CA1236453A - Organo-soluble c.sub.3-c.sub.4 hydroxyalkyl ethyl cellulose ethers - Google Patents
Organo-soluble c.sub.3-c.sub.4 hydroxyalkyl ethyl cellulose ethersInfo
- Publication number
- CA1236453A CA1236453A CA000504829A CA504829A CA1236453A CA 1236453 A CA1236453 A CA 1236453A CA 000504829 A CA000504829 A CA 000504829A CA 504829 A CA504829 A CA 504829A CA 1236453 A CA1236453 A CA 1236453A
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- Canada
- Prior art keywords
- cellulose
- cellulose ether
- substitution
- toluene
- soluble
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
Abstract
ABSTRACT
C3-C4 hydroxyalkyl ethylcellulose ethers which are substantially soluble in toluene, and toluene and heptane mixtures are disclosed. Such organo-soluble cellulose ethers are useful in thickening organic solvent systems comprised of toluene. A process for the preparation of the ethers is also provided.
C3-C4 hydroxyalkyl ethylcellulose ethers which are substantially soluble in toluene, and toluene and heptane mixtures are disclosed. Such organo-soluble cellulose ethers are useful in thickening organic solvent systems comprised of toluene. A process for the preparation of the ethers is also provided.
Description
~36~3 CELLULOSE ETHERS
This invention concerns to organo-soluble cellulose ethers, and in particular to hydroxyalkoxyl substituted ethylcellulose ethers.
Common commercially available cellulose ethers such as methylcellulose, hydroxyethyl methyl-cellulose, hydroxypropyl methylcellulose, hydroxypropyl-cellulose and the like are employed as thickeners, protective colloids, film formers and for other uses in aqueous systems. While -these cellulose ethers are useful in aqueous systems, the water-soluble ethers are generally insoluble in organic solvents and nonthermo-plastics. Accordingly, these cellulose ethers cannot be employed in organic systems. For example, it is difficult to employ such cellulose ethers as additives in organic solvent systems, such as inks and the like.
To meet the need for a cellulose ether with organic solubility, more hydrophobic cellulose deri-vatives have been developed. Such compositions include, for example, ethylcellulose, ethylhydroxypropyl methyl-, .
ceIlulose and ethylhydroxyethylcellulos~.
' ~ .
~' ~
,33,007-F
~' .
While these cellulose ethers are both organo-soluble and thermoplastic, they have other deficiencies which significantly limit their utility. For example, most ethylcellulose ethers are insoluble in nonpolar organic solvents, such as the hydrocarbons and their halo, nitro, and cyano substituted derivatives which have low solubility parameters. Generally, if solubility in such nonpolar solvents is required, the ethylcellulose must be substantially completely substituted, i.e., have an ethoxyl degree of substitution of about 3.
Unfortunately, ethylcellulose with a degree of sub-stitution greater than about 2.5 exhibits a tendency to crystalliæe, which renders the cellulose ether insoluble in most solvents.
Still another disadvantage of known technology involves the fact that the preparations of ethylhydroxy-ethylcellulose and ethylhydroxypropyl methylcellulose are not par-ticularly efficient nor effective. The ethylene oxide commonly used in the preparation of ethylhydroxyethylcellulose can react with water, ethyl chloride and other reagents present in the reaction mixture. Consequently, the overall yield of the pro-cess is greatly reduced and a variety of by-products are formed which are difficult to remove from the product.
.
Accordingly, a cellulose ether which is soluble in nonpolar organic solvents and is efficiently and effectively prepared would be highly desirable.
This invention provides a C3-C4 hydroxyalkyl ethylcellulose ether which is substantially soluble at ambient temperatures in toluene.
:, 33,007-F -2-, ~Z~6~i3 In ano-ther aspect, this invention is a pro-cess for preparing C3-C4 hydroxyalkyl ethylcellulose ethers, said process comprising contacting an amount of alkali-cellulose with an effective amount of a C3-C4 alkylene oxide, and an effective amount of an ethyl halide under reaction conditions, such that a C3-C~
hydroxyalkyl ethylcellulose is prepared which is sub-stantially soluble at ambient temperatures in toluene.
.
Surprisingly, this invention provides cellu-lose ether compositions which are soluble in nonpolar organic solvents and which are efficiently and effec-tively prepared. The cellulose ethers of the invention are useful ln thickening ink formulations such as -those comprised of nonhydrogen bonded organic solvent systems.
By the term "ambient temperatures" is meant that temperature at which the solution of polymer in solvent is employed. Typically, the temperature is room temperature (i.e., about 15C -to about 30C) at atmospheric pressure.
As used herein, the organo-soluble cellulose ethers of the inven-tion are those cellulose ethers which form thermodynamically stable mixtures with toluene, and toluene and nonhydrogen bonded organic solvent mixtures at ambient temperatures. Such mix-tures form spontaneously and include the solutions in which individual cellulose ether molecules are dis-persed in the organic solvent as well as micellular or colloidal solutions wherein the polymer molecules are aggregated to some extent, but wherein such aggregates are no larger than colloidal size. When employed as 33,007-F -3-i3 thickeners in ink compositions, true solutions are preferred, because interference with the dying pro-perties of the ink are avoided.
A cellulose ether is substantially soluble in organic solvents when a substantial amount of the ether can form such thermodynamically stable mixtures in such solvents at ambient temperatures. Preferably, such ethers are infinitely soluble in such solvents, and will form true solutions up to about a 10 weight per-cent solution, or up to the point where a highly vis-cous gel forms as determined by physical observation.
The cellulose ethers of this invention are derivatives of cellulose. Cellulose is a lonq-cha:in molecule comprised of repeating anhydroglucose units.
Such units have three hydroxyl sites available for etherification. When etherified, the cellulose ether is defined in terms of the extent to which the ether-ifying groups have substituted for the hydxoxyl groups on the anhydroglucose units. When a hydroxyalkoxyl group is an etherifying agent, the ex-tent of substi-tution is described as molar substitution; i.e., the average number of moles of the hydroxyalkoxyl group substituted on the anhydrog~ucose unit. In view of the fact that each hydroxyalkoxyl group provides an addi-tional hydroxyl group for substitution, there is theo-retically no limit to the amount of hydroxyalkoxyl substitution. When an alkoxyl group is an etherifying agent, the extent of substitution is described as the degree of substitution; i.e., the average number of hydroxyl groups substituted with alkoxyl groups. Such groups can substitute for the hydroxyls on the anhydro-glucose backbone, and the pendant hydroxyls on the ~ .
~, ~
~; 33,007-F -4-~L236~5;3 hydroxyalkoxyl group. Therefore, the alkoxyl degree of substitution can theoretically range from 0 to 3.
The C3-C4 hydroxyalkyl ethylcellulose ether~
of this invention have sufficient ethoxyl substitution to render the ether organo-soluble. Generally, as the ethoxyl substitution increases, the e-ther becomes . soluble in organic solvents which are less polar, and more poorly hydrogen bonded, for example toluene. The range of ethoxyl degree of substitution can vary from about 2.4 to about 2.7, although any ethoxyl degree of substitution which can render the ether substantially soluble in toluene is sufficient. Also, it is desirable that -the amount of ethoxyl employed is sufficient to cap the pendant hydroxyls on the hydroxyalkoxyl chains.
lS The amount o~ C3-C~ hydroxyalkoxyl groups on the ethylcellulose ether is sufficient to stabilize the ethylcellulose. By "stabilize" is meant that -the tendency of the highly ethoxylated cellulose ether to crystallize is inhibited. Such crystallization can be visually observed, can occu~ spontaneously and provides undesirable insolubility in most solvents. Therefore, such a tendency can be readily determined and avoided.
The upper limit on the amoun~t of the C3-C4 h~droxyalkoxyl substitution is that amount which inhibits the ethyl cellulose ether's solubility in the desired organic solvents.- The C3-C4 hydroxyalkoxyl molar substitution can vary from about 0.38 to about 0.63, although any effectively stabilizing amount is sufficient.
Preferably, the substitution of the ethoxyl and C3-C4 hydroxyalkoxyl groups on the anhydroglucose uni-ts are substantially uniform, i.e. that each anhydro-glucose unit has substantially similar -type and amount 33,007-F ~5~
~3~ ii3 of substitution. For examplë, in view of the fact that when a hydroxyalkoxyl group substitutes on -the unit a new hydroxyl group is provided for substitution, one anhydroglucose unit can have the entire hydroxyalkoxyl molar substitution. However, since the molar substitu-tion value refers to the average substitution, such a substituted polymer can have the same molar substitu-. tion value as a polymer having small substitution oneach anhydroglucose unit.
The organic-soluble cellulose ethers of this invention can be prepared by reacting alkali cellulose with an ethyl halide and a C3-C4 alkylene oxide ~propyl-ene or butylene oxide) under suitable reactlon condi-tions. Typically such conditions can include subjec-ting the reaction mixture to high temperatures, in an inert a-tmosphere, at super-atmospheric pressures and performing the reaction in the presence of an inert diluent.
Alkali cellulose is advantageously prepared by reacting cellulose pulp with a functionally effective amount of an alkali metal hydroxide. The alkali metal hydroxide functions to break up the crys-talline struc-ture of the cellulose, catal~ze the etherifying agent cellulose reaction and react with the cellulose and etherifying agen-t to attach ether groups to the cellu-lose. The alkali metal hydroxide is generally employed as an aqueous solution containing about 73 weight percent of the alkali metal hydroxide. Typically, caustic is employed as the alkali metal hydroxide because of economic considerations. Advantageously, about 1.1 parts by weight of cellulose pulp of caustic is employed, although any amount which can perform the functions is sufficie~t.
33,007-F -6-; _7~ ~ ~ 3 Preferably, to obtain a substantially uni-formly substituted cellulose ether, two charges of the alkali metal hydroxide are added. In addition to the ; initial charge of caustic, a functionally effective amount can be added after the etherifying agents have been added. Such second charge of caustic preferably is of a greater amount and strength than the initial charge. For example, about 2.5 parts by weight of cellulose of about a 100 percent concentrated bead caustic is suitable for the second charge.
Preferably, the cellulose ether of the inven-tion is prepared in a slurry in'an inert organic diluent such as, for example, benzene, toluene, or methyl ethyl ketone. In such a process, the alkalization and C3-C4 hydroxyalkoxyl substitution is performed substantially simultaneously; i.e., functionally effective amounts of the alkali metal hydroxide, cellulose pulp, C3-C4 alkylene oxide and organic diluent are charged to the reaction vessel simultaneously. A suitable amount of .
the C3-C4 alkylene oxide can vary from about 0.4 to about 1, preferably about 0.6 parts by weight of cellu-lose pulp, and a suitable amount of the diluent is about 11.6 parts by weight of cellulose pulp.
The reaction slurry is subjec-ted to reaction conditions, comprising a functionally effective time and temperature. A functionally effective amount of an ethyl halide is charged to the vessel, preferably simultaneously with the C3 4 alkylene oxide. A suitable amount can vary from about 2.3 to 5, preferably about 3.5 parts by weight of cellulose pulp. The reaction slurry thus comprising the ethyl halide is subjected -to 33,007-F -7-~2~ ii3 effective reaction conditions. To complete the ether-ification, the second charge of caustic is charged to the vessel, and subjected to effective reaction condi-tions. The reaction product can then be prepared for commercial utilization according to conventional means.
The organic solvents in ~hich the cellulose ethers can be soluble are, for example, mixtures of tolwene and nonhydrogen ~onded organic solvents which exhibit a solubility parameter of 7.8 [cal/cm3] 2 or greater. Such solvents include those solvents described in E. H. Immergut, PolYmer Handbook, 2d ed., 1975, as poorly hydrogen bonded solvents in the section discus-sing solubility parameters. For example, hydrocarbons and their halo-, nitro- and cyano-substitution products are such poorly hydrogen bonded solvents. The cellulose ethers of the inven-tion can also be soluble in mixtures of toluene and the constituents of petroleun~ which have distillation temperatures above about 60C. Another species of suitable solvents are Lactol Spirits~ (trade-mark of American Mineral Spirits Company) which can becomprised of about 40 percent toluene and 60 percent aliphatic hydrocarbon solvents, primarily heptane. The cellulose ethers of the invention can form true solu-tions at ambient temperatures in a 100 percent toluene solution, as well as in a 20 percent toluene and 80 percent heptane solution. The solubility parameter of -the 20/80 solution, as determined by a weighted average of the solvent's cohesive energy densities is 7.8 [cal/cm3] 2, while the solubility parameter of 100 percent toluene is 8.9 [cal/cm3]'2.
.
The viscosity of the organo-soluble cellulose ethers can vary from about 4 to greater than 1000 cps ., ~ 33,007-F -8-~2~ 3 g measured as a 5 percent solution in an 80 percent toluene and 20 percent ethanol solvent at 23C.
The cellulose ethers of this invention exhibit a higher viscosity effect in organic solvents compared with ethylhydroxyethylcellulose. For example, to obtain a substantiall~ similar thickening effect, less of the cellulose ether of this invention can be employed than the amount of ethylhydroxyethylcellulose; e.g., about 0.75 to 1. The cellulose ethers of this inven-tion provide similar ~uality compared with a system employing ethylhydroxyekhylcellulose when tested in the let down, metal resinate, and gloss tests employed by the printing industry when evaluating ink compositions.
The ~ollowing examples are intended to illus-trate the invention but not to limit the scope. Allparts and percentages are by weight unless otherwise indicated.
Example 1 Sample No. l is prepared by charging a 2-liter PARR reactor with 72 grams (g) of cellulose pulp (Buckeye E-7 ground through a l-2 mm screen) and 785 g of toluene as a diluent. Using a loop ~agitator, this mixture is agitated at 1100 rpm, heated to about 90QC, and contac-ted with 109.5 g o~ a 73 percent molten sodium hydroxide solution. Contact time is five minutes. The reactor is closed, the air evacuated, and purged with nitrogen.
A 93.2 g charge of a 46.4 percent propylene oxide in toluene solution and a 252 g charge oE ethyl chloride are added to the reactor. The reaction temperature is maintained at 90C a-t a 180 rpm agitation rate for one hour. The reaction temperature is then raised to ~ ' .
~ 33,007-F -9-~2~ 5i3 130C, and proceeds for two hours. To the heated reaction mixture is added 180 g of lO0 percent bead sodium hydroxide, the reaction temperature is raised to 140C, and proceeds for seven hours. The product dump mass is granulated by contacting with boiling water to evaporate the organic solvents, and to solubilize the remaining by-product salts and caustic.
The produc-t is water washed and hot air dried. The product has a hydroxypropoxyl molar substitution of 10 0.47 and an ethoxyl degree of substitution of 2.6. A
one weight percent portion of this cellulose ether is soluble in a Lactol Spirits~ composition, and the solution has a viscosity at 23C of 21.6 cps.
A one weight percent portion of this cellulose ether forms a true solution with a 100 percent toluene solution.
A one weight percent portion of this cellulose ether forms a true solution with a 20 percent toluene and 80 percent heptane solution.
Example 2 Sample No. 2 is prepared in the same manner as Sample No. 1, except 0.6 parts based on weight of cellulose pulp of butylene oxide is used rather than propylene oxide. The cellulose ether has a hydroxybutoxyl molar substitution of 0.42 and an ethoxyl degree of substitution of 2.7. The cellulose ether is soluble in Lactol Spirits~, yielding a hazy solution. A one weight percent portion in Lactol Spirits~ has a viscosity at 23C of 16.7 cps.
33,007-F -lO-
This invention concerns to organo-soluble cellulose ethers, and in particular to hydroxyalkoxyl substituted ethylcellulose ethers.
Common commercially available cellulose ethers such as methylcellulose, hydroxyethyl methyl-cellulose, hydroxypropyl methylcellulose, hydroxypropyl-cellulose and the like are employed as thickeners, protective colloids, film formers and for other uses in aqueous systems. While -these cellulose ethers are useful in aqueous systems, the water-soluble ethers are generally insoluble in organic solvents and nonthermo-plastics. Accordingly, these cellulose ethers cannot be employed in organic systems. For example, it is difficult to employ such cellulose ethers as additives in organic solvent systems, such as inks and the like.
To meet the need for a cellulose ether with organic solubility, more hydrophobic cellulose deri-vatives have been developed. Such compositions include, for example, ethylcellulose, ethylhydroxypropyl methyl-, .
ceIlulose and ethylhydroxyethylcellulos~.
' ~ .
~' ~
,33,007-F
~' .
While these cellulose ethers are both organo-soluble and thermoplastic, they have other deficiencies which significantly limit their utility. For example, most ethylcellulose ethers are insoluble in nonpolar organic solvents, such as the hydrocarbons and their halo, nitro, and cyano substituted derivatives which have low solubility parameters. Generally, if solubility in such nonpolar solvents is required, the ethylcellulose must be substantially completely substituted, i.e., have an ethoxyl degree of substitution of about 3.
Unfortunately, ethylcellulose with a degree of sub-stitution greater than about 2.5 exhibits a tendency to crystalliæe, which renders the cellulose ether insoluble in most solvents.
Still another disadvantage of known technology involves the fact that the preparations of ethylhydroxy-ethylcellulose and ethylhydroxypropyl methylcellulose are not par-ticularly efficient nor effective. The ethylene oxide commonly used in the preparation of ethylhydroxyethylcellulose can react with water, ethyl chloride and other reagents present in the reaction mixture. Consequently, the overall yield of the pro-cess is greatly reduced and a variety of by-products are formed which are difficult to remove from the product.
.
Accordingly, a cellulose ether which is soluble in nonpolar organic solvents and is efficiently and effectively prepared would be highly desirable.
This invention provides a C3-C4 hydroxyalkyl ethylcellulose ether which is substantially soluble at ambient temperatures in toluene.
:, 33,007-F -2-, ~Z~6~i3 In ano-ther aspect, this invention is a pro-cess for preparing C3-C4 hydroxyalkyl ethylcellulose ethers, said process comprising contacting an amount of alkali-cellulose with an effective amount of a C3-C4 alkylene oxide, and an effective amount of an ethyl halide under reaction conditions, such that a C3-C~
hydroxyalkyl ethylcellulose is prepared which is sub-stantially soluble at ambient temperatures in toluene.
.
Surprisingly, this invention provides cellu-lose ether compositions which are soluble in nonpolar organic solvents and which are efficiently and effec-tively prepared. The cellulose ethers of the invention are useful ln thickening ink formulations such as -those comprised of nonhydrogen bonded organic solvent systems.
By the term "ambient temperatures" is meant that temperature at which the solution of polymer in solvent is employed. Typically, the temperature is room temperature (i.e., about 15C -to about 30C) at atmospheric pressure.
As used herein, the organo-soluble cellulose ethers of the inven-tion are those cellulose ethers which form thermodynamically stable mixtures with toluene, and toluene and nonhydrogen bonded organic solvent mixtures at ambient temperatures. Such mix-tures form spontaneously and include the solutions in which individual cellulose ether molecules are dis-persed in the organic solvent as well as micellular or colloidal solutions wherein the polymer molecules are aggregated to some extent, but wherein such aggregates are no larger than colloidal size. When employed as 33,007-F -3-i3 thickeners in ink compositions, true solutions are preferred, because interference with the dying pro-perties of the ink are avoided.
A cellulose ether is substantially soluble in organic solvents when a substantial amount of the ether can form such thermodynamically stable mixtures in such solvents at ambient temperatures. Preferably, such ethers are infinitely soluble in such solvents, and will form true solutions up to about a 10 weight per-cent solution, or up to the point where a highly vis-cous gel forms as determined by physical observation.
The cellulose ethers of this invention are derivatives of cellulose. Cellulose is a lonq-cha:in molecule comprised of repeating anhydroglucose units.
Such units have three hydroxyl sites available for etherification. When etherified, the cellulose ether is defined in terms of the extent to which the ether-ifying groups have substituted for the hydxoxyl groups on the anhydroglucose units. When a hydroxyalkoxyl group is an etherifying agent, the ex-tent of substi-tution is described as molar substitution; i.e., the average number of moles of the hydroxyalkoxyl group substituted on the anhydrog~ucose unit. In view of the fact that each hydroxyalkoxyl group provides an addi-tional hydroxyl group for substitution, there is theo-retically no limit to the amount of hydroxyalkoxyl substitution. When an alkoxyl group is an etherifying agent, the extent of substitution is described as the degree of substitution; i.e., the average number of hydroxyl groups substituted with alkoxyl groups. Such groups can substitute for the hydroxyls on the anhydro-glucose backbone, and the pendant hydroxyls on the ~ .
~, ~
~; 33,007-F -4-~L236~5;3 hydroxyalkoxyl group. Therefore, the alkoxyl degree of substitution can theoretically range from 0 to 3.
The C3-C4 hydroxyalkyl ethylcellulose ether~
of this invention have sufficient ethoxyl substitution to render the ether organo-soluble. Generally, as the ethoxyl substitution increases, the e-ther becomes . soluble in organic solvents which are less polar, and more poorly hydrogen bonded, for example toluene. The range of ethoxyl degree of substitution can vary from about 2.4 to about 2.7, although any ethoxyl degree of substitution which can render the ether substantially soluble in toluene is sufficient. Also, it is desirable that -the amount of ethoxyl employed is sufficient to cap the pendant hydroxyls on the hydroxyalkoxyl chains.
lS The amount o~ C3-C~ hydroxyalkoxyl groups on the ethylcellulose ether is sufficient to stabilize the ethylcellulose. By "stabilize" is meant that -the tendency of the highly ethoxylated cellulose ether to crystallize is inhibited. Such crystallization can be visually observed, can occu~ spontaneously and provides undesirable insolubility in most solvents. Therefore, such a tendency can be readily determined and avoided.
The upper limit on the amoun~t of the C3-C4 h~droxyalkoxyl substitution is that amount which inhibits the ethyl cellulose ether's solubility in the desired organic solvents.- The C3-C4 hydroxyalkoxyl molar substitution can vary from about 0.38 to about 0.63, although any effectively stabilizing amount is sufficient.
Preferably, the substitution of the ethoxyl and C3-C4 hydroxyalkoxyl groups on the anhydroglucose uni-ts are substantially uniform, i.e. that each anhydro-glucose unit has substantially similar -type and amount 33,007-F ~5~
~3~ ii3 of substitution. For examplë, in view of the fact that when a hydroxyalkoxyl group substitutes on -the unit a new hydroxyl group is provided for substitution, one anhydroglucose unit can have the entire hydroxyalkoxyl molar substitution. However, since the molar substitu-tion value refers to the average substitution, such a substituted polymer can have the same molar substitu-. tion value as a polymer having small substitution oneach anhydroglucose unit.
The organic-soluble cellulose ethers of this invention can be prepared by reacting alkali cellulose with an ethyl halide and a C3-C4 alkylene oxide ~propyl-ene or butylene oxide) under suitable reactlon condi-tions. Typically such conditions can include subjec-ting the reaction mixture to high temperatures, in an inert a-tmosphere, at super-atmospheric pressures and performing the reaction in the presence of an inert diluent.
Alkali cellulose is advantageously prepared by reacting cellulose pulp with a functionally effective amount of an alkali metal hydroxide. The alkali metal hydroxide functions to break up the crys-talline struc-ture of the cellulose, catal~ze the etherifying agent cellulose reaction and react with the cellulose and etherifying agen-t to attach ether groups to the cellu-lose. The alkali metal hydroxide is generally employed as an aqueous solution containing about 73 weight percent of the alkali metal hydroxide. Typically, caustic is employed as the alkali metal hydroxide because of economic considerations. Advantageously, about 1.1 parts by weight of cellulose pulp of caustic is employed, although any amount which can perform the functions is sufficie~t.
33,007-F -6-; _7~ ~ ~ 3 Preferably, to obtain a substantially uni-formly substituted cellulose ether, two charges of the alkali metal hydroxide are added. In addition to the ; initial charge of caustic, a functionally effective amount can be added after the etherifying agents have been added. Such second charge of caustic preferably is of a greater amount and strength than the initial charge. For example, about 2.5 parts by weight of cellulose of about a 100 percent concentrated bead caustic is suitable for the second charge.
Preferably, the cellulose ether of the inven-tion is prepared in a slurry in'an inert organic diluent such as, for example, benzene, toluene, or methyl ethyl ketone. In such a process, the alkalization and C3-C4 hydroxyalkoxyl substitution is performed substantially simultaneously; i.e., functionally effective amounts of the alkali metal hydroxide, cellulose pulp, C3-C4 alkylene oxide and organic diluent are charged to the reaction vessel simultaneously. A suitable amount of .
the C3-C4 alkylene oxide can vary from about 0.4 to about 1, preferably about 0.6 parts by weight of cellu-lose pulp, and a suitable amount of the diluent is about 11.6 parts by weight of cellulose pulp.
The reaction slurry is subjec-ted to reaction conditions, comprising a functionally effective time and temperature. A functionally effective amount of an ethyl halide is charged to the vessel, preferably simultaneously with the C3 4 alkylene oxide. A suitable amount can vary from about 2.3 to 5, preferably about 3.5 parts by weight of cellulose pulp. The reaction slurry thus comprising the ethyl halide is subjected -to 33,007-F -7-~2~ ii3 effective reaction conditions. To complete the ether-ification, the second charge of caustic is charged to the vessel, and subjected to effective reaction condi-tions. The reaction product can then be prepared for commercial utilization according to conventional means.
The organic solvents in ~hich the cellulose ethers can be soluble are, for example, mixtures of tolwene and nonhydrogen ~onded organic solvents which exhibit a solubility parameter of 7.8 [cal/cm3] 2 or greater. Such solvents include those solvents described in E. H. Immergut, PolYmer Handbook, 2d ed., 1975, as poorly hydrogen bonded solvents in the section discus-sing solubility parameters. For example, hydrocarbons and their halo-, nitro- and cyano-substitution products are such poorly hydrogen bonded solvents. The cellulose ethers of the inven-tion can also be soluble in mixtures of toluene and the constituents of petroleun~ which have distillation temperatures above about 60C. Another species of suitable solvents are Lactol Spirits~ (trade-mark of American Mineral Spirits Company) which can becomprised of about 40 percent toluene and 60 percent aliphatic hydrocarbon solvents, primarily heptane. The cellulose ethers of the invention can form true solu-tions at ambient temperatures in a 100 percent toluene solution, as well as in a 20 percent toluene and 80 percent heptane solution. The solubility parameter of -the 20/80 solution, as determined by a weighted average of the solvent's cohesive energy densities is 7.8 [cal/cm3] 2, while the solubility parameter of 100 percent toluene is 8.9 [cal/cm3]'2.
.
The viscosity of the organo-soluble cellulose ethers can vary from about 4 to greater than 1000 cps ., ~ 33,007-F -8-~2~ 3 g measured as a 5 percent solution in an 80 percent toluene and 20 percent ethanol solvent at 23C.
The cellulose ethers of this invention exhibit a higher viscosity effect in organic solvents compared with ethylhydroxyethylcellulose. For example, to obtain a substantiall~ similar thickening effect, less of the cellulose ether of this invention can be employed than the amount of ethylhydroxyethylcellulose; e.g., about 0.75 to 1. The cellulose ethers of this inven-tion provide similar ~uality compared with a system employing ethylhydroxyekhylcellulose when tested in the let down, metal resinate, and gloss tests employed by the printing industry when evaluating ink compositions.
The ~ollowing examples are intended to illus-trate the invention but not to limit the scope. Allparts and percentages are by weight unless otherwise indicated.
Example 1 Sample No. l is prepared by charging a 2-liter PARR reactor with 72 grams (g) of cellulose pulp (Buckeye E-7 ground through a l-2 mm screen) and 785 g of toluene as a diluent. Using a loop ~agitator, this mixture is agitated at 1100 rpm, heated to about 90QC, and contac-ted with 109.5 g o~ a 73 percent molten sodium hydroxide solution. Contact time is five minutes. The reactor is closed, the air evacuated, and purged with nitrogen.
A 93.2 g charge of a 46.4 percent propylene oxide in toluene solution and a 252 g charge oE ethyl chloride are added to the reactor. The reaction temperature is maintained at 90C a-t a 180 rpm agitation rate for one hour. The reaction temperature is then raised to ~ ' .
~ 33,007-F -9-~2~ 5i3 130C, and proceeds for two hours. To the heated reaction mixture is added 180 g of lO0 percent bead sodium hydroxide, the reaction temperature is raised to 140C, and proceeds for seven hours. The product dump mass is granulated by contacting with boiling water to evaporate the organic solvents, and to solubilize the remaining by-product salts and caustic.
The produc-t is water washed and hot air dried. The product has a hydroxypropoxyl molar substitution of 10 0.47 and an ethoxyl degree of substitution of 2.6. A
one weight percent portion of this cellulose ether is soluble in a Lactol Spirits~ composition, and the solution has a viscosity at 23C of 21.6 cps.
A one weight percent portion of this cellulose ether forms a true solution with a 100 percent toluene solution.
A one weight percent portion of this cellulose ether forms a true solution with a 20 percent toluene and 80 percent heptane solution.
Example 2 Sample No. 2 is prepared in the same manner as Sample No. 1, except 0.6 parts based on weight of cellulose pulp of butylene oxide is used rather than propylene oxide. The cellulose ether has a hydroxybutoxyl molar substitution of 0.42 and an ethoxyl degree of substitution of 2.7. The cellulose ether is soluble in Lactol Spirits~, yielding a hazy solution. A one weight percent portion in Lactol Spirits~ has a viscosity at 23C of 16.7 cps.
33,007-F -lO-
Claims (13)
1. A C3-C4 hydroxyalkyl ethylcellulose ether which is substantially soluble at ambient temperatures in toluene.
2. The cellulose ether of Claim 1 characterized as having a C3-C4 hydroxyalkoxyl molar substitution from about 0.38 to about 0.63, and an ethoxyl degree of substitution from about 2.4 to about 2.7.
3. The cellulose ether of Claim 2, wherein the hydroxyalkoxyl group is hydroxypropoxyl.
4. The cellulose ether of Claim 3 characterized as having a hydroxypropoxyl molar substi-tution of about 0.47, and an ethoxyl substitution of about 2.6.
5. A process for preparing organo-soluble C3-C4 hydroxyalkyl ethylcellulose ethers, said process comprising contacting an amount of alkali cellulose with an effective amount of a C3-C4 alkylene oxide, and an effective amount of an ethyl halide under reaction conditions, such that a C3-C4 hydroxyalkyl ethylcellu-lose is prepared which is substantially soluble at ambient temperatures in toluene.
6. The process of Claim 5, wherein the C3-C4 alkylene oxide is propylene oxide, and the ethyl halide is ethyl chloride.
7. . The process of Claim 5 wherein said C3-C4 hydroxyalkyl ethylcellulose reaction product is characterized as having a C3-C4 hydroxyalkoxyl molar substitution of about 0.38 to about 0.63, and an ethoxyl degree of substitution of about 2.4 to about 2.7.
8. The cellulose ether of Claim 1, wherein said cellulose ether forms a solution with an organic solvent having a solubility parameter of greater than about 7.8 [cal/cm3]?.
9. The cellulose ether of Claim 8 wherein said solvent comprises about 20 percent toluene and about 80 percent heptane.
10. The process of Claim 5, wherein the C3-C4 alkylene oxide is butylene oxide, and the ethyl halide is ethyl chloride.
11. The cellulose ether of Claim 9, wherein said cellulose ether is present at about a 1 weight percent concentration.
12. The process of Claim 7 wherein the alkali cellulose is prepared by reacting cellulose .
.
pulp with a functionally effective amount of a 73 weight percent alkali metal hydroxide aqueous solu-tion.
.
pulp with a functionally effective amount of a 73 weight percent alkali metal hydroxide aqueous solu-tion.
13. The process of Claim 12, wherein the alkali metal hydroxide solution is caustic.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/719,183 US4609729A (en) | 1985-04-03 | 1985-04-03 | Organosoluble C3 -C4 hydroxyalkyl ethyl cellulose ethers |
| US719,183 | 1985-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1236453A true CA1236453A (en) | 1988-05-10 |
Family
ID=24889080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000504829A Expired CA1236453A (en) | 1985-04-03 | 1986-03-24 | Organo-soluble c.sub.3-c.sub.4 hydroxyalkyl ethyl cellulose ethers |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4609729A (en) |
| EP (1) | EP0200363B1 (en) |
| JP (1) | JPS61264002A (en) |
| CA (1) | CA1236453A (en) |
| DE (1) | DE3672668D1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077725A (en) * | 1992-09-03 | 2000-06-20 | Lucent Technologies Inc | Method for assembling multichip modules |
| US5676743A (en) * | 1995-12-20 | 1997-10-14 | Shell Oil Company | Ink formulations containing cycloparaffins |
| US7703456B2 (en) | 2003-12-18 | 2010-04-27 | Kimberly-Clark Worldwide, Inc. | Facemasks containing an anti-fog / anti-glare composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949452A (en) * | 1956-04-30 | 1960-08-16 | Dow Chemical Co | Process for preparing alkyl hydroxyalkyl cellulose ethers and the product obtained thereby |
| GB812510A (en) * | 1956-04-30 | 1959-04-29 | Dow Chemical Co | Process for preparing cellulose ethers and the product obtained thereby |
| JPS4819231B1 (en) * | 1970-03-06 | 1973-06-12 | ||
| JPS4917565B1 (en) * | 1970-12-29 | 1974-05-01 | ||
| US3870702A (en) * | 1971-03-19 | 1975-03-11 | Shinetsu Chemical Co | Cellulose ether compositions useful as enteric coatings |
| US3873518A (en) * | 1973-12-14 | 1975-03-25 | Dow Chemical Co | Water soluble ternary cellulose ethers |
| JPS5163927A (en) * | 1974-11-28 | 1976-06-02 | Shinetsu Chemical Co | Ketsugoseiryokonajozaihokaizaino seizohoho |
| FR2372177A2 (en) * | 1976-11-26 | 1978-06-23 | Hercules France Sa | Di:substd. hydroxypropyl-cellulose prepn. - contg. ionic and nonionic substits., by adding propylene oxide to alkali cellulose, homogenising and etherifying |
| JPS5949201A (en) * | 1982-09-16 | 1984-03-21 | Shin Etsu Chem Co Ltd | Preparation of hydroxyalkyl alkyl cellulose |
| US4429120A (en) * | 1982-12-29 | 1984-01-31 | The Dow Chemical Company | Ethylhydroxyalkylmethylcellulose ethers |
| US4477657A (en) * | 1983-07-08 | 1984-10-16 | The Dow Chemical Company | Process for preparing hydroxyalkylcellulose ethers |
-
1985
- 1985-04-03 US US06/719,183 patent/US4609729A/en not_active Expired - Fee Related
-
1986
- 1986-03-24 CA CA000504829A patent/CA1236453A/en not_active Expired
- 1986-03-27 DE DE8686302301T patent/DE3672668D1/en not_active Expired - Fee Related
- 1986-03-27 EP EP86302301A patent/EP0200363B1/en not_active Expired - Lifetime
- 1986-04-01 JP JP61072602A patent/JPS61264002A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0200363A1 (en) | 1986-11-05 |
| DE3672668D1 (en) | 1990-08-23 |
| EP0200363B1 (en) | 1990-07-18 |
| JPS61264002A (en) | 1986-11-21 |
| US4609729A (en) | 1986-09-02 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |