EP2225341A1 - Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation - Google Patents

Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation

Info

Publication number
EP2225341A1
EP2225341A1 EP08862493A EP08862493A EP2225341A1 EP 2225341 A1 EP2225341 A1 EP 2225341A1 EP 08862493 A EP08862493 A EP 08862493A EP 08862493 A EP08862493 A EP 08862493A EP 2225341 A1 EP2225341 A1 EP 2225341A1
Authority
EP
European Patent Office
Prior art keywords
polymer
glycidyl
group
groups
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08862493A
Other languages
German (de)
English (en)
Inventor
Andreas Kramer
Jürgen Finter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP08862493A priority Critical patent/EP2225341A1/fr
Publication of EP2225341A1 publication Critical patent/EP2225341A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4253—Rubbers
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/58—Epoxy resins
    • C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
    • 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

Definitions

  • the invention relates to a process for the preparation of polyurethanes based on the reaction of a hydroxyl-containing polymer and a polyisocyanate.
  • the present invention further relates to an isocyanate-terminated polyaddition product prepared by this process, an adhesive containing such an isocyanate-terminated polyaddition product, and to the use of the polyaddition product as a hardener component in adhesives.
  • Polyurethanes are plastics or synthetic resins which are formed from the polyaddition reaction of diols or polyols with polyisocyanates.
  • Polyurethanes may have different properties depending on the choice of isocyanate and polyol. In essence, the later properties are determined by the polyol component, because often to achieve desired properties not the isocyanate component is adjusted (ie chemically altered), but the polyol component.
  • Hoses, floors, paints, and in particular adhesives are hoses, floors, paints, and in particular adhesives.
  • liquid rubbers special copolymers have long been used in the art, which are referred to as so-called liquid rubbers.
  • chemically reactive groups such as epoxide, carboxyl-vinyl or amino groups
  • liquid rubbers are chemically incorporated into the matrix.
  • reactive liquid rubbers of butadiene / acrylonitrile copolymers which with Epoxide, carboxyl, vinyl or amino groups are terminated and offered by the company BV Goodrich, or Noveon, under the trade name Hycar ® .
  • the carboxyl-terminated butadiene / acrylonitrile copolymer (CTBN) is always used for this purpose, to which usually a strong excess of a diamine, diepoxide or glycidyl (meth) acrylate is added.
  • CBN carboxyl-terminated butadiene / acrylonitrile copolymer
  • Hydroxyl-functional variants thereof which are more interesting for polyurethane chemistry than amino-functional products and serve as polyols for reaction with the isocyanate component, are technically demanding and expensive to prepare and are usually obtained by reacting CTBN with ethylene oxide. This results in primary alcohol end groups. The resulting Polyethylenglycol phenomenon are also detrimental in contact with water.
  • US 4,444,692 discloses the preparation of hydroxyl-terminated reactive liquid polymers by reacting ethylene oxide in the presence of an amine catalyst with a carboxyl-terminated reactive liquid polymer. This results, as mentioned above, primary alcohol end groups in the polymer.
  • Adhesives and sealing materials are useful. These hydroxyl-terminated polymers are also prepared by reacting carboxyl-terminated polymers with ethylene oxides in the presence of a tertiary amino catalyst. Further ways of producing hydroxyl-functional variants are the reaction of the terminal carboxylic acids with amino alcohols or low molecular weight diols. In both cases, large surpluses must be used, which entails time-consuming workup.
  • US 4,489,008 discloses hydrolytically stable hydroxyl-terminated liquid polymers useful in the production of polyurethanes. These are prepared by reacting at least one aminoalcohol with a carboxyl-terminated polymer. The reaction of a carboxyl-terminated polymer with at least one compound which has at least one glycidyl group is not disclosed. Compared with the conventional polyurethanes, the improved hydrolytic stability of the end product is emphasized.
  • the present invention is based on the object, improved polyurethane compositions, in particular adhesives, sealants and
  • Polyurethanes give a final product which has improved adhesion properties over conventional products
  • the polyurethanes prepared according to the invention or the isocyanate-terminated polyaddition products resulting from a reaction of the above-mentioned polymers with polyisocyanate, are used in adhesives.
  • the hydroxyl-functional polymer is used as a hardener component or part of a hardener component in two-component adhesives. Ways to carry out the invention
  • the present invention relates to a process for the preparation of polyurethanes, comprising the steps:
  • carboxyl-terminated polymers of formula (I) are used to prepare polymers (A). It can be obtained by reacting hydroxyl, amine or thiol-terminated polymers with dicarboxylic acids or their anhydrides.
  • X stands for O, S or NR 4
  • R 4 stands for H or an alkyl group having 1 to 10 carbon atoms.
  • R 1 represents an n-valent radical of a polymer R 1 - [XH] n after removal of the terminal -XH groups.
  • R 2 is a radical of a dicarboxylic acid after removal of the two carboxyl groups, in particular a saturated or unsaturated, optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted, phenylene group.
  • hydroxyphenyl-terminated polymers of the formula (II) are used to prepare polymers (A). They can be by the implementation of hydroxyl, amine or thiol-terminated Polymers obtained with hydroxyphenyl-functional carboxylic acids or their esters.
  • X 1 is NR 4 , CH 2 , or C 2 H 4 and m is 0 or 1.
  • R 1 , X, NR 4 and n have already been previously defined.
  • phenolic groups in the present document are meant hydroxyl groups which are bonded directly to an aromatic nucleus, irrespective of whether one or more such hydroxyl groups are bonded directly to the nucleus.
  • the polymer (A) is obtained by reacting carboxyl group-terminated polymers having a functionality of at least 2 with aromatic glycidyl ethers.
  • the glycidyl group used according to the invention is preferably glycidyl ether, glycidyl ester, glycidylamine, glycidyl amide or glycidyl imide.
  • glycol ether group here is the group of formula, .o
  • Y 1 understood, where Y 1 is H or methyl.
  • glycol ester here is the group of the formula understood, wherein Y 1 is H or methyl.
  • the compound having at least one glycidyl group is selected from mono-, di- or higher-functional glycidyl ethers or glycidyl esters.
  • the diglycidyl ether is an aliphatic or cycloaliphatic diglycidyl ether, especially a diglycidyl ether of difunctional saturated or unsaturated, branched or unbranched, cyclic or open chain C2-C30 alcohols, e.g. Ethylene glycol, butanediol, hexanediol, octanediol diglycidyl ether, cyclohexane dimethanol di glycidyl ether, neopentyl glycol diglycidyl ether.
  • the diglycidyl ether is an aliphatic or cycloaliphatic diglycidyl ether, in particular a diglycidyl ether of the formula (III) or (IV)
  • formula (IV) is (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether and (poly) ethylene glycol / propylene glycol diglycidyl ether, wherein building blocks d and e may be block-like, alternating or random.
  • Particularly suitable aliphatic or cycloaliphatic diglycidyl ethers are propylene glycol diglycidyl ether, butanediol diglycidyl ether or hexanediol diglycidyl ether.
  • amine glycidyl compounds can also be used according to the invention as mentioned above. Examples of such examples include:
  • the polymer (A) is prepared by reacting at least one carboxyl-terminated polymer of the formula (I) with at least one glycidyl ether or glycidyl ester, so that a polymer of the formula (AI) is formed as the polymer of the formula (AI).
  • the polymer (A) is prepared by reacting at least one phenol group-containing polymer of the formula (II) with at least one glycidyl ether or glycidyl ester. The reaction then takes place correspondingly to form the polymer of the formula (A-II)
  • R 1 is a poly (oxyalkylene) polyol, polyester polyol, poly (oxyalkylene) polyamine, polyalkylene polyol, polycarbonate polyol, polymer cap tane or polyhydroxypolyurethane after removal of the hydroxyl, amine or mercaptan groups.
  • R 1 - [XH] n is a polyol.
  • Such polyols are preferably diols or triols, in particular
  • Polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and reported in milliequivalent
  • short DMC catalysts as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH or alkali metal alkoxides.
  • Particularly suitable are polyoxypropylenediols and -triols with a
  • Polyoxypropylenpolyoxyethylenpolyole for example, be obtained by the fact that pure Polyoxyprop- pylenpolyole be alkoxylated after completion of the polypropoxylation with ethylene oxide and thereby having primary hydroxyl groups.
  • Hydroxy-terminated polybutadiene polyols such as those obtained by polymerization of 1,3-butadiene and allyl alcohol or by Oxidation of polybutadiene are prepared, and their hydrogenation products;
  • Styrene-acrylonitrile grafted polyether polyols such as are supplied, for example, by Elastogran under the name Lupranol ®; Polyester polyols prepared, for example, from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo pentylglycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid,
  • R 1 - [X H] n is a polyamine.
  • Such polyamines are in particular diamines or triamines, preferably aliphatic or cycloaliphatic diamines or triamines.
  • these are polyoxyalkylene polyamines having two or three amino groups, for example available under the name Jeffamine ® (from Huntsman Chemicals), under the name polyetheramine (from BASF) or under the name PC Amine ® (from Nitroil), and mixtures of the aforementioned polyamines ,
  • Preferred diamines are polyoxyalkylene polyamines having two amino groups, especially those of the formula of the formula (V).
  • g ' represents the structural element derived from propylene oxide and h' the structural element derived from ethylene oxide.
  • g, h and i are each from 0 to 40, with the proviso that the sum of g , h and i> 1.
  • molecular weights between 200 and 10'000 g / mol are preferred.
  • Particularly preferred diamines are Jeffamine such as are sold under the D-line and ED-line by Huntsman Chemicals as to avoid importing Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine ® D-4000, Jeffamine ® ED-600, Jeffamine ® ED-900 or Jeffamine ® ED of 2003.
  • preferred triamines are marketed under the Jeffamine ® T-Line by Huntsman Chemicals, such as Jeffamine ® T-3000, Jeffamine ® T-5000 or Jeffamine ® T-403rd
  • R 1 - [X H] n is a polymercaptan.
  • Suitable polymercaptans are, for example, polymercaptocetates of polyols. It These are, in particular, polymercaptocetates of the following polyols:
  • Polyoxyalkylenpolyole also called polyether polyols, which are the polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized using a starter molecule having two or three active hydrogen Atoms such as water or compounds with two or three OH groups.
  • polyether polyols which are the polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized using a starter molecule having two or three active hydrogen Atoms such as water or compounds with two or three OH groups.
  • Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per mole) can be used
  • Grams of polyol (mEq / g)), prepared for example by means of so-called double metal cyanide complex catalysts (short DMC catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH or alkali metal alkoxides.
  • polyoxypropylene diols and triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 300-20,000 daltons
  • polyoxybutylene diols and triols polyoxypropylene diols and triols having a molecular weight of 400-8000 daltons
  • ethylene oxide-endcapped polyoxypropylene diols or triols the latter being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide upon completion of the polypropoxylation and thereby having primary hydroxyl groups.
  • Hydroxy-terminated polybutadiene polyols such as those prepared by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and their hydrogenation products; - styrene-acrylonitrile grafted polyether polyols, such as supplied, for example, from Elastogran under the name Lupranol ®; Polyester polyols prepared, for example, from dihydric to trihydric alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propane diol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, glycerol, 1, 1, 1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as Succinic acid, glutaric acid, a
  • Polyols as they are contained by reduction of dimerized fatty acids are contained by reduction of dimerized fatty acids.
  • glycol dimercaptoacetate trimethylolpropane trimercaptoacetate and butanediol dimercaptoacetate.
  • the most preferred polymercaptans are dimercaptans of the formula (VI).
  • y stands for a value from 1 to 45, in particular from 5 to 23.
  • the preferred molecular weights are between 800 and 7500 g / mol, in particular between 1000 and 4000 g / mol.
  • Such polymercaptans are commercially available under the Thiokol LP ® series of Toray Fine Chemicals Co.
  • Preferred hydroxyphenyl-functional carboxylic acid esters are methyl ortho, meta or para hydroxy hydroxybenzoate, ethyl ortho, meta or para hydroxy hydroxybenzoate, isopropyl ortho, meta or para hydroxy benzoate, benzoxazolinone, Benzofuran-2-one, benzodihydro-pyrone.
  • Preferred dicarboxylic anhydrides are phthalic anhydride, maleic anhydride, succinic anhydride, methylsuccinic anhydride, isobutene-succinic anhydride, phenylsuccinic anhydride, itaconic acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic acid anhydride , Hexahydro-4-methylphthalic anhydride, glutaric anhydride, 3-methyl-glutaric anhydride, ( ⁇ ) -1, 8,8-trimethyl-3-oxabicyclo [3.2.1] octane-2,4-diones, oxepan -2,7-dion.
  • This reaction is preferably carried out in the presence of a catalyst at elevated temperatures of 50 0 C to 150 0 C, preferably 70 ° C to 130 0 C.
  • the catalyst used is preferably triphenylphosphine, the reaction can optionally be carried out under protective gas or vacuum.
  • further usable catalysts are tertiary amines, quaternary phosphonium salts or quaternary ammonium salts.
  • the reaction is then carried out at elevated temperatures of 80 ° C to 200 ° C, preferably 90 0 C to 180 ° C.
  • a molar excess of the epoxide groups over the carboxyl and / or phenol groups in the reaction mixture is selected.
  • the ratio of the number of epoxy groups to the number of carboxyl and / or phenol groups is 1: 1 to 50: 1, preferably 1: 1 to 20: 1, particularly preferably 1: 1 to 10: 1.
  • a polyisocyanate (B) As a polyisocyanate (B), a diisocyanate or a triisocyanate is used in a preferred embodiment.
  • polyisocyanates it is possible to use aliphatic, cycloaliphatic or aromatic polyisocyanates, in particular diisocyanates. Particularly suitable are the following:
  • HDI 6-hexamethylene diisocyanate
  • TMDI 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate
  • Decamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, lysine and Lysinesterdiisocyanat, cyclohexane-1, 3 and -1, 4-diisocyanate and any mixtures of these isomers, 1-methyl-2,4- and -2,6-diisocyanatocyclohexan and any mixtures of these isomers (HTDI or H 6 TDI), 1-isocyanato-SS ⁇ -trimethyl- ⁇ -isocyanatomethyl-cyclohexane ( isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI or H 12 MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, m- and p-
  • TDI 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers
  • MDI 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers
  • MDI 1, 3 - and 1, 4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1, 4-diisocyanatobenzene, naphthalene-1, 5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI ), Dianisidine diisocyanate (DADI).
  • Oligomers e.g., biurets, isocyanurates
  • polymers of the foregoing monomeric diisocyanates e.g., biurets, isocyanurates
  • the polyisocyanate (B) is used in particular in such an amount that the ratio of NCO groups to OH groups of the described hydroxyl-containing polymer (A) in a ratio of> 1 to 2, so that isocyanate-terminated polyaddition formed.
  • Particularly suitable are such polyaddition products, which arise from a ratio of NCO / OH ratio between 1.5 and 2. It will be apparent to those skilled in the art that it should increase the amount of polyisocyanate (B) accordingly if other NCO-reactive compounds, such as the isocyanate-reactive polymers (C) described below, are present in this reaction.
  • At least one further isocyanate-reactive polymer (C) is additionally present in the reaction of the at least one polymer (A) with at least one polyisocyanate (B).
  • This isocyanate-reactive polymer (C) is preferably selected from the group consisting of poly (oxyalkylene) polyol, polyester polyol, polycarbonate polyol, poly (oxyalkylene) polyamine, polyalkylene polyol and polymercaptan.
  • polymer (A) and the other polymer (s) are present in a weight mixing ratio of 1: 100 to 100: 1.
  • the present invention relates to an isocyanate group-terminated polyaddition product of i) a polymer (A) as described above; and ii) a polyisocyanate (B).
  • the isocyanate-terminated polyaddition product of the present invention is further obtainable by a method as defined above.
  • the isocyanate group-terminated polyaddition product according to the invention can be used in particular in adhesives, and to that extent the present invention relates to an adhesive composition containing the same.
  • the polymers (A) having at least two hydroxyl groups described here and the isocyanate group-terminated polyaddition product described have a significantly lower viscosity, which brings significant advantages for their use and processing. Furthermore, the accessibility to the educts for their preparation is much easier, which on the one hand brings financial benefits and increases the ability to provide tailor-made products to specific requirements.
  • the present invention comprises the use of the polymer (A) in polyurethane chemistry, preferably as a hardener component or part of a hardener component in two-component adhesives.
  • polyurethane chemistry preferably as a hardener component or part of a hardener component in two-component adhesives.
  • many other applications are possible, for example in PU for seals, hoses, floors, paints, sealants, skis, textile fibers, raceways in stadiums, potting compounds, and much more.
  • Dynacoll® 7250 polyethylene glycol, OH value ca. 22.5 mg KOH / g, Evonik
  • 18.55g of hexahydrophthalic anhydride were combined mixture was stirred at 150 0 C for 2 h under a nitrogen atmosphere for 30 min. Under vacuum.
  • a polymer having an acid number of 21.6 mg KOH / g (theoretically 21.2 mg KOH / g) was obtained.
  • poly-THF® 2000 polyether polyol, OH number about 57.0 mg KOH / g, BASF
  • phthalic anhydride 90.3 g
  • hydroxy-functional polymer A-1 (OH number about 19.6 mg KOH / g), 10.3 g of isophorone diisocyanate, 0.12 g of butylhydroxytoluene (BHT) (radical scavenger) and 0.03 g of dibutyltin dilaurate were combined. It was during
  • compositions were prepared by mixing the ingredients according to Table 1 in parts by weight.
  • the isocyanate-terminated polymers P1 and P2 required for this purpose were prepared as follows:
  • polyoxypropylene diol (Acclaim ® 4200 N, Bayer MaterialScience AG; OH number 28.5 mg KOH / g) ;, 1180 g of polyoxypropylene polyoxyethylene triol (Caradol ® MD34-02, Shell Chemicals Ltd., UK; OH number 35.0 mg KOH / g) and 230 g of isophorone diisocyanate (IPDI; Vestanat ® IPDI, Degussa AG) were reacted by a known method at 80 0 C to give an NCO-terminated polyurethane polymer having a free isocyanate group content of 2.1 wt .-%.
  • IPDI isophorone diisocyanate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé de fabrication de polyuréthannes, fondé sur la réaction d'un polymère comportant des groupes hydroxyles et d'un polyisocyanate. La présente invention concerne également un produit de polyaddition à groupes isocyanates terminaux fabriqué par ce procédé, un adhésif qui contient un tel produit de polyaddition à groupes isocyanates terminaux et l'utilisation du produit de polyaddition en tant que composant de durcissement dans des adhésifs. Les polyuréthannes selon l'invention sont obtenus par réaction d'au moins un polymère (A), qui comporte au moins deux groupes hydroxyles et qui est obtenu par la réaction d'un polymère comportant au moins deux groupes carboxyles et/ou phénols de formule (I) ou (II) avec au moins un composé comportant au moins un groupe glycidyle, avec au moins un polyisocyanate (B).
EP08862493A 2007-12-17 2008-12-15 Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation Withdrawn EP2225341A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08862493A EP2225341A1 (fr) 2007-12-17 2008-12-15 Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07150049A EP2072556A1 (fr) 2007-12-17 2007-12-17 Procédé de fabrication de polymères hydroxyfonctionnels, produits de polyaddition à terminaison de groupes isocyanates ainsi obtenus et leur utilisation
PCT/EP2008/067478 WO2009077470A1 (fr) 2007-12-17 2008-12-15 Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation
EP08862493A EP2225341A1 (fr) 2007-12-17 2008-12-15 Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation

Publications (1)

Publication Number Publication Date
EP2225341A1 true EP2225341A1 (fr) 2010-09-08

Family

ID=39205068

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07150049A Withdrawn EP2072556A1 (fr) 2007-12-17 2007-12-17 Procédé de fabrication de polymères hydroxyfonctionnels, produits de polyaddition à terminaison de groupes isocyanates ainsi obtenus et leur utilisation
EP08862493A Withdrawn EP2225341A1 (fr) 2007-12-17 2008-12-15 Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07150049A Withdrawn EP2072556A1 (fr) 2007-12-17 2007-12-17 Procédé de fabrication de polymères hydroxyfonctionnels, produits de polyaddition à terminaison de groupes isocyanates ainsi obtenus et leur utilisation

Country Status (5)

Country Link
US (1) US20100256322A1 (fr)
EP (2) EP2072556A1 (fr)
JP (1) JP2011506724A (fr)
CN (1) CN101896570A (fr)
WO (1) WO2009077470A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130097789A (ko) 2010-10-15 2013-09-03 코넬 유니버시티 내분비, 위장관 또는 자가면역 장애 치료를 위한 조성물 및 방법
US10526277B2 (en) 2013-10-17 2020-01-07 Swimc Llc Food or beverage containers coated with polymers of di(amido(alkyl)phenol) compounds
JP6560211B2 (ja) * 2013-11-27 2019-08-14 ダウ グローバル テクノロジーズ エルエルシー ポリウレタン系アスファルト組成物
US9884981B2 (en) 2014-02-21 2018-02-06 IFS Industries Inc. Polyol compositions for hot melt adhesives
MX2016015219A (es) 2014-05-19 2017-03-23 Valspar Sourcing Inc Polieteres que contienen grupos ciclicos no bisfenolicos.
CN107075336B (zh) * 2014-10-20 2020-10-27 Dic株式会社 粘合剂组合物及粘合片
CN104629671B (zh) * 2015-02-25 2016-08-24 宁波江东飞创电子科技有限公司 一种改性聚氨酯密封胶
KR101859537B1 (ko) * 2015-11-06 2018-05-21 주식회사 케이씨씨 2액형 에폭시 접착제 조성물
CN106750129B (zh) * 2016-12-28 2019-12-27 中昊北方涂料工业研究设计院有限公司 一种低介电损耗聚氨酯树脂及其制备方法
CN109553766B (zh) * 2018-09-28 2021-11-02 长兴材料工业（广东）有限公司 改性聚酯多元醇及其制备方法与应用
TWI712627B (zh) * 2018-09-28 2020-12-11 長興材料工業股份有限公司 改性聚酯多元醇及其製備方法與應用
CN113150714B (zh) * 2020-01-07 2023-03-10 3M创新有限公司 聚氨酯基可uv固化组合物及包含其的胶膜、胶带和粘结构件
KR102337544B1 (ko) * 2021-01-19 2021-12-13 최광복 수용성 우레탄 몰탈 조성물
US20220356150A1 (en) * 2021-04-30 2022-11-10 Evoco Limited Biobased diisocyanates, and process for preparation of same

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3712916A (en) * 1968-05-22 1973-01-23 Goodrich Co B F Preparation of hydroxyl terminated polymers
US3551472A (en) * 1968-05-22 1970-12-29 Goodrich Co B F Liquid hydroxyl terminated polymers of butadiene-acrylonitrile
US3923739A (en) * 1969-02-25 1975-12-02 Minnesota Mining & Mfg Linear {62 -hydroxy-ester, {62 -hydroxy-ether and {62 -hydroxy-amine polymers
DE2009309A1 (de) * 1969-02-25 1970-08-27 Minnesota Mining and Manufacturing Company, St. Paul, Minn. (V.St.A.) Lineare beta-Hydroxyester-, beta-Hydroxyäther- und beta-Hydroxyaminpolymerisate
JPS4940863B1 (fr) * 1970-01-22 1974-11-06
US3699153A (en) * 1970-07-02 1972-10-17 Goodrich Co B F Preparation of hydroxyl terminated polymers
CA975494A (en) * 1970-09-29 1975-09-30 Gonzague L. Duchesne Propellants
DE2103117B2 (de) * 1971-01-23 1974-05-09 Dainippon Ink And Chemicals, Inc., Tokio Form- oder Überzugsmassen aus Polyestern und Aminoharzen oder Polyisocyanaten
JPS5040421B2 (fr) * 1972-02-29 1975-12-24
DE2746789C3 (de) * 1976-10-19 1981-04-30 Hitachi Chemical Co., Ltd., Tokyo Hitzehärtbare Harzzusammensetzung und ihre Verwendung
US4489008A (en) * 1978-10-17 1984-12-18 The B. F. Goodrich Company Hydroxyl-terminated liquid polymers
US4294940A (en) * 1979-01-12 1981-10-13 Sumitomo Chemical Company, Limited Resin composition for electrocoating
MX158102A (es) * 1980-03-24 1989-01-09 Sun Chemical Corp Procedimiento mejorado para la obtencion de una resina de eteres de poliamida
US4444692A (en) * 1981-05-18 1984-04-24 The B. F. Goodrich Company Process for making hydroxyl terminated liquid polymers
US4386191A (en) * 1981-10-08 1983-05-31 Stauffer Chemical Company Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom
FR2536753B2 (fr) * 1981-11-02 1987-06-19 Grace W R Ltd Compose thermoplastique a epoxy pendant, contenant de l'urethane, composition thermodurcissable le contenant et procede pour faire adherer deux substrats
ATE25392T1 (de) * 1982-12-23 1987-02-15 Akzo Nv Pigment enthaltende fluessige ueberzugszusammensetzung.
JPS60219219A (ja) * 1984-04-16 1985-11-01 Saiden Kagaku Kk ウレタンエマルシヨンの製造法
US4613660A (en) * 1985-02-19 1986-09-23 Ashland Oil, Inc. Polyol/polyepoxide/polyurethane adhesive
JPH0240272B2 (ja) * 1985-02-19 1990-09-11 Ashland Oil Inc Setsuchakuhohooyobisorenimochiirusetsuchakuzaisoseibutsu
US4728737A (en) * 1985-05-03 1988-03-01 Ashland Oil, Inc. High performance two-component epoxy structural adhesive with chemical thixotropy
US4578424A (en) * 1985-05-03 1986-03-25 Ashland Oil, Inc. High performance two-component epoxy structural adhesives with chemical thixotropy
US4740539A (en) * 1986-04-21 1988-04-26 Ashland Oil, Inc. Flexible two-component epoxy structural adhesives
US4762864A (en) * 1986-06-19 1988-08-09 Ashland Oil Inc. High performance induction curable two-component structural adhesive with nonsagging behavior
US4878978A (en) * 1986-06-19 1989-11-07 Ashland Oil, Inc. Bonding method employing high performance induction curable two-component structural adhesive with nonsagging behavior
US4695605A (en) * 1986-10-01 1987-09-22 Ashland Oil, Inc. Sag resistant, high performance epoxy structural adhesives
US4863525A (en) * 1986-11-13 1989-09-05 Ashland Oil, Inc Flush solvents for epoxy adhesives
US4769419A (en) * 1986-12-01 1988-09-06 Dawdy Terrance H Modified structural adhesives
US5096980A (en) * 1988-06-28 1992-03-17 Takeda Chemical Industries, Ltd. Polyurethane adhesive of epoxy resin, polyisocyanate, phosphorus oxy acid, and carboxylic acid
EP0399108A1 (fr) * 1989-05-26 1990-11-28 Akzo N.V. Copolymère bloc polyester/époxy utilisé comme liant pour revêtement primaire pour métaux
US5229214A (en) * 1989-07-31 1993-07-20 Akzo N.V. Preprimed metal substrates for formed metal applications
JPH0711225A (ja) * 1993-04-26 1995-01-13 Takeda Chem Ind Ltd ポリウレタン接着剤組成物
JP3590110B2 (ja) * 1994-11-14 2004-11-17 三井化学株式会社 ポリエステル変性ポリオール樹脂およびその製造方法
US5717054A (en) * 1995-06-07 1998-02-10 National Starch & Chemical Investment Holding Corp. Epoxy resins consisting of flexible chains terminated with glycidyloxyphenyl groups for use in microelectronics adhesives
TW592813B (en) * 2001-08-15 2004-06-21 Dow Global Technologies Inc Process to manufacture polyurethane products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009077470A1 *

Also Published As

Publication number Publication date
US20100256322A1 (en) 2010-10-07
EP2072556A1 (fr) 2009-06-24
WO2009077470A1 (fr) 2009-06-25
JP2011506724A (ja) 2011-03-03
CN101896570A (zh) 2010-11-24

Similar Documents

Publication Publication Date Title
EP2225341A1 (fr) Procédé de fabrication de polymères à fonction hydroxy, produits de polyaddition à groupes isocyanates terminaux pouvant être obtenus à partir de celui-ci et leur utilisation
EP2060592B1 (fr) Composition de résine époxy durcissant à la chaleur contenant des urées non aromatiques en tant qu'accélérateurs
EP2085426B1 (fr) Colles en résine époxy durcissant à la chaleur et résistantes au lavage
EP2542602B1 (fr) Agents anti-chocs comprenant des groupes amine terminaux et leur utilisation dans des compositions á base de resine époxy
EP2084200B1 (fr) Résine solide en époxy dérivée et ses applications
EP2137226B1 (fr) Polymères terminés par des groupes époxy, leur préparation et leur utilisation comme modificateurs résistants aux chocs
EP1313784B1 (fr) Dispersion (hybride polymere) de polyurethanne a hydrophilie reduite, son procede de production et son utilisation
EP0950675B1 (fr) Systèmes réactifs et leur utilisation pour la production de revêtements, adhésifs, matériaux d'étanchéité, matériaux de coulée ou des pièces moulées
WO1999048942A9 (fr) Polyurethane et preparation contenant du polyurethane
EP0688803B1 (fr) Prépolymères d'isocyanates bloqués par des agents de blocage différents, leur procédé de préparation et leur utilisation dans la production de systèmes de résines époxydes flexibilisées
EP3892659A1 (fr) Prépolymères d'isocyanate à faible viscosité bloqués ayant des phénols obtenus à partir de l'huile de noix de cajou, leur procédé de fabrication et leur utilisation
EP2125901A1 (fr) Améliorants de viscosité terminés par des groupes époxydes, pré-allongés par des esters et procédé de fabrication de ceux-ci
EP1204691B1 (fr) Systemes reactifs exempts de solvants et durcissant a temperature ambiante et leur utilisation pour la production d'adhesifs, de masses d'etancheite, de masses de remplissage, de pieces moulees ou de revetements
EP1578833B1 (fr) Systeme reactif durcissant a temperature ambiante
DE19935329A1 (de) Harnstoffgruppen aufweisende Polyamine, Verfahren zu ihrer Herstellung wie ihre Verwendung als Härter für Epoxidharze
WO2014044851A1 (fr) Agent de résilience de prépolymère pour des colles résistant à la fissuration pour des éoliennes
EP2143745B1 (fr) Polymères avec fonctions hybride
EP2620457A1 (fr) Durcissement accéléré de polyurethannes monocomposants
DE3010626A1 (de) Vernetzte polyuretan-kunststoffe
WO2006056320A1 (fr) Polyols stables a l'hydrolyse, hydrophobes et exempts de solvants

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100719

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130109

STAA Information on the status of an ep patent application or granted ep patent

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

18D Application deemed to be withdrawn

Effective date: 20130522