US2172447A - Increasing the reactivity of cellulose to esterification reagents - Google Patents
Increasing the reactivity of cellulose to esterification reagents Download PDFInfo
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- US2172447A US2172447A US187178A US18717838A US2172447A US 2172447 A US2172447 A US 2172447A US 187178 A US187178 A US 187178A US 18717838 A US18717838 A US 18717838A US 2172447 A US2172447 A US 2172447A
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- cellulose
- esterification
- salt
- reactivity
- increasing
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- 229920002678 cellulose Polymers 0.000 title description 74
- 239000001913 cellulose Substances 0.000 title description 69
- 238000005886 esterification reaction Methods 0.000 title description 28
- 230000032050 esterification Effects 0.000 title description 27
- 239000003153 chemical reaction reagent Substances 0.000 title description 19
- 230000009257 reactivity Effects 0.000 title description 17
- 235000010980 cellulose Nutrition 0.000 description 69
- 150000003839 salts Chemical class 0.000 description 29
- 238000000034 method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000021736 acetylation Effects 0.000 description 7
- 238000006640 acetylation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 6
- 229920002301 cellulose acetate Polymers 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- -1 amine salts Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ZKYHWNAIOKHVME-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;perchloric acid Chemical compound [O-]Cl(=O)(=O)=O.OCC[NH+](CCO)CCO ZKYHWNAIOKHVME-UHFFFAOYSA-N 0.000 description 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- 101150091111 ACAN gene Proteins 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound 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 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 238000006681 Combes synthesis reaction Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IYKJEILNJZQJPU-UHFFFAOYSA-N acetic acid;butanedioic acid Chemical compound CC(O)=O.OC(=O)CCC(O)=O IYKJEILNJZQJPU-UHFFFAOYSA-N 0.000 description 1
- SPTSIOTYTJZTOG-UHFFFAOYSA-N acetic acid;octadecanoic acid Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O SPTSIOTYTJZTOG-UHFFFAOYSA-N 0.000 description 1
- GAMPNQJDUFQVQO-UHFFFAOYSA-N acetic acid;phthalic acid Chemical compound CC(O)=O.OC(=O)C1=CC=CC=C1C(O)=O GAMPNQJDUFQVQO-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QYPCWXLVUAOBQG-UHFFFAOYSA-N ethanamine;perchloric acid Chemical compound CCN.OCl(=O)(=O)=O QYPCWXLVUAOBQG-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940117957 triethanolamine hydrochloride Drugs 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 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
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/02—Rendering cellulose suitable for esterification
Definitions
- This invention relates to cellulosic material and process of producing same; more particularly, it relates to a process for the treatment of cellulose with a salt whereby to greatly increase the reactivity of the cellulose to a subsequent acetylation or esterification reaction.
- cellulose which are available commercially have varying degrees of chemical reactivity, depending, among other factors, on whether the source of the cellulose is cotton, cotton linters, wood pulp, Wood chips, sisal, bagasse, and the like, and in accordance with the method by which the cellulose has been purified, and the extent of the purification treatment.
- cellulose derived from wood pulp is generally more diflicult to esterify than cellulose derived from cotton or cotton linters. It is therefore an object of the present invention to influence and control the esterifying reactivity of cellulose, particularly cellulose which has a low chemical reactivity and is therefore diflicult to esterify by previously known e'sterification processes.
- Another object of the present invention is to provide a process for the treatment ofcellulose whereby to insure a more rapid and more uniform penetration of the cellulose by the esterification reagents.
- a still further object of the present invention from the group consisting of sodium, potassium,
- the treatment of the cellulosie material by the abovedescribed salts is carried out prior to the-treatment of the cellulose with any of the usual esterifying agents, or agents especially preparing the cellulose for esterification, such as acetic anhydride, acetic acid, sulfuric acid or the like.
- the salts of the present invention with which the cellulosic material is to be treated have little,"if any, swelling action on the cellulose.
- the treatment of the cellulosic material is preferably carried out while the cellulose is still in a completely open and swollen condition from its manufacture.
- the cellulose veniently be made a standard practice, and
- I fibers will be uniformly impregnated with the salt substantially throughout their structure.
- the cellulose is preferably treated with an aqueous solution of the salt in such concentration thatthe salt will be present-in a quantity of 0.1 to 3% based on the dry weight of the cellulose.
- the cellulosic material impregnated with the salt, before esterification, is preferably dried to a moisture content of less than 12%, based on .the weight of the dry cellulose. The drying may be carried out by any suitable, known drying method which will not remove the salt.
- Example 1 Seventy-five kilograms of sulfite wood pulp cellulose is continuously agitated with a solution of- 10 kilograms of ammonium perchlorate dissolved in 600 liters of water for a suitable period of time, after which the liquid is pressed or centrifuged off and thewood pulp dried.
- the dried wood pulp has 1.3 to 2.0% of ammonium perchlorate uniformly distributed and deeply embedded throughout the cellulose fibers.
- Certain alkaline salts of the above sulfuric, hydrochloric, perchloric and phosphoric mentioned acids have also given very useful reacids, and drying the cellulose, impregnated with suits, for example sodium, chloride, potassium the salt, to a moisture content of less than 12%, 30 chloride, sodium sulfate, potassium perchlorate, based on the weight of the dry cellulose.
- the present invention does not comprehend 3.
- the process of increasing the reactivity of the use of salts having substantial swelling ac-- cellulose to esterification reagents which com--v tion on cellulose under normal conditions. prises the step of treating the cellulose, prior to The esterification of the salt impregnated celluits treatment with any esterification reagent, with 5 lose may be conducted in accordance with praca solution of a water-soluble, pentavalent nitrotically any of the known esterification methods, gen-containing salt, and drying the cellulose, im-
- the esterification maybe performed in pregnated with the salt, to a moisture content such a manner that the resulting cellulose ester of less than 12%, based on the weight of the dry dissolves or disperses to form a dope or, if desired, cellulose.
- fication of such pretreated cellulose may be d" W th an q e 5011mm! O a water-soluble, 45 rected to the preparation of other simple and pentavalent nitrogen-containing salt, and dryingmixed organic esters of cellulose, such as celluthe cellulose, impregnated with the salt, to a lose formate, cellulose propionate, cellulose bumoisture content of less than 12%, based on the tyrate, cellulose acetopropionate, cellulose acetoweight of the dry cellulose.
- the pretreatment based on the weight of the cellulose, and drying appearsalso to permit the esterifying reagents, 'the cellulose, impregnated with the salt, to a such as acetic acid, acetic anhydride, and sulfuric moisture content of less than 12%, based on the (.0 acid, to penetrate more uniformly and rapidly weight of the dry cellulose.
- the cellulose esters may, of course, cellulose to esterification reagents which combe converted by usual methods into useful strucprises the step of treating the cellulose, prior to tures, such as threads, films, lacquers, and its treatment with any esterification reagent, with plastics, a solution of triethanolamine perchlorate.
- Cellulose having a moisture content of less than 12% based on the weight of the dry cellulose, and having an increased reactivity to esterificasulfuric, hy ochloric, perchloric and phosphoric, acids. 1
- Cellulose having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing 0.1 to 3% of a salt the group consisting of sodium, po-
- Cellulose having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing a water-soluble, pentavalent nitrogen-containing salt.
- Cellulose having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing 0.1 to 3% of a water-
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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)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patented Sept. 12, 1939 UNITED STATES PATENT OFFICE INCREASING THE REACTIVITY OF CELLU- LOSE TO ESTERIFICATION REAGENTS Arnold Marschall, many, assignor Freiburg-in-Breisgau, Gerto E. I. du Pont de Nemours &
Company, Wilmington, Dcl., a corporation of Delaware 12 Claims.
This invention relates to cellulosic material and process of producing same; more particularly, it relates to a process for the treatment of cellulose with a salt whereby to greatly increase the reactivity of the cellulose to a subsequent acetylation or esterification reaction.
The various forms of cellulose which are available commercially have varying degrees of chemical reactivity, depending, among other factors, on whether the source of the cellulose is cotton, cotton linters, wood pulp, Wood chips, sisal, bagasse, and the like, and in accordance with the method by which the cellulose has been purified, and the extent of the purification treatment. Thus, cellulose derived from wood pulp is generally more diflicult to esterify than cellulose derived from cotton or cotton linters. It is therefore an object of the present invention to influence and control the esterifying reactivity of cellulose, particularly cellulose which has a low chemical reactivity and is therefore diflicult to esterify by previously known e'sterification processes.
Another object of the present invention is to provide a process for the treatment ofcellulose whereby to insure a more rapid and more uniform penetration of the cellulose by the esterification reagents.
A still further object of the present invention from the group consisting of sodium, potassium,
lithium, ammonium, amine, and substituted amine salts of an acid taken from the group consisting of sulfuric, hydrochloric, perchloric, phosphorlc, and similar strong inorganic acids. The treatment of the cellulosie material by the abovedescribed salts is carried out prior to the-treatment of the cellulose with any of the usual esterifying agents, or agents especially preparing the cellulose for esterification, such as acetic anhydride, acetic acid, sulfuric acid or the like. The salts of the present invention with which the cellulosic material is to be treated have little,"if any, swelling action on the cellulose.
In accordance with the process of the present invention the treatment of the cellulosic material is preferably carried out while the cellulose is still in a completely open and swollen condition from its manufacture. By so proceeding, the cellulose veniently be made a standard practice, and
I fibers will be uniformly impregnated with the salt substantially throughout their structure. To this end the application of the salt may conpart, or a continuation, of the final washing step in the customary methods of manufacturing cellulose. The cellulose is preferably treated with an aqueous solution of the salt in such concentration thatthe salt will be present-in a quantity of 0.1 to 3% based on the dry weight of the cellulose. The cellulosic material impregnated with the salt, before esterification, is preferably dried to a moisture content of less than 12%, based on .the weight of the dry cellulose. The drying may be carried out by any suitable, known drying method which will not remove the salt.
be understood that the invention is not to be limited by the examples.
Example 1 Seventy-five kilograms of sulfite wood pulp cellulose is continuously agitated with a solution of- 10 kilograms of ammonium perchlorate dissolved in 600 liters of water for a suitable period of time, after which the liquid is pressed or centrifuged off and thewood pulp dried. The dried wood pulp has 1.3 to 2.0% of ammonium perchlorate uniformly distributed and deeply embedded throughout the cellulose fibers. After acetylation by a, conventional. acetylation procedure, for example, the procedure described in U. S. No. 1,543,310, the ammonium perchlorate impregnated pulp surprisingly yields a cellulose acetate exhibiting the following improvement over the cellulose acetate derived by the same acetylation procedure from the same pulp without the tion at 15 C. in c. g. s. units) Example 2 Wood pulp cellulose, prepared according to while still somewhat wet, and swollen from the customary washing, is
salt pretreatment:
' Pre- Untreated treated pulp pu Time of acetylation in minutes 8'7 Clarity: comparative transparency of a layer of the acetylated solution in cm 205 139 Filterability in cc. per unit of time "288 87 Viscosity-(of a. 7% acetone solumixed with a solution of 15 kilograms of am- Since it is obvious that many changes and monium sulfate dissolved in 600 liters of water modifications of the above described processes can for a suitableperiod of time, after which the be made without departing from the nature and liquid is pressed or centrifuged off. After air dryspirit of the invention, it is to be understood that 5 ing, the wood pulp exhibits a salt content of the invention is not to be limited except as set 5 1.5-2.1% ammonium sulfate uniformly distributed forth in the appended claims.
throughout the fibers, including the interiors I claim:
thereof. Upon acetylation by any standard pro- 1. The process of increasing the reactivity of I cedure, the ammonium sulfate impregnated wood cellulose to esterification reagents which comm pulp acetylates quite rapidly to a cellulose aceprises the step of treating the cellulose, prior to tate superior in clarity and filterability to the its treatment with any esterification reagent, cellulose acetate derived by the same acetylation with a solution of a salt takenfrom the group procedure from the same pulp without the salt consisting of sodium, potassium, lithium, am-
' pretreatment.- monium, amine, and substituted aminesalts of Among the salts which may be used, in acan acid taken from the group consisting of sulcordance with the present invention, for the prefuric, hydrochloric, 'perchloric and phosphoric treatment of cellulosic material, the pentavalent acids, and drying the cellulose,'impregnated with nitrogen-containing salts of hydrochloric, sulthe salt, to a moisture content of less than 12%, furic, phosphoric and perchlorlc acids have been based on the weight of the dry cellulose. I
found tobe particularly useful. Particularly good 2. The process of increasing the reactivity of 20 results have been obtained with ammonium chlocellulose to esterification reagentswhichcomprises ride, ammonium phosphate, trimethylamt'ne hythe step of treating the cellulose, prior to its drochloride, triethylamine hydrochloride, tritreatment with any esterification reagen with ethylamine perchlorate, triethanolamine per-. an aqueous solution of a salt taken from the chlorate, triethanolamine hydrochloride, tetragroup consisting of sodium, potassium, lithium, 2
methyl ammonium chloride, tetraethyl ammoniammonium, amine, and substituted amine salts um chloride, and tetraethyl ammonium perof an acid taken from the group consisting of chlorate. Certain alkaline salts of the above sulfuric, hydrochloric, perchloric and phosphoric mentioned acids have also given very useful reacids, and drying the cellulose, impregnated with suits, for example sodium, chloride, potassium the salt, to a moisture content of less than 12%, 30 chloride, sodium sulfate, potassium perchlorate, based on the weight of the dry cellulose.
etc. The present invention does not comprehend 3. The process of increasing the reactivity of the use of salts having substantial swelling ac-- cellulose to esterification reagents which com--v tion on cellulose under normal conditions. prises the step of treating the cellulose, prior to The esterification of the salt impregnated celluits treatment with any esterification reagent, with 5 lose may be conducted in accordance with praca solution of a water-soluble, pentavalent nitrotically any of the known esterification methods, gen-containing salt, and drying the cellulose, im- Thus, the esterification maybe performed in pregnated with the salt, to a moisture content such a manner that the resulting cellulose ester of less than 12%, based on the weight of the dry dissolves or disperses to form a dope or, if desired, cellulose. 40 in such a fashion in the presence of a cellulose 4. The process of increasing the reactivity of ester nonsolvent that the resulting cellulose ester cellulose to esterification reagents which cornretains the fibrous form of the original cellulose. prises the step of treating the cellulose, prior to If desired, instead of cellulose acetate, the esteriits treatment with any esterification reagent,
fication of such pretreated cellulose may be d" W th an q e 5011mm! O a water-soluble, 45 rected to the preparation of other simple and pentavalent nitrogen-containing salt, and dryingmixed organic esters of cellulose, such as celluthe cellulose, impregnated with the salt, to a lose formate, cellulose propionate, cellulose bumoisture content of less than 12%, based on the tyrate, cellulose acetopropionate, cellulose acetoweight of the dry cellulose.
,0 butyrate, cellulose acetate succinate, cellulose 5. The process of increasing the reactivity of acetate phthalate, and cellulose acetate stearate; cellulose to esterification reagents which com- The process of the invention increases the prises the step of treating the cellulose, prior to chemical reactivity of. the cellulose and makes its treatment with any esterification reagent, with available for esterification certain commercially a solution of a water-soluble, pentavalent nitrooccurring low grade celluloses previously generalgen-containing salt in such concentration as to ly considered unsuitable because of their known impart to the cellulosic material 0.1 to 3% salt resistance toward estification. The pretreatment based on the weight of the cellulose, and drying appearsalso to permit the esterifying reagents, 'the cellulose, impregnated with the salt, to a such as acetic acid, acetic anhydride, and sulfuric moisture content of less than 12%, based on the (.0 acid, to penetrate more uniformly and rapidly weight of the dry cellulose.
into the interiors of the cellulose fibers, and re- 6'. The process of increasing the reactivity of sultsinamore rapid esterification. The cellulose, cellulose to esterification reagents which compretreated by the process of the invention, seemprises the step of'tfeating the cellulose, prior to ingly yields upon esterification a cellulose ester of its treatment with any esterification reagent, and
more uniform quality than normally, judging by while the cellulose is in an open or swollen condithe superior clarity and filterability exhibited. o w t a Solution of a Water-Soluble, D t Such uniformity arises, it is believed, from the valent nitrogen-containing salt, and drying the salts being uniformly and deeply distributed in cellulose, impregnated with thesalt, to a mo sture the fiber interior by the salt solutior treatment content of less than 12%, based on the weight of and from the salts being embedded in the fibers the dry cellulose. 70 by drying before subjecting the fibers to esterify- 7. The process of increasing the reactivity of ing reagents. The cellulose esters may, of course, cellulose to esterification reagents which combe converted by usual methods into useful strucprises the step of treating the cellulose, prior to tures, such as threads, films, lacquers, and its treatment with any esterification reagent, with plastics, a solution of triethanolamine perchlorate. n
' taken from 15 'tassium, nun
tuted amine salts of an acid taken from the group 8. Cellulose, having a moisture content of less than 12% based on the weight of the dry cellulose, and having an increased reactivity to esterificasulfuric, hy ochloric, perchloric and phosphoric, acids. 1
'9. Cellulose, having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing 0.1 to 3% of a salt the group consisting of sodium, po-
um, ammonium, amine, and substiconsisting of sulfuric, hydrochloric, perchloric and phosphoric acids.
10. Cellulose, having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing a water-soluble, pentavalent nitrogen-containing salt.
11. Cellulose, having a moisture content of less than 12%, based on the weight of the dry cellulose, and having an increased reactivity to esterification reagents, containing 0.1 to 3% of a water-
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US187178A US2172447A (en) | 1938-01-27 | 1938-01-27 | Increasing the reactivity of cellulose to esterification reagents |
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US187178A US2172447A (en) | 1938-01-27 | 1938-01-27 | Increasing the reactivity of cellulose to esterification reagents |
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US2172447A true US2172447A (en) | 1939-09-12 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2585516A (en) * | 1948-03-23 | 1952-02-12 | Du Pont | Preparation of impregnated cellulose and cellulose esters therefrom |
US2600031A (en) * | 1949-02-04 | 1952-06-10 | Du Pont | Cellulose ester manufacture |
-
1938
- 1938-01-27 US US187178A patent/US2172447A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2585516A (en) * | 1948-03-23 | 1952-02-12 | Du Pont | Preparation of impregnated cellulose and cellulose esters therefrom |
US2600031A (en) * | 1949-02-04 | 1952-06-10 | Du Pont | Cellulose ester manufacture |
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