US2144202A - Saponifying cellulose esters - Google Patents
Saponifying cellulose esters Download PDFInfo
- Publication number
- US2144202A US2144202A US17339A US1733935A US2144202A US 2144202 A US2144202 A US 2144202A US 17339 A US17339 A US 17339A US 1733935 A US1733935 A US 1733935A US 2144202 A US2144202 A US 2144202A
- Authority
- US
- United States
- Prior art keywords
- saponifying
- cellulose
- cellulose esters
- cellulose acetate
- grams
- 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.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title description 12
- 229920002301 cellulose acetate Polymers 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 229920002955 Art silk Polymers 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- AOSQFFSSIMTDFC-UHFFFAOYSA-N diethyl(13-phenyltridecyl)azanium;chloride Chemical compound [Cl-].CC[NH+](CC)CCCCCCCCCCCCCC1=CC=CC=C1 AOSQFFSSIMTDFC-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- RPXCBLQYHSHERM-UHFFFAOYSA-M dodecyl(trimethyl)azanium;thiocyanate Chemical compound [S-]C#N.CCCCCCCCCCCC[N+](C)(C)C RPXCBLQYHSHERM-UHFFFAOYSA-M 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- RJAVVKVGAZUUIE-UHFFFAOYSA-N stibanylidynephosphane Chemical compound [Sb]#P RJAVVKVGAZUUIE-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
- D06M11/385—Saponification of cellulose-acetate
Definitions
- My present invention relates to a process of saponifying shaped articles of cellulose esters.
- One of its objects is an improved process of saponifying shaped articles of cellulose esters.
- alkali tri-sodiumphosphate, sodium silicate or potassium carbonateas the efllcient agent
- Such compounds enter, into consideration which contain organic radicals having an Dodecyltrimethylammoniumbromide, octadec-' enyltrimethylammoniummethosulfate, dodecylpyridiniumsulfate, dietliylbengyldodecylammoniumchloride, the product of addition fromfdi- 30 methylsulfate and naphthalinsulfo-N-hvdroxyethyl-Nf -dimethyl+ 1.3 -propylenediamine, p-methoxyphenylacetophenoneu -trimethylammonium bromide, products of all'wlation.
- organic radicals having an Dodecyltrimethylammoniumbromide, octadec-' enyltrimethylammoniummethosulfate, dodecylpyridiniumsulfate, dietliylbengyldodecylammoniumchloride, the
- tertiary bases from aniinoalcohols or polyamines such as of 35 dimethylaminoethanol or as dimethylethylenediamine with allwlene oxides.
- the alkylene oxides react in this case by forming a polyglycol ether chain.
- the tertiary amines which result primarily from this reaction and which are sub- 0 stituted with the said polyglycol ether chain. are transformed into quaternary products by the addition of alkyl esters of inorganic or mixed organic-inorganic acids.
- the process is for instance applicable for the 46 superficial "saponiflcation of films from cellulose acetate or nitrocellulose, for the superficial sa- DOniflcation of mixed fabrics from threads of cellulose and cellulose acetate .silk for thepur- I solution of sodium hydroxide with the addition 50 directly dyeing cotton dyes for discharge printpose of applying a common ground color with sing, for the regular or irregular 'saponification of the moving thread of cellulose acetate silk," for instance, during its manufacture, for primsuch fabrics with color pastes whereby a local saponification shall take place, for instance, in directly printing mixed fabrics from. artificial silk of cellulose acetate and viscose with directly dyeing cotton dyes.
- the compounds which accelerate saponiflcation are brought to action simultaneously with the saponifying agent; they may be applied before saponification locally or uniformly, if required in the presence of a swelling agent, and the saponiilcation may be performed ina separate operation eventually even after an intercalated drying operation.
- the quantity of onium base to be .applied may vary' within wide limits. In the first instance it is dependent on the method of operation and especially on the proportion of material to treating liquid. When applying an aqueous saponi-- flcation liquid an addition of 0.5-3 grams of onlum base per liter'may be sufficient.
- Example 1 --'A fabric of cellulose acetate silk is 'saponified for 1 hour at 60 C. with a solution of sodium hydroxide containing 3 grams the quaternary ammonium salt the saponiilca-- tionprogresses much slower and the dyeing is lighter and less uniform.
- Example 2. A web of cellulose acetate silk is 'saponifled with a 1 .01 3 grams of p-ethoxyacetanilide-o-trimethylammonium bromide per liter for one hour at 50 C. The proportion of material to treating liquid is 1:70. Thesaponiflcation has progressed further than in a treatment under the same conditions but without the addition. 7
- Example 3 The operation is as described in Example 1, but the dodecyltrimethylammoniumbromide is replaced by 1 gram of diethylbenzyldodecylammoniumchloride. There is produced a stronger saponiiication than when saponifying under the same conditions but without the addition.
- Example 4. Cellulose acetate silk is treated at the spinning machine on its waytothe winding de-- vice with an aqueous solution containing per liter 30 grams of trimethyldodecylammoniumbrcmide and 30 grams of methylglycol.
- the dried threads are twisted together with similar threads, however, which have been treated with olive oil.
- the threads which should resist saponiflcation, for instance, in printing with alkaline pastes may be treated with resisting agents, for instance, with cresolsulfonic sodium, preferably in the presence of a protective colloid insoluble, under the conditions of saponiilcation, for in- 5 stance, methylcellulose.
- Example 5 A crape fabric from viscose and cellulose acetate silk is treated with a liquid containing 80 grams of sodium carbonate and 5 grams of dodecyltrimethylammoniumchloride per so liter for 15 minutes at 55 C.
- the uniformly saponifled piece can be dyed intensely with directly dyeing dyes which-are capable ofebeing etched, for instance, Cotonerol A (Schultz l 'arb-- stoiftabelien, 7th edition, Vol. II, page 64). when 35 suitably selecting the dyes the dyeing can easily be etched to a pure white. The acetate character of the fabric will be conserved.
- the content of acetic acid of the cellulose acetate has been reduced from 54.7% to 46.4% in the present instance, whereas in the case of saponifying' without the addition of. dodecyltrimethylammoniumchioride the content of acetic acid has been reduced to only 52.35%. The same effect is obtained with a reduced addition of onium base but operating at a higher temperature.
- Ezample'd-A cellulose acetate satin is printed with a printing paste consisting of 100 grams of dodecyltrimethylammoniumthiocyanate, 320 parts of water, 80 parts of potassium carbonate and m 500 parts of tragacanth 60:1000, and subjected for 20 minutes to the action of steam. After nsing the printed parts are intensely dyed by Direct Black AT (Schultz Farbstoiftabellen, 7th edition, suppl. vol. page 88) (6%). when operating in the same manner but without the addition of trimethyldodecylammoniumchloride the dyeings will be considerably weaker. i
- pEza'mple 7 A knit fabric from'cellulose acetateis saponiiied in the manner described in Example 5 by means of sodium carbonate whereby the dodecyltrimethylammoniumchlorlde is replaced by 3 grams of metbylethylcetyl-sulfoniummethosulfate.
- the dyeing can be provided with a white etching or color etching.
- Example 8- -Tbe operation is described in Example '1 however, the methylethylcetyl-sulfonium-methosulfate is replaced by the equivalent amount of cetyltrimethylphosphoniumiodide.
- Example 9 A spinning solution containing 20 parts of cellulose acetate with a content of 54% of acetic acid, 2.5 parts of dodecyltrimethylammoniumchloride and 77 .5 parts of acetone is spun to artificial threads according to the dry spinning system.
- the threads thus obtained are more quickly saponified by sodium hydroxide or alkali carbonate than are similar threads without the addition of onium base.
- The'term organic onium base used in the specification and the claims is intended to include'such bases which as to their strength are equal or approximately equal to that of the alkalies. This, as known from literature, holds true for bases containing pentavalent sulfur, pentavalent phosphorus, pentavalent arsenic or pentavalent antimony.
- a method of saponifying shaped articles made from cellulose esters which comprises performing the saponiflcation with a solution of aninorganic alkali in the presence of the prodnot of addition from dimethylsulfate and naphthalinsulfo -N-hydroxyethyl-N' -dimethyl- 1.3-propylenediamine.
- a process of saponifying shaped articles from cellulose esters which comprises performing the saponiiication with an aqueous medium containing inorganic alkali;-and an organic onium compound, capillary active and soluble in said medium.
- a process of saponifying shaped articles from cellulose esters which comprises performing the sapcniflcation with an aqueous medium containing inorganic alkali and an organic pentavalent ammonium compound, capillary active and soluble in said medium.
- a process of saponifying artificial fibrous material from cellulose esters which comprises performing the saponiflcation with an aqueous medium containing inorganic alkali and an organic pentavalent ammonium compound soluble and capillary active in said medium and containing in its molecule an aliphatic carbon chain of from 12 to'16 carbon atoms.
- a process which comprises saponifying cellulose acetate artificial silk with an aqueous solution of sodium hydroxide containing dodecyltrimethyl-ammonium bromide.
- a process which comprises saponifying artiflcial silk from cellulose'acetate by immersing said material in a solution containing trimethyldod ecyl-ammoniur n bromide, and treating the inaterial with an aqueous alkaline saponifying agent.
- a process which comprises saponifying artiiiciai fibrous material from cellulose acetate with an aqueous solution of an inorganic alkalian alkylene oxide, said product being alkylated 'by means of, a reactive alkyl ester to yield a quaternary ammonium compound.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patented Jan. 17, 1939 UNITED "STATES PATENT oer-ice saromr' zn'we onnwnosn nsmns Paul Berlin-Lichtenberg, Germany, asv,signor'to I. G. Farbenindustrle Aktiengeaellschai't, Frankfort-omthe-Maln, Germany No Drawing. ApplicationApril 19, 1935, Serial No. 17,339. In Germany April 21, 1934 'ICIaims.
My present invention relates to a process of saponifying shaped articles of cellulose esters.
One of its objects is an improved process of saponifying shaped articles of cellulose esters.
,5 Further objects will be seen from the detailed specification following hereafter.
I have found that the alkaline saponification o1 shaped articles from cellulose esters, for instance, of artificial silk from cellulose acetate,
l can be considerably accelerated, if there is added to the alkaline treating liquid,.padding solutions or printing pastes which may contain caustic,
alkali, tri-sodiumphosphate, sodium silicate or potassium carbonateas the efllcient agent, an
3 organic onium. base containing pentavalent nitrogen, phosphorus antimony, arsenic or tetravalent sulfur or the salts. of these bases.
Especially such compounds enter, into consideration which contain organic radicals having an Dodecyltrimethylammoniumbromide, octadec-' enyltrimethylammoniummethosulfate, dodecylpyridiniumsulfate, dietliylbengyldodecylammoniumchloride, the product of addition fromfdi- 30 methylsulfate and naphthalinsulfo-N-hvdroxyethyl-Nf -dimethyl+ 1.3 -propylenediamine, p-methoxyphenylacetophenoneu -trimethylammonium bromide, products of all'wlation. of tertiary bases from aniinoalcohols or polyamines such as of 35 dimethylaminoethanol or as dimethylethylenediamine with allwlene oxides. The alkylene oxides react in this case by forming a polyglycol ether chain. The tertiary amines which result primarily from this reaction and which are sub- 0 stituted with the said polyglycol ether chain. are transformed into quaternary products by the addition of alkyl esters of inorganic or mixed organic-inorganic acids.
The process is for instance applicable for the 46 superficial "saponiflcation of films from cellulose acetate or nitrocellulose, for the superficial sa- DOniflcation of mixed fabrics from threads of cellulose and cellulose acetate .silk for thepur- I solution of sodium hydroxide with the addition 50 directly dyeing cotton dyes for discharge printpose of applying a common ground color with sing, for the regular or irregular 'saponification of the moving thread of cellulose acetate silk," for instance, during its manufacture, for primsuch fabrics with color pastes whereby a local saponification shall take place, for instance, in directly printing mixed fabrics from. artificial silk of cellulose acetate and viscose with directly dyeing cotton dyes.
It is also possible to print fabrics with an alkaline saponifying .liquid and to dye them later with dyes dyeing regenerated cellulose or cellulose hydrate directly. Simultaneously the nonsaponifled parts of the'fabric may be dyed with the special dyes which enter into consideration.
It is not'necessary that the compounds which accelerate saponiflcation are brought to action simultaneously with the saponifying agent; they may be applied before saponification locally or uniformly, if required in the presence of a swelling agent, and the saponiilcation may be performed ina separate operation eventually even after an intercalated drying operation.
The quantity of onium base to be .applied may vary' within wide limits. In the first instance it is dependent on the method of operation and especially on the proportion of material to treating liquid. When applying an aqueous saponi-- flcation liquid an addition of 0.5-3 grams of onlum base per liter'may be sufficient.
The following examples serve to illustrate th invention:
Example 1.--'A fabric of cellulose acetate silk is 'saponified for 1 hour at 60 C. with a solution of sodium hydroxide containing 3 grams the quaternary ammonium salt the saponiilca-- tionprogresses much slower and the dyeing is lighter and less uniform. f V 1 Example 2.A web of cellulose acetate silk is 'saponifled with a 1 .01 3 grams of p-ethoxyacetanilide-o-trimethylammonium bromide per liter for one hour at 50 C. The proportion of material to treating liquid is 1:70. Thesaponiflcation has progressed further than in a treatment under the same conditions but without the addition. 7
Example 3.-The operation is as described in Example 1, but the dodecyltrimethylammoniumbromide is replaced by 1 gram of diethylbenzyldodecylammoniumchloride. There is produced a stronger saponiiication than when saponifying under the same conditions but without the addition.
Example 4..-Cellulose acetate silk is treated at the spinning machine on its waytothe winding de-- vice with an aqueous solution containing per liter 30 grams of trimethyldodecylammoniumbrcmide and 30 grams of methylglycol. The dried threads are twisted together with similar threads, however, which have been treated with olive oil.
Afterthe yarn obtained has been made into a fabric the latter is treated with a saponifying agent. After dyeing with directly dyeing dyes powerful eifects are produced.
The threads which should resist saponiflcation, for instance, in printing with alkaline pastes may be treated with resisting agents, for instance, with cresolsulfonic sodium, preferably in the presence of a protective colloid insoluble, under the conditions of saponiilcation, for in- 5 stance, methylcellulose.
Example 5.-A crape fabric from viscose and cellulose acetate silk is treated with a liquid containing 80 grams of sodium carbonate and 5 grams of dodecyltrimethylammoniumchloride per so liter for 15 minutes at 55 C. The uniformly saponifled piece can be dyed intensely with directly dyeing dyes which-are capable ofebeing etched, for instance, Cotonerol A (Schultz l 'arb-- stoiftabelien, 7th edition, Vol. II, page 64). when 35 suitably selecting the dyes the dyeing can easily be etched to a pure white. The acetate character of the fabric will be conserved.
The content of acetic acid of the cellulose acetate has been reduced from 54.7% to 46.4% in the present instance, whereas in the case of saponifying' without the addition of. dodecyltrimethylammoniumchioride the content of acetic acid has been reduced to only 52.35%. The same effect is obtained with a reduced addition of onium base but operating at a higher temperature.
Ezample'd-A cellulose acetate satin is printed with a printing paste consisting of 100 grams of dodecyltrimethylammoniumthiocyanate, 320 parts of water, 80 parts of potassium carbonate and m 500 parts of tragacanth 60:1000, and subjected for 20 minutes to the action of steam. After nsing the printed parts are intensely dyed by Direct Black AT (Schultz Farbstoiftabellen, 7th edition, suppl. vol. page 88) (6%). when operating in the same manner but without the addition of trimethyldodecylammoniumchloride the dyeings will be considerably weaker. i
pEza'mple 7.A knit fabric from'cellulose acetateis saponiiied in the manner described in Example 5 by means of sodium carbonate whereby the dodecyltrimethylammoniumchlorlde is replaced by 3 grams of metbylethylcetyl-sulfoniummethosulfate. The aaponifying trea; nt lasts minutes at 55 to so c.; the mate al is dyed with 3% of Sirius rum: Green as (smarts Farbstoii'tabellen, 7th edition, suppl. vol. page 131).
The dyeing can be provided with a white etching or color etching.
Example 8.- -Tbe operation is described in Example '1 however, the methylethylcetyl-sulfonium-methosulfate is replaced by the equivalent amount of cetyltrimethylphosphoniumiodide.
Example 9.A spinning solution containing 20 parts of cellulose acetate with a content of 54% of acetic acid, 2.5 parts of dodecyltrimethylammoniumchloride and 77 .5 parts of acetone is spun to artificial threads according to the dry spinning system. The threads thus obtained are more quickly saponified by sodium hydroxide or alkali carbonate than are similar threads without the addition of onium base.
The'term organic onium base used in the specification and the claims is intended to include'such bases which as to their strength are equal or approximately equal to that of the alkalies. This, as known from literature, holds true for bases containing pentavalent sulfur, pentavalent phosphorus, pentavalent arsenic or pentavalent antimony.
What I claim is:
1. A method of saponifying shaped articles made from cellulose esters which comprises performing the saponiflcation with a solution of aninorganic alkali in the presence of the prodnot of addition from dimethylsulfate and naphthalinsulfo -N-hydroxyethyl-N' -dimethyl- 1.3-propylenediamine.
2. A process of saponifying shaped articles from cellulose esters, which comprises performing the saponiiication with an aqueous medium containing inorganic alkali;-and an organic onium compound, capillary active and soluble in said medium.
3. A process of saponifying shaped articles from cellulose esters, which comprises performing the sapcniflcation with an aqueous medium containing inorganic alkali and an organic pentavalent ammonium compound, capillary active and soluble in said medium.
4. A process of saponifying artificial fibrous material from cellulose esters which comprises performing the saponiflcation with an aqueous medium containing inorganic alkali and an organic pentavalent ammonium compound soluble and capillary active in said medium and containing in its molecule an aliphatic carbon chain of from 12 to'16 carbon atoms.
5. A process which comprises saponifying cellulose acetate artificial silk with an aqueous solution of sodium hydroxide containing dodecyltrimethyl-ammonium bromide.
6. A process which comprises saponifying artiflcial silk from cellulose'acetate by immersing said material in a solution containing trimethyldod ecyl-ammoniur n bromide, and treating the inaterial with an aqueous alkaline saponifying agent.
7. A process which comprises saponifying artiiiciai fibrous material from cellulose acetate with an aqueous solution of an inorganic alkalian alkylene oxide, said product being alkylated 'by means of, a reactive alkyl ester to yield a quaternary ammonium compound.
"PAUL. scnriacx.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE455622X | 1934-04-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2144202A true US2144202A (en) | 1939-01-17 |
Family
ID=6539065
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US17339A Expired - Lifetime US2144202A (en) | 1934-04-21 | 1935-04-19 | Saponifying cellulose esters |
| US163741A Expired - Lifetime US2208857A (en) | 1934-04-21 | 1937-09-14 | Process of saponifying textile materials |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US163741A Expired - Lifetime US2208857A (en) | 1934-04-21 | 1937-09-14 | Process of saponifying textile materials |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US2144202A (en) |
| FR (1) | FR788985A (en) |
| GB (1) | GB455622A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2581832A (en) * | 1947-09-05 | 1952-01-08 | Du Pont | Heterogeneous, basic hydrolysis of carboxylic acid esters of polyvinyl alcohol with quaternary ammonium bases |
| US3414644A (en) * | 1965-01-04 | 1968-12-03 | Celanese Corp | Method for spinning bicomponent cellulose esters |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2427126A (en) * | 1941-10-24 | 1947-09-09 | Bonard Claude | Production of textiles and other articles having a basis of a polyvinyl compound |
| US2423643A (en) * | 1943-04-22 | 1947-07-08 | American Cyanamid Co | Condensation products of guanylurea with alkylene oxides |
| US2426912A (en) * | 1944-04-26 | 1947-09-02 | Gen Electric | Process of hydrolyzing dimethyldihalogenosilanes |
| US2481388A (en) * | 1945-08-24 | 1949-09-06 | Du Pont | Hydrolysis of polyvinyl esters |
| US2622075A (en) * | 1946-12-03 | 1952-12-16 | Sandoz Ltd | Polyamine-cyanamide resins |
| NL91282C (en) * | 1955-02-21 | |||
| US3140231A (en) * | 1961-08-14 | 1964-07-07 | Rohm & Haas | T-octylguanidines as antihypertensive agents |
-
1935
- 1935-04-18 FR FR788985D patent/FR788985A/en not_active Expired
- 1935-04-19 US US17339A patent/US2144202A/en not_active Expired - Lifetime
- 1935-04-23 GB GB12186/35A patent/GB455622A/en not_active Expired
-
1937
- 1937-09-14 US US163741A patent/US2208857A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2581832A (en) * | 1947-09-05 | 1952-01-08 | Du Pont | Heterogeneous, basic hydrolysis of carboxylic acid esters of polyvinyl alcohol with quaternary ammonium bases |
| US3414644A (en) * | 1965-01-04 | 1968-12-03 | Celanese Corp | Method for spinning bicomponent cellulose esters |
Also Published As
| Publication number | Publication date |
|---|---|
| US2208857A (en) | 1940-07-23 |
| FR788985A (en) | 1935-10-21 |
| GB455622A (en) | 1936-10-23 |
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