WO1992007823A1 - Isocyanates oxime-bloques a base d'isocyanate aliphatique insature tmir (meta) - Google Patents

Isocyanates oxime-bloques a base d'isocyanate aliphatique insature tmir (meta) Download PDF

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Publication number
WO1992007823A1
WO1992007823A1 PCT/US1991/007433 US9107433W WO9207823A1 WO 1992007823 A1 WO1992007823 A1 WO 1992007823A1 US 9107433 W US9107433 W US 9107433W WO 9207823 A1 WO9207823 A1 WO 9207823A1
Authority
WO
WIPO (PCT)
Prior art keywords
isopropenyl
carbamate
ketoxime
dimethyl benzyl
methyl
Prior art date
Application number
PCT/US1991/007433
Other languages
English (en)
Inventor
Frank C. Briden
Melvin Kaplan
Rose M. Trapasso
Original Assignee
Allied-Signal Inc.
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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Publication of WO1992007823A1 publication Critical patent/WO1992007823A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/728—Polymerisation products of compounds having carbon-to-carbon unsaturated bonds and having isocyanate or isothiocyanate groups or groups forming isocyanate or isothiocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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

Definitions

  • This invention relates to novel oxime blocked isocyanates based on TMI® (META) unsaturated aliphatic isocyanate. Specifically, the invention relates to novel compositions of methyl isobutyl ketoxime-N-(m- isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate, methyl amyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate, di-isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ - dimethyl benzyl) carbamate and di-isopropyl ketoxime-N- (m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate. These compounds are useful in a variety of industrial applications including coatings, adhesives and tackifiers, textile fibers and finishes, speciality plastics and rubber applications and agricultural chemical formulations.
  • TMI® uns
  • Blocked isocyanates are frequently used, for example, in high solids coating formulations and also in powder coating formulations to improve the stability of the formulation on storage.
  • the invention relates to novel compositions of methyl isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate, methyl a yl ketoxime-N-(m- isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamatye, di- isobutyl ketoxime N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate and di-isopropyl ketoxime-N-(m- isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate which are useful in a variety of industrial applications including coatings, adhesives and tackifiers, textile fibers and finishes, specialty plastics and rubber applications and agricultural chemical formulations.
  • TMI isocyanate novel oxime- blocked isocyanaytes based on TMI® (META) unsaturated aliphatic isocyanate* (hereinafter referred to as "TMI isocyanate”) have been discovered.
  • TMI isocyanate is a known material which is commercially available through American Cyanamid Co. Alternately, it may be synthesized by known techniques.
  • TMI isocyanate appearance colorless liquid molecular formula : C 13 H 15 NO molecular weight: 201.26
  • NCO content 20.9% (theoretical) boiling point: 270"C (latm) vapor pressure: 2mm Hg (100°C) viscosity: 3 cp (27°C) density: 1.01 g/ml solubility: vinyl monomers, most common solvents TMI isocyanate is a bifunctional monomer containing a tertiary aliphatic isocyanate group and a reactive double bond.
  • novel oxime-blocked TMI isocyanates of this invention may be prepared by reacting TMI isocyanate with the appropriate oxime.
  • R and R 1 comprise a methyl and isobutyl group respectively and the resulting oxime-blocked TMI isocyanate is methyl isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • R and R 1 comprise a methyl group and amyl group respectively and the resulting oxime-blocked TMI isocyanate is methyl amyl ketoxime-N-(m- isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • R and R 1 each comprise an isobutyl group and the resulting oxime-blocked TMI isocyanate is di-isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • R and R 1 each comprise an isobutyl group and the resulting oxime-blocked TMI isocyanate is di-isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • R and R 1 each comprise an isobutyl group and the resulting oxime-blocked TMI isocyanate is di-isobutyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • R and R 1 each comprise an isobutyl group and the resulting oxime-blocked TMI isocyanate is di-isobutyl keto
  • R 1 each comprise an isopropyl group and the resulting oxime-blocked TMI isocyanate is di-isopropyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • TMI isocyanate is di-isopropyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • the novel oxime-blocked TMI isocyanates of this invention may be blended together or with other known oxime-blocked TMI isocyanates depending on the properties desired.
  • blends may be used to improve the working viscosity during polymerization reactions with other reactants or to increase the solids content in order to reduce the level of volatile organic components.
  • the blends may be prepared in situ or by physically blending the oxime-blocked isocyanates together.
  • the oxime-blocked TMI isocyanates may be combined in any proportions.
  • Oxime-blocked TMI isocyanates are unqiue molecules.
  • the double bond in the oxime blocked TMI isocyanate undergoes free radical polymerization readily with various unsaturated monomers yielding copolymers with pendant, isocyanate functionality.
  • the resulting polymer is stable in the presence of a hydroxyl functionality (i.e. a polyol) , an amine functionality (i.e. a polyamine) and water and may be used 1.) as is, 2.) in a solvent such as a ketone, ester or aromatic or 3.) in a dispersion and/or 4.) in an emulsion in water.
  • a hydroxyl functionality i.e. a polyol
  • an amine functionality i.e. a polyamine
  • the blocked TMI isocyanate that has undergone copolymerization with, for example, acrylates, hydroxy acrylates, methyl methacrylates, hydroxy methacrylates, acrylonitrile or styrene can be belnded with a polyol (i.e. acrylic, polyester or polyether) or a polyamine (i.e. Jeffamine T-403*) to form a stable one package coating, adhesive or elastomer. Curing is effected by liberating the free isocyanate group at elevated temperature for subsequent reaction with the polyol or polyamine.
  • the reaction is schematically represented as follows for methyl amyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate.
  • AEROSOL® OT surfactant 2 1.38 n-Octyl mercaptan 0.78
  • AEROSOL® OT surfactant is a registered trademark of American Cyanamid Co.
  • the flask is maintained at 25°C by external water cooling.
  • the pH is 6.6 and the measured soldis are 44.1%. No coagulu was obtained.
  • the results indicate that methyl amyl ketoxime-N-(m- isopropenyl- ⁇ , ⁇ -dimethyl benzyl) carbamate can be used to produce one package coatings which are stable.
  • Example 5 The experiment outlined in Example 5 above is repeated except that the oxime blocked TMI isocyanates listed in Table II below are substituted for methyl amyl ketoxime-N-(m-isopropenyl- ⁇ , ⁇ -dimethyl benzyl carbamate. The results indicate that stable one package coatings may be prepared using the oxi e- blocked TMI isocyanates listed in Table II.

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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)

Abstract

On décrit de nouvelles compositions de méthylisobutylcétoxime-N-(m-isopropényl-α, α-diméthylbenzyle) carbamate, méthylamylcétoxime-N-(m-isopropényl-α, α-diméthylbenzyle) carbamate, di-isobutylcétoxime-N-(m-isopropényl-α, α-diméthylbenzyle) carbamate et di-isopropylcétoxime-N- (m-isopropényl-α, α-diméthylbenzyle) carbamate. Lesdites compositions sont utiles dans une variété d'applications industrielles, notamment pour des revêtements, des adhésifs et des colles, des fibres textiles et des apprêts, des applications de plastiques et de caoutchouc spéciales et des formulations chimiques agricoles.
PCT/US1991/007433 1990-10-26 1991-10-08 Isocyanates oxime-bloques a base d'isocyanate aliphatique insature tmir (meta) WO1992007823A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60519190A 1990-10-26 1990-10-26
US605,191 1990-10-26

Publications (1)

Publication Number Publication Date
WO1992007823A1 true WO1992007823A1 (fr) 1992-05-14

Family

ID=24422607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/007433 WO1992007823A1 (fr) 1990-10-26 1991-10-08 Isocyanates oxime-bloques a base d'isocyanate aliphatique insature tmir (meta)

Country Status (2)

Country Link
AU (1) AU8908191A (fr)
WO (1) WO1992007823A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571991A1 (fr) * 1992-05-28 1993-12-01 Kansai Paint Co., Ltd. Compositions de résine pour revêtement
WO1994008963A1 (fr) * 1992-10-20 1994-04-28 Cytec Technology Corp. Isopropenyl-alpha, alpha-dimethylbenzyl isocyanate a blocage n-hydroxysuccinimide, et ses copolymeres a autoreticulation
WO1994015984A1 (fr) * 1993-01-12 1994-07-21 Cytec Technology Corp. Composition de revetement superieur de polyurethane monobloc
US5425999A (en) * 1993-09-16 1995-06-20 Gencorp Inc. Low formaldehyde, high gel fraction latex binder
NL1006369C2 (nl) * 1997-06-20 1998-12-22 Tno Toepassing van met oxime beschermde isocyanaatgroepen bij de UV-uitharding van harsen bij lage temperatuur, alsmede UV-uithardbare harsen die dergelijke oxime-beschermde isocyanaatgroepen bevatten en de toepassing hiervan in UV-uithardbare bekledingssamenstellingen.
US6340719B1 (en) 1999-12-29 2002-01-22 3M-Innovative Properties Company Crosslinking process
FR2826366A1 (fr) * 2001-06-25 2002-12-27 Rhodia Chimie Sa Preparation d'isocyanates masques, notamment de polyisocyanates masques

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857818A (en) * 1972-09-18 1974-12-31 Cook Paint & Varnish Co Blocked polyurethane powder coating compositions
US4604439A (en) * 1985-05-28 1986-08-05 The Goodyear Tire & Rubber Company Functionalized monomers from 1-(1-isocyanato-1-methylethyl)-3- or 4-(1-methylethenyl) benzene
US4604417A (en) * 1984-12-10 1986-08-05 The Goodyear Tire & Rubber Company Polymerizable thioester synergists
EP0345748A2 (fr) * 1988-06-09 1989-12-13 MITSUI TOATSU CHEMICALS, Inc. Résines dures transparentes et procédé pour leur préparation
US4980497A (en) * 1988-06-09 1990-12-25 Mitsui Toatsu Chemicals, Inc. Monomer of carbonate ester having isopropenylphenyl group
EP0409745A1 (fr) * 1989-07-03 1991-01-23 Eastman Kodak Company Polyisocyantes bloqués par une oxime et compositions à base de polyesters ou compositions de revêtement en poudre à base de polyesters les contenant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857818A (en) * 1972-09-18 1974-12-31 Cook Paint & Varnish Co Blocked polyurethane powder coating compositions
US4604417A (en) * 1984-12-10 1986-08-05 The Goodyear Tire & Rubber Company Polymerizable thioester synergists
US4604439A (en) * 1985-05-28 1986-08-05 The Goodyear Tire & Rubber Company Functionalized monomers from 1-(1-isocyanato-1-methylethyl)-3- or 4-(1-methylethenyl) benzene
EP0345748A2 (fr) * 1988-06-09 1989-12-13 MITSUI TOATSU CHEMICALS, Inc. Résines dures transparentes et procédé pour leur préparation
US4980497A (en) * 1988-06-09 1990-12-25 Mitsui Toatsu Chemicals, Inc. Monomer of carbonate ester having isopropenylphenyl group
EP0409745A1 (fr) * 1989-07-03 1991-01-23 Eastman Kodak Company Polyisocyantes bloqués par une oxime et compositions à base de polyesters ou compositions de revêtement en poudre à base de polyesters les contenant

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571991A1 (fr) * 1992-05-28 1993-12-01 Kansai Paint Co., Ltd. Compositions de résine pour revêtement
WO1994008963A1 (fr) * 1992-10-20 1994-04-28 Cytec Technology Corp. Isopropenyl-alpha, alpha-dimethylbenzyl isocyanate a blocage n-hydroxysuccinimide, et ses copolymeres a autoreticulation
WO1994015984A1 (fr) * 1993-01-12 1994-07-21 Cytec Technology Corp. Composition de revetement superieur de polyurethane monobloc
US5981074A (en) * 1993-01-12 1999-11-09 Cytec Technology Corp. One-package polyurethane top coat composition
US5425999A (en) * 1993-09-16 1995-06-20 Gencorp Inc. Low formaldehyde, high gel fraction latex binder
US5494963A (en) * 1993-09-16 1996-02-27 Gencorp Inc. Low formaldehyde, high gel fraction latex binder
NL1006369C2 (nl) * 1997-06-20 1998-12-22 Tno Toepassing van met oxime beschermde isocyanaatgroepen bij de UV-uitharding van harsen bij lage temperatuur, alsmede UV-uithardbare harsen die dergelijke oxime-beschermde isocyanaatgroepen bevatten en de toepassing hiervan in UV-uithardbare bekledingssamenstellingen.
WO1998058980A1 (fr) * 1997-06-20 1998-12-30 Nederlandse Organistatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Utilisation de groupes isocyanate a protection oxime pour durcir des resines aux ultraviolets a basse temperature et resines durcissant aux ultraviolets et contenant ces groupes isocyanate a protection oxime et leur utilisation dans des compositions de revetement durcissant aux ultraviolets
US6340719B1 (en) 1999-12-29 2002-01-22 3M-Innovative Properties Company Crosslinking process
FR2826366A1 (fr) * 2001-06-25 2002-12-27 Rhodia Chimie Sa Preparation d'isocyanates masques, notamment de polyisocyanates masques
WO2003000763A1 (fr) * 2001-06-25 2003-01-03 Rhodia Chimie Preparation d'isocyanates masques, notamment de polyisocyanates masques

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Publication number Publication date
AU8908191A (en) 1992-05-26

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