CA1234832A - Unsaturated ester isocyanates and a process for the production thereof - Google Patents
Unsaturated ester isocyanates and a process for the production thereofInfo
- Publication number
- CA1234832A CA1234832A CA000464681A CA464681A CA1234832A CA 1234832 A CA1234832 A CA 1234832A CA 000464681 A CA000464681 A CA 000464681A CA 464681 A CA464681 A CA 464681A CA 1234832 A CA1234832 A CA 1234832A
- Authority
- CA
- Canada
- Prior art keywords
- radical
- formula
- mixture
- dihydrooxazine
- optionally
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
Abstract
Mo-2597 LeA 22,617 UNSATURATED ESTER ISOCYANATES AND A
PROCESS FOR THE PRODUCTION THEREOF
ABSTRACT OF THE DISCLOSURE
Unsaturated ester isocyanates are made by reacting a dihyrooxazine or an acid adduct thereof corresponding to specified formula(e) with phosgene in a water-immiscible solvent in the presence of an aqueous solution of a base at a temperature from -20 to 20°C.
These unsaturated ester isocyanates are useful in the production of oligourethanes which are either liquid at room temperature or have a lower melt viscosity than urethanes produced from 2-isocyanatoethyl methacrylate.
Mo-2597 LeA 22,617
PROCESS FOR THE PRODUCTION THEREOF
ABSTRACT OF THE DISCLOSURE
Unsaturated ester isocyanates are made by reacting a dihyrooxazine or an acid adduct thereof corresponding to specified formula(e) with phosgene in a water-immiscible solvent in the presence of an aqueous solution of a base at a temperature from -20 to 20°C.
These unsaturated ester isocyanates are useful in the production of oligourethanes which are either liquid at room temperature or have a lower melt viscosity than urethanes produced from 2-isocyanatoethyl methacrylate.
Mo-2597 LeA 22,617
Description
1234~33~
Mo-2597 LeA 22,617 UNSATURATED ESTE~ ISOCYANATES AND A
PROCESS FOR THE PRODUCTION THEREOF
BACKGROUND OF THE INVENTION
This invention relates to olefinically-unsatur~
ated ester isocyanates and a process for the production thereof.
It is known that unsaturated ester isocyanates such as 2-isocyanatoethyl methacrylates may be produced by phosgenating the corresponding oxazoline or dihydro-oxazine. The production of ~-isocyanatoethyl methacryl-ate (IEM) by phosgenating the appropriate oxazoline is described in detail in German Auslegeschrift 1,924,535 (believed to correspond to British Patent 1,252,099) and EP-PS 144. 2-vinyl-5,6-dihydro-1,3-oxazine and 2-iso-propenyl-5,6-dihydro-1,3~oxazine are mentioned as suit-able starting materials in German Auslegeschrift 1,924,535 (British Patent 1,252,099), but this reference does not disclose any specific method for producing the corresponding isocyanatopropyl acrylate or methacrylate from such starting materials. Indeed, the 2-isocyanato-ethyl methacrylate is the only unsaturated ester isocya-nate which has until now been of commercial signifi-cance.
Isocyana~oethyl methacrylate is an intermediate useful in a variety of applications. For example, IEM
may be used in the production of precursors of plastic materials which may be polymerized or copolymerized with other olefinically unsaturated monomers. More specifi-cally, IEM may be reacted with compounds which have at least two isocyanate-reactive groups, such as simple polyhydric alcohols ~e.g , butane-1,4-diol or tri-methylolpropane) to produce oligourethanes which have at least two olefinic double bonds. These oligourethanes are valuable monomers or comonomers in the production of polymers. However, there are also several disadvantages Mo-2597 LeA 22 617-US
3 ~ ~ 3 ~
~o use of IEM. More particularly, the high vap~r pres-sure of the intermedia~e products, the fact that many of the specified products (reaction products of IEM with simple polyhydric alcohols) are solid substances as well as frequent inadequate compatibility of the specified products with the comonomers used in the production of polymers are examples of such disadvantages.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide unsaturated ester isocyanates which have a lower vapor pressure and are more compatible with comonomers used in producing polymers than IEM.
It is also an object of the present invention to provide unsaturated ester isocyanates and mixtures of such isocyanates useful in the production of olefinical-ly unsaturated oligourethanes.
It is another object of the presen~ invention to provide a process for the production of unsaturated ester isocyanates and mixtures of such isocyanates.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting a dihydrooxazine (optionally as acid adduct~ correspond-ing to specified formula(e) with phosgene in a water-immiscible solvent in the presence of an aqueous solu-tion of base at a temperature from -20 to 20C.
The present invention relates to unsaturated ester isocyanates, which may optionally be present as isomer mixtures, in which from 0 to 95 wt % (based on the total mixture of compounds) corresponds to the formula:
OCN-CH2-Rl-O-CO-C=CH-R3 (I) Mo-2597 ~L23~ 33~
from 0 to 70 wt % (based on the total mixture of com-pounds) corresponds to the formula:
OCN-CH2-R'l-O-CO-C=CH-R3 (II) and from 0 to 70 wt % (based on the total mixture of compounds) corresponds to the formula:
OCN-CH2-R"l-O-CO-C=CH-R3 (III) and the above-mentioned percentages total 100. In each of the above-given formulae, Rl, R'l and R"l may each represent the same optionally alkyl-substituted 1,2-cycloalkylene radical having, in total, from S to 10 carbon atoms or Rl represents a 2,3-butylene radical, R'l represents a straight-chain 1,2-butylene radical and R", represents a 1,2-isobutylene radical;
and R2 and R3, which may be ~he same or different, each represent hydrogen or a methyl group.
The present invention also relates to a process for the production of these ester isocyanates by react-ing dihydrooxazines which may optionally be present as acid adducts with phosgene at from -20 to ~20C in a water-immiscible solvent in the presence of an aqueous solution of a base. The dihydrooxazines used as start-ing materials are made up of from 0 to 95 wt % of compounds corresponding to the formula:
1 \ / C-C-CH R3 (IV) Mo-2597 ~LZ3~33 from 0 to 70 wt % compounds corresponding to theformula:
R ~ C=CH-R3 (V) o and from 0 to 70 wt % compounds corresponding to the formula:
,,,~CH2-N
R"l ~C--C=CH-R3 (VI) \o with the above-~iven percentages totalling 100.
Rl, R'l, R"l, R2 and R3 are as defined above.
Within the context of the present invention, the term "1,2-cycloalkylene radical" is to be understood to mean divalent (optionally alkyl-substituted) cyclo-aliphatic hydrocarbon radicals, the cycloaliphatic rings of which are linked in the 1,2 position with the methyl-ene group or the oxygen atom of the ester isocyanates or the oxazines The terms "1,2-butylene radical", "2,3-butylene radical" and "1,2-isobutylene radical" are to be understood to mean aliphatic, divalent hydrocarbon radicals having 4 carbon atoms, which are linked in the 1,2 or 2,3 positions with the methylene group or the oxygen. In the case of asymmetric radicals, the higher substituted carbon atom is in each case linked with the oxygen atom.
The dihydrooxazines corresponding to the above-mentioned general formulae which are suitable starting materials for the process of the present invention may either be defined compounds (Rl = R'l =
R"l - optionally alkyl-substituted 1,2-cycloalkylene Mo-2597 , .
~2~34~33 radical having in total from 5 to 10 carbon atoms) or isomer mixtures (Rl, R'l and R"l represent various butylene or isobutylene radicals) as mentioned above.
The isomer distribution of the ester isocyanates corres-ponds to that of the dihydrooxazines used as s~artingmaterials. Dihydrooxazines which are preferably used as starting materials in the process of the present inven-tion are compounds corresponding ~o ~he formula:
Rl ~C-C=CH R3 ( IV) wherein Rl represents a 1,2-cyclohexylene, a 3- (and/or 4-)isopropyl-1,2-cyclohexylene or a 1-methyl-4-isopropyl-1,2-cyclohexylene radical, and R2 and R3 are each either hydrogen or methyl (R3 most preferably representing hydrogen).
Specific examples of these preferred compounds are:
Mo-2597 LeA 22,617 UNSATURATED ESTE~ ISOCYANATES AND A
PROCESS FOR THE PRODUCTION THEREOF
BACKGROUND OF THE INVENTION
This invention relates to olefinically-unsatur~
ated ester isocyanates and a process for the production thereof.
It is known that unsaturated ester isocyanates such as 2-isocyanatoethyl methacrylates may be produced by phosgenating the corresponding oxazoline or dihydro-oxazine. The production of ~-isocyanatoethyl methacryl-ate (IEM) by phosgenating the appropriate oxazoline is described in detail in German Auslegeschrift 1,924,535 (believed to correspond to British Patent 1,252,099) and EP-PS 144. 2-vinyl-5,6-dihydro-1,3-oxazine and 2-iso-propenyl-5,6-dihydro-1,3~oxazine are mentioned as suit-able starting materials in German Auslegeschrift 1,924,535 (British Patent 1,252,099), but this reference does not disclose any specific method for producing the corresponding isocyanatopropyl acrylate or methacrylate from such starting materials. Indeed, the 2-isocyanato-ethyl methacrylate is the only unsaturated ester isocya-nate which has until now been of commercial signifi-cance.
Isocyana~oethyl methacrylate is an intermediate useful in a variety of applications. For example, IEM
may be used in the production of precursors of plastic materials which may be polymerized or copolymerized with other olefinically unsaturated monomers. More specifi-cally, IEM may be reacted with compounds which have at least two isocyanate-reactive groups, such as simple polyhydric alcohols ~e.g , butane-1,4-diol or tri-methylolpropane) to produce oligourethanes which have at least two olefinic double bonds. These oligourethanes are valuable monomers or comonomers in the production of polymers. However, there are also several disadvantages Mo-2597 LeA 22 617-US
3 ~ ~ 3 ~
~o use of IEM. More particularly, the high vap~r pres-sure of the intermedia~e products, the fact that many of the specified products (reaction products of IEM with simple polyhydric alcohols) are solid substances as well as frequent inadequate compatibility of the specified products with the comonomers used in the production of polymers are examples of such disadvantages.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide unsaturated ester isocyanates which have a lower vapor pressure and are more compatible with comonomers used in producing polymers than IEM.
It is also an object of the present invention to provide unsaturated ester isocyanates and mixtures of such isocyanates useful in the production of olefinical-ly unsaturated oligourethanes.
It is another object of the presen~ invention to provide a process for the production of unsaturated ester isocyanates and mixtures of such isocyanates.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting a dihydrooxazine (optionally as acid adduct~ correspond-ing to specified formula(e) with phosgene in a water-immiscible solvent in the presence of an aqueous solu-tion of base at a temperature from -20 to 20C.
The present invention relates to unsaturated ester isocyanates, which may optionally be present as isomer mixtures, in which from 0 to 95 wt % (based on the total mixture of compounds) corresponds to the formula:
OCN-CH2-Rl-O-CO-C=CH-R3 (I) Mo-2597 ~L23~ 33~
from 0 to 70 wt % (based on the total mixture of com-pounds) corresponds to the formula:
OCN-CH2-R'l-O-CO-C=CH-R3 (II) and from 0 to 70 wt % (based on the total mixture of compounds) corresponds to the formula:
OCN-CH2-R"l-O-CO-C=CH-R3 (III) and the above-mentioned percentages total 100. In each of the above-given formulae, Rl, R'l and R"l may each represent the same optionally alkyl-substituted 1,2-cycloalkylene radical having, in total, from S to 10 carbon atoms or Rl represents a 2,3-butylene radical, R'l represents a straight-chain 1,2-butylene radical and R", represents a 1,2-isobutylene radical;
and R2 and R3, which may be ~he same or different, each represent hydrogen or a methyl group.
The present invention also relates to a process for the production of these ester isocyanates by react-ing dihydrooxazines which may optionally be present as acid adducts with phosgene at from -20 to ~20C in a water-immiscible solvent in the presence of an aqueous solution of a base. The dihydrooxazines used as start-ing materials are made up of from 0 to 95 wt % of compounds corresponding to the formula:
1 \ / C-C-CH R3 (IV) Mo-2597 ~LZ3~33 from 0 to 70 wt % compounds corresponding to theformula:
R ~ C=CH-R3 (V) o and from 0 to 70 wt % compounds corresponding to the formula:
,,,~CH2-N
R"l ~C--C=CH-R3 (VI) \o with the above-~iven percentages totalling 100.
Rl, R'l, R"l, R2 and R3 are as defined above.
Within the context of the present invention, the term "1,2-cycloalkylene radical" is to be understood to mean divalent (optionally alkyl-substituted) cyclo-aliphatic hydrocarbon radicals, the cycloaliphatic rings of which are linked in the 1,2 position with the methyl-ene group or the oxygen atom of the ester isocyanates or the oxazines The terms "1,2-butylene radical", "2,3-butylene radical" and "1,2-isobutylene radical" are to be understood to mean aliphatic, divalent hydrocarbon radicals having 4 carbon atoms, which are linked in the 1,2 or 2,3 positions with the methylene group or the oxygen. In the case of asymmetric radicals, the higher substituted carbon atom is in each case linked with the oxygen atom.
The dihydrooxazines corresponding to the above-mentioned general formulae which are suitable starting materials for the process of the present invention may either be defined compounds (Rl = R'l =
R"l - optionally alkyl-substituted 1,2-cycloalkylene Mo-2597 , .
~2~34~33 radical having in total from 5 to 10 carbon atoms) or isomer mixtures (Rl, R'l and R"l represent various butylene or isobutylene radicals) as mentioned above.
The isomer distribution of the ester isocyanates corres-ponds to that of the dihydrooxazines used as s~artingmaterials. Dihydrooxazines which are preferably used as starting materials in the process of the present inven-tion are compounds corresponding ~o ~he formula:
Rl ~C-C=CH R3 ( IV) wherein Rl represents a 1,2-cyclohexylene, a 3- (and/or 4-)isopropyl-1,2-cyclohexylene or a 1-methyl-4-isopropyl-1,2-cyclohexylene radical, and R2 and R3 are each either hydrogen or methyl (R3 most preferably representing hydrogen).
Specific examples of these preferred compounds are:
2 11 (VII) o - C-CH=CH2 ,CH3 CH --CH~ O - C-C--CH2 (VIII) and CH
CH3~c~ ~ CH2-N (IX) Ç~ O - C-C--CH2 20. Other preferred starting materials include isomer mixtures made up of 85-95 wt % 2-vinyl- or 2-iso-propenyl-5,6-dimethyl-5,6-dihydrooxazine and from 5 to Mo-2597 ~L23~3 15 wt % 2-vinyl- or 2-isopropenyl-6-ethyl-5,6-dihydro-oxazine. In these isomer mixtures, the 2-vinyl- or 2-propenyl-5,6-dimethyl-5,6-dihydrooxazines are prefer-ably cis/trans-isomer mixtures in the weight ratio cis:trans of (33+10):(66+10).
Other dihydrooxazines or dihydrooxazine-isomer mixtures corresponding to the above mentioned broad definition may be used in the process of the present invention in addition to the preferred starting compounds. By way of example, dihydrooxazine-isomer mixtures which contain up to 70 wt % (preferably up to 50 wt %) 2-vinyl or 2-isopropenyl-6,6-dimethyl-5,6-di-hydrooxazine as well as 2-vinyl or 2-isopropenyl-5,6-dimethyl-5,6-dihydrooxazine and/or 2-vinyl or 2-isopro-penyl-6-ethyl-5,6-dihydrooxazine may be employed. The 5,6-dimethyl-substituted dihydrooxazines which are cis/trans isomer mixtures in the above-mentioned ratio may also be included. Moreover, dihydrooxazines or dihydrooxazine isomer mixtures ~hich have an n-propenyl substituent corresponding to the formula -CH=CH-CH3 (X) in the 2-position on the dihydrooxazine ring instead of - a vinyl or isopropenyl substituent may also be used in the process of the present invention.
The dihydrooxazines and dihydrooxazine-isomer mixtures which are used as starting materials may be produced by processes analogous to known prior art processes. For example, the starting materials may be produced from N-hydroxy-methyl amides corresponding to the general formula:
HO-CH2-NH-CO-C=CH-R3 (XI~
Mo-2597 ~23~133 and an olefin corresponding to the radical Rl or an olefin mixture corresponding to the radicals Rl-R"l by the process described in Liebigs Annalen 697, pages 171-180 (1966).
The starting materials are, however, more advantageously obtained from formaldehyde, a nitrile corresponding to the general formula:
NC-C=CH-R3 (XII) and an olefin corresponding to the radical Rl or an olefin mixture corresponding to the radicals Rl-R"l reacted in the manner described in Synthesis (1971), pages 92-95. More specifically, formaldehyde is reacted with the nitrile corresponding to the general formula (XII) in a solvent in the presence of equimolar quanti-ties of a strong acid at a temperature of from 30 to100C, preferably from 50 to 60C. The resulting amido-~ethylium ion corresponding to the formula:
CH2= H-C0-C=CH-R3 (XIII) reacts with the olefin or the olefin mixture in a polar cycloaddition to the acid adduct of the dihydrooxazine.
The dihydrooxazine which is suitable as a starting material in the present invention is then produced by treatment with a base.
Formaldehyde may be produced by depolymeriza-?.5 tion from paraformaldehyde or from 1,3,5-trioxane.
Carboxylic acids, carboxylic acid anhydrides, ethers ~such as tetrahydrofuran, dioxane, glymes or dig~ymes), amides, N-methylpyrrolidone, urea, 1,3-dimethylpyrroli-done-2 or sulfolane may be used as a solvent.
Mo-2597 ~34~3 Carboxylic acids, particularly acetic acid, are preferred.
Sulfuric acid, phosphoric acid, hydrogen chloride, hydrogen fluoride, hydrofluoroboric acid and sulfonic acid may be included as strong acids. Sulfuric acid is most advantageously used. In each case, water should be excluded.
The nitrile is introduced into the solvent in an equimolar quantity at a temperature of from 30 to 100C, (pre~erably from 50 to 60C) to produce a solu-tion of formaldehyde and the strong acid. Compounds corresponding to the radical Rl or the radicals Rl-R"
may be included as olefin or olefin mixture. Conse-quently, if cyclohexane is used, dihydrooxazines corres-ponding to the above-mentioned ~eneral formula IV in which Rl represents a 1,2-cyclohexalene radical are obtained. The dihydrooxazine-isomer mixtures which are particularly suitable as starting materials in the present invention may be obtained if a butene mixture made up of about 20 wt % cis-butene-2, 37 wt % trans-butene-2, 12 wt % l-butene, 7 wt % iso-butane and 23 wt % n-butane is used as the olefin mixture in this process. Commercial butene mixtures which contain inert butanes in addition to reactive butenes are produced, ~or example, as a C4 fraction during the distillative separation of the cleavage products of cracked petro-leum. Other commercial C4-fractions of cracked petro-leum which have a high iso-butene content yield dihydro-oxazine-mixtures which have a high 6,6-dimethyl-substi-tuted isomer content. Since the l-butene in such fractions is slower to react than cis- and trans-butene-2, the 6-ethyl-2-vinyl-5,6-dihydrooxazine content of the dihydrooxazine mixtures is generally less than the l-butene content of the C4-fraction from which it is produced.
Mo-2597 ~ 2 3 ~ 8 3 ~
_g _ The acid adduct of the dihydrooxazine and the olefin or olefin mixture may be reacted in an open vessel by passing the olefin through acid adduct or by adding it in portions to the acid adduct. In the case of gaseous olefins, the reaction may be carried out under pressure.
The dihydrooxazine is formed from the amino-methylium ion (XIII) and the olefin in a stereospecific cis-addition (see Chem. Ber. 103, 3242 ~1970)). For this reason, a corresponding cis-/trans-mixture of 5,6-dimethyldihydrooxazine is produced from a cis-trans-olefin-mixture.
As mentioned above, the free dihydrooxazine may ~De released in known manner from the resulting acid adduct by means of a base, such as sodium hydroxide or potassium hydroxide. It is, however, also possible to use the dihydrooxazines in the process of the present invention in the form of acid adducts. That is, the acid adducts of dihydrooxazines which are produced during the reaction of the amidomethylium ions with the olefin may be used immediately as starting materials in the process of the present invention after the auxiliary solvent has been removed.
The process of the present invention, that is the phosgenation of dihydrooxazines or dihydrooxazine mixtures is preferably carried out according to the known two-phase phosgenation described, for example, in German Auslegeschrift 1,924,535. From 1 to 2 mols of phosgene are generally used for each mol of dihydrooxa-zine or the acid adduct of the dihydrooxazine ordihydrooxazine mixture. At least 2 mols of an aqueous base are used for each mol of phosgene. Should the acid adducts of the dihydrooxazines be used, a quantity of base which is equivalent to the acid is additionally required.
Mo-2597 ~lZ34l~3~
Aqueous solutions of alkali metal hydroxides and carbonates may be used as bases. Aqueous sodium hydroxide is preferred. The dihydrooxazine and the phosgene are generally used as solutions in a non-polar water-immiscible solvent. Hydrocarbons, hydrocarbon halides (such as methylene chloride, chloroform, 1,2-dichloropropane, chlorobenzene and dichloroben2ene), esters (such as ethyl acetate), or ethers (such as diethyl- or dibutylether) may be used as solvents. The use of hydrocarbon halides and particularly the use of methylene chloride is most advantageous.
The solutions of dihydrooxazine, phosgene and bases are simultaneously added in a uniform manner to the reaction vessel. It must be ensured that the compo-lS nents are intensively mixed together. The temperatureis maintained at from -20 to +20C, preferably from 0 to 5C. Because the reaction takes place very quickly, it is appropriate to carry it out continuously.
Since the stereochemistry of the carbon atoms 4-6 of the dihydrooxazine ring is not changed during the phosgenation reaction, the ester isocyanates which are produced from the preferred dihydrooxazine mixtures generally have the follow;ng composition:
60 + 10 wt % threo-1-isocyanato-2-methyl-but-
CH3~c~ ~ CH2-N (IX) Ç~ O - C-C--CH2 20. Other preferred starting materials include isomer mixtures made up of 85-95 wt % 2-vinyl- or 2-iso-propenyl-5,6-dimethyl-5,6-dihydrooxazine and from 5 to Mo-2597 ~L23~3 15 wt % 2-vinyl- or 2-isopropenyl-6-ethyl-5,6-dihydro-oxazine. In these isomer mixtures, the 2-vinyl- or 2-propenyl-5,6-dimethyl-5,6-dihydrooxazines are prefer-ably cis/trans-isomer mixtures in the weight ratio cis:trans of (33+10):(66+10).
Other dihydrooxazines or dihydrooxazine-isomer mixtures corresponding to the above mentioned broad definition may be used in the process of the present invention in addition to the preferred starting compounds. By way of example, dihydrooxazine-isomer mixtures which contain up to 70 wt % (preferably up to 50 wt %) 2-vinyl or 2-isopropenyl-6,6-dimethyl-5,6-di-hydrooxazine as well as 2-vinyl or 2-isopropenyl-5,6-dimethyl-5,6-dihydrooxazine and/or 2-vinyl or 2-isopro-penyl-6-ethyl-5,6-dihydrooxazine may be employed. The 5,6-dimethyl-substituted dihydrooxazines which are cis/trans isomer mixtures in the above-mentioned ratio may also be included. Moreover, dihydrooxazines or dihydrooxazine isomer mixtures ~hich have an n-propenyl substituent corresponding to the formula -CH=CH-CH3 (X) in the 2-position on the dihydrooxazine ring instead of - a vinyl or isopropenyl substituent may also be used in the process of the present invention.
The dihydrooxazines and dihydrooxazine-isomer mixtures which are used as starting materials may be produced by processes analogous to known prior art processes. For example, the starting materials may be produced from N-hydroxy-methyl amides corresponding to the general formula:
HO-CH2-NH-CO-C=CH-R3 (XI~
Mo-2597 ~23~133 and an olefin corresponding to the radical Rl or an olefin mixture corresponding to the radicals Rl-R"l by the process described in Liebigs Annalen 697, pages 171-180 (1966).
The starting materials are, however, more advantageously obtained from formaldehyde, a nitrile corresponding to the general formula:
NC-C=CH-R3 (XII) and an olefin corresponding to the radical Rl or an olefin mixture corresponding to the radicals Rl-R"l reacted in the manner described in Synthesis (1971), pages 92-95. More specifically, formaldehyde is reacted with the nitrile corresponding to the general formula (XII) in a solvent in the presence of equimolar quanti-ties of a strong acid at a temperature of from 30 to100C, preferably from 50 to 60C. The resulting amido-~ethylium ion corresponding to the formula:
CH2= H-C0-C=CH-R3 (XIII) reacts with the olefin or the olefin mixture in a polar cycloaddition to the acid adduct of the dihydrooxazine.
The dihydrooxazine which is suitable as a starting material in the present invention is then produced by treatment with a base.
Formaldehyde may be produced by depolymeriza-?.5 tion from paraformaldehyde or from 1,3,5-trioxane.
Carboxylic acids, carboxylic acid anhydrides, ethers ~such as tetrahydrofuran, dioxane, glymes or dig~ymes), amides, N-methylpyrrolidone, urea, 1,3-dimethylpyrroli-done-2 or sulfolane may be used as a solvent.
Mo-2597 ~34~3 Carboxylic acids, particularly acetic acid, are preferred.
Sulfuric acid, phosphoric acid, hydrogen chloride, hydrogen fluoride, hydrofluoroboric acid and sulfonic acid may be included as strong acids. Sulfuric acid is most advantageously used. In each case, water should be excluded.
The nitrile is introduced into the solvent in an equimolar quantity at a temperature of from 30 to 100C, (pre~erably from 50 to 60C) to produce a solu-tion of formaldehyde and the strong acid. Compounds corresponding to the radical Rl or the radicals Rl-R"
may be included as olefin or olefin mixture. Conse-quently, if cyclohexane is used, dihydrooxazines corres-ponding to the above-mentioned ~eneral formula IV in which Rl represents a 1,2-cyclohexalene radical are obtained. The dihydrooxazine-isomer mixtures which are particularly suitable as starting materials in the present invention may be obtained if a butene mixture made up of about 20 wt % cis-butene-2, 37 wt % trans-butene-2, 12 wt % l-butene, 7 wt % iso-butane and 23 wt % n-butane is used as the olefin mixture in this process. Commercial butene mixtures which contain inert butanes in addition to reactive butenes are produced, ~or example, as a C4 fraction during the distillative separation of the cleavage products of cracked petro-leum. Other commercial C4-fractions of cracked petro-leum which have a high iso-butene content yield dihydro-oxazine-mixtures which have a high 6,6-dimethyl-substi-tuted isomer content. Since the l-butene in such fractions is slower to react than cis- and trans-butene-2, the 6-ethyl-2-vinyl-5,6-dihydrooxazine content of the dihydrooxazine mixtures is generally less than the l-butene content of the C4-fraction from which it is produced.
Mo-2597 ~ 2 3 ~ 8 3 ~
_g _ The acid adduct of the dihydrooxazine and the olefin or olefin mixture may be reacted in an open vessel by passing the olefin through acid adduct or by adding it in portions to the acid adduct. In the case of gaseous olefins, the reaction may be carried out under pressure.
The dihydrooxazine is formed from the amino-methylium ion (XIII) and the olefin in a stereospecific cis-addition (see Chem. Ber. 103, 3242 ~1970)). For this reason, a corresponding cis-/trans-mixture of 5,6-dimethyldihydrooxazine is produced from a cis-trans-olefin-mixture.
As mentioned above, the free dihydrooxazine may ~De released in known manner from the resulting acid adduct by means of a base, such as sodium hydroxide or potassium hydroxide. It is, however, also possible to use the dihydrooxazines in the process of the present invention in the form of acid adducts. That is, the acid adducts of dihydrooxazines which are produced during the reaction of the amidomethylium ions with the olefin may be used immediately as starting materials in the process of the present invention after the auxiliary solvent has been removed.
The process of the present invention, that is the phosgenation of dihydrooxazines or dihydrooxazine mixtures is preferably carried out according to the known two-phase phosgenation described, for example, in German Auslegeschrift 1,924,535. From 1 to 2 mols of phosgene are generally used for each mol of dihydrooxa-zine or the acid adduct of the dihydrooxazine ordihydrooxazine mixture. At least 2 mols of an aqueous base are used for each mol of phosgene. Should the acid adducts of the dihydrooxazines be used, a quantity of base which is equivalent to the acid is additionally required.
Mo-2597 ~lZ34l~3~
Aqueous solutions of alkali metal hydroxides and carbonates may be used as bases. Aqueous sodium hydroxide is preferred. The dihydrooxazine and the phosgene are generally used as solutions in a non-polar water-immiscible solvent. Hydrocarbons, hydrocarbon halides (such as methylene chloride, chloroform, 1,2-dichloropropane, chlorobenzene and dichloroben2ene), esters (such as ethyl acetate), or ethers (such as diethyl- or dibutylether) may be used as solvents. The use of hydrocarbon halides and particularly the use of methylene chloride is most advantageous.
The solutions of dihydrooxazine, phosgene and bases are simultaneously added in a uniform manner to the reaction vessel. It must be ensured that the compo-lS nents are intensively mixed together. The temperatureis maintained at from -20 to +20C, preferably from 0 to 5C. Because the reaction takes place very quickly, it is appropriate to carry it out continuously.
Since the stereochemistry of the carbon atoms 4-6 of the dihydrooxazine ring is not changed during the phosgenation reaction, the ester isocyanates which are produced from the preferred dihydrooxazine mixtures generally have the follow;ng composition:
60 + 10 wt % threo-1-isocyanato-2-methyl-but-
3-yl-(meth)-acrylate 30 + 10 wt % erythro-1-isocyanato-2-methyl-but-3-yl-(meth)-acrylate, and 10 + 5 wt % 1-isocyanatopent-3-yl-(meth)-acrylate.
The unsaturated ester isocyanates of the present invention are, among other things, valuable intermediates for the production of several oligoure-thanes which have olefinic double bonds and may be used Mo-2597 123~33~
as monomers, or comonomers particularly in the produc-tion of cross-linked plastics materials. The ester isocyanates of the present invention may be reacted with compounds having isocyanate-r~active groups in an isocyanate-addition reaction to produce oligourethanes which have several olefinically unsaturations. This addi~ion reaction may be accelerated by conventional urethanization catalysts such as tertiary amines (e.g., triethylene diamine) or dibutyl tin dilaurate or tln dioctoate. The addition reaction may be carried out in the presence of an inert solvent, preferably, however in the absence of solvent, at a temperature of from 20 to 120~C, preferably from 50 to 80~, The ester isocyanates are generally used in at least equivalent quantities, based on the isocyanate reactive groups. Where an isocyanate excess is used that excess may be removed from the reaction mixture by distillation after the reaction is completed. It is - also possible, in principle, to use an isocyanate defi-cient quantity to produce compounds which have olefinic double bonds and groups which are reactive with respect to isocyanate groups which compounds would enable polymers containing isocyanate-reactive groups to be produced.
Suitable compounds which have isocyanate-reactive groups are in particular polyhydric aliphatic alcohols which optionally have ether or ester groups.
Hydroxyl group-containing polyurethanes may be used in the addition reaction as compounds which have isocyanate-reactive groups. The compounds which have isocyanate-reactive groups generally have a molecular weight of from 62 to 10,000 preferably from 62 to 4,000, most preferably from 62 to 400.
Mo-2597 3 4 ~ 3 If simple diols which have a molecular weight of from 62 to 400 (such as ethylene glycol, propane-1,2-diol, butane-1,3-diol, butane~l,4-diol or neopentylglycol) are reacted with the ester isocyanates of the present invention, while maintaining an NCO/OH
equivalent ratio of 1:1, urethanes are obtained which (unlike the compounds which are produced in analogous manner from 2-isocyanatoethyl methacrylate) are liquid at room temperature and/or have an improved compatibility with other olefinically unsaturated monomers. The reaction products of the ester isocyanate mixtures with butane-1,3-diol, butane-1,4-diol or neopentylglycol are, for example, liquid at room temperature. The reaction products of the same ester isocyanate mixtures with polyhydric alcohols (such as glycerine or trimethylolpropane) have a markedly lower melt viscosity than the urethanes which are produced in analogous manner from 2-isocyanato ethyl methacrylate.
Having thus described our invention, the following examples are given by way of illustra~ion. In these examples, all the percentages are percentages by weight.
In Examples 1 to 3, the following dihydrooxa-zines or dihydrooxazine mixtures were used:
Dihydrooxazine I
122 g of paraformaldehyde, 1600 ml of acetic acid and 392 g of 100% sulfuric acid were heated to 60C
over a period of 20 mins. A solution of 0.5 g of phenol thiazine was added at 50C over a period of 10 mins. to 212 g of acrylonitrile and stirred over a period of 30 mins. at 50C. The mixture was saturated at 70C for 2 hours with a mixture of 20% cis-butene-2, 37% trans-butene, 12% l-butene~ 7% iso-butane, 23% n-butane and 1%
unidentified hydrocarbons. The clear solution was Mo-2597 234~3Z
cooled to rosm temperature. The solvent was distilledoff under vacuum. The residue was stirred, with cool-ing, into 6.5 1 of 15% sodium hydroxide and 2 1 of methylene chloride and drawn off by suction. The organic phase was separated. The aqueous phase was extracted two more times with methylene chloride and dried over sodium sulfate. Distillation under vacuum produced 250 g (45% of the theoretical yield) of a mixture made up of (i) 90 parts, by weight, of 5,6-di-methyl-2-~inyl-5,6-dihydrooxazine (cis/trans-mixture) and (ii) 10 parts, by weight, of 6-ethyl-2-vinyl-5,6-di-hyrooxazine. The mixture had a boiling range of from 75 to 78C at 10 mbars.
Dihydrooxazine II
24 g of 1,3,5-trioxane, 320 g of acetic acid and 78 g of 100% sulfuric acid were stirred for 20 mins.
at 70C. 53.6 g of methacrylonitrile were added drop-wise at 50C, the mixture was stirred for 30 mins. at 50C, saturated for 2 hours at 70C with an olefin mixture corresponding to that used in preparing Dihydro-oxazine I and cooled to room temperature. The solvent was removed under vacuum and the residue was stirred, with cooling, into 2 1 of 15% sodium hydroxide and 500 ml of methylene chloride. The phases were separated and the aqueous phase was twice extracted with methylene chloride. The mixture was dried over sodium sulfate and distilled under vacuum. 50 g (41% of the theoretical yield) of a mixture made up of (i) 90 parts, by weight, of 5,6-dimethyl-2-isopropenyl-5,6-dihydrooxazine (cis-/trans-mixture) and ~ii) 10 parts, by weight, of 6-ethyl-2-isopropenyl-5,6-dihydrooxazine were obtained.
The mixture had a boiling range of from 85 to 90C at 20 mbars.
Mo-2597 :~3~l~33~
Dihydrooxazine III
31 g of paraformaldehyde, 60 g of acetic acid, 9B g of 100~ sulfuric acid and 30~ ml of tetrahydro~uran were refluxed over a period of 30 mins. 53 g of acrylo-5 nitrile were added at 50C, the mixture was stirred for 30 minutes at 50C and was satura~ed for 2 hours under reflux with an olefin mixture corresponding to that used in preparing Dihydrooxazine I, The solvent was removed under vacuu~. The residue was added with stirring to 1.2 1 of 15% sodium hydroxide and 800 ml of methylene chloride and worked-up in the same manner as described above with respect to Dihydrooxazines I and II.
Distillation under vacuum produced 57 g (41% of the theoretical yield) of a dihydrooxazine mixture, which corresponded, as far as the composition and boil-ing point thereof were concerned, to Dihydrooxazine I.
Dihydrooxazine IV
31 g of paraformaldehyde, 98 g of 100% sulfuric acid and 250 ml of acetic acid were heated to 70C over 2~ a period of 30 mins. 53 g of acrylonitrile were added at 50C and the mixture was subsequently stirred for 30 minutes at 50C. 82 g of cyclohexene were added drop-wise at 70C, the mixture was stirred over a period of 2 hours at 70C and then stirred with cooling, into 4 l of 10% sodium hydroxide and 1.5 1 of methylene chloride and worked-up as described above. 59 g (36X of the theoretical yield) of a dihydrooxazine corresponding to the formula:
(VII) O - C-CH=CH2 30 were obtained. This material had a boiling range at 0.1 mbars of from 55 to 57~C.
Mo-2597 ~;~3~33~
Example 1 Solutions of 226 g of Dihydrooxazine I (or III) in 300 ml of methylene chloride, 238 g of phosgene in 800 ml of methylene chloride and 217 g of sodium hydroxide in 1200 ml of water per hour were simultan-eously pumped into a reaction vessel equipped with an overflow with intensive stirring. The temperature was maintained at from 0 to 5C. The phases of the over-flowing solution were separated. The aqueous phase was lo extracted twice more with methylene chloride, the combined ~rganic phases were dried over sodium sulfate and distilled under vacuum. 232 g per hour (78% of the theoretical yield) of a mixture made up of l-isocya-nato-2-methyl-but-3-yl-acrylate and l-isocyanato-pent-3-yl-acrylate in a weight ratio of 90:10 and having a boiling range at 0.1 mbar of from 75 to 77C were obt~ined.
Example 2 Over a period of 10 mins., solutions of 30 g of phosgene in 80 ml of methylene chloride, 29 g of Dihydrooxazine II in 70 ml of methylene chloride and 26 g of sodium hydroxide in 170 ml of water were simul-taneously added dropwise to a reaction vessel with intensive stirring. The temperature was maintained at from 0 to 10C. The phases were separated and the aqueous phase was subsequently extracted twice with methylene chloride. The combined organic phases were dried over sodium sulfate and distilled under vacuumO
30 g (81%) of a mixture made up of 1-isocyanato-2-methyl-but-3-yl-methacrylate and 1-isocyanatopent-3-yl-methacrylate in a weight ratio of 90:10 and having a boiling range at 0.1 mbar of from 80 to 85C were obtained.
Mo-2597 . , , ~ ~ 3 ~ ~ 3 Example 3 Over a period of 10 minutes, solutions of 18 g of phosgene in 50 ml of methylene chloride, 20 g of Dihydrooxazine IV in 50 ml of methylene chloride and 5 18 g of sodium hydroxide in 130 ml of water were simul-taneously added dropwise to a reaction vessel with intensive stirring at from 0 to 5C. On completion of the addition, the phases were separated, the aqueous phase was extracted twice more with methylene chloride, the combined organic phases were dried over sodium sulfate and distilled under vacuum. 17.5 g (70%) of 2-isocyanatome~hylcyclohexyl acrylate. Bp~o 1 95~97 were obtained.
Example 4 122 g of paraformaldehyde, 212 g of acrylo-nitrile and 392 g of 100% sulfuric acid were reacted, as described for the production of Dihydrooxazine I, with the olefin mixture which is mentioned therein. After the solvent was distilled off, the residue was dissolved in 800 ml of methylene chloride. Solutions of 594 g of phosgene in 2000 ml of methylene chloride and 100~ g of sodium hydroxide in 6000 ml of water were pumped into a reaction vessel simultaneously with the dihydrooxazine solution over a period of three hours at from 0 to 5C
25 with thorough mixing. The reaction vessel (600 ml) was equipped with an overflow. The phases of the overflow-ing solution were separated. The aqueous phase was extracted twice more with methylene chloride and the combined organic phases were dried over sodium sulfate.
Distillation under vacuum produced 329 g (45%, based on acrylonitrile) of the isocyanatoacrylate mixture which is described in Example 1.
Mo-2597 :~Z34~3~
Example 5 109,8 g of the ester isocyanate mixture ~rom Example 1 were added dropwise to 27 g of butane-1,4-diol, 25 g o~ Ionol* and 50 mg of dibutyl tin dilaurate at 70C. The mi~ture was subsequently stirred over a period of 2 hours at 70C. A quantitative yield of the corresponding diurethane which had a viscosity of 11,100 mPas at 23C was obtained.
Example 6 The diurethane was produced from 27 g of butane-1,4-diol and 90 g of 2-isocyanatoethyl methacryl-ate in the presence of 25 mg of Ionol* and 50 mg of dibutyl tin dilaurate in a quantitative yield by the same procedure as was used in Example 5. The reaction product had a melting point of 50C.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
* Trademark Mo-2597-Ca - 17 -
The unsaturated ester isocyanates of the present invention are, among other things, valuable intermediates for the production of several oligoure-thanes which have olefinic double bonds and may be used Mo-2597 123~33~
as monomers, or comonomers particularly in the produc-tion of cross-linked plastics materials. The ester isocyanates of the present invention may be reacted with compounds having isocyanate-r~active groups in an isocyanate-addition reaction to produce oligourethanes which have several olefinically unsaturations. This addi~ion reaction may be accelerated by conventional urethanization catalysts such as tertiary amines (e.g., triethylene diamine) or dibutyl tin dilaurate or tln dioctoate. The addition reaction may be carried out in the presence of an inert solvent, preferably, however in the absence of solvent, at a temperature of from 20 to 120~C, preferably from 50 to 80~, The ester isocyanates are generally used in at least equivalent quantities, based on the isocyanate reactive groups. Where an isocyanate excess is used that excess may be removed from the reaction mixture by distillation after the reaction is completed. It is - also possible, in principle, to use an isocyanate defi-cient quantity to produce compounds which have olefinic double bonds and groups which are reactive with respect to isocyanate groups which compounds would enable polymers containing isocyanate-reactive groups to be produced.
Suitable compounds which have isocyanate-reactive groups are in particular polyhydric aliphatic alcohols which optionally have ether or ester groups.
Hydroxyl group-containing polyurethanes may be used in the addition reaction as compounds which have isocyanate-reactive groups. The compounds which have isocyanate-reactive groups generally have a molecular weight of from 62 to 10,000 preferably from 62 to 4,000, most preferably from 62 to 400.
Mo-2597 3 4 ~ 3 If simple diols which have a molecular weight of from 62 to 400 (such as ethylene glycol, propane-1,2-diol, butane-1,3-diol, butane~l,4-diol or neopentylglycol) are reacted with the ester isocyanates of the present invention, while maintaining an NCO/OH
equivalent ratio of 1:1, urethanes are obtained which (unlike the compounds which are produced in analogous manner from 2-isocyanatoethyl methacrylate) are liquid at room temperature and/or have an improved compatibility with other olefinically unsaturated monomers. The reaction products of the ester isocyanate mixtures with butane-1,3-diol, butane-1,4-diol or neopentylglycol are, for example, liquid at room temperature. The reaction products of the same ester isocyanate mixtures with polyhydric alcohols (such as glycerine or trimethylolpropane) have a markedly lower melt viscosity than the urethanes which are produced in analogous manner from 2-isocyanato ethyl methacrylate.
Having thus described our invention, the following examples are given by way of illustra~ion. In these examples, all the percentages are percentages by weight.
In Examples 1 to 3, the following dihydrooxa-zines or dihydrooxazine mixtures were used:
Dihydrooxazine I
122 g of paraformaldehyde, 1600 ml of acetic acid and 392 g of 100% sulfuric acid were heated to 60C
over a period of 20 mins. A solution of 0.5 g of phenol thiazine was added at 50C over a period of 10 mins. to 212 g of acrylonitrile and stirred over a period of 30 mins. at 50C. The mixture was saturated at 70C for 2 hours with a mixture of 20% cis-butene-2, 37% trans-butene, 12% l-butene~ 7% iso-butane, 23% n-butane and 1%
unidentified hydrocarbons. The clear solution was Mo-2597 234~3Z
cooled to rosm temperature. The solvent was distilledoff under vacuum. The residue was stirred, with cool-ing, into 6.5 1 of 15% sodium hydroxide and 2 1 of methylene chloride and drawn off by suction. The organic phase was separated. The aqueous phase was extracted two more times with methylene chloride and dried over sodium sulfate. Distillation under vacuum produced 250 g (45% of the theoretical yield) of a mixture made up of (i) 90 parts, by weight, of 5,6-di-methyl-2-~inyl-5,6-dihydrooxazine (cis/trans-mixture) and (ii) 10 parts, by weight, of 6-ethyl-2-vinyl-5,6-di-hyrooxazine. The mixture had a boiling range of from 75 to 78C at 10 mbars.
Dihydrooxazine II
24 g of 1,3,5-trioxane, 320 g of acetic acid and 78 g of 100% sulfuric acid were stirred for 20 mins.
at 70C. 53.6 g of methacrylonitrile were added drop-wise at 50C, the mixture was stirred for 30 mins. at 50C, saturated for 2 hours at 70C with an olefin mixture corresponding to that used in preparing Dihydro-oxazine I and cooled to room temperature. The solvent was removed under vacuum and the residue was stirred, with cooling, into 2 1 of 15% sodium hydroxide and 500 ml of methylene chloride. The phases were separated and the aqueous phase was twice extracted with methylene chloride. The mixture was dried over sodium sulfate and distilled under vacuum. 50 g (41% of the theoretical yield) of a mixture made up of (i) 90 parts, by weight, of 5,6-dimethyl-2-isopropenyl-5,6-dihydrooxazine (cis-/trans-mixture) and ~ii) 10 parts, by weight, of 6-ethyl-2-isopropenyl-5,6-dihydrooxazine were obtained.
The mixture had a boiling range of from 85 to 90C at 20 mbars.
Mo-2597 :~3~l~33~
Dihydrooxazine III
31 g of paraformaldehyde, 60 g of acetic acid, 9B g of 100~ sulfuric acid and 30~ ml of tetrahydro~uran were refluxed over a period of 30 mins. 53 g of acrylo-5 nitrile were added at 50C, the mixture was stirred for 30 minutes at 50C and was satura~ed for 2 hours under reflux with an olefin mixture corresponding to that used in preparing Dihydrooxazine I, The solvent was removed under vacuu~. The residue was added with stirring to 1.2 1 of 15% sodium hydroxide and 800 ml of methylene chloride and worked-up in the same manner as described above with respect to Dihydrooxazines I and II.
Distillation under vacuum produced 57 g (41% of the theoretical yield) of a dihydrooxazine mixture, which corresponded, as far as the composition and boil-ing point thereof were concerned, to Dihydrooxazine I.
Dihydrooxazine IV
31 g of paraformaldehyde, 98 g of 100% sulfuric acid and 250 ml of acetic acid were heated to 70C over 2~ a period of 30 mins. 53 g of acrylonitrile were added at 50C and the mixture was subsequently stirred for 30 minutes at 50C. 82 g of cyclohexene were added drop-wise at 70C, the mixture was stirred over a period of 2 hours at 70C and then stirred with cooling, into 4 l of 10% sodium hydroxide and 1.5 1 of methylene chloride and worked-up as described above. 59 g (36X of the theoretical yield) of a dihydrooxazine corresponding to the formula:
(VII) O - C-CH=CH2 30 were obtained. This material had a boiling range at 0.1 mbars of from 55 to 57~C.
Mo-2597 ~;~3~33~
Example 1 Solutions of 226 g of Dihydrooxazine I (or III) in 300 ml of methylene chloride, 238 g of phosgene in 800 ml of methylene chloride and 217 g of sodium hydroxide in 1200 ml of water per hour were simultan-eously pumped into a reaction vessel equipped with an overflow with intensive stirring. The temperature was maintained at from 0 to 5C. The phases of the over-flowing solution were separated. The aqueous phase was lo extracted twice more with methylene chloride, the combined ~rganic phases were dried over sodium sulfate and distilled under vacuum. 232 g per hour (78% of the theoretical yield) of a mixture made up of l-isocya-nato-2-methyl-but-3-yl-acrylate and l-isocyanato-pent-3-yl-acrylate in a weight ratio of 90:10 and having a boiling range at 0.1 mbar of from 75 to 77C were obt~ined.
Example 2 Over a period of 10 mins., solutions of 30 g of phosgene in 80 ml of methylene chloride, 29 g of Dihydrooxazine II in 70 ml of methylene chloride and 26 g of sodium hydroxide in 170 ml of water were simul-taneously added dropwise to a reaction vessel with intensive stirring. The temperature was maintained at from 0 to 10C. The phases were separated and the aqueous phase was subsequently extracted twice with methylene chloride. The combined organic phases were dried over sodium sulfate and distilled under vacuumO
30 g (81%) of a mixture made up of 1-isocyanato-2-methyl-but-3-yl-methacrylate and 1-isocyanatopent-3-yl-methacrylate in a weight ratio of 90:10 and having a boiling range at 0.1 mbar of from 80 to 85C were obtained.
Mo-2597 . , , ~ ~ 3 ~ ~ 3 Example 3 Over a period of 10 minutes, solutions of 18 g of phosgene in 50 ml of methylene chloride, 20 g of Dihydrooxazine IV in 50 ml of methylene chloride and 5 18 g of sodium hydroxide in 130 ml of water were simul-taneously added dropwise to a reaction vessel with intensive stirring at from 0 to 5C. On completion of the addition, the phases were separated, the aqueous phase was extracted twice more with methylene chloride, the combined organic phases were dried over sodium sulfate and distilled under vacuum. 17.5 g (70%) of 2-isocyanatome~hylcyclohexyl acrylate. Bp~o 1 95~97 were obtained.
Example 4 122 g of paraformaldehyde, 212 g of acrylo-nitrile and 392 g of 100% sulfuric acid were reacted, as described for the production of Dihydrooxazine I, with the olefin mixture which is mentioned therein. After the solvent was distilled off, the residue was dissolved in 800 ml of methylene chloride. Solutions of 594 g of phosgene in 2000 ml of methylene chloride and 100~ g of sodium hydroxide in 6000 ml of water were pumped into a reaction vessel simultaneously with the dihydrooxazine solution over a period of three hours at from 0 to 5C
25 with thorough mixing. The reaction vessel (600 ml) was equipped with an overflow. The phases of the overflow-ing solution were separated. The aqueous phase was extracted twice more with methylene chloride and the combined organic phases were dried over sodium sulfate.
Distillation under vacuum produced 329 g (45%, based on acrylonitrile) of the isocyanatoacrylate mixture which is described in Example 1.
Mo-2597 :~Z34~3~
Example 5 109,8 g of the ester isocyanate mixture ~rom Example 1 were added dropwise to 27 g of butane-1,4-diol, 25 g o~ Ionol* and 50 mg of dibutyl tin dilaurate at 70C. The mi~ture was subsequently stirred over a period of 2 hours at 70C. A quantitative yield of the corresponding diurethane which had a viscosity of 11,100 mPas at 23C was obtained.
Example 6 The diurethane was produced from 27 g of butane-1,4-diol and 90 g of 2-isocyanatoethyl methacryl-ate in the presence of 25 mg of Ionol* and 50 mg of dibutyl tin dilaurate in a quantitative yield by the same procedure as was used in Example 5. The reaction product had a melting point of 50C.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
* Trademark Mo-2597-Ca - 17 -
Claims (5)
1. An unsaturated ester isocyanate optionally present as an isomer mixture comprising (a) from 0 to 95 wt %, based on the total mixture, of a compound corresponding to the formula OCN-CH2-R1-O-CO-??CH-R3 (I), (b) from O to 70 wt %, based on the total mixture, of a compound corresponding to the formula:
OCN-CH2-R'1-O-CO-??CH-R3 (II) and (c) from O to 70 wt %, based on the total mixture, of a compound corresponding to the formula:
OCN-CH2-R"1-O-CO-??CH-R3 (III) with the sum of the percentages of (a), (b) and (c) totalling 100 in which R1, R'1 and R"1 either represent the same radical which is an optionally alkyl-substituted 1,2-cyclo-alkylene radical having a total of from 5 to 10 carbon atoms, or R1 represents a 2,3-butylene radical, R'1 represents a straight-chain 1,2-butylene radical and R"1 represents a 1,2-iso-butylene radical;
and R2 and R3 which may be the same or different, each represent hydrogen or a methyl group.
OCN-CH2-R'1-O-CO-??CH-R3 (II) and (c) from O to 70 wt %, based on the total mixture, of a compound corresponding to the formula:
OCN-CH2-R"1-O-CO-??CH-R3 (III) with the sum of the percentages of (a), (b) and (c) totalling 100 in which R1, R'1 and R"1 either represent the same radical which is an optionally alkyl-substituted 1,2-cyclo-alkylene radical having a total of from 5 to 10 carbon atoms, or R1 represents a 2,3-butylene radical, R'1 represents a straight-chain 1,2-butylene radical and R"1 represents a 1,2-iso-butylene radical;
and R2 and R3 which may be the same or different, each represent hydrogen or a methyl group.
2. The unsaturated ester isocyanate of Claim 1 in which R1, R'1 and R"1 each represent the same optionally Mo-2597 alkyl-substituted 1,2-cycloalkylene radical having a total of from 5 to 10 carbon atoms, R2 represents hydrogen or a methyl group and R3 represents hydrogen.
3. The unsaturated ester isocyanate of Claim 1 which is an isomer mixture made up of from 85 to 95 wt %, based on the total mixture, of a compound corresponding to formula I and from 5 to 15 wt %, based on the total mixture, of a compound corresponding to formula II.
4. A process for the production of an unsatur-ated ester isocyanate which may optionally be present as an isocyanate mixture by reacting a dihydrooxazine which may optionally be present as an acid adduct with phosgene at from -20 to +20°C in a water-immiscible solvent in the presence of an aqueous solution of a base characterized in that the dihydrooxazine employed is made up of (a) from 0 to 95 wt % of a compound corres-ponding to the formula:
(IV) (b) from 0 to 70 wt % of a compound corres-ponding to the formula:
(V) and (c) from 0 to 70 wt % of a compound corres-ponding to the formula:
Mo-2597 (VI), with the percentages of (a), (b) and (c) totalling 100, in which R1, R'1, R"1 elther represent the same radical which is an optionally alkyl-substituted 1,2-cyclo-alkylene radical having a total of from 5 to 10 carbon atoms, or R1 represents a 2,3-butylene radical, R'1 represents a straight chain 1,2-butylene radical and R"1 represents a 1,2-isobutylene radical;
R2 and R3, which may be the same or different, each represent hydrogen or a methyl group.
(IV) (b) from 0 to 70 wt % of a compound corres-ponding to the formula:
(V) and (c) from 0 to 70 wt % of a compound corres-ponding to the formula:
Mo-2597 (VI), with the percentages of (a), (b) and (c) totalling 100, in which R1, R'1, R"1 elther represent the same radical which is an optionally alkyl-substituted 1,2-cyclo-alkylene radical having a total of from 5 to 10 carbon atoms, or R1 represents a 2,3-butylene radical, R'1 represents a straight chain 1,2-butylene radical and R"1 represents a 1,2-isobutylene radical;
R2 and R3, which may be the same or different, each represent hydrogen or a methyl group.
5. A process for the production of olefini-cally unsaturated oligourethanes comprising reacting a compound having isocyanate-reactive groups with the unsaturated ester isocyanate of Claim 1, optionally in the presence of a catalyst.
Mo-2597
Mo-2597
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833338077 DE3338077A1 (en) | 1983-10-20 | 1983-10-20 | UNSATURATED ESTERISOCYANATES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN THE PRODUCTION OF OLEFINICALLY UNSATURATED OLIGOURETHANES |
| DEP3338077.5 | 1983-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1234832A true CA1234832A (en) | 1988-04-05 |
Family
ID=6212280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000464681A Expired CA1234832A (en) | 1983-10-20 | 1984-10-03 | Unsaturated ester isocyanates and a process for the production thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0141295B1 (en) |
| JP (1) | JPS60105655A (en) |
| AT (1) | ATE24482T1 (en) |
| CA (1) | CA1234832A (en) |
| DE (2) | DE3338077A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3522006A1 (en) * | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID DERIVATIVES OF TRICYCLODECANES AND THEIR USE |
| DE3522005A1 (en) * | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
| EP2436366B1 (en) | 2010-09-30 | 2015-07-29 | VOCO GmbH | Composite material comprising a monomer with a polyalicyclic structure as sealing material |
| US8915736B2 (en) | 2010-09-30 | 2014-12-23 | Voco Gmbh | Composition comprising a monomer with a polyalicyclic structure element for filling and/or sealing a root canal |
| US9079828B2 (en) | 2010-09-30 | 2015-07-14 | Voco Gmbh | Polymerizable compounds comprising a polyalicylic structure element |
| US8697769B2 (en) | 2010-09-30 | 2014-04-15 | Voco Gmbh | Lacquer composition comprising a monomer with a polyalicyclic structure element |
| US9023916B2 (en) | 2010-09-30 | 2015-05-05 | Voco Gmbh | Composite material comprising a monomer with a polyalicyclic structure element |
| EP2450025B1 (en) | 2010-11-08 | 2012-11-28 | VOCO GmbH | Polymerisable phosphoric acid derivatives comprising a polyalicyclic structure element |
| EP2578200B1 (en) | 2011-10-04 | 2018-03-28 | VOCO GmbH | Compounds for infiltrating and/or sealing of dental hard substance and method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1267214B (en) * | 1965-12-07 | 1968-05-02 | Bayer Ag | Process for the preparation of unsaturated ester isocyanates |
| GB1252099A (en) * | 1969-05-14 | 1971-11-03 | ||
| US4278809A (en) * | 1977-06-15 | 1981-07-14 | The Dow Chemical Company | Process for preparing 2-isocyanatoalkyl esters of organic carboxylic acids |
-
1983
- 1983-10-20 DE DE19833338077 patent/DE3338077A1/en not_active Withdrawn
-
1984
- 1984-10-03 CA CA000464681A patent/CA1234832A/en not_active Expired
- 1984-10-06 EP EP84111998A patent/EP0141295B1/en not_active Expired
- 1984-10-06 AT AT84111998T patent/ATE24482T1/en active
- 1984-10-06 DE DE8484111998T patent/DE3461789D1/en not_active Expired
- 1984-10-19 JP JP59218781A patent/JPS60105655A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3338077A1 (en) | 1985-05-09 |
| EP0141295B1 (en) | 1986-12-30 |
| ATE24482T1 (en) | 1987-01-15 |
| EP0141295A1 (en) | 1985-05-15 |
| JPS60105655A (en) | 1985-06-11 |
| DE3461789D1 (en) | 1987-02-05 |
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