Process for improving polymer fiber properties and fibers produced thereby

FIELD OF THE INVENTION
The present invention relates to the treatment of polymer fibers to permanently and substantially improve their hygroscopic, antistatic, dye receptive, and soil release properties, as well as altering the hand of such fibers. More particularly, the invention relates to the treatment of polymer fibers containing active hydrogen atoms to improve their surface properties.
BACKGROUND OF THE INVENTION
With the advent of technology to produce synthetic fibers that serve mankind not only by being more economical and stronger than natural fibers, but also by freeing up much needed agricultural land that heretofore had been needed to grow vast quantities of natural fibers, came a quest for a process that would impart to these synthetic fibers the same beneficial qualities possessed by natural fibers. The major quality that synthetic fibers lack, the one attribute that would make them cool and comfortable like the natural fibers, is the ability to substantially absorb moisture.
Throughout this application the terms "absorb" and "absorption" will be used to refer generally to the hygroscopic properties of the fibers and fabrics made therefrom. However, it will be understood that these terms refer to related hygroscopic properties such as adsorption, moisture transport, wicking, wettability, etc. Thus, although the term "adsorption" may be more appropriate for referring to the attraction of water to the outer surfaces of fibers per se, and the term "absorption" may be more appropriate for referring to the dispersal of moisture in the interstices between the fibers of a fabric, the term "absorption" will be used for convenience to refer to both phenomena.
The present invention satisfies this much sought after quest and provides to synthetic fibers permanent qualities once attributable only to natural fibers such as significant water absorbency, superior dye receptivity and anti-static qualities. At the same time, the present invention allows for the production of synthetic fibers that have superior soil release qualities.
It has been known in the prior art to attempt to graft-polymerize water-soluble monomers such as acrylic acid, acrylamide, and N,N'-methylene-bis-acrylamide (MBA) onto fibers to impart antistatic and water absorption properties to the fibers. However, such attempts at graft polymerization have been problematic due to the inability to obtain substantial or even any graft polymerization, a requirement of a long period of time, the tendency to form large amounts of homopolymers, and difficulties in controlling the process conditions. The raising and control of reaction temperature is extremely critical and sensitive to the formation of excess homopolymers. Excess homopolymers adhere to the inner walls of the processing equipment thus causing both a time and labor-consuming clean-up job. Also, disposal of the residue solution containing a large amount of homopolymers is a source of industrial pollution. Fabrics thus treated in an environment of excessive homopolymers have their surfaces coated with a thick homopolymer layer which imparts moisture-absorption and some antistatic properties to the fibers. Unfortunately, these properties are not permanent and are lost within about ten washings. Furthermore, excessive homopolymers tend to cause blotching on treated fabrics which interferes with acceptable commercial dyeing and results in inferior treated fabrics.
In an alternative polymerization process that comprises impregnating fibers with a solution containing a monomer and a polymerization initiator, such as peroxide or persulfate, and heating them, it takes a long period of time to start and advance the polymerization reaction; moreover, the polymers that adhere to fibers are removed quite easily by washing so that their antistatic and moisture-absorption properties can no longer be retained.
Still another process involves applying a water-soluble vinyl monomer together with a polymerization initiator to fibrous structures and heating them in a non-solvent of the monomer, such as hydrocarbons or the like. Such process has problems of industrial hygiene and workability including solvent recovery.
U.S. Pat. No. 3,313,591 to Tanner describes a process of graft polymerizing ethylenically unsaturated monomers to polycarbonamides to improve various properties of the polymer structure. Tanner uses a one step process using very long time durations (15 hours or more) and very high concentrations of monomer.
A more recent attempt to cure the deficiency in the prior art is disclosed in U.S. Pat. No. 4,135,877 to Aikawa et al. This patent also discloses a one step process of graft polymerizing certain selected vinyl monomers to polyamides or fiber structures. According to the process described in that patent, polymerization initiators are completely eliminated.
Other patents disclosing the graft polymerization of monomers to polyamides and other polymer structures include U.S. Pat. Nos. 3,097,185; 3,099,631; 3,252,880 and 3,278,639. However, the methods of these patents involve the use of ionizing radiation in the formation of a polymer melt in order to effect graft polymerization.
While many of these processes of the prior art result in improved antistatic, hygroscopic and dye receptive properties in the polymer, they have not been entirely successful commercially due to the difficulties in obtaining permanent and substantial results and other processing difficulties due to excessive formation of homopolymers which are difficult to remove from the final product and process equipment. Furthermore, some prior art methods require high concentrations of monomer, rather than low concentrations of monomer; and other prior art methods require long periods of time.
The possibility of improving such properties of synthetic fabrics in general, including but not limited to polyamides, is important since many of these fabrics exhibit characteristically undesirable properties such as static cling poor water absorbency, and poor dye receptivity. Hence, the commercial acceptance of nylon fabrics, for example, has been severely limited. Heretofore, I am aware of no commercially successful process which has resulted in a treated fiber having substantially improved antistatic, hygroscopic, and dye receptive properties which are permanent and can withstand repeated washings.
The principal object of the present invention is to provide a unique process and a product of that process which alleviates the past shortcomings of attempted graft polymerization.
The present invention is unique in that the process can be completed in very short periods of time, using a low concentration of chemicals, is not sensitive to changes in temperature, and forms relatively minute amounts of homopolymers and allows commercial products to be made which can be dyed and otherwise processed.
The product of the present invention is unique in that it is the first that has grafted onto fibers an economical, commercial, permanent, clean, and low add-on graft polymer.
Although the treatment method of this invention is particularly useful for nylon, which is not naturally absorbent and is subject to static electricity problems, it is also beneficial to enhance the properties of absorbent fibers such as cotton. Treating a blend consisting of cotton and synthetic fibers in accordance with the method of this invention may allow the use of less cotton in the blend to achieve a comparable fabric.
SUMMARY OF THE INVENTION
According to the present invention, polymer fibers or fibrous structures made thereof (hereinafter simply referred to as "polymer fibers") containing active hydrogen atoms are treated with a heated acidic solution of at least one unsaturated monomer, followed by polymerization of the monomer with a polymerization initiator in order to modify the surface characteristics of the polymer fibers. The treatment process comprises essentially three steps: (1) the polymer fibers are contacted with an aqueous solution having a pH below 7 but above where acid degradation of the polymer fiber occurs, and a temperature between about 75.degree. C. and about 100.degree. C. and containing at least one unsaturated monomer. In the first step, the surface of the polymer fiber is affected and has essentially single molecule addition of a monomer pendent to the polymer fiber. The solution is preferably agitated or forced to flow among the fibers for a sufficient time to allow uniform dispersal and intimate contact of the monomer with the fiber surfaces. (2) Thereafter polymerization of the monomer on the polymer fiber surfaces is initiated using a polymerization initiator, such as a persulfate or peroxide compound. (3) Then, the polymerization is continued for a sufficient time to allow substantial graft polymerization of the monomer on the fiber surfaces to modify the surface characteristics of the polymer fibers.
With most vinyl monomers and most synthetic polymer fibers the maximum weight percent of add-on graft polymer should be below about 1.0%. Thus, additional graft polymer above 1.0% is rapidly lost on washing.
With most vinyl monomers and natural polymer fibers, such as cotton, which are porous, the graft polymer add-on may go up to below about 2 weight percent.
It is usually disadvantageous to exceed these weight percent values of add-on polymer, since to do so may result in splotches on the outer surface of fabric formed from the polymer fibers, as well as material waste, cleanliness and pollution problems. The time duration for the first step of monomer attachment to the surface may vary between one second and thirty minutes. Longer durations may be used than thirty minutes. However, such longer durations will normally not significantly improve the monomer attachment.
The polymer fibers should not be degraded. Conditions resulting in polymer fiber degradation are to be avoided. By way of example, high concentrations of acrylic acid and other monomers may lead to degradation of the polymer fibers.
The polymer fibers are preferably immersed in the treating solution, usually in the form of a knitted, woven or nonwoven fabric, and many variations are possible in the order of addition of the various components to the treating solution. A preferred monomer for use in the invention is N,N'-methylene-bis-acrylamide. The pH of the solution may be adjusted by addition of an acid or by use of an acid monomer. The treatment is preferably carried out at low concentrations of monomer and polymerization initiator and for short periods of time so as to avoid as much as possible substantial homopolymerization of the monomer.
The fibers are preferably scoured prior to the treatment process to clean the fibers and remove surface chemicals which may interfere with the graft polymerization of the monomer on the fiber surfaces. Dyeing of the fibers is preferably carried out after the treatment process and after rinsing the fibers to remove acid and excess homopolymers which would otherwise interfere with the dyeing.
The fibers resulting from the process of the present invention have substantially improved water absorbency, dye receptivity, antistatic, soil release, inter-fiber adhesion and bonding properties, and fabric hand properties. The fibers so treated by the present invention will retain their enhanced properties even when subject to many vigorous washings.

DETAILED DESCRIPTION OF THE INVENTION
Polymer fibers having active hydrogen atoms to which the present invention is directed include both natural and synthetic polymers. The source of such active hydrogen atoms can be amine or hydroxy groups. Non-limiting examples of natural polymers suitable for treating according to the present invention include wool, cotton and silk. Non-limiting examples of synthetic polymers suitable for treatment according to the present invention include nylon, and cellulosic fibers, e.g., rayon and acetate. The treatment of polyesters and acrylics is covered by my copending application Ser. No. 426,498, filed Sep. 29, 1982 now U.S. Pat. No. 4,743,267.
Non-limiting examples of polymer fibers containing an amine ##STR1## or --NH.sub.2) group include nylon 6,6, nylon 6, wool and silk. Non-limiting examples of polymer fibers containing a hydroxy (--OH) group include cotton, rayon, and acetate.
The subject invention concerns the treating of polymer fibers per se and fibrous structures made thereof. The term "fibrous structures" includes continuous filaments, multifilament threads, batts, staple fibers, woven or knitted fabrics, and non-woven fabrics, and the like composed of at least one kind of the fibers mentioned above. As used herein, the term "polymer fibers" will be understood to include fibrous structures such as the above and others. Wherever the present disclosure refers to fiber surfaces or intimate contact of the monomer with fiber surfaces or like expressions, it will be understood that the individual fibers of filaments are being referred to, such that contact and attachment of the monomer and graft polymer is with the surfaces of individual filaments of a multifilament thread or bundle, for example.
Preferred polymers for use in the present invention are the polyamides, particularly the synthetic linear condensation polyamides containing a carbonamide unit as a linking unit in the main polymer chain. Such polyamides include for example poly(hexamethylamine adipamide), which is prepared by the well known reaction of polycarboxylic acid such as adipic acid (or an amide-forming derivative thereof) with a polyamide such as hexamethylene diamine. The most common commercially available polyamides of this type in the United States are nylon 6,6 which is polyhexamethylene adipamide, and nylon 6 which is poly(hexamethylene carprolactam). These types of nylons are commonly extruded as monofilaments over a wide dimensional range, oriented by cold-drawing and knitted into many different forms of fabrics. Nylons are excellent fabrics and can be produced very cheaply on a mass production basis, but nylon suffers from many drawbacks. Nylon lacks the ability to absorb water and is subject to static electricity problems. By treating nylon according to the process of the present invention, a most useful fabric is formed which has very good water absorbing, dye receptive, and antistatic properties which are retained after many washings.
The temperature at which fibers or fibrous structures are treated in accordance with the present invention is between about 75.degree. C. and about 100.degree. C., preferably between about 80.degree. C. and about 90.degree. C. for amine containing polymers and between about 85.degree. C. and about 100.degree. C. for hydroxy containing polymers.
The process of the present invention differs from those of the prior art in that polymerization of the monomer to be graft polymerized onto the polymer fibers is delayed until there has been intimate contact of the monomer and acid with the surface of the heated polymer fiber. Thus, while applicant does not wish to be bound by any particular theory or mechanism of reaction, it is believed that the unsaturated monomer first attaches to the polymer chain on a molecule by molecule basis in the presence of acid and heat. Thereafter, when the polymerization is initiated by addition or activation of a polymerization initiator, the monomer begins to polymerize so that there is chain addition of monomer to the sites of single monomer additions initially grafted onto the polymer fibers. If significant homopolymerization of the monomer takes place prior to the alteration and monomer attachment to the fibers, most of it will simply be washed off the fibers so that there will be no significant permanent improvement in the surface properties of the fibers.
Accordingly, the first step of the method according to the present invention comprises the formation of an aqueous treating solution with dissolved monomer having an acidic pH (i.e. below about 7 and above a pH where acid degradation occurs) and heated to a temperature of about 75.degree. C. to about 100.degree. C. and preferably in the range of about 80.degree. C. to 90.degree. C. for amine containing polymers and preferably about 85.degree. C. to about 100.degree. C. for hydroxy containing polymers, such as cotton, rayon and acetate. While temperatures above 100.degree. C. are possible, they make processing more difficult and may make subsequent polymerization difficult to control.
It is not necessary that the temperature be constant throughout the first step or throughout the process. For example, the treating solution could be formed at about 70.degree. C., or such temperature as will allow ready dissolving of the monomer and/or acid in the solution, and then the temperature could be raised to the desired level for the attachment of the monomer just prior to initiation of graft polymerization. The attachment of a monomer should be such as to effect essentially single molecule addition of the monomer pendent to the polymer chain to form a branched polymer with substantially no graft polymerization of said monomer. This single molecule addition is disclosed in my copending patent application Ser. No. 6/364,045 filed Mar. 31, 1982, the disclosure of which is incorporated herein by reference. Thus, since graft polymerization is to be avoided, it is not necessary to add any polymerization initiators, and the acid and heat are normally sufficient to induce the cleavage of the carbon-carbon double bond and the formation of carbene radicals. Moreover, in the case of acrylamide and other monomers having a low degree of reactivity, it is also not normally necessary to use a polymerization inhibitor in the treating solution. While applicant does not wish to be bound by any particular theory, it is believed that the acid may also act as a polymerization inhibitor as well as a catalyst for the reaction. That is, it is believed that the anions from the acid react with some of the carbene radicals to terminate the reaction and prevent significant polymerization. However, with some monomers which more rapidly polymerize upon the formation of carbene radicals, it may be necessary to include in the treating solution one or more polymerization inhibitors, which are known in the art for the particular monomer selected.
Those of ordinary skill in the art will recognize that the proper extent of treatment can be determined by detecting the onset of homopolymerization of the monomer in the treatment solution. Thus, since graft polymerization is normally accompanied or preceded by homopolymerization of the monomer, which homopolymerization appears as a precipitate or cloudiness in the treatment solution, the formation of homopolymers should be avoided in the first step. Of course, while the present invention seeks to obtain essentially single molecule additions of the monomer to the polymer chains, it will be understood that there will inevitably be some amounts of graft dimerization and/or trimerization on the polyamides and in the treatment solution. Theoretically, there can be a maximum addition of one molecule to every six units of the polymer chain in the case of nylon 6,6 or nylon 6. However, accurate determinations of the exact numbers of additions are difficult on a simple weight basis since nylon picks up about 5 percent water, and the total addition of monomer to a polymer is generally too small to measure. In one case the monomer addition was measured as less than 0.03 percent by weight.
Although the prefered practice of the present invention seeks to obtain essentially single molecule addition of the monomer to the polymer chains in the first step of the process, the addition of dimers and trimers of the monomer is also satisfactory. Therefore, as used in the present specification and claims, the term "essentially single molecule addition" will be understood to include additions of single, double and triple molecules of the monomer to the polymer chains in the first step of the process. Significant additions of anything larger than trimers would be considered graft polymerization and is therefore to be avoided.
The temperature in the second step is maintained at whatever level is necessary to obtain the optimum speed and degree of graft polymerization. For example, the temperature could be maintained at the same temperature as the first step or could be raised to about 85.degree. C. or 90.degree. C. at the end of the first step and maintained at that temperature for the remainder of the treatment process. Generally, there would normally be no occasion in which the temperature in the second step is below the temperature of the first step.
The acid, monomer, fabric and heat may be combined in the first step of the treatment process in virtually any desired order, so long as each of these four elements is present prior to initiating polymerization for a sufficient time to allow uniform dispersal and intimate contact of the monomer with the fiber surfaces. For example, the order of combination in the first step may be any of the following: (1) addition of acid and monomer to water, addition of a delayed initiator (to be activated in the second step), and heating to the desired temperature; (2) addition of monomer and a delayed initiator to water, addition of acid and heating to the desired temperature; (3) addition of monomer to water, heating to desired temperature and addition of acid and delayed initiator; or (4) addition of acid, monomer to water, addition of delayed initiator and heating to desired temperature. Other possible orders of carrying out the first step will be evident to those skilled in tha art based on the present disclosure.
Uniform dispersal and intimate contact may be assisted by various forms of agitation or flow of the aqueous treating solution around and between the fiber surfaces. For example, in the case of the treatment of fibers in the form of fabric piece goods, agitation may be accomplished by the paddles in a conventional paddle tub. Alternatively, for fibers in the form of fabrics which are processed in the form of rolls on a beam, the aqueous treating solution may be circulated around and through the beam by conventional pressure means.
The time necessary for attaining uniform dispersal intimate contact and attachment of the monomer to the polymer fibers will vary with the particular method of contacting the fibers with the aqueous solution, and may range from one second to thirty minutes. Although it is possible that the aqueous solution could be contacted with the fibers by spraying, paddling, dipping or other means, it is most preferable to immerse the fibers in a bath formed by the aqueous solution. Using such immersion techniques, relatively short periods of time are necessary before polymerization may begin. For example, about 10 minutes is usually sufficient with adequate agitation or circulation of the aqueous solution.
After uniform dispersal, intimate contact and attachment of the monomer to the polymer fibers have been achieved, graft polymerization of the monomer on the fibers may be commenced with the use of a suitable polymerization initiator such as peroxide or persulfate compounds which are known in the art. The particular initiator selected will depend upon the particular polymer fiber, the particular monomer used and the speed or other conditions of the polymerization desired. The weight ratio of initiator may range from about 5000 parts by weight of monomer to 1 part by weight of initiator up to about one part by weight of monomer to 20 parts by weight of initiator. Preferably, the weight ratio should be about 9 to 0.67 parts by weight of monomer per one part by weight of initiator. Increasingly the amount of initiator above the aforementioned weight ratio of 0.67 parts by weight of monomer to one part by weight of initiator confers minimal improvement to the process. If desired, the initiator may be added during the first step so long as it is not activated until uniform dispersal, intimate contact and attachment of the monomer with the fiber surfaces are achieved. The initiation of polymerization may then be carried out, such as by raising the temperature, changing the pH or changing some other condition which will activate the initiator.
Finally, the polymerization is allowed to continue until there has been substantial graft polymerization of the monomer on the polymer fibers to modify the surface properties of the fibers. Generally, a rather low degree of polymerization is desirable, since excessive polymerization will result in large amounts of homopolymer in the fibers and in the process equipment, which must be cleaned and washed out after completion of the process. Therefore, it is preferable to avoid polymerization which significantly clouds the treating solution, and such small polymers as will remain in solution are preferred.
To this end, it is preferable to carry out the process of the present invention using very low concentrations of monomer, such as in the range of about 0.01 to about 1.0 weight percent of the total solution and preferably about 0.02 to 0.5 weight percent of the solution. Such low concentrations allow easy control of the polymerization reaction so that a relatively clear solution is maintained throughout the process, and the processing equipment and fibers treated may be easily cleaned and washed out.
It appears that the add-on of graft polymer should be below 1.0 weight percent for synthetic fibers using MBA and N,N.sup.1 -(1,2 dihydroxyethylene)-bis-acrylamide (glyoxal acrylamide) and below 2.0 weight percent for natural fibers. Optimum processing according to the present invention results in the permanent add-on of about 0.6 weight percent or even less of graft polymer based upon the weight of the polymer fiber.
While the process of the present invention may be used at any of a number of stages during the usual processing of polymer fibers or fabrics or other structures made from such fibers, it has been found preferable to use the process before the dyeing of the fibers or before there is any treatment of the fibers which would result in encapsulation or coating of the fiber surface. Thus, it is usual practice to encapsulate or "lock on" the dye or other fiber treatment chemicals, and such coatings will often interfere with the addition of the monomer to the polymer fiber. To the extent that there would still be addition, this would be gradually washed off through many washings.
Therefore, it is preferable that the fibers be scoured (e.g. washed with detergent) and rinsed prior to carrying out the treatment process of the present invention in order to remove dirt and other chemicals which may be present on the fibers. The process may then be carried out before dyeing or even in the dye bath but before the after treatment to set the dye. However, it is preferable to drain the treating solution and rinse the fibers before dyeing, in order to remove acid and excess homopolymer, which may interfere with reaction of the dye with the dye sites on the surface of the polymer fibers.
Whereas many of the teachings of the prior art such as Aikawa and Tanner involved the treating of fibers in the absence of polymerization initiators to avoid homopolymerization, the present invention employs polymerization initiators. Polymerization initiators are generally of four basic types, namely, peroxides, persulfates, acids and ceric compounds.
Non-limiting examples of polymerization initiators that may possibly be utilized in this invention include inorganic peroxides, e.g., hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and various organic peroxy compounds illustrative examples of which are the dialkyl peroxides, e.g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, distearyl peroxide, di-(tert.-butyl) peroxide and di-(tert.-amyl) peroxide, such peroxides often being designated as ethyl, propyl, lauryl, oleyl, stearyl, tert.-butyl and tert.-amyl peroxides; the alkyl hydrogen peroxides, e.g., tert.-butyl hydrogen peroxide (tert.-butyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e.g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e.g., acetyl benzoyl peroxide, propionyl benzoyl peroxide, etc.; terpene oxides, e.g., ascaridole, etc.; and salts of inorganic peracids, e.g., ammonium persulfate and potassium persulfate.
When fibers are treated according to this invention, the reaction may also be initiated by ceric ions, for example, in the form of ceric salts such as ceric nitrate, ceric sulfate, ceric ammonium nitrate, ceric ammonium sulfate, ceric ammonium pyrophosphate, ceric iodate, and the like.
Non-limiting examples of suitable acids for use in the present invention include hydrochloric, phosphoric, sulfuric, nitric, acetic, formic, oxalic, tartaric, monochloroacetic, dichloroacetic, trichloroacetic and similar acids. Formic and hydrochloric acid have been found to be particularly suitable in carrying out the present invention. It is possible that an acid can function as both a catalyst and initiator, e.g., formic acid.
Non-limiting examples of unsaturated types of monomers that may possibly be utilized in this invention include N,N'methylene-bis-acrylamide (CH.sub.2 (NHCOCH:CH.sub.2).sub.2), N,N'-(1,2 dihyroxyethylene)-bis-acrylamide, acrylamide, acrylic acid, 2-propyn-1-ol, crotonic acid, tetraethylene glycol, styrene, alpha-methyl styrene, 1,1-diphenyl ethylene, alpha-vinyl naphthalene, vinylpyridine, 2-chloro-2,3-butadiene, methacrylic acid, methacrylamide, N-methylolacrylamide, N-methyl-N-vinyl formamide, N-vinyl pyrrolidone, 3-, 4- or 5-methyl-N-vinyl pyrrolidone, vinyl oxyethylformamide, methyl acrylate, ethyl acrylate, octyl methyl methacrylate, vinylacrylate, acrylonitrile, methacrylonitrile, acrylyl chloride, vinyl methyl ketone, methallylalcohol, acrolein, methacrolein, vinyl acetate, p-vinyl phenyl acetate, methylmethacrylate, vinyl chloride, vinylidene chloride, p-chlorostyrene, 2,5-dichlorostyrene, 1,1,7-trihydro-perfluoroheptyl acrylate, methyl alphachloroacrylate, acrylyl cyanide, styrene sulfonic acid, salts and esters of styrene sulfonic acid and glycidyl methacrylate. The preferred monomers are N,N'-methylene-bis-acrylamide (MBA) and N,N'(1,2 dihydroxyethylene)-bis-acrylamide.
A monomer may function as an acid. MBA, for example, is slightly acidic in aqueous solution. It is also possible to use specially modified monomer which can provide special characteristics to the fibers, or fabrics made therefrom, such as crease softness, lubricity (e.g. by including silicon groups on the monomer), adhesion, optical brightness, anti-bacterial, anti-fungal or anti-mildew properties, etc.
In a preferred embodiment of this invention with the monomer utilized selected from the group consisting of MBA and N,N'(1,2 dihydroxyethylene)-bis-acrylamide, and the polymer fibers are nylon 66, or nylon 6, the graft polymerization step of the process is conducted for a period of time between about 0.5 minutes and about 2 hours, preferably between about 1.0 minute and about 30 minutes, at a temperature of about 80.degree. C. to 90.degree. C. The amount of initiator in the treating solution is between about 1.times.10.sup.-4 weight percent and 5.0 weight percent.
An illustrative preferred embodiment would be to immerse the fibers in an aqueous solution at about 70.degree. C. containing about 0.01 weight percent hydrochloric acid or about 0.03 weight percent formic acid, and about 0.04 weight percent MBA, rapidly raising the temperature of the solution to about 90.degree. C. and agitating the fibers in the solution for about 10 minutes. Thereafter, about 0.02 weight percent of potassium persulfate is added to the solution to initiate polymerization. The polymerization is continued for about 10 minutes, followed by draining the solution from the fibers and rinsing the fibers in water, all weight percents being on the basis of percentage by weight of the total solution.
The particular concentrations of the monomer, acid and the initiator in the treating solution will vary widely depending upon such factors as the nature of the particular monomer, acid and initiator, the time and temperature of the treatment, and the nature and form of the fiber being treated. While certain concentrations may be fairly essential for a particular monomer, acid and initiator under a given set of treatment conditions, applicant cannot give general ranges which would apply to all monomers, acids and initiators under all conditions, but those of ordinary skill in the art will be able to optimize the concentrations by routine experimentation on the basis of the present disclosure.
Attaining the desired degree of treatment according to this invention would depend on the strength of the initiator and the concentration of the monomer and acid. Thus, for example, a strong initiator, one that is inherently strong and/or having a high concentration of initiator, would require a lower monomer concentration. Conversely, a weak initiator, one that is inherently weak and/or having a low concentration of initiator, would require a higher monomer concentration. In the latter case, the treatment according to this invention can be controlled by draining the initiator containing solution from the fabric once the desired extent of polymerization has been achieved.
After polymerization begins, such polymerization being a function of the concentration and type of the acid, the unsatured monomer, fabric, initiator and the speed and type of the agitation equipment being used, the polymer fibers are allowed to remain in solution at the required temperature long enough to assure that uniform graft polymerization ("substantial polymerization") has occurred, such time usually not exceeding 30 minutes. The fibers can then be rinsed to neutralize the pH and remove excess homopolymers, if any.
The invention will now be described in greater detail by reference to the following specific, non-limiting examples. The examples which follow are laboratory examples. For ease of performance in the laboratory, in many of the examples, the amount of the monomer was present in a higher concentration than would be used commercially. This was done for convenience, such as to facilitate rapid polymerization. The excess homopolymer was discarded. Conventionally, the amount of monomer would be dropped so as to minimize the loss of homopolymer.
In the data, there are a number of cases where the add-on is given as "0". This does not indicate that there was no add-on, but merely that such an add-on was not measureable with the equipment available to the applicant. Indeed, in some of the laboratory runs the final weight was below the initial weight, because the add-on was so low that it was below the weighing errors.
Routine skill could achieve the optimal commercial concentrations of monomer which would vary with the type of apparatus used, and the polymerization conditions that could be achieved with such apparatus in a given facility.
EXAMPLES 1-197
The following fabrics were treated in accordance with the method of the present invention in Examples 1-155:
(1) nylon 6,6
(2) cotton
(3) nylon 6
(4) wool
(5) silk
(6) cellulosic fibers (rayon)
(7) cellulosic fibers (acetate)
The fabric samples were vigorously hand washed with "IVORY" soap in tap water. The fabrics were then rinsed, dried and heated. While the fabric samples were still warm, they were weighed and the initial "drop test" (Init. Drop Test) was then performed. The weight (Init. Wt.) of the fabric was recorded. All samples were weighed in grams on a OHAUS, triple beam balance or a Mettler PC 180 scale.
The "drop test" consisted of using a common medicine dropper to place one drop of tap water onto the fabric sample from a height of approximately one inch above the fabric. After the water was dropped on the fabric, comparative observations were made as to the interaction between the fabric and the water. The scale of the drop test was relatively subjective and is as follows:
Very Poor--Fabric repels the water, i.e., waterproof
Poor--Water beads on fabric
Fair--Water will wet fabric
Good--Water will wick slowly
Very Good--Water will wick moderately
Excellent (Exc.)--Water wicks very quickly
Each fabric sample was then placed into a one liter glass beaker containing reaction solution containing a specified amount of either tap or distilled water. Distilled water was used when high concentrations of monomer and elevated temperatures could possibly cause premature polymerization. All water volumes were measured in milliliters with a plus or minus five percent error. To complete the reaction solution, a monomer and acid catalyst were added. The reaction solution was raised to a specified temperature by a hot plate with simultaneous agitation of the solution. The solution was allowed to stabilize (attain uniform pH and monomer concentration through) for about 60 seconds or more before initiator was introduced.
The catalysts that were used included formic acid (98%), concentrated hydrochloric acid (33%), and ferrous sulfate. Unless otherwise indicated on the Tables herein, the acid utilized refers to formic acid.
The monomers introduced into the reaction solution were chosen from the following:
(1) NBA: N,N'-methylene-bis-acrylamide, heretofore referred to as "MBA"
(2) NEBA: N,N'-(1,2 dihydroxyethylene)-bis-acrylamide, heretofore referred to as "glyoxal acrylamide"
(3) NBA/DMS: reaction product of NBA and dimethyl sulfate
(4) NEBA/DMS: reaction product of NEBA and dimethyl sulfate
(5) NBA/MCA: reaction product of NBA and monochloroacetic acid
(6) NEBA/MCA: reaction product of NEBA and monochloroacetic acid
(7) NBA/Formic: reaction product of NBA and 98% formic acid
(8) NEBA/Formic: reaction product of NEBA and 98% formic acid
(9) Acrylamide
(10) Acrylic Acid
(11) 2-propyl-1-ol
(12) Crotonic Acid
(13) Tetraethylene Glycol
After solution stabilization, an initiator was introduced into the reaction solution. The initiator was selected from the following:
A. Peroxide--30% hydrogen peroxide
B. Persulfate--potassium persulfate
C. Ceric--Ceric Ammonium Nitrate
D. Formic--98% formic acid
E. Sodium Peroxide
F. HCl
After polymerization began (onset of cloudiness in solution indicated polymerization), the fabric samples were allowed to remain in solution at the specified temperature until "substantial polymerization" occurred. The time to achieve "substantial polymerization" was between about 7 seconds and about 4 minutes depending upon several factors. The time interval from the addition of the initiator to the onset of cloudiness is referred to herein as "time to polymerize".
After "substantial polymerization" occurred, the sample was removed and vigorously washed with "IVORY" soap, then rinsed, dried and heated.
While each sample was still warm, the weight of the fiber was recorded. Then the final drop test was conducted. The percentage weight gain for each sample was calculated as follows: ##EQU1##
The results for Examples 1-197 are given in Table 1 hereinbelow.
Tables 2-21 hereinbelow summarize some of the results given in Table 1.
It is very difficult to present the data pointing up the effect of a single variable. Thus, varying one variable may result in the necessity to vary other variables as the variables are interrelated. Thus, a change in temperature will cause the same concentration of monomer and polymerization initiator to react differently.
Table 2 illustrates the variation of one variable, namely the presence of acid at different temperatures and initiator concentrations. The results are in the columns "Percent Add-On" and "Time To Polymerize".* Table 2 presents four (4) pairs, each showing the effect of acid.
* In the Tables the results are "Percent Add-On", "Time To Polymerize" and/or "Final Drop Test".
In Table 3, the first three examples are a comparative group, and the next three examples are a comparative group, with the final example being illustrative of no acid and low initiator. In Table 3 the acid is used as a catalyst, and the effect of initiator is shown. However, the chart also shows, which is why the last example is inserted, that the time can be varied to produce excellent results. This shows the interrelationship of the separate variables.
Table 4 demonstrates that at different concentrations, different monomers work if one varies some of the variables, such as acid concentration, or weight percent initiator.
Table 5 shows the effect of temperature in relation to different monomers, the data being presented in pairs with preferred temperature being compared to inoperative temperature in each pair.
Table 6 shows that poor results are always obtained below the threshold temperature of about 75.degree. C. not withstanding changes in the initiator, the type and weight percent monomer, the presence of acid catalyst and the time to polymerize. As heretofore noted, acid is not needed when the monomer itself is acid as in these examples.
Table 7 shows the effect of changes in temperature with NBA. The "Time To Polymerize" was not recorded in some instances. The weight percentage concentration of the monomer was varied as this was necessary to obtain a reaction.
Tables 8 and 9 likewise show the effect of variation in temperature with different monomers. The concentration of the monomer had to be adjusted to enable the reaction to go forward.
Tables 10 and 11 show the effect of temperature increments with different initiators. It is clear that the threshold temperature of 75.degree. C. is vital.
Tables 12 through 21 correspond to the preceding Tables 2 through 11 except that the fabric is cotton, whereas Tables 2 through 11 deal with nylon 6,6 as the fabric.
EXAMPLES 198-207
Examples 198-207 illustrate the permanency of enhanced qualities imparted to fabrics treated according to the present invention.
Preweighed, scoured, heat set nylon 6,6 and cotton fabric received an initial drop test. Two samples (one nylon 6,6 sample and one cotton sample) weighing approximately 60-70 g were put into a 5 liter stainless steel vessel containing 3 liters of tap water heated to a temperature of 95.degree. C. to 100.degree. C. by a hot plate. The solution contained 50 g of N,N'methylene-bis-acrylamide and 50 ml of formic acid. After 30 seconds, an initiator (potassium persulfate) was added to induce polymerization. After the solution remained cloudy for 30 seconds, the samples were removed, washed, dried, heated and weighed. Both the nylon 6,6 and the cotton samples were subjected to a wash test in a standard home washing machine that consisted of a 10 minute cycle of agitation in 55.degree. C. tap water containing 30 g of "TIDE" home laundry detergent. The water was then extracted and the samples were subjected to a warm rinse cycle with agitation and then a final water extraction (spin cycle). The samples were weighed after 2, 5, 10 and 15 washings. Table 22 lists the percentage weight gain (% add-on) found after each washing.
Table 22, given hereinbelow, clearly shows that fibers treated according to the present invention continue to have considerable percentage add-on of polymer even after a great number of washings. Since the percentage add-on is a reflection of the enhanced water absorbent and antistatic properties imparted to fabrics treated in accordance with this invention, it is clear that fabrics so treated are afforded permanent enhanced properties. The results shown in Table 22 are plotted in the Figure accompanying this specification.
EXAMPLE 208
Example 208 illustrates the beneficial soil release properties imparted to fabrics treated in accordance with the present invention.
Two pieces of Nylon 6,6 fabric were sewn together. One piece was treated in accordance with this invention; the other piece was untreated. The resultant piece of fabric was agitated in a warm aqueous solution of dirt, organic matter, oil, grape juice and mustard. It was then washed in a standard home washer with detergent. There was a substantial difference in fabric appearance. The side treated in accordance with the invention had a slight off-white appearance and the other side (untreated fabric) was stained brown with black specks.
TABLE 1__________________________________________________________________________ Amt. of Amt. Amt. Mono- of Vol. of of Time to Init. Init. Final Final %Ex. mer, Acid, Water, Temp., Initi- Polymer- Wt., Drop Wt., Drop Add-No. Fabric Monomer g. ml ml .degree.C. Initiator ator ize g Test g Test On__________________________________________________________________________ 1 Nylon NBA 10 20 600- 96-100 Persulfate 0.5 g 0.5 sec. 3.97 Poor 4.10 Exc. .7 6,6 2 Cotton NBA 10 20 600 96-100 Persulfate 0.5 g 0.5 sec. 3.29 Good 3.35 Exc. 1.8 3 Nylon NBA 10 0 600 96-100 Peroxide 10 ml 6 min., 2.44 Poor 2.47 Exc. 1.2 6,6 15 sec. 4 Cotton NBA 10 0 600 96-100 Peroxide 10 ml 6 min. 3.18 Good 3.21 Exc. .9 15 sec. 5 Nylon NBA 10 10 600 96-100 Peroxide 10 ml 2 min. 3.39 Poor 3.44 Exc. 1.5 6,6 10 sec. 6 Cotton NBA 10 10 600 96-100 Peroxide 10 ml 2 min. 3.63 Good 3.69 Exc. 1.9 10 sec. 7 Nylon NBA 10 0 600 89-93 Peroxide 5 ml 47 min., 2.60 Poor 2.62 Exc. .8 6,6 43 sec. 8 Cotton NBA 10 0 600 89-93 Peroxide 5 ml 47 min., 2.61 Good 2.69 Exc. 3.1 43 sec. 9 Nylon NBA 10 10 600 89-93 Peroxide 5 ml 6 min., 2.84 Poor 2.86 Exc. .7 6,6 40 sec. 10 Cotton NBA 10 10 600 89-93 Peroxide 5 ml 6 min., 2.59 Good 2.63 Exc. 1.5 40 sec. 11 Nylon NBA 10 0 600 89-93 Peroxide 2.5 ml 83 min., 2.94 Poor 2.97 Exc. 1.0 6,6 20 sec. 12 Cotton NBA 10 0 600 89-93 Peroxide 2.5 ml 83 min., 2.61 Good 2.67 Exc. 2.3 20 sec. 13 Nylon NBA 10 10 600 89-93 Peroxide 2.5 ml 10 min., 3.01 Poor 3.04 Exc. 1.0 6,6 16 sec. 14 Cotton NBA 10 10 600 89-93 Peroxide 2.5 ml 10 min., 2.89 Good 2.96 Exc. 2.4 16 sec. 15 Nylon NBA 10 0 600 88-92 Peroxide 1 ml 139 min., 4.98 Poor 5.01 Exc. .6 6,6 42 sec. 16 Cotton NBA 10 0 600 88-92 Peroxide 1 ml 139 min., 4.74 Good 4.85 Exc. 2.3 42 sec. 17 Nylon NBA 10 10 600 88-92 Peroxide 1 ml 11 min., 3.19 Poor 3.22 Exc. .9 6,6 16 sec. 18 Cotton NBA 10 10 600 88-92 Peroxide 1 ml 11 min., 2.70 Good 2.76 Exc. 2.2 16 sec. 19 Nylon NBA 1 10 600 89-92 Persulfate .1 g 35 sec. 3.05 Poor 3.07 Exc. .7 6,6 20 Cotton NBA 1 10 600 89-92 Persulfate .1 g 35 sec. 3.34 Good 3.36 Exc. .6 21 Nylon NBA 2 10 600 69-70 Persulfate .1 g -- 2.61 Poor 2.61 Poor 0 6,6 22 Cotton NBA 2 10 600 69-70 Persulfate .1 g -- 5.91 Good 5.91 Good 0 23 Nylon NEBA 2 20 600 89-92 Persulfate .5 g 4 min., 3.48 Poor 3.51 Exc. .9 6,6 10 sec. 24 Cotton NEBA 2 20 600 89-92 Persulfate .5 g 4 min., 3.50 Good 3.52 Exc. .6 10 sec. 25 Nylon NEBA 5 20 600 69-70 Persulfate 5 g 40 sec. 3.28 Poor 3.28 Poor 0 6,6 26 Cotton NEBA 5 20 600 69-70 Persulfate 5 g 40 sec. 3.41 Good 3.41 Good 0 27 Nylon NBA/For- 2 10 600 89-93 Persulfate .1 g 40 sec. 2.83 Poor 2.86 Exc. 1.06 6,6 mic 1:4 28 Cotton NBA/For- 2 10 600 89-92 Persulfate .1 g 40 sec. 4.94 Good 4.98 Exc. .8 mic 1:4 29 Nylon NBA/For- 2 10 600 69-70 Persulfate .5 g 2 min., 3.19 Poor 3.19 Poor 0 6,6 mic 1:4 55 sec. 30 Cotton NBA/For- 2 10 600 69-70 Persulfate .5 g 2 min., 3.02 Good 3.02 Good 0 mic 1:4 55 sec. 31 Nylon NBA/DMS 2 10 600 89-92 Persulfate .1 g 57 sec. 3.70 Poor 3.75 Exc. 1.4 6,6 1:3 32 Cotton NBA/DMS 2 10 600 89-92 Persulfate .1 g 57 sec. 3.44 Good 3.49 Exc. 1.5 1:3 33 Nylon NBA/DMS 2 10 600 69-70 Persulfate .5 g 3 min., 2.70 Poor 2.70 Poor 0 6,6 1:3 4 sec. 34 Cotton NBA/DMS 2 10 600 69-70 Persulfate .5 g 3 min., 2.85 Good 2.85 Good 0 1:3 4 sec. 35 Nylon NBA/ 2 10 600 89-92 Persulfate .05 g 1 min., 3.03 Poor 3.07 Exc. 1.3 6,6 MCA 13 sec. 1:2 36 Cotton NBA/ 2 10 600 89-92 Persulfate .05 g 1 min., 3.14 Good 3.18 Exc. 1.3 MCA 13 sec. 1:2 37 Nylon NBA/ 2 10 600 69-70 Persulfate 1.5 g 2 min., 2.9 Poor 2.9 Poor 0 6,6 MCA 10 sec. 1:2 38 Cotton NBA/ 2 10 600 69-70 Persulfate 1.5 g 2 min., 3.52 Good 3.52 Good 0 MCA 10 sec. 1:2 39 Nylon NEBA/ 3 20 600 89-92 Persulfate .5 g 7 min., 3.20 Poor 3.22 Exc. .6 6,6 FORMIC 44 sec. 1:4 40 Cotton NEBA/ 3 20 600 89-92 Persulfate .5 g 7 min., 3.62 Good 3.64 Exc. .6 FORMIC 44 sec. 1:4 41 Nylon NEBA/ 3 20 600 69-70 Persulfate 1 g 4 min., 2.58 Poor 2.58 Poor 0 6,6 FORMIC 30 sec. 1:4 42 Cotton NEBA/ 3 20 600 69-70 Persulfate 1 g 4 min., 2.4 Good 2.4 Good 0 FORMIC 30 sec. 1:4 43 Nylon NEBA/ 25.6 1 ml 500 89-92 Persulfate 1 g 10 sec. 1.546 Poor 1.556 Exc. .6 6,6 MCA (HCl) 1:3 44 Cotton NEBA/ 25.6 1 ml 500 89-92 Persulfate 1 g 10 sec. 1.819 Good 1.830 Exc. .6 MCA (HCl) 1:3 45 Nylon NEBA/ 25.6 1 ml 550 69-70 Persulfate 1 g 1 min., 1.089 Poor 1.090 Poor 0 6,6 MCA (HCl) 50 sec. 1:3 46 Cotton NEBA/ 25.6 1 ml 550 69-70 Persulfate 1 g 1 min., 1.627 Good 2.626 Good 0 MCA (HCl) 50 sec. 1:3 47 Nylon NBA .05 1 ml 500 98-100 Persulfate 1 g 45 sec. 1.204 Poor 1.203 Exc. 0 6,6 (HCl) 48 Cotton NBA .05 1 ml 500 98-100 Persulfate 1 g 45 sec. 1.639 Good 1.637 Exc. 0 (HCl) 49 Nylon NBA .25 20 500 98-100 Persulfate .03 g 1 min., 1.255 Poor 1.258 Exc. .2 6,6 50 sec. 50 Cotton NBA .25 20 500 98-100 Persulfate .03 g 1 min., 1.484 Good 1.483 Exc. 0 50 sec. 51 Nylon NBA 50 0 500 89-91 Peroxide .15 ml 0 1.377 Poor 1.398 Exc. 1.5 6,6 52 Cotton NBA 50 0 500 89-91 Peroxide .15 ml 0 1.757 Good 1.847 Exc. 5.1 53 Nylon NEBA 50 0 500 94-96 Persulfate .01 g 20 sec. 1.174 Poor 1.177 Good .3 6,6 54 Cotton NEBA 50 0 500 94-96 Persulfate .01 g 20 sec. 2.107 Good 2.370 Exc. 12.5 55 Nylon NBA/DMS .15 1 ml 500 98-100 Persulfate .1 g 2 min. 1.228 Poor 1.228 Exc. 0 6,6 1:3 (HCl) 56 Cotton NBA/DMS .15 1 ml 500 98-100 Persulfate .1 g 2 min. 1.635 Good 1.631 Exc. 0 1:3 (HCl) 57 Nylon NBA/DMS .5 1 ml 500 98-100 Persulfate .1 g 20 sec. 1.377 Poor 1.377 Exc. 0 6,6 1:3 (HCl) 58 Cotton NBA/DMS .5 1 ml 500 98-100 Persulfate .1 g 20 sec. 1.621 Good 1.628 Exc. .4 1:3 (HCl) 59 Nylon NBA/DMS 20 1 ml 500 98-100 Persulfate .03 g 30 sec. 1.369 Poor 1.385 Exc. 1.2 6,6 1:3 (HCl) 60 Cotton NBA/DMS 20 1 ml 500 98-100 Persulfate .03 g 30 sec. 1.450 Good 1.501 Exc. 4.2 1:3 (HCl) 61 Nylon NEBA 7.5 1 ml 500 98-100 Persulfate .1 g 6 sec. 1.605 Poor 1.614 Exc. .6 6,6 (HCl) 62 Cotton NEBA 7.5 1 ml 500 98-100 Persulfate .1 g 6 sec. 1.561 Good 1.569 Exc. .5 (HCl) 63 Nylon NEBA/ 37.5 1 ml 500 98-100 Persulfate .01 g 10 sec. 1.350 Poor 1.353 Exc. .2 6,6 DMS (HCl) 1:3 64 Cotton NEBA/ 37.5 1 ml 500 98-100 Persulfate .01 g 10 sec. 1.162 Good 1.175 Exc. 1.1 DMS (HCl) 1:3 65 Nylon NBA/ 3.75 1 ml 500 98-100 Persulfate .01 g 10 sec. 1.632 Poor 1.648 Exc. 1 6,6 FORMIC (HCl) 1:4 66 Cotton NBA/ 3.75 1 ml 500 98-100 Persulfate .01 g 10 sec. 1.652 Good 1.724 Exc. 4.4 FORMIC (HCl) 1:4 67 Nylon NBA/ 10 1 ml 500 98-100 Persulfate .01 g 4 sec. 1.471 Poor 1.474 Exc. .2 6,6 FORMIC (HCl) 1:4 68 Cotton NBA/ 10 1 ml 500 98-100 Persulfate .01 g 4 sec. 1.449 Good 1.457 Exc. .6 FORMIC (HCl) 1:4 69 Nylon NBA/ 30 20 500 69-70 Peroxide 2.5 ml -- 1.849 Poor 1.849 Poor 0 6,6 MCA (.003 g Fe) 1:3 70 Cotton NBA/ 30 20 500 69-70 Peroxide 2.5 ml -- 1.298 Good 1.298 Good 0 MCA (.003 g Fe) 1:3 71 Nylon NBA/ 30 0 500 89-91 Peroxide 1 ml -- 1.651 Poor 1.660 Exc. .5 6,6 MCA (.003 g Fe) 1:3 72 Cotton NBA/ 30 0 500 89-91 Peroxide 1 ml -- 1.659 Good 1.667 Exc. .5 MCA (.003 g Fe) 1:3 73 Nylon NBA/ 30 0 500 69-70 Formic 40 ml No 1.873 Poor 1.873 Poor 0 6,6 MCA reaction 1:3 74 Cotton NBA/ 30 0 500 69-70 Formic 40 ml No 1.682 Good 1.682 Good 0 MCA reaction 1:3 75 Nylon NBA/ 30 0 500 98-100 Formic 40 ml -- 1.158 Poor 1.161 Exc. .3 6,6 MCA 1:376 Cotton NBA/ 30 0 500 98-100 Formic 40 ml -- 1.516 Good 1.520 Exc. .3 MCA 1:3 77 Nylon NBA/ 30 30 500 69-70 Ceric .1 g 35 sec. .976 Poor .976 Poor 0 6,6 MCA 1:3 78 Cotton NBA/ 30 30 500 69-70 Ceric .1 g 35 sec. 1.724 Good 1.722 Good 0 MCA 1:3 79 Nylon NBA/ 30 0 500 89-91 Ceric .1 g 15 sec. 1.077 Poor 1.986 Exc. .8 6,6 MCA 1:3 80 Cotton NBA/ 30 0 500 89-91 Ceric .1 g 15 sec. 1.230 Good 1.237 Exc. .6 MCA 1:3 81 Cotton NBA 10 0 500 98-100 Formic 40 ml -- 1.361 Good 1.375 Exc. 1.0 82 Nylon NBA 80 0 500 69-70 Formic 40 ml No reac. 1.441 Poor 1.441 Poor 0 6,6 83 Cotton NBA 80 0 500 69-70 Formic 40 ml No reac. 1.478 Good 1.478 Good 0 84 Nylon NBA 40 10 500 69-70 Peroxide 10 ml 5 min., 1.250 Poor 1.248 Poor 0 6,6 (.003 g Fe) 20 sec. 85 Cotton NBA 40 10 500 69-70 Peroxide 10 ml 5 min., 1.736 Good 1.732 Good 0 (.003 g Fe) 20 sec. 86 Nylon NBA 40 10 500 69-70 Ceric 2 g 16 sec. 1.352 Poor 1.354 Poor 0 6,6 87 Cotton NBA 40 10 500 69-70 Ceric 2 g 16 sec. 1.683 Good 1.680 Good 0 88 Nylon NEBA 20 0 500 98-100 Formic 30 ml -- 1.307 Poor 1.324 Exc. 1.3 6,6 89 Cotton NEBA 20 0 500 98-100 Formic 30 ml -- 1.343 Good 1.359 Exc. 1.2 90 Nylon NEBA 20 0 500 89-91 Peroxide 5 ml 25 sec. 1.254 Poor 1.307 Exc. 4.2 6,6 (.003 g Fe) 91 Cotton NEBA 20 0 500 89-91 Peroxide 5 ml 25 sec. 1.019 Good 1.043 Exc. 2.4 (.003 g Fe) 92 Nylon NEBA 50 10 500 69-70 Peroxide 10 ml 6 min., 1.105 Poor 1.106 Poor 0 6,6 (.003 g Fe) 15 sec. 93 Cotton NEBA 50 10 500 69-70 Peroxide 10 ml 6 min., 1.251 Good 1.253 Good 0 (.003 g Fe) 15 sec. 94 Nylon NEBA 90 0 500 95-97 Ceric 6.4 g -- 1.115 Poor 1.130 Exc. 1.3 6,6 95 Cotton NEBA 90 0 500 95-97 Ceric 6.4 g -- 1.840 Good 1.858 Exc. 1.0 96 Nylon NEBA 100 20 500 69-70 Ceric 10 g -- 1.460 Poor 1.462 Poor 0 6,6 97 Cotton NEBA 100 20 500 69-70 Ceric 10 g -- 1.327 Good 1.327 Good 0 98 Nylon NBA 10 0 500 89-91 Ceric .3 g 1 min., 1.633 Poor 1.648 Exc. .9 6,6 15 sec. 99 Cotton NBA 10 0 500 89-91 Ceric .3 g 1 min., 1.364 Good 1.368 Good .3 15 sec.100 Nylon NBA 10 20 500 65 Persulfate .25 g 6 min., 1.572 Poor 1.574 Poor 0 6,6 35 sec.101 Nylon NBA 2 1 500 100 Persulfate .03 g 6 sec. 1.629 Poor 1.636 Exc. .4 6,6102 Cotton NBA 2 1 500 100 Persulfate .03 g 6 sec. 1.525 Good 1.529 Exc. .3103 Nylon NEBA 5 20 500 65 Persulfate 2 g 1 min., 1.652 Poor 1.652 Poor 0 6,6 55 sec.104 Nylon NEBA 5 20 500 70 Persulfate 2 g 55 sec. 1.514 Poor 1.514 Poor 0 6,6105 Cotton NEBA 5 20 500 70 Persulfate 2 g 55 sec. 1.523 Good 1.522 Good 0106 Nylon NEBA 5 20 500 73 Persulfate 2 g 48 sec. 1.500 Poor 1.502 Poor 0 6,6107 Nylon NEBA 5 20 500 75 Persulfate 2 g 40 sec. 1.694 Poor 1.693 Very 0 6,6 Good108 Nylon NEBA 5 20 500 77 Persulfate 2 g 20 sec. 1.381 Poor 1.380 Exc. 0 6,6109 Nylon NEBA 2 20 500 80 Persulfate .5 g 58 sec. 1.654 Poor 1.658 Exc. .2 6,6110 Cotton NEBA 2 20 500 80 Persulfate .5 g 58 sec. 1.147 Good 1.146 Good 0111 Cotton NEBA 3 20 500 95 Persulfate .5 g 35 sec. 1.596 Good 1.595 Good 0112 Cotton NEBA 3 20 500 87 Persulfate .5 g 20 sec. 1.466 Good 1.470 Exc. .3113 Nylon NEBA 3 2 500 90 Persulfate .5 g 10 sec. 1.879 Poor 1.884 Exc. .3 6,6114 Cotton NEBA 3 2 500 90 Persulfate .5 g 10 sec. 1.702 Good 1.714 Exc. .7115 Nylon NEBA 10 20 500 100 Persulfate 2 g -- 1.803 Poor 1.813 Exc. .6 6,6116 Cotton NEBA 10 20 500 100 Persulfate 2 g -- 2.003 Good 2.025 Exc. 1.1117 Nylon NBA/DMS 8 10 500 65 Persulfate 2 g 4 min., 1.760 Poor 1.761 Poor 0 6,6 1:3 30 sec.118 Nylon NBA/DMS 8 10 500 70 Persulfate .5 g 4 min., 1.371 Poor 1.372 Poor 0 6,6 1:3 25 sec.119 Cotton NBA/DMS 8 10 500 70 Persulfate .5 g 4 min., 1.367 Good 1.368 Good 0 1:3 25 sec.120 Nylon NBA/DMS 8 10 500 73 Persulfate .5 g 3 min., 1.418 Poor 1.419 Poor 0 6,6 1:3 20 sec.121 Nylon NBA/DMS 8 10 500 75 Persulfate .5 g 2 min., 1.297 Poor 1.301 Exc. .3 6,6 1:3 35 sec.122 Nylon NBA/DMS 8 10 500 77 Persulfate .5 g 1 min., 1.743 Poor 1.749 Exc. .3 6,6 1:3 47 sec.123 Nylon NBA/DMS 8 10 500 80 Persulfate .5 g 1 min., 1.661 Poor 1.667 Exc. .4 6,6 1:3 7 sec.124 Cotton NBA/DMS 8 10 500 80 Persulfate .5 g 1 min., 1.525 Good 1.526 Very 0 1:3 7 sec. Good125 Cotton NBA/DMS 40 10 500 85 Persulfate .05 g 40 sec. 1.932 Good 1.930 Good 0 1:3126 Cotton NBA/DMS 15 10 500 87 Persulfate .15 g 3 min., 1.767 Good 1.784 Very 1.0 1:3 5 sec. Good127 Cotton NBA/DMS 40 10 500 90 Persulfate .05 g 10 sec. 2.210 Good 2.245 Very 1.6 1:3 Good128 Nylon NBA 1 1 500 99 Peroxide 1 ml 2 sec. 1.649 Poor 1.653 Exc. .2 6,6 (.005 g Fe)129 Cotton NBA 1 1 500 99 Peroxide 1 ml 2 sec. 1.540 Good 1.543 Exc. .2 (.005 g Fe)130 Nylon NBA 10 10 500 90 Peroxide .5 ml 7 sec. 1.234 Poor 1.242 Exc. .6 6,6 (.005 g Fe)131 Cotton NBA 10 10 500 90 Peroxide .5 ml 7 sec. 1.451 Good 1.489 Exc. 2.6 (.005 g Fe)132 Cotton NBA 10 1 500 87 Peroxide .5 ml 12 sec. 1.225 Good 1.233 Exc. .7 (.005 g Fe)133 Cotton NBA 10 1 500 85 Peroxide .5 ml 9 sec. 1.188 Good 1.187 Good 0 (.005 g Fe)134 Nylon NBA 10 5 500 80 Peroxide 1 ml 9 sec. 1.255 Poor 1.262 Exc. .6 6,6 (.005 g Fe)135 Cotton NBA 10 5 500 80 Peroxide 1 ml 9 sec. 1.469 Good 1.467 Good 0 (.005 g Fe)136 Nylon NBA 10 5 500 77 Peroxide 1 ml 1 min., 1.275 Poor 1.282 Exc. .5 6,6 (.005 g Fe) 25 sec.137 Nylon NBA 10 5 500 75 Peroxide 1 ml 1 min., 1.647 Poor 1.650 Very .2 6,6 (.005 g Fe) 35 sec. Good138 Nylon NBA 10 5 500 73 Peroxide 1 ml 1 min., 1.213 Poor 1.214 Poor 0 6,6 (.005 g Fe) 50 sec.139 Nylon NBA 10 10 500 70 Peroxide 5 ml 1 min., 1.433 Poor 1.433 Poor 0 6,6 (.005 g Fe) 30 sec.140 Cotton NBA 10 10 500 70 Peroxide 5 ml 1 min., 1.949 Good 1.948 Good 0 (.005 g Fe) 30 sec.141 Nylon NBA 10 10 500 65 Peroxide 5 ml 2 min., 1.842 Poor 1.843 Poor 0 6,6 (.005 g Fe) 33 sec.142 Nylon NBA 10 1 500 100 Ceric .3 g 4 sec. 1.242 Poor 1.247 Exc. .4 6,6143 Cotton NBA 10 1 500 100 Ceric .3 g 4 sec. .983 Good .994 Exc. 1.1144 Nylon NBA 10 1 500 90 Ceric .3 g 3 min., 1.101 Good 1.109 Exc. .7 6,6 45 sec.145 Cotton NBA 10 1 500 90 Ceric .3 g 3 min., 1.327 Good 1.337 Very .8 45 sec. Good146 Cotton NBA 10 1 500 87 Ceric .3 g 2 min., 1.237 Good 1.242 Very .4 3 sec. Good147 Cotton NBA 10 1 500 85 Ceric .3 g -- 1.280 Good 1.280 Good 0148 Nylon NBA 20 5 500 80 Ceric 1 g 10 sec. 1.427 Poor 1.432 Exc. .4 6,6149 Cotton NBA 20 5 500 80 Ceric 1 g 10 sec. 1.458 Good 1.460 Good 0150 Nylon NBA 20 5 500 77 Ceric 1 g 25 sec. 1.289 Poor 1.296 Very .5 6,6 Good151 Nylon NBA 20 5 500 75 Ceric 1 g 30 sec. 1.288 Poor 1.293 Good .4 6,6152 Nylon NBA 20 5 500 73 Ceric 1 g 33 sec. 1.033 Poor 1.034 Poor 0 6,6153 Nylon NBA 10 10 500 70 Ceric 2 g 35 sec. 1.347 Poor 1.349 Poor 0 6,6154 Cotton NBA 10 10 500 70 Ceric 2 g 35 sec. 1.305 Good 1.303 Good 0155 Nylon NBA 10 10 500 65 Ceric 2 g 40 sec. 1.113 Poor 1.113 Poor 0 6,6156 Cotton NBA 10 10 600 95-100 Peroxide 5 ml 0-1 min. 4.23 Good 4.47 Exc. 5.6157 Wool NBA 10 10 600 95-100 Peroxide 5 ml 0-1 min. 3.45 Poor 3.51 Very 1.7 Good158 Silk NBA 10 10 600 95-100 Peroxide 5 ml 0-1 min. 3.49 Poor 3.54 Good 1.4159 Cellu- NBA 10 10 600 95-100 Peroxide 5 ml 0- 1 min. 8.5 Poor 8.68 Exc. 2.1 lose (Ray- on)162 Nylon NBA 10 10 600 95-100 Peroxide 5 ml 0-1 min. 4.58 Poor 4.68 Exc. 2.2 6163 Nylon NBA 10 10 600 95-11 Peroxide 5 ml 0-1 min. 4.21 Poor 4.30 Exc. 2.1 6,6164 Ace- NBA 10 10 600 95-11 Peroxide 5 ml 0-1 min. 6.1 Very 6.18 Exc. 1.3 tate Good165 Nylon NBA 2 10 600 70* Persulfate 2.61 Poor 2.61 Poor 0 6,6166 Nylon NBA 2 10 600 73 Persulfate 2.37 Poor 2.37 Poor 0 6,6167 Nylon NBA 2 10 600 75 Persulfate -- -- 5.71 Poor 5.71 Poor 0 6,6168 Nylon NBA 2 10 600 77 Persulfate -- -- 3.08 Poor 3.08 Good 0 6,6169 Nylon NBA 2 10 600 80 Persulfate -- -- 2.62 Poor 2.64 Exc. 0.8 6,6170 Nylon NBA 2 10 600 90 Persulfate -- -- 3.15 Poor 3.18 Exc. 1.0 6,6171 Nylon NBA 2 10 600 73 Persulfate -- -- 4.65 Poor 4.65 Poor 0 6172 Nylon NBA 2 10 600 80 Persulfate -- -- 2.77 Poor 2.79 Good 0.7 6173 Wool NBA 2 10 600 73 Persulfate -- -- 4.00 Poor 4.00 Poor 0174 Wool NBA 2 10 600 80 Persulfate -- -- 6.22 Poor 6.31 Exc. 1.4175 Silk NBA 2 10 600 73 Persulfate -- -- 2.86 Poor 2.86 Poor 0176 Silk NBA 2 10 600 80 Persulfate -- -- 2.61 Poor 2.64 Exc. 1.1177 Cotton NBA 2 10 600 70* Persulfate -- -- 5.91 Good 5.91 Good 0178 Cotton NBA 2 10 600 75 Persulfate -- -- 5.09 Good 5.09 Good 0179 Cotton NBA 2 10 600 80 Persulfate -- -- 5.59 Good 5.59 Good 0180 Cotton NBA 2 10 600 85 Persulfate -- -- 5.74 Good 5.74 Good 0181 Cotton NBA 2 10 600 87 Persulfate -- -- 7.19 Good 7.22 Exc. 0.4182 Cotton NBA 2 10 600 89 Persulfate -- -- 5.51 Good 5.55 Exc. 0.7183 Rayon NBA 2 10 600 85 Persulfate -- -- 11.29 Good 11.29 Good 0184 Rayon NBA 2 10 600 89 Persulfate -- -- 5.50 Good 5.55 Exc. 0.9185 Ace- NBA 2 10 600 85 Persulfate -- -- 3.84 Good 3.84 Good 0 tate186 Ace- NBA 2 10 600 89 Persulfate -- -- 4.45 Good 4.49 Exc. 0.9 tate187 Nylon NBA 10 10 600 95-100 Persulfate -- -- 2.7 Poor 2.76 Exc. 2.2 6,6188 Nylon NEBA 10 10 600 95-100 Persulfate -- -- 3.4 Poor 3.48 Exc. 2.3 6,6189 Nylon NBA/DMS 10 10 600 95-100 Persulfate -- -- 2.33 Poor 2.41 Exc. 3.4 6,6 1:4190 Nylon Acryl- 10 10 600 95-100 Ceric -- -- 4.25 Poor 4.30 Very 1.2 6,6 amide Poor191 Nylon Acrylic 10 10 600 95-100 Ceric -- -- 3.35 Poor 3.40 Very 1.5 6,6 Acid Poor192 Nylon 2-propyn- 10 10 600 95-100 Ceric -- -- 2.65 Poor 2.69 Very 1.5 6,6 1-OL Poor193 Nylon Crotonic 10 10 600 95-100 Ceric -- -- 2.62 Poor 2.71 Very 3.4 6,6 Acid Poor194 Nylon Tetra- 10 10 600 95-100 Ceric 2.10 Poor 2.22 Very 5.2 6,6 ethylene Poor glycol195 Nylon NBA 10 -- 600 95-100 Formic 25 ml 2 min. 4.2 Poor 4.31 Exc. 2.6 6,6 Acid196 Nylon NBA 10 -- 600 95-100 HCl 10 ml 8 sec. 2.0 Poor 2.04 Exc. 2.0 6,6197 Nylon NBA 10 -- 600 95-100 Sodium 0.3 g 1 min., 3.41 Poor 3.45 Exc. 1.2 6,6 Peroxide 30 sec.__________________________________________________________________________ *comparative example
TABLE 2__________________________________________________________________________Fabric: Nylon 6,6 Time toEx. No. Acid/No Acid Monomer % Formic % Temp., .degree.C. Initiator % % Add-On Polymerize__________________________________________________________________________ 3 No Acid NBA 1.67* 0 96-100 Peroxide 1.9 1.2 6 min., 15 sec. 5 Acid NBA 1.67 2 96-100 Peroxide 1.9 1.5 2 min., 10 sec. 7 No Acid NBA 1.67 0 89-93 Peroxide .96 .8 47 min., 43 sec. 9 Acid NBA 1.67 2 89-93 Peroxide .96 .7 6 min., 40 sec.11 No Acid NBA 1.67 0 89-93 Peroxide .48 1.0 83 min., 20 sec.13 Acid NBA 1.67 2 89-93 Peroxide .48 1.0 10 min., 16 sec.15 No acid NBA 1.67 0 88-92 Peroxide .19 .6 139 min., 42 sec.17 Acid NBA 1.67 2 88-92 Peroxide .19 .9 11 min., 16__________________________________________________________________________ sec. *NBA is acid having a pH of about 4.5 to 5.0
TABLE 3__________________________________________________________________________Fabric: Nylon 6,6 Time to FinalEx. No. Monomer % Formic % Temp., .degree.C. Initiator % Polymerize Drop Test % Add-On__________________________________________________________________________1 NBA 1.67 4.1 96-100 Persulfate .96 0.55 sec. Exc. .75 NBA 1.67 2 96-100 Peroxide 1.9 2 min., 10 sec. Exc. 1.53 NBA 1.67 0 96-100 Peroxide 1.9 6 min., 15 sec. Exc. 1.213 NBA 1.67 2 89-93 Peroxide .48 10 min., 16 sec. Exc. 1.07 NBA 1.67 0 89-93 Peroxide .96 47 min., 43 sec. Exc. .811 NBA 1.67 0 89-93 Peroxide .48 83 min., 20 sec. Exc. 1.015 NBA 1.67 0 88-92 Peroxide .19 139 min., 42 sec. Exc. .6__________________________________________________________________________
TABLE 4__________________________________________________________________________Fabric: Nylon 6,6Ex. Time to Final %No. Monomer % Monomer Formic % Temp., .degree.C. Initiator % Polymerize Drop Test Add-On__________________________________________________________________________47 .01 NBA .24 98-100 Persulfate 45 sec. Exc. 0 (HCl) .255 .03 NBA/DMS .24 98-100 Persulfate 2 min. Exc. 0 1:3 (HCl) .0249 .05 NBA 4.9 98-100 Persulfate 1 min., Exc. .2 .006 50 sec.57 0.1 NBA/DMS .24 98-100 Persulfate 20 sec. Exc. 0 1:3 (HCl) .0235 0.33 NBA/MCA 2.0 89-92 Persulfate 1 min., Exc. 1.3 1:2 .008 13 sec.65 0.75 NBA/Formic .24 98-100 Persulfate 10 sec. Exc. 1.0 1:4 (HCl) .00261 1.5 NEBA .24 98-100 Persulfate 6 sec. Exc. .6 (HCl) .0267 2 NBA/Formic .24 98-100 Persulfate 4 sec. Exc. .2 1:4 (HCl) .00259 4 NBA/DMS .24 98- 100 Persulfate 30 sec. Exc. 1.2 1:4 (HCl) .00643 5.1 NEBA/MCA .24 89-92 Persulfate 10 sec. Exc. .6 1:3 (HCl) .263 7.5 NEBA/DMS .24 98-100 Persulfate 10 sec. Exc. .2 1:3 (HCl) .00253 10 NEBA 0 94-96 Persulfate 20 sec. Good .3 .002__________________________________________________________________________
TABLE 5__________________________________________________________________________Fabric: Nylon 6,6 Time to FinalEx. No. Monomer % Temp., .degree.C. Formic % Initiator % Polymerize Drop Test % Add-On__________________________________________________________________________19 NBA .17 89-92 2.0 Persulfate 35 sec. Exc. .7 .01721 NBA .33 69-70 2.0 Persulfate -- Poor 0 .01723 NEBA .33 89-92 4.1 Persulfate 4 min., 10 sec. Exc. .9 .08325 NEBA .83 69-70 4.1 Persulfate 40 sec. Poor 0 .8327 NBA/Formic 89-92 2.0 Persulfate 40 sec. Exc. 1.06 1:4 .33 .01729 NBA/Formic 69-70 2.0 Persulfate 2 min., 55 sec. Poor 0 1:4 .33 .08331 NBA/DMS 89-92 2.0 Persulfate 57 sec. Exc. 1.4 1:3 .33 .01733 NBA/DMS 69-70 2.0 Persulfate 3 min., 4 sec. Poor 0 1:3 .33 .08335 NBA/MCA 89-92 2.0 Persulfate 1 min., 13 sec. Exc. 1.3 1:2 .33 .008337 NBA/MCA 69-70 2.0 Persulfate 2 min., 10 sec. Poor 0 1:2 .33 .2539 NEBA/ 89-92 4.1 Persulfate 7 min., 44 sec. Exc. .6 Formic 1:4 .083 .541 NEBA/ 69-70 4.1 Persulfate 4 min., Poor 0 Formic 1:4 .167 30 sec. .543 NEBA/MCA 89-92 .2 Persulfate 10 sec. Exc. .6 1:3 5.12 (HCl) .245 NEBA/MCA 69-70 .18 Persulfate 1 min., 50 sec. Poor 0 1:3 4.65 (HCl) .18__________________________________________________________________________
TABLE 6__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Init. Time to Drop %No. Initiator Monomer % Temp., .degree.C. % % Polymerize Test Add-On__________________________________________________________________________ 3 Peroxide NBA 1.67 96-100 0 1.9 6 min., 15 sec. Exc. 1.284 Peroxide NBA 8 69-70 2.4 2.3 5 min., 20 sec. Poor 090 Peroxide NEBA 4 89-91 0 1.15 25 sec. Exc. 4.292 Peroxide NEBA 10 69-70 2.4 2.3 6 min., 15 sec. Poor 071 Peroxide NBA/MCA 89-91 0 .23 -- Exc. .5 1:3 6 ml69 Peroxide NBA/MCA 69-70 4.9 .57 -- Poor 0 1:3 6 ml19 Persulfate NBA 1.67 89-92 2.0 .017 35 sec. Exc. .721 Persulfate NBA .33 69-70 2.0 .017 -- Poor 023 Persulfate NEBA .33 89-92 4.1 .083 4 min., 10 sec. Exc. .925 Persulfate NEBA .83 69-70 4.1 .83 40 sec. Poor 035 Persulfate NBA/MCA 89-92 2.0 .0083 1 min., 13 sec. Exc. 1.3 1:3 .3333 Persulfate NBA/MCA 69-70 2.0 .083 3 min., 4 sec. Poor 0 1:3 .33144 Ceric NBA 1.6 90 .2 .05 3 min., 45 sec. Exc. .786 Ceric NBA 6.67 69-70 2.0 .33 16 sec. Poor 094 Ceric NEBA 15 95-97 0 1.07 -- Exc. 1.396 Ceric NEBA 16.7 69-70 4.1 1.67 -- Poor 079 Ceric NBA/MCA 89-91 0 .017 15 sec. Exc. .8 1:3 577 Ceric NBA/MCA 69-70 6.1 0.17 35 sec. Poor 0 1:3 5195 Formic NBA 1.67 95-100 -- 5.08 2 min. Exc. 2.688 Formic NEBA 4 98-100 0 7.3 -- Exc. 1.375 Formic NBA/MCA 98-100 0 9.76 -- Exc. .3 1:3 6__________________________________________________________________________
TABLE 7__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________100 65 NBA 2 4.88 Persulfate 6 min., 35 sec. Poor 0 .05165 70 NBA .33 2.0 Persulfate -- Poor 0166 73 NBA .33 2.0 Persulfate -- Poor 0167 75 NBA .33 2.0 Persulfate -- Good 0168 77 NBA .33 2.0 Persulfate -- Exc. 0169 80 NBA .33 2.0 Persulfate -- Exc. .8170 90 NBA .33 2.0 Persulfate -- Exc. 1.0101 100 NBA .4 .24 Persulfate 6 sec. Exc. .4 .006__________________________________________________________________________
TABLE 8__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________117 65 NBA/DMS 2.44 Persulfate 4 min., 30 sec. Poor 0 1:3 1.6 .4118 70 NBA/DMS 2.44 Persulfate 4 min., 25 sec. Poor 0 1:3 1.6 .1120 73 NBA/DMS 2.44 Persulfate 3 min., 20 sec. Poor 0 1:3 1.6 .1121 75 NBA/DMS 2.44 Persulfate 2 min., 35 sec. Exc. .3 1:3 1.6 .1122 77 NBA/DMS 2.44 Persulfate 1 min., 47 sec. Exc. .3 1:3 1.6 .1123 80 NBA/DMS 2.44 Persulfate 1 min., 7 sec. Exc. .4 1:3 1.6 .1 31 89-92 NBA/DMS 2.44 Persulfate 57 sec. Exc. 1.4 1:3 .4 .02 59 98-100 NBA/DMS .24 Persulfate 30 sec. Exc. 1.2 1:3 4 (HCl) .006__________________________________________________________________________
TABLE 9__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________103 65 NEBA 1 4.88 Persulfate 1 min., 55 sec. Poor 0 .4104 70 NEBA 1 4.88 Persulfate 55 sec. Poor 0 .4106 73 NEBA 1 4.88 Persulfate 48 sec. Poor 0 .4107 75 NEBA 1 4.88 Persulfate 40 sec. Very 0 .4 Good108 77 NEBA 1 4.88 Persulfate 20 sec. Exc. 0 .4109 80 NEBA 1 4.88 Persulfate 58 sec. Exc. .2 .1113 90 NEBA .6 .49 Persulfate 10 sec. Exc. .3 .1115 100 NEBA 2 4.88 Persulfate -- Exc. .6 .4__________________________________________________________________________
TABLE 10__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Monomer Time to Drop %No. Temp., .degree.C. Initiator % % % Polymerize Test Add-On__________________________________________________________________________141 65 Peroxide 1.15 2.44 NBA 2 2 min., 33 sec. Poor 0139 70 Peroxide 1.15 2.44 NBA 2 1 min., 30 sec. Poor 0138 73 Peroxide .23 1.22 NBA 2 1 min., 50 sec. Poor 0137 75 Peroxide .23 1.22 NBA 2 1 min., 35 sec. Very .2 Good136 77 Peroxide .23 1.22 NBA 2 1 min., 25 sec. Exc. .5134 80 Peroxide .23 1.22 NBA 2 9 sec. Exc. .6130 90 Peroxide .12 2.44 NBA 2 7 sec. Exc. .6128 99 Peroxide .23 .24 NBA 2 2 sec. Exc. .2__________________________________________________________________________
TABLE 11__________________________________________________________________________Fabric: Nylon 6,6 FinalEx. Formic Monomer Time to Drop %No. Temp., .degree.C. Initiator % % % Polymerize Test Add-On__________________________________________________________________________155 65 Ceric .4 2.44 NBA 2 40 sec. Poor 0153 70 Ceric .4 2.44 NBA 2 35 sec. Poor 0152 73 Ceric .2 1.22 NBA 4 33 sec. Poor 0151 75 Ceric .2 1.22 NBA 4 30 sec. Good .4150 77 Ceric .2 1.22 NBA 4 25 sec. Very .5 Good148 80 Ceric .2 1.22 NBA 4 10 sec. Exc. .4144 90 Ceric .06 .24 NBA 2 3 min., 45 sec. Exc. .7142 100 Ceric .06 .24 NBA 2 4 sec. Exc. .4__________________________________________________________________________
TABLE 12__________________________________________________________________________Fabric: Cotton Acid/ % Time toEx. No. No Acid Monomer % Formic % Temp., .degree.C. Initiator % Add-On Polymerize__________________________________________________________________________ 4 No Acid NBA 1.67 0 96-100 Peroxide 1.9 .9 6 min., 15 sec. 6 Acid NBA 1.67 2 96-100 Peroxide 1.9 1.9 2 min., 10 sec. 8 No Acid NBA 1.67 0 89-93 Peroxide .96 3.1 47 min., 43 sec.10 Acid NBA 1.67 2 89-93 Peroxide .96 1.5 6 min., 40 sec.12 No Acid NBA 1.67 0 89-93 Peroxide .48 2.3 83 min., 20 sec.14 Acid NBA 1.67 2 89-93 Peroxide .48 2.4 10 min., 16 sec.16 No Acid NBA 1.67 0 88-92 Peroxide .19 2.3 139 min., 42 sec.18 Acid NBA 1.67 2 88-92 Peroxide .19 2.2 11 min., 16 sec.__________________________________________________________________________
TABLE 13__________________________________________________________________________Fabric: Cotton Time to FinalEx. No. Monomer % Formic % Temp., .degree.C. Initiator % Polymerize Drop Test % Add-On__________________________________________________________________________2 NBA 1.67 4.1 96-100 Persulfate .96 0.5 sec. Exc. 1.86 NBA 1.67 2 96-100 Peroxide 1.9 2 min., 10 sec. Exc. 1.94 NBA 1.67 0 96-100 Peroxide 1.9 6 min., 15 sec. Exc. .914 NBA 1.67 2 89-93 Peroxide .48 10 min., 16 sec. Exc. 2.48 NBA 1.67 0 89-93 Peroxide .96 47 min., 43 sec. Exc. 3.112 NBA 1.67 0 89-93 Peroxide .48 83 min., 20 sec. Exc. 2.316 NBA 1.67 0 88-92 Peroxide .19 139 min., 42 sec. Exc. 2.3__________________________________________________________________________
TABLE 14__________________________________________________________________________Fabric: CottonEx. Time to Final %No. Monomer % Monomer Formic % Temp., .degree.C. Initiator % Polymerize Drop Test Add-On__________________________________________________________________________48 .01 NBA .24 98-100 Persulfate 45 sec. Exc. 0 (HCl) .256 .03 NBA/DMS .24 98-100 Persulfate 2 min. Exc. 0 1:3 (HCl) .0250 .05 NBA 4.9 98-100 Persulfate 1 min., Exc. 0 .006 50 sec.58 .1 NBA/DMS .24 98-100 Persulfate 20 sec. Exc. .4 1:3 (HCl) .0236 .33 NBA/MCA 2.0 89-92 Persulfate 1 min., Exc. 1.3 1:2 .008 13 sec.66 .75 NBA/Formic .24 98-100 Persulfate 10 sec. Exc. 4.4 1:4 (HCl) .00262 1.5 NEBA .24 98-100 Persulfate 6 sec. Exc. .5 (HCl) .0268 2 NBA/Formic .24 98-100 Persulfate 4 sec. Exc. .6 1:4 (HCl) .00260 4 NBS/DMS .24 98-100 Persulfate 30 sec. Exc. 4.2 1:4 (HCl) .00644 5.1 NEBA/MCA .24 89-92 Persulfate 10 sec. Exc. .6 1:3 (HCl) .264 7.5 NEBA/DMS .24 98-100 Persulfate 10 sec. Exc. 1.1 1:3 (HCl) .00254 10 NEBA 0 94-96 Persulfate 20 sec. Exc. 12.5 .002__________________________________________________________________________
TABLE 15__________________________________________________________________________Fabric: Cotton Time to FinalEx. No. Monomer % Temp., .degree.C. Formic % Initiator % Polymerize Drop Test % Add-On__________________________________________________________________________20 NBA .17 89-92 2 Persulfate 35 sec. Exc. .6 .01722 NBA .33 69-70 2 Persulfate -- Good 0 .01724 NEBA .33 89-92 4.1 Persulfate 4 min., 10 sec. Exc. .6 .08326 ENBA .83 69-70 4.1 Persulfate 40 sec. Good 0 .8328 NBA/Formic 89-92 2 Persulfate 40 sec. Exc. .8 1:4 .33 .01730 NBA/Formic 69-70 2 Persulfate 2 min., 55 sec. Good 0 1:4 .33 .08332 NBA/DMS 89-92 2 Persulfate 57 sec. Exc. 1.5 1:3 .33 .01734 NBA/DMS 69-70 2 Persulfate 3 min., 4 sec. Good 0 1:3 .33 .08336 NBA/MCA 89-92 2 Persulfate 1 min., 13 sec. Exc. 1.3 1:2 .33 .008338 MBA/MCA 69-70 2 Persulfate 2 min., 10 sec. Good 0 1:2 .33 .2540 NEBA/Formic 89-92 4.1 Persulfate 7 min., 44 sec. Exc. .6 1:4 .5 .08342 NEBA/Formic 69-70 4.1 Persulfate 4 min., 30 sec. Good 0 1:4 .5 .16744 NEBA/MCA 89-92 .2 Persulfate 10 sec. Exc. .6 1:3 5.12 (HCl) .246 MEBA/MCA 69-70 .18 Persulfate 1 min., 50 sec. Good 0 1:3 4.65 (HCl) .18__________________________________________________________________________
TABLE 16__________________________________________________________________________Fabric: Cotton FinalEx. Formic Init. Time to Drop %No. Initiator Monomer % Temp., .degree.C. % % Polymerize Test Add-On__________________________________________________________________________ 4 Peroxide NBA 1.67 96-100 0 1.9 6 min., 15 sec. Exc. .985 Peroxide NBA 8 69-70 2.4 2.3 5 min., 20 sec. Good 091 Peroxide NEBA 4 89-91 0 1.15 25 sec. Exc. 2.493 Peroxide NEBA 10 69-70 2.4 2.3 6 min., 15 sec. Good 072 Peroxide NBA/MCA 89-91 0 .23 -- Exc. .5 1:3 670 Peroxide NBA/MCA 69-70 4.9 .57 -- Good 0 1:3 620 Persulfate NBA .167 89-92 2.0 .017 35 sec. Exc. .622 Persulfate NBA .33 69-70 2.0 .017 -- Good 024 Persulfate NEBA .33 89-92 4.1 .083 4 min., 10 sec. Exc. .626 Persulfate NEBA .83 69-70 4.1 .83 40 sec. Good 036 Persulfate NBA/MCA 89-92 2.0 .0083 1 min., 13 sec. Exc. 1.334 Persulfate NBA/MCA 69-70 2.0 .083 3 min., 4 sec. Good 0 1:3 .33145 Ceric NBA 1.6 90 .2 .05 3 min., 45 sec. Very .8 Good87 Ceric NBA 6.67 69-70 2.0 .33 16 sec. Good 095 Ceric NEBA 15 95-97 0 1.07 -- Exc. 1.097 Ceric NEBA 16.7 69-70 4.1 1.67 -- Good 080 Ceric NBA/MCA 89-91 0 .017 15 sec. Exc. .6 1:3 578 Ceric NBA/MCA 69-70 6.1 .017 35 sec. Good 0 1:3 581 Formic NBA 2 98-100 0 9.76 -- Exc. 1.089 Formic NEBA 4 98-100 0 7.3 -- Exc. 1.276 Formmic NBA/MCA 98-100 0 9.76 -- Exc. .3 1:3 6__________________________________________________________________________
TABLE 17__________________________________________________________________________Fabric: Cotton FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________177 70 NBA .33 2.0 Persulfate -- Good 0179 80 NBA .33 2.0 Persulfate -- Good 0180 85 NBA .33 2.0 Persulfate -- Good 0181 87 NBA .33 2.0 Persulfate -- Exc. .4182 89 NBA .33 2.0 Persulfate -- Exc. .7102 100 NBA .4 .24 Persulfate 6 sec. Exc. .3 .006__________________________________________________________________________
TABLE 18__________________________________________________________________________Fabric: Cotton FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________119 70 NBA/DMS 2.44 Persulfate 4 min., 25 sec. Good 0 1:3 1.6 .1124 80 NBA/DMS 2.44 Persulfate 1 min., 7 sec. Very 0 1:3 1.6 .1 Good125 85 NBA/DMS 2.44 Persulfate 40 sec. Good 0 1:3 8 .01126 87 NBA/DMS 2.44 Persulfate 3 min., 5 sec. Very 1.0 1:3 3 .03 Good127 90 NBA/DMS 2.44 Persulfate 10 sec. Very 1.6 1:3 8 .01 Good 60 98-100 NBA/DMS .24 Persulfate 30 sec. Exc. 4.2 1:3 4 (HCl) .006__________________________________________________________________________
TABLE 19__________________________________________________________________________Fabric: Cotton FinalEx. Formic Time to Drop %No. Temp., .degree.C. Monomer % % Initiator % Polymerize Test Add-On__________________________________________________________________________105 70 NEBA 1 4.88 Persulfate 55 sec. Good 0 .4110 80 NEBA .4 4.88 Persulfate 58 sec. Good 0 .1111 85 NEBA .6 4.88 Persulfate 35 sec. Good 0 .1112 87 NEBA .6 4.88 Persulfate 20 sec. Exc. .3 .1114 90 NEBA .6 .49 Persulfate 10 sec. Exc. .7 .1116 100 NEBA 2 4.88 Persulfate -- Exc. 1.1 .4__________________________________________________________________________
TABLE 20__________________________________________________________________________Fabric: Cotton FinalEx. Formic Monomer Time to Drop %No. Temp., .degree.C. Initiator % % % Polymerize Test Add-On__________________________________________________________________________140 70 Peroxide 1.15 2.44 NBA 2 1 min., 30 sec. Good 0135 80 Peroxide .23 1.22 NBA 2 9 sec. Good 0133 85 Peroxide .12 .24 NBA 2 9 sec. Good 0132 87 Peroxide .12 .24 NBA 2 12 sec. Exc. .7131 90 Peroxide .12 2.44 NBA 2 7 sec. Exc. 2.6129 99 Peroxide .23 .24 NBA .2 2 sec. Exc. .2__________________________________________________________________________
TABLE 21__________________________________________________________________________Fabric: Cotton FinalEx. Formic Monomer Time to Drop %No. Temp., .degree.C. Initiator % % % Polymerize Test Add-On__________________________________________________________________________154 70 Ceric .4 2.44 NBA 2 35 sec. Good 0149 80 Ceric .2 1.22 NBA 4 10 sec. Good 0147 85 Ceric .06 0.24 NBA 2 -- Good 0146 87 Ceric .06 0.24 NBA 2 2 min., 3 sec. Very .4 Good145 90 Ceric .06 0.24 NBA 2 3 min., 45 sec. Very .8 Good143 100 Ceric .06 0.24 NBA 2 4 sec. Exc. 1.1__________________________________________________________________________
TABLE 22______________________________________WASH TEST %Example No. Type of Fabric Number of Washings Add-On______________________________________198 Cotton 0 4.7199 Nylon 6,6 0 3.9200 Cotton 2 2.1201 Nylon 6,6 2 0.5202 Cotton 5 1.3203 Nylon 6,6 5 0.4204 Cotton 10 1.2205 Nylon 6,6 10 0.4206 Cotton 15 1.2207 Nylon 6,6 15 0.3______________________________________
A graph of Table 22 is annexed revealing the effect of washings on percent add-on.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

	Number	Date
Parent	390732	Jun 1982
Parent	296656	Aug 1981
Parent	273713	Jun 1981
Parent	223056	Jan 1981

Process for improving polymer fiber properties and fibers produced thereby

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CPC

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