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

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2007
  • 2007-12-17 EP EP07150049A patent/EP2072556A1/de not_active Withdrawn
• 2008
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  • 2008-12-15 WO PCT/EP2008/067478 patent/WO2009077470A1/de not_active Ceased
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