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
- -1 Vinyloxy Chemical group 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000003701 inert diluent Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 4
- OVSQVDMCBVZWGM-QSOFNFLRSA-N quercetin 3-O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OVSQVDMCBVZWGM-QSOFNFLRSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UPDKZJXRKWABAB-UHFFFAOYSA-N 3-[3-(2-hydroxyethyl)cyclopentyl]butan-1-ol Chemical compound OCCC(C)C1CCC(CCO)C1 UPDKZJXRKWABAB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IXFFLCQKZXIGMH-UHFFFAOYSA-N ethenoxyethene;ethyl carbamate Chemical class C=COC=C.CCOC(N)=O IXFFLCQKZXIGMH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
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 |
---|---|---|---|---|
PL2726450T3 (en) | 2011-07-01 | 2018-05-30 | 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 WO PCT/US1990/000034 patent/WO1990009364A1/en not_active Application Discontinuation
- 1990-01-04 AU AU49557/90A patent/AU628479B2/en not_active Ceased
- 1990-01-04 JP JP2502275A patent/JPH04503952A/en active Pending
- 1990-01-04 EP EP19900902012 patent/EP0456658A4/en not_active Withdrawn
- 1990-01-04 CA CA002045645A patent/CA2045645A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
JPH04503952A (en) | 1992-07-16 |
AU628479B2 (en) | 1992-09-17 |
AU4955790A (en) | 1990-09-05 |
EP0456658A4 (en) | 1992-10-07 |
EP0456658A1 (en) | 1991-11-21 |
WO1990009364A1 (en) | 1990-08-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5183946A (en) | Vinyloxy hydroxyalkylcycloalkane and preparation therefor | |
US5106885A (en) | Radiation curable compositions containing multifunctional vinyl ether monomers and protective coatings formed therefrom | |
US5039716A (en) | Alk-1-enyl ether silicates and radiation curable composition containing alk-1-enyl ether silicates | |
JP4136886B2 (en) | Polymers of novel alicyclic vinyl ethers | |
CA2045645A1 (en) | Vinyloxy hydroxyalkylcycloalkane and preparation therefor | |
US5334772A (en) | Polyalk-1-enyl ethers | |
CA2031114A1 (en) | Alkenyl ethers and radiation curable compositions | |
US5095154A (en) | Trivinyl ether of 1,1,1-tris(hydroxymethyl) ethane | |
JP4452037B2 (en) | New alicyclic vinyl ether | |
US7880030B2 (en) | Stereoregular polymer and monomer thereof and process for production of both | |
AU639312B2 (en) | Vinyl ether compounds | |
AU644108B2 (en) | Trivinyl ethers of polyols | |
CN1335829A (en) | New method for making photocurable halofluorinated acrylates | |
US3714202A (en) | Vinyl glycerol acetals | |
US4594458A (en) | Vinyl ether monomers derived from alkyl perfluoro-ω-(2-iodoethoxy) compounds | |
US5082874A (en) | Aryloxy polyvinyl ethers | |
US5147727A (en) | Aryloxy polyvinyl ethers | |
EP0275558B1 (en) | Perfluoroalkenyloxybenzoic acid derivative, process for preparing the same and prepolymer of the derivative | |
US5342860A (en) | Radiation curable alk-1-enyl ether polyester prepolymers | |
US5557010A (en) | Preparation of a 2,3-dihaloperfluorocarbonyl halide | |
US5043490A (en) | Novel fluorinated dienes | |
US5094917A (en) | Alk-1-enyl ether silicates | |
US5254710A (en) | Alkenyl ether polycarbonates | |
US7531701B2 (en) | Allyloxytrifluoropropenes | |
JP3145821B2 (en) | Process for producing octadienyl ether and novel compound 3-ethyl-3-[(2,7-octadienyloxy) methyl] -oxetane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |