CA2208853C - Ultraviolet curable epoxidized alkyds - Google Patents
Ultraviolet curable epoxidized alkyds Download PDFInfo
- Publication number
- CA2208853C CA2208853C CA002208853A CA2208853A CA2208853C CA 2208853 C CA2208853 C CA 2208853C CA 002208853 A CA002208853 A CA 002208853A CA 2208853 A CA2208853 A CA 2208853A CA 2208853 C CA2208853 C CA 2208853C
- Authority
- CA
- Canada
- Prior art keywords
- fatty acid
- alkyd
- accordance
- resin
- anhydride
- 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.)
- Expired - Fee Related
Links
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
-
- 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
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/109—Polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
Abstract
The epoxidation of alkyds containing anhydrides or diacids with cycloaliphatic unsaturation results in epoxy resins which cure rapidly in UV light to produce uniform films without the use of flow modifiers. The fatty acid portion of the alkyd functions as an internal plasticizer. Crosslinking occurs through oxirane rings in both the anhydride and fatty acid moieties of the alkyd to produce hard, but not brittle films. Excellent water resistance is obtained without thermal post curing.
Description
CA 022088~3 1997-06-26 ULTRAVIOLET CURABLE EPOXIDIZED ALKYDS
BACKGROUND OF THE INVENTION
This invention relates to solventless, internally plasticized epoxy 5 compositions which cure rapidly in ultraviolet light. A suitable photoinitiator, such as triphenylsulfonium hexafluorophosphate [(q~ 3 S+ PF6],iS required. Sunlight or UV lamps may be used as radiation sources. The mechanism of cure is cationic rather than free radical. When a photon strikes the photoinitiator, a strong acid (HPF6) is generated. This acid initiates crosslinking through oxirane rings resulting 10 in a network polymer.
A comparison of this invention with related technologies is shown in Table 1.
Table I
1!~ Comparison Conventional Conventional Cycloaliphatic Invention Alkyd Epo~y Epo~y Nurnber of Comr~npntc On~ Two One (plu~ One (plus pho-(plus drier) photoinitiator) toinitiator) Cure Type ~llto~ on ('llprnic:~l W W
Cure Merhs~icm Free Radical Addition Cationic Cationic Cure Tirne Moderale to slow Moderate to slow Rapid Rapid Latent Cure Yes No Yes Yes Solvent Use Yes Yes No No Externally pl~tiri7pd No No Yes No Internally Pl~tiri7Pd Yes Yes No Yes (by fatty acid) (by a nng agent) (by fatty acid) Conventional alkyds are oil modified polyesters. Without oil modification, the polyester is a brittle solid. By incorporating unsaturated fatty acids into the polyester, a film with the desired flexibility can be obtained. Alkyds are comprised of an anhydride or diacid, a polyol, and unsaturated fatty acids.
Examples of these would be phthalic anhydride, glycerine, and tall oil fatty acid.
30 Vegetable oils, such as soybean oil, contribute both polyol and unsaturated fatty acids to an alkyd formulation. The cure of an alkyd is through autoxidation by afree radical mechanism. The sites of crosslinking are carbons adjacent to unsaturation. Alkyds are one of the most widely used protective coatings due to CA 022088~3 1997-06-26 their durability and relatively low cost. Alkyds typically contain solvents for viscosity reduction.
Conventional epoxy resins are multifunctional glycidyl ethers derived from the reaction of bisphenol A and epichlorhydrin. The oxirane rings of these resins react with amine curing agents, such as reactive polyamides, by chemical addition. The resulting polymer is widely used in protective coatings when superior corrosion and water resistance is required. Solvents are used to reduce the viscosity of the two component reaction mixture.
Cycloaliphatic epoxy resins, such as (3,4 - epoxycyclohexyl) methyl -3,4 - epoxycyclohexane carboxylate [ ~,\ !1 ~ ] have previously been employed as solventless epoxy compositions which cure rapidly in ultraviolet light. These resins produce rigid films without the addition of aplasticizer. A flow modifier is typically added to prevent surface defects. Reactive diluents, such as propylene glycol monomethylether, may be added to reduce the viscosity of the formulation.
Cationic polymerization of epoxy resin materials by the use of certain radiation sensitive aromatic onium salts of Group Vla elements was disclosed in U.S. Patent Number 4,058,401 to Crivello. Epoxy resins polymerizable to a highermolecular weight were identified. Examples of photoinitiators identified were tri-phenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimoniate, and triphenylsulfonium tetrafluoroborate. Disclosure of this type of photoinitiator was expanded by Crivello in U.S. Patent Number 4,161,478 which specifically addresses triphenylsulfonium hexafluorophosphate. A method for effecting the cationic polymerization of epoxy resins with this type of photoinitiator was disclosed by Crivello in U.S. Patent Number 4,138,255.
Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials were disclosed by Smith in U.S. Patent Number 4,256,828. A process for this polymerization was disclosed by Smith in U.S.
Patent Number 4,318,766. Crivello discussed the use of a hydroxy functional flexibilizer in U.S. Patent Number 4,175,972. These patents also involved the use of photosensitive aromatic sulfonium salts.
CA 022088~3 1997-06-26 Simultaneous free radical and cationic cure of mixtures of certain oxirane containing and aliphatically unsaturated containing organic resins was addressed by Crivello in U.S. Patent Number 4,245,029. Arylsulfonium salt-solvent mixtures were disclosed as photoinitiators by Crivello in U.S. Patent Number 4,273,668. Propylene carbonate was specifically identified as a solvent.
Additional photoinitiators were identified by Crivello in U.S. Patent Numbers 4,407,759 and 4,417,061. General structures for these photoinitiators are S \ MFo and S ~) MFo , respectively.
It is an object of the present invention to produce a durable ultraviolet curable epoxidized alkyd resin coating that cures through a cationic mechanism.
It is a further object to produce a durable ultraviolet curable epoxidized alkydcoating that is internally plasticized to produce hard but not brittle films without the use of external plasticizers.
It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is water resistant without thermal post-curing.
It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is uniform without the use of flow modifiers.
It is an object of the invention to produce a film which is internally plasticized through the use of tall oil fatty acids. These fatty acids act as aninternal plasticizer due to their long aliphatic chains. Further, they provide a site for curing by epoxidation of their unsaturation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An epoxidized aikyd prepared from tall oil fatty acid, glycerine, and tetrahydrophthalic anhydride (THPA~ is illustrated as follows:
_ < ~ 1=0 Il ~ 1 11 R--C--O--CH~-CH-CH~--O--C C--O--CH-CH-CH,--O--C--R
O O O . X
C--O
R / \
R = CH3-(CH2)7--CH-CH--(CH~)7 or / \
CH;--(CH~34-CH-CH-CH2-C~I-CH- (CH2)7--A suitable photoinitiator, such as triphenyl sulfonium hexafluor-ophosphate, is mixed with the epoxy resin at a concenttation of 3% by weight.
This mixture is stable in the absence of UV light. When a photon strikes the 30 photoinitiator, a strong acid is generated which initiates rapid cationic cure through the oxirane rings of the epoxy resin.
CA 022088~3 1997-06-26 The use of an epoxy grade of tall oil fatty acid (TOFA), such as ACINTOL~ EPG from Arizona Chemical Company, precludes the need to remove dimethoxystilbene (DMS) from the alkyd with a wiped film evaporator (WFE).
When DMS is present during epoxidation of the alkyd, a dark red complex results.5 Oleic acid, such as EMERSOL3 221 from the Emery Industries Division of Henkel Corporation, gave similar results to those from ACINTOL~ EPG without a WFE step.Other TOFAs, such as ACINTOL~ FA-2, gave similar results to ACINTOL~ EPG
when DMS was removed from the alkyd by WFE distillation. Crosslinking of the oxirane rings in the TOFA or Qleic acid moieties of the epoxidized alkyd in addition 10 to cross linking of the cycloaliphatic oxirane rings of the anhydride moiety result in hard, but not brittle films.
Glycerine is the preferred polyol of this invention. Trimethylolpropane can be used when a more flexible coating is desired, although a slower cure rateis obtained. Stoichiometric amounts of polyols and acids are used to form the 15 alkyd . A preferred anhydride of this invention is 1,2,3, 6-tetrahydrophthalic anhydride.
The intended applications for this invention are those in which the epoxy resin viscosity can be reduced by heat or by a reactive diluent, such as limonene dioxide. An example would be the coating of optical fibers. Another 20 example would be protective coatings applied by thermal spraying.
The following examples are illustrative of alkyd resins and ultraviolet curable epoxidized alkyd resins embodying the invention and are not intended as limiting the scope thereof.
CA 022088~3 1997-06-26 EXAMPLE I
The preparation of an alkyd of this invention using an epoxy grade of tall oil fatty acid can be accomplished as follows:
Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63.29 THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.8g Glycerine (96%) (polyol) 0.1 25g Phosphoric Acid ~quipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distilla-tion head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap.
~rocedure: (1) Charge all ingredients.
BACKGROUND OF THE INVENTION
This invention relates to solventless, internally plasticized epoxy 5 compositions which cure rapidly in ultraviolet light. A suitable photoinitiator, such as triphenylsulfonium hexafluorophosphate [(q~ 3 S+ PF6],iS required. Sunlight or UV lamps may be used as radiation sources. The mechanism of cure is cationic rather than free radical. When a photon strikes the photoinitiator, a strong acid (HPF6) is generated. This acid initiates crosslinking through oxirane rings resulting 10 in a network polymer.
A comparison of this invention with related technologies is shown in Table 1.
Table I
1!~ Comparison Conventional Conventional Cycloaliphatic Invention Alkyd Epo~y Epo~y Nurnber of Comr~npntc On~ Two One (plu~ One (plus pho-(plus drier) photoinitiator) toinitiator) Cure Type ~llto~ on ('llprnic:~l W W
Cure Merhs~icm Free Radical Addition Cationic Cationic Cure Tirne Moderale to slow Moderate to slow Rapid Rapid Latent Cure Yes No Yes Yes Solvent Use Yes Yes No No Externally pl~tiri7pd No No Yes No Internally Pl~tiri7Pd Yes Yes No Yes (by fatty acid) (by a nng agent) (by fatty acid) Conventional alkyds are oil modified polyesters. Without oil modification, the polyester is a brittle solid. By incorporating unsaturated fatty acids into the polyester, a film with the desired flexibility can be obtained. Alkyds are comprised of an anhydride or diacid, a polyol, and unsaturated fatty acids.
Examples of these would be phthalic anhydride, glycerine, and tall oil fatty acid.
30 Vegetable oils, such as soybean oil, contribute both polyol and unsaturated fatty acids to an alkyd formulation. The cure of an alkyd is through autoxidation by afree radical mechanism. The sites of crosslinking are carbons adjacent to unsaturation. Alkyds are one of the most widely used protective coatings due to CA 022088~3 1997-06-26 their durability and relatively low cost. Alkyds typically contain solvents for viscosity reduction.
Conventional epoxy resins are multifunctional glycidyl ethers derived from the reaction of bisphenol A and epichlorhydrin. The oxirane rings of these resins react with amine curing agents, such as reactive polyamides, by chemical addition. The resulting polymer is widely used in protective coatings when superior corrosion and water resistance is required. Solvents are used to reduce the viscosity of the two component reaction mixture.
Cycloaliphatic epoxy resins, such as (3,4 - epoxycyclohexyl) methyl -3,4 - epoxycyclohexane carboxylate [ ~,\ !1 ~ ] have previously been employed as solventless epoxy compositions which cure rapidly in ultraviolet light. These resins produce rigid films without the addition of aplasticizer. A flow modifier is typically added to prevent surface defects. Reactive diluents, such as propylene glycol monomethylether, may be added to reduce the viscosity of the formulation.
Cationic polymerization of epoxy resin materials by the use of certain radiation sensitive aromatic onium salts of Group Vla elements was disclosed in U.S. Patent Number 4,058,401 to Crivello. Epoxy resins polymerizable to a highermolecular weight were identified. Examples of photoinitiators identified were tri-phenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimoniate, and triphenylsulfonium tetrafluoroborate. Disclosure of this type of photoinitiator was expanded by Crivello in U.S. Patent Number 4,161,478 which specifically addresses triphenylsulfonium hexafluorophosphate. A method for effecting the cationic polymerization of epoxy resins with this type of photoinitiator was disclosed by Crivello in U.S. Patent Number 4,138,255.
Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials were disclosed by Smith in U.S. Patent Number 4,256,828. A process for this polymerization was disclosed by Smith in U.S.
Patent Number 4,318,766. Crivello discussed the use of a hydroxy functional flexibilizer in U.S. Patent Number 4,175,972. These patents also involved the use of photosensitive aromatic sulfonium salts.
CA 022088~3 1997-06-26 Simultaneous free radical and cationic cure of mixtures of certain oxirane containing and aliphatically unsaturated containing organic resins was addressed by Crivello in U.S. Patent Number 4,245,029. Arylsulfonium salt-solvent mixtures were disclosed as photoinitiators by Crivello in U.S. Patent Number 4,273,668. Propylene carbonate was specifically identified as a solvent.
Additional photoinitiators were identified by Crivello in U.S. Patent Numbers 4,407,759 and 4,417,061. General structures for these photoinitiators are S \ MFo and S ~) MFo , respectively.
It is an object of the present invention to produce a durable ultraviolet curable epoxidized alkyd resin coating that cures through a cationic mechanism.
It is a further object to produce a durable ultraviolet curable epoxidized alkydcoating that is internally plasticized to produce hard but not brittle films without the use of external plasticizers.
It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is water resistant without thermal post-curing.
It is a further object to produce a durable ultraviolet curable epoxidized alkyd coating which is uniform without the use of flow modifiers.
It is an object of the invention to produce a film which is internally plasticized through the use of tall oil fatty acids. These fatty acids act as aninternal plasticizer due to their long aliphatic chains. Further, they provide a site for curing by epoxidation of their unsaturation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An epoxidized aikyd prepared from tall oil fatty acid, glycerine, and tetrahydrophthalic anhydride (THPA~ is illustrated as follows:
_ < ~ 1=0 Il ~ 1 11 R--C--O--CH~-CH-CH~--O--C C--O--CH-CH-CH,--O--C--R
O O O . X
C--O
R / \
R = CH3-(CH2)7--CH-CH--(CH~)7 or / \
CH;--(CH~34-CH-CH-CH2-C~I-CH- (CH2)7--A suitable photoinitiator, such as triphenyl sulfonium hexafluor-ophosphate, is mixed with the epoxy resin at a concenttation of 3% by weight.
This mixture is stable in the absence of UV light. When a photon strikes the 30 photoinitiator, a strong acid is generated which initiates rapid cationic cure through the oxirane rings of the epoxy resin.
CA 022088~3 1997-06-26 The use of an epoxy grade of tall oil fatty acid (TOFA), such as ACINTOL~ EPG from Arizona Chemical Company, precludes the need to remove dimethoxystilbene (DMS) from the alkyd with a wiped film evaporator (WFE).
When DMS is present during epoxidation of the alkyd, a dark red complex results.5 Oleic acid, such as EMERSOL3 221 from the Emery Industries Division of Henkel Corporation, gave similar results to those from ACINTOL~ EPG without a WFE step.Other TOFAs, such as ACINTOL~ FA-2, gave similar results to ACINTOL~ EPG
when DMS was removed from the alkyd by WFE distillation. Crosslinking of the oxirane rings in the TOFA or Qleic acid moieties of the epoxidized alkyd in addition 10 to cross linking of the cycloaliphatic oxirane rings of the anhydride moiety result in hard, but not brittle films.
Glycerine is the preferred polyol of this invention. Trimethylolpropane can be used when a more flexible coating is desired, although a slower cure rateis obtained. Stoichiometric amounts of polyols and acids are used to form the 15 alkyd . A preferred anhydride of this invention is 1,2,3, 6-tetrahydrophthalic anhydride.
The intended applications for this invention are those in which the epoxy resin viscosity can be reduced by heat or by a reactive diluent, such as limonene dioxide. An example would be the coating of optical fibers. Another 20 example would be protective coatings applied by thermal spraying.
The following examples are illustrative of alkyd resins and ultraviolet curable epoxidized alkyd resins embodying the invention and are not intended as limiting the scope thereof.
CA 022088~3 1997-06-26 EXAMPLE I
The preparation of an alkyd of this invention using an epoxy grade of tall oil fatty acid can be accomplished as follows:
Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63.29 THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.8g Glycerine (96%) (polyol) 0.1 25g Phosphoric Acid ~quipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distilla-tion head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap.
~rocedure: (1) Charge all ingredients.
(2) Start a nitrogen sweep of the flask.
(3) Heat gradually to 220~C with agitation. The head temperature should not exceed 1 00~C during heat up.
(4) Hold 16 hours at 220~C.
(5) Gradually pull a vacuum (25" Hg) at 220~C and maintain for 5 -10 minutes. Break vacuum with N2.
(6) Cool and analyze.
Results:
Acid Number 4.3 Color, Gardner 3 +
Viscosity, 25~C 13,360 cps lodine Value 123 Hydroxyl Value 14 Yield 92.4%
CA 022088~3 1997-06-26 EXAMPLE ll The preparation of an alkyd of this invention using an oleic acid can be accompiished as follows:
Charge: 145.59 EMERSOL~ 221 (oleic acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.89 Glycerine (96%) (polyol) 0.1 25g Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap.
Procedure: ( 1 ) Charge all ingredients.
~2) Start a nitrogen sweep of the flask.
(3) Heat gradually to 220eC with agitation. The head temperature should not exceed 100~C during heat up.
(4) Hold 8 hours at 220~C.
(5) Gradually pull a vacuum (25" Hg) at 220~C and maintain for 5 - 10 minutes. Break vacuum with N2.
(6) Cool and analyze.
Results:
Acid Number 6.4 Color, Gardner 4 Viscosity, 25~C 9,900 cps lodine Value 99 Hydroxyl Value 14 Yield 90.2%
CA 022088~3 1997-06-26 EXAMPLE lll The preparation of an alkyd of this invention using a standard grade of tall oil fatty acid can be accomplished as follows:
Charge: 145.5g ACINTOL~ FA-2 (tall oil fatty acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.89 Glycerine (96%) (polyol) 0.1259 Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inletthermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, bubble trap and a wiped film evaporator (WFE).
Procedure: (1) Charge all ingredients.
(2) Start a nitrogen sweep of the flask.
(3) Heat gradually to 220~C with agitation. The head temperature should not exceed 1 00~C during heat up.
(4) Hold 16 hours at 220~C.
(5) Gradually pull a vacuum (25" Hg) at 220~C and main-tain for 5 - 10 minutes. Break vacuum with N2.
(6) Cool and analyze.
Results:
Acid Number 4.3 Color, Gardner 3 +
Viscosity, 25~C 13,360 cps lodine Value 123 Hydroxyl Value 14 Yield 92.4%
CA 022088~3 1997-06-26 EXAMPLE ll The preparation of an alkyd of this invention using an oleic acid can be accompiished as follows:
Charge: 145.59 EMERSOL~ 221 (oleic acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.89 Glycerine (96%) (polyol) 0.1 25g Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inlet thermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, and bubble trap.
Procedure: ( 1 ) Charge all ingredients.
~2) Start a nitrogen sweep of the flask.
(3) Heat gradually to 220eC with agitation. The head temperature should not exceed 100~C during heat up.
(4) Hold 8 hours at 220~C.
(5) Gradually pull a vacuum (25" Hg) at 220~C and maintain for 5 - 10 minutes. Break vacuum with N2.
(6) Cool and analyze.
Results:
Acid Number 6.4 Color, Gardner 4 Viscosity, 25~C 9,900 cps lodine Value 99 Hydroxyl Value 14 Yield 90.2%
CA 022088~3 1997-06-26 EXAMPLE lll The preparation of an alkyd of this invention using a standard grade of tall oil fatty acid can be accomplished as follows:
Charge: 145.5g ACINTOL~ FA-2 (tall oil fatty acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 42.89 Glycerine (96%) (polyol) 0.1259 Phosphoric Acid Equipment: 500 ml, 3 neck flask equipped with an agitator, nitrogen inletthermometer with thermowatch, steam heated precondenser, distillation head with thermometer, water cooled condenser, vacuum adapter, receiver, vacuum apparatus, heating mantle, bubble trap and a wiped film evaporator (WFE).
Procedure: (1) Charge all ingredients.
(2) Start a nitrogen sweep of the flask.
(3) Heat gradually to 220~C with agitation. The head temperature should not exceed 1 00~C during heat up.
(4) Hold 16 hours at 220~C.
(5) Gradually pull a vacuum (25" Hg) at 220~C and main-tain for 5 - 10 minutes. Break vacuum with N2.
(6) Cool and analyze.
(7) Pass the reaction mixture through a wiped film evapora-tor at 21 0~C under a 0.1 mm Hg vacuum. The reaction mixture should be warmed to facilitate its flow.
Results:
Before WFE Acid Number 7.1 Color, Gardner 4-Yield 94.3%
After WFE
Residue Distillate Acid Number 4.0 Acid Number 109 Color, Gardner 3 Color, Gardner 11-Viscosity, 25~C 13,900 cps Yield 2.4%
lodine Value 123 Hydroxyl Value 19 Yield 97.6%
CA 022088~3 1997-06-26 EXAMPLE IV
Epoxidation of the alkyds of this invention can be accomplished as follows:
Charge: 75.0g Alkyd from Examples 1&3 75.0g Alkyd from Example 2 150.09 Methylene Chloride 150.0g Methylene Chloride 96.69 Peracetic Acid (32%) 78.2g Peracetic Acid (32%) 2.5g Sodium Acetate 2.0g Sodium Acetate 23.09 Water (distilled) 18.69 Water (distilled) ~quipment: 500 ml, 3 neck flask with agitator, N2 inlet, thermometer with thermowatch, e~uilibrium addition funnel, ice bath, heating mantle, bubble trap, and separatory funnels.
~rocedure: (1) Charge the alkyd and CH2CI2.
(2) Start a nitrogen sweep of the flask.
(3) Cool the alkyd solution to 20~C with agitation.
(4) Dissolve the sodium acetate in water.
(5) Add the sodium acetate solution to the peracetic acid.
(6) Add the buffered peracetic acid solution dropwise below the surface of the reaction mixture.
(7) Allow the reaction mixture to exotherm to 30~C, then maintain the temperature at 25-30~C.
Results:
Before WFE Acid Number 7.1 Color, Gardner 4-Yield 94.3%
After WFE
Residue Distillate Acid Number 4.0 Acid Number 109 Color, Gardner 3 Color, Gardner 11-Viscosity, 25~C 13,900 cps Yield 2.4%
lodine Value 123 Hydroxyl Value 19 Yield 97.6%
CA 022088~3 1997-06-26 EXAMPLE IV
Epoxidation of the alkyds of this invention can be accomplished as follows:
Charge: 75.0g Alkyd from Examples 1&3 75.0g Alkyd from Example 2 150.09 Methylene Chloride 150.0g Methylene Chloride 96.69 Peracetic Acid (32%) 78.2g Peracetic Acid (32%) 2.5g Sodium Acetate 2.0g Sodium Acetate 23.09 Water (distilled) 18.69 Water (distilled) ~quipment: 500 ml, 3 neck flask with agitator, N2 inlet, thermometer with thermowatch, e~uilibrium addition funnel, ice bath, heating mantle, bubble trap, and separatory funnels.
~rocedure: (1) Charge the alkyd and CH2CI2.
(2) Start a nitrogen sweep of the flask.
(3) Cool the alkyd solution to 20~C with agitation.
(4) Dissolve the sodium acetate in water.
(5) Add the sodium acetate solution to the peracetic acid.
(6) Add the buffered peracetic acid solution dropwise below the surface of the reaction mixture.
(7) Allow the reaction mixture to exotherm to 30~C, then maintain the temperature at 25-30~C.
(8) Agitate overnight at 25-30~C.
(9) Pour the reaction mixture into 400 mls of distilled water.
(10) Separate the organic layer.
(1 1 ) Extract the water phase with 75 mls of CH2CI2.
(12) Combine the CH2CI2 extract with the organic phase.
( 13) Wash the organic phase with 2 x 100 ml portions of distilled water.
(14) Wash the organic phase with 4 x 100 ml portions of 0.1 %
Na2CO 3.
(15) Wash the organic phase with 100 mls of distilled water.
( 1 6) Dry the organic phase with Na2S04 .
(17) Remove CH2CI2 under vacuum with a roto-evaporator.
Results:
Analvsis Epoxidized Epoxidized Epoxidized Alkyd Alkyd Alkyd (Example 1) (Examr~le ll) (Example lll) Acid Number 5.0 5.4 5.2 Color, Gardner < 1 ~ 1 < 1 Viscosity, 25~C26,000 cps 12,200 cps 34,900 cps lodine Value 0. 6 2 . 6 1 . 9 Yield 79.29 79.1 g 79.39 CA 022088~3 1997-06-26 , ' 10 EXAMPLE V
A description of the cure and evaluation of the products of this invention is as follows:
Cure Ingredients: 10.0g of epoxidized alkyd/0.3g of 3M's FX-512 (photoinitiator) ~rocedure: The ingredients were mixed well in a 50 ml beaker with a spatula.
A 3 mil film was drawn on a cold rolled steel panel with a draw down bar. The film was placed in direct sunlight.
EVALUATION OF CURED MATERIAL
The panels remained outside for 4-7 days before evaluation. The following results were obtained with films from the alkyds in examples 1-3 after they had been epoxidized as in example 4:
Analysis Cured Film FromCured Film FromCured Film From FpAYi~ d Alkydrp~ i,. A AlkydFrAYiAi7~d Alkyd (Example 1)(ExamDle ll)(ExamDle lll) Film Apptc.ance Smooth, GlossySmooth, GlossySmooth, Glossv Cure Rate~ 1 minute ~3 1 minute ~ 1 minute Hardness, Pencil'2~ 4H 4H 4H
Adhesion, Cross Hatch~3' 5 5 5 Impact Rc~;atal~cc" P80F P120F P100F
We a ~ 5~
Yellowing yes ycs yes Film deterioration - - none observed Water Rc;~ia~a~ No effect Chemical R~,~iala~ccl7~
HCI (10%) - - No effect NaOH 110~) - - Pnrtial film loss Acetic Acid (5%) - - Dcrkened, blisters MEK - - No effect CH2CI2 - - No effect Methanol - - No effect Ethyl Acetate - - No effect Xylene - - No effect Xylene/lPA (50150) - - No effect Gasoline - - No effect Mineral Oil - - No effect Ethanol (200 proof) - - No effect Ethanol (3A) - - Blisters (1) Dry to touch in direct sunlight (2) 8H i5 hardest ~ HB (soft) ~ 6B (very soft~
(3) On a scaio of 1 - 5, 5 is best (4) P = pass, F ~ forward, R = reverse. Highest is 160. Units are in.-lbs. This is a measure of flexibility.
(5) After three months of outside exposure. Slight yellowing is evident within dsys.
(6) After six months of water ' ~1 aiOU of thc panel (7) Seven day chemical spot test EXAMPLE Vl The use of Limonene Dioxide (LD0) to reduce the viscosity of an expoxi-dized alkyd is described as follows:
Analvsis Epoxidized Alkyd Epoxidized Alkyd/LD0 (80/201 Viscosity, 25~C 31,300 cps 4,060 cps Viscosity, 40~C 7,560 cps 1,350 cps Cured Film (Refer to Example V) Analysis Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate _ 1 minute E 1 minute Hardness, Pencil 4H 4H
Adhesion, Cross Hatch 5 5 Impact Resistance P120F P80F
CA 022088~3 1997-06-26 EXAMPLE Vll The use of trimethylolpropane (TMP) as the polyol instead of glycerine is described as follows:
Alkyd Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 61.6g Trimethylolpropane (TMP) (polyol) 0.1259 Phosphoric Acid Alkyd Equipment and Procedure:Same as Example I
Results:
Analysis TMP Based GlYcerine Based Alkyd Alkyd Acid Number 13.7 4.3 Color, Gardner 3+ 3+
Viscosity, 25~C10,500 cps 13,360 cps lodine Value 114 123 Hydroxyl Value 23 14 Yield 89.0% 92.4%
Epoxidation: Same as Example IV
Epoxidation Results:
Analysis TMP Based Glycerine Based Epoxidized Epoxidized Alkyd Alkyd (Example 1) Acid Number 10.1 5.0 Color, Gardner < 1 c 1 Viscosity, 25~C22,850 cps 26,000 cps lodine Value 3.1 0.6 Yield 81.3g 79.2g .
Cure and Evaluation:Same as Example V
Results:
Analvsis TMP Based Glycerine Based Cured Material Cured Material Film AppearanceSmooth, Glossy Smooth, Glossy Cure Rate s 2.5 minutes - 1 minute Hardness, Pencil 2H 4H
Adhesion, Cross Hatch 5 5 Impact Resistance P160F P80F
An increase in film flexibility is gained at the expense of cure rate.
CA 022088~3 1997-06-26 EXAMPLE Vlll The use of methyl tetrahydrophthalic anhydride (MTHPA) instead of THPA
as a diacid with cycloaliphatic unsaturation is described as follows:
Alkyd Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63 . 2g MTHPA
40.7g Glycerine (96%) (polyol) 0.1259 Phosphoric Acid Alkyd Equipment and Procedure:Same as Example lll Results:
Analvsis MTHPA Based Alkyd THPA Based AlkYd Acid Number 11.9 4.0 Color, Gardner 2+ 3 Viscosity, 25~C 9,300 cps 13,900 cps lodine Value 120 123 Hydroxyl Value 25 19 Yield 90.5% 92.0%
Epoxidation: Same as Example IV
Epoxidation Results:
Analysis MTHPA Based THPA Based Epoxidized Epoxidized Alkyd Alkyd (Example lll) Acid Number 6.3 5.2 Color, Gardner < 1 < 1 Viscosity, 25~C 24,500 cps 34,900 cps lodine Value 2 . 2 1 . 9 Yield 82.9g CA 022088~3 1997-06-26 Cure and Evaluation: Same as Example V
Results:
Analvsis MTHPA BasedTHPA Based Cured Material Cured Material Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate _ 1.5 minutes - 1 minute Hardness, Pencil 4H 4H
Adhesion, Cross Hatch 3 5 Impact Resistance P140F P100F
While the invention has been described and illustrated with specific materials and procedures, it is understood that the invention is not restricted to those employed for this purpose. Numerous variations of such materials and procedures can be employed, as will be appreciated by those skilled in the art.
(1 1 ) Extract the water phase with 75 mls of CH2CI2.
(12) Combine the CH2CI2 extract with the organic phase.
( 13) Wash the organic phase with 2 x 100 ml portions of distilled water.
(14) Wash the organic phase with 4 x 100 ml portions of 0.1 %
Na2CO 3.
(15) Wash the organic phase with 100 mls of distilled water.
( 1 6) Dry the organic phase with Na2S04 .
(17) Remove CH2CI2 under vacuum with a roto-evaporator.
Results:
Analvsis Epoxidized Epoxidized Epoxidized Alkyd Alkyd Alkyd (Example 1) (Examr~le ll) (Example lll) Acid Number 5.0 5.4 5.2 Color, Gardner < 1 ~ 1 < 1 Viscosity, 25~C26,000 cps 12,200 cps 34,900 cps lodine Value 0. 6 2 . 6 1 . 9 Yield 79.29 79.1 g 79.39 CA 022088~3 1997-06-26 , ' 10 EXAMPLE V
A description of the cure and evaluation of the products of this invention is as follows:
Cure Ingredients: 10.0g of epoxidized alkyd/0.3g of 3M's FX-512 (photoinitiator) ~rocedure: The ingredients were mixed well in a 50 ml beaker with a spatula.
A 3 mil film was drawn on a cold rolled steel panel with a draw down bar. The film was placed in direct sunlight.
EVALUATION OF CURED MATERIAL
The panels remained outside for 4-7 days before evaluation. The following results were obtained with films from the alkyds in examples 1-3 after they had been epoxidized as in example 4:
Analysis Cured Film FromCured Film FromCured Film From FpAYi~ d Alkydrp~ i,. A AlkydFrAYiAi7~d Alkyd (Example 1)(ExamDle ll)(ExamDle lll) Film Apptc.ance Smooth, GlossySmooth, GlossySmooth, Glossv Cure Rate~ 1 minute ~3 1 minute ~ 1 minute Hardness, Pencil'2~ 4H 4H 4H
Adhesion, Cross Hatch~3' 5 5 5 Impact Rc~;atal~cc" P80F P120F P100F
We a ~ 5~
Yellowing yes ycs yes Film deterioration - - none observed Water Rc;~ia~a~ No effect Chemical R~,~iala~ccl7~
HCI (10%) - - No effect NaOH 110~) - - Pnrtial film loss Acetic Acid (5%) - - Dcrkened, blisters MEK - - No effect CH2CI2 - - No effect Methanol - - No effect Ethyl Acetate - - No effect Xylene - - No effect Xylene/lPA (50150) - - No effect Gasoline - - No effect Mineral Oil - - No effect Ethanol (200 proof) - - No effect Ethanol (3A) - - Blisters (1) Dry to touch in direct sunlight (2) 8H i5 hardest ~ HB (soft) ~ 6B (very soft~
(3) On a scaio of 1 - 5, 5 is best (4) P = pass, F ~ forward, R = reverse. Highest is 160. Units are in.-lbs. This is a measure of flexibility.
(5) After three months of outside exposure. Slight yellowing is evident within dsys.
(6) After six months of water ' ~1 aiOU of thc panel (7) Seven day chemical spot test EXAMPLE Vl The use of Limonene Dioxide (LD0) to reduce the viscosity of an expoxi-dized alkyd is described as follows:
Analvsis Epoxidized Alkyd Epoxidized Alkyd/LD0 (80/201 Viscosity, 25~C 31,300 cps 4,060 cps Viscosity, 40~C 7,560 cps 1,350 cps Cured Film (Refer to Example V) Analysis Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate _ 1 minute E 1 minute Hardness, Pencil 4H 4H
Adhesion, Cross Hatch 5 5 Impact Resistance P120F P80F
CA 022088~3 1997-06-26 EXAMPLE Vll The use of trimethylolpropane (TMP) as the polyol instead of glycerine is described as follows:
Alkyd Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63.2g THPA (1,2,3,6 - tetrahydrophthalic anhydride) 61.6g Trimethylolpropane (TMP) (polyol) 0.1259 Phosphoric Acid Alkyd Equipment and Procedure:Same as Example I
Results:
Analysis TMP Based GlYcerine Based Alkyd Alkyd Acid Number 13.7 4.3 Color, Gardner 3+ 3+
Viscosity, 25~C10,500 cps 13,360 cps lodine Value 114 123 Hydroxyl Value 23 14 Yield 89.0% 92.4%
Epoxidation: Same as Example IV
Epoxidation Results:
Analysis TMP Based Glycerine Based Epoxidized Epoxidized Alkyd Alkyd (Example 1) Acid Number 10.1 5.0 Color, Gardner < 1 c 1 Viscosity, 25~C22,850 cps 26,000 cps lodine Value 3.1 0.6 Yield 81.3g 79.2g .
Cure and Evaluation:Same as Example V
Results:
Analvsis TMP Based Glycerine Based Cured Material Cured Material Film AppearanceSmooth, Glossy Smooth, Glossy Cure Rate s 2.5 minutes - 1 minute Hardness, Pencil 2H 4H
Adhesion, Cross Hatch 5 5 Impact Resistance P160F P80F
An increase in film flexibility is gained at the expense of cure rate.
CA 022088~3 1997-06-26 EXAMPLE Vlll The use of methyl tetrahydrophthalic anhydride (MTHPA) instead of THPA
as a diacid with cycloaliphatic unsaturation is described as follows:
Alkyd Charge: 145.5g ACINTOL~ EPG (tall oil fatty acid) 63 . 2g MTHPA
40.7g Glycerine (96%) (polyol) 0.1259 Phosphoric Acid Alkyd Equipment and Procedure:Same as Example lll Results:
Analvsis MTHPA Based Alkyd THPA Based AlkYd Acid Number 11.9 4.0 Color, Gardner 2+ 3 Viscosity, 25~C 9,300 cps 13,900 cps lodine Value 120 123 Hydroxyl Value 25 19 Yield 90.5% 92.0%
Epoxidation: Same as Example IV
Epoxidation Results:
Analysis MTHPA Based THPA Based Epoxidized Epoxidized Alkyd Alkyd (Example lll) Acid Number 6.3 5.2 Color, Gardner < 1 < 1 Viscosity, 25~C 24,500 cps 34,900 cps lodine Value 2 . 2 1 . 9 Yield 82.9g CA 022088~3 1997-06-26 Cure and Evaluation: Same as Example V
Results:
Analvsis MTHPA BasedTHPA Based Cured Material Cured Material Film Appearance Smooth, Glossy Smooth, Glossy Cure Rate _ 1.5 minutes - 1 minute Hardness, Pencil 4H 4H
Adhesion, Cross Hatch 3 5 Impact Resistance P140F P100F
While the invention has been described and illustrated with specific materials and procedures, it is understood that the invention is not restricted to those employed for this purpose. Numerous variations of such materials and procedures can be employed, as will be appreciated by those skilled in the art.
Claims (18)
1. An internally plasticized, ultraviolet cured epoxy resin derived from the epoxidation of an alkyd comprised of:
(a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol.
(a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol.
2. A resin in accordance with claim 1, where the unsaturated fatty acid is a tall oil fatty acid which does not contain dimethoxystilbene.
3. An ultraviolet cured and resin in accordance with claim 1, where the unsaturated fatty acid is a tall oil fatty acid and dimethoxystilbene is subsequently distilled from the alkyd with a wiped film evaporator.
4. An ultraviolet cured resin in accordance with claim 1, where the unsaturated fatty acid is oleic acid.
5. An ultraviolet cured resin in accordance with claim 1, where the anhydride is 1,2,3,6 - tetrahydrophthalic anhydride.
6. An ultraviolet cured resin in accordance with claim 1, where the anhydride is methyl tetrahydrophthalic anhydride.
7. An ultraviolet cured resin in accordance with claim 1, where the polyol is glycerine.
8. An ultraviolet cured resin in accordance with claim 1, where the polyol is trimethylolpropane.
9. An alkyd resin comprised of:
(a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol.
(a) an unsaturated fatty acid, (b) an anhydride or diacid containing cycloaliphatic unsaturation, and (c) a polyol.
10. An alkyd resin in accordance with claim 9, where the unsaturated fatty acid is a tall oil fatty acid which does not contain dimethoxystilbene.
11. An alkyd resin in accordance with claim 9, where the unsaturated fatty acid is a tall oil fatty acid and dimethoxystilbene is subsequently distilled from the alkyd resin with a wiped film evaporator.
12. An alkyd resin in accordance with claim 9, where the unsaturated fatty acid is oleic acid.
13. An alkyd resin in accordance with claim 9, where the anhydride is 1,2,3,6 -tetrahydrophthalic anhydride.
14. An alkyd resin in accordance with claim 9, where the anhydride is methyl tetrahydrophthalic anhydride.
15. An alkyd resin in accordance with claim 9, where the polyol is glycerine.
16. An alkyd resin in accordance with claim 9, where the polyol is trimethylolpropane.
17. A process for the production of an internally plasticized, ultraviolet cured epoxy resin as claimed in claim 1 comprising the steps of:
(a) mixing together (1) said unsaturated fatty acid;
(2) said anhydride or diacid containing cycloaliphatic unsaturation;
and (3) said polyol to form a mixture in a vat;
(b) heating said mixture rapidly to approximately 100°C, then gradually to 220°C;
(c) holding said mixture at approximately 220°C for eight hours to sixteen hours;
(d) vacuum drying said mixture for 5 to 10 minutes;
(e) cooling said mixture;
(f) passing said mixture through a wiped film evaporator at 210°C to form a desired alkyd product;
(g) mixing the alkyd product with CH2Cl2 in a nitrogen environment to farm a first solution;
(h) cooling said solution with agitation;
(i) adding an aqueous sodium acetate and peracetic acid solution to said first solution to form a mixture;
(j) allowing the mixture to exotherm to 30°C, then maintaining the temperature at 25-30°C with agitation;
(k) pouring the mixture into distilled water and separating an organic layer;
(l) extracting said water with CH2Cl2 to form an extract;
(m) combining said extract with said organic layer;
(n) washing said organic layer with water and sodium carbonate;
(o) drying the organic phase with sodium sulfate; and (p) removing CH2Cl2 with a roto-evaporator.
(a) mixing together (1) said unsaturated fatty acid;
(2) said anhydride or diacid containing cycloaliphatic unsaturation;
and (3) said polyol to form a mixture in a vat;
(b) heating said mixture rapidly to approximately 100°C, then gradually to 220°C;
(c) holding said mixture at approximately 220°C for eight hours to sixteen hours;
(d) vacuum drying said mixture for 5 to 10 minutes;
(e) cooling said mixture;
(f) passing said mixture through a wiped film evaporator at 210°C to form a desired alkyd product;
(g) mixing the alkyd product with CH2Cl2 in a nitrogen environment to farm a first solution;
(h) cooling said solution with agitation;
(i) adding an aqueous sodium acetate and peracetic acid solution to said first solution to form a mixture;
(j) allowing the mixture to exotherm to 30°C, then maintaining the temperature at 25-30°C with agitation;
(k) pouring the mixture into distilled water and separating an organic layer;
(l) extracting said water with CH2Cl2 to form an extract;
(m) combining said extract with said organic layer;
(n) washing said organic layer with water and sodium carbonate;
(o) drying the organic phase with sodium sulfate; and (p) removing CH2Cl2 with a roto-evaporator.
18. A process as claimed in claim 17, wherein a nitrogen sweep of said vat is conducted prior to initial heating of said mixture.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/388,926 | 1995-02-15 | ||
US08/388,926 US5612445A (en) | 1995-02-15 | 1995-02-15 | Ultraviolet curable epoxidized alkyds |
PCT/US1996/000938 WO1996025447A1 (en) | 1995-02-15 | 1996-02-06 | Ultraviolet curable epoxidized alkyds |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2208853A1 CA2208853A1 (en) | 1996-08-22 |
CA2208853C true CA2208853C (en) | 2002-04-30 |
Family
ID=23536108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002208853A Expired - Fee Related CA2208853C (en) | 1995-02-15 | 1996-02-06 | Ultraviolet curable epoxidized alkyds |
Country Status (7)
Country | Link |
---|---|
US (2) | US5612445A (en) |
EP (1) | EP0809665A4 (en) |
JP (1) | JPH11501957A (en) |
AU (1) | AU4765596A (en) |
CA (1) | CA2208853C (en) |
MX (1) | MX9706220A (en) |
WO (1) | WO1996025447A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1290432B1 (en) * | 1997-03-21 | 1998-12-03 | Lonza Spa | CYCLOALIFATIC EPOXY RESINS |
US6632859B1 (en) | 1999-03-17 | 2003-10-14 | Raymond H. Jones | Alkyd-based ink vehicles and ink compositions |
MXPA02006937A (en) * | 2000-01-14 | 2004-11-12 | Abb Power T & D Co | Transparent epoxy structures. |
ITMI20010259A1 (en) * | 2001-02-09 | 2002-08-09 | Lonza Spa | SOLID OXYDRYLATED CYCLOALIPHATIC EPOXY RESINS PROCEDURE FOR THE PREPARATION AND COMPOSITIONS OF COATED POWDER PAINTS |
US6706404B2 (en) | 2001-06-26 | 2004-03-16 | Strathmore Products, Inc. | Radiation curable composition |
JP3469567B2 (en) * | 2001-09-03 | 2003-11-25 | 三菱電機株式会社 | Acoustic encoding device, acoustic decoding device, acoustic encoding method, and acoustic decoding method |
US7001667B2 (en) * | 2002-07-17 | 2006-02-21 | Ppg Industries Ohio, Inc. | Alkyd-based free radical wood coating compositions |
NZ523931A (en) | 2003-01-31 | 2005-06-24 | Anzpac Systems Ltd | Article carrier for a grading apparatus |
US6794055B2 (en) | 2003-02-03 | 2004-09-21 | Ppg Industries Ohio, Inc. | Alkyd-based free radical cured wood stains |
US7691946B2 (en) * | 2005-09-30 | 2010-04-06 | The United States Of America As Represented By The Secretary Of Agriculture | Soy-based thermosensitive hydrogels for controlled release systems |
AU2010216379A1 (en) * | 2009-02-20 | 2011-09-15 | Encore Rail Systems, Inc. | Methods for repair and preventative maintenance of railroad ties using UV curable polymers |
DE102009049479A1 (en) * | 2009-06-08 | 2010-12-09 | Sms Siemag Ag | Integration of an optical waveguide of a measuring sensor into a component |
KR102007046B1 (en) * | 2011-01-26 | 2019-08-02 | 나믹스 가부시끼가이샤 | Electroconductive paste and method for manufacturing same |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1875408A (en) * | 1932-09-06 | of san francisco | ||
US1811115A (en) * | 1927-04-07 | 1931-06-23 | Ellis Carleton | Resinous composition and process of making same |
US1847783A (en) * | 1929-06-17 | 1932-03-01 | Armstrong Cork Co | Resinous product and process of making |
US2088612A (en) * | 1934-06-27 | 1937-08-03 | Jpolyhydric aicohol-folybasic acto | |
US2251298A (en) * | 1941-01-31 | 1941-08-05 | United Gas Improvement Co | Synthetic resin and process for making the same |
US2528946A (en) * | 1947-11-19 | 1950-11-07 | Sherwin Williams Co | Method of manufacture of modified alkyd resins and products |
US3112284A (en) * | 1958-12-22 | 1963-11-26 | Johnson & Son Inc S C | Polyepoxide polyesters of tetrahydrophthalic acid and glycols esterified with long-chain saturated aliphatic acids and preparation of same |
US3113932A (en) * | 1959-02-09 | 1963-12-10 | Johnson & Son Inc S C | Drying compositions comprising polyepoxide polyesters of tetrahydrophthalic acid and aliphatic glycols modified with unsaturated monocarboxylic acid |
US3477976A (en) * | 1967-04-02 | 1969-11-11 | Nippon Synthetic Chem Ind | Polyester resins from methy-cyclohexene tricarboxylic acid,methylcyclohexane tricarboxylic acid or anhydride thereof and process of making the same |
FR1566276A (en) * | 1968-01-12 | 1969-05-09 | ||
US3816365A (en) * | 1968-09-12 | 1974-06-11 | Ciba Geigy Ag | Adducts,containing epoxide groups,from polyglycidyl compounds and acid polyesters of aliphatic-cycloaliphatic dicarboxylic acids,process for their manufacture and use |
US3673140A (en) * | 1971-01-06 | 1972-06-27 | Inmont Corp | Actinic radiation curing compositions and method of coating and printing using same |
US3714090A (en) * | 1971-03-22 | 1973-01-30 | Whittaker Corp | High temperature polyester coating composition |
GB1342198A (en) * | 1972-04-21 | 1973-12-25 | Whittaker Corp | Preparation of polyester resins and polyester resins so prepared |
US3893959A (en) * | 1973-10-24 | 1975-07-08 | American Cyanamid Co | Alkyl resin containing an oligomer mixture of unsaturated long chain fatty acids |
US3920595A (en) * | 1974-04-10 | 1975-11-18 | Ppg Industries Inc | High solids alkyd coating compositions |
US4161478A (en) * | 1974-05-02 | 1979-07-17 | General Electric Company | Photoinitiators |
US4407759A (en) * | 1974-05-02 | 1983-10-04 | General Electric Company | Photoinitiators |
US4175972A (en) * | 1974-05-02 | 1979-11-27 | General Electric Company | Curable epoxy compositions containing aromatic onium salts and hydroxy compounds |
US4417061A (en) * | 1974-05-02 | 1983-11-22 | General Electric Company | Photoinitiators |
US4058401A (en) * | 1974-05-02 | 1977-11-15 | General Electric Company | Photocurable compositions containing group via aromatic onium salts |
JPS51131594A (en) * | 1975-05-12 | 1976-11-16 | Daicel Chem Ind Ltd | A process for producing alkyd resin |
US4256828A (en) * | 1975-09-02 | 1981-03-17 | Minnesota Mining And Manufacturing Company | Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials |
US4318766A (en) * | 1975-09-02 | 1982-03-09 | Minnesota Mining And Manufacturing Company | Process of using photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials |
USRE30660E (en) * | 1975-10-21 | 1981-06-30 | Water soluble insulating varnish | |
DE2637955A1 (en) * | 1976-08-24 | 1978-03-02 | Hoechst Ag | LOW-VISCOSE ALKYDE RESINS AND THE METHOD FOR MANUFACTURING THEM |
US4138255A (en) * | 1977-06-27 | 1979-02-06 | General Electric Company | Photo-curing method for epoxy resin using group VIa onium salt |
US4273668A (en) * | 1977-09-14 | 1981-06-16 | General Electric Company | Arylsulfonium salt-solvent mixtures |
US4181638A (en) * | 1978-05-08 | 1980-01-01 | Lasher Edward Abe | High solids polyester resin-based coating composition and method of making same |
US4217257A (en) * | 1979-02-08 | 1980-08-12 | Celanese Corporation | Alkyd resins with use of multifunctional monomers |
US4248745A (en) * | 1979-05-01 | 1981-02-03 | Schenectady Chemicals, Inc. | Water soluble insulating varnish |
US4245029A (en) * | 1979-08-20 | 1981-01-13 | General Electric Company | Photocurable compositions using triarylsulfonium salts |
US4335027A (en) * | 1981-04-27 | 1982-06-15 | Battelle Development Corporation | Air-driable alkyd resins and process for their preparation |
DE3243532A1 (en) * | 1982-11-25 | 1984-05-30 | Basf Farben + Fasern Ag, 2000 Hamburg | PRINT INK |
DE3246615A1 (en) * | 1982-12-16 | 1984-06-20 | Henkel KGaA, 4000 Düsseldorf | ALKYD RESIN CONTAINING FUNCTIONAL EPOXIES |
DE3246618A1 (en) * | 1982-12-16 | 1984-07-05 | Henkel KGaA, 4000 Düsseldorf | ALKYD RESIN CONTAINING RING OPENING PRODUCTS EPOXY FATTY ALCOHOLS OR FATTY ACID DERIVATIVES AS HYDROXYL COMPOUNDS |
JPS6128562A (en) * | 1984-07-18 | 1986-02-08 | Kansai Paint Co Ltd | Thermosetting nitrogen-containing alkyd resin paint |
US4686275A (en) * | 1986-02-25 | 1987-08-11 | Valvoline Oil & Chemicals Ltd. | Saturated linear polyester resin composition suitable for coating a metal for anti-corrosion and/or decorative purposes |
US4719254A (en) * | 1986-05-23 | 1988-01-12 | International Coating & Chemical Company, Inc. | Epoxy ester-modified alkyd resin enamel formulations |
US4997480A (en) * | 1987-04-07 | 1991-03-05 | The Sherwin-Williams Company | Alkyd resins and the use thereof for high solids coatings |
US5158608A (en) * | 1987-10-12 | 1992-10-27 | Synthopol Chemie Dr. Rer. Pol. Koch Gmbh & Co. Kg | Environmentally benign alkyd resins and coating materials made using the resins |
US5269839A (en) * | 1987-10-12 | 1993-12-14 | Synthopol Chemie Dr. Rer. Pol. Koch Gmbh & Co., Kg | Process for producing alkyd resins |
US4927669A (en) * | 1988-07-15 | 1990-05-22 | Westvaco Corporation | Oil field corrosion inhibition |
US5096959A (en) * | 1990-03-06 | 1992-03-17 | The Valspar Corporation | Hydrolysis resistant alkyl resin coating composition |
US5055548A (en) * | 1990-10-11 | 1991-10-08 | Westvaco Corporation | Sovlent-borne alkyd resin compositions |
US5053483A (en) * | 1990-12-03 | 1991-10-01 | Westvaco Corporation | Anhydride containing solvent-borne alkyd resin compositions |
US5244985A (en) * | 1991-03-29 | 1993-09-14 | New Japan Chemical Co., Ltd. | Epoxidized polyesters and method of production thereof |
DE4206698A1 (en) * | 1992-03-04 | 1993-09-09 | Hoechst Ag | CYCLOPENTADIEN-MODIFIED ALKYD RESINS |
TW312701B (en) * | 1992-12-01 | 1997-08-11 | Dsm Nv | |
US5378757A (en) * | 1993-11-15 | 1995-01-03 | Eastman Chemical Company | Water-dissipatable alkyd resins and coatings prepared therefrom |
US5538760A (en) * | 1995-05-22 | 1996-07-23 | Eastman Chemical Company | Alkyd/acrylic latexes for cleaning and protecting hard surfaces |
-
1995
- 1995-02-15 US US08/388,926 patent/US5612445A/en not_active Expired - Lifetime
-
1996
- 1996-02-06 WO PCT/US1996/000938 patent/WO1996025447A1/en not_active Application Discontinuation
- 1996-02-06 EP EP96903643A patent/EP0809665A4/en not_active Withdrawn
- 1996-02-06 JP JP8524955A patent/JPH11501957A/en active Pending
- 1996-02-06 CA CA002208853A patent/CA2208853C/en not_active Expired - Fee Related
- 1996-02-06 AU AU47655/96A patent/AU4765596A/en not_active Abandoned
- 1996-02-06 MX MX9706220A patent/MX9706220A/en unknown
- 1996-12-09 US US08/762,251 patent/US5821324A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US5821324A (en) | 1998-10-13 |
JPH11501957A (en) | 1999-02-16 |
EP0809665A4 (en) | 1998-05-20 |
US5612445A (en) | 1997-03-18 |
EP0809665A1 (en) | 1997-12-03 |
MX9706220A (en) | 1997-12-31 |
AU4765596A (en) | 1996-09-04 |
CA2208853A1 (en) | 1996-08-22 |
WO1996025447A1 (en) | 1996-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2208853C (en) | Ultraviolet curable epoxidized alkyds | |
KR920005277B1 (en) | Composition of thermosetting powder coating | |
KR910006330B1 (en) | Crosslinkahle compositions containing polyepoxides and polyacid curing agent | |
CA1334699C (en) | Hybrid powder coating curing system | |
US5494977A (en) | Compositions, epoxized compositions, a heat curable resin composition, an epoxy resin composition, radically polymerized compositions, a curable resin composition and a polymer having epoxy groups | |
US5013791A (en) | Beta-hydroxyalkylamide cured acid polymer/polyepoxide powder coating | |
US6218482B1 (en) | Epoxy resin, process for preparing the resin and photo-curable resin composition and resin composition for powder coatings containing the epoxy resin | |
JP2001200200A (en) | Curable composition | |
JP3077277B2 (en) | New energy ray-curable resin composition | |
CA1340156C (en) | Coating compositions based on polyepoxides and polyacid curing agents | |
US5242996A (en) | Modified epoxy resins having acetylenically unsaturated functions | |
JP3000117B2 (en) | Alicyclic epoxy resins, their production methods, and ultraviolet and electron beam curable resin compositions containing them | |
US4440913A (en) | Coating composition for pliable substrates | |
US11203661B2 (en) | Process for the manufacture of an epoxy-functional polyester, epoxy-functional polyester obtained by such process and coating composition comprising such epoxy-functional polyester | |
US6075099A (en) | Epoxidized polyester-based powder coating compositions | |
US20070031759A1 (en) | Radiation curable polymer films having improved laser ablation properties and radiation curable sensitizers therefor | |
EP0776949A2 (en) | Heat-curable powder coating | |
CA2072270A1 (en) | Production of unsaturated cycloaliphatic esters and derivatives thereof | |
Verschueren et al. | Cycloaliphatic epoxide resins for cationic UV-Cure | |
JPH08134178A (en) | Photocurable epoxy resin composition | |
JP3393735B2 (en) | Resin composition for powder coating | |
JPH11116855A (en) | Resin composition for powder coating material | |
JP2004528405A (en) | Solid epoxy cycloaliphatic hydroxylate resin, preparation method, and composition of curable powder-based coating containing the resin | |
WO2003085028A1 (en) | Novel polyether compound containing acid group and unsaturated group, process for producing the same, and resin composition | |
KR100518793B1 (en) | Components and preparation of high solid type polyester resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |