EP0496789A4 - Trivinyl ethers of polyols - Google Patents
Trivinyl ethers of polyolsInfo
- Publication number
- EP0496789A4 EP0496789A4 EP19900915681 EP90915681A EP0496789A4 EP 0496789 A4 EP0496789 A4 EP 0496789A4 EP 19900915681 EP19900915681 EP 19900915681 EP 90915681 A EP90915681 A EP 90915681A EP 0496789 A4 EP0496789 A4 EP 0496789A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compound
- acetylene
- trivinyl ether
- ether
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
- C07C43/16—Vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
Definitions
- This invention relates to trivinyl ether monomers and resin formulations thereof useful in applications which require high speed cationic initiated radiation curing.
- Radiation curable coatings and films such as those formed from an acrylate oligomer are in great demand because of their rapid curing properties.
- these compounds are normally highly viscous liquids or solids and thus are unsuitable as diluents for other polymeric components of a radiation curable formulation.
- such compounds themselves require the incorporation of a diluent or solvent for uniform substrate coating, control of coating thickness and curing at low temperatures.
- low viscosity monofunctional diluents are usually included in their formulations. While these diluents are reactive, they materially reduce the cross-linked density of the finished product and consequently lower abrasion resistance and ability to withstand chemical attack.
- unsubstituted acrylates are sensitizers and skin irritants as well as being carcinogenic, so that specialized safety precautions must be taken to protect operators from exposure.
- X and Y are independently H or CH 3 .
- compositions of formula (II) include:
- compositions of formula (II) are those having from about 45 to about 95 wt. % of component (a) wherein:
- component (b) from about 0.5 to about 2 wt. % of component (b) ; and from about 0 to about 50 wt. % of component (c) .
- Preferred trivinyl ether compounds (a) of formula (II) include the trivinyl ether of an ethoxylated glycerol having the formula:
- the monomer of formula (I) may be prepared by direct vinylation of l,l,l-tris(hydroxymethyl) ethane with acetylene.
- the mole ratio of polyol to acetylene can vary between about 1:3 and about 1:4.5.
- the acetylene gas is bubbled through the polyol liquid itself, or a solution of the polyol in a suitable solvent, such as the dimethyl ether of tetraethylene glycol.
- Other methods of preparation also may be used for synthesis of the compound of the invention, such as catalytic transetherification of the polyol with a suitable vinyl ether having a boiling point higher than the monomer product.
- the acetylene can be introduced into the reaction zone without dilution if present at low pressures; however, at elevated pressures, it is recommended that an inert non-oxygen containing gaseous diluent, such as nitrogen, a c l ⁇ c 3 alJcane or helium be used to dilute the acetylene reactant.
- an inert non-oxygen containing gaseous diluent such as nitrogen, a c l ⁇ c 3 alJcane or helium
- an acetylene concentration as low as 10% can be used, although between about 40 and about 60 wt. % acetylene in a diluent is most preferred.
- the reaction is carried out in an oxygen free atmosphere which is generally achieved by purging with nitrogen and in the presence of a basic catalyst, such as an alkali metal hydroxide, e.g. potassium hydroxide, sodium hydroxide, and sodium, potassium or lithium metal, or hydride thereof.
- a basic catalyst such as an alkali metal hydroxide, e.g. potassium hydroxide, sodium hydroxide, and sodium, potassium or lithium metal, or hydride thereof.
- concentration of catalyst employed can range from about 0.01% to about 5% by weight.
- the process is effected at a temperature of between about 120° and about 180°C. , under from about 10 to about 200 psig. total pressure, in a period of from about 2 to about 100 hours reaction time.
- Preferred conditions include a temperature of between about 140° to about 170 ⁇ C., under between about 50 and about 100 psig. acetylene pressure and a reaction period of from about 4 to 70 hours.
- the trivinyl ether monomers of formula (II) may be prepared by direct vinylation of an ethoxylated or propoxylated glycerol with acetylene to provide monomers of the general formula above.
- the acetylene gas is bubbled through the alkoxylated glycerol liquid itself, or a solution of the alkoxylated glycerol in a suitable solvent, such as the dimethyl ether of tetraethylene glycol.
- Examples of the cationic photoinitiator, component (b) include the triphenyl sulfonium salt of phosphorous hexafluoride, diphenyl iodium salt, tetrazolium chloride, a phenyl onium salt and an alkyl aryl onium salt.
- a preferred cationic photoinitiator is triphenyl sulfonium hexafluorophosphate.
- Suitable examples of the oligomer component (c) include any of the mono- and di- vinyl ethers of di-, tri- or tetra- ethylene or propylene glycols; C 2 to C 20 alkylene divinyl ethers; benzene divinyl ether; and the corresponding thioethers and epoxides; and acrylates such as pentaerythritol triacrylate. Mixtures of such compounds also may be used.
- Preferred oligo ers are bisphenol.
- diepoxide diepoxide; triethylene glycol divinyl ether; acrylated epoxides; vinyl ether functionalized oligomers; and hexanediol diacrylate or methacrylate, pentaerythritol triacrylate and trimethacrylate.
- compositions are readily prepared by mixing the components in any order until a uniform mixture is obtained.
- the resulting composition which is a viscous liquid is easily applied to a substrate in a thickness of from about 0.1 to about 20 mils, preferably from about 0.5 to about 10 mils.
- Suitable substrates include glass, ceramic, metal, plastic, wood, masonary and fabrics. Because of the improved liquid viscosity, it is possible to retain higher thicknesses of film build-up on the substrate surface.
- the desired viscosity e.g. between about 30 and about 1,000 cps, is achieved without the introduction of extraneous chemical solvents and the like.
- the presence of the multifunctional vinyl ethers also permits rapid radiation curing, for example within a period of less than one second exposure to between about 100 to about 800 millijoules/cm 2 of uv light; between about 0.5 and about 5 megarads dosage of radiation from an electron beam or equivalent dosage from laser emissions. It is to be understood that many other, sources of radiation can be used to effect curing.
- the radiation curing process is carried out at about room temperature under ambient pressure in the absence of solvent normally required with highly viscous materials.
- the present compositions also lend themselves to thermal curing procedures effected at a temperature between about 70°C. and about 150°C. for a period of from about 5 to about 25 minutes in the presence of conventional initiators. Because of their sensitivity to curing by exposure to a source of radiation, the present products are also useful as photoresists when coated on a photographic film.
- compositions of this invention when cured, provide clear films or coatings of superior toughness, abrasion resistance, and resistance to chemical attack in acid or basic media.
- Tris(hydroxymethyl) ethane (1201.5 g) , tetraethylene glycol dimethyl ether (1000 g) and potassium hydroxide, 85% pellets (30 g) were charged into a one-gallon autoclave.
- the autoclave was purged three times with nitrogen, heated to 110 ⁇ C. and held under vacuum at 20 mm Hg for 10 minuts.
- Propane (100 psig.) was then added and the temperature was raised to 140°C.
- the propane pressure was readjusted to 100 psig. and acetylene (100 psig.) was introduced to start the vinylation.
- the reaction was complete in 62 hours.
- the autoclave was then cooled to room temperature, purged two times with nitrogen and discharged. 2797 g of crude product was obtained which contained 86.4% of the trivinyl ether of tris(hydroxymethyl) ethane, as determined by glc analysis.
- the crude product (2788 g) was distilled with a 30 plates Oldershaw column at a reduced pressure of 7 mm Hg.
- a total of 646.9 g of the trivinyl ether of tris(hydroxymethyl) ethane with 99% purity was collected between 69° and 71°C.
- the structure of the trivinyl ether was identified by nmr analysis.
- Glycerol (870 g., 9.4 moles) and sodium hydroxide (1.0 g.) were charged into a one-gallon autoclave. The mixture was purged three times with nitrogen, heated to 140 ⁇ C. and subjected to a vacuum of 30 mm Hg for one-half hour. The temperature of the solution was then brought to 155°C. and ethylene oxide (2080 g., 47.3 moles) was added at 30 psig. After all the ethylene oxide was consumed, the autoclave was cooled to 30°C., purged two times with nitrogen and discharged.
- Glycerol (552 g. , 6 moles) and sodium hydroxide (0.6 g.) where charged into a one-gallon stainless steel autoclave.
- the autoclave was purged three times with nitrogen, heated to 115°C. and subjected to a vacuum of 30 mm Hg for one-half hour.
- Propylene oxide (2088 g., 36 moles) was added at 30 psig. After all the propylene oxide was consumed, the autoclave was cooled to 30°C. , purged two times with nitrogen and discharged.
- the crude trivinyl ether was distilled with a thin film evaporator to give pure trivinyl ether of propyoxylated glycerol as a clear liquid.
- the structure of the trivinyl ether was confirmed by nmr analysis.
- Example 2 To a 4-ounce amber colored bottle is added 25 g. of trivinyl ether of ethoxylated glycerol prepared in Example 2 and 0.5 g. of triphenyl sulfonium hexafluorophosphate at a temperature of 60°C. with constant agitation.
- the formulation is coated onto a polyester plate by hand draw-down using a No. 3 Mayer bar to give a coating thickness of about 0.2 mil.
- the plate is subjected to a UV light exposure of 15 joules/cm 2 by passing it under two 200 watt/inch UV lamps at 700 feet/minute. This is followed by a thermal bake at 177°C. for 10 minutes.
- a protective chemical coating on the polyester is formed.
- triphenyl sulfonium hexafluoro ⁇ phosphate are added and mixed therein at about 45°C.
- This formulation is coated on a aluminumn panel by hand draw-down using a No. 3 Mayer bar to give a coating thickness of 0.4 mil.
- the panel is subjected to a UV light exposure of 15 joules/cm 2 by passing them under two 200 watt/inch UV lamps at 100 feet/minute. This was followed by a thermal bake at 177°C. for 10 minutes.
- a highly cross-linked protective polymer film is formed which is chemical and abrasion resistant.
- Example 5 The formulation from Example 5 is repeated except that an acrylated epoxy oligomer (Ebecryl 3700, Radcure Specialties) is used in place of the bisphenol diepoxide. Two grams of 1-hydroxycyclohexylphenyl ketone was also added as a free radical photoinitiator. This formulation is coated on an oak panel using a #24 Mayer bar to give a coating thickness of 1.0 mil. The panel is subjected to uv light exposure of 15 joules/cm 2 by passing them under two 200 watt/inch UV lamps at 100 feet/minute. A highly cross-linked protective polymer film which is chemical and abrasion resistant is formed.
- an acrylated epoxy oligomer (Ebecryl 3700, Radcure Specialties) is used in place of the bisphenol diepoxide.
- Two grams of 1-hydroxycyclohexylphenyl ketone was also added as a free radical photoinitiator.
- This formulation is coated on an oak panel using a #24 Mayer bar
- Example 5 The formulation from Example 5 is repeated except that a vinyl ether functional urethane prepared from a hydroxy vinyl ether and a toluene diisocyanate was used in place of the bisphenol diepoxide.
- This formulation is coated on a polyester film using a #3 Mayer bar to give a coating thickness of 0.3 mil.
- the panel is exposed to UV light of 15 joules/cm 2 by passing them under two 200 watt/inch UV lamps at 100 feet/minute. A fully cured protective coating is formed.
- the compound of the invention exhibits a high speed cationic initiated radiation curing property, which enables its use in applications which require high speed curing, such as radiation curable coatings, photoresists in the electronic industry, and printing inks, which applications require ultraviolet or electronic beam activation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US437706 | 1982-10-29 | ||
US42441989A | 1989-10-20 | 1989-10-20 | |
US424419 | 1989-10-20 | ||
US43770689A | 1989-11-17 | 1989-11-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0496789A1 EP0496789A1 (en) | 1992-08-05 |
EP0496789A4 true EP0496789A4 (en) | 1992-10-21 |
Family
ID=27026322
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19900915681 Withdrawn EP0496789A4 (en) | 1989-10-20 | 1990-10-11 | Trivinyl ethers of polyols |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0496789A4 (en) |
AU (1) | AU644108B2 (en) |
CA (1) | CA2027747A1 (en) |
WO (1) | WO1991005756A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4215076A1 (en) * | 1992-05-07 | 1993-11-11 | Wacker Chemie Gmbh | Siloxane copolymers containing vinyloxy groups, their preparation and use |
DE4215030A1 (en) * | 1992-05-07 | 1993-11-11 | Wacker Chemie Gmbh | Siloxane copolymers containing vinyloxy groups, their preparation and use |
DE19509352A1 (en) * | 1995-03-15 | 1996-09-19 | Basf Ag | Process for working up reaction mixtures resulting from addition reactions to acetylene or propyne |
DE10017222A1 (en) * | 2000-04-06 | 2001-10-11 | Basf Ag | Process for the preparation of alkenyl ethers |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR724955A (en) * | 1930-10-30 | 1932-05-06 | Ig Farbenindustrie Ag | Process for the production of vinyl ethers |
GB1518141A (en) * | 1974-05-02 | 1978-07-19 | Gen Electric | Polymerizable compositions |
US4026705A (en) * | 1975-05-02 | 1977-05-31 | General Electric Company | Photocurable compositions and methods |
US4142042A (en) * | 1976-06-23 | 1979-02-27 | Diamond Shamrock Corporation | Alkenyl ethers from high molecular weight polyols |
US4751273A (en) * | 1986-08-19 | 1988-06-14 | Allied-Signal, Inc. | Vinyl ether terminated urethane resins |
US4766252A (en) * | 1987-10-16 | 1988-08-23 | Gaf Corporation | Solvent and stain resistant coatings |
US4828873A (en) * | 1987-10-16 | 1989-05-09 | Gaf Corporation | Solvent and stain resistant coating |
US4885319A (en) * | 1988-02-29 | 1989-12-05 | Gaf Corporation | Solvent resistant irradiation curable coatings |
-
1990
- 1990-10-11 WO PCT/US1990/005773 patent/WO1991005756A1/en not_active Application Discontinuation
- 1990-10-11 AU AU65484/90A patent/AU644108B2/en not_active Ceased
- 1990-10-11 EP EP19900915681 patent/EP0496789A4/en not_active Withdrawn
- 1990-10-16 CA CA 2027747 patent/CA2027747A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
No further relevant documents have been disclosed. * |
See also references of WO9105756A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU6548490A (en) | 1991-05-16 |
AU644108B2 (en) | 1993-12-02 |
EP0496789A1 (en) | 1992-08-05 |
WO1991005756A1 (en) | 1991-05-02 |
CA2027747A1 (en) | 1991-04-21 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19920509 |
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RBV | Designated contracting states (corrected) |
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A4 | Supplementary search report drawn up and despatched |
Effective date: 19920828 |
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AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19950530 |