EP1636283A1 - Prepolymeres a terminaisons alcoxysilane - Google Patents

Prepolymeres a terminaisons alcoxysilane

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Publication number
EP1636283A1
EP1636283A1 EP04735887A EP04735887A EP1636283A1 EP 1636283 A1 EP1636283 A1 EP 1636283A1 EP 04735887 A EP04735887 A EP 04735887A EP 04735887 A EP04735887 A EP 04735887A EP 1636283 A1 EP1636283 A1 EP 1636283A1
Authority
EP
European Patent Office
Prior art keywords
prepolymers
prepolymer
molecular weight
isocyanate
alkoxysilane
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Withdrawn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
EP04735887A
Other languages
German (de)
English (en)
Inventor
Volker Stanjek
Carolin Kinzler
Wolfram Schindler
Richard Weidner
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.)
Wacker Chemie AG
Original Assignee
Consortium fuer Elektrochemische Industrie GmbH
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 Consortium fuer Elektrochemische Industrie GmbH filed Critical Consortium fuer Elektrochemische Industrie GmbH
Publication of EP1636283A1 publication Critical patent/EP1636283A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G18/65—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

Definitions

  • the invention relates to alkoxysilane-terminated prepolymers and compositions containing prepolymers.
  • Prepolymer systems which have reactive alkoxysilyl groups have been known for a long time and are widely used for the production of elastic sealants and adhesives in the industrial and construction sectors.
  • these alkoxysilane-terminated prepolymers are capable of condensing with one another at room temperature, with elimination of the alkoxy groups and formation of an Si-O-Si bond. This means that these prepolymers can be use as one-component systems, which have the advantage of simple handling, since no second component has to be metered in and mixed in.
  • alkoxysilane-terminated prepolymers Another advantage of alkoxysilane-terminated prepolymers is that. no acids, oximes or amines are released during curing. In contrast to isocyanate-based adhesives or sealants, there is also no CO2, which as a gaseous component can lead to the formation of bubbles. In contrast to isocyanate-based systems, alkoxysilane-terminated prepolymer mixtures are also toxicologically harmless in any case. Depending on the content of alkoxysilane groups and their structure, long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly cross-linked systems (thermosets) are formed when this prepolymer type is cured.
  • thermoplastics thermoplastics
  • elastomers relatively wide-meshed three-dimensional networks
  • thermalosets highly cross-linked systems
  • Alkoxysilane-terminated prepolymers can be made up of different building blocks. These prepolymers usually have an organic backbone, ie they are composed, for example, of polyurethanes, polyethers, polyesters, polyacrylates, polyvinyl esters, ethylene-olefin copolymers, styrene-butadiene copolymers or polyolefins, described inter alia in EP 0 372 561, EP 0 269 819, WO 00/37533, US 6,207,766 and US 3,971,751.
  • systems are also widely used, the backbone of which consists entirely or at least partially of organosiloxanes, described, inter alia, in WO 96/34030 and US Pat. No. 5,254,657).
  • alkoxysilane-terminated prepolymers are obtained by converting polyols, e.g. of polyester or polyether polyols, implemented with a ⁇ -isocyanatopropyl alkoxysilane.
  • polyols e.g. of polyester or polyether polyols
  • OH-terminated prepolymers made from a polyol and a deficiency of a di- or polyisocyanate can also be reacted with a ⁇ -isocyanatopropylalkoxysilane to give alkoxysilane-terminated prepolymers.
  • Such systems are described for example in EP 0 931 800, EP 0 070 475 or US 5,068,304.
  • polyols e.g. from polyether or polyester polyols, which are reacted with an excess of a di- or polyisocyanate in a first reaction step.
  • the isocyanate-terminated prepolymers obtained are then reacted with a ⁇ -aminopropyl-functional alkoxysilane to give the desired alkoxysilane-terminated prepolymer.
  • Systems of this type are described, for example, in EP 1 256 595, EP 0 569 360 or EP 0 082 528 or DE 198 49 817.
  • Methoxysilyl terminations but the even more unreactive ethoxysilyl terminations are used. However, especially ethoxysilyl-terminated prepolymers would be particularly advantageous in many cases because only ethanol is released as a cleavage product when they cure.
  • titanium-containing catalysts are conceivable, e.g. Titanium tetraisopropoxylate or bis (acetylacetonato) diisobutytitanate (described inter alia in EP 0 885 933).
  • titanium catalysts have the disadvantage that they cannot be used together with numerous nitrogen-containing compounds, since the latter act here as catalyst poisons.
  • nitrogen containing compounds e.g. as an adhesion promoter, would be desirable in many cases.
  • Nitrogen compounds are also used, e.g. Aminosilanes, in many cases as starting materials in the production of the silane-terminated prepolymers.
  • prepolymer systems as described, for example, in DE 101 42 050. These prepolymers are distinguished by the fact that they contain alkoxysilyl groups which are separated from an electronegative heteroatom with at least one lone pair of electrons only by a methyl spacer, ie from an oxygen, nitrogen or sulfur atom. As a result, these prepolymers have an extremely high reactivity to (atmospheric) moisture, so that they become prepolymer Mixtures can be processed that can get by with little or even no catalysts that contain titanium, tin or other (heavy) metals, and yet cure at room temperature with sufficiently short adhesive free periods or at a sufficiently high speed.
  • DE 101 42 050 also states that, in principle, monomeric alcohols / amines with at least two OH / NH functions can also be used in combination with di- or polyisocyanates and organofunctional silanes for the preparation of alkoxysilane-terminated prepolymers. However, there are no alcohol or amine levels here
  • Ratios of amounts between the monomeric alcohols / amines and other prepolymer building blocks described which lead to an improvement in the properties of the prepolymer. Neither is it described that the use of monomeric alcohols / amines in prepolymer synthesis could be suitable at all in order to improve properties of silane-terminated prepolymers or their curing products.
  • Silane-crosslinking mixtures that cure to form compositions with high tensile strength and elongation at break are required above all in adhesive applications, for example in the automotive industry.
  • One approach to improving the tear strength of alkoxysilane-crosslinking adhesives can be the use of optimized filler mixtures that are incorporated into the alkoxysilane-terminated polymer.
  • Such a method is described in EP 1 256 595.
  • a certain type of carbon black and finely divided coated calcium carbonate are mixed into an alkoxysilane-terminated prepolymer.
  • excellent elongations at break of 4.0 - 5.9 MPa could be achieved, but the achievable elongations at break, however, were not yet satisfactory with 250 - 300%.
  • only black adhesives can be produced with such soot-filled compositions.
  • Other colors, although often desired, are not possible.
  • the object was to provide compositions based on silane-terminated prepolymers with improved tear strength and elongation at break, which do not have the aforementioned disadvantages.
  • the invention relates to prepolymers (A) with end groups of the general formula [1]
  • R 1 is an optionally halogen-substituted alkyl, cycloalkyl, alkenyl or aryl radical with 1-10 carbon atoms
  • R 2 is an alkyl radical with 1-6 carbon atoms or an ⁇ -oxaalkyl alkyl radical with a total of 2-10 carbon atoms
  • a is a number 0 mean to 2
  • the prepolymers (A) being obtainable by reacting 1) polyol (AI) with an average molecular weight Mn of 1000 to 25000,
  • Alkoxysilane (A4) which have an isocyanate group or an isocyanate-reactive group, the low molecular weight alcohol (A2) and the polyol (AI) being used in a molar ratio of 0.3: 1 to 7: 1.
  • the alkoxysilane-crosslinking prepolymers (A) in addition to di- or polyisocyanates and organofunctional silanes, a certain mixture of long-chain polyols (AI) and low molecular weight alcohols (A2) is used. After crosslinking, the prepolymers (A) produced in this way have a considerably improved tear strength and a considerably improved elongation at break, regardless of any fillers used. Compositions (M) which contain the silane-terminated prepolymers (A) also show the improved tensile strength and elongation at break.
  • the prepolymers (A) are preferably free of isocyanate.
  • a molar ratio of the low molecular weight alcohol (A2) to the polyol (Al) of 0.5: 1 to 5: 1 is preferred, a ratio of these two components of 0.7: 1 to 3: 1 being particularly preferred.
  • Both low-molecular alcohol (A2) and polyol (Al) prefer compounds with two OH groups, which lead to linear and unbranched prepolymers (A) in prepolymer synthesis.
  • the mode of action of the combination of a low molecular weight alcohol (A2) and a polyol (AI) during prepolymer synthesis is on the one hand that the use of alcohol (A2) in prepolymer synthesis by its reaction with the isocyanate groups of the di- or polyisocyanate (A3) or with an optionally present isocyanate-functional silane (A4) leads to an increased density of urethane units in the resulting polymer chain. This improves the mechanical properties of the prepolymers (A) and compositions (M) containing prepolymers (A) after they have hardened.
  • the use of the low molecular weight alcohol (A2) in combination with one or more long-chain polyols (Al) leads to the formation of prepolymer chains in which the urethane units are not uniformly distributed.
  • the incorporation of a polyol molecule (AI) in the prepolymer chain always forms a long chain section free of urethane groups, while the incorporation of the low molecular weight alcohol (A2) always leads to (at least) two urethane units, which are only due to a very short chain section consisting of a few carbon atoms are separated.
  • polyol (Al) and low molecular weight alcohol (A2) are used in the relative relationship according to the invention, • this uneven arrangement of the urethane units in the polymer has an unusually positive effect on the tensile strength of the cured mass (M).
  • the prepolymers (A) can be used to produce compositions (M) with significantly better tear strength than is possible with conventional prepolymers with a relatively uniform distribution of the urethane units in the prepolymer chain.
  • the prepolymers (A) and prepolymers not according to the invention have the same characteristics such as average chain length, urethane, urea and silyl group density and both polymers are made up of the same type of polyol (e.g. polypropylene glycol), types of isocyanate and silane.
  • the alkoxysilane-terminated polymers (A) have end groups of the general formula [2]
  • A is a double-bonded group selected from -0-, -S-, - (R 3 ) N-, -0-CO-N (R 3 ) -, -N (R 3 ) -CO-O-, -NH-CO -NH-, -N (R 4 ) -CO- NH-, -NH-CO-N (R 4 ) -, -N (R 4 ) -CO-N (R 4 ) -, R 3 hydrogen, one optionally halogen-substituted cyclic, linear or branched C] _ to C ] _s alkyl or alkenyl radical or a Cg to C ] _8 ⁇ aryl radical,
  • R 4 is an optionally halogen-substituted cyclic, linear or branched C] _- bis -Alkyl- or alkenyl radical or a Cg to C ⁇ aryl radical and R ⁇ 'R 2 and a have the meanings given in the general formula [1].
  • the polymers (A) with end groups of the general formula [2] are distinguished by the fact that they contain alkoxysilyl groups which are separated from an electronegative heteroatom with at least one lone pair of electrons only by a methyl spacer.
  • these polymers have an extremely high reactivity to (atmospheric) moisture, so that they can be processed into polymer mixtures (M) which also with little or even no tin catalyst, preferably without tin or titanium catalyst, particularly preferably without a heavy metal catalyst Cure the room temperature with sufficiently short adhesive release times or at a sufficiently high speed.
  • radicals R 1 methyl, ethyl or phenyl groups are preferred.
  • the radicals R 2 are preferably methyl or ethyl groups and hydrogen is preferred as the radical R 3 , while the radicals R 4 are preferably alkyl radicals with 1-4 carbon atoms, cyclohexyl and phenyl radicals.
  • Prepolymers (A) with a proportion of dialkoxysilyl groups of the general formula [2] of at least 70% are particularly preferred, with prepolymers (A) containing exclusively dialkoxysilyl groups of the general formula [2] not only being particularly preferred but also being logistically easily accessible , since only one type of silane (A4) is required to manufacture them.
  • the main chains of the alkoxysilane-terminated polymers (A) can be branched or unbranched, with unbranched or only slightly branched main chains being preferred.
  • the average chain lengths can be adjusted as desired, depending on the properties desired in each case, both of the uncrosslinked mixture and of the cured composition.
  • polyols with an average molecular weight Mn of 1000 to 25000 can be used as polyols (AI) for the preparation of the prepolymers (A).
  • These can be, for example, hydroxyl-functional polyethers, polyesters, polyacrylates and polyacrylates, polycarbonates, polystyrenes, polysiloxanes, polyamides, polyvinyl esters, Act polyvinyl hydroxides or polyolefins such as polyethylene, polybutadiene, ethylene-olefin copolymers or styrene-butadiene copolymers.
  • Particularly suitable polyols (AI) are aromatic and / or aliphatic polyester polyols and polyether polyols, as have been described many times in the literature.
  • the polyethers and / or polyesters used as polyols (AI) can be either linear or branched, but unbranched, linear polyols are preferred.
  • polyols (AI) can also have substituents such as Have halogen atoms.
  • polysiloxanes of the general formula [3]
  • R 5 is a hydrocarbon radical having 1 to 12 carbon atoms, preferably methyl radicals,
  • R is a branched or unbranched hydrocarbon chain with 1-12 carbon atoms, preferably n-propyl, n is a number from 1 to 3000, preferably a number from 10 to 1000 and
  • Z is an OH or NHR 3 group
  • R 3 has the meanings given in the general formula [2].
  • linear polyether polyols in particular polypropylene glycols, are particularly preferably used as polyols (AI). II
  • low molecular weight alcohols with at least two hydroxyl groups per molecule (A2).
  • low molecular weight diols are preferably used here, such as e.g. Glycol, 1, 3-propanediol, 1,3-
  • a particularly preferred low molecular weight alcohol (A2) is 1,4-butanediol.
  • di- or polyisocyanates A3 for the preparation of the prepolymers (A), as are often described in the literature.
  • Common diisocyanates (A3) are, for example, diisocyanatodiphenylmethane (MDI), both in the form of crude or technical MDI and in the form of pure 4,4 'or 2,4' isomers or mixtures thereof, tolylene diisocyanate (TDI) in the form of its various regioisomers, Diisocyanatonaphthalene (NDI), isophorone diisocyanate (IPDI), perhydrogenated MDI (H-MDI) or also of hexamethylene diisocyanate (HDI).
  • MDI diisocyanatodiphenylmethane
  • TDI tolylene diisocyanate
  • NDI Diisocyanatonaphthalene
  • IPDI isophorone diisocyanate
  • H-MDI perhydrogenated MDI
  • HDI he
  • polyisocyanates (A3) are polymeric MDI (P-MDI), triphenylmethane triisocanate or isocyanurate or biuret triisocyanates. All di- and / or polyisocyanates (A3) can be used individually or in mixtures. However, only diisocyanates are preferably used. If the UV stability of the prepolymers (A) or the cured materials produced from these prepolymers is important due to the particular application, aliphatic isocyanates are preferably used as component (A3).
  • alkoxysilanes which either have an isocyanate function or an isocyanate-reactive group can be used as alkoxysilanes (A4) for the preparation of the prepolymers (A).
  • the alkoxysilanes are used to incorporate the alkoxysilyl terminations into the prepolymers (A).
  • alkoxysilanes (A4) preference is given to using compounds which are selected from silanes of the general formulas [4] and [5] OCN ⁇ SiR 1 a (OR 2 ) 3 .a [4]
  • B 1 is an OH, SH, NH 2 or an HR 4 N group
  • R 1 , R 2 , R 4 and a have the meanings given in the general formulas [1] and [2].
  • the isocyanate-reactive group B ⁇ in the general formula [5] preferably represents an HR 4 N group.
  • silanes (A4) and mixtures of different silanes (A4) can be used.
  • the corresponding silanes can be obtained by a reaction from chloromethyl trialkoxysilane, chloromethyl dialkoxymethyl silane or
  • Formula NH 2 R 4 ie from very simple and inexpensive starting materials, can be easily produced in one reaction step.
  • the prepolymers (A) are prepared by simply combining the components described, it being possible, if appropriate, to add a catalyst and / or to work at elevated temperature.
  • the isocyanate groups of the di- and / or polyisocyanates (A3) and, if present, the isocyanate groups of the silane of the general formula [4] react with the OH or NH functions of the added polyols (AI) and low molecular weight alcohols (A2) and - if present - with the OH or NH functions of the silanes of the general formula [5].
  • AI added polyols
  • A2 low molecular weight alcohols
  • the order and speed of addition of each Components can be designed as desired.
  • the various raw materials can also be introduced or added individually or in mixtures. Continuous prepolymer production, for example in a tubular reactor, is also possible.
  • the concentrations of all isocyanate groups and all isocyanate-reactive groups involved in all reaction steps and the reaction conditions are preferably chosen so that all isocyanate groups react in the course of prepolymer synthesis.
  • the finished prepolymer (A) is therefore free of isocyanate.
  • the concentration ratios and the reaction conditions are chosen such that almost all chain ends (> 80% of the chain ends, particularly preferably> 90% of the chain ends) of the prepolymers (A) are terminated with alkoxysilyl groups.
  • the isocyanate component (A3) is reacted in a first reaction step with the polyol component (AI) and with the alcohol component (A2), a hydroxyl- or isocyanate-terminated prepolymer being obtained, depending on the proportions used.
  • Components (AI) and (A2) can be used in succession or as a mixture.
  • these hydroxyl- or isocyanate-terminated prepolymers are then reacted with a silane of the general formula [4] or [5], the concentrations being chosen so that all the isocyanate groups react.
  • the result is the silane-terminated prepolymer (A).
  • a separate cleaning or other processing of the prepolymer (A) is not necessary.
  • the silane is used in excess.
  • the excess is preferably 20-400%, particularly preferably 50- 200%.
  • the excess silane can be added to the prepolymer at any time, but the excess silane is preferably added during the synthesis of the prepolymers (A).
  • the prepolymers (A) can be used to produce compositions (M) with particularly high tear strength.
  • the reactions between isocyanate groups and isocyanate-reactive groups which occur in the preparation of the prepolymers (A) can optionally be accelerated by a catalyst.
  • a catalyst is preferably used, which also below as
  • Hardening catalysts (C) are listed. It may even be possible for the preparation of the prepolymers (A) to be catalyzed by the same catalysts which later also serve as curing catalyst (C) in the curing of the finished prepolymer mixtures. This has the advantage that the
  • Hardening catalyst (C) is already contained in the prepolymer (A) and no longer has to be added separately when compounding the finished prepolymer blend (M). Of course, combinations of several catalysts can also be used instead of one catalyst.
  • a curing catalyst (C) can optionally be added.
  • the organic tin compounds commonly used for this purpose such as, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate or dibutyltin dioctoate etc., are suitable here.
  • titanates for example titanium (IV) isopropylate, iron (III) compounds, for example iron (III) acetylacetonate, or amines, for example triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane , 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, N, -Bis- (N, N-dimethyl-2-amino- ethyl) -methylamine, N, N-dimethylcyclohexylamine, N, N-dimethyl-phenlyamine, N-ethylmorpholinin, etc.
  • organic or inorganic Bronsted acids such as acetic acid, trifluoroacetic acid or benzoyl chloride, hydrochloric acid, phosphoric acid, their mono- and / or diesters, such as, for example
  • Butyl phosphate, (iso) propyl phosphate, dibutyl phosphate etc. are suitable as catalysts [C].
  • numerous other organic and inorganic heavy metal compounds as well as organic and inorganic Lewis acids or bases can also be used here.
  • the crosslinking rate can also be increased further by the combination of different catalysts or of catalysts with different cocatalysts or can be tailored precisely to the respective need.
  • Mixtures (M) which contain prepolymers (A) with highly reactive alkoxysilyl groups of the general formula [2] and thus do not require heavy metal-containing catalysts (C) are clearly preferred in order to achieve sufficiently short curing times even at room temperature.
  • the prepolymers (A) are preferably used in mixtures (M) which also have low molecular weight alkoxysilanes (D) contain.
  • These alkoxysilanes (D) can perform several functions. For example, they can serve as water scavengers, ie they should intercept any traces of moisture and thus increase the storage stability of the corresponding silane-crosslinking compositions (M). Of course, these must have at least a comparable reactivity to traces of moisture as the prepolymer (A). Suitable water scavengers are therefore especially highly reactive alkoxysilanes (D) of the general formula [6]
  • B 2 an R 4 0-CO-NH-, R 4 R 3 N-CO-NH-, OH-, OR 4 -, SH-, SR 4 -, NH 2 -, NHR 4 -, or N (R 4 ) 2 group means and
  • R0-, R 2 , R, R 4 and a have the meanings given in the general formulas [1] and [2].
  • a particularly preferred water scavenger is the carbamatosilane, in which
  • B 2 represents an R 4 0-CO-NH group.
  • the low molecular weight alkoxysilanes (D) can also serve as crosslinkers and / or reactive diluents.
  • all silanes which have reactive alkoxysilyl groups and via which they can be incorporated into the resulting three-dimensional network during the curing of the polymer mixture are suitable for this purpose.
  • the alkoxysilanes (D) can contribute to an increase in the network density and thus to an improvement in the mechanical properties, for example the tensile strength, of the cured mass (M). They can also lower the viscosity of the corresponding prepolymer blends.
  • Suitable alkoxysilanes (D) in this function are, for example, alkoxymethyltrialkoxysilanes and alkoxymethyldialkoxyalkylsilanes. Methoxy and ethoxy groups are preferred as alkoxy groups.
  • the inexpensive alkyltrimethoxysilanes, such as methyltrimethoxysilane and vinyl or phenyltrimethoxysilane, and their partial hydrolyzates may be suitable.
  • the low molecular weight alkoxysilanes (D) can also serve as adhesion promoters. Above all, alkoxysilanes can be used here via amino functions or
  • Epoxy functions examples include ⁇ -
  • the low molecular weight alkoxysilanes (D) can even serve as curing catalysts or cocatalysts.
  • All basic aminosilanes are particularly suitable for this purpose, e.g. all aminopropylsilanes, N-
  • the alkoxysilanes (D) can be added to the prepolymers (A) at any time. If they have no NCO-reactive groups, they can even be added during the synthesis of the prepolymers (A). Based on 100 parts by weight of prepolymer (A), up to 100 parts by weight, preferably 1 to 40 parts by weight, of a low molecular weight alkoxysilane (D) can be added.
  • fillers (E) Mixtures of the alkoxysilane-terminated prepolymers (A) are also usually added to fillers (E).
  • the fillers (E) lead to a considerable improvement in the properties of the resulting mixtures (M). Above all, the tensile strength as well as the elongation at break can be increased considerably by using suitable fillers. All materials are suitable as fillers (E), as are often described in the prior art. Examples of fillers are non-reinforcing fillers, i.e.
  • fillers with a BET surface area of up to 50 m 2 / g such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, calcium carbonate, metal oxide powders such as aluminum, titanium, iron or Zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powder; reinforcing fillers, ie fillers with a BET surface area of at least 50 m 2 / g, such as pyrogenic silica, precipitated silica, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides of large BET surface area; fibrous fillers such as asbestos and plastic fibers.
  • BET surface area such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, calcium carbonate, metal oxide powders such as aluminum, titanium, iron or Zinc
  • the fillers mentioned can be hydrophobicized, for example by treatment with organosilanes or organosiloxanes or by etherification of hydroxyl groups to alkoxy groups.
  • One kind of filler (E) it can also be a 'mixture of réelle-, two fillers (E) are used.
  • the fillers (E) are preferably used in a concentration of 0-90% by weight, based on the finished mixture, with concentrations of 30-70% by weight being particularly preferred.
  • filler combinations (E) which, in addition to calcium carbonate, also contain pyrogenic silica and / or carbon black.
  • Masses (M) which contain no fillers (E) are also preferred. After curing, the prepolymers (A) already have a relatively high elongation at break, so that they also enable unfilled masses (M). The advantages of unfilled systems are significantly lower viscosity and transparency.
  • the mixtures (M) containing the prepolymers (A) may also contain small amounts of an organic solvent (F).
  • This solvent serves to lower the viscosity of the uncrosslinked masses (M).
  • solvents (F) are all solvents and solvent mixtures. Compounds which have a dipole moment are preferably used as the solvent (F).
  • Particularly preferred solvents have a heteroatom with free electron pairs that can form hydrogen bonds.
  • Preferred examples of such solvents are ethers such as t-butyl methyl ether, esters such as ethyl acetate or butyl acetate and alcohols such as methanol, ethanol, n-butanol or - particularly preferably - t-butanol.
  • the solvents (F) are preferably in a concentration of 0-20 vol .-% based on the finished prepolymer ischung incl. all fillers (E) are used, solvent concentrations of 0-5% by volume being particularly preferred.
  • the polymer mixtures (M) can contain, as further components, auxiliaries known per se, such as water scavengers and / or reactive thinners which differ from components (D), and also adhesion promoters, plasticizers, thixotropic agents, fungicides, flame retardants, pigments etc. Also, auxiliaries known per se, such as water scavengers and / or reactive thinners which differ from components (D), and also adhesion promoters, plasticizers, thixotropic agents, fungicides, flame retardants, pigments etc. Also, auxiliaries known per se, such as water scavengers and / or reactive thinners which differ from components (D), and also adhesion promoters, plasticizers, thixotropic agents, fungicides, flame retardants, pigments etc. Also, auxiliaries known per se, such as water scavengers and / or reactive thinners which differ from components (D), and also adhesion promoters, plasticizers,
  • Light stabilizers, antioxidants, radical scavengers and other stabilizers can be added to the compositions (M). Additives of this type are preferred for generating the desired property profiles, both the uncrosslinked polymer blends (M) and the cured compositions (M).
  • the compositions (M) are particularly suitable for adhesive applications.
  • the use of prepolymers (A) and polymer mixtures (M) in adhesives is therefore preferred. They are suitable for countless different substrates, such as mineral substrates, metals, plastics, glass, ceramics, etc.
  • the polymer mixtures (M) can be used both in pure form and in the form of solutions or dispersions.
  • the skin formation times are given as a measure of the reactivities of the polymer blends (M) - or of the reactivities of the polymer blends not according to the invention in the comparative examples. Skin formation times are to be understood as the period of time after the prepolymer has been released into the air until the polymer surface has hardened to such an extent that after the surface has been touched with a pencil, the polymer composition no longer adheres to it.
  • Solvents are completely introduced into a 4 liter 4-neck flask and then rendered inert with nitrogen. The mixture is heated to a temperature of 85 ° C. and 773.4 g (5 mol) of chloromethyl-methyldimethoxysilane are added dropwise over 2 hours (temperature ⁇ 95 ° C.) and the mixture is stirred at 95 ° C. for a further 2 hours. After adding about 300 g of the silane, cyclohexylamine hydrochloride increasingly precipitated out as a salt, but the suspension remained readily stirrable until the end of the metering. The suspension is left to stand overnight and then about 300 ml of cyclohexane are added.
  • the excess amine and the solvent cyclohexane are removed by distillation at 60-70 ° C. in a partial vacuum.
  • the residue is cooled and a further 300 ml of cyclohexane are added in order to completely precipitate the hydrochloride.
  • the suspension is filtered and the solvent is again removed in a partial vacuum at 60-70 ° C.
  • the residue is purified by distillation (106-108 ° C at 15 mbar). A yield of 761 g, ie 70% of theory, is achieved with a product purity of approx. 99.5%.
  • the solvent methanol is removed at 60 ° C. in a partial vacuum.
  • the residue is purified by distillation (78-93 ° C at 90 mbar). A yield of 140 g, i.e. 70% of theory achieved.
  • a prepolymer (A) 152 g (16 mmol) of a polypropylene glycol with an average molecular weight of 9500 g / mol (Acclaim 12200 from Bayer) are placed in a 250 ml reaction vessel with stirring, cooling and heating facilities and added for 30 minutes 80 ° C dewatered in a vacuum. The heating is then removed and 2.16 g (24 mmol) of 1,4-butanediol, 12.43 g (56 mmol) of isophorone diisocyanate and 80 mg of dibutyltin dilaurate (corresponds to a tin content of 100 ppm) are added under nitrogen. The mixture is stirred at 80 ° C.
  • NCO-terminated polyurethane prepolymer obtained is then cooled to 75 ° C. and 11.13 g (51.2 mmol) of N-cyclohexylaminomethyldimethoxymethylsilane are added and the mixture is stirred at 80 ° C. for 60 min. None can be found in the resulting prepolymer mixture by IR spectroscopy
  • Carbamatomethyltrimethoxysilane (C-TMO - produced according to Example 3) is added to the prepolymer described above and mixed in a speed mixer (DAC 150 FV from Hausschild) for 15 seconds at 27000 rpm. Then chalk (BLR 3 from Omya), HDK V 15 (Wacker Chemie GmbH, Germany) and
  • Methoxymethyltrimethoxysilane (MeO-TMO prepared according to Example 2) was added and 2 times 20 seconds at a revolution of 30000 rpm mixed. Finally, aminopropyltrimethoxysilane (A-TMO - Silquest Allio "from Crompton) is added and likewise mixed for 20 seconds at a rotation of 30,000 rpm.
  • Comparative Example 1 This comparative example relates to Example 4 - However, instead of a mixture of 1,4-butanediol and a polypropylene glycol with a mass of 9500, a polypropylene glycol with a mass of 4000 is used. The concentration ratios are chosen so that the prepolymers from Example 4 and Comparative Example 1 largely have the same average molecular weights, urethane and urea group density and the same silane group content:
  • Preparation of a prepolymer not according to the invention 160 g (40 mmol) of a polypropylene glycol with an average molecular weight of 4000 g / mol are placed in a 250 ml reaction vessel with stirring, cooling and heating possibilities and dewatered at 80 ° C. in vacuo for 30 minutes. The heating is then removed and 12.43 g (56 mmol) of isophorone diisocyanate and 80 mg of dibutyltin dilaurate are added under nitrogen. The mixture is stirred at 80 ° C. for 60 minutes. The NCO-terminated polyurethane prepolymer obtained is then cooled to 75 ° C.
  • Carbamatomethyltrimethoxysilane (C-TMO prepared according to Example 3) is added to the prepolymer described above and mixed for 15 seconds at 27000 rpm in a speed mixer (DAC 150 FV from Hausschild). Then chalk (BLR 3 from Omya), HDK V 15 (Wacker Chemie GmbH, Germany) and methoxymethyltrimethoxysilane (MeO-TMO produced according to Example 2) are mixed and 2 times 20 seconds at a rotation of 30,000 rpm. Finally, aminopropyltrimethoxysilane (A-TMO)
  • This comparative example relates to example 4. However, the use of 1,4-butanediol is dispensed with and the amount of isophorone diisocyanate to be used is reduced accordingly.
  • Carbamatomethyltrimethoxysilane (C-TMO prepared according to Example 3) is added to the prepolymer described above and mixed for 15 seconds at 27000 rpm in a speed mixer (DAC 150 FV from Hausschild). Then chalk (BLR 3 from Omya), HDK V 15 (Wacker Chemie GmbH, Germany) and methoxymethyltrimethoxysilane (MeO-TMO produced according to Example 2) are added and mixed 2 times 20 seconds at a rotation of 30,000 rpm. Finally, aminopropyltrimethoxysilane (A-TMO Silquest A1110 s from Crompton) is added and likewise mixed for 20 seconds at a rotation of 30,000 rpm.
  • A-TMO Silquest A1110 s from Crompton aminopropyltrimethoxysilane
  • Example 5 Properties of the cured prepolymer blends
  • the finished prepolymer blends are spread with the aid of a doctor blade into a 2 mm high Teflon mold, the through-hardening speed being approx. 2 mm per day. After two weeks of storage, SI test specimens are punched out, the tensile properties of which are measured in accordance with EN ISO 527-2 on the Z010 from the Zwick company.
  • the properties of the respective prepolymer blends determined here are listed in Table 4.
  • the blends of • Example 4.1, Comparative Example 1.1 and Comparative Ex. 2.1, • Example 4.2, Comparative Example 1.2 and Comparative Ex. 2.2 • Example 4.3, Comparative Example 1.3 and Comparative Ex. 2.3 each identical and differ only in the prepolymer used. Ie the properties of these masses can be compared directly with each other.
  • Example 6 This example is intended to show that the prepolymers (A) are also suitable for the production of unfilled prepolymer mixtures which are suitable for compositions with an exceptionally high tear strength for such systems.
  • a prepolymer (A) 152 g (16 mmol) of a polypropylene glycol with an average molecular weight of 9500 g / mol ( Acclaim® 12200 from Bayer) are placed in a 250 ml reaction vessel with stirring, cooling and heating facilities and 30 minutes dewatered at 80 ° C in a vacuum. The heating is then removed and 2.88 g (32 mmol) of 1,4-butanediol, 14.21 g (64 mmol) of isophorone diisocyanate and 80 mg of dibutyltin dilaurate are added under nitrogen. The mixture is stirred at 80 ° C. for 60 minutes.
  • NCO-terminated polyurethane prepolymer obtained is then cooled to 75 ° C. and 13.91 g (64 mmol) of N-cyclohexylaminomethyl-dimethoxymethylsilane are added and the mixture is stirred at 80 ° C. for 60 min.
  • isocyanate groups can no longer be detected by IR spectroscopy.
  • a slightly cloudy prepolymer is obtained which can be easily poured and further processed at 20 ° C. with a viscosity of 620 Pas.
  • Comparative Example 3 This comparative example relates to Example 6. However, the use of 1,4-butanediol is dispensed with and the amount of the isophorone diisocyanate to be used is reduced accordingly.
  • Example 7 Specimens are prepared as in Example 5 described and 'measured: Example 7.. However, the prepolymers prepared in Example 6 and Comparative Example 3 are used. The properties of the respective prepolymer blends determined here are listed in Table 7.
  • This example serves to further demonstrate the performance of the prepolymers (A).
  • NCO-terminated polyurethane prepolymer obtained is then cooled to 60 ° C. and 13.91 g (64 mmol) of N-cyclohexylaminomethyldimethoxymethylsilane are added and the mixture is stirred at 80 ° C. for 60 minutes.
  • isocyanate groups can no longer be detected by IR spectroscopy.
  • a slightly cloudy prepolymer is obtained which can be easily poured and further processed at 20 ° C. with a viscosity of 505 Pas.
  • specimens are produced and measured from this mixture. These had a skin formation time of 15 minutes, a tensile strength of 5.4 MPa, an elongation at break of 667% and a 100% modulus of 1.8 MPa.
  • Example 9 This example serves to further demonstrate the performance of the prepolymers (A).
  • prepolymer (A) The prepolymer is prepared as described in Example 4, with the exception that instead of 11.13 g (51.2 mmol) of N-cyclohexylaminomethyldimethoxymethylsilane, 7.42 g (34.1 mmol) and an additional 4.64 g ( 17.1 mmol) of N-cyclohexylaminomethyltrimethoxysilane can be used.
  • specimens are produced and measured from this mixture. These had a skin formation time of 5 minutes, an elongation at break of 502%, a tear strength of 4.2 MPa and a 100% modulus of 1.71 MPa.
  • Example 10 This example serves to further demonstrate the performance of the prepolymers.
  • the prepolymer is prepared as described in Example 8. Corresponding test specimens are produced in which the prepolymer is mixed with Triveron ® before mixing.
  • This prepolymer is mixed with 5% by weight Triveron ® and processed entspechend Example 4 to a prepolymer blend.
  • the recipe shown in Table 10 is used.
  • specimens are produced and measured from this mixture. These had a skin formation time of 5 minutes, an elongation at break of 633%, a tear strength of 5.74 MPa and a 100% modulus of 2.09 MPa.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des prépolymères (A) comportant des groupes terminaux de formule générale (1), dans laquelle R1 désigne un reste alkyle, cycloalkyle, alkényle ou aryle éventuellement substitué par halogène, ayant entre 1 et 10 atomes de carbone, R2 désigne un reste alkyle ayant entre 1 et 6 atomes de carbone ou un reste φ-oxa-alkyle-alkyle ayant au total entre 2 et 10 atomes de carbone, a est un nombre valant entre 0 et 2, les prépolymères (A) étant obtenus par réaction de 1) polyol (A1) de poids moléculaire moyen Mn de l'ordre de 1.000 à 25.000, 2) d'alcool de faible poids moléculaire (A2) comportant au moins deux groupes hydroxyle par molécule et de poids moléculaire de l'ordre de 62 à 300, 3) de di- ou du polyisocyanate (A3) et 4) d'alcoxysilane (A4) qui dispose d'un groupe isocyanate ou d'un groupe réagissant à l'isocyanate. L'alcool de poids moléculaire moyen (A2) et le polyol (A1) sont utilisés dans un rapport molaire de 0,3:1 à 7:1.
EP04735887A 2003-06-26 2004-06-03 Prepolymeres a terminaisons alcoxysilane Withdrawn EP1636283A1 (fr)

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DE10328844A DE10328844A1 (de) 2003-06-26 2003-06-26 Alkoxysilanterminierte Prepolymere
PCT/EP2004/006010 WO2005000931A1 (fr) 2003-06-26 2004-06-03 Prepolymeres a terminaisons alcoxysilane

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