EP0514482A4 - Vinyl ether compounds - Google Patents
Vinyl ether compoundsInfo
- Publication number
- EP0514482A4 EP0514482A4 EP19910904850 EP91904850A EP0514482A4 EP 0514482 A4 EP0514482 A4 EP 0514482A4 EP 19910904850 EP19910904850 EP 19910904850 EP 91904850 A EP91904850 A EP 91904850A EP 0514482 A4 EP0514482 A4 EP 0514482A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkylene
- lower alkyl
- oco
- radicals
- carbon atoms
- 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- Withdrawn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
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
Definitions
- B is a divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or polyalkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy;
- R is hydrogen or lower alkyl and n has a value of from 1 to 10.
- alkenyl ether polycarbonates having the formula
- R and R" are each independently a divalent radical having from 2 to 20 carbon atoms and are selected from the group of alkylene, mono- or poly- alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, alkyl, cyano, nitro or alkoxy;
- R 1 is hydrogen or lower alkyl; (n) has a value of from 1 to 10 and (m) has a value of from 0 to 10; with the proviso that R" contains at least 3 carbon atoms when m is zero.
- R is a C 3 to C 50 saturated or unsaturated, linear, branched or cyclic polyhydroxylated hydrocarbon radical optionally substituted with halo, alkoxy, lower alkyl, cyano or nitro;
- R' is hydrogen or lower alkyl
- R" is the same as R except that it contains at least one less hydroxy group.
- B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono- or poly- alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy
- m has a value of from 1 to 10
- (b) has a value of from at least 1 up to the number of hydroxy groups in ROH and
- n represents the number of hydroxy groups in ROH, generally from 3 to 10 hydroxy groups.
- Polyhydroxylated reactant (I) contains at least 3, preferably not more than 10, hydroxy groups and includes hydroxylated derivatives of alkylene, alkenylene, alkynylene, arylene, alkarylene, aralkylene and ethoxylated or propoxylated species of these radicals.
- Specific examples of hydroxylated reactant (I) are represented by trihydroxy benzene, trihydroxy nitrobenzene, tetrahydroxy diphenyl dimethyl methane, hexahydroxy * .
- diphenyl methane tetrahydroxy styrene, tetrahydroxy oluene, dichlorotrihydroxy benzene, trihydroxy cyanomethyl benzene, dinitrotrihydroxybenzene, hexahydroxy anthranol, and alkoxylated derivatives thereof 1,2,5,7,9-penta- hydroxynonane, 1,2,4-trihydroxybutane, 4,5-dichloro-l,3,6,10-tetrahydroxydecane, decahydroxy tetracosane, decahydroxy pentacontane, 1,2,11,12-tetrahydroxy dodec-6-yne,
- 3,5-bromo-l,2,13,14-tetradecane trimethylol ethane, trimethylol propane, 3-ethoxy-l,2,4,5-tetrahydroxypentane, pentaerythritol, starches, cellulose, sugars and alkoxylated drivatives thereof.
- dialkenyloxy carbonate coreactants (II) are preferably those wherein R' is hydrogen or methyl, m is l and B is butylene, di ethylene cyclohexane or ethoxylated or propoxylated derivatives thereof.
- suitable coreactants include bis(ethenyloxy butyl) carbonate, bis(ethenyloxy dimethylcyclohexyl) carbonate, bis(prop-1-enyloxy butyl) carbonate, and the polyethoxylated or polypropoxylated derivatives thereof, such as for example the polyethoxylated derivative of bis(ethenyloxy butyl) carbonate, having the formula
- p has a value of from 1 to 10.
- R is a polymeric radical selected from the group of polyester, polyacetal, polyurethane, polyether, polybutadiene and polycarbonate, said polymers containing from about 10 to 50 repeating monomer units;
- A is hydrogen, lower alkyl or hydroxy
- R* is hydrogen or lower alkyl
- B is a linear, branched or cyclic divalent radical having from 2 to 12 carbon atoms and is selected from the group of alkylene, mono or poly alkoxylated alkylene, alkenylene, alkynylene, arylene, alkarylene and aralkylene radicals, which radicals are optionally substituted with halo, lower alkyl, cyano, nitro or alkoxy (m) has a value of from 1 to 10; (a) is zero when A is hydroxy and (a) is one when A is hydrogen or lower alkyl.
- Reactant (I) includes hydroxylated compounds having the formulae:
- R is a linear, branched---or cyclic radical having from 2 to 20 carbon atoms and is selected from the group of alkylene, alkyleneoxy alkylene, polyalkylenenxy alkylene, arylene, alkarylene, alkarylalkylene and aralkylene;
- X is oxygen or sulfur;
- A is branched or linear alkylene having from 1 to 20 carbon atoms;
- B is halo or lower alkyl; n has a value of from 1 to 20 and p has a value of from 0 to 4.
- the invention also relates to the preparation and use of said aryloxy divinyl ethers.
- Preferred compounds are those wherein X is oxygen; A is >C(CH 3 ) 2 ; p is zero; n has a value of from 1 to 4 and R is a radical having from 2 to 8 carbon atoms.
- the above carbonates (A) are synthesized by reacting a hydroxylated al -1-enyl ether with a dialkyl carbonate according to the following equation.
- REACTANT I REACTANT II PRODUCT III wherein x is 1 or 2; each R* is represented by lower alkyl and R, A, B and n are as defined above.
- the reaction is carried out under mild conditions such as a temperature of between about 65°C. and about 150°C. under a pressure ranging from about atmospheric to about 50 psig. for a period of from about 1 to about 30 hours, preferably at a temperature of between about 75° and about 125°C. under ambient pressure for a period of from about 1.5 to about 10 hours.
- This reaction is effected in an oxygen-free atmosphere under a blanket of inert gas, e.g. nitrogen.
- the reaction is promoted with between about 0.01 and about 5 wt.
- a base catalyst including such catalysts as sodium or potassium alkoxides, particularly-meth ⁇ xides; sodium or potassium metal; sodium or potassium-..hydroxide, hydride or phenoxide, alkaline earth metal hydroxides or alkoxides and alkaline or alkali earth salts of reactant I.
- the ratio of reactant I to II can vary within the range of between about 1:5 and about 15:1, preferably between about 1.2:1 and about 5:1.
- an inert liquid at a concentration of up to 50 wt. % of the reaction mixture can be employed.
- Suitable diluents include toluene, xylene, benzene, alkyl ethers, N-methyl- pyrrolidone, butyrolactone, ethyl acetate and the like which are normally liquid and have a boiling point below that of the reaction product.
- the compounds of this invention where A is lower alkyl can be prepared by reacting a C- ⁇ to C g alcohol with a divinyloxy carbonate according to the equation:
- the present polycarbonates (B) are synthesized by reacting a hydroxyalkyl alk-1-enyl ether, a diol and a dialkyl carbonate according to the following equation.
- each R* • ' is represented by lower alkyl and R, R*, R", A, m and n are as defined above.
- the mole ratio of reactant I to II to reactant III can vary within the range of between about 1:10:20 and about 1:0.5:2, preferably between about 4:1:4 and about 2:1:2.
- an inert liquid at a concentration of up to 50 wt. % of the reaction mixture can be employed.
- Suitable diluents include toluene, xylene, benzene, alkyl ethers, N-methylpyrrolidone, butyrolactone, ethyl acetate and the like which are normally liquid and have a boiling point below that of the reaction product.
- dialkenyloxy dicarbonate products can be prepared by reacting the diol (HOR'OH) with a dialkenyloxy monocarbonate (A) above.
- the reaction conditions for this alternative reaction are substantially the same as those described above except that the mole ratio of diol to carbonate reactant:is..about 1:2. This reaction can be defined by the equation.
- the reaction for synthesizing the above compounds (C) is conducted in the presence of between about 0.01 and about 5 wt. %, preferably between about 0.1 and about 1 wt. % of a basic catalyst such as particulate sodium, potassium or lithium metal, sodium, potassium or lithium hydroxide, hydride or alkoxide, e.g. methoxide, and the like.
- a basic catalyst such as particulate sodium, potassium or lithium metal, sodium, potassium or lithium hydroxide, hydride or alkoxide, e.g. methoxide, and the like.
- the reactants may be diluted with up to 80% of a suitable inert solvent such as xylene, toluene, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, etc. Although dilution is usually recommended for more viscous reaction mixtures, it is also within the scope of this invention to carry out the reaction in the absence of solvent.
- the reaction conditions include a temperature of from about 50° to about 200°C, a pressure of from about 1 mm Hg to about 100 atmospheres for a period of from about 0.5 to about 24 hours. Within the above operating parameters, between about 90° and about 120°C. under from about 1 to about 10 mm Hg for a period of from about 3 to about 7 hours are preferred. High conversions in excess of 80% are achieved by the present reaction.
- the ratio of polyhydroxylated reactant to dialkenyloxy alkyl carbonate is as close to stoichiometry of the product desired as is convenient to maintain.
- the amount of dialkenyloxy alkyl carbonate varies from about 1 to about 2 moles..of. carbonate per equivalent of hydroxyl groups.
- excess amount of. the. alkenyloxy alkyl carbonate up to about a 10 mole excess, can be employed without detriment to the reaction; the only objection being that such high excesses of the carbonate reactant are wasteful and inefficient.
- the crude product of the above reaction generally contains a mixture of products.
- ROH is HOCH 2 -CH(OH)CH(OH)CH 2 OH
- the crude product contains one or more of the following derivatives, depending upon the amount of coreactant employed.
- R'HC CH0(B) Jn 0C0-R(0H) 3
- the products can be separated by any conventional means, e.g. fractional distillation, if desired.
- dialkenyloxy alkyl carbonate coreactants (II) are the (A) compounds described above and are preferably those wherein R* is hydrogen or methyl, m is 1 and B is butylene, dimethylene cyclohexane or ethoxylated or propoxylated derivatives thereof.
- suitable coreactants include bis(ethenyloxy butyl) carbonate, bis(ethenyloxy dimethylcyclohexyl) carbonate, bis(prop-l-enyloxy butyl) carbonate, bis(l-propenyloxy phenyl) carbonate, bis(ethenyloxy benzyl) carbonate, bis(ethenyloxy xylyl) carbonate and the polyethoxylated or polypropoxylated derivatives thereof, such as for example the polyethoxylated derivative of bis(ethenyloxy butyl) carbonate, having the formula 0
- p has a value of from 1 to 10.
- the above divinyl ethers (E) are synthesized by reacting a hydroxyvinyl ether with a diepoxide of a bisphenol such as bisphenol A epoxy resin, or a bisphenol F epoxy resin.
- the reaction is effected according to the following equation.
- the synthesis reaction can be carried out in the presence of air or in the absence of oxygen under a blanket of inert gas.
- the present condensation reaction is carried out at a temperature of between about 100° and about 175°C under atmospheric pressure for a period of from 0.5 to 200 hours.
- Preferred reaction parameters include a temperature of from about 120° to about 160°C for a period of from about 2 to about 100 hours.
- the reaction is also conducted in the presence of a base catalyst such as particulate sodium, potassium, or lithium metal, sodium or potassium hydroxide or hydride.
- a base catalyst such as particulate sodium, potassium, or lithium metal, sodium or potassium hydroxide or hydride.
- the catalyst is present in an amount of from about 0.01 to about 2 wt. %, preferably from .about.;0 * 1 to about 1 wt. % of the total mixture.
- Suitable solvents include toluene, xylene, triethylene glycol dimethyl ether, N-methylpyrrolidone and the like. Such solvents can be employed in concentrations up to about 50% of the reaction mixture.
- the hydroxy vinyl ether reactant and the phenylic coreactant of the present process are generally employed in a mole ratio of from about 1:1 to about 10:1, preferably from about 1.05:1 to about 3:1.
- Suitable hydroxylated vinyl ether reactants include the mono vinyl ether of cyclohexanedimethanol, tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxypropyl) vinyl ether, the onovinyl ether of 3-ethyl-l,6-hexanediol, (4-hydroxybutyl) vinyl ether, 6-hydroxyhexyl vinyl ether, the monovinyl ether of 2-methyl-l,8-octanediol, (vinyloxy) cresol, vinyloxymethyl cyclohexyl methanol and alkoxylated derivatives thereof containing from 1 to .6 ethyleneoxy or propyleneoxy units.
- Suitable coreactants include the mono vinyl ether of cyclohexanedimethanol, tetra(hydroxyethyl) vinyloxy hexane, (2-hydroxyethyl) vinyl ether, (3-hydroxyprop
- the initiators suitable to effect polymerization reactions of the present invention can also comprise a mixture including the above 'named.--cationic initiators and a free radical initiator to provide- a hybrid, initiated system.
- Suitable free radical initiators include 1-hydrocyclohexyl phenyl ketone (HPK) , 2-hydroxy-2-methyl-l-phenyl-l-propan-l-one (HMPPO) , 2,2-dichloro-l-(4-phenoxyphenyl) ethanone (DPPE) and the like.
- the free radical component can comprise up to 75%, preferably between about 30 and about 70%, of the initiator component.
- the present cationic initiator or cationic/free radical initiator mixtures provide the benefits of this invention when used for cross-linking blends of the present vinyl ether carbonate and vinyl ether or epoxide monomers. However, when the blend contains an aerylate polymerizable comonomer the initiator mixture is recommended.
- the total amount of initiator employed is generally between about 0.1 and about 5 wt. % with respect to reactant or reactants.
- UV light radiation dosages at room temperature of from about 100 to about 1500 " illi J/cm 2 are effective and dosages of from about 200 to about 600 milli J/cm 2 are preferred.
- Equivalent dosages for curing are employed when using alternative sources of radiation.
- curing with electron beam radiation can be carried out at between about 0.5 and about 20 Mrads, preferably between about 1 and about 10 Mrads. Specific techniques for radiation curing are well known, thus further amplification is not required.
- the present products can be mixed with a vinyl ether, epoxide, aerylate or vinyloxy alkyl urethane monomer or polymer, or other monomers and oligomers which otherwise would not be amenable to cationic radiation curing, to incorporate and combine the advantages of instant compounds with the beneficial properties of those coating materials or other monomers and oligomers.
- Examples of monomers or polymers'- • with--which the present products can be combined to form-coatings include the 1,4-butanediol diglycidyl ether; 3,4>-epoxycyclohexyl methyl-3,4-epoxy cyclohexane carboxylate / diglycidyl ethers of bisphenol A or bisphenol F; polyglycidyl ethers of phenol-formaldehyde, e.g. epoxy novolac resins and other functional monomers and polymers which possess properties beneficial in durable protective coatings.
- the mixture contains at least 5% of the present alkenyl ether carbonate.
- the ho opolymerized and copolymerized products of this invention have high resistance to solvents, acids and bases and form hard abrasion resistant films and coatings, possessing good substrate substantivity.
- the individual products of this invention, as monomers or oligomers or as mixtures thereof are also useful as chemical intermediates and as materials which, upon hydrolysis, are capable of forming hydrogels. Also, because of their high radiation sensitivity, the present compounds are suitable as photoresist materials.
- A A 250 ml three-necked round bottom glass flask, equipped with a thermometer, magnetic stirrer, distillation head, water condenser, receiver and a nitrogen inlet was charged with 116 g. (1 mole) of hydroxybutyl vinyl ether, 45 g. (0.5 mole) of dimethyl carbonate and 0.5 g. of sodium methoxide. The mixture was heated under a blanket of nitrogen to 82°C. for 2.5 hours. An azeotrope of ethanol by-product, dimethyl carbonate and hydroxybutyl vinyl ether was distilled off at a head temperature..of about 32°C. The reaction mixture was then cooled and filtered.
- the separated filtrate (130 g.) was flash: distilled at 65-85°C. under 3 mm Hg.
- the resulting distillate was subjected to gas chromatography analysis which indicated 70% unreacted hydroxybutyl vinyl ether and 30% product.
- Fractional distillation under 3 mm Hg resulted in a fraction separated at 150-160°C. (34 g.) which was analyzed as 82.4% bis[ (ethenyloxy)butyl] carbonate and 15.7% mono[ (ethenyloxy)butyl] methyl carbonate.
- Four grams of methanol and dimethyl carbonate were collected in the trap.
- the product fraction separated at 150-160°C. was then evaluated for a radiation cured coating according to the following procedure.
- the product mixed with 2 wt. % of triphenyl sulfonium hexafluorophosphate was coated in about 0.15 mil thickness on an aluminum panel and then subjected to less than 1 second exposure at room temperature to 400 milli J/cm 2 radiation from 2 medium pressure mercury vapor lamps.
- the cured coating had strong adhesion to the substrate and had excellent resistance to chemical attack from acids and bases.
- Example 2 The procedure described-in Example 1 was repeated except that the reaction was carried out with, an excess of dimethyl carbonate 100 g. (1.11 mole) of dimethyl carbonate together with 116 g. (1 mole) of hydroxybutyl vinyl ether and 0.5 g. sodium methoxide was charged into the reactor and progressively heated from 85°C. to 110°C. The reaction mixture was distilled over a 26 hour period at a head temperature of from 40 to 63°C. to remove 38.4 g. of methanol/dimethyl carbonate azeotrope. The filtered product (117 g.) was then distilled in an Oldershaw 5 plate column and the fraction separated (38.3 g.) at pot temperature of 112-125°C.
- Example 1 In the apparatus described in Example 1 was charged 250 g. (2.15 mole) of hydroxybutyl vinyl ether, 90 g. (1 mole) of dimethylcarbonate and 1 g. of sodium methylate. The reaction mixture, under a blanket of nitrogen was heated for 18 hours at a head temperature of about 45°C. to remove 39 g. of azeotropic distillate from the reaction pot containing 48% hydroxybutyl vinyl ether, 46% bis[(ethenyloxy)butyl] carbonate and 4% mono[(ethenyloxy)butyl] methyl carbonate. The pot temperature was gradually raised from.85°C. to 148°C. over a period of 18 hours and the product'mixture filtered to remove undissolved catalyst and 240 g. of filtrate, containing
- Example 3 was repeated using a 2 liter glass flask, except that 1000 g. (8.6 moles) of hydroxybutyl vinyl ether, 360 g. (4 moles) of dimethylcarbonate and 4 g. of NaOCH 3 were charged and heated under a blanket of nitrogen. In this example 243 g. of the azeotrope were removed at a head temperature of 28-65°C. Also, the pot temperature was gradually increased over a 27 hour period.
- Example 4 was repeated except that a charge of 900 g. of hydroxybutyl vinyl ether, 472 g. of diethylcarbonate and 4.1 g. of NaOCH 3 was substituted. Also, the resulting mixture was heated at a pot temperature gradually increasing from 115° to 155°C. over 28.5 hours. The head temperature varied from 42°C. to 100°C. The corresponding ethanol/diethylcarbonate azeotrope (318 g.) was removed. The remaining product mixture was found to be 20% hydroxybutyl vinyl ether, 14.8% mono[ (ethenyloxy)butyl] ethyl carbonate and ' 63.5% bis[ (ethenyloxy)butyl] carbonate.
- Example 4 The product from Example 4 was.mixed with an equal weight amount of a diglycidyl ether, of.-.bisphenol A, 1 part per hundred parts of resin of a fluorochemical surfactant, and 4 parts per hundred parts of resin of a cationic photoinitiator at 50°C. until a homogeneous low viscosity liquid was obtained. This mixture was then coated on an aluminum substrate at a thickness of 1.2 mil. The coated surface was exposed for less than 1 second to 400 milli •j•oules/crr_? from a mercury vapor lamp. A tack free, film was produced. Coating properties reported in the following table were determined immediately after UV exposure and after a post cure at 177°C. for 15 minutes.
- Example 6 The mixture described in Example 6 was coated on a polyester substrate at a thickness of 0.5 mil. The coated surface was exposed to 400 m ⁇ ll ⁇ joules/cm ⁇ UV light for less than 1 second and post cured for 2 hours at 50°C. Chemical resistance was tested by the covered spot test (ASTM D 1308) . No attack was observed after 24 hours exposure to 1% H 2 S0 4 , 1% NaOH, 10% acetic acid, or distilled water.
- the product from Example 4 (25.0 gm) was mixed with the divinyl ether of triethyle ⁇ e.
- glycol (25.0 gm) a bisphenol A epoxy acrylate oligomer, 2 phr* cationic photoinitiator, 2 phr* free radical photo-initiator and l phr* fluorochemical surfactant at 50°C. until a homogeneous low viscosity liquid was obtained, this mixture was then coated on a polyester substrate at a thickness of 0.5 mil. The coated surface was exposed to 400 millijoules/cm 2 from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced.
- Example 4 The product from Example 4 (12.5 gm) was mixed with the divinyl ether of triethylene glycol (12.5 gm) and a divinyl ether urethane oligomer (25.0 gm) ; 4 phr cationic photoinitiator, and 1 phr fluorochemical surfactant at 50°C. until a homogeneous low viscosity liquid was obtained. This mixture was then coated on a aluminum panel (0.50 mil) and exposed to 400 millijoules/cir from a mercury vapor lamp for less than 1 second. A tack free coating with the following properties was produced
- a 500 ml, round bottom flask was charged with 30 g of triethylene glycol (0.2 mole), 105 g bis(ethenyloxy- butyl) carbonate (0.41 mole) and 0.1 g sodium methoxide.
- the flask was heated under vacuum of 3 mm Hg at 100-105°C. in a Kugelrohr apparatus for a period of 4.5 hours, after which a total of 44.3 g of distillate was collected.
- the distillate was analyzed by gas chro atography (GC) , and identified as a mixture of 95% hydroxybutyl vinyl ether, 3.8% bis(ethenyloxybutyl) carbonate and 0.8% triethylene glycol.
- GC gas chro atography
- Example 1 was repeated..except that 21 g of diethylene glycol (0.2 mole) was used- in-the place of 30 g triethylene glycol.
- the contents of the flask was worked up as described in Example 1.
- the filtrate was a clear colorless liquid weighing 83.3 g indicating about 90% yield.
- Example l A 500 ml round bottom flask was charged with 36 g butenediol (0.41 mole), 220 g bis(ethenyloxybutyl) carbonate (0.85 mole) and 0.4 g sodium methoxide. The procedure described in Example l was repeated except that the flask was heated at 100°C. under vacuum of 6 mm Hg for 2 hours.
- Example 4 The product from Example 4 (46.7 g) was charged into a 100 ml round bottom flask and heated to 130°C. under a vacuum of 3 mm Hg for 1 hour. Distillate weighing 5 g, primarily bis(ethenyloxybutyl carbonate) was removed. Spectral analysis of the pot content showed oligomerization of Example 5 product, i.e.
- Example l The procedure described, in Example l was repeated except that the reaction mixture-charged, to the flask was 18.6 g. 1-dodecanol and 25.8 g bisethenyloxybutyl carbonate and 0.1 g sodium methoxide. The flask was heated at 90°C. under vacuum of 5 mm Hg for 5 hours.
- Example 1 was repeated except that 62.6 g of the bis-ethoxylate of bisphenol A was used in place of triethylene glycol.
- the reaction mixture was heated under vacuum at 3-5 mm Hg at 100°C. After 2 hours 52 grams of distillate was removed. The resulting yellowish liquid was treated with charcoal at 50°C. , and filtered. The final product was a clear viscous liquid.
- the - ⁇ H NMR spectrum is consistent with the following structure.
- a four-necked 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, distillation head and water condenser, additional funnel and nitrogen inlet was charged with 76 g of butanediol (0.86 mole), 150 g of dimethyl carbonate (1.7 mole), 11.6 g of hydroxybutyl vinyl ether (0.1 mole), and 1 g of sodium methoxide.
- the pot temperature was maintained at about 100°C. under a blanket of nitrogen for a period of 12 hours, during which an azeotrope containing methanol and dimethyl carbonate was distilled off at a head temperature of 31-35°C.
- reaction mixture was filtered and flash distilled at 120-150°C. under 3 mm Hg. A solid residue (A) weighing 85 g was recovered. The residue (A) comprised 66% of
- H 2 C HCO(CH 2 ) 4 -[0-C-0(CH 2 ) 4 ] 4 OCOCH 3
- a four necked, 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, distillation head with a water condenser and a N 2 inlet was charged with 70 g of butanediol (0.78 mole), 150 g of dimethyl carbonate (1.67 mole), 11.6 g of hydroxy butyl vinyl ether (0.1 mole) and 0.5 g of sodium methoxide.
- the flask was heated under N 2 by gradually raising the temperature to 105°C. , and maintained at 90°C. for 1 hour followed by continued heating up to 105°C. for a total period of 12.5 hours. During this period 90.4 g of distillate was removed at a head temperature of about 6a.°.C.. N ..distillate, (an azeotrope of methanol and dimethylcarb ⁇ jiate) came off during the distillation.
- the solid product C (75.4 g) was charged into a 500 ml 3-necked round-bottom flask equipped with a mechanical stirrer, thermometer-vertical water condenser and N 2 inlet.
- the condenser was connected to a source of vacuum via a trap and 100 g of hydroxybutyl vinyl ether and 0.3 g of sodium methoxide were added to the flask.
- the flask was heated and maintained at 100°C. at a reduced pressure of 150 mm Hg for a period of 9.5 hours.
- the contents of the flask was then filtered and 162.4 g of filtrate was flash distilled at 110°C. under reduced pressure of 3 mm Hg during which unreacted hydroxy vinyl ether was removed, leaving 89.4 g residue which solidified on cooling.
- This solid product was::found to be
- Example 11 was repeated except that the charge to the reactor was 50 g of residue A obtained from Example 9, 100 g of hydroxy butylvinyl ether and 0.2 g sodium methoxide. The mixture was heated to 105°C. under a vacuum of 160 mm Hg for a period of 12 hours and the crude product was then filtered. The filtrate, weighing 141 g, was flash-distilled at 100°C. under a reduced pressure of 3 mm Hg for a period of 2.5 hours. The resulting product,
- Example 9 was repeated except that the charge to the reactor contained excess dimethyl carbonate.
- 90 g butanediol (1 mole) 360 g dimethyl carbonate (4 moles) and 1 g sodium methoxide.
- the flask was heated gradually heated and maintained at 85-95°C. for 20.5 hours during which 165.6 g distillate, an azeotrope of methanol and unreacted dimethyl carbonate, was collected at a head temperature of 42-45°C. Analysis of a 5 g aliquot of the remaining liquid in the flask showed it to be a methyl end-capped carbonate oligomer intermediate having the structure
- a four-necked 1 liter flask equipped with a mechanical stirrer, thermometer, distillation head with a horizontal condenser, nitrogen inlet and a receiver was charged with 250 g of commercially available poly THF* (polyoxybutylene diol - 250 having an average molecular weight about 250), 360 g (4 moles) of dimethyl carbonate (DMC) and 1 g titanium isopropoxide.
- the flask was heated and maintained at 90°C. for a period of 9 hours during which 169.5 g of distillate (an azeotrope of methanol and dimethyl carbonate) was collected at a head-temperature of 36°C.
- reaction product was found to be a mixture: ⁇ f- methyl terminated and OH terminated carbonate oligomers.
- a third addition of DMC (100 g) was then made and heating continued at a pot temperature of 95-101°C. for 3 hours under N 2 during which an additional 118.4 g of distillate was removed. Analysis showed the OH number of tries reaction mixture to be 85.5 mg KOH/g. indicating almost 80% conversion.
- a final addition of DMC (100 g) made and, heating continued under N 2 at pot temperature 105-115°C, during which 101.5 g distillate was collected at a head temperature of 67-75°C. over a period of 6 hours. Thus, a total of 445 g distillate was collected.
- the reaction mixture analyzed by ⁇ NMR data, showed practically complete methyl terminated polycarbonate of the poly THF diol as an intermediate product, (i.e. polyoxybutylene diol).
- the OH number was found to be 20.8 mg KOH/g.
- Hydroxybutyl vinyl ether (240 g, 2.07 moles) was then added to the flask and heating was continued at a pot temperature from 130 to 156°C. for 6.5 hours under N 2 . During this period 59 g distillate ⁇ .. ostly methanol was removed at a head temperature".about.67°C. The remaining liquid was then flash distilled, at 15.0°C. under a reduced pressure of 3 mm Hg, leaving 311 g- ⁇ f a yellow oil in the flask as the final product (D) .
- the OH number of product D 2.8 was 8.0 mg KOH/g.
- Example 9 was repeated except that 75 g commercially available triethylene glycol (0.5 mole), 360 g dimethyl carbonate (4 moles), and 0.4 g sodium methoxide were charged to the flask.
- the flask was heated under N 2 at 85°C. and 96 g of distillate was collected over a period of 5 hours at a head temperature of 51°C.
- the remaining volatile components were removed by heating under vacuum (140-180 mm Hg) at a temperature 50-55°C. whereupon 42.5 g additional distillate was removed at a head temperature of 42°C.
- • '-HNMR analysis of the intermediate product showed the composition to be methyl terminated carbonate oligomer having the formula
- reaction mixture was ' then filtered and 208 g of filtrate was flash-distilled at 170°C. under 3 mm Hg over a period of 4 hours to provide 130 g of final product in the flask as pale yellow oil having the formula
- Example 2 The product of Example 2 was mixed with an equal amount of a diglycidyl ether of bisphenol A, 1 phr* of a fluorochemical surfactant and 4 phr of cationic photoinitiator until a homogeneous low viscosity liquid was obtained. This mixture was then coated on an aluminum substrate in a thickness of 1.6 mil. The coated surface was exposed for less than 1 second to 400 millijoules/cm 2 radiation from a mercury vapor lamp. A tack-free film was produced. Coating properties reported in the following table were determined immediately after UV exposure and after a post cure of 177°C. for 15 minutes.
- Example 3 The product of Example 3 was mixed with an equal weight of triethylene glycol divinyl ether, 1 phr fluorochemical surfactant and 4 phr cationic photoinitiator until a homogeneous low viscosity liquid was obtained. This mixture was then coated on an aluminum substrate in a thickness of 1.4 mil. The coated surface was exposed for less than 1 second to 400 millijoules/cm 2 radiation from a mercury vapor lamp. A tack-free film was produced. Coating properties reported in the following table were determiend immediately after UV exposure and after a post cure of 177°C. for 15 minutes.
- Example 10 was repeated .except-that the reaction product of Example 1 is substituted for the reaction product of Example 3. The following properties were determined for the product.
- Example 10 is repeated except that the reaction product of Example 4 is substituted for the reaction product of Example 3.
- the following properties for the product were determined. - 37
- Example 2 The product of Example 2 (50.0 gm) is mixed with 50 g of a bisphenol a epoxy acrylate oligomer, 2 phr cationic photoinitiator, 2 phr free radical photoinitiator* and 1 phr fluorochemical surfactant-at,50°C. until a homogeneous, low viscosity.,liquid:-,is.obtained. This mixture is then coated on a polyester, substrate at a thickness of 0.5 mil. The coated surface, is exposed to 400 millijoules/cm 2 radiation free coating having a good pencil hardness of about 3H, 100% adhesion and high chemical resistance is obtained.
- Example 3 The product from Example 3 (50.0 gm) is mixed with 25 g of a divinyl ether urethane oligomer, 4 phr cationic photoinitiator and 1 phr fluorochemical surfactant at 50°C. until a homogeneous low viscosity liquid is obtained. This mixture is then coated on a aluminum panel in a thickness of 0.50 mil and exposed to 400 millijoules/cm 2 radiation from a mercury vapor lamp for less than 1 second. A tack free coating having a good pencil hardness of about 3B, a Mandrel bend of at least 3/8 inch is obtained. PREPARATION OF COMPOUNDS (C)
- Example 2 The product from Example 1 is mixed with an equal weight of triethylene glycol divinyl ether, 1 phr (part pe hundred) fluorochemical surfactant and 4 phr cationic photoinitiator.
- the resulting low viscosity liquid is coated on a polyester substrate (2.0 mil thickness) and exposed to 400 millijoules/cm 2 from a mercury vapor lamp. A tack free, chemically resistant coating is produced.
- Example 1 was repeated: except that 25 g. of 1,2,6-trihydroxyhexane was substituted.for trimethylolpropane.
- the resulting:-product was a yellow viscous oil.
- the 1 H NMR and IR spectra of this material indicated a mixture of the compounds:
- the above product was then evaluated for a radiation cured coating by coating in about 0.15 mil thickness on an aluminum panel and then exposing for less than 1 second at room temperature to 400 milli J/cm 2 radiation from 2 medium pressure mercury vapor lamps.
- the cured coating had strong adhesion to the substrate and had excellent resistance to chemical attack from acids and bases.
- the cyclohexanedimethanol monovinyl ether product (469.3 g) , bisphenol A epoxy resin (150 g) and potassium hydroxide (85% pellets, 0.5 g) were charged into a flask equipped as described in Example 1. The solution was heated to 150°C. for 48 hours and then cooled to room temperature. The resulting crude product (300 g) , 500 ml of toluene and 2 g of magnesium silicate were then transferred into a 1 liter flask wherein the mixture was stirred for 1 hour at room temperature and then filtered. After toluene and unreacted cyclohexane methanol vinyl ether were stripped off, the divinyl ether of bisphenol A epoxy resin product having the structure
Abstract
Description
Claims
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US475535 | 1990-02-06 | ||
US07/475,535 US5082874A (en) | 1990-02-06 | 1990-02-06 | Aryloxy polyvinyl ethers |
US49086790A | 1990-03-09 | 1990-03-09 | |
US49139590A | 1990-03-09 | 1990-03-09 | |
US490854 | 1990-03-09 | ||
US491362 | 1990-03-09 | ||
US491395 | 1990-03-09 | ||
US07/490,854 US5364691A (en) | 1990-03-09 | 1990-03-09 | Alk-1-enyloxy carbonates |
US07/491,362 US5276174A (en) | 1990-03-09 | 1990-03-09 | Alk-1-enyloxy carbonates |
US490867 | 1990-03-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0514482A1 EP0514482A1 (en) | 1992-11-25 |
EP0514482A4 true EP0514482A4 (en) | 1993-04-21 |
Family
ID=27541715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19910904850 Withdrawn EP0514482A4 (en) | 1990-02-06 | 1991-01-30 | Vinyl ether compounds |
Country Status (5)
Country | Link |
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EP (1) | EP0514482A4 (en) |
JP (1) | JPH05506849A (en) |
AU (1) | AU639312B2 (en) |
CA (1) | CA2075367A1 (en) |
WO (1) | WO1991013052A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0496828A4 (en) * | 1989-10-20 | 1993-03-31 | Isp Investments Inc. | Vinyl ethers synthesized from hydroxylated vinyl ethers and polyepoxides |
MY121218A (en) * | 1995-08-09 | 2006-01-28 | Sanyo Chemical Ind Ltd | Photo-curing resin composition |
WO2017065957A1 (en) | 2015-10-16 | 2017-04-20 | Basf Se | Energy curable high reactivity multi vinylether or acrylate functional resins |
CN109369392B (en) * | 2018-11-02 | 2021-11-23 | 安徽工程大学 | Synthesis method of ether oxygen bond-containing straight-chain dimethyl dicarbonate |
US20220033334A1 (en) * | 2018-11-27 | 2022-02-03 | Maruzen Petrochemical Co., Ltd. | Method for producing divinyl ether compound having alkylene skeleton |
WO2023168562A1 (en) * | 2022-03-07 | 2023-09-14 | 上纬创新育成股份有限公司 | Carbonate-containing unsaturated compound, preparation method therefor, cured product prepared therefrom, and method for degrading cured product |
TW202336005A (en) * | 2022-03-07 | 2023-09-16 | 上緯創新育成股份有限公司 | Carbonate-containing unsaturated compound, preparation method thereof, curable product prepared thereby and a method for degrading curable product |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2384125A (en) * | 1942-03-07 | 1945-09-04 | Pittsburgh Plate Glass Co | Unsaturated esters and polymers thereof |
US2385933A (en) * | 1942-03-07 | 1945-10-02 | Pittsburgh Plate Glass Co | Unsaturated alcohol esters of triethylene glycol bis(acid carbonate) and polymers thereof |
US2384143A (en) * | 1944-02-29 | 1945-09-04 | Pittsburgh Plate Glass Co | Vinyl esters |
US4273726A (en) * | 1979-11-13 | 1981-06-16 | Ppg Industries, Inc. | Polyol (allyl carbonate) synthesis utilizing solid alkali metal hydroxide |
US4293503A (en) * | 1980-01-10 | 1981-10-06 | Ppg Industries, Inc. | Synthesis of polyol bis(allyl carbonate) utilizing reagent recovery and recycle |
-
1991
- 1991-01-30 CA CA 2075367 patent/CA2075367A1/en not_active Abandoned
- 1991-01-30 JP JP91505552A patent/JPH05506849A/en active Pending
- 1991-01-30 WO PCT/US1991/000639 patent/WO1991013052A1/en not_active Application Discontinuation
- 1991-01-30 AU AU73350/91A patent/AU639312B2/en not_active Expired - Fee Related
- 1991-01-30 EP EP19910904850 patent/EP0514482A4/en not_active Withdrawn
Non-Patent Citations (2)
Title |
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No further relevant documents disclosed * |
See also references of WO9113052A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2075367A1 (en) | 1991-08-07 |
EP0514482A1 (en) | 1992-11-25 |
AU7335091A (en) | 1991-09-18 |
WO1991013052A1 (en) | 1991-09-05 |
AU639312B2 (en) | 1993-07-22 |
JPH05506849A (en) | 1993-10-07 |
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