US2418071A - Process of treating animal fibers and products thereof - Google Patents
Process of treating animal fibers and products thereof Download PDFInfo
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- US2418071A US2418071A US455368A US45536842A US2418071A US 2418071 A US2418071 A US 2418071A US 455368 A US455368 A US 455368A US 45536842 A US45536842 A US 45536842A US 2418071 A US2418071 A US 2418071A
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- wool
- linkages
- cystine
- substituted
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- 239000000835 fiber Substances 0.000 title description 22
- 238000000034 method Methods 0.000 title description 16
- 241001465754 Metazoa Species 0.000 title description 14
- 210000002268 wool Anatomy 0.000 description 57
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 17
- 229960003067 cystine Drugs 0.000 description 17
- 239000003638 chemical reducing agent Substances 0.000 description 16
- 238000011282 treatment Methods 0.000 description 15
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 14
- 125000003396 thiol group Chemical group [H]S* 0.000 description 12
- 238000009950 felting Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 9
- 150000003568 thioethers Chemical class 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000002152 alkylating effect Effects 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 102000011782 Keratins Human genes 0.000 description 6
- 108010076876 Keratins Proteins 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- -1 alkyl mercaptans Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 125000002228 disulfide group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical class C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001350 alkyl halides Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- YEESUBCSWGVPCE-UHFFFAOYSA-N azanylidyneoxidanium iron(2+) pentacyanide Chemical compound [Fe++].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.N#[O+] YEESUBCSWGVPCE-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229960002460 nitroprusside Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/78—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin or cold insoluble globulin [CIG]
Definitions
- Our invention relates to the treatment of ma: terials which contain keratin and more particularly to animal fibers of the epidermal type such as hair and wool. With greater particularity, the invention relates to such materials which contain keratin and which are characterized by having a plurality of disulfide (or cystine) linkages in the molecule. This invention also relates to the product produced by the treatment which will be hereinafter described.
- wool and hair and the like fibrous materials which contain keratin are subject to attack by insects such as moths and are likewise subject to shrinkage when subjected to treatment by hot water or steam, particularly when the water has been made alkaline as by the addition of soap.
- Attempts have been made to reduce thesusceptibility of such materials to attack by moths by various chemical treatments, generally the surface treatment of the fibers with chemicals known to be repugnant to moths or suspected of being toxic towards moths and their larvae.
- Other types of treatment have been resorted to such as fumigating the fibers or fabrics made therefrom, with camphor, naphthalene or halogen derivatives of aromatic compounds.
- Our invention has for one of its objects the treatment of animal fibers of the epidermal type which contain keratin and which are characterized by having a plurality of disulfide (or cystine) linkages in the molecule, in a series of easily controlled and readily duplicated steps to produce a modified animal fiber which is resist- So far as we are aware, none of the- 2 tion of such a modified animal fiber which is resistant to both moths and felting, with a permanency not hitherto attained.
- our invention con-' templates the treatment of animal fibers of the epidermal type as well as materials fabricated partially or completely therefrom by subjecting the material, which contains keratin and which is characterized by having a plurality of disulfide (or cystine) linkages in the molecule, to the action of a reducing agent while controlling the pH value of the reaction.
- This treatment disrupts some, or all, or a predetermined proportion of the disulfide groups of the cystine in the molecule and converts the said disulfide groups into sulfhydryl groups.
- a convenient way of adjusting the pH is by means of a bulfer solution of any well-known type, the amount and strength of the solution being so adjusted that the acid formed in the ensuing reaction will not reduce the hydrogen ion concentration of the reaction medium below pH 7.5.
- Methyl iodide, CHJI was added to the reaction mixture and agitated to insure thorough contact between the methyl iodide and the reduced wool. The treatment with the methyl iodide was continued until a sample of the wool, when treated with nitroprusside reagent, failed to give a positive test for the sulfhydryl group. The modified wool was then removed from the reaction bath, washed thoroughly with water and dried in the air.
- CHJI Methyl iodide
- reducing agents such as mercaptan acids, for example thioglycglic acid, mercaptans, for example H28 or NaSH, more particularly alkyl mercaptans, such as butyl or, ethyl mercaptans and mercaptan glycols, such as beta-mercapto ethanol, are unique in their ability to reduce animal fibers, such as wool, without causing undesired solution or degradation under'the conditions of reduction. 7
- mercaptan acids for example thioglycglic acid
- mercaptans for example H28 or NaSH
- alkyl mercaptans such as butyl or, ethyl mercaptans and mercaptan glycols, such as beta-mercapto ethanol
- the reduction can be performed with a solution of the reducing agent in an anhydrous solvent, as a solution of thioglycolic acid in alcohol or benzene or other non-aqueous solvent.
- the reducing step in the illustrative example we have described the reducing step as being performed'at room temperature and over a period of about twentyfour hours. Lower temperatures may be employed and longer periods of exposure to the reducing agent, if desired; or higher temperatures may be employed while shortening the period of exposure of the wool to the reducing agent. We prefer, however, to operate within a temperature range of between about 25 C. and about 50 C. and we prefer to expose the wool to the action of the reducing agent for a period of time between 30 minutes and twenty-four hours. The temperature employed and the length of exposure to the reducing agent will vary, depending upon whether we wish to effect a complete or partial reduction of all of the disulfide (or crystine) linkages.
- the concentration of the reducing agent is of importance. It has been found desirable to use at all times a considerable excess of the amount of reducing agent over and above that theoretically necessary to reduce all the disulfide (crystine) linkages of the molecule. Itis preferred to use at least20 times the amount of reducing agent theoretically necessary. It has been determined that the amount of reduction increased rapidly with some increase in the concentration of the reducing agent. Thus, there was a noticeable rapid increase when the reducing agent was increased from 0.01' M to 0.2 M. There was an increase, although a less marked one, between 0.2 M and 0.5 M. Increase in the concentration beyond 0.5 M had relatively less effect. V
- a buffer solution we may use borax, soda ash, phosphate buffers and the like.
- alkylating agents a wide variety of compounds may be employed: alkyl compounds, substituted alkyl compounds, aralkyl compounds or substituted aralkyl compounds. Some aryl compounds have been found by us to be reactive. As examples of compounds which we have tested and found to be effective as alkylating agents are:
- solvents such as benzol, toluol, methyl alcohol, ethyl alcohol, propyl alcohol, cyclohexane, aliphatic liquid hydrocarbons and mixtures thereof, such as naphtha, in carrying out the alkylating step.
- the alkylation step may be carried out with gaseous or vaporized reagents.
- wool illustrated in this specification may be employed on wool fibers, wool yarn, wool cloth, piece goods or unfabricated wool in the bulk. While we have used wool as a representative example of the epidermal type of animal fiber to which our invention relates, other keratin-containing and epidermal type fibers and materials fabricated therefrom may be treated by our process.
- X and X are identical or substantially 7 similar side chain complexes containing C, H, N and 0, i. e. X and X represent the portions of the wool molecule to which the disulfidelinkages are attached, and a is a number greater than 1.
- The'reduction step of our process affects the disruption of the disulflde linkages, i. e, cystine, and forms cysteine, i. e. sulfhydryl, groups. Consequently, after the reduction step, that is, after the disruption of the disulflde linkages, the wool molecule may be represented as follows:
- the alkylating step of our process accomplishes the replacement of the hydrogen of th sulfhydryl groups of the reduced wool with the selected nucleus.
- the final product will be:
- R represents an alkyl, a substituted alkyl, an aralkyl ora substituted aralkyl nucleus, and a is a number greater than 1.
- the molecule may [be represented as:
- R represents an alkyl, a substituted alkyl, an aralkyl, or a substituted aralkyl nucleus
- b and c are numbers the sum of which equals the number a which is greater than 1.
- W001 fiber characterized by resistance to moths and felting, in which at'least about onethird of the disulflde linkages of the wool molecule have been disrupted and changed to thioethers of the type in which X and X* represent portions of the f wool molecule to which the disrupted disulflde linkages are attached and R is selected from the group consisting of substituted and unsubstituted alkyl radicals.
- Wool fiber characterized [by resistance to moths and felting, in which at least about onethird of the disulflde linkages ,of ⁇ the wool molecule have been disrupted and" changed to thioethers of the type in which X and X represent portions of the wool molecule to which the disrupted disulfide linkages are attached and R is an alkyl radical.
- the process 01 treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action of a reducing agent selected from the group consisting of lower alkyl mercaptans, .thioglycolic acid and betamercaptoethanol while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulflde linkages of the wool have been converted to sulfhydryl groups,
- a reducing agent selected from the group consisting of lower alkyl mercaptans, .thioglycolic acid and betamercaptoethanol
- pH '7 and pH 9 with a compound selected from the group consisting of substituted and unsubstituted alkyl monohalides to convert the sulfhydryl group into thioethers.
- the process of treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action of thioglycolic acid while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulphide linkages of the wool have been converted to sulfhydryl groups, then treating the wool at a pH between about pH 7 and pH 9 with a compound selected from the group consisting of substituted and unsubstituted alkyl monohallides to convert the sulfhydryl group into thioet ers.
- the process of treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action oi. beta-mercaptoethanol while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulflde linkages oi the wool have been converted tosulihydryl groups, then treating the wool at a pH between about pH 7 and pH 9 with a compound selected from the 10 group consisting of substituted and unsubstituted alkyl monohalides to convert the sulfhydryl group into thioethers.
- a compound selected from the 10 group consisting of substituted and unsubstituted alkyl monohalides to convert the sulfhydryl group into thioethers.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Gastroenterology & Hepatology (AREA)
- Zoology (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Mar. 25, 1947 PROCESS OF TREATING ANIMAL FIBERS AND PRODUCTS THEREOF Milton Harris, Bethesda, Md., and Wilbur I. Patterson, Chagrin Falls, Ohio, assignors to Textile Foundation, Washington, D. C., a corporation of the District of Columbia No Drawing. Application August 19, 1942, Serial No. 455,368
Claims.
Our invention relates to the treatment of ma: terials which contain keratin and more particularly to animal fibers of the epidermal type such as hair and wool. With greater particularity, the invention relates to such materials which contain keratin and which are characterized by having a plurality of disulfide (or cystine) linkages in the molecule. This invention also relates to the product produced by the treatment which will be hereinafter described.
This application is a continuation in part of our copending application, Serial No. 336,312, filed May 20, 1940.
It is known that wool and hair and the like fibrous materials which contain keratin are subject to attack by insects such as moths and are likewise subject to shrinkage when subjected to treatment by hot water or steam, particularly when the water has been made alkaline as by the addition of soap. Attempts have been made to reduce thesusceptibility of such materials to attack by moths by various chemical treatments, generally the surface treatment of the fibers with chemicals known to be repugnant to moths or suspected of being toxic towards moths and their larvae. Other types of treatment have been resorted to such as fumigating the fibers or fabrics made therefrom, with camphor, naphthalene or halogen derivatives of aromatic compounds.
None of these types of treatment have, so far as we are aware, been successful in permanently mothproofing animal fibers, such as hair and wool or the fabrics made therefrom, to such an extent as to resist repeated washing or dry cleaning.
Attempts have been made to reduce or eliminate the shrinkage and felting tendency of such animal fibers by subjecting the fibers to chemical treatment with either oxidizing or reducing agents. treatments which have been heretofore attempted have resulted in reducingthe natural shrinkage of animal fibers to any marked degree without leaving the molecule and particularly the sulfur thereof in a highly reactive form which renders it more susceptible to damage and degradation in service.-
Our invention has for one of its objects the treatment of animal fibers of the epidermal type which contain keratin and which are characterized by having a plurality of disulfide (or cystine) linkages in the molecule, in a series of easily controlled and readily duplicated steps to produce a modified animal fiber which is resist- So far as we are aware, none of the- 2 tion of such a modified animal fiber which is resistant to both moths and felting, with a permanency not hitherto attained.
In one of its broad aspects, our invention con-' templates the treatment of animal fibers of the epidermal type as well as materials fabricated partially or completely therefrom by subjecting the material, which contains keratin and which is characterized by having a plurality of disulfide (or cystine) linkages in the molecule, to the action of a reducing agent while controlling the pH value of the reaction. This treatment disrupts some, or all, or a predetermined proportion of the disulfide groups of the cystine in the molecule and converts the said disulfide groups into sulfhydryl groups. is then reacted with an agent which contains a substituent reactive with the hydrogen. of the sulfhydryl group to form a substituted mmether in which the substit'uent may be an alkyl ant to moths and which is resistant to felting.
nucleus, an aralkyl nucleus, a substituted alkyl nucleus or a substituted aralkyl nucleus. There results from this novel treatment a novel product which we have found to be resistant to moths and resistant to felting.
The following example given by way of illustration discloses one manner in which our novel process may be employed. A given amount of wool was immersed in such a volume of approximately 0.3 M thioglycolic acid solution, which had been brought to pH 6 by. NaOH, that the molar ratio of thioglycolic acid to the disulfide room temperature i. e. 20 to 30 C. for twentyhours. The wool was then removed from the solution, washed with water to remove the excess thioglyeolic acid; and the washed wool was then placed in an aqueous solution having a pH of about 7.5 to 8.0. A convenient way of adjusting the pH is by means of a bulfer solution of any well-known type, the amount and strength of the solution being so adjusted that the acid formed in the ensuing reaction will not reduce the hydrogen ion concentration of the reaction medium below pH 7.5. Methyl iodide, CHJI, was added to the reaction mixture and agitated to insure thorough contact between the methyl iodide and the reduced wool. The treatment with the methyl iodide was continued until a sample of the wool, when treated with nitroprusside reagent, failed to give a positive test for the sulfhydryl group. The modified wool was then removed from the reaction bath, washed thoroughly with water and dried in the air. The
The so-treated material wool subjected to this treatment had had its disulfide groups or cystine linkages disrupted and converted into methyl substituted thio-ethers.'
Analysis of the untreated, i. e. original, wool showed a cystine' content of 12% while the cystine content of the modified wool produced by this illustrative example was the method of analysis in both instances being the cystine content analysis of Sullivan, Public Health Reports 86 (1930), and Research Paper RP 810,
Journal of Research of the National Bureau of Standards, vol. 15, 1935.
' The process illustrated in the above example may be subjected to many variations. Hereto- .fore it was believed that strongly alkaline solutions of thioglycolic acid were required for the reduction of the disulfide groups of wool to sulfhydryl groups because neutral and slightly acid solutions of thioglycolic acid do not dissolve the wool. It was assumed that dissolution of the treatment, as well as the concentration of the reducing agent, we have found it possible to effect the reduction of the disulfide or crystine linkages at hydrogen ionconcentrations between pH 0.0 and pH 12.0, without substantial dissolution or degradation of the wool. Nevertheless, it hasbeen found that with an alkalinity above about pH 9 there will be undesirable side reactions and an undesired amount of dissolving of the fiber in an alkaline reducing bath of this degree of alkalinity. Since it is desired to perform the process of this application with a minimum amount of undesired side reactions and a minimum amount of degradation of the animal fiber to be treated, it is preferred to carry out the reducing step at a hydrogen ion concentration below about pH 9. It has also been found that the undesired side reactions and undesired solution are minimized to a far more satisfactory extent bycarrying out the reducing step of the process in a neutral or acid medium preferably below pH '7 and more desirably atabout pH 5.
During the alkylation step of our process, we prefer to maintain the hydrogen ion concentration at a pH of between about 7.5 and about 8.0, as determined in aqueous media. We have found that alkylation may be satisfactorily accomplished under hydrogen ion concentrations between about pH 7.0 and about pH 9.0, provided dueprecautions are taken with regard to temperature, concentration of reagents and other operating conditions.
- It has been found in developing the invention described in this application that reducing agents such as mercaptan acids, for example thioglycglic acid, mercaptans, for example H28 or NaSH, more particularly alkyl mercaptans, such as butyl or, ethyl mercaptans and mercaptan glycols, such as beta-mercapto ethanol, are unique in their ability to reduce animal fibers, such as wool, without causing undesired solution or degradation under'the conditions of reduction. 7
The reduction can be performed with a solution of the reducing agent in an anhydrous solvent, as a solution of thioglycolic acid in alcohol or benzene or other non-aqueous solvent.
In the illustrative example we have described the reducing step as being performed'at room temperature and over a period of about twentyfour hours. Lower temperatures may be employed and longer periods of exposure to the reducing agent, if desired; or higher temperatures may be employed while shortening the period of exposure of the wool to the reducing agent. We prefer, however, to operate within a temperature range of between about 25 C. and about 50 C. and we prefer to expose the wool to the action of the reducing agent for a period of time between 30 minutes and twenty-four hours. The temperature employed and the length of exposure to the reducing agent will vary, depending upon whether we wish to effect a complete or partial reduction of all of the disulfide (or crystine) linkages. We may, if desired, subject the wool to the action of the reducing agent under such conditions and forsuch a period of time as to effect the reduction of, for example, 25% or 50% or more or less, of the disulfide (or crystlne) linkages.
The concentration of the reducing agent is of importance. It has been found desirable to use at all times a considerable excess of the amount of reducing agent over and above that theoretically necessary to reduce all the disulfide (crystine) linkages of the molecule. Itis preferred to use at least20 times the amount of reducing agent theoretically necessary. It has been determined that the amount of reduction increased rapidly with some increase in the concentration of the reducing agent. Thus, there was a noticeable rapid increase when the reducing agent was increased from 0.01' M to 0.2 M. There was an increase, although a less marked one, between 0.2 M and 0.5 M. Increase in the concentration beyond 0.5 M had relatively less effect. V
In preparing for and accomplishing the alkylating step so as to effect the substitution of the sulfhydryl hydrogens with alkyl or other nuclei, we may adjust the hydrogen ion concentration in any well-known manner as by means of a buffer solution. As a buffering agent we may use borax, soda ash, phosphate buffers and the like.
- As alkylating agents a wide variety of compounds may be employed: alkyl compounds, substituted alkyl compounds, aralkyl compounds or substituted aralkyl compounds. Some aryl compounds have been found by us to be reactive. As examples of compounds which we have tested and found to be effective as alkylating agents are:
Methyl iodide, CHaI Ethyl bromide, CsHsB! Allyl chloride, CH2=CHCH2C1 Benzyl chloride, CaH-sCHzCl Chloroacetone, ClCHzCOCHa Chloroacetic acid, ClCHzCOOH Diazomethane, CHzNz p-Nitrofluorobenzene, NOPO-J p-Nitroiodobenzene, NO -I It will be observed that the compounds given above by way of illustration fall under groups such as alkyl halides, which may be either-saturated or unsaturated, aralkyl halides, substituted aliphatic compounds in which one or more hydrogens have been replaced by nitrogen or oxygen and halogenated aromatic compounds. All of the compoundsjhowever, are characterized'by having in the molecule a substituent which will react with the hydrogen of the sulfhydryl groups formed by disrupting the disulflde linkages of the wool. We have found that the alkylating step of our process and the completeness of reaction may be controlled by changing the solvent medium employed during the alkylating step. We have found an aqueous medium, particularly one which contains a buffering agent, to be very effective in this stage of our process, especially when the alkylating reagent is normally liquid, We have also found that an alcoholic solution, containing, for example, ammonia, or other soluble basic reagent, is an efilcient medium for the alkylating step. We may, however, employ other suitably inert solvents such as benzol, toluol, methyl alcohol, ethyl alcohol, propyl alcohol, cyclohexane, aliphatic liquid hydrocarbons and mixtures thereof, such as naphtha, in carrying out the alkylating step.
Moreover, we have ascertained that the use of a liquid medium is not in all cases necessary in the successful performance of the alkylation. With suitable alkylating agents, possessing the requisite volatility, the alkylation stepmay be carried out with gaseous or vaporized reagents.
wool illustrated in this specification may be employed on wool fibers, wool yarn, wool cloth, piece goods or unfabricated wool in the bulk. While we have used wool as a representative example of the epidermal type of animal fiber to which our invention relates, other keratin-containing and epidermal type fibers and materials fabricated therefrom may be treated by our process.
We have found that representative wool may have a cystine content as great as 12%. ducing such wool by our process, we may convert practically all of the disulflde groups or cystine content into substituted thio-ethers by reduction and alkylation in accordance with our invention. The product of such complete reduction and alkylation we have found to be a new and valuable product. We may likewise effect a partial reduction and subsequent partial alkylation so as to leave a desired portion, for example, between 4 and 8%, of the cystine unchanged. We have found that better resistance to moths (than unmodified wool) is demonstrated when our modified wool contains between about 4% and about 8% of cystine, the remainder of the cystine having been converted to substituted thio-ethers. We have found that where the cystine of wool has been converted to substituted thio-ethers by our invention, the modified wool 'is much more resistant to felting .than natural wool. We find this result increases as the cystine content is decreased to 8% cystine and below.
While we do not wish to be bound by any theory which we may advance, it is our belief, based upon our knowledge of wool and upon its reported In re--.
molecular structure, that wool and all other animal fibers of the epidermal type which contain formula:
in which X and X are identical or substantially 7 similar side chain complexes containing C, H, N and 0, i. e. X and X represent the portions of the wool molecule to which the disulfidelinkages are attached, and a is a number greater than 1. The'reduction step of our process affects the disruption of the disulflde linkages, i. e, cystine, and forms cysteine, i. e. sulfhydryl, groups. Consequently, after the reduction step, that is, after the disruption of the disulflde linkages, the wool molecule may be represented as follows:
(II) x -s s-)x' (a i in which X and X are as in (I) above and represent the portions of the wool molecule to which the now disrupted disulflde linkages are attached, and a is a number greater than 1.
The alkylating step of our process accomplishes the replacement of the hydrogen of th sulfhydryl groups of the reduced wool with the selected nucleus. Thus, where methyl iodide or benzyl chloride is used as the alkylating agent, the final product will be:
(III) x -s s- )x' x -s s- )X' 01 41E: JJH: q HiCtHt HICEB respectively.
This may be more broadly stated as:
where R represents an alkyl, a substituted alkyl, an aralkyl ora substituted aralkyl nucleus, and a is a number greater than 1.
Where the wool has been but partially reduced,
i. e. part only of the disulflde linkages have been disrupted and converted to substituted thioethers, the molecule may [be represented as:
x[ -s s- }x' (it).
where R represents an alkyl, a substituted alkyl, an aralkyl, or a substituted aralkyl nucleus, and b and c are numbers the sum of which equals the number a which is greater than 1.
Having now described our invention in such manner that the nature of our invention may be understood and the invention may be practiced by others, we declare that what we claimis:
1. W001 fiber, characterized by resistance to moths and felting, in which at'least about onethird of the disulflde linkages of the wool molecule have been disrupted and changed to thioethers of the type in which X and X* represent portions of the f wool molecule to which the disrupted disulflde linkages are attached and R is selected from the group consisting of substituted and unsubstituted alkyl radicals.
2. Wool fiber, characterized [by resistance to moths and felting, in which at least about onethird of the disulflde linkages ,of \the wool molecule have been disrupted and" changed to thioethers of the type in which X and X represent portions of the wool molecule to which the disrupted disulfide linkages are attached and R is an alkyl radical.
3. The process 01 treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action of a reducing agent selected from the group consisting of lower alkyl mercaptans, .thioglycolic acid and betamercaptoethanol while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulflde linkages of the wool have been converted to sulfhydryl groups,
pH '7 and pH 9 with a compound selected from the group consisting of substituted and unsubstituted alkyl monohalides to convert the sulfhydryl group into thioethers.
4. The process of treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action of thioglycolic acid while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulphide linkages of the wool have been converted to sulfhydryl groups, then treating the wool at a pH between about pH 7 and pH 9 with a compound selected from the group consisting of substituted and unsubstituted alkyl monohallides to convert the sulfhydryl group into thioet ers.
then treating the wool at a pH between about 5. The process of treating wool to render it resistant to moths and felting which comprises subjecting the wool to the action oi. beta-mercaptoethanol while maintaining the pH of the reaction below about pH 9 until at least about one-third of the disulflde linkages oi the wool have been converted tosulihydryl groups, then treating the wool at a pH between about pH 7 and pH 9 with a compound selected from the 10 group consisting of substituted and unsubstituted alkyl monohalides to convert the sulfhydryl group into thioethers. MILTON HARRIS.
WILBUR I PATTERSON.
REFERENCES CITED The following references are of record the file of this patent:
UNITED STATES PATENTS Number OTHER REFERENCES Michaelis, "A Study of Keratin," Jr. American Leather Chemists Assn., vol. 30, 1935, pages 561- 568.
Pillemer et al., Specificity of Kerateine De- 30 rivatives, Proceedings of the Soc. for Exp. Biol-
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2508714A (en) * | 1946-10-07 | 1950-05-23 | Harris Res Lab | Process of treating keratinous materials |
US2540494A (en) * | 1949-09-03 | 1951-02-06 | Milton H Schwarz | Permanent hair waving |
US2615782A (en) * | 1950-08-11 | 1952-10-28 | Procter & Gamble | Modification of keratin |
US2739033A (en) * | 1951-03-19 | 1956-03-20 | Du Pont | Treatment of reduced keratinous materials with alpha,alpha'-dihalodicarboxylic acid |
US2751409A (en) * | 1951-08-02 | 1956-06-19 | Kuhn Richard | Preparation of thiolalkylamides |
US2955016A (en) * | 1956-10-15 | 1960-10-04 | Joseph E Moore | Modification of keratins with sulphones and related compounds |
US3055727A (en) * | 1961-01-11 | 1962-09-25 | Nathan H Koenig | Treatment of wool with haloketones in the presence of dimethylformamide |
DE1178439B (en) * | 1958-09-04 | 1964-09-24 | Mitop Vyroba Plsti Narodni Pod | Process for the modification of proteins |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2238672A (en) * | 1940-04-09 | 1941-04-15 | Du Pont | Textile treatment |
US2261194A (en) * | 1935-06-15 | 1941-11-04 | Vickers Inc | Hydraulic rammer |
-
1942
- 1942-08-19 US US455368A patent/US2418071A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2261194A (en) * | 1935-06-15 | 1941-11-04 | Vickers Inc | Hydraulic rammer |
US2238672A (en) * | 1940-04-09 | 1941-04-15 | Du Pont | Textile treatment |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2508714A (en) * | 1946-10-07 | 1950-05-23 | Harris Res Lab | Process of treating keratinous materials |
US2540494A (en) * | 1949-09-03 | 1951-02-06 | Milton H Schwarz | Permanent hair waving |
US2615782A (en) * | 1950-08-11 | 1952-10-28 | Procter & Gamble | Modification of keratin |
US2739033A (en) * | 1951-03-19 | 1956-03-20 | Du Pont | Treatment of reduced keratinous materials with alpha,alpha'-dihalodicarboxylic acid |
US2751409A (en) * | 1951-08-02 | 1956-06-19 | Kuhn Richard | Preparation of thiolalkylamides |
US2955016A (en) * | 1956-10-15 | 1960-10-04 | Joseph E Moore | Modification of keratins with sulphones and related compounds |
DE1178439B (en) * | 1958-09-04 | 1964-09-24 | Mitop Vyroba Plsti Narodni Pod | Process for the modification of proteins |
US3055727A (en) * | 1961-01-11 | 1962-09-25 | Nathan H Koenig | Treatment of wool with haloketones in the presence of dimethylformamide |
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