room temperature and amorphous, liquid and amorphous or / and (partially) crystalline.
  • di- or polycarboxylic acids it is possible to use all organic acids known to the person skilled in the art with two or more carboxy functionalities present.
  • carboxy functionalities are also understood as meaning their derivatives, for example esters or anhydrides.
  • the di- or polycarboxylic acids may in particular be aromatic or saturated or unsaturated aliphatic or saturated or unsaturated cycloaliphatic di- or polycarboxylic acids. Preference is given to using bifunctional dicarboxylic acids.
  • linear aliphatic di- or polycarboxylic acids examples include oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, glutaric acid, dimethyl glutarate, 3,3-dimethylglutaric acid, adipic acid, adipic acid dimethyl ester, pimelic acid, suberic acid, azelaic acid, dimethyl azelate, sebacic acid, dimethyl sebacate, undecanedicarboxylic acid, 1, 10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, brassylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedioic acid, 1,8-octadecanedioic acid, dimer fatty acids and mixtures thereof.
  • Examples of unsaturated linear di- and / or polycarboxylic acids include itaconic acid,
  • Fumaric acid maleic acid or maleic anhydride.
  • saturated cycloaliphatic di- and / or polycarboxylic acids include derivatives of 1,4-cyclohexanedicarboxylic acids, 1,3-cyclohexanedicarboxylic acids and 1,2-cyclohexanedicarboxylic acids.
  • the type of diols or polyols used for the preparation of the polyester polyols is arbitrary per se.
  • Polyols are compounds which carry more than two hydroxyl groups. Thus, linear or branched aliphatic and / or cycloaliphatic and / or aromatic diols or polyols may be contained.
  • Suitable diols or polyols are ethylene glycol, propanediol 1, 2, propanediol 1, 3, butanediol-1, 4, butanediol-1, 3, butanediol-1, 2, butanediol-2,3, pentanediol-1, 5 , Hexanediol-1, 6,
  • aromatic diols or polyols are reaction products of aromatic
  • Polyhydroxy compounds such. As hydroquinone, bisphenol A, bisphenol F, dihydroxynaphthalene, etc. with epoxides such. For example, to understand ethylene oxide or propylene oxide. As diols or polyols also ether diols, d. H. Oligomers or polymers, for. B. based on ethylene glycol,
  • Propylene glycol or butanediol-1, 4 may be included.
  • polyols or polycarboxylic acids having more than two functional groups for example trimellitic anhydride, trimethylolpropane, pentaerythrol or glycerol.
  • lactones and hydroxycarboxylic acids can be used as constituents of the polyester.
  • the synthesis of the polyester polyols is preferably carried out via a melt condensation.
  • a melt condensation for this purpose, in each case one or more of the abovementioned di- or polycarboxylic acids and di- or polyols, preferably in an equivalent ratio of hydroxyl to carboxyl groups of 0.5 to 1.5, preferably 1 .0 to 1.3, are initially charged and melted.
  • the polycondensation is carried out in the melt, preferably at temperatures between 150 and 280 ° C within 3 to 30 hours.
  • a large part of the amount of water released is distilled off at normal pressure. In the course of the remaining reaction water and volatile diols is split off until the desired molecular weight is reached.
  • the reaction may additionally be accelerated by adding an entraining agent and / or a catalyst before or during the reaction.
  • Suitable entrainers are, for example, toluene and xylenes.
  • Typical catalysts are organotitanium or tin compounds such as tetrabutyl titanate or dibutyltin oxide.
  • catalysts which are based on other metals such as zinc or antimony based, and metal-free esterification catalysts.
  • other additives and driving aids such as antioxidants or color stabilizers are possible.
  • the characterization of the polyester polyols can be based on the hydroxyl end groups
  • Acid end groups molecular weight distribution, iodine number and by means of dynamic
  • the concentration of hydroxyl end groups is preferably between 0 and 300 mg KOH Ig, preferably between 5 and 50 mg KOH Ig.
  • the concentration of acid end groups is preferably between 0 and 300 mg KOH / g, but preferably below 2 mg KOH / g.
  • the number-average molecular weight of the polyester-polyol is preferably 500-30,000 g / mol, preferably 1,000-20,000 g / mol. It is in accordance with DIN 55672-1
  • the iodine value of the polyester polyols, determined by the DGF unit method C-B 11 b, is preferably at most 260 g iodine / 100 g polymer, preferably at most 100 g iodine / 100 g polymer, more preferably at most 30 g iodine / 100 g polymer.
  • the thermal properties of the polyester polyols are determined by differential scanning calorimetry (DSC) according to the DSC method DIN 53765.
  • the functionality of the polyester polyols is generally in the range of 1, 0 to 10, preferably in the range of 1, 5 to 5.0, particularly preferably in the range of 1, 9 to 3.0. In the context of the present invention, the functionality is determined by the correlation of molecular weight to OH number (OH number) or acid number (SZ).
  • Preferred polyesters have the formula (III)
  • P ' polyester-polyol radical
  • X' hydrocarbon radical, preferably 1, 1, 3,3-tetramethylcyclohexanrest, toluene radical or methylene-1, 1 '-Dibenzolrest
  • Y' aliphatic radical
  • the polyesters according to the invention can be obtained by a stepwise reaction of one of the polyester polols described above with di- or polyisocyanates to isocyanate-terminated prepolymers and subsequent reaction with, for example, an OH group-containing (meth) acrylate or by reacting one of the polyester polyols described above with an adduct of di- or polyisocyanates and an OH group-containing (meth) acrylate, preferably a 1: 1 monoadduct of IPDI and 2-hydroxyethyl (meth) acrylate (for example VESTANAT EP DC 1241, from Evonik Resource Efficiency GmbH ).
  • the reaction of the polyester polyols with an isocyanato acrylate takes place in an OH / NCO ratio of 1: 0.5 to 1: 1, 5.
  • OH group-containing (meth) acrylates are 2-hydroxyethyl (meth) acrylate,
  • di- or polyisocyanates may di- and / or multifunctional, aromatic, aliphatic and / or cycloaliphatic isocyanates and carbodiimide-modified isocyanates or
  • isocyanate-terminated prepolymers are used.
  • polyisocyanates are 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, toluene diisocyanate isomers, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and mixtures thereof.
  • Aliphatic polyisocyanates are particularly preferred.
  • polyesters according to the invention can be used alone or in combination with other starting materials as a constituent of radiation-crosslinking adhesive, sealant or coating formulations.
  • Another object of the present invention are therefore radiation-crosslinking adhesive or sealant formulations at least containing the inventive, preferably (Meth) acryl-terminated, polyester.
  • adhesive or sealant according to the invention formulations may at least one other (meth) acrylic-functionalized polymer, in particular based on functionalized polyester OH, OH-functionalized polyether, OH-functionalized polybutadiene (z. B. POLYVEST ® HT) and OH functionalized poly (meth) acrylates.
  • the additionally used (meth) acrylic-functionalized polymers are basically freely selectable and generally known to the person skilled in the art.
  • a (meth) acryl-functionalized polyester or a (meth) acryl-functionalized polybutadiene as further component in the adhesive or sealant formulations according to the invention, particularly preferably a polyester.
  • Embodiment of the present invention is the at least one further polymer selected from polyesters, which were preferably synthesized by melt condensation of di- or polyols and Dioder polycarboxylic acids or their derivatives, or by
  • the adhesive or sealant formulations according to the invention are preferably one-component radiation-crosslinking polyurethane adhesives.
  • Percent by weight preferably 5 to 85 percent by weight and more preferably 10 to 70
  • the adhesive formulation may contain up to 50% by weight, based on the total formulation, of other additives.
  • additives may be: non-functionalized polymers, e.g. Thermoplastic polyurethanes (TPU) and / or polyacrylates and / or ethylene-vinyl acetate copolymers (EVA); Pigments or fillers, eg. Talc, silica, titania, barium sulfate, calcium carbonate, carbon black or colored pigments; Tackifier, such. As rosins, hydrocarbon resins, phenolic resins and anti-aging and auxiliary agents.
  • non-functionalized polymers e.g. Thermoplastic polyurethanes (TPU) and / or polyacrylates and / or ethylene-vinyl acetate copolymers (EVA); Pigments or fillers, eg. Talc, silica, titania, barium sulfate, calcium carbonate, carbon black or colored pigments; Tackifier, such.
  • Talc silica
  • titania titanium dioxide
  • barium sulfate
  • the adhesive or sealant formulations comprise a mixture of preferred, (meth) acryl-terminated polyesters according to the invention, in particular 5-75% by weight, and at least one further polyester, in particular 25-95 wt .-% and at least one polyisocyanate, wherein the NCO: OH ratio of polyesters to isocyanate 2.0-3.5.
  • the formulation may optionally contain up to 50% by weight of fillers. In sum, the weight proportions of the individual components are 100% by weight.
  • the adhesive systems described above can be applied at temperatures between room temperature and 200 ° C., preferably between 80 and 150 ° C., depending on the viscosity of the particular formulation.
  • Another object of the present invention is the use of adhesive or sealant formulations according to the present invention for bonding or sealing of substrates, in particular for bonding and sealing non-polar substrates.
  • the adhesive or sealant formulations of the invention are particularly suitable for the production of bonds of a variety of substrates, eg. As plastics, metals, woods, mineral substrates such. As asphalt, concrete, especially for bonding metallic substrates, textiles and especially for bonding various plastics.
  • substrates eg. As plastics, metals, woods, mineral substrates such.
  • the type and extent of the bond are not limited.
  • formulations according to the invention are suitable for use in nonpolar surfaces.
  • the substrates bonded according to the invention are substrates having a surface tension of less than 40 mN / m, preferably less than 35 mN / m, for example polyethylene or polypropylene.
  • the adhesions are preferably adhesions in the wood and
  • the adhesive formulations according to the invention can be applied by all known methods, for. B. by extruder, caterpillar, nozzle, brushing, dipping, spraying, pouring, Rolling, spraying, printing, wiping, washing, tumbling, centrifuging or as a powder (electrostatic).
  • a further subject of the present invention are coating compositions at least comprising the inventive, preferably (meth) acryl-terminated, polyesters.
  • the inventive preferably (meth) acryl-terminated, polyesters.
  • it is one-component radiation-crosslinking
  • the coating compositions of the invention may at least one other (meth) acrylic-functionalized polymer, in particular based on OH-functionalized polyesters, OH-functionalized polyether, OH-functionalized polybutadiene (z. B. POLYVEST ® HT) and OH and / or COOH functionalized poly (meth) acrylates.
  • the additionally used acrylic-functionalized polymers are basically freely selectable and generally known to the person skilled in the art.
  • polyesters Melt condensation of di- or polyols and di- or polycarboxylic acids or their derivatives were synthesized or were prepared by ring-opening polymerization. Furthermore, the polyesters have in particular a linear or branched structure, preferably they are weakly branched.
  • the proportion of the inventive, preferably (meth) acryl-terminated, polyester in the formulation is, based on the total formulation, 0, 1-99 wt .-%, preferably 0, 1 - wt .-% and particularly preferably 0, 1 - 25 wt .-%. Furthermore, the coating compositions can the expert from the prior
  • the substrate is coated with a previously described coating composition according to the invention and the coating is subsequently dried and / or calcined.
  • Coating compositions there are several embodiments. In the simplest,
  • the coating is carried out directly on the substrate.
  • a process is used in which the formulation according to the invention is applied to the substrate in organic solution together with further formulation constituents as "organosol" and the coated layer is subsequently dried.
  • Curtain Coating, Spray Coating is used in which the formulation according to the invention is applied to the substrate in organic solution together with further formulation constituents as "organosol" and the coated layer is subsequently dried.
  • the coating according to the invention can optionally be provided with one or more further functional layers.
  • This can be, for example, a scratch-resistant coating, a conductive layer, an antisoiling coating and / or a reflection-enhancing layer or other optically functional layers.
  • additional layers can be applied, for example, by means of Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD).
  • scratch-resistant coating can optionally be applied to further improve scratch resistance.
  • scratch-resistant coatings it may, for.
  • silicon oxide layers can be applied directly by PVD or CVD.
  • the number average molecular weight of the hybrid polyesters according to the invention and the polyolefins used according to the invention is determined according to DIN 55672-1
  • the produced polyesters may have hydroxyl groups as end groups.
  • the concentration of OH groups is determined according to DIN 53240-2 titrimetrically in mg KOH / g polymer.
  • the concentration of acid end groups is determined according to DIN EN ISO 21 14 titrimetrically in mg KOH / g polymer.
  • the NCO number of the reaction products prepared from polyester-polyol with isocyanate was determined by titrimetry in% by weight based on DIN EN 1242.
  • the adhesive properties of the adhesive formulations produced are measured by means of a roller peel test on the basis of DIN EN 2850 in N.
  • Reaction temperature of 245 ° C is distilled off within about two to four hours, most of the water formed. Thereafter, 0.15 g of a titanium catalyst are added and the pressure at the same temperature gradually reduced to 10 mbar. The reaction is complete when no more acid end groups are present (acid number ⁇ 1 mg KOH / g) and a concentration of hydroxyl end groups of 30 mg KOH / g was achieved.
  • the polyester polyol has a glass transition point of -46 ° C.
  • the amount of polyol shown in Table 1 is in a 1 liter glass flask with 0.3 g
  • VESTANAT EP DC 1241 NCO number 1 1, 8%, NCO: OH ratio 1: 1 is slowly added dropwise while stirring continuously. After complete addition of VESTANAT EP DC 1241, the reaction is kept at 60 ° C. and stirred until the NCO number is ⁇ 0.1% by weight.
  • the acryl-terminated polymers 1 & 2 described above are each mixed with 2.0% by weight Omnirad 1173 as photoinitiator and heated to 100 ° C. Subsequently, the polymer is on
  • the silicone paper with the polymer is then irradiated in an ultraviolet belt dryer (UN50023 from Technigraf GmbH) at an intensity of 65 J / cm 2 . Obtained are self-adhesive films.
  • the successful crosslinking of the polymer films was investigated and confirmed by adding a small sample of the film to acetone which did not dissolve even after several days.

Abstract

La présente invention concerne des polyesters, de préférence des polyesters à terminaison (méth)acryle, à base d'un polyester polyol à base d'acides dicarboxyliques ou polycarboxyliques et de diols ou de polyols, au moins 0,1 % en poids de polyoléfines à fonctionnalité OH et/ou COOH étant présentes dans le polyester polyol comme acides dicarboxyliques ou polycarboxyliques et diols ou polyols, rapporté à la somme totale d'acides dicarboxyliques ou polycarboxyliques et de diols ou de polyols. L'invention est caractérisée en ce que le polyester présente au moins un motif constitutif, de préférence terminal, de formule (I), dans laquelle Y représente un groupe hydrocarbure aliphatique et Z représente H ou CH3. L'invention concerne par ailleurs l'utilisation de ces polyesters dans des adhésifs ou des produits d'étanchéité, ainsi que dans des compositions de revêtement.
PCT/EP2017/078632 2016-11-11 2017-11-08 Polyesters réticulables par irradiation et leur utilisation WO2018087158A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3838592A1 (fr) * 2019-12-17 2021-06-23 Evonik Operations GmbH Composition comprenant des polyesters pour fabrication additive

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316157A (ja) * 1996-05-24 1997-12-09 Nippon Synthetic Chem Ind Co Ltd:The 光硬化性樹脂組成物及びその用途
US20110184125A1 (en) * 2008-09-23 2011-07-28 Cytec Surface Specialties S.A. Radiation curable adhesive
JP2015048431A (ja) * 2013-09-03 2015-03-16 Dic株式会社 光硬化型樹脂組成物
DE102013220239A1 (de) * 2013-10-08 2015-04-23 Evonik Industries Ag Polyfunktionelle Urethan(meth)acrylate aus Monomer armen Diisocyanat-Monoaddukten

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316157A (ja) * 1996-05-24 1997-12-09 Nippon Synthetic Chem Ind Co Ltd:The 光硬化性樹脂組成物及びその用途
US20110184125A1 (en) * 2008-09-23 2011-07-28 Cytec Surface Specialties S.A. Radiation curable adhesive
JP2015048431A (ja) * 2013-09-03 2015-03-16 Dic株式会社 光硬化型樹脂組成物
DE102013220239A1 (de) * 2013-10-08 2015-04-23 Evonik Industries Ag Polyfunktionelle Urethan(meth)acrylate aus Monomer armen Diisocyanat-Monoaddukten

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199808, Derwent World Patents Index; AN 1998-082700, XP002777365 *
DATABASE WPI Week 201521, Derwent World Patents Index; AN 2015-18186F, XP002777364 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3838592A1 (fr) * 2019-12-17 2021-06-23 Evonik Operations GmbH Composition comprenant des polyesters pour fabrication additive
WO2021122058A1 (fr) * 2019-12-17 2021-06-24 Evonik Operations Gmbh Procédé de fabrication additive avec une composition comprenant des polyesters

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