EP2440591A1 - Matières polymérisables, compositions durcissables et procédé - Google Patents

Matières polymérisables, compositions durcissables et procédé

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Publication number
EP2440591A1
EP2440591A1 EP10725609A EP10725609A EP2440591A1 EP 2440591 A1 EP2440591 A1 EP 2440591A1 EP 10725609 A EP10725609 A EP 10725609A EP 10725609 A EP10725609 A EP 10725609A EP 2440591 A1 EP2440591 A1 EP 2440591A1
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EP
European Patent Office
Prior art keywords
polymerizable composition
weight
composition according
polyurethane
polymerizable
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.)
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Application number
EP10725609A
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German (de)
English (en)
Inventor
Albert Geipert
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.)
Kunststoff- und Farben-gesellschaft MbH
KUNSTSTOFF und FARBEN GmbH
Original Assignee
Kunststoff- und Farben-gesellschaft MbH
KUNSTSTOFF und FARBEN GmbH
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Publication date
Application filed by Kunststoff- und Farben-gesellschaft MbH, KUNSTSTOFF und FARBEN GmbH filed Critical Kunststoff- und Farben-gesellschaft MbH
Publication of EP2440591A1 publication Critical patent/EP2440591A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to polymerizable compositions and curable compositions which cure into bonds, moldings and coatings with high impact strength.
  • Methyl methacrylate resins have been used as coatings for industrial flooring, road marking and the like. a. found a great application. These systems are usually prepared by dissolving copolymers of methacrylic acid esters such as methyl methacrylate, butyl methacrylate and acrylic acid esters such as butyl acrylate or ethylhexyl acrylate in monomers of the same base, in particular methyl methacrylate. Such so-called coating compositions are processed alone or with fillers and cured with redox systems.
  • compositions for the production of highly impact-resistant cast plates based on crosslinked polyurethane / polymethacrylate systems with 3-8% by weight of polyurethane are known from DE 69120843. According to this teaching, a polyurethane network is first formed, after which the alkyl methacrylate is subsequently polymerized. Interestingly, this patent demonstrates that in this mixing system, the impact strength as a function of polyurethane content is optimum goes.
  • the polymerization is carried out in 2 stages.
  • the urethane catalyst e.g. Dibutyltin dilaurate
  • a polyurethane network prepared and then carried out at elevated temperature, the vinyl polymerization (DE 20 03 365).
  • Another object can be seen to provide a polymerizable composition which can be used as a coating composition, adhesive and / or casting compound.
  • the cured compositions should have excellent impact resistance, wear resistance, tear resistance, vibration resistance and tensile strength.
  • the elastic modulus should be variable over a wide range, so that articles with a very high or relatively low modulus of elasticity can be obtained. These properties should be preserved over a long period of time.
  • the cured masses should show a high permanent elasticity and a relatively high temperature stability. Furthermore, the cured masses should have a high chemical resistance.
  • the masses should be able to be polymerized under very different conditions, whereby the processing time (pot life) should be able to be adapted to the most diverse requirements.
  • the polymerizable compositions should be exposed to weathering after a short time.
  • the polymerizable materials should also be able to be processed by relatively low skilled people.
  • the polymerizable compositions should be inexpensive to produce.
  • the subject of the present invention is accordingly a polymerisable
  • the cured compositions have excellent impact resistance, wear resistance, tear resistance, vibration resistance and tensile strength. These properties are retained over a long period of time.
  • the cured materials show a high permanent elasticity and a relatively high temperature stability.
  • the cured compositions show surprisingly good mechanical properties even at very low temperatures, in particular outstanding impact toughness.
  • the cured compositions have a high chemical resistance and a low tendency to form stress cracks.
  • the polymerized compositions show a high weathering stability.
  • the modulus of elasticity can be varied over a wide range, so that articles with a very high or relatively low modulus of elasticity can be obtained.
  • the polymerizable compositions can be used on a variety of substrates as an adhesive, the adhesive is particularly suitable for bonding a variety of materials.
  • the present invention provides polymerizable compositions having the said properties, which can be produced and processed particularly easily.
  • the masses can be polymerized under a wide variety of conditions, with the processing time (pot life) being able to be adapted to a wide variety of requirements.
  • the polymerizable compositions can be exposed to weathering after a short time.
  • the compositions can be cured even at temperatures of -20 0 C.
  • the polymerizable compositions can also be processed by relatively low skilled people.
  • the polymerizable compositions are inexpensive to produce.
  • a polymerizable composition comprising A 5 - 30 wt.% Polyurethane with at least one soft segment with a
  • B 70-95% by weight of alkyl methacrylate having 1-6 carbon atoms in the alkyl radical, C 0-20% by weight of one or more monomers copolymerizable with the alkyl methacrylates mentioned under B, which is characterized in that the polyurethane has a molecular weight in the range 5,000 - 200,000 Daltons and which is further characterized in that it contains vinyl polymers with a molecular weight in the range 5,000- 5,000,000 daltons only in proportions ⁇ 5 wt.%, Preferably ⁇ 1 wt.% And most preferably not at all, as a casting or Coating composition particularly suitable.
  • polymerizable compositions which additionally contain 0.03-3% by weight of polymerization regulators with at least 2 thiol groups in the molecule.
  • Suitable polymerization regulators are e.g. Thioglycolic acid esters of more than one alcohol such as ethylene glycol dithioglycolate, pentaerythritol tetrathioglycolate.
  • Preferred polymerizable compositions furthermore comprise crosslinkers such as alkanediol di (meth) acrylate or propanetrioltri (meth) acrylate in proportions of 0.03-5% by weight and preferably in proportions of 0.1-1% by weight.
  • crosslinkers such as alkanediol di (meth) acrylate or propanetrioltri (meth) acrylate in proportions of 0.03-5% by weight and preferably in proportions of 0.1-1% by weight.
  • a polymerizable composition which contains 0.1-5% by weight of a solvent-free, low-viscosity isocyanate prepolymer having a functionality in the range from 2 to 3.5.
  • compositions preferably comprise a redox system for carrying out a free-radical polymerization, particularly preferably a redox system which consists of at least one tert. aromatic amine and at least one peroxy compound, preferably benzoyl peroxide.
  • paraffins having a melting range of 40- 60 0 C, in particular having a melting range of 52- 54 ° C are preferred.
  • the polymerizable compositions according to the invention are suitable for the production of impact-resistant articles.
  • the paraffin-containing compositions are used as coating compositions.
  • the polyurethane A is a polyurethane A
  • An essential constituent of the polymerizable composition of the invention is a content of 5 to 50, in particular 5 to 30, preferably 6 to 25 wt.%, Preferably 8 to 20 wt.%, Particularly preferably 10 to 17 wt.% Polyurethane A, dissolved in the monomers B and, if used, the monomers C.
  • Polyurethanes are polymers in which repeat units are linked by urethane repeats -NH-CO-O-.
  • Polyurethanes are generally formed by polyaddition of dihydric or higher alcohols to dibasic or higher isocyanates (Rompp Chemie Lexikon, 9th edition, S 3575 or Kunststoffe 80, 1193).
  • Technically important polyurethanes are e.g. produced from polyester diols and polyether diols on the one hand and toluidine diisocyanate or hexamethylene diisocyanate on the other hand.
  • Polyurethanes which are suitable for use in the polymerizable compositions of the invention have at least one soft segment.
  • the soft segment is used to improve the impact resistance of the obtainable by polymerization of the monomers B composite.
  • the soft segment is a glass transition temperature Tg of less than 20 0 C, preferably ⁇ 0 ° C, and most preferably ⁇ - 2O 0 C.
  • the glass transition temperature may be according to conventional methods, for example with a dynamic mechanical analysis (DMA) or differential scanning calorimetry (DSC ), for example according to DIN 53765, ISO 11357-2 (heating rate 10 K / min) or DIN 53445, ASTM D-5279.
  • DMA dynamic mechanical analysis
  • DSC differential scanning calorimetry
  • polyurethanes with a high glass transition temperature does not lead to an improvement in impact resistance.
  • polyurethanes based on polyester diols and / or polyether diols and aliphatic and / or aromatic diisocyanates are particularly suitable.
  • Suitable longer-chain diols having at least 2 terminal hydroxyl groups in the molecule are preferably polyesters, polyethers, polyacetals, polycarbonates, polyester amides and polyamides, with polyesters and polyethers being preferred.
  • the suitable hydroxyl-containing polyesters are, for example, reaction products of dihydric alcohols with dibasic carboxylic acids.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to prepare the polyesters.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature, and optionally, e.g. by halogen atoms, substituted and / or unsaturated.
  • succinic acid adipic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, terephthalic acid dimethylester, terephthalic acid bis-glycol ester, 1, 12-dodecanedicarboxylic acid.
  • polyhydric alcohols e.g.
  • the polyethers in question having two hydroxyl groups are also of the type known per se and are, for example, by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 , or by addition of these Epoxides, optionally in admixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, for example water, ethylene glycol, propylene glycol (1, 3) or - (1, 2), 4,4'-dihydroxydiphenylpropane or aniline produced. Particular preference is given to those polyethers which are predominantly (up to 90% by weight, based on all OH groups present in the polyether) primary OH groups.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin
  • reactive hydrogen atoms such as alcohols or amines
  • polyesters which have high proportions, preferably at least 50% by weight, particularly preferably at least 80% by weight, of aliphatic or cycloaliphatic diol and / or dicarboxylic acid repeat units.
  • the preferred di- or higher-valent isocyanates include in particular aliphatic and cycloaliphatic isocyanates which have a particularly high light stability, such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) 1 4,4'-diisocyanatodicyclohexylmethane (H12MDI) and 1,4-cyclohexyl diisocyanate (CHDI ).
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-diisocyanatodicyclohexylmethane
  • CHDI 1,4-cyclohexyl diisocyanate
  • Aromatic isocyanates having at least two isocyanate groups, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate (NDI) and polymeric diphenylmethane diisocyanate (PMDI) being mentioned by way of example.
  • Aromatic isocyanates are characterized by a particularly high reactivity, so that they are usually preferred if the light resistance has a subordinate importance for the particular application.
  • Preferred polyurethanes are e.g. composed of an adipic acid-hexanediol polyester and toluene diisocyanate. Furthermore, polyurethanes having a high polyester content are preferred over polyurethanes having a high polyether content.
  • Polyurethane A has a molecular weight in the range from 5,000 to 200,000 daltons, in particular from 5,000 to 150,000 daltons, preferably in the range from 8,000 to 100,000 daltons, more preferably from 30,000 to 150,000 and most preferably from 30,000 to 100,000.
  • the molecular weight here refers to the individual molecules, so that the polymerizable composition has at least 5% by weight of polyurethane molecules having a molecular weight in the range mentioned.
  • the mixture may also have polyurethane components which are outside the range mentioned in claim 1.
  • the Part of polyurethanes having a molecular weight in the range mentioned can be determined from the molecular weight distribution of the polyurethanes used. For this purpose, in particular an analysis by means of gel permeation chromatography (GPC) can be carried out, wherein the measurement can be carried out, for example, at 25 ° C.
  • GPC gel permeation chromatography
  • the number-average molecular weight M n of the polyurethanes used is preferably in the range from 5,000 to 200,000 daltons, particularly preferably 10,000 to 150,000 daltons and particularly preferably in the range from 30,000 to 100,000 daltons.
  • the weight average molecular weight M w of the polyurethanes used is preferably in the range from 10,000 to 250,000 daltons, particularly preferably 20,000 to 200,000 daltons and particularly preferably in the range from 30,000 to 150,000 daltons.
  • the polydispersity index M w / M n of polyurethanes to be used in particular may be in the range from 1.0 to 10, particularly preferably 1.2 to 5.
  • the polyurethane may have a viscosity in the range of 5,000 mPa.s to 200,000 mPa.s, more preferably 20,000 mPa.s to 60,000 mPa.s, measured according to DIN EN ISO 3219 / A3 at 23 ° C. as a 30 weight percent solution in ethyl acetate.
  • Preferred polyurethanes contain free hydroxyl end groups, preferably having a functionality of about 2.
  • the functionality is preferably in the range from 1.8 to 3.0, more preferably from 1.9 to 2.5, based on the hydroxyl groups.
  • the functionality relates to the average number of hydroxyl groups per polyurethane molecule and can be determined according to DIN 53240.
  • Exemplary are Impranil C and Impranil CHW from Bayer and Irostic 6514-007N.
  • polyurethanes are miscible, i. give a homogeneous melt mixture or a homogeneous, clear solution in the monomers B and C
  • mixtures of polyurethanes A can be used.
  • polymerizable compositions which contain no polymers other than polyurethane A are preferred.
  • the polymerizable mass contains vinyl polymers, such as PMMA, with a molecular weight of 5,000-5,000,000 DaI tons only in proportions ⁇ 20 wt.%, In particular ⁇ 10 wt.%, Preferably ⁇ 5 wt.%, particularly preferably ⁇ 1% by weight.
  • Particularly preferred are polymerizable compositions containing the high molecular weight polyurethane A as the only dissolved polymer component.
  • Theological properties of the polymerizable composition by the content of polyurethane A, its molecular weight and the interaction of the polymer with the monomers B and C are determined.
  • the molecular weight and the content of polyurethane A are chosen so that a polymerizable composition having a viscosity of 50 to 10,000 cP, more preferably 100 to 5000 cP, and most preferably from 150 to 1500 cP results.
  • a polymerizable composition having a viscosity of 50 to 10,000 cP, more preferably 100 to 5000 cP, and most preferably from 150 to 1500 cP results.
  • surprising advantages can be achieved with polymerizable compositions whose viscosity enables bubble-free processing.
  • the alkyl methacrylates B are methacrylates of the C1 - C6 alkanols. Here are methyl, butyl and cyclohexyl be mentioned. Particularly preferred is MMA (methyl methacrylate).
  • the proportion of these monomers in the polymerizable composition is generally from 30 to 95% by weight, preferably from 50 to 95% by weight, in particular from 70 to 95% by weight, preferably from 80 to 92% by weight.
  • monomers C which may be present in proportions of preferably 0-65 wt.%, Particularly preferably 0-45 wt .-% and particularly preferably 0 to 20 wt.%
  • monomers are to be mentioned with MMA are radically copolymerizable.
  • MMA are radically copolymerizable.
  • C 1 -C 8 -alkyl esters of acrylic acid such as butyl acrylate, 2-ethylhexyl acrylate, alkyl esters of methacrylic acid, which differ from those mentioned under B, or functional monomers, such as hydroxyethyl methacrylate.
  • the term functional monomers is understood in particular to mean compounds which have at least one further reactive group in addition to an unsaturated CC double bond. These include in particular monomers having two or more ethylenically unsaturated CC double bonds, monomers having hydroxyl groups or monomers having acid groups.
  • the polymerizable mass may preferably contain from 0.05 to 40% by weight, in particular from 0.1 to 20% by weight and particularly preferably from 1 to 15% by weight, of C 1 -C 8 -alkyl esters of acrylic acid.
  • polymerization crosslinkers also referred to herein as crosslinkers, such as acrylic and methacrylic esters of polyhydric alcohols.
  • crosslinkers such as acrylic and methacrylic esters of polyhydric alcohols.
  • These include in particular (meth) acrylates derived from unsaturated alcohols, such as. Allyl (meth) acrylate, vinyl (meth) acrylate, and (meth) acrylates derived from diols or higher alcohols, e.g.
  • Glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glyceryl di (meth) acrylate and diurethane dimethacrylate; (Meth) acrylates having three or more double bonds, e.g.
  • Glycerol tri (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate.
  • the term (meth) acrylate includes esters of acrylic acid, methacrylic acid and mixtures thereof.
  • the preferred acrylates include, for example, propanetriol triacrylate.
  • Crosslinkers with two or more acrylate or methacrylate groups are preferred over crosslinkers having exactly one (meth) acrylate group. Particular advantages can be achieved with methacrylic acid esters of polyhydric alcohols, such as butanediol dimethacrylate.
  • the proportion of these crosslinkers may be from 0.01 to 10% by weight, preferably from 0.03 to 5% by weight, more preferably from 0.1 to 3% by weight and most preferably one portion from 0.1 to 1% by weight.
  • the polymerizable composition may comprise monomers having a hydroxyl group.
  • monomers having a hydroxyl group include, but are not limited to, hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate.
  • the proportion of monomers having a hydroxyl group may preferably be in the range from 0 to 40% by weight, in particular 0.05 to 30% by weight, particularly preferably 0.1 to 20% by weight and particularly preferably in the range from 0.5 to 5 % By weight.
  • polymerizable compositions comprising monomers having an acid group.
  • the preferred monomers having an acid group include, in particular, acrylic acid, methacrylic acid, mono- (2-methacryloxy) succinate, hydroxyethyl methacrylate phosphate (HEMA phosphate), fumaric acid and maleic acid.
  • the proportion of monomers having an acid group may preferably be in the range from 0 to 10% by weight, more preferably 0.1 to 5% by weight and particularly preferably in the range from 1 to 2% by weight.
  • Acid group-containing monomers can improve the adhesiveness of the polymerized composition, particularly to metals such as steel, and to inorganic substrates, particularly glass. However, high levels may undesirably increase water absorption.
  • compositions which contain 0.03-3.% By weight or, preferably, proportions of 0.1-1% by weight of polymerization regulators having at least 2 thiol groups in the molecule, such as ethanedithiol or pentaerythritol tetra-thioglycolate.
  • the polymerizable compositions contain small amounts, e.g. 0.1-5 wt.% Of a solvent-free low-viscosity isocyanate prepolymers having a functionality in the range 2- 3.5.
  • the functionality relates to the average number of isocyanate groups per isocyanate prepolymer molecule and can be determined volumetrically in accordance with DIN-EN ISO 11909.
  • isocyanate prepolymers is Conipur 1335 from BASF.
  • no special urethanization catalyst such as dibutyltin dilaurate is added.
  • the redox system for the radical polymerization is chosen so that this example of dibenzoyl peroxide and a tert. aromatic amine, wherein the tert. aromatic amine also acts as a catalyst for the reaction of the diol groups of the polyurethane A with the isocyanate prepolymers.
  • the polymerizable compositions comprise only small amounts, more preferably no specific urethane-forming catalyst.
  • Special urethane catalyst are characterized in that isocyanates with hydroxyl groups at a temperature of 25 0 C within 24 hours to at least 50% are implemented.
  • the content of specific urethane-forming catalysts is preferably limited to not more than 0.02% by weight, more preferably not more than 0.001% by weight.
  • Dibutyltin dilaurate belongs in particular to the customary specific urethane-forming catalysts.
  • the viscosity of the polymerizable composition increases at a storage of 10 days at 25 0 C by at most 100%, preferably by at most 50%, more preferably by at most 20% and most preferably by at most 10%.
  • This property can be achieved in particular by the absence of specific urethane-forming catalysts.
  • the polymerizable compositions are free-radically cured by using initiators.
  • initiators can be used depending on the type of use of the composition of the invention.
  • thermal initiators can be used.
  • adhesive or coating agent systems are preferably used which allow curing at room temperature.
  • Suitable thermal initiators include azo compounds, peroxy compounds, persulfate compounds or azoamidines.
  • Non-limiting examples include dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, Diisopropylperoxidicar- carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, xidisulfat Dikaliumpersulfat, Ammoniumpero-, 2,2'-azobis (2-methylpropionitrile) (AIBN), 2,2 '- Azobis (isobutyric amide) hydrochloride, benzpinacol, dibenzyl derivatives, methyl ethylene peroxide, 1,1-azobiscyclohexanecarbonitrile, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, didecanoyl peroxide, tert-butyl peroxy-2-ethylhexano
  • ®Vazo free-radical generator available from DuPont under the name ®Vazo, for example ®Vazo V50 and ®Vazo WS.
  • Photoinitiators include, but are not limited to, q ⁇ -diethoxyacetophenone (DEAP, Upjon Corp), n-butyl benzoin ether (®Trigonal-14, AKZO) and 2,2-dimethoxy-2-phenylacetophenone (®lgacure 651) and 1-benzoylcyclohexanol (®lgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (®lgacure 819) and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one (®lgacure 2959) , each from the company Ciba Geigy Corp. are commercially available.
  • Redox initiators may preferably comprise at least one amine compound in addition to a free radical generator.
  • Butyl mono- permaleinate (for example 25% (about 1.2%)) + calcium hydroxide (shepherd lime for example 0.3%) + pentaerythritol tetrakis-3-mercapto-propionate (for example about 0.01 to 0, 15%) proven.
  • Curing systems comprising at least one hydroperoxide, in particular cumyl hydroperoxide, and a p-toluenesulfonic acid halide, in particular tosyl chloride, are of particular interest.
  • Polymerizable compositions with these components are characterized by a high adhesion of the cured plastic to metal.
  • This system may preferably with an amine, for example 3.5 diethyl-1, 2-dihydro-1-phenyl-2-propylpyridine be polymerized even at very low temperatures.
  • the curing systems set forth above can be added to the curable composition for curing, for example in the form of a solution or paste, or as a contact hardener.
  • a contact hardener the curing composition is applied to a substrate, after which the solvent is evaporated. Subsequently, the curable composition is brought into contact with the dried curing composition.
  • aromatic tertiary amines are used, such as dimethylaniline or di-isopropoxy- p -toluidine.
  • the concomitant use of 0.1-5 wt.%, In particular 0.2-2 wt.% Paraffin with a melting point in the range 40- 6O 0 C advantageous.
  • curable compositions comprising a proportion of the above-described polymerizable compositions and a proportion of fillers.
  • the polymerizable compositions are particularly suitable for the production of moldings in the kitchen and sanitary sector, in particular kitchen plates, kitchen sinks and polenitärurgirentn, such as shower trays and the like.
  • These curable compositions usually comprise from 5 to 85% by weight, preferably from 20 to 80% by weight of fillers, which are preferably of an inorganic nature.
  • the fillers to be used are described inter alia in the publications EP 0 659 786 B1, filed 16.12.1994 in the European Patent Office with the application number 94119906.9, WO 2006 / 048214A1, filed 05.04.2008 the European Patent Office with the application number PCT / EP2005 / 011627, and WO 2008/122428 A1, filed Apr. 5, 2008, filed with the European Patent Office with the application number PCT / EP2008 / 002722, wherein the fillers set out and the processing of the polymerizable compositions for the preparation of the corresponding articles are included in the present application for the purpose of disclosure.
  • the curable compositions may also contain other inorganic or organic fillers, in particular reinforcing fibers of plastics or of inorganic substances, for example glass fibers or carbon fibers. These fibers can be used as tissue.
  • the present invention describes processes for the production of coatings or impact-resistant articles in which a polymerizable composition of the invention or a curable composition according to the invention is polymerized.
  • the invention accordingly also relates to a preferred process for the production of impact-resistant articles or coatings, in which a polymerizable composition comprising
  • a method in which a polymerizable composition is used which contains polymerization inhibitor for example in proportions of 50-500 ppm, which delays the start of polymerization until the composition is filled and so the polymerization does not already take place when the components are stirred together.
  • Polymerization inhibitors such as hydroquinones, hydroquinone such as hydroquinone monomethyl ether or di-tert-butylcatechol, phenothiazine, N 1 N'-(diphenyl) -p-phenylenediamine, p-phenylenediamine, or sterically hindered phenols, are well known in the art. These compounds can be used singly or in the form of mixtures and are generally available commercially.
  • the effect of the stabilizers is usually that they act as radical scavengers for the free radicals occurring during the polymerization.
  • the stabilizers act as radical scavengers for the free radicals occurring during the polymerization.
  • Aromatic amine present as a mixture, thereupon, if present, the isocyanate prepolymers and finally the peroxide usually added in phlegmatized form.
  • the molecular weight of the polyurethane used is only slightly increased.
  • the number average molecular weight of the polyurethane used preferably increases by at most a factor of ten, in particular by at most a factor of two, preferably by at most 50%.
  • the polyurethane is not crosslinked in the cured state.
  • the process according to the invention leads to impact-resistant moldings or tough coatings (see examples).
  • the homogeneity and transparency of the articles and coatings obtained by the process according to the invention suggests that both polymer phases, the polyurethane and the vinyl polymer formed in the free-radical polymerization, are intimately mixed next to one another.
  • polyvalent thiols at the beginning of the polymerization leads to a shortening of the polymer chains and towards the end of the polymerization to a chain extension and with the help of crosslinkers to a fixation of the two-phase structure of high molecular weight polyurethane and polymethacrylate network.
  • the castings of the present invention can be reshaped by heat treatment.
  • the reduction in impact strength can be reduced by a heat treatment with the measures mentioned.
  • polymerizable compositions In addition to the above-mentioned Bestan turnover the polymerizable compositions, as stated above, small portions of polymerization inhibitors such as 2.6 di- tert. Butyl p - cresol, phenothiazine, light stabilizers, mold release agents, dyes and inorganic and organic fillers such as glass fibers or highly crosslinked Polyvinylpo- lymerisate, e.g. crosslinked PMMA beads with a particle diameter of 3- 3.000 .mu.m included. Furthermore, the polymerizable compositions can be provided with flame retardants.
  • polymerization inhibitors such as 2.6 di- tert. Butyl p - cresol, phenothiazine, light stabilizers, mold release agents, dyes and inorganic and organic fillers such as glass fibers or highly crosslinked Polyvinylpo- lymerisate, e.g. crosslinked PMMA beads with a particle diameter of 3- 3.000 .mu.m included
  • the above-described polymerizable compositions or curable compositions may contain thixotropic agents, for example aerosils or polymers, in particular Borchigen PB 60.
  • the proportion of thixotropic agent in the polymerizable compositions or curable compositions according to the invention may preferably be in the range of 0 to 10 wt .-%, particularly preferably 0.5 to 4 wt .-%.
  • adhesion promoters may be added to the polymerizable compositions or curable compositions, with polyesters being preferred. Particularly preferred polyesters can be obtained commercially under the trade name Tego® Addbond.
  • the proportion of adhesion promoter may preferably be in the range from 0 to 20% by weight, particularly preferably 1 to 10% by weight.
  • the polymerizable compositions consist of> 90% by weight, preferably> 98% by weight, of the abovementioned components.
  • the polymerizable compositions according to the invention are advantageously used for the production of impact-resistant articles. Particularly interesting is the use of paraffin-containing compositions as coating compositions.
  • the present polymerizable compositions can be used as adhesives and as sealing compounds, in particular for floor coatings and as connecting compound mass.
  • the polymerizable resins and the curable composition can be used in orthopedic applications.
  • insoles for shoes can be manufactured.
  • reinforcing materials for example nonwovens or fabrics made of plastic
  • reinforcing materials can be used during the manufacture of roofing seals, wherein in a first step a polymerizable composition provided with an initiator is applied to a roof to be sealed, in a further step a planar reinforcing material, for example a non-woven fabric made of polyester, is applied to the applied mass and in a third step, a further layer polymerizable composition on the non-woven fabric.
  • a planar reinforcing material for example a non-woven fabric made of polyester
  • a further layer polymerizable composition on the non-woven fabric.
  • the resulting coating can be pressed in order to achieve a densification and thus a good adhesion of the polymerizable composition to the fiber material.
  • the polymerizable resins and the curable composition are suitable as potting compound for electronic parts.
  • the previously discussed fiber matrix Semi-finished products can be used to build boats, planes and motor vehicles.
  • preferred moldings obtainable according to the present invention have an impact strength of at least 5 kJ / m 2 , particularly preferably at least 20 kJ / m 2 and very particularly preferably at least 50 kJ / m 2 , according to DIN ISO 179 / 1eU can be measured (25 ° C / 50% relative humidity). In this case, this high impact strength decreases in preferred embodiments, even after a heat treatment of 11 O 0 C for 2 hours relatively small.
  • the impact strength of preferred shaped articles is at least 5 kJ / m 2 , more preferably at least 25 kJ / m 2 and most preferably at least 45 kJ / m 2 , measured according to the conditions set out above.
  • preferred moldings provided by the present invention have a high tensile modulus (1 mm / min), preferably at least 1000 MPa 1, more preferably at least 1500 MPa and most preferably at least 2500 MPa, measured according to EN ISO 527 at 25 0 C, is.
  • preferred moldings of the present invention are characterized by a high tensile elongation at break and a high maximum tensile stress.
  • the tensile elongation is preferably at break at least 10%, more preferably at least 15%, measured according to EN ISO 527 at 25 0 C.
  • the tensile strength of preferred shaped body is at least 10 MPa, more preferably at least 15 MPa, measured according to EN ISO 527 at 25 ° C ,
  • test specimens were milled from this plate and the impact strength was measured on these test specimens:
  • a homogeneous, transparent solution was obtained.
  • the viscosity was 1190 cP.
  • 200g of this polymerizable composition were mixed and cured as described in Example 1 with benzoyl peroxide. An approximately 4 mm thick plate was obtained.
  • Example 3 (10% polyurethane, 2% isocyanate prepolymer)
  • a homogeneous, transparent solution was obtained.
  • the viscosity was 164 cP on the 1st day after preparation of the solution and 209 cp on the 4th day.
  • the plate remained homogeneous even after heating to 110 0 C. Impact resistance of the heated plate at 23 0 C / 50% rel. Humidity: 82.4 kJ / m 2 .
  • Example 8 fiber reinforced panels, especially for orthopedic purposes.
  • a resin of 8% by weight of polyurethane (Impranil C) dissolved in 91% by weight of methyl methacrylate was added with 0.4% by weight, based on the resin weight, of dimethylaniline and 0.6% by weight, based on the weight of the resin, of dibenzoyl peroxide added.
  • the obtained composition several layers of fabrics were laminated and cured between metal plates. The fabrics used were made of polyester. After curing, blanks can be cut from which insoles can be produced by deformation. These shoe inserts have a high permanent elasticity.
  • the above resin has been used for lamination of glass fibers, carbon fibers and polyamide.
  • the bond between carbon fibers and resin could be improved by addition of isocyanate, in particular of about 2% of an isocyanate prepolymer (Conipur 1335, BASF SE).
  • shoe inserts were obtained, which were characterized by a high permanent elasticity.
  • Example 1 The resin described in Example 1 was rolled on a standard quartz sand filled methacrylate coating and cured.
  • the hardened seal showed high durability and high stability against weathering and temperature fluctuations. Furthermore, the resulting seal was characterized by a low brittleness.
  • a reactive resin based on (meth) acrylate was prepared by mixing 77.99% of methyl methacrylate, 14.5% of polyurethane (Impranil® C from Bayer), 5% by weight of polyester-based adhesion promoter (TEGO Addbond LTH® from Evonik). , 0.1% co-stabilizer (Alkanox® 240), 0.03 stabilizer S 18, 0.78% stabilizer (Macrolex® (0.05%), 0.15% Tinuvin® P, 0.2% pentaerythritol tetrathioglycolate , 0.5% butanediol dimethacrylate, 0.6% di-isopropoxy-p-toluidine and 0.15% defoaming agent (Byk® A 515).
  • Example 11 was essentially repeated except that the resin was thixotroped. Accordingly, 86 parts by weight of the reactive resin described in Example 11 were mixed with 3 parts by weight of Aerosil 200 and 1 part by weight of Borchigen® PB 60. The resulting thixotropic reactive resin was cured with 10 parts by weight of a hardener solution consisting of 13% by weight of benzoyl peroxide (50% solution in cyclohexyl phthalate) and 87% by weight of propoxy-dibenzoate (Benzoflex 2088).
  • a hardener solution consisting of 13% by weight of benzoyl peroxide (50% solution in cyclohexyl phthalate) and 87% by weight of propoxy-dibenzoate (Benzoflex 2088).
  • Example 12 was essentially repeated, but using a different hardener composition. Accordingly, 90% by weight of thixotropic reactive resin according to Example 12 were cured with 10% by weight of a hardener solution consisting of 13% by weight of benzoyl peroxide (50% solution in cyclohexyl phthalate), 84% by weight of plasticizer (Ultramoll III), 2% by weight % Aerosil and 1% by weight thixotropic agent (Borchigen PB 60).
  • a hardener solution consisting of 13% by weight of benzoyl peroxide (50% solution in cyclohexyl phthalate), 84% by weight of plasticizer (Ultramoll III), 2% by weight % Aerosil and 1% by weight thixotropic agent (Borchigen PB 60).
  • the materials listed in Table 1 were roughened with a SchleifOige sandpaper and glued overlapping about 1 cm 2 .
  • the loadability of the splices was examined by means of a PCE-SH 10k force gauge, whereby the adhesive tensile strength was measured. If the material was destroyed under the load instead of the splice, this is indicated by the ">" sign in Table 1.
  • the measured tensile strengths are given in Table 1 in kg / cm 2 .
  • polymerizable compositions according to the present invention can be used as adhesives on a wide variety of substrates.
  • Adhesives according to the prior art do not have this variability, so that they are very specific for a particular material. When connecting different materials, therefore, many problems arise that can be solved by the polymerizable compositions of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne des matières polymérisables, contenant A 5 - 50 % en poids de polyuréthane comportant au moins un segment souple et B 30 - 95 % en poids de méthacrylate d'alkyle comportant 1 - 6 atomes de carbone dans le reste alkyle, le polyuréthane ayant un poids moléculaire de l'ordre de 5000 à 200000 daltons. La présente invention concerne également des compositions durcissables qui contiennent lesdites matières polymérisables. Les matières polymérisables peuvent être utilisées pour fabriquer des revêtements et des objets résistant aux chocs ainsi que pour coller des objets.
EP10725609A 2009-06-10 2010-06-08 Matières polymérisables, compositions durcissables et procédé Withdrawn EP2440591A1 (fr)

Applications Claiming Priority (2)

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DE102009024452A DE102009024452A1 (de) 2009-06-10 2009-06-10 Polymerisierbare Masse
PCT/EP2010/003456 WO2010142429A1 (fr) 2009-06-10 2010-06-08 Matières polymérisables, compositions durcissables et procédé

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KR20230167139A (ko) * 2017-04-21 2023-12-07 카티바, 인크. 유기 박막을 형성하기 위한 조성물 및 기술

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US3509234A (en) * 1965-08-13 1970-04-28 Ford Motor Co Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate
GB1239701A (fr) * 1969-01-27 1971-07-21 Ici Ltd
DE2029898C2 (de) * 1970-06-18 1986-01-30 Karl Ullrich GmbH & Co, 6451 Mainhausen Überzugsmittel für mineralische Baustoffe oder Asphalte
CA1068449A (fr) 1975-07-02 1979-12-18 Franciszek Olstowski Ensembles de polyurethannes et de polymeres vinyliques
FR2608095B1 (fr) 1986-12-11 1988-12-30 Altulor Sa Plaques coulees a haute resistance au choc, leur procede de fabrication et articles faconnes obtenus
EP0447309B1 (fr) 1990-03-15 1996-07-17 Elf Atochem S.A. Plaques coulées â haute résistance au choc, leur procédé de fabrication
DE102005055793A1 (de) 2005-11-21 2007-05-24 Röhm Gmbh Transparente TPU (thermoplastische Polyurethane)/ PMMA (Polymethyl(meth)acrylat) Abmischungen mit verbesserter Kältesschlagzähigkeit
DE102006039849A1 (de) 2006-08-25 2008-02-28 Evonik Röhm Gmbh Methacrylatharze zur Herstellung von Fahrbahnmarkierungen

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US20120083569A1 (en) 2012-04-05
DE102009024452A1 (de) 2010-12-16

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