WO1984000173A1 - Urethane modified vinyl ester resins having secondary hydroxyl groups - Google Patents
Urethane modified vinyl ester resins having secondary hydroxyl groups Download PDFInfo
- Publication number
- WO1984000173A1 WO1984000173A1 PCT/US1982/000895 US8200895W WO8400173A1 WO 1984000173 A1 WO1984000173 A1 WO 1984000173A1 US 8200895 W US8200895 W US 8200895W WO 8400173 A1 WO8400173 A1 WO 8400173A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl ester
- reaction product
- hydroxyl groups
- secondary hydroxyl
- ester resins
- Prior art date
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
- 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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- 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
- C08F299/065—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 from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
Definitions
- This invention is directed to a curable
- the reaction product In the uncured state, the reaction product has a lower f viscosity than the corresponding unmodified resin.
- the increased cross-linking density provides improved heat distortion temperatures and hardness and a decrease in water and solvent sorption.
- the vinyl ester resins useful in making the reaction product must have more than one secondary hydroxyl group in the polymer chain.
- the vinyl ester resin can be prepared from any glycidyl polyether.
- Useful glycidyl ethers are those of polyhydric alcohols and phenols. Such glycidyl polyethers are commercially available or are readily prepared by reacting at least two moles of an epihalohydrin or glycerol dihalohydrin with one mole of the polyhydric alcohol or phenol together with a sufficient amount of caustic to react with the halogen of the halohydrin. The products are characterized by the presence of more than one glycidyl ether group per molecule.
- the useful acids for making the vinyl ester resins are those ethylenically unsaturated monocar- boxylic acids such as acrylic, methacrylic, cinnamic acids and their halogenated isomers. Also included are the hydroxyalkyl acrylate or methacrylate half esters of dicarboxylic acids as described in U.S. Patent No. 3,367,992 wherein the hydroxyalkyl group preferably contains from 2 to 6 carbon atoms.
- the glycidyl ether and the acid are reacted in about stoichiometric equivalency generally with 5 heating in the presence of a catalyst, such as a tri- valent chromium salt, as, for example, chromium tri ⁇ chloride or a tertiary amine, as, for example, tris- (N,N-dimethylaminomethyl phenol).
- a catalyst such as a tri- valent chromium salt, as, for example, chromium tri ⁇ chloride or a tertiary amine, as, for example, tris- (N,N-dimethylaminomethyl phenol).
- Vinyl polymerization inhibitors are also commonly included to prevent pre- 10 mature polymerization.
- a reactive diluent usually a copolymerizable monomer.
- Suitable monomers for this use include vinyl 15 aromatic monomers, such as styrene and vinyltoluene, and acrylate or methacrylate esters of lower alkanols.
- the reactive diluent may be an amount of up to 60 weight percent of the combined resin/monomer weight.
- the isocyanatoethyl methacrylate is employed 20 in an amount of 0.05 to 1.00 equivalent per equivalent of hydroxyl. Less than about 0.05 equivalent imparts little observable change in the cured product. Any isocyanate in excess of 1.0 equivalent has no place to react and thus could detract from the desired proper- 25 ties of the cured product.
- the polymer or polymer precur ⁇ sor, the reactive diluent and a catalyst, such as 30 stannous octoate, are thoroughly mixed together and
- the potential for cross-linking in the iso- cyanato product can be adjusted in several ways.
- the amount of unsaturation in the polymer or precursor can be varied.
- the number of hydroxyls in that starting material can vary.
- the amount of unsaturated isocyanate can be adjusted to that providing the desired number of cross-links. Some of the hydroxyls can be reacted with a saturated aliphatic isocyanate.
- the products have improved, properties, par- ticularly heat distortion temperature, hardness and low solvent sorption.
- the products find use as neat resins and in reinforced plastics. Of particular note are their use in fiberglass reinforced filament wound pipe, electrical laminates, electrical insulating varnishes and coatings, bulk and sheet molding compounds, and corrosion resistant vessels and linings for vessels.
- trimethacrylate of tris(4-glycidylphenyl)methane 25 parts of styrene and 0.1 part stannous octoate were mixed while heated to 50°C. To that mix while stirred was slowly added 47.02
- IEM isocyanatoethyl methacrylate
- trimethacrylate with 20 percent styrene was cured in an identical manner.
- the samples were tested according to standard methods with the following results.
- the heat distortion temperature of the nonmodified resin was 203°C and of the IEM modified resin was greater than 230°C.
- the Barcol Hardness of the former was 42 and of the latter was 50.
- a resin was prepared according to the pro ⁇ cedure and stoichiometry of Example 1 using the di eth- acrylate of the diglycidyl ether of bisphenol A as the polymer and vinyltoluene as the reactive diluent.
- the resin was cured with 1.5 parts benzoyl peroxide per 100 parts of resin for one-half hour at 150°C.
- the samples were tested according to standard procedures with the following results.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR8208087A BR8208087A (en) | 1982-07-02 | 1982-07-02 | URETANE-MODIFIED ESTER-VINYL RESINS, CONTAINING SECONDARY HYDROXYLIC GROUPS |
JP57502399A JPS59500969A (en) | 1982-07-02 | 1982-07-02 | Method for producing vinyl ester resin with reduced viscosity |
EP19820902423 EP0112824A4 (en) | 1982-07-02 | 1982-07-02 | Urethane modified vinyl ester resins having secondary hydroxyl groups. |
PCT/US1982/000895 WO1984000173A1 (en) | 1982-07-02 | 1982-07-02 | Urethane modified vinyl ester resins having secondary hydroxyl groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1982/000895 WO1984000173A1 (en) | 1982-07-02 | 1982-07-02 | Urethane modified vinyl ester resins having secondary hydroxyl groups |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1984000173A1 true WO1984000173A1 (en) | 1984-01-19 |
Family
ID=22168074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1982/000895 WO1984000173A1 (en) | 1982-07-02 | 1982-07-02 | Urethane modified vinyl ester resins having secondary hydroxyl groups |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0112824A4 (en) |
JP (1) | JPS59500969A (en) |
BR (1) | BR8208087A (en) |
WO (1) | WO1984000173A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110273645A1 (en) * | 2007-07-29 | 2011-11-10 | Cree, Inc. | Led backlight system for lcd displays |
CN108884208A (en) * | 2016-04-06 | 2018-11-23 | 三菱化学株式会社 | Compositions of thermosetting resin, sheet molding compound and its manufacturing method and fibre reinforced composites |
US10899856B2 (en) | 2016-05-13 | 2021-01-26 | Mitsubishi Chemical Corporation | Molding material, sheet molding compound and fiber-reinforced composite material |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0459405A (en) * | 1990-06-29 | 1992-02-26 | Nissan Motor Co Ltd | Suspension device for vehicle |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2503209A (en) * | 1948-01-30 | 1950-04-04 | American Cyanamid Co | Unsaturated alkyd reacted with unsaturated isocyanate |
US2958704A (en) * | 1958-09-02 | 1960-11-01 | Goodrich Co B F | Alkenyl isocyanate-substituted carbamates |
US3118922A (en) * | 1959-03-03 | 1964-01-21 | Bayer Ag | Method of preparing organic isocyanates |
US3373221A (en) * | 1964-11-04 | 1968-03-12 | Shell Oil Co | Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates |
US3471449A (en) * | 1965-11-19 | 1969-10-07 | Bayer Ag | Preparation of high molecular weight amines containing urethane and urea groups |
US3478126A (en) * | 1967-05-26 | 1969-11-11 | Scm Corp | Urethane modified epoxy ester resin compositions and products |
US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
US3664861A (en) * | 1968-03-01 | 1972-05-23 | Kansai Paint Co Ltd | Coating process |
US3713864A (en) * | 1971-01-06 | 1973-01-30 | Inmont Corp | Method of printing or coating using actinic radiation setting of applied coating and coated product |
US3776889A (en) * | 1971-01-07 | 1973-12-04 | Powers Chemco Inc | Allyl carbamate esters of hydroxy-containing polymers |
US3871908A (en) * | 1970-12-31 | 1975-03-18 | Basf Ag | Production of urethane group containing coatings by curing with ionizing radiation |
US4004997A (en) * | 1972-01-30 | 1977-01-25 | Seiko Shimada | Process of curing a polymerizable composition containing a magnetized powered ferromagnetic material with radioactive rays |
US4035523A (en) * | 1975-05-07 | 1977-07-12 | Pampouchidis Georgios Georg | Process for producing improved coating compositions |
US4162274A (en) * | 1975-12-19 | 1979-07-24 | Bayer Aktiengesellschaft | Crosslinkable urethane resins containing vinyl and carboxyl groups |
US4221686A (en) * | 1975-01-22 | 1980-09-09 | Sumitomo Chemical Company, Limited | Ultraviolet radiation curable printing ink |
US4233425A (en) * | 1978-11-15 | 1980-11-11 | The Dow Chemical Company | Addition polymerizable polyethers having pendant ethylenically unsaturated urethane groups |
US4239866A (en) * | 1976-08-13 | 1980-12-16 | Basf Aktiengesellschaft | Curable coating composition |
US4320221A (en) * | 1980-12-12 | 1982-03-16 | The Dow Chemical Company | Addition polymerizable isocyanate-polyol anaerobic adhesives |
-
1982
- 1982-07-02 EP EP19820902423 patent/EP0112824A4/en not_active Withdrawn
- 1982-07-02 WO PCT/US1982/000895 patent/WO1984000173A1/en not_active Application Discontinuation
- 1982-07-02 BR BR8208087A patent/BR8208087A/en unknown
- 1982-07-02 JP JP57502399A patent/JPS59500969A/en active Granted
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2503209A (en) * | 1948-01-30 | 1950-04-04 | American Cyanamid Co | Unsaturated alkyd reacted with unsaturated isocyanate |
US2958704A (en) * | 1958-09-02 | 1960-11-01 | Goodrich Co B F | Alkenyl isocyanate-substituted carbamates |
US3118922A (en) * | 1959-03-03 | 1964-01-21 | Bayer Ag | Method of preparing organic isocyanates |
US3373221A (en) * | 1964-11-04 | 1968-03-12 | Shell Oil Co | Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates |
US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
US3471449A (en) * | 1965-11-19 | 1969-10-07 | Bayer Ag | Preparation of high molecular weight amines containing urethane and urea groups |
US3478126A (en) * | 1967-05-26 | 1969-11-11 | Scm Corp | Urethane modified epoxy ester resin compositions and products |
US3664861A (en) * | 1968-03-01 | 1972-05-23 | Kansai Paint Co Ltd | Coating process |
US3871908A (en) * | 1970-12-31 | 1975-03-18 | Basf Ag | Production of urethane group containing coatings by curing with ionizing radiation |
US3713864A (en) * | 1971-01-06 | 1973-01-30 | Inmont Corp | Method of printing or coating using actinic radiation setting of applied coating and coated product |
US3776889A (en) * | 1971-01-07 | 1973-12-04 | Powers Chemco Inc | Allyl carbamate esters of hydroxy-containing polymers |
US4004997A (en) * | 1972-01-30 | 1977-01-25 | Seiko Shimada | Process of curing a polymerizable composition containing a magnetized powered ferromagnetic material with radioactive rays |
US4221686A (en) * | 1975-01-22 | 1980-09-09 | Sumitomo Chemical Company, Limited | Ultraviolet radiation curable printing ink |
US4035523A (en) * | 1975-05-07 | 1977-07-12 | Pampouchidis Georgios Georg | Process for producing improved coating compositions |
US4162274A (en) * | 1975-12-19 | 1979-07-24 | Bayer Aktiengesellschaft | Crosslinkable urethane resins containing vinyl and carboxyl groups |
US4239866A (en) * | 1976-08-13 | 1980-12-16 | Basf Aktiengesellschaft | Curable coating composition |
US4233425A (en) * | 1978-11-15 | 1980-11-11 | The Dow Chemical Company | Addition polymerizable polyethers having pendant ethylenically unsaturated urethane groups |
US4320221A (en) * | 1980-12-12 | 1982-03-16 | The Dow Chemical Company | Addition polymerizable isocyanate-polyol anaerobic adhesives |
Non-Patent Citations (1)
Title |
---|
See also references of EP0112824A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110273645A1 (en) * | 2007-07-29 | 2011-11-10 | Cree, Inc. | Led backlight system for lcd displays |
US20110317093A1 (en) * | 2007-07-29 | 2011-12-29 | Cree, Inc. | Led backlight system for lcd displays |
CN108884208A (en) * | 2016-04-06 | 2018-11-23 | 三菱化学株式会社 | Compositions of thermosetting resin, sheet molding compound and its manufacturing method and fibre reinforced composites |
US10920009B2 (en) | 2016-04-06 | 2021-02-16 | Mitsubishi Chemical Corporation | Thermosetting resin composition, sheet-molding compound and production method therefor, and fiber-reinforced composite material |
US10899856B2 (en) | 2016-05-13 | 2021-01-26 | Mitsubishi Chemical Corporation | Molding material, sheet molding compound and fiber-reinforced composite material |
Also Published As
Publication number | Publication date |
---|---|
JPS59500969A (en) | 1984-05-31 |
EP0112824A4 (en) | 1984-11-05 |
JPS6339008B2 (en) | 1988-08-03 |
EP0112824A1 (en) | 1984-07-11 |
BR8208087A (en) | 1984-07-17 |
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