Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
  • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
  • C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
• • 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
  • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
  • C07C43/1781—Unsaturated ethers containing hydroxy or O-metal groups containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

• This invention relates to compounds having a vinyl group and a hydroxyl group as terminal groups of the compound. More particularly, this invention relates to monomers which possess a vinyl ether substituent and a hydroxyl substituent.
• Urethane polymers have had great commercial success when used as protective coatings, films and adhesives.
• the genesis for these polymers is usually a monomer having both an acrylic functional group and a hydroxyl functional group.
• the hydroxyl group is converted to a urethane group by reaction with an isocyanate.
• the resulting acrylic urethane monomer is then applied to a surface and cured thereon by radiation.
• this process for producing urethane coatings and films has many shortcomings.
• Another object is to provide an economical and commercially feasible process for the manufacture of the present compounds.
• Still another object is to provide a substrate coated with the present compound which possesses superior stability.
• x has a value of from 1 to 10; x* has a value of from 0 to 10 and A is a cycloalkylene group having from 3 to 8 carbon atoms in the ring and is optionally substituted with lower alkyl.
• Preferred of this group are those compounds wherein x and x* each have a value of from 1 to 4 and, most preferably, where A is cyclohexylene.
• the compounds of this invention are useful chemical intermediates. For example, these products can be polymerized to branched structures having repeating units of
• the polymer chains in turn, can be cross-linked at the terminal hydroxy group by condensation, by dehydration or by reaction with polyols, such as diols, to form the corresponding ethers. Additionally, they can be reacted with diacids, both aliphatic and aromatic dicarboxylic acids, to form the corresponding esters.
• These polymers because of branching and/or cross-linking provide coatings which are more resistant to chemical attack and abrasion than linear types and are adapted to curing by irradiation at a reasonably high rate. Also, the polymers provide a harder more durable surface on the substrate after curing than the linear polymerized products.
• a major advantage of the present products is their ability to be converted to vinyl ether urethanes by reaction with an isocyana * te, e.g. according to the equation:
• the present compounds can also be employed as monomers in copolymerizations with other monomers selected from the groups consisting of olefinic compounds, maleic anhydride, vinyl pyrrolidone, acrylics, methacrylics, etc.
• monomers selected from the groups consisting of olefinic compounds, maleic anhydride, vinyl pyrrolidone, acrylics, methacrylics, etc.
• the products in their non-polymerized state are also useful in the formation of many non-polymeric compounds through condensation, dehydration, esterification, substitution at the hydroxy site or addition to the terminal vinyl group; thus providing useful ' multifunctional reaction intermediates.
• diols examples include l,4-di(hydroxymethyl) cyclohexane; l,5-di(hydroxydecyl) cyclooctane; l,3-di(hydroxyethyl) ethylcyclopentane; 4(4-hydroxycyclohexyl) butanol;
• the mole ratio of diol to acetylene can vary between about 1:1 and about 1:1.5.
• the acetylene can be introduced into the reaction zone without dilution; however, at elevated pressures, it is recommended that an inert non-oxygen containing gaseous diluent such as nitrogen, a C,-C, - 5 -
• alkane or helium be used to dilute the acetylene reactant.
• acetylene concentration as low as 10% can be used although between about 40 and about 60 wt. % acetylene in diluent is most preferred.
• the above reaction is carried out in an oxygen free atmosphere which is generally achieved by purging with nitrogen and is effected in the presence of a basic catalyst such as an alkali metal hydroxide, e.g. potassium hydroxide, or sodium hydroxide as potassium alkoxide or an amine.
• a basic catalyst such as an alkali metal hydroxide, e.g. potassium hydroxide, or sodium hydroxide as potassium alkoxide or an amine.
• concentration of catalyst employed can range from about 0.1% to about 5% by weight.
• the process is effected at a temperature of between about 120°C. and about 200°C. under from about 10 to about 200 psig. in a period of from about 2 to about 20 hours reaction time.
• Preferred conditions include a temperature of between about 140 ⁇ C. and about 170°C, under between about 50 and about 100 psig. for a period of from about 4 to about 8 hours.
• the crude product (1,816 g.) was distilled under vacuum (1 mm Hg) using a 15 plate Oldershaw column, and a clear water white fraction boiling between 95°C. and 110°C. was collected.
• the fraction boiling at 102°C. weighed 263 grams and was identified as 99.3% pure monovinyl ether of 1,4-bis-hydroxymethyl cyclohexane by nmr, using CD Cl, solvent.
• Example 1 was repeated except that l,5-bis-(hydroxyethyl) cyclooctane is substituted for l,4-bis-(hydroxymethyl) cyclohexane.
• the divinyl ether product is recovered in greater than 90% yield.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1990
  • 1990-01-04 CA CA002045645A patent/CA2045645A1/en not_active Abandoned
  • 1990-01-04 JP JP2502275A patent/JPH04503952A/ja active Pending
  • 1990-01-04 EP EP19900902012 patent/EP0456658A4/en not_active Withdrawn
  • 1990-01-04 AU AU49557/90A patent/AU628479B2/en not_active Ceased
  • 1990-01-04 WO PCT/US1990/000034 patent/WO1990009364A1/en not_active Application Discontinuation

Non-Patent Citations (2)

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