EP0456658A1 - Vinyloxy hydroxyalkylcycloalkane and preparation therefor - Google Patents

Vinyloxy hydroxyalkylcycloalkane and preparation therefor

Info

Publication number
EP0456658A1
EP0456658A1 EP90902012A EP90902012A EP0456658A1 EP 0456658 A1 EP0456658 A1 EP 0456658A1 EP 90902012 A EP90902012 A EP 90902012A EP 90902012 A EP90902012 A EP 90902012A EP 0456658 A1 EP0456658 A1 EP 0456658A1
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP90902012A
Other languages
German (de)
French (fr)
Other versions
EP0456658A4 (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.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
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 ISP Investments LLC filed Critical ISP Investments LLC
Publication of EP0456658A1 publication Critical patent/EP0456658A1/en
Publication of EP0456658A4 publication Critical patent/EP0456658A4/en
Withdrawn legal-status Critical Current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.

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.The invention describes a vinyloxy hydroxyalkyl cycloalkylene having the formula HO (CH2) x-A- (CH2) x'OCH = CH2 where x is between 1 and 10; x 'is between 0 and 10 and A is a cycloalkylene group having 3 to 8 carbon atoms in the ring and which can optionally be substituted by lower alkyl. A method of synthesizing the above-mentioned compounds is also described.

Description

- 1 -
VINYLOXY HYDROXYALKYLCYCLOALKANE AND PREPARATION THEREFOR
BACKGROUND OF THE INVENTION
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. In the process for making a protective coating or film 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. However, this process for producing urethane coatings and films has many shortcomings.
Since the polymerization and curing of acrylic functional groups proceeds by a free radical mechanism, polymerization and curing must be carried out in the absence of air, a known free radical inhibitor. The oxygen free atmosphere can be achieved by effecting the polymerization under a blanket of nitrogen; however. his requirement greatly increases the cost of the process.
Another disadvantage in the preparation of acrylic urethane coatings is that a curing rate sufficiently high to meet certain requirements such as coatings for automotive fascia, etc., are not achievable by radiation exposure. Finally, it is found that urethane coatings made from acrylic urethane monomers have poor adhesion to hard, smooth surfaces such as metal or glass. It is therefore an object of this invention to provide a compound which can be converted to a urethane monomer having a high radiation cure rate in the absence or presence of air to produce a coating of excellent adherence to hard surfaces such as glass or metal.
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.
These and other objects of the invention will become apparent from the following description and disclosure.
THE INVENTION
In accordance with this invention, there is provided a vinyloxy hydroxyalkyl cycloalkane compound having the structure
HO(CH2)χ-A-(CH2)χ,OCH=CH2
wherein 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
(CH2)χOH
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:
2HO(CH2)χ-A-(CH2)χlOCH=CH2 + C6H4( CO)2
(CH2)X-A-(CH2)χIOCH=CH2 These urethanes polymerize and are rapidly cured by a cationic mechanism activated by radiation, e.g. from UV light or an electron beam source, to form hard, durable coatings; thus eliminating the need for formation under a blanket of nitrogen which is required by free radical polymerization and curing.
It is readily apparent that 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. 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.
The present products are readily synthesized by reacting a diol corresponding to the formula
HO(CH2)χ-A-(CH2)χfOH
with acetylene. Examples of suitable diols include l,4-di(hydroxymethyl) cyclohexane; l,5-di(hydroxydecyl) cyclooctane; l,3-di(hydroxyethyl) ethylcyclopentane; 4(4-hydroxycyclohexyl) butanol;
(3-hydroxy)-2,5-dimethyl-cyclooctyl decanol; etc. In this reaction the mole ratio of diol to acetylene can vary between about 1:1 and about 1:1.5. At low reaction pressure, 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. When the diluent is employed, 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. The 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 140βC. and about 170°C, under between about 50 and about 100 psig. for a period of from about 4 to about 8 hours.
Having thus generally described the invention, reference is now had to the following examples which illustrate preferred embodiments but which are not to be construed as limiting to the scope of the invention, as more broadly set forth above and in the appended claims.
EXAMPLE I
Molten l,4-bis-(hydroxymethyl) cyclohexane (1802.6 grams) and 36 grams of potassium hydroxide pellets (85%) were charged with a one gallon autoclave. The autoclave was purged three times with nitrogen, then evacuated to 10 mm of mercury pressure and heated at 90°C. for 30 minutes to remove water of reaction. Propane gas was introduced into the autoclave to 60 psi and the autoclave heated to 160°C. Additional propane gas was added at 160βC. until the pressure reached 100 psi. Acetylene was then introduced until a total pressure of 200 psi was achieved. After 6.5 hours at 200 psi and 160°C. the autoclave was cooled to room temperature, purged 3 times with nitrogen, and its contents discharged.
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.
For example. 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.

Claims

WHAT IS CLAIMED :
1. A method of synthesizing the compound having the structural formula
HO(CH2)χ-A-(CH2)χ,OCH=CH2
wherein 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 which comprises reacting a diol having the structure
HO(CH2)χ-A-(CH2)χ,OH
wherein x, x1 and A are as defined with acetylene in an inert diluent in an oxygen free atmosphere at a temperature of from about 120°C. and about 200°C. under a pressure of from about 10 psig. to about 200 psig. and recovering the product of the process.
2. The method of Claim 1 wherein the reaction is effected under a pressure of from about 20 psig. to about 100 psig. and the acetylene is diluted withran inert gas.
3. The method of Claim 2 wherein the concentration of acetylene in said gas is between about 10° and about 60% by weight.
4. The method of Claim 2 wherein said gas is selected from the group of nitrogen, a C1 to C3 alkane and helium.
5. The method of Claim 4 wherein said gas is propane.
6. The method of Claim 2 wherein acetylene is diluted to a concentration of between about 40% and about 60% by weight...
7. The method of Claim 1 wherein said reaction is effected at a temperature of between about 140°C. and about 170°C. under from about 50 psig. to about 100 psig. in the presence of a basic catalyst.
8. The method of Claim 7 wherein said catalyst is an alkali metal hydroxide.
9. The method of Claim 2 wherein said diol is bis(hydroxymethyl) cyclohexane.
10. The product of the method of claim 1 in at least 90% purity.
EP19900902012 1989-02-08 1990-01-04 Vinyloxy hydroxyalkylcycloalkane and preparation therefor Withdrawn EP0456658A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US30745789A 1989-02-08 1989-02-08
US307457 1989-02-08
US37116889A 1989-06-26 1989-06-26
US371168 1989-06-26

Publications (2)

Publication Number Publication Date
EP0456658A1 true EP0456658A1 (en) 1991-11-21
EP0456658A4 EP0456658A4 (en) 1992-10-07

Family

ID=26975767

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900902012 Withdrawn EP0456658A4 (en) 1989-02-08 1990-01-04 Vinyloxy hydroxyalkylcycloalkane and preparation therefor

Country Status (5)

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013004579A2 (en) 2011-07-01 2013-01-10 Basf Se Ethers of bis(hydroxymethyl)cyclohexanes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62288666A (en) * 1986-06-06 1987-12-15 Asahi Glass Co Ltd Coating compound composition
AU605534B2 (en) * 1986-12-05 1991-01-17 Commonwealth Scientific And Industrial Research Organisation Control of molecular weight and end group functionality of polymers
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 (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents have been disclosed. *
See also references of WO9009364A1 *

Also Published As

Publication number Publication date
JPH04503952A (en) 1992-07-16
EP0456658A4 (en) 1992-10-07
WO1990009364A1 (en) 1990-08-23
AU4955790A (en) 1990-09-05
CA2045645A1 (en) 1990-08-09
AU628479B2 (en) 1992-09-17

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