EP0112824A1 - Urethane modified vinyl ester resins having secondary hydroxyl groups - Google Patents

Urethane modified vinyl ester resins having secondary hydroxyl groups

Info

Publication number
EP0112824A1
EP0112824A1 EP82902423A EP82902423A EP0112824A1 EP 0112824 A1 EP0112824 A1 EP 0112824A1 EP 82902423 A EP82902423 A EP 82902423A EP 82902423 A EP82902423 A EP 82902423A EP 0112824 A1 EP0112824 A1 EP 0112824A1
Authority
EP
European Patent Office
Prior art keywords
vinyl ester
reaction product
hydroxyl groups
secondary hydroxyl
ester resins
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.)
Withdrawn
Application number
EP82902423A
Other languages
German (de)
French (fr)
Other versions
EP0112824A4 (en
Inventor
Lawrence Bruce Burton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0112824A1 publication Critical patent/EP0112824A1/en
Publication of EP0112824A4 publication Critical patent/EP0112824A4/en
Withdrawn legal-status Critical Current

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.

Abstract

Produit de réaction polymérisable d'une résine d'ester vinylique portant des groupes hydroxyles secondaires et de 0,05 à 1 d'équivalent par équivalent d'hydroxyles secondaires de méthacrylate d'isocyanatoéthyle. On peut utiliser ces produits en tant que résines pures et dans des plastiques renforcés.Polymerizable reaction product of a vinyl ester resin carrying secondary hydroxyl groups and from 0.05 to 1 equivalent per equivalent of secondary hydroxyls of isocyanatoethyl methacrylate. These products can be used as pure resins and in reinforced plastics.

Description

URETHANE MODIFIED VINYL ESTER RESINS HAVING SECONDARY HYDROXYL GROUPS
In many resin applications, low viscosity and good physical properties after a minimal heat cure are necessary. Frequently, however, those objectives are antithetical♦ Certain polymer systems that are based 5 on a polyglycidyl ether, such as the vinyl ester resins, have hydroxyl groups along the molecular structure. Those hydroxyl groups cause an appreciable increase in viscosity which requires extensive dilution with a monomer to permit facile fabrication.
10 It would be desirable to have a procedure for reducing the viscosity of hydroxyl containing polymers while at least retaining the properties of the polymer when cured.
This invention is directed to a curable
15 reaction product of a vinyl ester resin having secondary hydroxyl groups and from 0.05 to 1 equivalent based on
^ the secondary hydroxyls of isocyanatoethyl methacrylate.
In the uncured state, the reaction product has a lower f viscosity than the corresponding unmodified resin. In
20 the cured state, 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.
Bowen in U.S. Patent Nos. 3,066,112 and 3,179,623 describes the preparation of vinyl ester resins by esterifying acrylic or methacrylic acid with a polyepoxide. That patentee also describes the alter- nate procedure wherein a glycidyl acrylate or meth¬ acrylate is reacted with the sodium salt of bisphenols. Vinyl ester resins based upon epoxy novolacs are taught in U.S. Patent. No. 3,301,743.
For use herein, 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). Vinyl polymerization inhibitors are also commonly included to prevent pre- 10 mature polymerization.
It is commonplace in the vinyl ester resin art to adjust the viscosity of the liquid uncured resin with 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 reaction of the isocyanate with the s secondary hydroxyl is conducted using known techniques.
In a typical reaction, the polymer or polymer precur¬ sor, the reactive diluent and a catalyst, such as 30 stannous octoate, are thoroughly mixed together and
f OMP brought to a mildly elevated temperature of, for example, 50°C. The isocyanate is slowly added with stirring. Heating is maintained until absence of the isocyanate band in the infrared spectrum is attained which indi- cates the reaction to be complete.
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.
The concept of the invention will be more apparent from the following illustrative examples wherein all parts and percentages are by weight.
Example 1
One hundred parts of the 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
- ϊmϊ -5-
parts isocyanatoethyl methacrylate (IEM) and the temper¬ ature raised to 60°C. Heating and stirring were con¬ tinued until the absence of the isocyanate band in the IR spectrum at 2280 cm" indicated the reaction to be complete. The IEM was employed in the amount of 0.7 equivalent per equivalent of hydroxyl.
To the product was added 11.75 grams styrene. The resin was cured with 1.5 parts benzoyl peroxide per 100 parts resin at a temperature schedule of 2 hours at 90°C, 4 hours at 165°C and 16 hours at 200°C.
For comparison, the trimethacrylate with 20 percent styrene was cured in an identical manner. The samples were tested according to standard methods with the following results.
Nonmodified IEM Modified
Viscosity*, cstks 11,510 7,565 (mVs) (0.01151) (0.007565)
HDT, °C at 264 psi >230 >230 (1820 kPa)
T °C 245 266
Flex. Mod. , psi 9.38 x 105 8.03 x 10 (GPa) (6.47) (5.54)
Flex. Strength, psi 17,470 9,466 (MPa) (120.45) (65.27)
Barcol Hardness 41 53
Gardner Color 17 17
* Before cure
Other samples of the above-described resins were cured with 1.5 parts benzoyl peroxide at 2 hours -6-
at 90°C and 4 hours at 165°C. 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.
Example 2
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.
Nonmodified IEM Modified
Viscosity cstks >1,646 1,445 (mVs) (>.001646) (0.001445)
HDT, °C at 264 psi 110 137 (1820 kPa)
Flex. Mod., psi 4.99 x 105 5.29 x 105 (GPa) (3.44) (3.65)
Flex. Strength, psi 21,510 17,240 (MPa) (148.31) (118.87)
Tensile Strength, psi 9,100 6,460 (kPa) (62.74) (44.54)
24 Hr. H„0 Boil, % Δ wt. 1.827 1.758
Barcol Hardness 45 49
Gardner Color >1 1

Claims

1. A curable reaction product of a vinyl ester resin having secondary hydroxyl groups and from 0.05 to 1 equivalent based on the secondary hydroxyls of isocyanatoethyl methacrylate.
2. The reaction product of Claim 1 wherein the vinyl ester resin is the diester of a polyglycidyl ether with an unsaturated monocarboxylic acid.
3. The reaction product of Claim 1 wherein the vinyl ester resin is the diester of a diglycidyl ether of bisphenol A and a monocarboxylic acid.
4. The reaction product of either Claim 2 or 3 wherein the monocarboxylic acid is methacrylic acid.
5. The reaction product of Claim 1 addi¬ tionally containing up to 60 weight percent of an ethylenically unsaturated monomer.
6. The reaction product of Claim 5 wherein the unsaturated monomer is styrene.
OMPI
EP19820902423 1982-07-02 1982-07-02 Urethane modified vinyl ester resins having secondary hydroxyl groups. Withdrawn EP0112824A4 (en)

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 (2)

Publication Number Publication Date
EP0112824A1 true EP0112824A1 (en) 1984-07-11
EP0112824A4 EP0112824A4 (en) 1984-11-05

Family

ID=22168074

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820902423 Withdrawn EP0112824A4 (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)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0459405A (en) * 1990-06-29 1992-02-26 Nissan Motor Co Ltd Suspension device for vehicle
US7872705B2 (en) * 2007-07-29 2011-01-18 Cree, Inc. LED backlight system for LCD displays
JP6256649B1 (en) * 2016-04-06 2018-01-10 三菱ケミカル株式会社 Thermosetting resin composition, sheet molding compound and method for producing the same, and fiber reinforced composite material
EP3456761B1 (en) 2016-05-13 2020-06-03 Mitsubishi Chemical Corporation Molding material, sheet molding compound and fiber-reinforced composite material

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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
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Title
No relevant documents have been disclosed. *
See also references of WO8400173A1 *

Also Published As

Publication number Publication date
JPS59500969A (en) 1984-05-31
EP0112824A4 (en) 1984-11-05
WO1984000173A1 (en) 1984-01-19
BR8208087A (en) 1984-07-17
JPS6339008B2 (en) 1988-08-03

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