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WO1990009364A1 - Vinyloxy hydroxyalkylcycloalcane et sa preparation - Google Patents

Vinyloxy hydroxyalkylcycloalcane et sa preparation Download PDF

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Publication number
WO1990009364A1
WO1990009364A1 PCT/US1990/000034 US9000034W WO9009364A1 WO 1990009364 A1 WO1990009364 A1 WO 1990009364A1 US 9000034 W US9000034 W US 9000034W WO 9009364 A1 WO9009364 A1 WO 9009364A1
Authority
WO
WIPO (PCT)
Prior art keywords
psig
acetylene
reaction
gas
vinyloxy
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.)
Ceased
Application number
PCT/US1990/000034
Other languages
English (en)
Inventor
Kou-Chang Liu
Paul D. Taylor
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.)
GAF Chemicals Corp
Original Assignee
GAF Chemicals Corp
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 GAF Chemicals Corp filed Critical GAF Chemicals Corp
Publication of WO1990009364A1 publication Critical patent/WO1990009364A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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.

Landscapes

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

Abstract

L'invention décrit un cycloalkylène vinyloxy hydroxyalkyle ayant la formule HO(CH2)x-A-(CH2)x'OCH=CH2 où x est compris entre 1 et 10; x' est compris entre 0 et 10 et A est un groupe cycloalkylène ayant de 3 à 8 atomes de carbone dans l'anneau et pouvant éventuellement être substitué par un alkyle inférieur. On décrit également un procédé de synthèse des composés susmentionnés.
PCT/US1990/000034 1989-02-08 1990-01-04 Vinyloxy hydroxyalkylcycloalcane et sa preparation Ceased WO1990009364A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US30745789A 1989-02-08 1989-02-08
US307,457 1989-02-08
US37116889A 1989-06-26 1989-06-26
US371,168 1989-06-26

Publications (1)

Publication Number Publication Date
WO1990009364A1 true WO1990009364A1 (fr) 1990-08-23

Family

ID=26975767

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/000034 Ceased WO1990009364A1 (fr) 1989-02-08 1990-01-04 Vinyloxy hydroxyalkylcycloalcane et sa preparation

Country Status (5)

Country Link
EP (1) EP0456658A4 (fr)
JP (1) JPH04503952A (fr)
AU (1) AU628479B2 (fr)
CA (1) CA2045645A1 (fr)
WO (1) WO1990009364A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004579A2 (fr) 2011-07-01 2013-01-10 Basf Se Éthers de bis(hydroxyméthyl)cyclohexanes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62288666A (ja) * 1986-06-06 1987-12-15 Asahi Glass Co Ltd 塗料組成物
US4775732A (en) * 1988-01-11 1988-10-04 Allied-Signal Inc. Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU605534B2 (en) * 1986-12-05 1991-01-17 Commonwealth Scientific And Industrial Research Organisation Control of molecular weight and end group functionality of polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62288666A (ja) * 1986-06-06 1987-12-15 Asahi Glass Co Ltd 塗料組成物
US4775732A (en) * 1988-01-11 1988-10-04 Allied-Signal Inc. Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0456658A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004579A2 (fr) 2011-07-01 2013-01-10 Basf Se Éthers de bis(hydroxyméthyl)cyclohexanes
US9452962B2 (en) 2011-07-01 2016-09-27 Basf Se Ethers of bis(hydroxymethyl)cyclohexanes
EP3296283A1 (fr) 2011-07-01 2018-03-21 Basf Se Éthers de bis(hydroxyméthyl)cyclohexanes
US9981897B2 (en) 2011-07-01 2018-05-29 Basf Se Ethers of bis(hydroxymethyl)cyclohexanes

Also Published As

Publication number Publication date
EP0456658A1 (fr) 1991-11-21
JPH04503952A (ja) 1992-07-16
CA2045645A1 (fr) 1990-08-09
AU4955790A (en) 1990-09-05
EP0456658A4 (en) 1992-10-07
AU628479B2 (en) 1992-09-17

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