EP1218332A1 - Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee - Google Patents

Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee

Info

Publication number
EP1218332A1
EP1218332A1 EP00967760A EP00967760A EP1218332A1 EP 1218332 A1 EP1218332 A1 EP 1218332A1 EP 00967760 A EP00967760 A EP 00967760A EP 00967760 A EP00967760 A EP 00967760A EP 1218332 A1 EP1218332 A1 EP 1218332A1
Authority
EP
European Patent Office
Prior art keywords
transesterification
polyols
polyurethane
polyol
oil
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Withdrawn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
EP00967760A
Other languages
German (de)
English (en)
Inventor
Lothar Thiele
Lars Zander
Johann Klein
Bernd Beuer
Nicole Knips
Peter Döbrich
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1218332A1 publication Critical patent/EP1218332A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids

Definitions

  • the invention relates to the production and use of low-viscosity, essentially solvent-free polyurethane prepolymers based on transesterification products of castor oil
  • Polyurethanes have been used for years as adhesives, sealants, casting compounds or coating agents in one or more components because of their high specific adhesion to numerous materials as well as their flexibility and resistance to cold.
  • Ricinusol as a polyol made from renewable raw materials is an ecologically advantageous polyurethane raw material, among others for aforementioned fields of application
  • ricinusol as a sole polyol is not suitable for many areas of application because the cured polyurethane binders prepared in this way have mechanically unsatisfactory properties.
  • GB 671368 discloses dehydrated ricinusol oils with hydroxyl numbers between about 17 and 40 which have also been proposed several times for use as a polyol in polyurethane chemistry
  • DE-A-4114022 describes the use of partially dehydrated castor oils with hydroxyl numbers between 80 and 135 mg KOH / g as a reactive component of a polyol mixture with the use of further 2, 3 and / or polyhydric alcohols.
  • WO 95/23172 proposes the use of polyol mixtures of dehydrated ricinusol, polypropylene glycols (diols) and monoalcohols which are liquid at room temperature and have a hydroxyl number below 250 for the preparation of low-viscosity, at least predominantly solvent-free polyurethane adhesives with good storage stability.
  • EP-A-709414 describes the use of partially dehydrated castor oils as a polyol component for the preparation of aqueous polyurethane dispersions and their use as coatings. It is said that the partially dehydrated castor oil can be used as the sole polyol component or to a significant percentage. It is further disclosed that the use of partially dehydrated castor oil in the production of aqueous polyurethane dispersions brings about a reduction in the prepolymer viscosity. Low-viscosity, one-component, essentially solvent-free and non-aqueous polyurethane prepolymers are not disclosed in this document.
  • the main object of the present invention is to provide one- or multi-component reactive polyurethane compositions based on castor oil derivatives which are reproducibly low j
  • a particularly preferred use of the polyurethane prepolymers produced according to the invention are moisture-curing adhesives for use in wood bonding and in panel production.
  • a foam or rock wool core is preferably glued with plywood, chipboard and fibreboard, plastic or primed metal cover layers.
  • solvent- and water-free adhesives with viscosities between 1,000 and 15,000 mPa.s are used for these applications; these adhesives should preferably have viscosities between 3,000 and 12,000 mPas.
  • dehydration polyols of ricinusol according to GB 671368 which have hydroxyl numbers as disclosed in DE-A-4406211, no prepolymers with constant viscosity can be produced.
  • cloudy products are formed which then have phase separation or other inhomogeneities over a longer storage period.
  • the dehydration of castor oils according to the prior art takes place at temperatures above 230 ° C. in the presence of acid catalysts. This process has the disadvantage that side reactions, for example transesterification, polymerization and hydrolysis, can easily produce products with comparatively very high or very low molecular weights. It is also rather difficult to determine the hydroxyl number narrow a very small specification range reproducibly.
  • Viscosity changes These fluctuations in viscosity create problems when processing such products. OH number fluctuations lead, especially in the case of two-component polyurethane systems, to reactivity and
  • Another object of the present invention is the production of such transesterified castor oils using castor oil and essentially OH group-free native triglycerides.
  • native oils can be used for the OH group-free oils
  • the rapeseed oil, the sunflower oil or the soybean oil are particularly preferred oils.
  • the OH number can be precisely predetermined by specifying the mixing ratio of ricinusol to the OH group-free oil or oils. It is particularly surprising here that, in the transesterification reaction according to the invention, molecules with strongly deviating higher or lower molar masses do not form as in the dehydration. This is particularly advantageous because it enables a very high viscosity constancy paired with an OH number to be achieved in a narrow specification window in accordance with the specified goal.
  • Castor oil products produced according to the invention have hydroxyl numbers of less than 160 mg KOH / g according to DIN 53240.
  • a particularly preferred range is between 20 and 130, values between 30 and 100 mg KOH / g are very particularly preferred.
  • These polyols have an average functionality between about 0.3 and 3.
  • Another advantage is that reproducibly clear prepolymers with a defined viscosity range can be produced by the process according to the invention.
  • the range of viscosity of the polyurethane prepolymer can pass through the functionality or OH number of the transesterification polyol, the functionality of the polyisocyanate used and the ratio of polyisocyanate to
  • Transesterification polyol can be set.
  • esterification or transesterification catalysts known from organic chemistry such as e.g. acidic catalysts, organotin compounds, organotitanates and especially alkali or. Alkaline earth metal.
  • Lithium hydroxide is very particularly preferred, since it has surprisingly been found that this transesterification catalyst can remain in the polyol during the preparation of the polyurethane prepolymer without adversely affecting the storage stability of the polyurethane prepolymer.
  • polyurethane prepolymers according to the invention are preferably based on the dehydration polyol as the sole polyol
  • further di- or trifunctional polyols known in polyurethane chemistry can be used, e.g. Polyethylene glycols, polypropylene glycols, polytetraethylene glycols, polybutylene glycols and / or their copolymers and polyester polyols based on aliphatic or aromatic dicarboxylic acids and low molecular weight diols or triols, and hydroxyfunctional polycaprolactones can also be used.
  • polys to be used examples include di- and / or trifunctional polypropylene glycols in the molecular weight range from 200 to 6000, preferably in the range from 400 to 3000.
  • polyethers which are preferably to be used are the polytetramethylene glycols which are prepared, for example, by the acidic polymerization of tetrahydrofuran, the molecular weight range of the polytetramethylene glycols being between 200 and 6000, preferably in the range from 400 to 4000.
  • liquid polyesters which pass through
  • Glutaric acid azelaic acid, suberic acid, 3,3-dimethylglutaric acid, terephthalic acid,
  • Diols or triplets such as Ethylene glycol, propylene glycol, diethylene glycol,
  • Triethylene glycol dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol,
  • Dimer fatty alcohol, glycerin or trimethylolpropane can be produced.
  • Another group of the polyols to be used according to the invention are:
  • Polyester based on ⁇ -caprolactone also called “polycaprolactone”.
  • polyester polyols of oleochemical origin can also be used.
  • Such polyester polyols can, for example, by complete
  • Triglyceride derivatives to alkyl ester polyols with 1 to 12 carbon atoms in the alkyl radical are prepared.
  • Other suitable polyols are polycarbonate polyols and
  • Dimer diols from Henkel.
  • the hydroxy-functional polybutadienes such as those e.g. are available under the trade name "Poly-bd” can be used as polyols for the compositions according to the invention.
  • polyisocyanates known in polyurethane chemistry can be used as polyisocyanates, but liquid products of 4,4'-diphenylmethane diisocyanate (MDI) are particularly preferred.
  • MDI 4,4'-diphenylmethane diisocyanate
  • solid pure MDI can also be used, and low-viscosity prepolymers are also obtained with this.
  • its use includes additional reaction steps before the prepolymer formation, in particular the melting of the solid MDI, and this also has a significantly higher price than the so-called "raw MDI".
  • the so-called raw MDI can therefore be used with a particularly great advantage.
  • This technical MDI mainly consists of a mixture of homologues and isomers of
  • 4,4'-diphenylmethane diisocyanate usually has a
  • the transesterification polyol or its mixture with other polyols is reacted with the polyisocyanate in such a way that there is a stoichiometric excess of isocyanate groups over hydroxyl groups.
  • This stoichiometric excess of the isocyanate groups is in the range between 1, 3 and 7, preferably between 2 and 5.
  • a conventional polyurethane catalyst can be added in a manner known per se to form the prepolymer.
  • organometallic compounds such as tin (II) salts of carboxylic acids, e.g. Tin (II) acetate, ethylhexoate and diethylhexoate or strong bases such as alkali hydroxides, alcoholates and phenolates can be used.
  • tin (II) salts of carboxylic acids e.g. Tin (II) acetate, ethylhexoate and diethylhexoate or strong bases such as alkali hydroxides, alcoholates and phenolates
  • Dialkyltin (IV) carboxylates represent a preferred class of compounds.
  • the carboxylic acids have 2, preferably at least 10, in particular 14 to 32, carbon atoms. Dicarboxylic acids can also be used.
  • acids adipic acid, maleic acid, fumaric acid, malonic acid, succinic acid, pimelic acid, terephthalic acid, phenylacetic acid, benzoic acid, acetic acid, propionic acid and 2-ethylhexanoic, caprylic, capric, lauric, myristic, palmitic and stearic acids.
  • Specific compounds are dibutyl and dioctyl tin diacetate, maleate, bis (2-ethylhexoate), dilaurate, tributyltin acetate, bis (ß-methoxycarbonylethyi) tin dilaurate and bis (ß-acetyl-ethyl) tin dilaurate.
  • Tin oxides and sulfides and thiolates are also preferred.
  • Specific compounds are: bis (thbutyltin) oxide, bis (trioctyltin) oxide, dibutyl and dioc tyltin bis (2-ethylhexylthiolate) dibutyl and dioctyltin didodecyl thiolate, bis (ß-methoxycarbonyl-ethyl) tin didododyl thiolate, bis (ß-acetylethyl) tin bis (2-ethylhexylthiolate), dibutyl and dodecylthiolate - and octyltin tris (thioglycolic acid 2-ethylhexoate), dibutyl- and dioctyltin bis (thioglycolic acid 2-ethylhexoate), tributyl- and trioctyltin (thio
  • aliphatic tertiary amines in particular with a cyclic structure.
  • tertiary amines those which additionally carry groups which are reactive toward the isocyanates, in particular hydroxyl and / or amino groups.
  • trimerization reaction of the isocyanate groups with themselves or with urethane and urea groups to form allophanate or biuret groups can also be used for crosslinking the polyurethane skeleton of two-component systems. Trimening catalysts can be used for this. DABCO TMR-2 etc. from Air Products may be mentioned as the trimerization catalyst, which are quaternary ammonium salts dissolved in ethylene glycol.
  • the prepolymer can be produced without additional heating.
  • the prepolymer has a very good shelf life in the absence of moisture.
  • the products have a weaker smell than products that were manufactured at high temperatures of 100 ° C and higher.
  • the prepolymers have a lower intrinsic odor than products containing solvents.
  • the adhesives, sealants, casting compounds and coating compositions according to the invention generally also contain, in addition to the abovementioned binder constituents, a significant proportion of fillers.
  • fillers can be used such as calcium carbonate in the form of chipped or ground chalk or as
  • Limestone powder also dolomite (CaMg (CO 3 ) 2 ), barium sulfate (heavy spar),
  • Rubber flour, rubber chips, foam glass granulate or ground glass can be used.
  • the filler content depends on the
  • the polyurethane binder can make up to 85% by weight of the polyurethane binder. If the fillers have high water contents, it may be necessary to dry them in a known manner before mixing them with the prepolymers.
  • the 3 figures according to FIG. 1 show a comparison of the gel permeation chromatograms of the dehydration and transesterification polyols with castor oil. It can clearly be seen that the transesterification polyol has significantly fewer high and low molecular weight fractions than the dehydration polyol. The gel permeation chromatogram of the transesterification polyol consequently does not differ as much as that of the dehydration polyol from the castor oil chromatogram.
  • the prepolymer produced was brown in color and slightly cloudy.
  • the viscosity of the product was 18500 mPas and the NCO content was 10.0%.
  • Example 3 The dehydrated castor oil sol from Example 3 was replaced by a transesterification polyol according to Example 2 with an OH number of 61 mg KOH / g. The other products and the manufacturing process did not differ from Example 3.
  • This prepolymer was brown and not cloudy.
  • the viscosity was 7100 mPas and the NCO content was 10.2%.

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)
  • Fats And Perfumes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)

Abstract

Polyols de transestérification préparés à partir d'huile de ricin et de triglycérides natifs exempts de groupes OH, qui conviennent en tant que polyols pour la préparation de prépolymères de polyuréthanne. Ces produits de réaction de polyols de transestérification avec des polyisocyanates présentent, même en tant que compositions exemptes de solvant ou exemptes d'eau, une viscosité faible et constante. Ils sont appropriés pour la préparation d'adhésifs, de masses d'étanchéité, de masses de remplissage ou de matières de revêtement à un ou plusieurs constituants.
EP00967760A 1999-10-02 2000-09-23 Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee Withdrawn EP1218332A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19947563 1999-10-02
DE1999147563 DE19947563A1 (de) 1999-10-02 1999-10-02 Umesterungspolyole für Polyurethan-Prepolymere mit gezielt einstellbarer Viskosität
PCT/EP2000/009312 WO2001025184A1 (fr) 1999-10-02 2000-09-23 Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee

Publications (1)

Publication Number Publication Date
EP1218332A1 true EP1218332A1 (fr) 2002-07-03

Family

ID=7924319

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00967760A Withdrawn EP1218332A1 (fr) 1999-10-02 2000-09-23 Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee

Country Status (4)

Country Link
EP (1) EP1218332A1 (fr)
JP (1) JP2003511486A (fr)
DE (1) DE19947563A1 (fr)
WO (1) WO2001025184A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10162344A1 (de) * 2001-12-18 2003-07-10 Henkel Kgaa Schwerbrennbare Polyurethanklebstoffe
MX2007000022A (es) 2004-06-25 2007-05-23 Pittsburg State University Polioles basados en aceite vegetal modificado.
DE102005001565A1 (de) * 2005-01-13 2006-07-27 Bayer Materialscience Ag Holzklebstoffe
US9284401B2 (en) * 2006-11-13 2016-03-15 Bayer Materialscience Llc Process for the preparation of polyether-ester polyols
DE102007052207A1 (de) * 2007-10-30 2009-05-14 Henkel Ag & Co. Kgaa Modifizierte Polyurethanklebstoffe
BRPI0904802B1 (pt) 2008-06-12 2019-05-21 Dow Global Technologies Inc. Prepolímero de poliol tendo pelo menos um grupo uretano, espuma de poliuretano flexível, método para produzir um prepolímero de poliol e método para produzir uma espuma de poliuretano flexível
EP2635618A4 (fr) * 2010-11-03 2014-07-30 Henkel China Co Ltd Adhésifs à base de polyuréthane à deux composants présentant un effet thixotropique
JP6161866B2 (ja) * 2010-12-21 2017-07-12 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 接着剤組成物
KR101766439B1 (ko) 2015-06-26 2017-08-14 켄스코 주식회사 바이오 폴리우레탄의 제조방법 및 이로부터 제조된 바이오 폴리우레탄 및 이를 코팅한 바이오 폴리우레탄코팅 섬유
JP6992301B2 (ja) * 2017-07-20 2022-01-13 東ソー株式会社 イソシアネート基末端プレポリマー及び該組成物を用いた膜モジュールの膜シール材用ポリウレタン樹脂形成性組成物
CN111303823A (zh) * 2020-01-09 2020-06-19 万华节能科技集团股份有限公司 一种透水路面用聚氨酯双组份胶粘剂
JP7470403B2 (ja) 2020-06-12 2024-04-18 積水フーラー株式会社 湿気硬化型ホットメルト接着剤

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59226016A (ja) * 1983-06-04 1984-12-19 Ito Seiyu Kk 硬化性組成物
CA1290631C (fr) * 1985-05-13 1991-10-15 Hirohisa Maki Couche protectrice pour construction en beton
US4603188A (en) * 1985-07-10 1986-07-29 Itoh Seiyu Kabushiki Kaisha Curable urethane composition
JP3005646B2 (ja) * 1990-11-07 2000-01-31 出光石油化学株式会社 液状重合体組成物
DE19607470A1 (de) * 1996-02-28 1997-09-04 Henkel Kgaa Polyurethanharze
US5986119A (en) * 1997-12-18 1999-11-16 Hansotech Inc. Reconstituted castor oil

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0125184A1 *

Also Published As

Publication number Publication date
DE19947563A1 (de) 2001-04-19
JP2003511486A (ja) 2003-03-25
WO2001025184A1 (fr) 2001-04-12

Similar Documents

Publication Publication Date Title
EP1674546B1 (fr) Composition réticulable à l'humidité et adhésif thermofusible
EP1237971B1 (fr) Renforcateur d'adherence pour polyurethannes reactifs exempts de monomeres
EP2794707B1 (fr) Compositions de polyuréthane réactives peu visqueuses
EP1456266B1 (fr) Polyurethanes reactifs a faible teneur en di-isocyanates monomeres
EP1490418B2 (fr) Adhesif Polyurethane a une composante de couleur neutre
EP1619215B1 (fr) Prépolymères de polyuréthanne à viscosité reduite à base de 2,4'-MDI
EP2493951B1 (fr) Adhésif polyuréthane contenant un régulateur de viscosité
EP1218332A1 (fr) Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee
EP1543052A1 (fr) Systemes de polyurethanne stables
EP1351824B1 (fr) Panneaux composites en pierre
WO2003016368A1 (fr) Colle polyurethane 1 k a prise rapide
EP0794977B1 (fr) Compositions du type polyurethane a reactivite stable
DE102004060284A1 (de) Reaktive Polyurethan-Prepolymere mit einem geringen Gehalt an monomeren Diisocyanaten
DE19957351A1 (de) Polyurethan-Zusammensetzungen mit niedrigem Gehalt an Isocyanatmonomeren
EP0746577B1 (fr) Adhesifs a base de polyurethane a un composant
EP1811006B1 (fr) Système adhésif
DE19958774A1 (de) Steinverbundplatten
DE2415467A1 (de) Fluessiger klebstoff
DE10055786A1 (de) Haftungsverstärker für monomerfreie reaktive Polyurethane
EP2603538A1 (fr) Polyuréthanes stables à la lumière et leur utilisation
EP2386586A1 (fr) Colle PU dotée d'une limite d'écoulement
WO2009056375A1 (fr) Colles à base de polyuréthane modifiées
DE102012200018A1 (de) Reaktive Polyurethan-Zubereitungen

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: 20020320

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20030415

RBV Designated contracting states (corrected)

Designated state(s): BE DE FR GB IT NL

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: 20041110