US2017171A - Preparation of moisture resistant thread - Google Patents
Preparation of moisture resistant thread Download PDFInfo
- Publication number
- US2017171A US2017171A US624149A US62414932A US2017171A US 2017171 A US2017171 A US 2017171A US 624149 A US624149 A US 624149A US 62414932 A US62414932 A US 62414932A US 2017171 A US2017171 A US 2017171A
- Authority
- US
- United States
- Prior art keywords
- thread
- cellulose
- preparing
- electrical insulation
- bath
- 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
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- 238000000034 method Methods 0.000 description 24
- 229920002678 cellulose Polymers 0.000 description 22
- 239000001913 cellulose Substances 0.000 description 21
- 238000010292 electrical insulation Methods 0.000 description 19
- 239000004014 plasticizer Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000397 acetylating effect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QOVYKRHZCJGNIA-UHFFFAOYSA-N (4-methylphenyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(C)C=C1 QOVYKRHZCJGNIA-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical class CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- -1 fatty acid compounds Chemical class 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Patented Oct. 15, 1935 PREPARATION OF MOISTURE RESISTANT THREAD Cyril J. Stand and Russel H. Van Dyke, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New York I No Drawing. Application July 22, 1932, Serial No. 624,149
17 Claims.
The present invention relates to a process of preparing moisture resistant thread by treating it with an acetylation bath containing a non-esterifiable plasticizer.
a It is known to treat cotton yarn with a mixture of acetic anhydrid, acetic acid and a catalyst such as zinc chloride to produce dye resistant effect threads for use in fabrics to produce various effects due to the fact that those threads will resist dyes which other threads of the fabric are susceptible to. Maximum moisture resistance in those effect threads was of little importance as the main concern was to acetylate the threads only to impart dye-resistant properties thereto.
The electrical industry has been in need of thread, for insulation purposes, characterized by high electrical insulating ability, 10w moisture absorption, high tensile strength and low inflammability. Obviously the last characteristic desired would exclude thread of the nitrocellulose type. We therefore directed our attention to the use of a thread of cellulose which had been acetylated. It is known that cellulose triacetate has a much lower moisture absorption value than that of una'cetylated cellulose and that its value for electrical insulation is much higher. However we found that when we attempted to acetylate thread to the triacetate or nearly so, the resulting thread was so weak as to lack utility for insulation purposes. On the other hand when the thread was only partially acetylated so that the tensile strength would not be unduly decreased, the moisture absorption was not lowered as much as might be desired. One object of our invention is to provide a process of preparing threads suitable for electrical insulation purposes which threads are satisfactory as to insulating value, moisture resistance, tensile strength and inflammability. Another object of our invention is to provide a process. of preparing threads, for electrical insulation purposes which is'simple in that it involves merely the step of treating the thread with an acetylating bath. Other objects will hereinafter appear.
We have found that a cotton thread may be subjected toan acetylating treatment and still exhibit both high tensile strength and low moisture absorption. We have found that a thread eminently suited for electrical insulation pur- (ops-20) poses may be prepared by treating a cotton thread with an acetylating bath containing a non-esterifiable plasticizer. We have found that if a small amount of some one of the non-esterifiable plasticizers frequently employed to plasti- 5 cize cellulose acetate is added to the acetylation mixture used in the acetylation of thread, that the resulting thread has a moisture absorption which is 60-70% lower than that of the original thread and 25-30% lower than that of a thread 10 acetylated in the absence of a plasticizer under conditions by which it will not lose its tensile strength.
The following examples illustrate the application of our invention in the preparation of par- 15 tially acetylated thread and are not for the purpose of limiting the scope of our invention.
' Ezvample I sulfuric and phosphoric acids such as disclosed in 30 Gray & Staud U. S. Patent No. 1,683,347) and 5 lbs. of triphenyl phosphate. The temperature of the mass was raised from 20 to 40 C. over a period of 2 hours and it was then maintained at 40 for 4 hours. The thread was separated from 35 the reaction bath and washed to neutrality using only water. The thread obtained was analyzed for acetyl and plasticizer content and for tensile strength and moisture absorption with the following results: 40
Acetyl content 27.7 Triphenyl phosphate 10.18% Tensile strength 330 gms. Moisture absorption 2.34%
at 55% relative humidity.
When some of the same kind of unbleached thread was acetylated in the same manner as in the above example except that no plasticizer was employed in the bath, the thread obtained tested as follows:
Acetyl content 27.7%
Tensile strength 340 gms.
Moisture absorption 4.05% at 55% relative humidity.
The original unacetylated thread which was employed in the example was tested in the same manner with the following results:
Acetyl content 0% Tensile strength 300 gms.
Moisture absorption 5.89% at 59% relative humidity.
Thus it may be seen that in the three samples tested that one prepared by the process of our invention only exhibited that happy combination of high moisture resistance coupled with high tensile strength.
Example II An unbleached cotton thread such as employed in the preceding example was acetylated in the same manner as in that example except that tricresyl phosphate was substituted in like amount for triphenyl phosphate. The resulting product tested as follows:
Acetyl content 29.1% Tricresyl phosphate 8.6% Tensile strength 380 gms. Moisture absorption 2.5%
at 55% relative humidity.
Example III Example I was repeated except that diethyl phthalate was substituted in like amount for triphenyl phosphate. The thread prepared by this example tested as follows:
Acetyl content 29.6 Diethyl phthala'te 4.50% Tensile strength 345 grams Moisture absorption 2.58%
at 55% relative humidity.
Example IV Example I was repeated except that o-cresyl ptoluene sulfonate was substituted in like amount for the triphenyl phosphate. The following data on the resulting product were obtained:
Acetyl content 30.8% O-cresyl p-toluene sulfonate 9.13%. Tensile strength 310 grams Moisture absorption 2.89%
at 55% relative humidity.
The term fibrous esterifying bath is to be understood as referring to an esteriflcation bath which is a non-solvent of the cellulose ester which is formed therein.
Example V About 10 lbs. of unbleached cotton thread was pretreated for 16 hours at 20-25 C. with 70 lbs. of glacial acetic acid. The mass was then Dressed down to lbs. and a mixture of 26 lbs. of acetic anhydrid (99%) about a lb. of a catalyst such as employed in Example I, 42 lbs. of henzene and 5 lbs. of diphenyl phthalate was added thereto. The temperature of the mass was raised from 20 to 40 C. over a. period of 2 hours and was maintained at 40 for about 4 hours. The thread was removed and washed to neutrality with water. The following data were obtained on this sample:
Acetyl content 26.9% Diphenyl phthalate 9.53% 5 Tensile strength 360 grams Moisture absorption 2.14%
at 67% relative humidity.
The examples given are obviously fibrous esteriiication processes so that other suitable nonsolvents of cellulose acetate such as ether, benzine, toluene, etc. may be employed as diluents in the thread esterification processes. Also in stead of the phosphoric-sulfuric acid catalyst employed, other wellknown esterification catalysts may be employed in the carrying out of our invention. Also other fatty acid compounds than acetic may be employed in the process of preparing moisture-resistant thread according to our invention. For example the acetic anhydrid may be replaced wholly or in part by propionio or butyric anhydrides or a mixture of those anhydrides.
Various other modifications of our process such 25 as are made possible by variations in materials, time, temperature, proportions or other conditions of a technical nature are obvious to those skilled in the art and also come within the scope of our invention. For example the cellulose to so be treated instead of being in thread form may be in the form of sheets, strips or some other desired physical form.
We claim as our invention:
1. The process of preparing an acylated cellu- 2. The process of preparing an acetylated 081- 40 lulose suitable for electrical insulation which comprises treating the cellulose with an esterifying bath comprising an acetic acid anhydrid in the presence of a non-esterifiable plasticizer.
3. The process of preparing an acetylated cellulose thread suitable for electrical insulation which comprises treating the thread with an esterifying bath comprising an acetic acid anhydrid in the presence of a non-esterifiable plasticizer.
4. The process of preparing an acylated cellulose suitable for electrical insulation which comprises treating the cellulose with a fibrous esterifying bath comprising a lower fatty acid anhydrid in the presence of a non-esterifiable plasticizer.
5. The process of preparing an acylated ce1- lulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising a lower fatty acid anhydrid in the presence of a non-esterifiable plasticizer.
6. The process of preparing an acetylated cellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous 05 esterifying bath comprising acetic anhydrid in the presence of a non-esterifiable plasticizer.
7 The process of preparing an acylated cellulose thread suitable for electrical insulation which comprises treating the thread with an esterl. ying bath comprising a lower fatty acid anhydrid in the presence of a triaryl phosphate.
8. The process of preparing an acetylated cellulose suitable for electrical insulation which comprises treating the cellulose with an esterifying 76 bath comprising acetic anhydrid in the presence of a triaryl phosphate.
9. The process of preparing an acylated cellulose thread suitable for electrical insulation which comprises treating the thread with an esterifying bath comprising a lower fatty acid anhydrid in the presence of triphenyl phosphate.
10. The process of preparing an acetylated cellulose suitable for electrical insulation which comprises treating the cellulose with an esterifying bath comprising acetic anhydrid in the presence 7 of a triphenyl phosphate.
11. The process of preparing an acylated cellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising a lower fatty acid anhydrid, and a diluent in the presence of a nonesterifiable plasticizer.
12. The process of preparing an acetylated cellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising acetic anhydrid, and a diluent in the presence of a non-esterifiable plasticizer.
13. The process of preparing an acetylated cellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising acetic anhydrid, and a diluent in the presence of a non-esterifiable triaryl phosphate.
14. The process of preparing an acylated cellulose thread suitablefor electrical insulation which comprises treating the thread with a fibrous esterifying bath, comprising a lower fatty acid anhydrid and as a diluent, carbon tetrachloride, in the presence of a non-esterifiable plasticizer.
15. The process of preparing an acetylatedlcellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising acetic anhydrid and as a diluent, carbon tetrachloride, in the presence of a non-esterifiable plasticizer.
16. The process of preparing an acetylated cellulose thread suitable for electrical insulation which comprises treating the thread with a fibrous esterifying bath comprising acetic anhydrid and as a diluent, carbon tetrachloride, in the presence of a triaryl phosphate.
17. The partially acetylated cellulose resulting from the fibrous acetylation of cellulose in the presence of a non-esterifiable plasticizer.
CYRIL J. STAUD. RUSSEL H. VAN DYKE.
CER'i'iFiCRTE OF CGRRECTION,
Patent No. 2,017,172. October 15, 1935.
KJYRKL J. STAUD, ET AL.
It is hereby certified thai error appears in the printed specification of the aimve numbered paient requiring correctien as follows: Page i, seaond mlumn, line 42, far "27.7%" read 34.2%; and that the: said Letters Patent should be read with this correc ion therein that the same may reniorm to the record of the case in the Patent Office.
Signed and sealed this 10th day 0i Desember, A. D. 1935.
Leslie Frazer (Seal) Acting Commissioner oi Patents.
IERTiFiG iTE OF C(JRRECTION.
Patent No. 2,017,171. October 15, 1935.
CYREL J. STAUD, ET AL.
it is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page I, second column, line 42, for "27.7%" read 34.2%; and that the said Letters Patent should be read with this correc ion therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 10th day of December, A. D. 1935.
Leslie Frazer (Seal) Acting Commissioner of Patents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US624149A US2017171A (en) | 1932-07-22 | 1932-07-22 | Preparation of moisture resistant thread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US624149A US2017171A (en) | 1932-07-22 | 1932-07-22 | Preparation of moisture resistant thread |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2017171A true US2017171A (en) | 1935-10-15 |
Family
ID=24500839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US624149A Expired - Lifetime US2017171A (en) | 1932-07-22 | 1932-07-22 | Preparation of moisture resistant thread |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2017171A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799608A (en) * | 1950-07-14 | 1957-07-16 | Int Standard Electric Corp | Electric cables |
-
1932
- 1932-07-22 US US624149A patent/US2017171A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799608A (en) * | 1950-07-14 | 1957-07-16 | Int Standard Electric Corp | Electric cables |
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