US2822297A - Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof - Google Patents
Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof Download PDFInfo
- Publication number
- US2822297A US2822297A US431593A US43159354A US2822297A US 2822297 A US2822297 A US 2822297A US 431593 A US431593 A US 431593A US 43159354 A US43159354 A US 43159354A US 2822297 A US2822297 A US 2822297A
- Authority
- US
- United States
- Prior art keywords
- substituted
- salicylaldoxime
- cellulosic material
- decay
- product
- 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
- 239000000463 material Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 11
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical class O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 title claims description 11
- 239000000460 chlorine Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 239000004744 fabric Substances 0.000 description 13
- 229910052794 bromium Inorganic materials 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000002689 soil Substances 0.000 description 7
- 239000004576 sand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 238000009933 burial Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- IURRXCRWRKQLGC-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 IURRXCRWRKQLGC-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- ROBIUDOANJUDHD-ONNFQVAWSA-N (ne)-n-[(3,4-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C\C1=CC=C(Cl)C(Cl)=C1 ROBIUDOANJUDHD-ONNFQVAWSA-N 0.000 description 1
- ONJQBRVMFRQQIG-WMZJFQQLSA-N (nz)-n-[(2,4-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C/C1=CC=C(Cl)C=C1Cl ONJQBRVMFRQQIG-WMZJFQQLSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- -1 3-nitro-5- chlorosalicylaldoxime Chemical compound 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- ONIQTTDQIOTCLD-UHFFFAOYSA-N n-[(4-chloro-3-nitrophenyl)methylidene]hydroxylamine Chemical compound ON=CC1=CC=C(Cl)C([N+]([O-])=O)=C1 ONIQTTDQIOTCLD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
- B27K3/42—Aromatic compounds nitrated, or nitrated and halogenated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/907—Resistant against plant or animal attack
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]
Definitions
- the present invention relates to the treatment of celluor cellulose-containing materials, for example, cotton,
- hemp, jute, ramie, wood and the like, and the cellulosic material may be in any form suitable for the use intended and may be in the form of separate fibers or in the form of felted or woven fibers.
- substituted salicylaldoximes of the present invention may be used singly or in combination and they have the following structural formula:
- the substituted salicylaldoxime is dissolved in a solvent and cellulosic material impregnated with the solution.
- the solvent may be any inert solvent which does not adversely affect the substituted salicylaldoximes; and ethanol, acetone, dioxane or the like may be used to form the solution which can be readily applied to the cellulosic material and then the material dried to remove the solvent.
- the amount of substituted salicylaldoxime used to impregnate the cellulosic material depends upon a number of factors including the type of cellulosic material being impregnated, the severity of its exposure and the useful life demanded of the material.
- the substituted salicylaldoximes of the present invention may be prepared in any suitable manner.
- the 3,S-dichlorosalicylaldOxime and 3-nitro-5- chlorosalicylaldoxime as well as 3-chloro-S-br0mosa1icylaldoxime and 3-nitro-5-bromosalicylaldoxirne may be prepared by reacting the appropriate aldehyde with hydroxylamine.
- S-chlorosalicylaldehyde may be brominated in glacial acetic acid to give an 83% yield of '3-br0mo-5-chlorosalicylaldehyde which can be reacted with hydroxylamine to produce the corresponding oxime.
- salicylaldehyde may be brominated to form the 3,5-dibromo compound which may be reacted with hydroxylamine to form 3,S-dibromosalicylaldoxime.
- the cellulosic materials may, if desirable under the particular conditions to be encountered, also be treated with other compounds and the only active ingredient need not be the present oximes although the present oximes are highly satisfactory for normal purposes.
- R is selected from the group consisting of Cl, Br, and N and R" is selected from the group consisting of Cl and Br.
- R is selected from the group consisting of Cl, Br,
- N0 and R" is selected from the group consisting of Cl and Br.
- a cellulosic material having decay resistant properties which comprises callulosic material and at least one substituted salicylaldoxime having the following structural formula: 1
- R is selected from the group consisting of Cl, Br, and N0 and R" is selected from the group consisting of Cl and Br.
- a cellulosic material having decay resistant properties which comprises cellulosic fibrous material impregnated with at least one substituted salicylaldox-ime having the following structural formula:
- R is selected from the group consisting of Cl, Br, and N0 and R is selected from the group consisting of Cl and Br.
- a cellulosic material having decay resistant properties which comprises a cellulosic fabric impregnated with from 0.75% to 2.5% by weight of at least one substituted salicylaldoxime having the following structural formula:
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
a Unlted States Patent ice 4,
may be used, however, best results at low cost are obtained 2,822,297 when the cellulose fabric is impregnated With from 0.75%
PROCESS OF PRESERVING CELLULOSIC MATE- RIAL WITH A SUBSTITUTED SALICYLALDOX- IME AND THE PRODUCT THEREOF David X. Klein, Montclair, James P. Scullin, Pompton Lakes, and Adolph J. Deinet, Westwood, N. J., assignors to Heyden Newport Chemical Corporation, New York, N. Y., a corporation of Delaware N 0 Drawing. Application May 21, 1954 Serial No. 431,593
Claims. (Cl. 117-138.5)
The present invention relates to the treatment of celluor cellulose-containing materials, for example, cotton,
hemp, jute, ramie, wood and the like, and the cellulosic material may be in any form suitable for the use intended and may be in the form of separate fibers or in the form of felted or woven fibers.
It is well known that when cellulosic materials are in contact with the soil they tend to rapidly decay or degenerate and this is due, at least partly, to the action of microorganisms in the soil. This problem of decay in soil is particularly acute with sand bags although not confined to this product. While many substances have been suggested for treating sand bags and other cellulosic materials which are exposed to the soil, few, if any of these substances have proven entirely satisfactory, despite the fact that at least some of the substances have had antibacterial and anti-fungal activity when tested in vitro. Copper compounds and especially copper 8-hydroxyquinolinate have been used to protect cellulose fibers against decay but while these compounds do increase the resistance of sand bags to decay, their use is limited as they are quite expensive and they impart an undesirable color to the material.
It has been discovered that when cellulosic material is treated with certain substituted salicylaldoximes, the resistance of the material to decay when exposed to the soil is greatly increased. The substituted salicylaldoximes of the present invention may be used singly or in combination and they have the following structural formula:
RI! R! where R'=Cl, Br or N0 and R"=Cl or Br.
These compounds may be applied to the celulosic material in any suitable manner. In a preferred procedure, the substituted salicylaldoxime is dissolved in a solvent and cellulosic material impregnated with the solution. The solvent may be any inert solvent which does not adversely affect the substituted salicylaldoximes; and ethanol, acetone, dioxane or the like may be used to form the solution which can be readily applied to the cellulosic material and then the material dried to remove the solvent. The amount of substituted salicylaldoxime used to impregnate the cellulosic material depends upon a number of factors including the type of cellulosic material being impregnated, the severity of its exposure and the useful life demanded of the material. Improved results have been obtained with cellulose fabrics impregnated with as little as 0.75 of the compound based on the weight of the fabric. Large amounts of the compound tensile strength of the to 2.5% of the. compounds. Larger or smaller amounts of the compound may be used depending upon the material impregnated and other factors.
The effectiveness of the present compounds in preventing decay, as wellas the ineflectiveness of closely related compounds, isshown in the following table which sets forth the results obtained in a soil burial procedure carried out in accordance with Federal Specification Textile Test Methods, approved May 15, 1951, by the Commissioner Federal Supply Service, General Services Administration, printed by the Government Printing Ofiice. In thisv comparative test, one inch wide strips of 12 oz. duck cloth were impregnated for five minutes in a solution containing the active ingredients in an amount calculated to give the desired concentration on the fiber after drying. The amount used ofthe substituted salicylaldoximes of the present invention were such that 1.25% by weight of the compound was deposited on the fabrics. Similar amounts of the related compounds No. 5-9 were applied to other strips of the same cloth. Strips of this cloth were also treated with copper 8-hydroxyquinolinate in amounts such that'the strips-contained 1.38%-or 0.83% of the compound. These strips, along with strips of untreated cloth were buried in the soil consisting of sand, humus and leaf mold. The strips were removed at the end of the periods indicated in Table I and tested to determine their tensile strength. The percentages set forth in this table were obtained in each instance by dividing the strip after burial by the tensile strength of a similar strip of the same cloth not treated or buried and .then multiplying the result by 100. All tensile strength tests were conducted in the same manner and the total tensil strength of the strip prior to treatment and burial was 167 pounds. The tensile strength of such samples aftersuch test periods is a gen erally accepted criterion. of the protection against decay imparted by the impregnant. The results in Table I which are comparative clearly show that the substituted salicylaldoximes of the present invention greatly increase the resistance of the cloth to decay and are much better than closely related compounds, at least some of which have been recognized as having fungicidal properties. The compounds of the present invention compare favorably with the copper 8-hydroxy quinolinate without imparting the undesirable color to the fabric.
Table I Percentage of Tensile Strength Retained After- No. Weeks Weeks Weeks Weeks Weeks 1. 3,5-Dichlorosallcylaldoxlme 113 78 58 2. 3-Nitro-5-chlorosalioyaldoxhne 74 74 3. 3-Br0mo-5-chlorosalicylaldoxime 106 94 4. 3,5-Dibromosalicy1aldoxime 103 82 41 r 5. 3,4Dichlorobenzaldoxime. 0 6. 2,4-Dichlorobenzaldoxime 7. 2,4,5-Triehlorobenzab doxime 8. 3-Nitro-4-chlorobenzaldoxime O 9. 5Ohlorosallcylaldoxime 6 10. Copper 8-hydroxyqninolinate (1.38% 117 114 105 11. Copper S-hydroxyquiuolinate (0.83 103 87 69 29 12. Untreated Cloth 0 The substituted salicylaldoximes of the present invention may be prepared in any suitable manner. For example, the 3,S-dichlorosalicylaldOxime and 3-nitro-5- chlorosalicylaldoxime as well as 3-chloro-S-br0mosa1icylaldoxime and 3-nitro-5-bromosalicylaldoxirne may be prepared by reacting the appropriate aldehyde with hydroxylamine. S-chlorosalicylaldehyde may be brominated in glacial acetic acid to give an 83% yield of '3-br0mo-5-chlorosalicylaldehyde which can be reacted with hydroxylamine to produce the corresponding oxime. Similarly, salicylaldehyde may be brominated to form the 3,5-dibromo compound which may be reacted with hydroxylamine to form 3,S-dibromosalicylaldoxime.
The cellulosic materials may, if desirable under the particular conditions to be encountered, also be treated with other compounds and the only active ingredient need not be the present oximes although the present oximes are highly satisfactory for normal purposes.
We claim:
1. The process of imparting decay resistance to cellulosic material which comprises applying at least one substituted salicylaldoxime to such material, said substituted salicylaldoxime having the following structural formula:
where R is selected from the group consisting of Cl, Br, and N and R" is selected from the group consisting of Cl and Br.
2. The process of imparting decay resistance to cellulosic fibrous material which comprises impregnating such a material with at least one substituted salicylaldoxime having the following structural formula:
R" RI where R is selected from the group consisting of Cl, Br,
and N0 and R" is selected from the group consisting of Cl and Br.
4. The process claimed in claim 3 in which R and 'R" are both chlorine.
5. The process claimed in claim 3 in which R is N0 and R" is Cl.
6. The process claimed in claim 3 in which R is Br and R" is Cl.
7. The process claimed in claim 3 in which R and R are both bromine.
8. A cellulosic material having decay resistant properties which comprises callulosic material and at least one substituted salicylaldoxime having the following structural formula: 1
Where R is selected from the group consisting of Cl, Br, and N0 and R" is selected from the group consisting of Cl and Br.
9. A cellulosic material having decay resistant properties which comprises cellulosic fibrous material impregnated with at least one substituted salicylaldox-ime having the following structural formula:
where R is selected from the group consisting of Cl, Br, and N0 and R is selected from the group consisting of Cl and Br.
10. A cellulosic material having decay resistant properties which comprises a cellulosic fabric impregnated with from 0.75% to 2.5% by weight of at least one substituted salicylaldoxime having the following structural formula:
Claims (1)
1. THE PROCESS OF IMPARTING DECAY RESISTANCE TO CELLULOSIC MATERIAL WHICH COMPRISES APPLYING AT LEAST ONE SUBSTITUTED SALICYALDOXIME TO SUCH MATERIAL, SAID SUBSTITUTED SALICYLALDOXIME HAVING THE FOLLWOING STRUCTURAL FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US431593A US2822297A (en) | 1954-05-21 | 1954-05-21 | Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US431593A US2822297A (en) | 1954-05-21 | 1954-05-21 | Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2822297A true US2822297A (en) | 1958-02-04 |
Family
ID=23712626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US431593A Expired - Lifetime US2822297A (en) | 1954-05-21 | 1954-05-21 | Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2822297A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426864A (en) * | 1946-01-30 | 1947-09-02 | Hynson Westcott & Dunning Inc | Fungicides |
-
1954
- 1954-05-21 US US431593A patent/US2822297A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426864A (en) * | 1946-01-30 | 1947-09-02 | Hynson Westcott & Dunning Inc | Fungicides |
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