CA2045645A1 - Vinyloxy hydroxyalkylcycloalkane and preparation therefor - Google Patents
Vinyloxy hydroxyalkylcycloalkane and preparation thereforInfo
- Publication number
- CA2045645A1 CA2045645A1 CA002045645A CA2045645A CA2045645A1 CA 2045645 A1 CA2045645 A1 CA 2045645A1 CA 002045645 A CA002045645 A CA 002045645A CA 2045645 A CA2045645 A CA 2045645A CA 2045645 A1 CA2045645 A1 CA 2045645A1
- Authority
- CA
- Canada
- Prior art keywords
- psig
- acetylene
- reaction
- gas
- under
- 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.)
- Abandoned
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a vinyloxy hydroxyalkyl cycloalkylene having the formula HO(CH2)x-A-(CH2)x'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. The invention also relates to the method for synthesizing the above compounds.
is a cycloalkylene group having from 3 to 8 carbon atoms in the ring and is optionally substituted with lower alkyl. The invention also relates to the method for synthesizing the above compounds.
Description
wo so/os364 Pcr/usso/00034 VINYLOXY HYDRO~YALKX~CY~
AND PRE~E~5~L THE~EEQ~
BACKGROUND OF THE INV~ION
This invention relates to compounds having a vinyl group and a hydro~yl group as terminal groups of the compound. More particularly, this invention relates to monomers which possess a vinyl ether substituent and a hydrosyl 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 hydro~yl functional qroup. 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 osygen free atmosphere can be achieved by effecting the polymerization under a blanket of nitrogen; however this 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 ~y radiation esposure. Finally, it is found that urethane coatings made from acrylic urethane monomers have poor adhesion to hard, smooth surfaces such as metal or glass.
wogo/09364 Pcr/usgo/0~034 ,~ ~
AND PRE~E~5~L THE~EEQ~
BACKGROUND OF THE INV~ION
This invention relates to compounds having a vinyl group and a hydro~yl group as terminal groups of the compound. More particularly, this invention relates to monomers which possess a vinyl ether substituent and a hydrosyl 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 hydro~yl functional qroup. 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 osygen free atmosphere can be achieved by effecting the polymerization under a blanket of nitrogen; however this 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 ~y radiation esposure. Finally, it is found that urethane coatings made from acrylic urethane monomers have poor adhesion to hard, smooth surfaces such as metal or glass.
wogo/09364 Pcr/usgo/0~034 ,~ ~
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 e~cellent adherence to hard surfaces such as qlass 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 vinylo~y hydro~yalkyl cycloalkane compound having the structure HO(CH2)s-A-(CH2)~,0CH=CH2 wherein ~ 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 s and ~' each have a value of from 1 to 4 and, most preferably, where A is cyclohe~ylene.
WO90/09~ PCT/US90/00~
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 vinylo~y hydro~yalkyl cycloalkane compound having the structure HO(CH2)s-A-(CH2)~,0CH=CH2 wherein ~ 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 s and ~' each have a value of from 1 to 4 and, most preferably, where A is cyclohe~ylene.
WO90/09~ PCT/US90/00~
3 _ ~ , ,3 ~
The compounds of this invention are useful chemical intermediates. For example, these products can be polymerized to branched structures having repeating units of (CH-CH2)n~
t CH2 ) ~ A- ( CH2 ) SOH
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 isocyanate, e.g. according to the equation:
2Ho(cH2)x-A-(cH2)x,ocH=cH2 + C6H4(NCO) O; O
CH2 CHO~CH2)x,-A-~CH2)xoc_HN ~ NH-eo(cH2)x-A-(cH2)xlocH=cH2 W090/09~ PCT/US90/000~
~J' These urethanes polymerize and are rapidly cured by a cationic mechanism activated by radiation, e.g. from W
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 polyrnerization 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 ~0(CH2),C-A-(CH2),~,O~l with acetylene. Ezamples of suitable diols include 1,4-di~hydro~ymethyl~ cyclohe2ane; 1,5-di(hydrosydecyl) cyclooctane; 1,3-di(hydroxyethyl) ethylcyclopentane;
4(4-hydrosycyclohe~yl) butanol;
(3-hydro~y)-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-ozygen containing gaseous diluent such as nitrogen, a Cl-C3 wo so/os364 Pcr/ussl)/00034 ) - 5 - ~J ~ ~ `J~ S
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 osygen 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 hydroside, e.g. potassium hydroside, or sodium hydroside as potassium alkoside 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 120C. and about 200C. 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 140C. and about 170C., under between about S0 and about 100 psig. for a period of from about 4 to about 8 hours.
~ aving thus generally described the invention, reference is now had to the following esamples 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.
EXAMPL~I
Molten 1,4-bis-(hydrosymethyl) cyclohesane (1802.6 grams) and 36 grams of potassium hydroside 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 90C.
for 30 minutes to remove water of reaction.
WO90/09~ f~ J - 6 - PCT/US90/~00~
Propane gas was introduced into the autoclave to 60 psi and the autoclave heated to 160C. Additional propane gas was added at 160C. 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 160C. 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 95C. and 110C. was collected. The fraction boiling at 102C.
weighed 263 grams and was identified as 99.3% pure monovinyl ether of 1,4-bis-hydrosymethyl cyclohesane by nmr, using CD C13 solvent.
For esample, Ezample 1 was repeated except that 1,5-bis-(hydrozyethyl) cyclooctane is substituted for 1,4-bis-(hydrozymethyl) cyclohesane. The divinyl ether product is recovered in greater than 90% yield.
The compounds of this invention are useful chemical intermediates. For example, these products can be polymerized to branched structures having repeating units of (CH-CH2)n~
t CH2 ) ~ A- ( CH2 ) SOH
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 isocyanate, e.g. according to the equation:
2Ho(cH2)x-A-(cH2)x,ocH=cH2 + C6H4(NCO) O; O
CH2 CHO~CH2)x,-A-~CH2)xoc_HN ~ NH-eo(cH2)x-A-(cH2)xlocH=cH2 W090/09~ PCT/US90/000~
~J' These urethanes polymerize and are rapidly cured by a cationic mechanism activated by radiation, e.g. from W
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 polyrnerization 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 ~0(CH2),C-A-(CH2),~,O~l with acetylene. Ezamples of suitable diols include 1,4-di~hydro~ymethyl~ cyclohe2ane; 1,5-di(hydrosydecyl) cyclooctane; 1,3-di(hydroxyethyl) ethylcyclopentane;
4(4-hydrosycyclohe~yl) butanol;
(3-hydro~y)-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-ozygen containing gaseous diluent such as nitrogen, a Cl-C3 wo so/os364 Pcr/ussl)/00034 ) - 5 - ~J ~ ~ `J~ S
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 osygen 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 hydroside, e.g. potassium hydroside, or sodium hydroside as potassium alkoside 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 120C. and about 200C. 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 140C. and about 170C., under between about S0 and about 100 psig. for a period of from about 4 to about 8 hours.
~ aving thus generally described the invention, reference is now had to the following esamples 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.
EXAMPL~I
Molten 1,4-bis-(hydrosymethyl) cyclohesane (1802.6 grams) and 36 grams of potassium hydroside 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 90C.
for 30 minutes to remove water of reaction.
WO90/09~ f~ J - 6 - PCT/US90/~00~
Propane gas was introduced into the autoclave to 60 psi and the autoclave heated to 160C. Additional propane gas was added at 160C. 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 160C. 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 95C. and 110C. was collected. The fraction boiling at 102C.
weighed 263 grams and was identified as 99.3% pure monovinyl ether of 1,4-bis-hydrosymethyl cyclohesane by nmr, using CD C13 solvent.
For esample, Ezample 1 was repeated except that 1,5-bis-(hydrozyethyl) cyclooctane is substituted for 1,4-bis-(hydrozymethyl) cyclohesane. The divinyl ether product is recovered in greater than 90% yield.
Claims (10)
1. A method of synthesizing the compound having the structural formula HO(CH2)X-A-(CH2)x'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)x-A-(CH2)x'OH
wherein x, x' 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.
wherein x, x' 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 with an 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.
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.
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.
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 |
|---|---|
| CA2045645A1 true CA2045645A1 (en) | 1990-08-09 |
Family
ID=26975767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002045645A Abandoned CA2045645A1 (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)
| 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)
| 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 |
-
1990
- 1990-01-04 JP JP2502275A patent/JPH04503952A/en active Pending
- 1990-01-04 WO PCT/US1990/000034 patent/WO1990009364A1/en not_active Application Discontinuation
- 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 CA CA002045645A patent/CA2045645A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04503952A (en) | 1992-07-16 |
| EP0456658A1 (en) | 1991-11-21 |
| WO1990009364A1 (en) | 1990-08-23 |
| AU4955790A (en) | 1990-09-05 |
| AU628479B2 (en) | 1992-09-17 |
| EP0456658A4 (en) | 1992-10-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |