US2019920A - Process for the fibrous esterification of cellulose - Google Patents
Process for the fibrous esterification of cellulose Download PDFInfo
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- US2019920A US2019920A US635856A US63585632A US2019920A US 2019920 A US2019920 A US 2019920A US 635856 A US635856 A US 635856A US 63585632 A US63585632 A US 63585632A US 2019920 A US2019920 A US 2019920A
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- Prior art keywords
- cellulose
- esterification
- ether
- fibrous
- pretreated
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- 229920002678 cellulose Polymers 0.000 title description 71
- 239000001913 cellulose Substances 0.000 title description 68
- 230000032050 esterification Effects 0.000 title description 53
- 238000005886 esterification reaction Methods 0.000 title description 53
- 238000000034 method Methods 0.000 title description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- 235000014113 dietary fatty acids Nutrition 0.000 description 21
- 229930195729 fatty acid Natural products 0.000 description 21
- 239000000194 fatty acid Substances 0.000 description 21
- 150000004665 fatty acids Chemical class 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HKQOBOMRSSHSTC-UHFFFAOYSA-N cellulose acetate Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(O)C(O)C1O.CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(COC(C)=O)O1.CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 HKQOBOMRSSHSTC-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- PNVPNXKRAUBJGW-UHFFFAOYSA-N (2-chloroacetyl) 2-chloroacetate Chemical compound ClCC(=O)OC(=O)CCl PNVPNXKRAUBJGW-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- -1 aliphatic ethers Chemical class 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/20—Esterification with maintenance of the fibrous structure of the cellulose
Definitions
- the present invention relates to the fibrous esterification of cellulose in Which an ether having a boiling point higher than C. is employed as the non-solvent or diluent in the esterification bath proper.
- the processes for the esterification of cellulose at the present time may be broadly divided into the two classes of (1) the dope-forming and (2) the fibrous or non-dope-forming types.
- This customary manner comprises the addition of the non-solvent to the pretreatment mixture.
- Our process broadly comprises the esterification of cellulose by pretreating the cellulose with the usual pretreatment bath such as a fatty acid or acids with or without a catlyst, then'treating the mass with an esterification bath comprising mainly one or more fatty acid anhydrides in the presence of a catalyst.
- the ether may be added to the esterification bath according to our invention either at the same time as the other esterification ingredients or at any time thereafter up to the time when the desired softeni'ngaction by the esterification ingredients has been obtained or in other Words up to that point at which the cellulose ester may go into solution unless this or some other non-solvent be added.
- the ideal condition for carrying out curinvention which in practice should be approached as nearly as possible by those performing the process, is to add the non-solvent to the esterification mixture at such a rate and in such a total amount as to keep the reaction mixture just an increment below the solubility point.
- Example I 50 lbs. of cellulose was pretreated for about 3 hours at approximately 150 F. with a mixture of 175 lbs. of 100% propionic acid and 50 lbs. 5 of glacial acetic acid. The mass was then cooled to a temperature of about 70 F. and a mixture of 100 lbs. of acetic anhydride, 75 lbs. of propionic anhydride and .2 1b. of 70% perchloric acid was added thereto. The 10 whole was maintained at a temperature of 75 F. fon 1 hour at the end of which time 150 lbs. of iso-amyl ether Was added thereto. The temperature of the mass was then uniformly increased from 75 to F.
- Example II 50 lbs. of cellulose was pretreated for 3 hours at about 100 F. with a mixture of 250 lbs. of 25 glacial acetic acid and 3 lbs. of a catalyst consisting of 1 part of sulfuric acid and 2 parts of phosphoric acid. The mass was then cooled to approximately 70 F. and. lbs. of 85% acetic anhydride was then added. After maintaining 'driven off as in the preceding example. The product was stabilized by treating it with boiling n-amyl alcohol for several'hours such stabilization process being disclosed and claimed in application Serial No. 635,854 of C. J. Malm and C. R. Fordyce filed of even date herewith.
- Example III 50 lbs. of cellulose was pretreated for 3 hours at 150 F, with 150 lbs. of 100% butyric acid and 50 lbs. of glacial acetic acid. The mass was then 50 cooled to a temperature of 70 F. and a mixture of 100 lbs. of 85% acetic anhydride 100 lbs. of 100% butyric anhydride, 25 'lbs. of n-butyl ether,
- Example IV The procedure of the preceding example was duplicated except that instead of the n-butyl ether being added in two parts it was added continuously after the addition of the anhydrides and at such a rate as to keep the fibers just insoluble in the esterification bath. This condition of just insoluble in the esterification bath may be determined by the appearance of the fibers which condition is easily recognized by those skilled in the art.
- the ethers having a boiling point about 70 C'. especially the aliphatic ethers, may be employed as the non-solvent in the esterification of cellulose.
- isomeric ethers such as iso-amyl ether, iso-butyl ether etc. may be employed.
- Cotton linters is preferred as the starting material in the examples as due to its economy and satisfactory susceptibility to esterification that material is usually employed in the preparation of cellulose esters at the present time.
- Other cellulosic materials such as cotton fibre tissue paper, clean cotton, surgical cotton wool (preferably bleached) and carefully prepared sulfite wood pulp which has been bleached may however be employed as the starting material if desired.
- cellulosic materials such as so-called hydro-cellulose, reverted cellulose such as may be derived from the viscose or cuprammonium process and even cellulose nitrates, acetates, formates or ethers, which contain free hydroxyl groups available for esterification by processes carried out according to our invention, are also suitable as the starting material of our process of preparing cellulose esters.
- cellulosic material as employed herein refers to materials comprising either cellulose none of Whose hydroxyl groups have been replaced or cellulose which has been partially esterified or etherified but which still contains free and esterifiable hydroxyl groups.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass at a point subsequent to the mixing of the esterifying materials with the cellulose but before the dissolution of the resulting ester in the esterification bath would otherwise occur.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esterifying bath.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass in a step subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esterifying bath.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esteri- 5 fyihg bath.
- the step which comprises incorporating an iso-amyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
- the step which comprises incorporating an amyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
- the step which comprises incorporating isoamyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
- the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point about 70 C. in the esterification mass subsequent to its pretreatment but within not more than approximately one hour after the cellulose has been immersed in the esterifying bath.
- the step which comprises incorporating an ether selected from the group consisting of iso-amyl ether, n-propyl 1 ether and n-butyl ether in the esterification mass subsequent to the miin'ng of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
- the step which comprises incorporating an amyl ether in the esterification mass subsequent to its pretreatment but within not more than approximately one hour after the cellulose has been immersed in the esterifying bath.
- the step subsequent to the pretreatment which comprises continuously adding to the esterification bath after the addition of cellulose, an unsubstituted aliphatic ether having a boiling point above 70 C. at a rate which will maintain the bath nonsolvent of the cellulose material while it is undergoing esterification.
- the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of the pretreated cellulose thereto, an ether selected from the group consisting of iso-amyl ether, n-butyl ether and n-propyl ether at a rate which will maintain the bath nonsolvent of the cellulose material while it is undergoing esterification.
- the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of thepretreated cellulose thereto, an amyl ether at a rate which will maintain the bath non-solvent of the cellulose material while it is undergoing esterification.
- the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of the pretreated cellulose thereto, an unsubstituted aliphatic ether having a boiling point about 70 C. at a rate which will maintain the bath nonsolvent of the cellulosematerial while it is undergoing esterification.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
Patented Nov. 5, 1935 UNITED STTES PROCESS FOR THE FIBROUS ESTERIFI- CATION OF CELLULOSE Carl J. Malm and Charles L. Fletcher, Rochester, N. Y., assigncrs to Eastman Kodak Company, Rochester, N. Y., a corporation of New York No Drawing. Application October 1, 1932, Serial No. 635,856
17 Claims.- (01. 260-101) The present invention relates to the fibrous esterification of cellulose in Which an ether having a boiling point higher than C. is employed as the non-solvent or diluent in the esterification bath proper.
The processes for the esterification of cellulose at the present time may be broadly divided into the two classes of (1) the dope-forming and (2) the fibrous or non-dope-forming types. We have disclosed and claimed a process of the latter type in our application Serial No. 590,509 filed February 2, 1932 in which an ether having a boiling point higher than 70 C. is employed as a nonsolvent or diluent in the esterification of cellulose, in the customary manner. This customary manner comprises the addition of the non-solvent to the pretreatment mixture.
We have now found that in the esterification of cellulose by a fibrous method employing a higher ether, when the ether is added not to the pretreatment but to the esterification step proper the time for the completion of the reaction is greatly reduced. We have also found that in a process according to our invention a productis formed which gives a more brillian dope in the common solvents than an ester prepared by the fibrous esterification of cellulose according to previous methods. We have found that in the case of our invention there is present in the ester mass formed only a minimum of unesterified products such as fiber or grain.
Our process broadly comprises the esterification of cellulose by pretreating the cellulose with the usual pretreatment bath such as a fatty acid or acids with or without a catlyst, then'treating the mass with an esterification bath comprising mainly one or more fatty acid anhydrides in the presence of a catalyst. The ether may be added to the esterification bath according to our invention either at the same time as the other esterification ingredients or at any time thereafter up to the time when the desired softeni'ngaction by the esterification ingredients has been obtained or in other Words up to that point at which the cellulose ester may go into solution unless this or some other non-solvent be added.
The ideal condition for carrying out curinvention which in practice should be approached as nearly as possible by those performing the process, is to add the non-solvent to the esterification mixture at such a rate and in such a total amount as to keep the reaction mixture just an increment below the solubility point.
Example I 50 lbs. of cellulose was pretreated for about 3 hours at approximately 150 F. with a mixture of 175 lbs. of 100% propionic acid and 50 lbs. 5 of glacial acetic acid. The mass was then cooled to a temperature of about 70 F. and a mixture of 100 lbs. of acetic anhydride, 75 lbs. of propionic anhydride and .2 1b. of 70% perchloric acid was added thereto. The 10 whole was maintained at a temperature of 75 F. fon 1 hour at the end of which time 150 lbs. of iso-amyl ether Was added thereto. The temperature of the mass was then uniformly increased from 75 to F. over a period of 4 15 hours and was held at that temperature for about 4 or 5 hours or until solubility in acetone was obtained. The product, cellulose acetatepropionate, was washed free of acid with isoamyl ether and was freed of the residual ether 20 by applying heat thereto.
Example II 50 lbs. of cellulose was pretreated for 3 hours at about 100 F. with a mixture of 250 lbs. of 25 glacial acetic acid and 3 lbs. of a catalyst consisting of 1 part of sulfuric acid and 2 parts of phosphoric acid. The mass was then cooled to approximately 70 F. and. lbs. of 85% acetic anhydride was then added. After maintaining 'driven off as in the preceding example. The product was stabilized by treating it with boiling n-amyl alcohol for several'hours such stabilization process being disclosed and claimed in application Serial No. 635,854 of C. J. Malm and C. R. Fordyce filed of even date herewith.
Example III 50 lbs. of cellulose was pretreated for 3 hours at 150 F, with 150 lbs. of 100% butyric acid and 50 lbs. of glacial acetic acid. The mass was then 50 cooled to a temperature of 70 F. and a mixture of 100 lbs. of 85% acetic anhydride 100 lbs. of 100% butyric anhydride, 25 'lbs. of n-butyl ether,
1 lb. of sulfuric acid and 2.7 lbs. of phosphoric acid was added. The temperature of 70 Fpwas 55 maintained for one hour after which 125 lbs. of n-butyl ether was added and the temperature was uniformly increased to 120 F. over a period of 10 hours. The temperature was maintained at 120 F. for about 20-25 hours or until the fibers in the bath were found to be soluble in acetone. The fibers were then separated from the bath, washed free of acid with n-butyl ether and dried by applying heat. The product, cellulose acetatebutyrate may be stabilized by treating with an alcohol at an elevated temperature as set forth in the preceding example.
Example IV The procedure of the preceding example was duplicated except that instead of the n-butyl ether being added in two parts it was added continuously after the addition of the anhydrides and at such a rate as to keep the fibers just insoluble in the esterification bath. This condition of just insoluble in the esterification bath may be determined by the appearance of the fibers which condition is easily recognized by those skilled in the art.
As pointed out above, the ethers having a boiling point about 70 C'., especially the aliphatic ethers, may be employed as the non-solvent in the esterification of cellulose. In addition to the normal ethers which the examples show are suitable, isomeric ethers such as iso-amyl ether, iso-butyl ether etc. may be employed.
An important feature of the use of a higher boiling ether as a diluent in an esterification process is that that process may be carried out in the presence of only a relatively small amount of catalyst. Processes in which an appreciable amount of catalyst, such as sulfuric acid, is employed often result in a product of little, if any, value. The large amount of catalyst in such processes apparently has a marked degrading action on the cellulose which may even result in the conversion of the cellulose to a cellobiose or some other compound resulting from the degradation of cellulose.
Cotton linters is preferred as the starting material in the examples as due to its economy and satisfactory susceptibility to esterification that material is usually employed in the preparation of cellulose esters at the present time. Other cellulosic materials such as cotton fibre tissue paper, clean cotton, surgical cotton wool (preferably bleached) and carefully prepared sulfite wood pulp which has been bleached may however be employed as the starting material if desired. Also easily esterifiable cellulosic materials such as so-called hydro-cellulose, reverted cellulose such as may be derived from the viscose or cuprammonium process and even cellulose nitrates, acetates, formates or ethers, which contain free hydroxyl groups available for esterification by processes carried out according to our invention, are also suitable as the starting material of our process of preparing cellulose esters. The term cellulosic material as employed herein refers to materials comprising either cellulose none of Whose hydroxyl groups have been replaced or cellulose which has been partially esterified or etherified but which still contains free and esterifiable hydroxyl groups.
Various conditions in the carrying out of the esterification of cellulose according to our invention may be varied in accordance with the judgment of the individual operator. modifications such as the employment of other Various other anhydrides and acids are apparent to those skilled in the art. For example a substituted fatty acid anhydride such as a chloracetic anhydride as disclosed in Clarke and Malm application Serial No. 179,177 filed March 28, 1927, now 5 Patent No. 1,880,808, Oct. 4, 1932, may be employed instead of or supplementary to the unsubstituted anhydrides and/or substituted fatty acids such as chloracetic or alkoxyacetic acid may be employed instead of or supplementary to the unsubstituted acids the only condition being that a source of acyl groups is provided in the reaction mixture.
We claim:
1. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass at a point subsequent to the mixing of the esterifying materials with the cellulose but before the dissolution of the resulting ester in the esterification bath would otherwise occur.
2. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esterifying bath.
3. In the fibrous preparation of a cellulose acetate-propionate in which cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass in a step subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
4. In the fibrous preparation of a cellulose acetate-propionate in which cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above 70 C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esterifying bath.
5. In the fibrous acetylation of cellulose in in the esterification mass in a step subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
6. In the fibrous acetylation of cellulose in which the cellulose is pretreated with a lower 0 fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point above C. in the esterification mass shortly after the pretreated cellulose has been mixed with the esteri- 5 fyihg bath.
7. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an amyl ether in the 70 esterification mass subsequent to its pretreatment but before its dissolution would otherwise occur.
8. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an iso-amyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
9. In the fibrous preparation of a cellulose acetate-propionate in which cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an amyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
10. In the fibrous preparation of a cellulose acetate-propionate in which cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating isoamyl ether in the esterification mass subsequent to the mixing of the esterifying materials with the cellulose but before its dissolution would otherwise occur.
11. In the fibrous esterificationof cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an unsubstituted aliphatic ether having a boiling point about 70 C. in the esterification mass subsequent to its pretreatment but within not more than approximately one hour after the cellulose has been immersed in the esterifying bath.
12. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an ether selected from the group consisting of iso-amyl ether, n-propyl 1 ether and n-butyl ether in the esterification mass subsequent to the miin'ng of the esterifying materials with the cellulose but before its dissolution would otherwise occur. 7
13; In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step which comprises incorporating an amyl ether in the esterification mass subsequent to its pretreatment but within not more than approximately one hour after the cellulose has been immersed in the esterifying bath.
14. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step subsequent to the pretreatment which comprises continuously adding to the esterification bath after the addition of cellulose, an unsubstituted aliphatic ether having a boiling point above 70 C. at a rate which will maintain the bath nonsolvent of the cellulose material while it is undergoing esterification.
15. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of the pretreated cellulose thereto, an ether selected from the group consisting of iso-amyl ether, n-butyl ether and n-propyl ether at a rate which will maintain the bath nonsolvent of the cellulose material while it is undergoing esterification.
16. In the fibrous esterification of cellulose in which the cellulose is pretreated with a lower fatty acid and then esterified, the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of thepretreated cellulose thereto, an amyl ether at a rate which will maintain the bath non-solvent of the cellulose material while it is undergoing esterification.
17. In the fibrous preparation of a cellulose acetate-propionate in which the cellulose is pretreated with a lower fatty acid and then esterified, the step subsequent to the pretreatment which comprises continuously adding to the esterification bath, after the addition of the pretreated cellulose thereto, an unsubstituted aliphatic ether having a boiling point about 70 C. at a rate which will maintain the bath nonsolvent of the cellulosematerial while it is undergoing esterification.
CARL J. MALM. CHARLES L. FLETCHER.
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US635856A US2019920A (en) | 1932-10-01 | 1932-10-01 | Process for the fibrous esterification of cellulose |
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US635856A US2019920A (en) | 1932-10-01 | 1932-10-01 | Process for the fibrous esterification of cellulose |
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1932
- 1932-10-01 US US635856A patent/US2019920A/en not_active Expired - Lifetime
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