WO1995005403A1 - Prepolymeres d'alk-1-enyl ether-polyester durcissables par rayonnement - Google Patents

Prepolymeres d'alk-1-enyl ether-polyester durcissables par rayonnement Download PDF

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Publication number
WO1995005403A1
WO1995005403A1 PCT/US1994/008203 US9408203W WO9505403A1 WO 1995005403 A1 WO1995005403 A1 WO 1995005403A1 US 9408203 W US9408203 W US 9408203W WO 9505403 A1 WO9505403 A1 WO 9505403A1
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prepolymer
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formula
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PCT/US1994/008203
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English (en)
Inventor
Jeffrey S. Plotkin
Mark M. Miller
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ISP Investments LLC
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ISP Investments LLC
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Filing date
Publication date
Priority claimed from US08/108,212 external-priority patent/US5373032A/en
Priority claimed from US08/107,867 external-priority patent/US5342860A/en
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Priority to AU73687/94A priority Critical patent/AU7368794A/en
Publication of WO1995005403A1 publication Critical patent/WO1995005403A1/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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44—Adipic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • 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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to novel prepolymers containing polyurethanyl groups and a plurality of alk-1-enyl ether crosslinking sites.
  • the invention relates to the preparation of said prepolymers and in still another aspect the invention relates to cured coatings of said prepolymers.
  • polyester coating materials can be cured thermally or by radiation in the presence of a free radical photoinitiator but these materials do not lend themselves to cationically induced polymerization. It is well recognized that thermal curing is not cost efficient and that radiation curing in free radical systems is oxygen inhibited, thus requiring an inert atmosphere or the minimizing affect of a hydrogen donating component. The later expedient is not completely satisfactory since such hydrogen donating components significantly reduce the rate of reaction. Also, it has been found that polymerization or curing in free radical systems ceases almost immediately upon removing the source of radiation; thus, the cured product often contains significant amounts of unpolymerized components.
  • Another object is to provide a polyester prepolymer containing many crosslinking sites which is rapidly cured to a high density material under mild conditions.
  • Another object of this invention is to provide a convenient process for the preparation of the present prepolymer.
  • Still another object of this invention is to provide a protective coating with a cured high density prepolymer having improved hardness, flexibility, resistance to abrasion and chemical attack.
  • A is C 2 to C 12 alkylene, C 6 to C 1 aryl, both groups optionally substituted with lower alkyl, halo lower alkyl, alkyleneoxy, halogen or aryl;
  • R x is alkylene containing from 1 to 6 carbon atoms
  • R 2 is a saturated or unsaturated divalent radical containing from 1 to 14 carbon atoms and is selected from the group of alkylene, alkenylene and arylene, each group optionally substituted with oxygen, halogen, lower alkyl and/or hydroxy and
  • R 3 is hydrogen or C ⁇ to C 6 alkyl.
  • hydroxylated alk-1-enyl ether compounds of this invention are dihydroxylated and most preferred are those wherein R-L and R 2 are lower alkyl and R 3 is hydrogen, methyl or ethyl.
  • Suitable hydroxylated alk-1-enyl ether reactants include: 1,2-dihydroxyethyl ethyl prop-1-enyl ether, 1,2-dihydroxypropyl butyl prop-1-enyl ether, 1,2-dihydroxypropyl ethyl vinyl ether, 1,3-dihydroxybutyl ethyl prop-1-enyl ether.
  • 1,3-dihydroxybutyl octyl vinyl ether 1,3-dihydroxyhexyl dodecyl but-1-enyl ether, 1,2-dihydroxybutenyl ethyl prop-1-enyl ether, 1,3-dihydroxyoctenyl ethyl vinyl ether, 1,3-dihydroxydecyl hexyl hex-1-enyl ether, 1,2-dihydroxyethyl phenyl vinyl ether, 1,3-dihydroxypropyl bromophenyl vinyl ether, 1,3-dihydroxyethyl chlorophenyl vinyl ether, 1,3-dihydroxyethyl tolyl vinyl ether, 1,3-dihydroxyethyl hydroxyphenyl vinyl ether, 1,3-dihydroxyethyl oxyphenyl vinyl ether, 1,3-dihydroxyethyl dibromohexyl vinyl ether, 1,3-dihydroxyethyl di
  • Suitable examples of reactant II include dimethyl terephthalate, dimethyl-amino-terephthalate, dimethyl-amino-isophthalate, dimethyl adipate, dibutyl malonate, diethyl oxalate, dioctyl oxalate, didecyl malonate, diethyl succinate, dimethyl glutarate, dibutyl adipate, dioctyl succinate, didodecyl phthalate, etc.
  • the transesterification reaction of I and II is carried out in the liquid phase with agitation under a blanket of an inert gas.
  • a temperature of between about 95° and about 210°C, preferably, between about 140° and about 180°C, for a period of from about 1 to about 5 hours.
  • the alcohol by-product is continuously removed by distillation; or, when the reaction is conducted in a sealed system, the by-product can be subsequently distilled off at above its vaporization temperature.
  • the mole ratio of the polyhydroxy alk-1-enyl ether (I) to diester (II) is dependent on the number of functional -OH and R 3 COO-groups in the respective reactants.
  • a -OH to R 3 COO- mole ratio of between about 1:1 and about 1:2.5 can be employed, however, a slight excess of reactant II is preferred. Further, this reaction can be carried out in the presence of from about 0.1 to about 3 wt. %, based on reaction mixture, of a catalyst such as titanium isopropoxide, titanium butoxide, titanium methoxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, potassium methoxide, potassium butoxide, sodium phenoxide, potassium phenoxide, zinc, zinc acetate, manganese acetate, dibutyl tin dioxide or another base catalyst.
  • a catalyst such as titanium isopropoxide, titanium butoxide, titanium methoxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium t-butoxide, potassium methoxide, potassium butoxide, sodium phenoxide, potassium phenoxide, zinc, zinc acetate, manganese a
  • the intermediate monomer or oligomer (III) is then reacted with an end capping compound, preferably a monohydroxy alk-1-enyl ether of the formula
  • R 4 is C ⁇ to C 6 alkylene, C 6 to C 14 arylene, xylylene, each optionally substituted with alkyl, halogen or alkenyl and R 6 is hydrogen or C ⁇ to C 4 alkyl.
  • the monohydroxy alk-1-enyl ether reactants (IV) include hydroxyhexyl prop-1-enyl ether, 1-hydroxy- dimethylene-propylene vinyl ether, hydroxyethyl-prop-1- enyl ether, hydroxycyclohexyl vinyl ether, hydroxybutyl- vinyl ether, hydroxybutyl but-1-enyl ether, hydroxypropyl prop-1-enyl ether, ⁇ -hydroxyoctyl-vinyl ether, 2-hydroxypropyl prop-1-enyl ether, hydroxyphenyl prop-1-enyl ether, hydroxy tolyl but-1-enyl ether, hydroxybutyl but-1-enyl ether, the vinyl ether or prop-1-enyl ether of hydroxymethyl benzyl alcohol, cyclohexane dimethanol mono vinyl ether, etc.
  • the end capping reaction involving reactant IV is carried out under conditions similar to the reaction between reactants I and II including the presence
  • the Brookfield viscosity of the liquid prepolymeric product which ranges from about 5,000 to about 500,000 cps, is inversely affected by the amount of end capping diluent added.
  • the above reactions can be effected in a single stage or in a two-stage process.
  • the polyhydroxylated alk-1-enyl ether, the difunctional ester and the end capping component diluent are contacted with constant agitation under a pressure of from about atmospheric to about 20 psig.
  • the cationically curable prepolymer of this invention exhibits many advantages over the polyester prepolymers of the art in that the present prepolymer offers an increased number of crosslinking sites, which, when polymerized, provides a coating of extremely high density having excellent resistance to abrasion and chemical attack.
  • the present prepolymer obtained in a liquid state, allows for improved uniform coating applications on a substrate of metal, plastic, ceramic, wood, paper, glass, etc.
  • the cured prepolymer also maintains flexibility resulting from their many unsaturated sites where polymer units are extended by addition to double bonds. Further, coatings of the present cured polymer preserve the finish of a painted surface, e.g. as automotive, aircraft and ship coatings.
  • the present prepolymers III are prepared for curing by the addition of a cationic initiator and between about 10 and about 80 wt. % of a diluent.
  • the present prepolymers which are useful as high density curable molding resins and highly solvent resistant adhesive coatings.
  • the product can be diluted with a suitable solvent, applied to a surface in a thickness of between about 0.1 to about 5 mils and cured by exposure to a source of radiation such as UV light, electron beam, laser emission. X-rays, gamma-rays, etc.
  • an onium photoinitiator such as, for example a diary1 iodonium salt, a polyphenyl sulphonium fluoride, a triaryl sulphonium salt and the like.
  • Curing by UV light exposure is generally effected at between about 300 and about 3,000 milli joules/cm 2 . Radiation curing of the prepolymer is extremely rapid, so that a coated substrate can be processed at a rate of up to 700 feet/sec and; whereas curing by heat requires a longer treatment up to about 2 hours.
  • Examples of the reactive diluents employed in formulations of the present curable products are divinyl ether of triethylene glycol (DVE) and cyclohexane dimethanol divinyl ether (CHVE) , the propenyl propylene ether of propylene carbonate (PEPC) , tetrahydrofurfuryl vinyl ether and epoxides, e.g. 3,4-epoxycyclohexyl-3,4-epoxycyclohexane.
  • the present coatings are clear, colorless, flexible films which find many applications as indicated above.
  • EXAMPLE 4 The products of Examples 1-3 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) . The resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table. TABLE
  • EXAMPLE 1 H 100 1/8 >200 64 880 6.4
  • Example 5 The procedure of Example 5 was repeated using 7.8 grams of 1,2-propanediol in place of 1-propenyloxy propanediol.
  • the product of this example was identified as having the formula
  • Example 6 The procedure of Example 6 was repeated using 15.5 grams of 1,2-propanediol in place of 1-propenyloxy propanediol.
  • the product of this example is identical to that obtained in Example 7
  • Example 6 The procedure of Example 6 was repeated using 37.06 grams of n-butanol in place of hydroxybutyl vinyl ether. The product of this example
  • CH 2 OCH CHCH 3 CH 3 possesses a non-reactive end-capping group but would retain internal cross-linking properties because of the reactive-chain extender. However, this product exhibits poor pencil hardness, little or no adhesive properties and low tensile properties.
  • Examples 5-9 were tested as radiation curable formulations containing 49% of the respective products, 49% of divinyl ether of triethylene glycol and 2% of triphenyl sulfonium salt initiator (FX-512) .
  • the resulting formulations were each coated on an aluminum panel and subjected to curing using a 400 mJ/cm2 PPG model QC-1202A/N U.V. processor. The coating performance of each of these formulations was compared and the results summarized in the following Table.
  • Example 5 is repeated, except that 3 moles of -hydroxybutyl vinyl ether, 2 moles of toluene diisocyanate and 0.8 grams of dibutyl tin dilaurate are substituted for the amounts shown therein (a 4-fold excess) .
  • the product of this reaction has the formula

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des prépolymères séquencés d'alk-1-enyl ether-polyester qui sont durcissables par rayonnement initié par voie cationique et qui sont définis par la formule (I) dans laquelle m vaut entre 1 et 25; A est alkylène C2-C12, arylène C6-C14, ces deux groupes étant éventuellement substitués avec alkyle inférieur halo-alkyle inférieur, alkylèneoxy, halogène, aryle ou bien NHA'NH où A' est identique à A; R1 est akylène contenant de 1 à 6 atomes de carbone; R2 est un radical bivalent saturé ou insaturé contenant de 1 à 14 atomes de carbone et est choisi dans le groupe composé d'alkylène, alcénylène et arylène, chaque groupe étant éventuellement substitué avec oxygène, halogène, alkyle inférieur et/ou hydroxy; R5 est hydrogène ou alkyle C1-C6; R4 est alkylène C1-C6, arylène C6-C14, phénylène ou xylylène à substitution alkyle inférieur, et R6 est hydrogène ou alkyle C1-C4. L'invention concerne également un procédé de préparation et de durcissement du prépolymère précité, ainsi que l'utilisation de ce prépolymère durci comme revêtement protecteur souple et dur présentant une densité élevée et une résistance supérieure à l'abrasion et à l'attaque chimique.
PCT/US1994/008203 1993-08-18 1994-07-20 Prepolymeres d'alk-1-enyl ether-polyester durcissables par rayonnement Ceased WO1995005403A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73687/94A AU7368794A (en) 1993-08-18 1994-07-20 Radiation curable alk-1-enyl ether polyester prepolymers

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/108,212 US5373032A (en) 1993-08-18 1993-08-18 Radiation curable alk-1-enyl urethanyl prepolymers
US08/108,212 1993-08-18
US08/107,867 1993-08-18
US08/107,867 US5342860A (en) 1993-08-18 1993-08-18 Radiation curable alk-1-enyl ether polyester prepolymers

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122282A1 (fr) * 2000-01-24 2001-08-08 Schenectady International, Inc. Masses électriquement isolantes à faible émission

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485733A (en) * 1966-03-02 1969-12-23 Ppg Industries Inc Highly radiation-sensitive telomerized polyesters
US4091141A (en) * 1977-04-28 1978-05-23 Armstrong Cork Company Photocurable elastomeric polyester composition, fibrous articles impregnated therewith and method of making same
US4749807A (en) * 1987-02-17 1988-06-07 Allied-Signal Inc. Vinyl ether terminated ester oligomers
US4751273A (en) * 1986-08-19 1988-06-14 Allied-Signal, Inc. Vinyl ether terminated urethane resins
US4845265A (en) * 1988-02-29 1989-07-04 Allied-Signal Inc. Polyfunctional vinyl ether terminated ester oligomers
US5019636A (en) * 1989-05-10 1991-05-28 Allied-Signal Inc. Polyester chain-extended vinyl ether urethane oligomers
US5045572A (en) * 1990-01-26 1991-09-03 Gaf Chemicals Corporation Radiation curable cross linkable compositions containing an aliphatic polyfunctional alkenyl ether
US5139872A (en) * 1990-08-29 1992-08-18 Allied-Signal Inc. Vinyl ether based optical fiber coatings
US5140054A (en) * 1991-09-09 1992-08-18 Isp Investments Inc. Radiation curable polypropenyl ether resins
US5153237A (en) * 1991-09-09 1992-10-06 Isp Investments Inc. Radiation curable propenyl ether resins

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485733A (en) * 1966-03-02 1969-12-23 Ppg Industries Inc Highly radiation-sensitive telomerized polyesters
US4091141A (en) * 1977-04-28 1978-05-23 Armstrong Cork Company Photocurable elastomeric polyester composition, fibrous articles impregnated therewith and method of making same
US4751273A (en) * 1986-08-19 1988-06-14 Allied-Signal, Inc. Vinyl ether terminated urethane resins
US4749807A (en) * 1987-02-17 1988-06-07 Allied-Signal Inc. Vinyl ether terminated ester oligomers
US4845265A (en) * 1988-02-29 1989-07-04 Allied-Signal Inc. Polyfunctional vinyl ether terminated ester oligomers
US5019636A (en) * 1989-05-10 1991-05-28 Allied-Signal Inc. Polyester chain-extended vinyl ether urethane oligomers
US5045572A (en) * 1990-01-26 1991-09-03 Gaf Chemicals Corporation Radiation curable cross linkable compositions containing an aliphatic polyfunctional alkenyl ether
US5139872A (en) * 1990-08-29 1992-08-18 Allied-Signal Inc. Vinyl ether based optical fiber coatings
US5140054A (en) * 1991-09-09 1992-08-18 Isp Investments Inc. Radiation curable polypropenyl ether resins
US5153237A (en) * 1991-09-09 1992-10-06 Isp Investments Inc. Radiation curable propenyl ether resins

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122282A1 (fr) * 2000-01-24 2001-08-08 Schenectady International, Inc. Masses électriquement isolantes à faible émission

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Publication number Publication date
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