CA1140541A - Modified nonionic cellulose ethers - Google Patents
Modified nonionic cellulose ethersInfo
- Publication number
- CA1140541A CA1140541A CA000343498A CA343498A CA1140541A CA 1140541 A CA1140541 A CA 1140541A CA 000343498 A CA000343498 A CA 000343498A CA 343498 A CA343498 A CA 343498A CA 1140541 A CA1140541 A CA 1140541A
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- Canada
- Prior art keywords
- cellulose
- water
- soluble
- amount
- ether
- 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
MODIFIED NONIONIC CELLULOSE ETHERS
Abstract of the Disclosure Cellulose ethers are disclosed which have sufficient nonionic substitution to render them water soluble and which are further modified with a C10 to C24 long chain alkyl group in an amount between about 0.2% by weight and the amount which makes them less than 1% soluble in water.
hydroxyethyl cellulose is a preferred water-soluble cellu-lose ether for modification according to the invention.
These products exhibit substantially improved viscosifying effect compared to their unmodified cellulose ether counter-parts and also exhibit some surface activity.
Abstract of the Disclosure Cellulose ethers are disclosed which have sufficient nonionic substitution to render them water soluble and which are further modified with a C10 to C24 long chain alkyl group in an amount between about 0.2% by weight and the amount which makes them less than 1% soluble in water.
hydroxyethyl cellulose is a preferred water-soluble cellu-lose ether for modification according to the invention.
These products exhibit substantially improved viscosifying effect compared to their unmodified cellulose ether counter-parts and also exhibit some surface activity.
Description
This invention relates to a new class of modified water-soluble polymers. Specifically it relates to modi~ied water-soluble cellulose ethers.
Nonionic water-soluble cellulose ethers are employed in a wide variety of industrial applications, as thickeners, as watar retention aids, and as suspension aids in certain polymerization processes, among others. For some of these applications, specific cellulose ethers are required, but for many, dif~erent ethers can ~e employed, depending upon price and in many cases simply on the preference of the user. Widely used, commercially available nonionic cellu-lose ethers includ~ methyl cellulose, hydroxpropyl methyl cellulose, hydroxethyl cellulose, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose.
As is generally the case with high polymers, better thickening efficiency s realized wi~h higher molecular weight cellulose ethers. Production of very high molecular weight materials requires the use of more expensive cellu-lose furnishes such as co~ton linters in lieu of the more common wood pulp types. Moreovee, even when very high molecular weight furnishes are employed, the etherification process is extremely harsh on the furnish and causes signif-icant reductions in the molecular weight of the cellulose.
High viscosity solutions then become difficult to obtain without resorting to follow-up s~eps such as crosslinking.
This is not a practical alternative with nonionic cellu losics since good crosslinking techniques are not known and those that are known are troublesome and inefficient. T'ne only other way presently known ~or attaining high viscosity is to use high concentrations o~ the polymer. This tech-nique is frequently inefficient, impractical, and othe~wise undesirable.
t~
~ . . ' ' .
It is the object of this invention to provide nonionic cellulose ethers of relatively low molecular weight which are capable of producing highly viscous aqueous solutions in practical concentrations. It is a further object to pro-duce such cellulose ethers which addltionally exhibit arelatively high degree of surface activity compared to that of more conventional nonionic water-soluble cellulose ethers.
The cellulose ethers of this invention are nonionic cellulose ethers having a sufficient degree of nonionic sub-stitution selected from the class consisting of methyl, hydroxyethyl and hydroxypropyl to cause them to be water-soluble and which are further substituted with a hydrocarbon radical having about 10 to 24 carbon atoms in an amount be-tween about 0.2 weight percent and the amount which renderssaid cellulose ether less than 1% by weight soluble in water. The cellulose ether to be modified is pre~erably one of low to medium molecular wei~ht, i.e., less than about 800,000 and preferably between about 20,000 and 500 ,oao (about 75 to 1800 D.P.).
Cellulose ethers have hereto~ore been modified with small hydrophobic groups such as ethyl, butyl, benzyl and phenylhydroxyethyl groups. Such modifications or such modi-field products are shown in U.S. patents 3,091,542;
3,272,640; and 3,435,027 inter alia. These modifications are usually effected for the purpose of reducing the hydro-philicity and thus reducing the hydration rate o~ the cellu-lose ether. These modifiers have not been found to effect the property improvements caused by the modifications con-templated by this invention. ~his is to say, there is nosignificant alteration of the rheological properties or the surface-active properties of the ether.
Any nonionic water-soluble cellulose ether can be em-ployed as the cellulose ether substrate used to form the products of this invention. Thus, e.g.~ hydroxyethyl cellu-.lose, hydroxypropyl cellulose, methyl cellulose, hydroxy-propyl methyl cellulose~ ethyl hydroxyethyl cellulose, and methyl hydroxyethyl cellulose can all be modified. The 4~L
., amount o nonionic substituent such as methyl, hydroxyethyl or hydroxypropyl does not appear to be critical so long as there is sufficient to assure that the ether is water soluble.
S The preEerred cellulose ether substrate is hydroxy-ethyl cellulose ~HEC) of about 50,000 to 400,000 molecular weight~ Hydroxyethyl cellulose of this molecular weight level is the most hydrophilic of the materials contemplated.
It can thus be modified to a greater extent than can other water-soluble cellulose ether substrates before insolubility is achieved. Accordingly, control of the modification pro-cess and control of the properties o~ the modified product can be more precise with this substrate. Hydrophillcity of the most commonly used nonionic cellulose ethers varies in the general direction: hydroxyethyl hydroxypropyl hydroxy-propyl methyl methyl.
The long chain alkyl modifier can be attached to the cellulose ether substrate via an ether, ester or urethane linkage. Preferred is the ether linkage as the reagents most commonly used to effect etherification are readily obtained, the reaction is similar to that commonly used Eor the initial etheriication, and the reagents are usually more easily handled than the reagents employed for modifica-tion via the other linkages. The resuLting linkage is also usually more resistant to further reactions.
Methods of preparing mi~ed ethers of cellulose, i.e., products having more than one etherifying modifier attached to the same cellulose molecule are known to the art. The products of this invention can be prepared via essentiaily khe same methods. Briefly, the preferred procedure for pre-paring the mixed ethers of this invention comprises slurry-ing the nonionic cellulose ether in an inert organic diLuent such as a lower aliphatic alcohol, ketone, or hydrocarbon and adding a solution o~ alkali metal hydroxide to the resultant slurry at a low temperature. When the ether is thoroughly wetted and swollen by the alkali, a Cl~ ~o C24 epoxlde is added and the reaction is continued, with agitation, until complete. Residual alkali is then -.~
5~
neutralized and the product is recovered, washed with inert diluents, and dried. The etherification can also be effected with a ClO to C~4 halide or halohydride but these are sometimes less reactive, less efficient and more corrosive so it is preferred to use the epoxide~
Substantially the same procedure is used to attach the hydrocarbon modifier via the ester or urethane linkage.
Conventional slurry methods of reacting this type oE modi-fier with cellulose ethers, i.e., without the alkali, are ineffective. The alkali steep is required in order to assure that the cellulose ether is swollen to the point that the modifier can react substantially uniformly on all cellulose ether molecules throughout. If reactio~ is nGt substantially uniform throughout the cellulose ether mass, the improved rheological properties are not realized.
Although the products of this invention are referred to as being "long chain alkyl group modified", it will be recognized that except in the case where modiication is effected with an alkyl halide, the modifier is not a simple long chain alkyl group. The group i5 actually an alpha-hydroxyalkyl radical in the case o~ an epoxide, a urethane radical in the case of an isocyanate, or an acyl radical in the case of an acid or acyl chloride. ~onetheless, the ter-minology "long chain alkyl group" is used since the size and effect oE the hydrocarbon portion of the modifying molecule complete obscure any noticeable effect from the connecting group. Properties are not significantly dlferent from those of the product modified with the simple long chain alkyl group.
Examples 1 to 10 To a one-liter jacketed resin kettle, fitted with an air ~tirrer, argon inlet-vacuum takeoff valver equilibracing addition funnel, and Friederich condenser vented through oil filled gas bubbler, were charged 80 grams oE low moleculac weight (I.V. 1.5) hydroxyethyl cellulose (HEC) of 2.5 M.S., and 500 ml. of degassed isopropyl alcohol (IPA). After stirring to slurry the HEC, the system was evacuated and filled with argon three times, ~inally leaving the system under slight argon positive pressure~ A solution of 25.6 g.
of NaOH in 464 ml. o~ H2O, degassed and charged to the addition funnel, was added, drop~ise, at Q-5C. over 45 minutes. The slurry was stirred overnight at 0-5C~
5 (using a refrigeration unit) to allow e~uilibrium swelling.
The desired alkyl epoxide was dissolved in 30-50 cc. of de-gassed IPA, charged to the addition funnel, and added over 5 minutes. The slurry was then heated at time and tempera-ture conditions specified in Table I.
Upon completion of the reaction, the slurry was cooled with circulating tap water. The diluent was removed ~y vacuum filtration using a filter stick. When large amourlts of epoxide (>20 g.) were used, a hexane wash followed. The remaining solids were diluted with 500 ml. of 90~ a~ueous acetone, and adjusted to pH 8 with concen-trated HNO3. The final adjustment to a phenol-phthalein endpoint was made witb acetic acid. The diluent was filtered out, and the solids washed twice with 500-cc. portions o 80~ aqueous acetone, allowing 30 minutes steeping time for each wash.
Finally, the solids were washed with 100~ acetone, filtered dry, and vacuum dried. The products were usually tan powders.
Simultaneously a control speciment of HEC was subjected to the reaction conditions in the absence of modifying re-agents to monitor the degradative effect of the reaction onits viscosity.
Pertinent data are recorded in Table I.
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O~ ~ Z ~ O O æ
r~ l ~ H co 1~ H
O O
o~o o ~
U~ ~J
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a) .,~ u~
. u~ ~ 4~ tn O ~ # c~ ~ ~
Z tl~ ~ Il~r-l ~ ~1 ~ (~ t~ ~I ~ ~ ~1 ~ 1~1 .,~.,.. , . , . . . . ~ ~ O O
) ~1 1~ ~ o ~ ~ ~ ai ~ s ~-rl ~ O ~ ~ ~ ~ ~
s~ o ~ 3 a~
o\
o . o ,a s~ 11 oP-rl CO ~ U~ In ~ O
~ o .. ,, . . . . . . . . . . ~ s~
3 0 o eJ~ ~ ~ o o ~_1 ~ ~ (1) H ~ )~
~ $ ~
m ~ ~ U~
o _~ a .,~
~ U~ ~ o C)-rl 5~
-- o ~ ~
~ 5~ o O
C~
~ ~ o . Q OV
O ~ ~ ~ ~ O O. ~ ~ ~ ~ ~ ~ ~ 'i' ~ ~ ~ ~ ~ O
a~
~t h v~
~ O rl ~:
o ~ .C O
I I I I * t:
O ~ ~ ~`I ~ er O O O O #
V V
~:
a) ~
~1 O
O ~) ~ ~ O
~a ;z X O ~e P~ ~
Examples ll_to 14 Viscosity measurements were made on low molecular weight hydroxyethyl cellulose (~300 D.P.) specimens modified according to the procedure of Examples 1 through 11. To illustrate the improved viscosity concentration relationship of the materials, 2 and 3~ solutions were prepared and vis-cosities were compared with those of conventional unmodified low molecular weight HEC. Pertinent data are shown in Table II.
TABLE II
Av~. No.
of Example ~t. %Modifiers/ 2% 3~
No. Modifier Modifier Chain _ V1scosity Viscosity 15 Control ~ ~ - 10 cps. 20 cps.
11 C10 1.70 g.6 18 " 44.5 "
12 C12 1.28 6.1 17.5 " 60 "
13 C12 1.82 8.7 34 " 1~6 "
14 c2o 0.19 0.5 9 " 9~ "
Example 15 Methyl cellulose having a molecular weight of about 40,000 (D.P. about 200) and a 2% aqueous solution viscosity of about 400 cps. was modified by reacting it according to the procedure of Examples 1 through 10 above with a C12 epoxide for 3.S hours un-til the product contained abou-t 1.8%
by weight of the hydrophobic modifier (average of 4.3 modi-fier molecules per polymer chain). The viscosity of a 2%
solu~ion of the modified product was 22,500 cps.
A second specimen modified in the same manner to con-tain 2.8% modifier (average 6.7 per chain) was insoluble.
Example 16 The same methyl cellulose used in Example 15 was modi-ith a C20_24 (average C21) epoxide mixture, At 0.25~ modifie.r (0.35 modi~ier/chain), the viscosity of a ~g solution of the product was 100,000 cps. At 1.6% modifier (2,2 modi f iers/chain) the product was insoluble.
Example 17 Methyl hydroxypropyl cellulose (M.W. ~26,000, methyl 5~
D.S. 1.3, hydroxypropyl M.S. ~Ø2) was modified with 0.67 weight percent of the C20 24 modifier (0.59 modifier/-chain).
The viscosity of a 2~ solution of this product was 29,000 cps, compared to 100 cps. for the starting material.
Example 18 Forty parts hydroxypropyl cellulose (M.W. ~75,000, M.S.
~3.5) was dissolved in 395 parts isopropanol with 1.5 parts NaOH and 2 parts H2O. Twenty-five parts C20 24 epoxide was added and allowed to react for 2.5 hours at 75C.
After cooling, the reaction mass was cooled and precipitated in hexane. The product recovered contained 0.8 weight % of C20 24 modifier (2.04 modifiers/chain). Its 2% solution viscosity was 5650 cps. compared to 15 cps. ~or the unmcdi-fied starting material.
Exam~le_l9 Hydroxyethyl cellulose (MW = 80,000, M.~. = 1.8) (25 parts) was dissolved in 468 parts dry dimethylacetamide.
Oleyl chloride (0.40 part) was added and the solution stirred 24 hours at ambient conditions. The product was re-covered by precipitating in acetone. Two per~ent Brookfield viscosity o the product was 7900 cps. compared to 10 cpsO
for the starting material. The level of modification was 1.4% (~5.2 modifiers per chain).
Example 20 Example l9 was repeated using stearyl isocyanate (0.5 gram) in place of oleyl chloride. The final product contained 0.86~ of Cl8 modifier (2.6 modifiers~chain) and had a 2% Rrookfield viscosity of 200 cps.
Example l9 was repeated using hydroxypropyl cellulose (M.W. 75,000, M.S. ~4) in place of HEC, and stearyl chloride (1.0 g.) in place of oleyl chloride. The product obtained had a 2% Brookfield viscosity of 1750 cps. compared to 20 cps. for the starting material, and contained 1.5~ stearyl groups (~4.5 modifiers/chain).
Example 22 HEC was modified according to the procedure ofExample 2 using a higher l.nolecular weight starting material.
_9_ The product had an ~ = 190,000, contained 0.85% by weight C20 24~ and had a ~rookfield viscosity of 15,200 cps. An unmodified H~C, MW = 240,000, has a Brookfield viscosity of 400 cps. by comparison.
Example 23 A slurry of 34.5 parts wood pulp, 241.2 parts t-butyl alcohol and 26.1 parts acetone with a solution of 11 parts NaOH in 52 parts water was agitated for 30 minutes at room temperature. Ethylene oxide (38.9 parts) was added and the slurry was heated with agitation to 75C. or one hour, following which 25 parts of C14 epoxide was added. This slurry was heated at 50 for 3 hours. After cooling, the product was neutralized, washed with hexane and aqueous ace-tone, then dried. The product contained 0.55% Cl~l had an intrinsic viscosity of 3.45, and ~ solution viscosity of 70,000 cps. ~ydroxyethyl cellulose o~ comparable intrinsic viscosity has 2~ solution viscosity of approximately 500 cps .
Example 24 The modified hydroxyethyl cellulose identified above as Example 14 was dissolved in water to form a 2~ by weight solu-tion. Sixty parts of this solution was used to prepare a 40/60 mineral oil/water emulsion by passing it through a laboratory size hand homogenizer. This emulsion was stable for more than 48 hours. A similar emulsion prepared in the same way with an unmodified hydroxyethyl cellulose emulsion broke in less than 15 minutes.
Example 25 A low p~ hair shampoo was prepared using the following recipe which, except for the thickener, represents a commer-cially available shampoo which is dificult to thicken and with which conventional HEC is incompatible:
, ~ d~
N-carboxymethyl, N-ethoxyacetic aceticll) acid substituted 2-dodecyl imidazoline (40~ solution) 30 parts Lauryl sulfate triethanolamine (40% solution) 8 parts Lauric diethanolamine 5 parts o CH3 R C NH(CH2)3 1 2 5 C2~5S 4 12 parts R = lanolin radical(2) Propylene glycol 6.5 parts Thickener solution (2~) 38.5 parts . 10 (1) Miranol H2MSF (M1rand Chemical CQ. )
Nonionic water-soluble cellulose ethers are employed in a wide variety of industrial applications, as thickeners, as watar retention aids, and as suspension aids in certain polymerization processes, among others. For some of these applications, specific cellulose ethers are required, but for many, dif~erent ethers can ~e employed, depending upon price and in many cases simply on the preference of the user. Widely used, commercially available nonionic cellu-lose ethers includ~ methyl cellulose, hydroxpropyl methyl cellulose, hydroxethyl cellulose, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose.
As is generally the case with high polymers, better thickening efficiency s realized wi~h higher molecular weight cellulose ethers. Production of very high molecular weight materials requires the use of more expensive cellu-lose furnishes such as co~ton linters in lieu of the more common wood pulp types. Moreovee, even when very high molecular weight furnishes are employed, the etherification process is extremely harsh on the furnish and causes signif-icant reductions in the molecular weight of the cellulose.
High viscosity solutions then become difficult to obtain without resorting to follow-up s~eps such as crosslinking.
This is not a practical alternative with nonionic cellu losics since good crosslinking techniques are not known and those that are known are troublesome and inefficient. T'ne only other way presently known ~or attaining high viscosity is to use high concentrations o~ the polymer. This tech-nique is frequently inefficient, impractical, and othe~wise undesirable.
t~
~ . . ' ' .
It is the object of this invention to provide nonionic cellulose ethers of relatively low molecular weight which are capable of producing highly viscous aqueous solutions in practical concentrations. It is a further object to pro-duce such cellulose ethers which addltionally exhibit arelatively high degree of surface activity compared to that of more conventional nonionic water-soluble cellulose ethers.
The cellulose ethers of this invention are nonionic cellulose ethers having a sufficient degree of nonionic sub-stitution selected from the class consisting of methyl, hydroxyethyl and hydroxypropyl to cause them to be water-soluble and which are further substituted with a hydrocarbon radical having about 10 to 24 carbon atoms in an amount be-tween about 0.2 weight percent and the amount which renderssaid cellulose ether less than 1% by weight soluble in water. The cellulose ether to be modified is pre~erably one of low to medium molecular wei~ht, i.e., less than about 800,000 and preferably between about 20,000 and 500 ,oao (about 75 to 1800 D.P.).
Cellulose ethers have hereto~ore been modified with small hydrophobic groups such as ethyl, butyl, benzyl and phenylhydroxyethyl groups. Such modifications or such modi-field products are shown in U.S. patents 3,091,542;
3,272,640; and 3,435,027 inter alia. These modifications are usually effected for the purpose of reducing the hydro-philicity and thus reducing the hydration rate o~ the cellu-lose ether. These modifiers have not been found to effect the property improvements caused by the modifications con-templated by this invention. ~his is to say, there is nosignificant alteration of the rheological properties or the surface-active properties of the ether.
Any nonionic water-soluble cellulose ether can be em-ployed as the cellulose ether substrate used to form the products of this invention. Thus, e.g.~ hydroxyethyl cellu-.lose, hydroxypropyl cellulose, methyl cellulose, hydroxy-propyl methyl cellulose~ ethyl hydroxyethyl cellulose, and methyl hydroxyethyl cellulose can all be modified. The 4~L
., amount o nonionic substituent such as methyl, hydroxyethyl or hydroxypropyl does not appear to be critical so long as there is sufficient to assure that the ether is water soluble.
S The preEerred cellulose ether substrate is hydroxy-ethyl cellulose ~HEC) of about 50,000 to 400,000 molecular weight~ Hydroxyethyl cellulose of this molecular weight level is the most hydrophilic of the materials contemplated.
It can thus be modified to a greater extent than can other water-soluble cellulose ether substrates before insolubility is achieved. Accordingly, control of the modification pro-cess and control of the properties o~ the modified product can be more precise with this substrate. Hydrophillcity of the most commonly used nonionic cellulose ethers varies in the general direction: hydroxyethyl hydroxypropyl hydroxy-propyl methyl methyl.
The long chain alkyl modifier can be attached to the cellulose ether substrate via an ether, ester or urethane linkage. Preferred is the ether linkage as the reagents most commonly used to effect etherification are readily obtained, the reaction is similar to that commonly used Eor the initial etheriication, and the reagents are usually more easily handled than the reagents employed for modifica-tion via the other linkages. The resuLting linkage is also usually more resistant to further reactions.
Methods of preparing mi~ed ethers of cellulose, i.e., products having more than one etherifying modifier attached to the same cellulose molecule are known to the art. The products of this invention can be prepared via essentiaily khe same methods. Briefly, the preferred procedure for pre-paring the mixed ethers of this invention comprises slurry-ing the nonionic cellulose ether in an inert organic diLuent such as a lower aliphatic alcohol, ketone, or hydrocarbon and adding a solution o~ alkali metal hydroxide to the resultant slurry at a low temperature. When the ether is thoroughly wetted and swollen by the alkali, a Cl~ ~o C24 epoxlde is added and the reaction is continued, with agitation, until complete. Residual alkali is then -.~
5~
neutralized and the product is recovered, washed with inert diluents, and dried. The etherification can also be effected with a ClO to C~4 halide or halohydride but these are sometimes less reactive, less efficient and more corrosive so it is preferred to use the epoxide~
Substantially the same procedure is used to attach the hydrocarbon modifier via the ester or urethane linkage.
Conventional slurry methods of reacting this type oE modi-fier with cellulose ethers, i.e., without the alkali, are ineffective. The alkali steep is required in order to assure that the cellulose ether is swollen to the point that the modifier can react substantially uniformly on all cellulose ether molecules throughout. If reactio~ is nGt substantially uniform throughout the cellulose ether mass, the improved rheological properties are not realized.
Although the products of this invention are referred to as being "long chain alkyl group modified", it will be recognized that except in the case where modiication is effected with an alkyl halide, the modifier is not a simple long chain alkyl group. The group i5 actually an alpha-hydroxyalkyl radical in the case o~ an epoxide, a urethane radical in the case of an isocyanate, or an acyl radical in the case of an acid or acyl chloride. ~onetheless, the ter-minology "long chain alkyl group" is used since the size and effect oE the hydrocarbon portion of the modifying molecule complete obscure any noticeable effect from the connecting group. Properties are not significantly dlferent from those of the product modified with the simple long chain alkyl group.
Examples 1 to 10 To a one-liter jacketed resin kettle, fitted with an air ~tirrer, argon inlet-vacuum takeoff valver equilibracing addition funnel, and Friederich condenser vented through oil filled gas bubbler, were charged 80 grams oE low moleculac weight (I.V. 1.5) hydroxyethyl cellulose (HEC) of 2.5 M.S., and 500 ml. of degassed isopropyl alcohol (IPA). After stirring to slurry the HEC, the system was evacuated and filled with argon three times, ~inally leaving the system under slight argon positive pressure~ A solution of 25.6 g.
of NaOH in 464 ml. o~ H2O, degassed and charged to the addition funnel, was added, drop~ise, at Q-5C. over 45 minutes. The slurry was stirred overnight at 0-5C~
5 (using a refrigeration unit) to allow e~uilibrium swelling.
The desired alkyl epoxide was dissolved in 30-50 cc. of de-gassed IPA, charged to the addition funnel, and added over 5 minutes. The slurry was then heated at time and tempera-ture conditions specified in Table I.
Upon completion of the reaction, the slurry was cooled with circulating tap water. The diluent was removed ~y vacuum filtration using a filter stick. When large amourlts of epoxide (>20 g.) were used, a hexane wash followed. The remaining solids were diluted with 500 ml. of 90~ a~ueous acetone, and adjusted to pH 8 with concen-trated HNO3. The final adjustment to a phenol-phthalein endpoint was made witb acetic acid. The diluent was filtered out, and the solids washed twice with 500-cc. portions o 80~ aqueous acetone, allowing 30 minutes steeping time for each wash.
Finally, the solids were washed with 100~ acetone, filtered dry, and vacuum dried. The products were usually tan powders.
Simultaneously a control speciment of HEC was subjected to the reaction conditions in the absence of modifying re-agents to monitor the degradative effect of the reaction onits viscosity.
Pertinent data are recorded in Table I.
,_ U~
o ~
n . , o o U~ o o U~
O~ ~ Z ~ O O æ
r~ l ~ H co 1~ H
O O
o~o o ~
U~ ~J
.,1 -,~
4~ ~ a O
a) .,~ u~
. u~ ~ 4~ tn O ~ # c~ ~ ~
Z tl~ ~ Il~r-l ~ ~1 ~ (~ t~ ~I ~ ~ ~1 ~ 1~1 .,~.,.. , . , . . . . ~ ~ O O
) ~1 1~ ~ o ~ ~ ~ ai ~ s ~-rl ~ O ~ ~ ~ ~ ~
s~ o ~ 3 a~
o\
o . o ,a s~ 11 oP-rl CO ~ U~ In ~ O
~ o .. ,, . . . . . . . . . . ~ s~
3 0 o eJ~ ~ ~ o o ~_1 ~ ~ (1) H ~ )~
~ $ ~
m ~ ~ U~
o _~ a .,~
~ U~ ~ o C)-rl 5~
-- o ~ ~
~ 5~ o O
C~
~ ~ o . Q OV
O ~ ~ ~ ~ O O. ~ ~ ~ ~ ~ ~ ~ 'i' ~ ~ ~ ~ ~ O
a~
~t h v~
~ O rl ~:
o ~ .C O
I I I I * t:
O ~ ~ ~`I ~ er O O O O #
V V
~:
a) ~
~1 O
O ~) ~ ~ O
~a ;z X O ~e P~ ~
Examples ll_to 14 Viscosity measurements were made on low molecular weight hydroxyethyl cellulose (~300 D.P.) specimens modified according to the procedure of Examples 1 through 11. To illustrate the improved viscosity concentration relationship of the materials, 2 and 3~ solutions were prepared and vis-cosities were compared with those of conventional unmodified low molecular weight HEC. Pertinent data are shown in Table II.
TABLE II
Av~. No.
of Example ~t. %Modifiers/ 2% 3~
No. Modifier Modifier Chain _ V1scosity Viscosity 15 Control ~ ~ - 10 cps. 20 cps.
11 C10 1.70 g.6 18 " 44.5 "
12 C12 1.28 6.1 17.5 " 60 "
13 C12 1.82 8.7 34 " 1~6 "
14 c2o 0.19 0.5 9 " 9~ "
Example 15 Methyl cellulose having a molecular weight of about 40,000 (D.P. about 200) and a 2% aqueous solution viscosity of about 400 cps. was modified by reacting it according to the procedure of Examples 1 through 10 above with a C12 epoxide for 3.S hours un-til the product contained abou-t 1.8%
by weight of the hydrophobic modifier (average of 4.3 modi-fier molecules per polymer chain). The viscosity of a 2%
solu~ion of the modified product was 22,500 cps.
A second specimen modified in the same manner to con-tain 2.8% modifier (average 6.7 per chain) was insoluble.
Example 16 The same methyl cellulose used in Example 15 was modi-ith a C20_24 (average C21) epoxide mixture, At 0.25~ modifie.r (0.35 modi~ier/chain), the viscosity of a ~g solution of the product was 100,000 cps. At 1.6% modifier (2,2 modi f iers/chain) the product was insoluble.
Example 17 Methyl hydroxypropyl cellulose (M.W. ~26,000, methyl 5~
D.S. 1.3, hydroxypropyl M.S. ~Ø2) was modified with 0.67 weight percent of the C20 24 modifier (0.59 modifier/-chain).
The viscosity of a 2~ solution of this product was 29,000 cps, compared to 100 cps. for the starting material.
Example 18 Forty parts hydroxypropyl cellulose (M.W. ~75,000, M.S.
~3.5) was dissolved in 395 parts isopropanol with 1.5 parts NaOH and 2 parts H2O. Twenty-five parts C20 24 epoxide was added and allowed to react for 2.5 hours at 75C.
After cooling, the reaction mass was cooled and precipitated in hexane. The product recovered contained 0.8 weight % of C20 24 modifier (2.04 modifiers/chain). Its 2% solution viscosity was 5650 cps. compared to 15 cps. ~or the unmcdi-fied starting material.
Exam~le_l9 Hydroxyethyl cellulose (MW = 80,000, M.~. = 1.8) (25 parts) was dissolved in 468 parts dry dimethylacetamide.
Oleyl chloride (0.40 part) was added and the solution stirred 24 hours at ambient conditions. The product was re-covered by precipitating in acetone. Two per~ent Brookfield viscosity o the product was 7900 cps. compared to 10 cpsO
for the starting material. The level of modification was 1.4% (~5.2 modifiers per chain).
Example 20 Example l9 was repeated using stearyl isocyanate (0.5 gram) in place of oleyl chloride. The final product contained 0.86~ of Cl8 modifier (2.6 modifiers~chain) and had a 2% Rrookfield viscosity of 200 cps.
Example l9 was repeated using hydroxypropyl cellulose (M.W. 75,000, M.S. ~4) in place of HEC, and stearyl chloride (1.0 g.) in place of oleyl chloride. The product obtained had a 2% Brookfield viscosity of 1750 cps. compared to 20 cps. for the starting material, and contained 1.5~ stearyl groups (~4.5 modifiers/chain).
Example 22 HEC was modified according to the procedure ofExample 2 using a higher l.nolecular weight starting material.
_9_ The product had an ~ = 190,000, contained 0.85% by weight C20 24~ and had a ~rookfield viscosity of 15,200 cps. An unmodified H~C, MW = 240,000, has a Brookfield viscosity of 400 cps. by comparison.
Example 23 A slurry of 34.5 parts wood pulp, 241.2 parts t-butyl alcohol and 26.1 parts acetone with a solution of 11 parts NaOH in 52 parts water was agitated for 30 minutes at room temperature. Ethylene oxide (38.9 parts) was added and the slurry was heated with agitation to 75C. or one hour, following which 25 parts of C14 epoxide was added. This slurry was heated at 50 for 3 hours. After cooling, the product was neutralized, washed with hexane and aqueous ace-tone, then dried. The product contained 0.55% Cl~l had an intrinsic viscosity of 3.45, and ~ solution viscosity of 70,000 cps. ~ydroxyethyl cellulose o~ comparable intrinsic viscosity has 2~ solution viscosity of approximately 500 cps .
Example 24 The modified hydroxyethyl cellulose identified above as Example 14 was dissolved in water to form a 2~ by weight solu-tion. Sixty parts of this solution was used to prepare a 40/60 mineral oil/water emulsion by passing it through a laboratory size hand homogenizer. This emulsion was stable for more than 48 hours. A similar emulsion prepared in the same way with an unmodified hydroxyethyl cellulose emulsion broke in less than 15 minutes.
Example 25 A low p~ hair shampoo was prepared using the following recipe which, except for the thickener, represents a commer-cially available shampoo which is dificult to thicken and with which conventional HEC is incompatible:
, ~ d~
N-carboxymethyl, N-ethoxyacetic aceticll) acid substituted 2-dodecyl imidazoline (40~ solution) 30 parts Lauryl sulfate triethanolamine (40% solution) 8 parts Lauric diethanolamine 5 parts o CH3 R C NH(CH2)3 1 2 5 C2~5S 4 12 parts R = lanolin radical(2) Propylene glycol 6.5 parts Thickener solution (2~) 38.5 parts . 10 (1) Miranol H2MSF (M1rand Chemical CQ. )
(2) Lanoquat DES25 (Malstrom Chemicals) The first four ingredients were combined and heated to 70C. with agitation for four minutes. The warm blend was then stirred into the thickener solution at room temperature followed by additlon of the propylene glycol. Stirring was continued for about ten minutes at which time the viscosity was checked with a Brookfield viscometerO Viscosity was rechecked after five weeks room tempera~ure storage. A con-trol containing no thickener and several shampoos thickenedwith HEC modified according to the invention were prepared.
Viscosities and other pertinent data are recorded in the following table.
Example Wt. % Shampoo Appear-~o. odifier on HEC I.V. Viscosi-ty ance Control - - - 56 cps. Clear 24-a Cl~ 2.42 1.3 330 cps. Clear 24-b C16 1.35 1.4 700 cps. Clear 24-c C14 2.91 1.4 9S0 cps. Clear ~
A number of flat white interior acrylic latex paint formulations were prepared as follows: A premix recipe con-sisting of the following lngredients c~ r l Water 3.~3 parts Potassium tripolyphosphate~12 part Dispersing aid (30~ solids)* .55 part Eth~lene glycol 1.20 parts ~examethylene glycol 2.85 parts Defoamer .16 part Cellulose ether thickener solution 10.61 parts 7''-~'?~ *Sodium~salt o~ polyacrylic acid (TAMOL~850 - ~ohm & Haas) was prepared by mixing thoroughly at 1800 r.p.m. on a Cowles Mixer. To this was added, still at 1800 r.p.m., TiO2 24.43 parts Anhydrous aluminum silicate 6.12 parts Silica 5.71 parts When the pigments were mixed thoroughly, the agitator speed was increased to 3500 r.p.m. for 20 minutes to homogenize the mixture. After 20 minutes' mixing, the~e was added with low speed stirring until completely incorporated:
Acrylic latex 38.35 parts Water 1.20 parts Stabilizer .06 part DefoameL .08 part Cellulose ether thickener solution 4.65 parts 2S The cellulose ether solution concentration was varied as required to vary the concentration of cellulose ether in the formulation.
Details as to thickener added and the properties re-sulting are tabulated in the following table:
aJ~ Ma~k Paint Properties Example Thic~ener Description Stormer No. Conc. Modifier Amount Viscosity* S~atter**
Control L 1.2~ None - 100 K.~. -25a .23% C20 1.1~ 88 K.U. iO
25b .2% c2o 1.16~111 K.U. 9 Control 2 .22'~ None - 94 K.U. 3 *ASTMD-562-55 **ASTME-2486-74-A
lHydroxyethyl cellulose - medium viscosity type 2Hydroxyethyl cellulose - low viscosity type 3Subs~rate for thickener was low viscosity type ~EC, 2.5 M.S.
4Substrate for thickener was medium viscosity type HEC, 2.5 M.S.
Several notable and unusual effects have been observed to be caused by the products of this invention in aqueous media. The increased viscosity of the products compared to their unmodified counterparts has already been mentioned.
Beyond the optimum modification for maximum viscosity, further modification leads to lo~s of viscosity and insolu-bility.
For a given modification level, there is a greater vis-cosity increase relative to the unmodified polymer as the polymer concentration increases. That is to say, as the solution concentr~tion is increased from 1 to 3%, or higher, a greater viscosity increase is noted with the products of the invention than with their unmodified counterparts. This behavior is shown in Examples 11 to 14. Thus, a lightly modifiad polymer, whose viscosifying power at 1~ is insig-nificant, can eect useful viscosity increases at higher concentrations even though the same polymer, unmodified, mi~ht still not be useful at the higher concentration.
The modified products of the invention also display a degree of surface activity not exhibited by unmodified non-ionic cellulose ethers. This is believed to be due to the relatively long unsubstituted and uninterrupted carbon chain attached thereto which is not prssent in the unmodified ~ ~ .
, .
substrate. The products appear to be analogous to known surfactants having hydrophilic moieties combined with ex-tended hydrophobic carbon chains. In fact, the behavior of the modified polymers in exhibiting surface activity, as well as their rheological character, suggest that the long chain modified molecules are aggregated into micelle-like clusters in aqueous solution much as is known to happen in the case of more conventional surfactants.
The surface activity of the modified cellulose ethers of the invention is observed particularly with non-polar suspended matter. For example, emulsions of mineral oils in water prepared with the products of the invention are stable for extended periods as sho-~n in Example 24 above. Enzy-matic degradation of the cellulose substrate is observed in some instances before such emulsion~ break. Surface activ-ity is also noticeable to a significant degree with latex paints where the long-chain alkyl substituted products show a tendency to adsorb on non-polar latex particles.
Another interesting characteristic o the modified callulose ethers of this invention is their ability to interact with nonionic surfactants so that their viscosify-ing power is further and very dramatically increased. Thus, materials of very low degree of long chain alkyl modifica tion can cause viscosity increases of 1000-fold and more in the presence of such surfactants. This behavior, which is rarely exhibited by unmodified nonionic cellulose ethers, can be of significant commercial value in many applications, for example, detergent systems and shampoos.
The minimum amount of modification which has been found to be useful for effecting viscosity changes is about Q.2~
by weight. Below this level increases in viscosifying power appear to be limited to instances where the polymer is used at impractically high concentrations. Moreover, this is a practical limit based on the cost of effecting the modi~ica-tion compared to the improvement realized~ It will also berecognize~ that this minimum level of modification will apply only in the case where the carbon number of hydro-phobic modifier is on the higher end of the permissible .
~a~
range, i.e., about 20 to 24. In the case of these higher hydrophobes, 0.2% modiEier is the lower practical limit to provide useful property changes. It is theorized that so little modifier is present in this case that polymer chains do not aggregate. For whatever reason, little rheological effect is noted. A preferred lower lirnit o~ modification is about 0.4% for the smaller hydrophobes as these are gener-ally less e~fec~ive in obtaining u~eful property ch~nges than the larger hydrophobes.
Modifier content (wt. ~) is determined using a modified Zeisel method. Ether-bound hydrophobe is cleaved by use of 35% HBr in acetic acid. Brominated hydrocarbon reaction product is extracted with hexane an~ analy~ed via a temper-ature programmed 1ame ionization instrument.
The maximum weight percent o~ modifier which can be added to the cellulose ether is determined principally by the size of the long chain alkyl modifier and to a lesser e~tent by the molecular weight and the hydrophilicity of the cellulose ether substrate. The amoun~ of modifier is best 2~ expressed in terms of the average number of modifiers per polymer chain. It has been experimentally determined that for a'L nonionic water-soluble cellulose ethers, the rela-tionship between the amount which results in insolubility (NINS) and modi~ier carbon number Cn is defined by the formula:
log NINS = K - 0.07 + .005 CN
The constant K varies from about 1.3 to 2.3 preferably about 1.4 to 2.1 and i5 a function of the hydrophilicity of the cellulose ether substrate. K is about 1.5 to 1.3 Eor methyl cellulose, about l.9 to 2.2 for hydroxyethyl cellulose of low to medium D.P. and about 1.4 for hydroxypropyl cellu-lose and hydroxypropyl methyl cellulose.
Overall, NINS varies from about 1 to 25. A ranye can be calcula~ed within this overall range for each water-soluble cellulose ether which is usable in the invention.Thus, ~or methyl cellulose (K = 1.3) NINS is about 13 whe~
a Cl0 hydrocarbon modifler is employed and about 3 when the modifier has ~0 carbon atoms. NI~S for medium D.P.
35~
hydroxyethyl cellulose is about 25 with a C10 hydrocarbon ~odifier and about 5 with a C2~ modifier.
Modified cellulose ethers of this invention are useful as stabiliz~rs in emulsion polymerizations, as thickeners in cosmetics, and as flocculants in mineral processing. One particularly good utility is as a thickener in latex paint.
Very small amounts of low molecular weight modified nonionic cellulose ethers of this invention can outperform larger quantities of higher molecular weight conventional nonionic cellulose ethers.
Viscosities and other pertinent data are recorded in the following table.
Example Wt. % Shampoo Appear-~o. odifier on HEC I.V. Viscosi-ty ance Control - - - 56 cps. Clear 24-a Cl~ 2.42 1.3 330 cps. Clear 24-b C16 1.35 1.4 700 cps. Clear 24-c C14 2.91 1.4 9S0 cps. Clear ~
A number of flat white interior acrylic latex paint formulations were prepared as follows: A premix recipe con-sisting of the following lngredients c~ r l Water 3.~3 parts Potassium tripolyphosphate~12 part Dispersing aid (30~ solids)* .55 part Eth~lene glycol 1.20 parts ~examethylene glycol 2.85 parts Defoamer .16 part Cellulose ether thickener solution 10.61 parts 7''-~'?~ *Sodium~salt o~ polyacrylic acid (TAMOL~850 - ~ohm & Haas) was prepared by mixing thoroughly at 1800 r.p.m. on a Cowles Mixer. To this was added, still at 1800 r.p.m., TiO2 24.43 parts Anhydrous aluminum silicate 6.12 parts Silica 5.71 parts When the pigments were mixed thoroughly, the agitator speed was increased to 3500 r.p.m. for 20 minutes to homogenize the mixture. After 20 minutes' mixing, the~e was added with low speed stirring until completely incorporated:
Acrylic latex 38.35 parts Water 1.20 parts Stabilizer .06 part DefoameL .08 part Cellulose ether thickener solution 4.65 parts 2S The cellulose ether solution concentration was varied as required to vary the concentration of cellulose ether in the formulation.
Details as to thickener added and the properties re-sulting are tabulated in the following table:
aJ~ Ma~k Paint Properties Example Thic~ener Description Stormer No. Conc. Modifier Amount Viscosity* S~atter**
Control L 1.2~ None - 100 K.~. -25a .23% C20 1.1~ 88 K.U. iO
25b .2% c2o 1.16~111 K.U. 9 Control 2 .22'~ None - 94 K.U. 3 *ASTMD-562-55 **ASTME-2486-74-A
lHydroxyethyl cellulose - medium viscosity type 2Hydroxyethyl cellulose - low viscosity type 3Subs~rate for thickener was low viscosity type ~EC, 2.5 M.S.
4Substrate for thickener was medium viscosity type HEC, 2.5 M.S.
Several notable and unusual effects have been observed to be caused by the products of this invention in aqueous media. The increased viscosity of the products compared to their unmodified counterparts has already been mentioned.
Beyond the optimum modification for maximum viscosity, further modification leads to lo~s of viscosity and insolu-bility.
For a given modification level, there is a greater vis-cosity increase relative to the unmodified polymer as the polymer concentration increases. That is to say, as the solution concentr~tion is increased from 1 to 3%, or higher, a greater viscosity increase is noted with the products of the invention than with their unmodified counterparts. This behavior is shown in Examples 11 to 14. Thus, a lightly modifiad polymer, whose viscosifying power at 1~ is insig-nificant, can eect useful viscosity increases at higher concentrations even though the same polymer, unmodified, mi~ht still not be useful at the higher concentration.
The modified products of the invention also display a degree of surface activity not exhibited by unmodified non-ionic cellulose ethers. This is believed to be due to the relatively long unsubstituted and uninterrupted carbon chain attached thereto which is not prssent in the unmodified ~ ~ .
, .
substrate. The products appear to be analogous to known surfactants having hydrophilic moieties combined with ex-tended hydrophobic carbon chains. In fact, the behavior of the modified polymers in exhibiting surface activity, as well as their rheological character, suggest that the long chain modified molecules are aggregated into micelle-like clusters in aqueous solution much as is known to happen in the case of more conventional surfactants.
The surface activity of the modified cellulose ethers of the invention is observed particularly with non-polar suspended matter. For example, emulsions of mineral oils in water prepared with the products of the invention are stable for extended periods as sho-~n in Example 24 above. Enzy-matic degradation of the cellulose substrate is observed in some instances before such emulsion~ break. Surface activ-ity is also noticeable to a significant degree with latex paints where the long-chain alkyl substituted products show a tendency to adsorb on non-polar latex particles.
Another interesting characteristic o the modified callulose ethers of this invention is their ability to interact with nonionic surfactants so that their viscosify-ing power is further and very dramatically increased. Thus, materials of very low degree of long chain alkyl modifica tion can cause viscosity increases of 1000-fold and more in the presence of such surfactants. This behavior, which is rarely exhibited by unmodified nonionic cellulose ethers, can be of significant commercial value in many applications, for example, detergent systems and shampoos.
The minimum amount of modification which has been found to be useful for effecting viscosity changes is about Q.2~
by weight. Below this level increases in viscosifying power appear to be limited to instances where the polymer is used at impractically high concentrations. Moreover, this is a practical limit based on the cost of effecting the modi~ica-tion compared to the improvement realized~ It will also berecognize~ that this minimum level of modification will apply only in the case where the carbon number of hydro-phobic modifier is on the higher end of the permissible .
~a~
range, i.e., about 20 to 24. In the case of these higher hydrophobes, 0.2% modiEier is the lower practical limit to provide useful property changes. It is theorized that so little modifier is present in this case that polymer chains do not aggregate. For whatever reason, little rheological effect is noted. A preferred lower lirnit o~ modification is about 0.4% for the smaller hydrophobes as these are gener-ally less e~fec~ive in obtaining u~eful property ch~nges than the larger hydrophobes.
Modifier content (wt. ~) is determined using a modified Zeisel method. Ether-bound hydrophobe is cleaved by use of 35% HBr in acetic acid. Brominated hydrocarbon reaction product is extracted with hexane an~ analy~ed via a temper-ature programmed 1ame ionization instrument.
The maximum weight percent o~ modifier which can be added to the cellulose ether is determined principally by the size of the long chain alkyl modifier and to a lesser e~tent by the molecular weight and the hydrophilicity of the cellulose ether substrate. The amoun~ of modifier is best 2~ expressed in terms of the average number of modifiers per polymer chain. It has been experimentally determined that for a'L nonionic water-soluble cellulose ethers, the rela-tionship between the amount which results in insolubility (NINS) and modi~ier carbon number Cn is defined by the formula:
log NINS = K - 0.07 + .005 CN
The constant K varies from about 1.3 to 2.3 preferably about 1.4 to 2.1 and i5 a function of the hydrophilicity of the cellulose ether substrate. K is about 1.5 to 1.3 Eor methyl cellulose, about l.9 to 2.2 for hydroxyethyl cellulose of low to medium D.P. and about 1.4 for hydroxypropyl cellu-lose and hydroxypropyl methyl cellulose.
Overall, NINS varies from about 1 to 25. A ranye can be calcula~ed within this overall range for each water-soluble cellulose ether which is usable in the invention.Thus, ~or methyl cellulose (K = 1.3) NINS is about 13 whe~
a Cl0 hydrocarbon modifler is employed and about 3 when the modifier has ~0 carbon atoms. NI~S for medium D.P.
35~
hydroxyethyl cellulose is about 25 with a C10 hydrocarbon ~odifier and about 5 with a C2~ modifier.
Modified cellulose ethers of this invention are useful as stabiliz~rs in emulsion polymerizations, as thickeners in cosmetics, and as flocculants in mineral processing. One particularly good utility is as a thickener in latex paint.
Very small amounts of low molecular weight modified nonionic cellulose ethers of this invention can outperform larger quantities of higher molecular weight conventional nonionic cellulose ethers.
Claims (6)
1. A nonionic cellulose ether having a sufficient degree of nonionic substitution selected from the class con-sisting of methyl, hydroxyethyl and hydroxypropyl to cause it to be water-soluble and being further substituted with a long chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders said cellulose ether less than 1% by weight soluble in water.
2. The nonionic cellulose ether of claim 1 wherein the long chain alkyl radical is attached via an ether linkage.
3. Water-soluble hydroxypropyl cellulose substituted with a long chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders the hydroxypropyl cellulose less than 1% by weight soluble in water.
4. Water-soluble hydroxyethyl cellulose substituted with a long chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders the hydroxyethyl cellulose less than 1% by weight soluble in water.
5. The product of claim 4 wherein the hydroxyethyl cellulose prior to substitution with the long chain alkyl group has a molecular weight of about 50,000 to 400,000.
6. The product of claim 5 wherein the long chain alkyl group is attached via an ether linkage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11,613 | 1979-02-12 | ||
| US06/011,613 US4228277A (en) | 1979-02-12 | 1979-02-12 | Modified nonionic cellulose ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1140541A true CA1140541A (en) | 1983-02-01 |
Family
ID=21751208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000343498A Expired CA1140541A (en) | 1979-02-12 | 1980-01-11 | Modified nonionic cellulose ethers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4228277A (en) |
| JP (1) | JPS55110103A (en) |
| CA (1) | CA1140541A (en) |
| DE (1) | DE3004161A1 (en) |
| GB (1) | GB2043646B (en) |
| NL (1) | NL188649C (en) |
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| US3894839A (en) * | 1972-09-21 | 1975-07-15 | Us Of Amercia As Represented B | Process for acylating functional groups bearing active hydrogen with isopropenyl esters of long chain fatty acids |
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| US4107426A (en) * | 1976-07-06 | 1978-08-15 | Roy Gerald Gordon | Process for treating cellulose |
-
1979
- 1979-02-12 US US06/011,613 patent/US4228277A/en not_active Expired - Lifetime
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1980
- 1980-01-11 CA CA000343498A patent/CA1140541A/en not_active Expired
- 1980-02-05 DE DE19803004161 patent/DE3004161A1/en active Granted
- 1980-02-08 NL NLAANVRAGE8000786,A patent/NL188649C/en not_active IP Right Cessation
- 1980-02-12 GB GB8004709A patent/GB2043646B/en not_active Expired
- 1980-02-12 JP JP1590680A patent/JPS55110103A/en active Granted
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|---|---|
| NL188649C (en) | 1992-08-17 |
| NL8000786A (en) | 1980-08-14 |
| US4228277B1 (en) | 1992-10-20 |
| DE3004161A1 (en) | 1980-08-21 |
| JPH0128041B2 (en) | 1989-05-31 |
| GB2043646A (en) | 1980-10-08 |
| US4228277A (en) | 1980-10-14 |
| DE3004161C2 (en) | 1990-06-28 |
| NL188649B (en) | 1992-03-16 |
| JPS55110103A (en) | 1980-08-25 |
| GB2043646B (en) | 1982-12-08 |
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