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WO2006024885A1 - Procede de preparation de resines de polyaddition et de resines hybrides a base de polyisocyanate/acide polysilicique au moyen de polyisocyanates bloques et polyisocyanates bloques utilises selon ce procede - Google Patents

Procede de preparation de resines de polyaddition et de resines hybrides a base de polyisocyanate/acide polysilicique au moyen de polyisocyanates bloques et polyisocyanates bloques utilises selon ce procede Download PDF

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Publication number
WO2006024885A1
WO2006024885A1 PCT/HU2005/000094 HU2005000094W WO2006024885A1 WO 2006024885 A1 WO2006024885 A1 WO 2006024885A1 HU 2005000094 W HU2005000094 W HU 2005000094W WO 2006024885 A1 WO2006024885 A1 WO 2006024885A1
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WIPO (PCT)
Prior art keywords
blocked
polyisocyanate
isocyanate groups
group
compound
Prior art date
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Ceased
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PCT/HU2005/000094
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English (en)
Inventor
Gábor Nagy
Péter Bakó
Árpád GÁL
Katalin Vilimi
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Budapesti Mueszaki Egyetem
Polinvent Fejleszto Kivitelezo es Ertekesito Kft
Original Assignee
Budapesti Mueszaki Egyetem
Polinvent Fejleszto Kivitelezo es Ertekesito Kft
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Priority to DE112005001991T priority Critical patent/DE112005001991T5/de
Publication of WO2006024885A1 publication Critical patent/WO2006024885A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8074—Lactams
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen

Definitions

  • the invention relates to a process for the preparation of polyisocyanate/poly- silicic acid based, environmentally sound polyaddition and hybrid resins using blocked polyisocyanates. Some of the blocked polyisocyanates usable in the process according to the invention are new; the invention also relates to these new compounds.
  • Combined polyisocyanate/polysilicic acid resin systems prepared by reacting polyisocyanates (also including diisocyanates) with water glass, are the ones which form the industrially most important group of resins over polyurethanes and poly- ureas, and have been elaborated in part to replace the latter two resin types. They have become well-known in the late seventies mainly from the works of D. Dietrich,
  • polyurea derivatives too, which are also more stable than the urethane bonds.
  • the main catalyst of these reactions is the alkali present in water glass; the rate of the reactions can be controlled with additives listed in the above references.
  • the resin always solidifies within some minutes or hours from admixing the polyisocyanate with water glass even at a temperature of 0 to 1O 0 C; the reaction can be frozen only at very low temperatures, usually below -2O 0 C.
  • water glass or a master batch comprising further additives compatible with water glass and on the other hand polyisocyanate or a master batch comprising further additives compatible with polyisocyanate should always be stored and delivered as separate components to be admixed with one another just at the place (e.g. for use in building industry even at the open area of building) where the resin is to be formed.
  • polyisocyanates particularly monomeric diisocyanates, as substances potentially hazardous to health and environment
  • handling and storage of pure polyisocyanates and mixtures comprising them in amounts exceeding prescribed limits require safety measures which are difficult, sometimes even impossible, to meet.
  • Blocked polyisocyanates which, when reacted with water glass, release volatile blocking agents at the reaction temperature are obviously unsuitable to form a polyisocyanate/polysilicic acid resin, because this would lead to uncontrollable foaming and porosity.
  • Blocked polyisocyanates which deblock at temperatures higher than the boiling point of water should also be excluded from principal reasons, because reactive isocyanate groups cannot be liberated from these compounds under the conditions of resin formation.
  • Blocked polyisocyanates which are relatively large and rigid molecules with softening points much above room temperature are difficult to handle, if at all, in water glass/polyisocyanate systems, thus it is advisable to exclude them from practical aspects.
  • the blocking agent which splits off from the blocked polyisocyanate must not have adverse influences on the reaction of polyisocyanate and water glass, furthermore the blocking agent, which remains in the product, must not be hazardous to the environment. It should also be considered that the blocking agent which remains in the product, sometimes in relatively high amounts exceeding even the amount of the polyisocyanate, acts as a plasticizer which impairs the mechanical characteristics of the product and may even render the product mechanically unacceptable. From the above it follows that blocked polyisocyanates suitable to
  • polyisocyanate/polysilicic acid based resins should satisfy very specific, frequently contradicting requirements. This explains why blocked polyisocyanates have not been used before in the production of polyisocyanate/polysilicic acid based resins to replace, at least in part, the polyisocyanates.
  • AMH compounds AMH compounds
  • substituted AMH compounds substituted monohydroxy compounds
  • the AMH compounds are effective cocatalysts of resin formation, and the substituted AMH compounds can be utilized favourably to control the processability period (gelling time or pot life) of the resin-forming mixture.
  • the use of polyisocyanates blocked with such compounds does not disturb but influences very favourably the reactions leading to resin formation.
  • blocked polyisocyanates in the prepartion of polyisocyanate/polysilicic acid resins wherein part of the isocyanate groups is blocked with a blocking agent listed in points (a) to (c) above (further on: first blocking agent), and an other part of the isocyanate groups is blocked with a different blocking agent listed in points (a) to (c) above or with a blocking agent other than those defined in points (a) to (c) above comprising an isocyanate-reactive -OH, -SH or -NH- group (further on: second blocking agent).
  • the softening point (which is a negative figure for liquids) of polyisocyanates blocked with two or more different blocking agents is always lower than that of polyisocyanates blocked with a single blocking agent. This enables one to use compounds as blocking agents which, when used alone, would yield blocked polyisocyanates which soften at temperatures much above room temperature being thus difficult or even impossible to incorporate into the reaction mixture. When the two types of blocking agents split off from the isocyanate groups at different temperatures, this leads to further advantages.
  • This method is a very advantageous way to form preimpregnated semifinished products to be cured later by heat treatment.
  • the second blocking agent itself may also be a mixture of two or more different blocking agents.
  • second blocking agent As it appears from the above, it is not absolutely necessary to use a compound listed in points (a) to (c) above as second blocking agent, but other compounds comprising isocyanate-reactive -OH, -SH or -NH- groups (the majority of which is commonly used as blocking agent for isocyanates) can also be applied for this purpose. From these blocking agents even those which deblock in water glass medium at temperatures above 100 0 C and those which are released as volatile compounds are not excluded. When the second blocking agent belongs to these latter compounds the ratio of the reactants should be selected so that the isocyanate groups which liberate when the first blocking agent is split off should react with and consume thereby the full amount of water present in water glass.
  • the splitting of the second blocking agent at a temperature above 100 0 C no more disturbs the formation of the polyisocyanate/polysilicic acid matrix, and an additional cross-linked polymer, intimately built together with the polyisocyanate/polysilicic acid matrix, forms from the isocyanate groups liberated upon splitting off the second blocking agent.
  • a liberated blocking agent comprising nonaromatic unsaturated carbon-carbon bonds can be crosslinked in this method, too.
  • the invention is based on the above recognitions.
  • the invention relates to a process for preparing polyiso ⁇ cyanate/polysilicic acid based resins wherein one or more polyisocyanates is/are reacted with water glass optionally in the presence of one or more additives and/or auxiliary agents conventionally used in the preparation of polyisocyanate/polysilicic acid based resins.
  • at least 5 % by weight of the polyiso- cyanate is replaced by a polyisocyanate in which at least 30 % of the isocyanate groups are blocked, and at least 50 % of the blocked isocyanate groups are blocked with
  • R 10 and R 11 each represent a hydrocarbyl group or one of them may also represent hydrogen, or R 10 and R 11 form, together with the adjacent carbon atom, a cyclic hydrocarbyl group, with the proviso that at least one of R 10 and R 11 comprises a nonaromatic unsaturated carbon-carbon bond; (c) a compound comprising a single isocyanate-reactive -OH group bound to a carbon atom and at least one nonaromatic unsaturated carbon-carbon bond or with any combination thereof.
  • At least 10 % by weight Preferably at least 10 % by weight, more preferably at least 30 % by weight, particularly at least 60 % by weight, sometimes even the full amount of the polyisocyanates can be replaced by the blocked polyisocyanates defined above.
  • polyisocyanate as used throughout the description and claims covers diisocyanates, too.
  • a monomeric diisocyanate When a monomeric diisocyanate is utilized in the process, it is preferred to block at least 50 %, more preferably at least 80 %, particularly all of the reactive iso- cyanate groups (the latter means in practice a blocking degree of at least 95 %, depending on the completeness of the blocking reaction).
  • the reactive iso- cyanate groups For prepolymeric diisocyanates and polyisocyanates comprising more than two isocyanate groups it may be sufficient to block at least 30 % of the isocyanate groups in order to eliminate or reduce the health- and environment-damaging effects, however, it is preferred to block at least 50 %, more preferably at least 80 %, of the isocyanate groups in such instances, too.
  • the polyisocyanate mixture comprises both monomeric and prepolymeric diisocyanates and/or also comprises polyisocyanates with two or more isocyanate groups (the majority of
  • polyisocyanates produced on large scale is such a mixture), within the blocking degree of at least 30 % (preferably at least 50 %, particularly at least 80 %) it is preferred to block at least 50 % (more preferably at least 80 %, particularly at least 90 %) of the isocyanate groups of monomeric diisocyanates, whereas for
  • prepolymeric diisocyanates and polyisocyanates bearing more than two isocyanate groups more than 70 % of the isocyanate groups may remain in unblocked (free) state.
  • the isocyanate groups of the individual components of the mixture get blocked usually in such ratios under conventional blocking conditions.
  • hydrocarbyl as used in the definition of groups X, R 10 and R 11 covers alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and homocyclic aryl groups and combined groups formed from two or more of these groups (examples of such combined groups are arylalkyl and cycloalkyl-alkyl groups), said hydrocarbyl groups bearing optionally one or more non isocyanate-reactive substituents, such as halo, alkoxy or tertiary amino groups. Similar considerations apply to the hydrocarbyl portions of the monohydroxy compounds mentioned in point (c) above, with the proviso that at least one nonaromatic unsaturated carbon-carbon bond must be present. Of the combined groups which may stand for X hydrocarbyl groups bearing a halo, hydrocarbyl-oxy, hydrocarbyl-carbonyl or hydrocarbyl-carbonyl-oxy substituent are mentioned as examples.
  • ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent preferred: ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent; cyclic ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent; cyclic ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent; cyclic ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent; cyclic ⁇ , ⁇ -diketones and derivatives thereof bearing an X substituent; cyclic ⁇ , ⁇ -
  • esters of ⁇ , ⁇ , ⁇ -diketomonocarboxylic acids esters of ⁇ , ⁇ -diketomonocarboxylic acids
  • mixed esters of ⁇ , ⁇ -ketocarboxylic acids and vinylcarboxylic acids formed with glycols diesters of
  • ketophosphonates ⁇ , ⁇ -ketoacid ester phosphonates; ⁇ , ⁇ -diphosphonates.
  • Y represents hydrogen, halo, phenyl, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, phenyl-(C1-C6 alkyl), (C1-C6 alkoxy)-(C1-C6 alkyl), (C1-C6 alkoxy)-carbonyl
  • R and R 1 each stand for
  • C2-C10 alkenyl bearing optionally a phenyl substituent may also represent (C1-C6 alkoxy)-carbonyl or a group of formula -0-(AIk-O) n -CO-AIk 2 or -0-(AIk-O) n -(AIk 1 -O) n -AIk 2 , and in these latter groups n amounts to 1-600, AIk 2 stands for C1-C6 alkyl or C2-C6 alkenyl and AIk and AIk 1 each stand for C1-C6 alkylene which may be the same or different, or
  • R and R 1 form together a C2-C4 alkylene chain or a methylenedioxy group which may bear optionally one or more C1-C6 alkyl substituent(s), or
  • R and Y form together a C2-C4 alkylene or C2-C4 alkyleneoxy chain which may bear optionally one or more C1-C6 alkyl substituent(s); furthermore compounds of formulae (III) and (IV),
  • R 6 and R 7 each stand for C1-C6 alkyl and R ⁇ represents C1-C6 alkyl, C1-C6
  • acetoacetate cinnamylalcohol acetoacetate, 3-methyl-2-buten-1-ol acetoacetate, glycerol-dimethacrylate acetoacetate, diethyl allylmalonate, diethyl isobutyrylidene- malonate and diethyl ethoxymethylenemalonate.
  • AMH compounds and substituted AMH compounds usable as blocking agents are known and commercially available.
  • the new or commercially not available AMH compounds and substituted derivatives thereof can be prepared by methods analogous to those utilized in the production of structurally related known compounds.
  • Preferred representatives of the unsaturated oximes of formula (I) usable as blocking agents are as follows: benzylideneacetone oxime, benzylideneacetophenon oxime, diacetonealcohol acrylate oxime, diacetonealcohol methacrylate oxime,
  • oxime mesityloxide oxime, citronellal oxime, phoron oxime and isophoron oxime.
  • the majority of the unsaturated oximes of formula (I) usable as blocking agents are known and commercially available.
  • the new or commercially not available oximes of formula (I) can be prepared by methods well known from the literature by reacting the appropriate oxo compound with hydroxylamine.
  • Preferred representatives of the unsaturated monohydroxy compounds mentioned in point (c) above are as follows: cinnamyl alcohol, citronellol, glycerol dimethacrylate, ner.olidol, 3-methyl-2-buten-1-ol, eugenol, isoeugenol; ethyl-hydr- oxyethyl-fumarate, ethyl-hydroxyethyl-itaconate, ethyl-hydroxyethyl-maleate, the respective hydroxypropyl compounds and structurally related other hemiesters (such as methyl, isopropyl, butyl etc.
  • the majority of the unsaturated monohydroxy compounds mentioned above are known and commercially available compounds.
  • the new or commercially not available compounds can be prepared by prepared by methods analogous to those utilized in the production of structurally related known compounds.
  • Blocking agents other than those listed in points (a) to (c) above, which may block up to 50 % of the blocked isocyanate groups, may be selected from compounds comprising isocyanate-reactive -OH, -SH or -NH- groups, with the ex ⁇ ception of the unsaturated monohydroxy compounds mentioned in point (c) above. Examples of the main types of such compounds are listed below: phenols other than those mentioned in point (c) above, such as phenol, toluene and cresols;
  • lactams such as caprolactam, valerolactam and butyrolactam
  • alcohols other than those mentioned in point (c) above such as methanol, ethanol,
  • mercaptans such as butyl mercaptan and hexyl mercaptan
  • acid amides such as acetanilide, acrylamide, methacrylamide and acetamide
  • imides such as succinimide, phthalimide and maleinimide
  • amines such as diphenyl amine, phenyl-naphthyl amine and butyl amine - it should be noted here that amines are regarded nowadays as objectionable from the aspects of environment protection thus it is preferred to use them in minor amounts; imidazoles; pyrazoles, such as dimethyl pyrazole; ureas; carbamates; imines, such as ethylene imine; hydroxamic acids and esters thereof, such as benzyl-methacryl hydroxamate.
  • R 10 and R 11 each represent a hydrocarbyl group or one of them may also represent hydrogen, or R 10 and R 11 form, together with the adjacent carbon atom, a cyclic hydrocarbyl group, with the proviso that at least one of R 10 and R 11 comprises at least a single nonaromatic unsaturated carbon-carbon bond,
  • the blocking agent is any of acetoacetic acid-ethyl- eneglycol acrylate (AAEA), acetoacetic acid-ethyleneglycol methacrylate (AAEMA),
  • acetoacetic acid-propyleneglycol acrylate AAPA
  • acetoacetic acid-propyleneglycol acrylate AAPA
  • AAPMA acetoacetic acid-butyleneglycol acrylate
  • AABA acetoacetic acid-butyleneglycol methacrylate
  • AABMA acetoacetic acid-butyleneglycol methacrylate 1 ethyl acetoacetate, diethyl malonate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate
  • this blocking agent blocks less than 50 % of the blocked isocyanate groups and the remainder of the at least 50 % of the blocked isocyanate groups is blocked with at least one other blocking agent as defined in points (a) to (c) above.
  • a particular group of new compounds comprises polyisocyanates of mixed blocking, i.e. polyisocyanates wherein at least 30 % of the isocyanate groups are blocked and at least 50 % of the blocked isocyanate groups are blocked with a blocking agent as defined in points (a) to (c) above, whereas up to 50 % of the blocked isocyanate groups are blocked with a different blocking agent listed in points (a) to (c) above or with a blocking agent other than those defined in points (a) to (c) above cmprising an isocyanate-reactive -OH, -SH or -NH- group or with a mixture of such compounds.
  • the invention also relates to these new compounds.
  • the new blocked polyisocyanates can be prepared by methods utilized for the preparation of known blocked polyisocyanates in such a way that the non-blocked polyisocyanate is reacted, optionally in the presence of a catalyst, with a calculated amount of the blocking agent or with a calculated amount of a blocking agent mixture of predetermined composition. Examples for the preparation of blocked polyisocyanates and for the new blocked polyisocyanates will be given later on.
  • diisocyanates too) used in the preparation of known polyisocyanate/polysilicic acid s ⁇ stems can be used with the proviso that at least 5 % by weight of the polyisocyanate must be used in a blocked form as defined above.
  • polyisocyanates also comprising diisocyanates
  • the MDI (methylene-diphenyl-diisocyanate) compound family should be mentioned at the first place, being the most important member of polyurethane chemistry produced worldwide in the highest amounts.
  • Commercially available members of this family are the so-called monomeric MDI's, which comprise two aromatic rings, such as pure 4,4'-MDI, various mixtures of 4,4'-MDI and 2,4'-MDl, furthermore the more complex isomeric and oligomeric mixtures, such as the crude MDl (CR-MDI) series.
  • the viscosity of the members of this latter series varies within about from 150 mPa.s to about 3000 mPa.s.
  • P-MDI polymeric MDI's
  • diisocyanates prepared from polyether and/or polyester polyols wherein one MDI molecule, each, has been reacted with the two terminal -OH groups.
  • the properties of the resin can be controlled within wide limits by the appropriate selection of the molecular weight (chain length) and/or chemical structure of the starting polyol.
  • polyether prepolymers formed from polyols when used in higher amounts, also exert cocatalytic effects; despite of this fact these compounds are classified here not into the group of optionally used other cocatalysts but into the group of polyisocyanates.
  • tolylene-diisocyanate (TDI) and prepolymers formed therefrom analogously to the MDI derivatives can also be used in the process of the invention.
  • the weight ratio of polyisocyanates to water glass may vary within the limits well known from the literature.
  • the polyisocyanate : water glass weight ratio may be generally 1 :(0.1-1.5), preferably 1:(0.2-1), particularly 1 -.(0.3-0.8).
  • the reaction of polyisocyanates and water glass can be performed optionally in the presence of one or more additives and/or auxiliary agents conventionally used in the preparation of polyisocyanate/ polysilicic acid resins.
  • additives and/or auxiliary agents may be those listed in the above references, of which the following ones are mentioned as examples: borax, mono- and polyols, plasticizers, diluents, fire retardants, antifoaming agents, adhesion-increasing agents, tixotropic agents, thickeners, pigments, colourants, mono-, di- or polyester-type compounds which are partially or fully built into the resin
  • AMH compounds and substituted AMH compounds used as blocking agents are effective cocatalysts of the polyaddition reactions leading to the formation of the polyisocyanate/polisilicic acid based resin matrix. These compounds are also encompassed by the group of cocatalysts.
  • polyisocyanates blocked with an AMH compound and/or substituted AMH compound are utilized, it is sometimes not required to add a further cocatalyst to the reaction mixture, because the AMH or substituted AMH compound which liberates upon deblocking is sufficient for this purpose.
  • AMH compounds ensure a relatively quick gelling, whereas substituted AMH compounds ensure a relatively slow gelling.
  • processability period of the resin-forming components can be controlled within very wide limits.
  • AMH compounds and substituted AMH compounds or polyisocyanates blocked with these types sometimes no plasticizer is required.
  • the cocatalyst is an AMH compound (which may be released from a polyisocyanate blocked with an AMH compound) and
  • a plasticizer and/or an other cocatalyst ensuring a more prolonged processability period should also be added to the mixture.
  • Preferred representatives of said other cocatalysts are
  • the amount of the blocked polyisocyanate in question should be kept around the lower limits (5-20 % by weight related to the total weight of polyisocyanates).
  • the cocatalyst is a substituted AMH compound (which may liberate from a polyisocyanate blocked with such a compound) and the processability period attainable using this compound should be shortened, it is preferred to add to the mixture an other known cocatalyst which ensures short processability period.
  • any of the blocking agents, additives and auxiliary agents comprises one or more unsaturated bonds capable of radical polymerization
  • an inorganic and/or organic free radical initiator character representatives of which are the peroxy compounds
  • the free radical initiator can be introduced either as a separate component or as a master batch formed with additional components which are compatible with the initiator.
  • master batch “A” comprises water glass in admixture with other water glass-compatible additives
  • master batch “B” comprises the polyisocyanates in admixture with other polyisocyanate-compatible additives
  • master batch “C” comprises the free radical initiator(s) in admixture with a part of additives and/or auxiliary agents compatible with them.
  • compositions of the individual master batches are given as weight percentages, and the mixing ratios of the master batches are given as a volume ratios.
  • the densities required to recalculate these figures are given in the examples.
  • B is the amount of hydrochloric acid solution consumed when titrating the blind (ml)
  • S is the amount of hydrochloric acid solution consumed when titrating the sample
  • N is the titer of the hydrochloric acid solution
  • W is the weight of the introduced sample (g)
  • ECI ethyl cinnamate (capable of radical polymerization at the unsaturated carbon-carbon bond)
  • EGDMA ethyleneglycol-dimethyl acrylate (capable of radical polymerization at the unsaturated carbon-carbon bond)
  • BEA benzylidene acetone (capable of radical polymerization at the unsaturated carbon-carbon bond)
  • DEF diethyl fumarate (capable of radical polymerization at the unsaturated carbon-carbon bond)
  • PP-4 s1000 TDI-based prepolymer prepared by reacting 1 mole of polypropylene glycol 425 with 2 moles of Ongronat T80
  • the Ongronat type polyisocyanates are industrial products of Borsodchem Rt, Hungary.
  • the TMXDI type polyisocyanate is c/> U3 r ⁇ produced by Citec.
  • the PP-2 - PP-6 type prepolymers are produced by Polinvent Kft, Hungary.
  • Exolite OP 55 is produced by m
  • B11 Blocked PP-3 (see Table 2) (blocking agents: 1 mole of cyclohexanedione + 1 mole of DEECMP)
  • Master batch "A” (weight: 155 g; volume: 100 ml) 100 % by weight of Betol 3P type sodium water glass produced by Woellner Silikat
  • Composition for variant Ref.1 (see Table 4): Reactive components: 70 % by weight of Ongronat CR 30-40 type polymeric MDI (marked with P-MDI in
  • plasticizer and antifoaming agent its density is 1.12 g/cm 3
  • Ongronat CR 30-40 type polymeric MDI (marked with P-MDI in
  • additives 10 % by weight of tritolyl phosphate (marked with TTF) produced by Bayer; it is a known phosphoric ester type plasticizer and fire retardant (and optionally a cocatalyst, too), its density is 1.20 g/cm 3 5 % by weight of tributyl phosphate (marked with TBF) produced by Bayer; it is a plasticizer and antifoaming agent, its density is 1.12 g/cm 3 10 % by weight of tributyl-acetyl citrate (marked with TRBAC) produced by Merck; it is a plasticizer
  • Examples 1 and 2 serve for comparison purposes.
  • Master batch "A” was admixed with master batch “B”, variant Ref.1 in Example 1 and with master batch “B”, variant Ref.2 in Example 2.
  • master batch "C” composed of 50 % by weight of Fivenox B50G (a mixture of 50 % by weight of benzoyl peroxide and 50 % by weight of dicyclohexyl phthalate; produced by F ⁇ nomvegyszer Kft, Hungary) and of 50 % by weight of benzyl-butyl phthalate (solvent and plasticizer), was prepared, and when master batches "A” and “B” were weighed together, 2 % by weight (related to the total weight of the resin- forming mixture) of master batch “C” were also added, and the three master batches were homogenized as described above.
  • the introduced amount of master batch "C” composed of 50 % by weight of Fivenox B50G (a mixture of 50 % by weight of benzoyl peroxide and 50 % by weight of dicyclohexyl phthalate; produced by F ⁇ nomvegyszer Kft, Hungary) and of 50 % by weight of benzyl-butyl phthalate (solvent and
  • organic free radical initiator (benzoyl peroxide)
  • master batch "B” 300 g (240 ml) of master batch "B" was admixed with master batch "A” of the amount and composition as indicated in Examples 1-18.
  • the compositions of master batches "B” were as follows:
  • additive a plasticizer capable of radical polymerization
  • Example 20 10 % by weight of Ongronat PA-08 (PP1) type MDI-based polyether prepolymer
  • B15 blocked polyisocyanate also comprising 30 % by weight of
  • additive a plasticizer capable of radical polymerization
  • additive a plasticizer capable of radical polymerization
  • additive a plasticizer capable of radical polymerization
  • polyisocyanate served as plasticizer in master batch "B". These receptures are marked with code numbers 3.5 to 3.8 in Table 4.
  • master batches "A” and “B” 2 % weight of master batch "C", composed of 50 % by weight of diallyl phthalate and 50 % by weight of tertbutyl-perbenzoate, were also added, which means that 1 % by weight of an organic free radical initiator was introduced into the resin-forming mixture with master batch "C".
  • the unsaturated components were simultaneously subject-ed to radical polymerization, like in Examples 3, 5, 7, 8, 10-14 and 16-18.
  • the processability period of the resin-forming mixture was 190 minutes for Example 19, 210 minutes for Example 20, 100 minutes for Example 21 and 120 minutes for Example 22.
  • test pieces poured into the mould were subjected to heat treatment at 80 0 C for 8 hours and then at 10O 0 C for 2 hours.
  • the bending/tensile force was measured 1 week after heat treatment.
  • the bending/tensile force was 2800 N for Example 19, 3100 N for Example 20, 2700 N for Example 21 and 2900 N for Example 22; thus in all instances much exceeded those measured in Examples 1- 18, which results in part from the further deblocking under heat treatment (release of the blocking agent which splits off at higher temperatures) followed by radical poly ⁇ merization and in part from further polyaddition reactions.
  • Example Blocked polyisocyaates Non-blocked polvisocvanates Code of Pot life Bending/tensile No. Code Amount in master Type Amount in master recepture min. forces, N batch "B”, % by wt. batch “B”, % by wt. 1 day 1 week

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  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un procédé de préparation de résines à base de polyisocyanate/acide polysilicique selon lequel on fait réagir un ou plusieurs polyisocyanates avec du silicate de sodium, facultativement en présence d'un ou plusieurs additifs et/ou agents auxiliaires traditionnellement utilisés dans la préparation de résines à base de polyisocyanate/acide polysilicique. Selon l'invention, on remplace au moins 5 % en poids du polyisocyanate par un polyisocyanate dans lequel au moins 30 % des groupes isocyanate sont bloqués, et au moins 50 % des groupes isocyanate bloqués sont bloqués avec: (a) un composé comprenant des unités strucurelles avec deux hydrogènes mobiles à caractère acide et des dérivés de ce dernier dans lesquels l'un des hydrogènes mobiles est remplacé par un substituant X, où X représente un groupe halo, hydrocarbyle, hydrocarbyl-oxy, hydrocarbyle-carbonyle ou hydrocarbyl-oxy-carbonyle ou un groupe combiné formé d'au moins deux des groupes précités; (b) un oxime insaturé de la formule (I) dans laquelle R10 et R11 représentent chacun un groupe hydrocarbyle ou l'un d'eux peut également représenter un hydrogène, ou R10 et R11 forment ensemble avec l'atome de carbone adjacent un groupe hydrocarbyle cyclique, à condition que R10 et/ou R11 comprenne(nt) une liaison carbone-carbone insaturée non aromatique; (c) un composé renfermant un unique groupe OH réactif avec l'isocyanate lié à un atome de carbone et au moins une liaison carbone-carbone insaturée non aromatique; ou avec une quelconque combinaison de ces derniers. L'invention se rapporte également aux nouveaux polyisocyanates bloqués utilisés selon le procédé précité.
PCT/HU2005/000094 2004-09-02 2005-09-01 Procede de preparation de resines de polyaddition et de resines hybrides a base de polyisocyanate/acide polysilicique au moyen de polyisocyanates bloques et polyisocyanates bloques utilises selon ce procede Ceased WO2006024885A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112005001991T DE112005001991T5 (de) 2004-09-02 2005-09-01 Verfahren zur Herstellung von Polyadditions- und Hybridkunstharzen auf Basis von Polyisocyanat/Polykieselsäure unter Verwendung blockierter Polyisocyanate und Verfahren zur Herstellung der in dem Verfahren verwendbaren blockierten Polyisocyanate

Applications Claiming Priority (2)

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HU0401799A HU227574B1 (hu) 2004-09-02 2004-09-02 Eljárás poliizocianát/polikovasav alapú poliaddíciós és hibrid mûgyanták elõállítására blokkolt poliizocianátok felhasználásával és az eljárásban felhasználható blokkolt poliizocianátok
HUP0401799 2004-09-02

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2008033348A1 (fr) * 2006-09-14 2008-03-20 Bayer Materialscience Llc Nouveaux diisocyanates liquides préparés par modification avec des composés de 1,3-dicarbonyle
WO2016035328A1 (fr) * 2014-09-01 2016-03-10 キヤノン株式会社 Composé, dispersant et toner
US9546122B2 (en) 2013-03-11 2017-01-17 Ndsu Research Foundation Monomers and polymers derived from natural phenols
WO2017200054A1 (fr) * 2016-05-20 2017-11-23 三井化学株式会社 Composition durcissable, matériau de revêtement, matériau de revêtement pour batterie solaire, matériau de revêtement pour feuille de support de batterie solaire, adhésif, adhésif pour batterie solaire, adhésif pour feuille de support de batterie solaire, procédé de fabrication de feuille, et agent de durcissement
CN118852954A (zh) * 2024-09-25 2024-10-29 江苏甬金金属科技有限公司 一种奥氏体抗菌不锈钢材料及其加工工艺

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
EP4289878A1 (fr) 2022-06-08 2023-12-13 Evonik Operations GmbH Système à un composant comprenant des prépolymères de polyuréthane bloqués

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DE2639491B1 (de) * 1976-09-02 1978-02-02 Hoechst Ag Einbrennlacke auf der Grundlage von freie Hydroxylgruppen enthaltenden Polyester- und/oder Alkydharzen und blockierten Polyisocyanaten
US4315091A (en) * 1979-04-10 1982-02-09 Bayer Aktiengesellschaft Coatings for thermoplastics
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EP0424713A2 (fr) * 1989-10-12 1991-05-02 Vianova Kunstharz Aktiengesellschaft Durcisseurs pour liants de lacque, plus spécialement pour des lacques électrodéposables, leur procédé de préparation et leur utilisation pour des lacques
JPH1025331A (ja) * 1996-07-12 1998-01-27 Dainippon Ink & Chem Inc 熱硬化性樹脂組成物
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GB1483270A (en) * 1973-11-30 1977-08-17 Bayer Ag Inorganic-organic plastics
DE2639491B1 (de) * 1976-09-02 1978-02-02 Hoechst Ag Einbrennlacke auf der Grundlage von freie Hydroxylgruppen enthaltenden Polyester- und/oder Alkydharzen und blockierten Polyisocyanaten
US4315091A (en) * 1979-04-10 1982-02-09 Bayer Aktiengesellschaft Coatings for thermoplastics
US4444954A (en) * 1982-09-30 1984-04-24 The Sherwin-Williams Company Water reducible quaternary ammonium salt containing polymers
EP0424713A2 (fr) * 1989-10-12 1991-05-02 Vianova Kunstharz Aktiengesellschaft Durcisseurs pour liants de lacque, plus spécialement pour des lacques électrodéposables, leur procédé de préparation et leur utilisation pour des lacques
JPH1025331A (ja) * 1996-07-12 1998-01-27 Dainippon Ink & Chem Inc 熱硬化性樹脂組成物
WO2003033605A1 (fr) * 2001-10-11 2003-04-24 Basf Coatings Ag Susbtance de revetement non aqueuse constituee d'un composant unique, durcissable thermiquement et par rayonnement actinique, son procede de production et son utilisation

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008033348A1 (fr) * 2006-09-14 2008-03-20 Bayer Materialscience Llc Nouveaux diisocyanates liquides préparés par modification avec des composés de 1,3-dicarbonyle
US9546122B2 (en) 2013-03-11 2017-01-17 Ndsu Research Foundation Monomers and polymers derived from natural phenols
US9630897B2 (en) 2013-03-11 2017-04-25 Ndsu Research Foundation Monomers and polymers derived from natural phenols
WO2016035328A1 (fr) * 2014-09-01 2016-03-10 キヤノン株式会社 Composé, dispersant et toner
US9505723B2 (en) 2014-09-01 2016-11-29 Canon Kabushiki Kaisha Compound, dispersant and toner
WO2017200054A1 (fr) * 2016-05-20 2017-11-23 三井化学株式会社 Composition durcissable, matériau de revêtement, matériau de revêtement pour batterie solaire, matériau de revêtement pour feuille de support de batterie solaire, adhésif, adhésif pour batterie solaire, adhésif pour feuille de support de batterie solaire, procédé de fabrication de feuille, et agent de durcissement
US11421135B2 (en) 2016-05-20 2022-08-23 Mitsui Chemicals, Inc. Curable composition, coating material, solar cell coating material, solar cell back sheet coating material, adhesive, solar cell adhesive, solar cell back sheet adhesive, producing method of sheet, and curing agent
CN118852954A (zh) * 2024-09-25 2024-10-29 江苏甬金金属科技有限公司 一种奥氏体抗菌不锈钢材料及其加工工艺

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HUP0401799A2 (en) 2006-06-28
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HU0401799D0 (en) 2004-11-29

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