CN101883805A - Single-component polyurethane adhesive - Google Patents

Single-component polyurethane adhesive Download PDF

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Publication number
CN101883805A
CN101883805A CN2008801189282A CN200880118928A CN101883805A CN 101883805 A CN101883805 A CN 101883805A CN 2008801189282 A CN2008801189282 A CN 2008801189282A CN 200880118928 A CN200880118928 A CN 200880118928A CN 101883805 A CN101883805 A CN 101883805A
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molecular weight
foam
isocyanate
additive
reactive group
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H-J·里斯
S·克瓦兹克
S·乌尔曼
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3806—Polyhydroxy compounds having chlorine and/or bromine atoms
    • C08G18/381—Polyhydroxy compounds having chlorine and/or bromine atoms having bromine atoms
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/08—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers using foamed adhesives
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/02—Adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/12—Ceramic
    • C09J2400/123—Ceramic in the substrate

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

Abstract

The present invention relates to a kind of method of bonding object, the binder blend that wherein will contain isocyanate groups is applied at least a adherent object for the treatment of by pressure tank, described binder blend can obtain by following material is mixed: a) polymeric polyisocyanate and b) have macromolecular compound, a c of isocyanate-reactive group) whipping agent, d) foam regulates additive, e) catalyzer and f) other additives randomly, wherein used polymeric polyisocyanate amount a) is for making that existing isocyanate groups is more than isocyanate-reactive group in the described mixture; Wherein said foam is regulated additive (d) and is comprised silicone oil, and described binder blend is used after the foaming that causes because of pressure drop immediately.

Description

Single-component polyurethane adhesive
The present invention relates to the method for bonding object, described method is administered at least a bonded object (article) for the treatment of by the binder blend that will contain isocyanate groups and carries out from pressurizing vessel, described binder blend can obtain by following material is mixed: a) polymeric polyisocyanate and b) have a higher molecular weight compound of isocyanate-reactive group, c) whipping agent, d) foam is regulated additive, e) catalyzer and f) if suitable other additive, used polymeric polyisocyanate amount a) would be to make isocyanate groups that described mixture comprised more than isocyanate-reactive group; Wherein said foam is regulated additive (d) and is comprised silicone oil, and described binder blend is administered to adhesive face (bond area) immediately after step-down.
More embodiments of the present invention see among claim, specification sheets and the embodiment.Should be understood that the above-mentioned feature of theme of the present invention and treat that still the feature of elucidated hereinafter not only can be used for indicated concrete binding substances, and under the situation that does not depart from the scope of the invention, also can be used for other binding substancess.
From the one-component polyurethane foam of aerosol container (aerosol container) ejection is combination tool commonly used the building, is used to install building doors and windows, and as the through walls cavity that be used for pipe laying relevant with building or the packing material of opening.This aerosol container contains the end capped polyurethane prepolymer of NCO, and whipping agent and auxiliary agent.By discharging content by whipping agent, and the foaming by subsequently and the curing of air moisture, required foam formed.These foams are mainly as combination foam.A very big advantage of this combination foam is its ease for operation.
For example, a kind of such single component combination foam has been described among the WO2005/054324.---for example sash---assembly or be used for cavity foam-filled except being used for as combination foam, it also can be used as spray adhesive.In this case, for example, can be with insulcrete and roof cladding bonding mutually or be adhered to matrix (substrate).
Using known single component combination foam is that they have the trend that after takes place after using as a shortcoming of tackiness agent.In other words, constantly form bubble, cause and treat that the bonded object does not remain on their prepositions in adhint.Especially for the situation that insulcrete is attached to external surface of buildings, it is uneven that this mode may cause the surface of finishing to occur.
Therefore, an object of the present invention is to provide a kind of easy-operating binder blend, more especially be used for building, described binder blend can make treats that the adherent parts obtain best location.More specifically, the purpose of this invention is to provide a kind of method in conjunction with object, wherein after does not take place in binder blend.
Surprisingly, the present invention at the method for purpose by a kind of bonding object realize, described method is administered at least a bonded object for the treatment of by the binder blend that will contain isocyanate groups and carries out from pressurizing vessel, described binder blend can obtain by following material is mixed: a) polymeric polyisocyanate and b) have a higher molecular weight compound of isocyanate-reactive group, c) whipping agent, d) foam is regulated additive, e) catalyzer and f) if suitable other additive, used polymeric polyisocyanate amount a) would be to make isocyanate groups that described mixture comprised more than isocyanate-reactive group; Wherein said foam is regulated additive (d) and is contained silicone oil, and described binder blend is administered to adhesive face immediately after step-down.
Binder blend of the present invention is administered to from pressurizing vessel treats the bonded object.This binder blend can only be administered to by the ubiquitous internal pressure of institute in the aerosol container and treat the bonded object.This internal pressure is to produce by the evaporation of propellant gas mixture or step-down.Another kind may be by means of gas under pressure---for example pressurized air---discharges binder blend of the present invention from described aerosol container, and it is administered to the adhesive face for the treatment of in conjunction with object.In this case, to regulate that additive (d) contains silicone oil and use described binder blend immediately after step-down be necessary for the present invention for described foam.For example, using binder blend of the present invention by the metering rifle from pressurizing vessel is exactly this situation.For this metering rifle, the content in whole rifle all be in pressurizing vessel in the identical pressure of ubiquitous pressure.When the content that will discharge in the pressurizing vessel,, drop at this valve place pressure and to reach external pressure substantially the valve open in rifle exit.If described binder blend at first by for example gauge line, then can not reach effect of the present invention after pressure descends generation.
The example of suitable polymeric polyisocyanate comprises aliphatics, alicyclic and more particularly aromatic vulcabond or polymeric polyisocyanate.Concrete example comprises: aliphatic diisocyanate, for example 1, hexamethylene-diisocyanate, 1,5-(2-methyl pentylidene) vulcabond, 1, the mixture, 1 of 4-(2-ethyl butylidene) vulcabond or at least two kinds of described C6 alkylidene group vulcabond, 5-pentylidene vulcabond and tetramethylene vulcabond; Alicyclic diisocyanate, 1-isocyanato-3 for example, 3,5-trimethylammonium-5-isocyanato methylcyclohexane (isophorone diisocyanate), 1,4-cyclohexyl diisocyanate, 2,4-and 2,6-(1-methylcyclohexane) vulcabond and corresponding isomer mixture, 4,4 '-, 2,4 '-and 2,2 '-dicyclohexyl methane diisocyanate and corresponding isomer mixture; And aromatic diisocyanate preferably, as 1,5-naphthalene diisocyanate (1,5-NDI), 2,4-and 2,6-tolylene diisocyanate (TDI) and composition thereof, 2,4 '-, 2,2 '-and preferably 4,4 '-'-diphenylmethane diisocyanate (MDI) and at least two kinds of these mixture of isomers, polyphenylene-polymethylene-polymeric polyisocyanate (the polymeric MDI that has two or more aroma systems, PMDI), the mixture of PMDI and tolylene diisocyanate, the polyphenylene polymeric polyisocyanate, polyurethane-modified liquid 4,4 '-and/or 2, the 4-'-diphenylmethane diisocyanate, and 1,2-two (4-isocyanato phenyl) ethane.
If suitable, a) also can use isocyanate prepolymer or low monomeric diisocyanate as polymeric polyisocyanate, described in for example EP1 518 874, WO 2005/054324 or DE 103 11 607.
As isocyanate prepolymer, can use at least a vulcabond and/or polymeric polyisocyanate, and/or the reaction product of at least a isocyanate activity compound and at least a vulcabond and/or polymeric polyisocyanate reaction, wherein the functional prepolymer of these isocyanatos can prepare by known method.As the reaction product that contains isocyanate groups, preferably use the prepolymer of NCO content as 4%-30%.
The polymeric polyisocyanate that more particularly is to use PMDI a), preferably its viscosity under 25 ℃ more preferably is 100-400mPas less than 600mPas, particularly preferably is 150-300mPas.More particularly be to use thick MDI, the 4-that its 3-that contains 2-ring MDI, 26 ± 6 weight % of 35 ± 17 weight % encircles MDI, 12 ± 4 weight % encircles the 5-ring MDI of MDI, 5 ± 3 weight % and 6-ring MDI and the more MDI that encircles of 23 ± 10 weight % more.
As higher molecular weight compound b with isocyanate-reactive group), can use typical compound with isocyanate-reactive group.Preferred Aethoxy Sklerol and/or the polyesterols of using more particularly only uses Aethoxy Sklerol.
Aethoxy Sklerol of the present invention prepares by currently known methods, for example by using alkali metal hydroxide or alkali metal alcoholates to prepare, perhaps by using Lewis acid as catalyzer and the starting molecule generation anionoid polymerization that adds at least a 2-4 of comprising active hydrogen atom that exists with bonding scheme---for example antimony pentachloride or contain one or more ethers that in alkylidene group, have the oxirane of 2-4 carbon atom close boron fluoride---the generation cationoid polymerisation prepares.Suitable oxirane is for example tetrahydrofuran (THF), 1,1,2-or 2,3-butylene oxide ring, and preferably oxyethane and 1,2 epoxy prapane.In addition,, also can use multimetal cyanide compounds, be also referred to as dmc catalyst as catalyzer.Described oxirane can use separately, also can replace in succession or uses as mixture.The mixture of preferred 1,2 epoxy prapane and oxyethane, wherein used oxyethane exists with oxyethane end-block (" EO end-blocking ") form with the amount of 10%-50%, so that the gained polyvalent alcohol has the uncle OH end group more than 70%.
Suitable starting molecule comprises water or binary, ternary and tetravalent alcohol, preferred trivalent alcohol, for example glycerine, TriMethylolPropane(TMP), thanomin, diethanolamine, trolamine, and other trivalent alcohols or amine with three active hydrogen atoms.
The functionality of polyether glycol---preferred polyoxypropylene-polyoxyethylene polyols---is that 2-4, preferred 2.5-3.5, more preferably 2.6-3.4, and number-average molecular weight are preferred 600-8000, more preferably 1000-6000,1000-4000g/mol more especially.
As higher molecular weight compound b with isocyanate-reactive group), preferably by the number-average molecular weight of trifunctional initiator preparation be 4000 ± 2000g/mol Aethoxy Sklerol (b1), be the Aethoxy Sklerol (b2) of 1000 ± 200g/mol and be the mixture of the Aethoxy Sklerol (b3) of 600 ± 100g/mol by the molecular weight of trifunctional initiator preparation by the number-average molecular weight of two functional initiator preparation.Particularly preferably, as Aethoxy Sklerol (b1), use Aethoxy Sklerol based on propylene oxide and oxyethane by the initial preparation of glycerine by the preparation of trifunctional initiator; As Aethoxy Sklerol (b2), use Aethoxy Sklerol based on propylene oxide and oxyethane by the initial preparation of glycerine by the preparation of trifunctional initiator; And, use Aethoxy Sklerol based on oxyethane by the initial preparation of ethylene glycol as Aethoxy Sklerol (b3) by the preparation of two functional initiator.In this case, (b1): (b2): weight ratio (b3) is preferably 4 ± 1: 8 ± 2: 1 ± 0.5.
Higher molecular weight compound b with isocyanate-reactive group) can comprise further that also molecular weight is preferably 350-1000, more preferably 400-600g/mol and functionality are preferably the bromination Aethoxy Sklerol of 2-4.As the bromination polyether glycol, more especially use by the preparation of two senses and/or trifunctional initiator, based on Epicholorohydrin and by the polyvalent alcohol of bromination and dehydrochlorination.Suitable bromination Aethoxy Sklerol can get, for example from Solvay with trade name IXOL
Figure GPA00001143621200041
Buy.More particularly, as the bromination Aethoxy Sklerol, can use IXOL
Figure GPA00001143621200042
M125 and IXOL
Figure GPA00001143621200043
B 251.
In addition, except that described polyvalent alcohol, have the higher molecular weight compound b of isocyanate-reactive group) also can further comprise common hydroxy functional compound, for example, as the short-chain diol of chain extension agent, as ethylene glycol, propylene glycol, 1,4-butyleneglycol; Be at least 3 short chain alcohol, for example glycerol or TriMethylolPropane(TMP) as the functionality of linking agent; And/or as the monohydroxy-alcohol of molecular weight regulator.Preferably there are not chain extension agent, linking agent or molecular weight regulator.
As whipping agent, can use known whipping agent, for example, under atmospheric pressure boiling point is-40 ℃ to 120 ℃ a compound; Gas and/or liquid blowing agent, for example: carbonic acid gas, alkane and/or naphthenic hydrocarbon, as Trimethylmethane, propane, normal butane or Trimethylmethane, pentane and pentamethylene; Ether is as ether, methyl-isobutyl ether and dme; Nitrogen; Oxygen; Helium; Argon gas; Laughing gas; Halon is as Dichloromonofluoromethane, fluoro trichloromethane, Freon 113; And/or partially halogenated hydrocarbon, as trifluoromethane, 1,1-two chloro-1-fluoroethanes, a chloro-tetrafluoroethane, chlorotrifluoroethane, chlorodifluoroethane, C2H4F2 C2H4F2, dichloro C2H4F2 C2H4F2, pentafluoride ethane, Tetrafluoroethane or dichloro one fluoroethane; Or comprise the mixture of at least two kinds of institute's example whipping agents.
Based on component a) to f) weight, the common add-on of whipping agent is 0.5 weight %-40 weight %, be preferably 10 weight %-32 weight %.
Can use all known foams that comprises silicone oil to regulate additive and regulate additive d) as foam.In this article, preferably use at the dimethyl siloxane of 25 ℃ of following viscosity as 10-1000mPas.Except that silicone oil, foam is regulated additive d) also can further comprise suds-stabilizing agent commonly used and/or whiteruss.As whiteruss, can use saturated aliphatic hydrocarbon.Preferably, used whiteruss is liquid down at 25 ℃.The available suds-stabilizing agent comprises for example polyalkylene glycol polysiloxane copolymer, the trade mark of preferred Goldschmidt Tegostab by name
Figure GPA00001143621200051
Product, and more preferably Tegostab
Figure GPA00001143621200052
B2219 or Tegostab
Figure GPA00001143621200053
BF2270.
Particularly preferably, the weight ratio of described suds-stabilizing agent, silicone oil and whiteruss is 150 ± 50: 2 ± 1.2: 2 ± 1.2.With component a) to f) gross weight be benchmark, foam is regulated additive d) ratio be preferably 0.5-5 weight %, 1-3 weight % more preferably.Based on component a) to f) gross weight, the ratio of silicone oil is preferably 0.02 weight %-0.2 weight %.
Catalyzer e) more particularly promotes the NCO group of described vulcabond and the reaction between the described hydroxyl groups; As catalyzer e), can use: typical strong basicity acid amides in the prior art, for example 2,3-dimethyl-3,4,5, the 6-tetrahydropyrimidine, three (dialkyl aminoalkyl)-s-Hexahydrotriazines are as three (N, N-dimethylaminopropyl)-s-Hexahydrotriazines, preferably typical tertiary amine, triethylamine for example, Tributylamine, dimethyl benzylamine, N-ethylmorpholine, N-methylmorpholine, positive cyclohexyl morpholine, dimethylcyclohexylamine, dimorpholine base Anaesthetie Ether, 2-(dimethylamino oxyethyl group) ethanol, 1,4-diazabicyclo [2.2.2] octane, 1-azabicyclic [3.3.0] octane, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl-hexane-1, the 6-diamines, five methyl diethylentriamine, tetramethyl-diamino ethyl ether, two (dimethylaminopropyl) urea, N, N '-lupetazin, 1,2 dimethylimidazole, two (4-N, N-dimethylamino cyclohexyl) methane etc.; And organometallic compound for example, titanic acid ester (titanic ester), iron cpd such as acetylacetonate iron (III), tin compound is the tin of organic carboxyl acid (II) salt such as oxalic acid tin (II) for example, the tin of 2 ethyl hexanoic acid (II) salt (stannous octoate (II)), two lauric acid tin (II), or the dialkyl tin of organic carboxyl acid (IV) salt such as dibutyltin diacetate (IV), dibutyl tin laurate (IV), toxilic acid dibutyl tin (IV) or oxalic acid dioctyl tin (IV) etc., and two mercaptan dibutyl tin (IV), perhaps at least two kinds of described mixture of catalysts, and the synergistic combinations of strong basicity amine and organometallic compound.Especially preferably use dimorpholine base Anaesthetie Ether as catalyzer e).Described catalyzer e) can usual amounts use, for example, based on higher molecular weight compound b with isocyanate-reactive group), be 0.002 weight %-5 weight %.
As auxiliary agent and additive f), can use for example weighting agent, fire retardant, nucleator, oxidation retarder, dye well pigment, inhibitor, the stablizer of opposing hydrolysis, light, heat or decolouring, organic and/or inorganic filler, toughener and/or softening agent.
The more details of above-mentioned auxiliary agent and additive can be available from technical literature, the monograph of J.H.Saunders and K.C.Frisch " High Polymers " for example, Volume XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 1962 and 1964; " Kunststoff-Handbuch " that G.Oertel writes, Volume 7, Polyurethanes, 3 RdEdition, 1993, Carl-Hanser-Verlag, Munich; Or DE 29 01 774.
For preparing binder blend of the present invention, with polymeric polyisocyanate a) with higher molecular weight compound b with isocyanate-reactive group), whipping agent c), foam regulates additive d), catalyzer e) and if suitable other additives f) place container, with described container sealing, and with component a) to f) homogenize, a) isocyanate-reactive group is excessive relatively for wherein used polymeric polyisocyanate.
Preferably, respectively with component a) to f) place described pressurizing vessel separately, then with described pressurizing vessel sealing and with described component---for example by rocking---homogenize.Perhaps, polymeric polyisocyanate a) with have the higher molecular weight compound b of isocyanate-reactive group) and catalyzer e) reaction also can outside described pressurizing vessel, take place.Then with the reaction product that obtains with whipping agent c), foam regulates additive d) and if suitable other additives f) place described pressurizing vessel.
Method of the present invention is fit to bonding object highlightedly, especially at building field, more especially for mineral substrate.The feature of binder blend of the present invention on this effectiveness is that the bonding coat after does not take place.This makes method of the present invention more be particularly suitable for the bonding of surface portion, to be used for for example insulcrete or surface elements being applied to mineral substrate---for example other parts of plaster, stone or building---.The bonded object can remain on selected position by this way, thereby make---for example surface elements---, and best orientation becomes possibility.
The present invention will be described below by embodiment.
The preparation of polyol component
Polyol component by following material by being mixed with: 330g is the Aethoxy Sklerol of 1000g/mol by the initial preparation of glycerine based on propylene oxide and oxyethane and number-average molecular weight, 147g is the Aethoxy Sklerol of 4000g/mol by the initial preparation of glycerine based on propylene oxide and oxyethane and number-average molecular weight, the 40g number-average molecular weight is the polyoxyethylene glycol of 600g/mol, the 60g bromine content be about 31 weight % originate from Solvay, trade mark Ixol by name The bromination polyether-tribasic alcohol of B 251,25g (originates from Goldschmidt, trade mark Tegostab by name as the polysiloxane-polyxyalkyl-blockpolymer of suds-stabilizing agent
Figure GPA00001143621200062
B 2219), 0.3g originates from Bayer, trade name Baysilone
Figure GPA00001143621200063
The polydimethylsiloxane of M100,60g Pyranton, 8g be as 2 of catalyzer, 2-dimorpholine base Anaesthetie Ether, and 330g trichloropropyl phosphate.
The preparation of binder blend in the aerosol container
With the described polyol component of 286g and 394g in the PMDI that 25 ℃ of following viscosity are approximately 200mPas packs the 1L aerosol container into.Described aerosol container is sealed with rifle valve (gun valve).Can in described aerosol container, be metered into the process gas mixture of 43g dme, 27g 30 weight % propane and 70 weight % butane subsequently by described valve, add 79g Tetrafluoroethane (R134a) at last.
By acutely shaking content homogenize with jar.Described prepolymer reaction causes aerosol container to heat up.
After storing 24 hours under the highest 50 ℃ heat condition, described prepolymerization reaction is stopped, so that described content can be used as tackiness agent.
Use as one-package adhesive
Described aerosol container is spun on the foam gun (foam gun), and by shaking the content homogenize with this jar.By driving this rifle, the foam mixture extruded is applied to the insulcrete surface with the form of the wide foam band of about 3cm.
The foam of (collapsing) will break---some air pocket---slightly, and shape is smooth sprawls with band, with can be fully bonding.The insulcrete that will have binder foam subsequently is fixed on the concrete walls.No after takes place, and described insulcrete remains on original position.

Claims (9)

1. the method for a bonding object, described method is administered at least a bonded object for the treatment of by the binder blend that will contain isocyanate groups from pressurizing vessel carries out, and described binder blend can obtain by following material is mixed:
A) polymeric polyisocyanate, with
B) has the higher molecular weight compound of isocyanate-reactive group;
C) whipping agent;
D) foam is regulated additive;
E) catalyzer and
F) if suitable other additives
Used polymeric polyisocyanate amount a) is to make isocyanate groups that described mixture comprised more than isocyanate-reactive group,
Wherein said foam is regulated additive (d) and is comprised silicone oil, and described adhesive mixture is used after step-down immediately.
2. the process of claim 1 wherein that described foam regulates additive d) contain whiteruss, suds-stabilizing agent and silicone oil.
3. the method for claim 2, wherein said foam is regulated additive d) weight ratio of the suds-stabilizing agent, silicone oil and the whiteruss that are contained is 150 ± 50: 2 ± 1.2: 2 ± 1.2.
4. each method among the claim 1-3, wherein said higher molecular weight compound b) with isocyanate-reactive group comprise average functionality be 2.9 ± 0.4 and number-average molecular weight be the polyether glycol b1 of 4000-600g/mol) with number-average molecular weight be the bromination polyether glycol b2 of 500 ± 100g/mol) mixture.
5. each method among the claim 1-4, wherein said polyether glycol b1) for being Aethoxy Sklerol, being the Aethoxy Sklerol of 1000 ± 200g/mol and being the mixture of the Aethoxy Sklerol of 600 ± 100g/mol based on oxyethane and number-average molecular weight of 4000 ± 2000g/mol based on propylene oxide and oxyethane and number-average molecular weight by the initial preparation of glycerine by the initial preparation of ethylene glycol based on propylene oxide and oxyethane and number-average molecular weight by the initial preparation of glycerine.
6. each method among the claim 1-5, wherein said catalyzer e) comprise N,N-Dibenzylamine.
7. each method among the claim 1-6, wherein said polymeric polyisocyanate is at the PMDI of 25 ℃ of following viscosity less than 500mPas a).
8. each method among the claim 1-7 wherein is bonded to mineral substrate with object.
9. each method among the claim 1-8 wherein is bonded to buildings with surface elements or insulcrete.
CN2008801189282A 2007-12-03 2008-11-26 Single-component polyurethane adhesive Pending CN101883805A (en)

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EP07122120.4 2007-12-03
EP07122120 2007-12-03
PCT/EP2008/066177 WO2009071470A1 (en) 2007-12-03 2008-11-26 Single-component polyurethane adhesive

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JP2011505481A (en) 2011-02-24
WO2009071470A1 (en) 2009-06-11

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