WO1992020738A1 - Degradable cellulose polymers - Google Patents
Degradable cellulose polymers Download PDFInfo
- Publication number
- WO1992020738A1 WO1992020738A1 PCT/US1992/004243 US9204243W WO9220738A1 WO 1992020738 A1 WO1992020738 A1 WO 1992020738A1 US 9204243 W US9204243 W US 9204243W WO 9220738 A1 WO9220738 A1 WO 9220738A1
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- WIPO (PCT)
- Prior art keywords
- acid
- accordance
- composition
- cellulose
- lactone
- Prior art date
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- 0 COC(C(*)C1O)OC1=O Chemical compound COC(C(*)C1O)OC1=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
Definitions
- the present invention is directed to a cellulose ester composition which may be used to form thermoplastic polymeric materials having improved degradation properties upon exposure to moisture.
- the compositions include at least one degradation promoter that will leach from the polymeric materials in the presence of moisture after disposal of the polymeric composition in the environment.
- the present invention is directed to a thermoplastic cellulose acetate polymer composition having improved degradation properties upon exposure to moisture which includes cellulose acetate, a plasticizer for the cellulose acetate and a hydrophilic degradation promoter.
- Some of the first polymers developed for commercial use were based on cellulose. These included regenerated cellulose (rayon) and various cellulose esters, such as cellulose acetate, cellulose butyrate, cellulose propionate and mixed esters of cellulose (acetate, acetate butyrate and acetate propionate).
- regenerated cellulose rayon
- various cellulose esters such as cellulose acetate, cellulose butyrate, cellulose propionate and mixed esters of cellulose (acetate, acetate butyrate and acetate propionate).
- Regenerated cellulose materials such as cellophane and rayon, are environmentally degradable at a very slow rate.
- a high level of plasticizer is required to provide cellulose ester compositions which can be formed into a thermoplastic film by melt-fabrication methods.
- Cellulose acetate in its pure form is not a thermoplastic when melt-fabricated by methods such as extrusion.
- the use of such high levels of plasticizer produced plastic materials which are highly stable and which do not degrade when exposed to the environment, even in highly moist conditions.
- the present invention is directed to a thermoplastic cellulose ester polymer composition having improved degradation properties upon exposure to moisture.
- the composition includes a cellulose ester and a degradation promoter.
- the degradation promoter after formation of the polymer composition into an end- product and in the presence of moisture, is water soluble and leachable from the polymer end-product or in the presence of moisture, hydrolyzes to form water soluble by-products which are leachable from the polymer end-product.
- the degradation promoter also acts as a catalyst to enhance the hydrolysis of the cellulose acetate, resulting in a mixture of cellulose and acetic acid. The cellulose can then depolymerize into saccharides that are more biodegradable.
- the degradation promoter can act as a plasticizer for the cellulose ester polymer or can be used in combination with other known plasticizers.
- Cellulose is a polysaccharide formed from anhydroglucose units. Each of the anhydroglucose units contains three free hydroxyl groups which can be reacted to form esters. The extent to which substitution of an acid takes place is known as the degree of substitution and is expressed as the average number of hydroxyl groups, of the three available in the anhydroglucose unit, that have been replaced.
- Cellulose esters useful in the present invention have a degree of substitution of from about 2.0 to about 2.6. Expressed in other terms, the cellulose acetates useful in the present invention have an ester content of from about 39% to about 42.5% on an acetyl equivalent basis.
- U.S. Patent 2,067,310 to Auden discloses a process of making molded articles that can use molding temperatures as low as 120° C. to 180° C. and molding pressures of 2,000 to 3,000 psi, which are lower than the usual molding temperatures and pressures for cellulose triacetate.
- the process of the Auden patent consists in mixing cellulose triacetate and a material taken from group consisting of lactides, and the anhydrides of maleic, succinic and phthalic acids. The addition of the lactides and the anhydrides in combination with the use of plasticizers produced a moldable cellulose triacetate composition.
- U.S. Patent No. 2,805,171 to Williams also discloses a method for providing a moldable composition of cellulose triacetate.
- cellulose triacetate having an acetyl content of 52.5% to 53.5% are acetone insoluble cellulose esters.
- the cellulose esters useful in the present invention, having an acetyl content of from between about 39% and about 42.5%, are characterized in the Williams patent as being acetone soluble.
- the degradable thermoplastic cellulose ester compositions of the present invention are mixtures of a cellulose ester having an ester content, on an acetyl basis, of from between about 39% and about 42.5% and a degree of substitution of from about 2.0 to about 2.6, a plasticizer and a degradation promoter. While not wishing to be bound by any theory, it is believed that the degradable functionality of the compositions of the invention are at least partially attributable to access by water to the polymer and hydrolysis of the polymer at the pendant acetyl groups and at the acetal linkages.
- the degradation promoters of the present invention are hydrophilic materials.
- the degradation promoters are cyclic internal monoesters, cyclic internal double esters and oligomers of such acids having from 2 to 50 acid moieties.
- the monoesters have a single oxygen molecule in the ring and can be prepared from any of the hydroxy acids except the ⁇ -hydroxy acids.
- Monoester lactones useful as degradation promoters in the present invention are usually prepared from hydroxy acids.
- the cyclic double esters can be prepared from ⁇ -hydroxy acids.
- Cyclic internal esters are generally referred to as lactones.
- the cyclic double 6-membered esters are sometimes referred to as dioxanediones.
- cyclic internal esters of the invention can be prepared from suitable hydroxy acids, other chemical pathways for their preparation are available.
- the 7- and ⁇ -lactones are commonly prepared by either hydrolysis or distillation of 7- or ⁇ -halo acids, by treatment of unsaturated acids with aqueous hydrobromic or sulfliric acids, or by partial reduction of cyclic acid anhydrides.
- ⁇ -Lactones result from the reaction of a ketene with aldehydes or ketones. The reaction of ketene with formaldehyde is shown below.
- lactones can be made by oxidation of cyclic ketones with Caro's acid; thus, cyclohexanone yields e-caprolactone.
- Some lactones are prepared from the reaction of a dicarboxylic acid with a polyhydric alcohol, such as the reaction of malonic acid with ethylene glycol.
- Suitable hydroxy acids and dicarboxylic acids for preparation of the lactones useful as degradation promoters of the present invention include 3- hydroxypropionic acid, 2-hydroxy, 1,2,3 propanetricarboxylic acid (citric acid), 3- hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxy-valeric acid, 5-hydroxyvaleric acid, 6-hydroxycaproicacid, 2-hydroxyaceticacid (glycolicacid), 2-hydroxy-propionic acid (lactic acid), 2 hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxycaproic acid, 2-hydroxy-heptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy-pelargonic acid, 2-hydroxyphenylaceticacid, 1-hydroxy-cyclohexane 1-carboxylicacid, oxalic acid plus ethylene glycol, oxalic acid plus propylene glycol, malonic acid plus ethylene glycol, and malonic acid plus propylene glycol.
- lactones useful in the present invention have from 3 to 6 carbon atoms and 1 or 2 oxygen atoms in the ring.
- the lactones produced from the hydroxy acids will have structures corresponding to the following formulae:
- any R can be hydrogen, C ⁇ C ⁇ alkyl, or an aryl group selected from benzene, napthalene, benzene substituted with C t -C 4 alkyl and napthalene substituted with C r C 4 alkyl.
- R t and R 2 are H when 3-hydroxypropionic acid is used to produce propiolactone;
- R t is H and R 2 is methyl when 3-hydroxybutyric acid is used to produce butyrolactone;
- R j is methyl and R 2 is methyl when 3- hydroxyisobutyric acid is used to produce 2,3-dimethyl propiolactone;
- R j is phenyl and R 2 is H when 3-hydroxy 3-phenyl is used to produce 3-phenyl propio-lactone and R j is H and R 2 is phenyl when 3-hydroxy, 2-phenyl is used to produce 2-phenyl propiolactone.
- R t , R 2 and R 3 are H when 4-hydroxybutyric acid is used to produce valerolactone and R ! is methyl, R 2 is H and R 3 is H when 4- hydroxyvaleric acid is used to produce 4-methyl valerolactone.
- R j through R 5 are H when 6-hydroxycaproic acid is used to produce e-caprolactone and R x is methyl, R 2 -R 5 are H, when 6- hydroxyheptylic acid is used to produce 6-methyl-caprolactone.
- R ⁇ and R 3 are methyl, R 2 and R 4 are H when lactic acid is used to produce lactide; Rj and R 3 are phenyl, R 2 and R 4 are H when phenyl-2 hydroacetic acid is used to produce 2,5-diphenyl-dioxane-3,6-dione and R j and R 3 are hexyl, R 2 and R 4 are H, when 2-hydroxyoctanoic acid is used to produce 2,5-dihexyldioxane-3,6-dione.
- R j and R 2 are H, when oxalic acid and ethylene glycol are used to produce l,4-dioxane-2,3-dione and R ⁇ is methyl, R 2 is H, when oxalic acid and propylene glycol are used to produce 5-methyl-l,4-dioxane-2,3-dione.
- RrR are H when malonic ester and ethylene glycol are used to produce l,4-dioxepine-5-7,dione;
- R is methyl
- R_-R 4 are H when malonic ester and propylene glycol are used to produce 2-methyl-l,4-dioxepineand
- R R 3 are H
- R 4 is methyl when methyl malonic ester and ethylene glycol are used to produce
- R ! -R 4 are H when 5-hydroxyvaleric acid is used to produce delta-valerolactone and Rj is methyl
- R 2 -R are H, when 5-hydroxycaproic acid is used to produce 5-methyl-valerolactone.
- Oligomers of certain of the hydroxy acids that can be used to make the lactones can also be used as a degradation promoter, either by itself or in combination with a lactone. Oligomers of lactic acid having from 2 to 50 lactic acid moieties are particularly suitable.
- a preferred degradation promoter is a mixture of lactone from lactic acid or hydroxycaproic acid and oligomers of lactic acid or hydroxycaproic acid having from about 10% to about 95% of the lactone.
- Plasticizers useful in the polymer compositions of the present invention are conventional plasticizers used in the preparation of thermoplastic cellulose ester compositions. Suitable plasticizers include diethyl phthalate, dimethyl phthalate, ethoxyethylphthalate, methoxyethyl phthalate, dibutyl tartrate, diethylene glycol-butyl ether, diethylene glycol mono-ethyl ether, tripropionin, benzoyl benzoate, triphenyl phosphate, triacetin, diamyl phthalate and ortho-cresyl para-toluene sulfonate.
- thermoplastic cellulose ester compositions are highly hydrophobic and provide extreme resistance to moisture in the finished polymer product. Some of the plasticizers, however, are relatively hydrophilic.
- the degradation promoters of the present invention are hydrophilic. Consequently, in one embodiment of the invention, it is desirable to provide a hydrophilic lipophilic balance (HLB) of hydrophobic plasticizers and degradation promoters of the present invention which is within the range of from about 10 to about 40.
- HLB hydrophilic lipophilic balance
- the cellulose ester is present in the compositions of the present invention at a level of from about 20 to about 80% by weight. All percentages used herein are by weight unless otherwise indicated.
- the cellulose esters useful in the present invention may be selected from cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate and cellulose acetate-propionate.
- the cellulose esters have a molecular weight of at least about 5,000 and preferably have a molecular weight of from between about 5,000 and about 500,000.
- the cellulose acetate-butyrate preferably has from about 90 to about 99% acetate and from about 10 to about 1 % of butyrate.
- the cellulose acetate-propionate preferably has an acetate level of from about 80 to about 99% and a propionate level of from about 20 to about 1%.
- the plasticizer is present in the polymeric compositions of the invention at a level of from 0% to about 50% by weight of the composition.
- the hydrophilic degradation promoter is preferably present in the polymeric compositions at a level of from about 1 to about 60% by weight of the composition. The sum of the total level of use of the plasticizer and the hydrophilic degradation promoter is from about 20% to about 80% by weight of the composition.
- Some of the degradation promoters useful in the present invention also act as plasticizers and can be used without the addition of other conventional hydrophobic plasticizers.
- Degradation promoters which can be used without a plasticizer include oligomers of lactic acid and lactones made from lactic acid and citric acid. While not wishing to be bound by any theory, it is believed that degradation of the degradable cellulose ester formulations of the inventions result from leaching of the relatively hydrophilic degradation promoter from the composition by water leaving behind a somewhat more open or porous molecular lattice exposed to the water. The cellulose ester is present in an amorphous state when extensively plasticized during melt-fabrication.
- porous cellulose ester is in intimate contact with water after leaching of the degradation promoter, there is a higher concentration of water present than with conventional hydrophobic plasticized cellulose esters and the mass action of the water promotes hydrolysis.
- An acidic degradation promoter provides a source of acid that catalyzes the hydrolysis. Enzymatic degradation is also possible as a result of the exposed, moistened cellulose ester lattice structure.
- the hydrolysis is accelerated by the formation of an acidic medium arising from certain of the degradation promoters and their hydrolysis and from hydrolysis of the cellulose ester to form an organic acid.
- plasticized, degradable cellulose esters can expand the market for cellulose esters by significant quantities.
- the degradable cellulose esters of the present invention provides a plasticized system that is low cost and provides the biodegradability to serve a growing market, particularly in sheet materials, which are used for common products, such as garbage bags.
- the following examples further illustrate various features of the invention but are intended to in no way limit the scope of the invention which is defined in the appended claims.
- Sample 2-5 containing 1% fumaric acid
- sample 2-6 containing 24% lactic acid
- Sample 2-7 containing 1% phosphoric acid
- the inorganic acids are buried in a conventional hydrophobic plasticizer matrix, they are effectively shut off from moisture and serving their purpose of promoting hydrolysis.
- Organic acids combined with the leachable degradation promoters of the invention can accelerate hydrolysis.
- the leachable degradation promoters work well in promoting hydrolysis, particularly if they form acids, in situ. Compare the results of -8 and -9 of Table 1, for example.
- Tensile strength testing was performed according to ASTM D638.
- the moduli, or measures of stiffness varied with the amount of plasticizer and/or degradation promoter. In general, the total amount of plasticizer needs to be greater than 40 weight percent to obtain films that mimic the foldability and extensibility of polyolefins.
- Samples -37 and -42-5 were thermoformed into a stiff, transparent, colorless salad cover shape.
- Sample -42-2 was formed into a trash bag shape.
- Oligomeric lactic acid and polyethyl lactate are commercially attractive degradation promoters which also function as plasticizers. They are easily prepared by the condensation of lactic acid and ethyl lactate, a simple process that uses economical precursors. Both of these materials intimately melt-disperse with cellulose acetate and provide well behaved thermoplastics.
- the cellulose acetate used was a commercial grade that had a weight- average molecular weight of 85,000, as judged by GPC. Higher molecular weights would have provided better strength and higher percent elongations under stress.
- DEP diethyl phthalate
- FA fumaric acid
- LA lactic acid
- PA phosphoric acid
- LD lactide
- OLA oligomeric polylactic acid having 5 lactic acid moieties
- PC propylene carbonate
- EtI_-,A ethyl lactoyllactate
- the following example illustrates the use of a 7-membered ring lactone as a plasticizer.
- the cellulose acetate chosen was a polymer (Eastman Chemicals).
- the mixture was placed on an open, two-roll mill preheated to 350° F.
- the counter-rotating mill was set at a tight nip at approximately 10 rpm. Within 5 minutes the mixture clears as evidence of complete mixing.
- the mix was sheeted out off the mill. The mix fused very easily with no dripping, but some fuming of the caprolactone.
- melt-blend formulation was compression molded at 300° F to provide approximately 8 to 10 mil, thick films. These were completely colorless and transparent, thus providing evidence of plasticization.
- the films were pliable, tear- resistant, and easily elongateable at about 37° C with heat supplied by holding in the hand.
- the films were evaluated on an Instron tester for tensile properties by ASTM 882, and the results are shown in Table 2.
- the caprolactone content was estimated as 22.7 percent by isothermal weight loss at 200° C by TGA.
- the tensile strength, modulus, and elongation-to-break values which are reported in Table 2 resemble those found to be useful for packaging applications, similar to some grades of high-density polyethylene and polypropylene.
- Example 2 illustrates the use of a 5-membered ring lactone.
- the procedure of Example 2 was repeated using 4-valerolactone in place of the caprolactone and using the same cellulose acetate.
- 55 parts of cellulose acetate was mixed by hand with 45 parts of 4-valeroIactone, mill-rolled 5 minutes at 350° F, and compression molded into 8 to 10 mil films, which were completely transparent and devoid of color.
- the film was tough, strong, elongateable, and tear resistant.
- the percent lactone content was 17.0 percent by TGA.
- Tensile data are shown in Table 2. The properties are approximately those found for crystalline polypropylene used in molding and packaging applications.
- Example 2 The same cellulose acetate (powder) as used in Example 2, 55 parts by weight, was intimately stirred with 45 parts of granular, pure, glycolide, a 6- membered ring, cyclic dilactone. The mixture easily fused on the mill roll at 350° F and compression molded to clear, colorless films. The films turned hazy at the surface upon handling, which indicated a trace amount of the glycolide had bloomed to the surface. The percent glycolide by TGA was 22.3 percent. Tensile properties are shown in Table 2 and are approximately similar to those encountered with low- density polyethylene.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5500278A JPH06507929A (en) | 1991-05-21 | 1992-05-20 | Degradable cellulose polymer |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70340191A | 1991-05-21 | 1991-05-21 | |
US703,401 | 1991-05-21 | ||
US87635692A | 1992-04-30 | 1992-04-30 | |
US876,356 | 1992-04-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992020738A1 true WO1992020738A1 (en) | 1992-11-26 |
Family
ID=27107133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/004243 WO1992020738A1 (en) | 1991-05-21 | 1992-05-20 | Degradable cellulose polymers |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0586575A1 (en) |
JP (1) | JPH06507929A (en) |
AU (1) | AU2144492A (en) |
CA (1) | CA2109618A1 (en) |
WO (1) | WO1992020738A1 (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994010238A1 (en) * | 1992-10-26 | 1994-05-11 | Eastman Kodak Company | Method for increasing the biodegradability of cellulose esters |
EP0597478A1 (en) * | 1992-11-13 | 1994-05-18 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article produced from the same |
DE4325352C1 (en) * | 1993-07-28 | 1994-09-01 | Rhodia Ag Rhone Poulenc | Plasticised cellulose acetate, process for the preparation thereof, and the use thereof for the production of filaments |
WO1994028061A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Polyester composition |
WO1994028062A1 (en) * | 1993-05-28 | 1994-12-08 | Eastman Chemical Company | Cellulose ester blends |
US5639865A (en) * | 1994-02-16 | 1997-06-17 | Wolff Walsrode Aktiengesellschaft | Thermoplastic biodegradable polysaccharide derivatives, process for the manufacture thereof and use thereof |
US6770658B2 (en) | 1998-09-09 | 2004-08-03 | Inflazyme Pharmaceuticals Ltd. | Substituted γ-phenyl-Δ-lactams and uses related thereto |
US7517924B1 (en) * | 1992-10-07 | 2009-04-14 | Japan Corn Starch Co., Ltd. | Starch ester blends with linear polyesters |
WO2010043293A1 (en) * | 2008-10-14 | 2010-04-22 | Rhodia Acetow Gmbh | Biodegradable plastic and use thereof |
EP2230953A1 (en) * | 2007-12-17 | 2010-09-29 | Celanese Acetate LLC | Degradable cigarette filter |
US8227059B2 (en) | 2007-07-26 | 2012-07-24 | Alcare Co., Ltd. | Water-disintegrable sheet and pouch made of the same for excreta-holding wear |
WO2015172101A1 (en) * | 2010-10-20 | 2015-11-12 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications |
WO2016040434A1 (en) * | 2014-09-09 | 2016-03-17 | Celanese Acetate Llc | Cellulose ester plastics and methods and articles relating thereto |
US9320601B2 (en) | 2011-10-20 | 2016-04-26 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants |
US10010609B2 (en) | 2013-05-23 | 2018-07-03 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants |
US10525169B2 (en) | 2010-10-20 | 2020-01-07 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications |
US10857261B2 (en) | 2010-10-20 | 2020-12-08 | 206 Ortho, Inc. | Implantable polymer for bone and vascular lesions |
US11058796B2 (en) | 2010-10-20 | 2021-07-13 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications |
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US11291483B2 (en) | 2010-10-20 | 2022-04-05 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants |
US11484627B2 (en) | 2010-10-20 | 2022-11-01 | 206 Ortho, Inc. | Method and apparatus for treating bone fractures, and/or for fortifying and/or augmenting bone, including the provision and use of composite implants, and novel composite structures which may be used for medical and non-medical applications |
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1992
- 1992-05-20 CA CA 2109618 patent/CA2109618A1/en not_active Abandoned
- 1992-05-20 AU AU21444/92A patent/AU2144492A/en not_active Abandoned
- 1992-05-20 EP EP19920913240 patent/EP0586575A1/en not_active Withdrawn
- 1992-05-20 JP JP5500278A patent/JPH06507929A/en active Pending
- 1992-05-20 WO PCT/US1992/004243 patent/WO1992020738A1/en not_active Application Discontinuation
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US7517924B1 (en) * | 1992-10-07 | 2009-04-14 | Japan Corn Starch Co., Ltd. | Starch ester blends with linear polyesters |
WO1994010238A1 (en) * | 1992-10-26 | 1994-05-11 | Eastman Kodak Company | Method for increasing the biodegradability of cellulose esters |
US5609677A (en) * | 1992-11-13 | 1997-03-11 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article |
EP0597478A1 (en) * | 1992-11-13 | 1994-05-18 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article produced from the same |
US5720803A (en) * | 1992-11-13 | 1998-02-24 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article |
EP0792913A3 (en) * | 1992-11-13 | 1997-09-24 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article |
EP0792913A2 (en) * | 1992-11-13 | 1997-09-03 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article |
US5478386A (en) * | 1992-11-13 | 1995-12-26 | Daicel Chemical Industries, Ltd. | Biodegradable cellulose ester composition and article |
WO1994028062A1 (en) * | 1993-05-28 | 1994-12-08 | Eastman Chemical Company | Cellulose ester blends |
US5594068A (en) * | 1993-05-28 | 1997-01-14 | Eastman Chemical Company | Cellulose ester blends |
US6313202B1 (en) | 1993-05-28 | 2001-11-06 | Eastman Chemical Company | Cellulose ester blends |
WO1994028061A1 (en) * | 1993-06-02 | 1994-12-08 | Zeneca Limited | Polyester composition |
US5753782A (en) * | 1993-06-02 | 1998-05-19 | Zeneca Limited | Polyester composition |
EP0636649A3 (en) * | 1993-07-28 | 1995-10-25 | Rhodia Ag Rhone Poulenc | Plasticised cellulose acetate, process for obtaining the same and its use in the production of filaments. |
EP0636649A2 (en) * | 1993-07-28 | 1995-02-01 | Rhone-Poulenc Rhodia Aktiengesellschaft | Plasticised cellulose acetate, process for obtaining the same and its use in the production of filaments |
DE4325352C1 (en) * | 1993-07-28 | 1994-09-01 | Rhodia Ag Rhone Poulenc | Plasticised cellulose acetate, process for the preparation thereof, and the use thereof for the production of filaments |
US5639865A (en) * | 1994-02-16 | 1997-06-17 | Wolff Walsrode Aktiengesellschaft | Thermoplastic biodegradable polysaccharide derivatives, process for the manufacture thereof and use thereof |
US6770658B2 (en) | 1998-09-09 | 2004-08-03 | Inflazyme Pharmaceuticals Ltd. | Substituted γ-phenyl-Δ-lactams and uses related thereto |
US8227059B2 (en) | 2007-07-26 | 2012-07-24 | Alcare Co., Ltd. | Water-disintegrable sheet and pouch made of the same for excreta-holding wear |
EP2230953A1 (en) * | 2007-12-17 | 2010-09-29 | Celanese Acetate LLC | Degradable cigarette filter |
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US9155335B2 (en) | 2007-12-17 | 2015-10-13 | Celanese Acetate Llc | Degradable cigarette filter |
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US9010338B2 (en) | 2008-10-14 | 2015-04-21 | Solvay Acetow Gmbh | Biodegradable plastic and use thereof |
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Also Published As
Publication number | Publication date |
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CA2109618A1 (en) | 1992-11-26 |
JPH06507929A (en) | 1994-09-08 |
EP0586575A1 (en) | 1994-03-16 |
AU2144492A (en) | 1992-12-30 |
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