CA1047196A - Copolymer of blocks of alternating poly(dioxa-amide) and polyamide - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Novel alternating block copolymer formed by melt blending a melt spinnable polyamide, such as nylon-6, and an alternating poly(dioxa-amide), such as a copolymer prepared from the mixture of caprolactam and the salt of adipic acid and 4,7-dioxadecamethylenediamine, is disclosed. The copolymer has utility as a fiber. The fiber, for example, resulting from melting blending of nylon-6 and the aforementioned alter-nating poly(dioxa-amide) has moisture absorption character-istics similar to that of cotton. Furthermore, the resulting fiber still maintains the other desirable properties of the major constituent, for example, nylon-6.

Description

1047~6 CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to Canadian Serial Nos.
213,635 , 213,636, and 213,634, all filed same date by Robert M. Thompson. These three applications have as subject matter various block copolymers of polyamides. This application is also related to Canadian Serial No. 213,637 , filed same date by Elmer J. Hollstein. Subject matter of the latter - application relates to a method for hydrogenation of a dinitrile which is a precursor of a hydrophilic polymer dis-closed within the aforementioned related applications.

BACKGROUND OF T~IE INVENTION

I~ is kno~nthat commercially important polyamides, such as nylon-6 and n~lon-6,6, have excellent physical proper-ties in many respects. However, for certain textile applica-tion fabrics and similar products prepared from such nylons are somewhat deficient in moisture absorption. This characteristic is important because according to Encyclopedia ~f Polymer Science & Technology, Vol. 10, Section Polyamide Fibers, mois-~ure absorption determines rate of drying, comfort, ease and cost of dyeing and hand or feel of the fabric. To overcome this moisture absorption deficiency many attempts have been made but none have been commercially successful to date.

Disclosed herein is a novel copolymer which can be converted into a fiber having moisture absorption properties similar to that of cotton, a commercial standard of comparison.
This novel copolymer consists of blocks of alternating poly-(dioxa-amide) and blocks of polyamidei Surprisingly, the incor-poration of blocks of certain alternating poly(dioxa-amide) with a certain polyamide does not adversely effect the many ~ -2-~L~47~916 desirable ~iber properties o~ the polyamide and yet substan-tially improves its moisture absorption property. Also the copolymer can be formed into a desired shape by extrusion, in-jecting molding and other well known thermoplas-tic ~orming methods.

Generally, copolymers containing the amide ~unction, O
~ 11 i.e., -N-C-, can be formed by melting two polyamides. Thus when ~wo different polyamides are mixed and heated above their melting points they form copolymers. This process is also known as melt blending. However, the length o~ time the polymers are maintained at a temperature abo~e their melting points has a pro~ound e~fect on the resulting structure. As the mixing at the elevated temperature begins the molecule is a combina-tion of blocks o~ alternating poly(dioxa-amide) and blocks o~
polyamide. But gradually as the heating and mixing continues the length of the blocks of polyamide decreases because seg-ments o~ the alternating polymer transamidate. Also portions of the polyamide block transamidate into portions o~ the alternating component and the length of the latter block de-creases. Thus if the blending and heating occurs for a su~
cient time all the "blocks" disappear and only alternating sequences exist. At present there is no known direct way of de-termining chain sequences o~ such a polymer. But indirect methods exist and these are discussed in detail hereinà~ter.
Controlled decomposition of such a copolymer will yield all identifiable components that make up -the copolymer but will not indicate sequence.

As inferred ~rom the previous discussion, the terms "block" and "alternating" can easily be misapplied.

~(~147~
However, facilitating the characterizing of a polymer and/or copolymer is consideration o~ its starting materials and the methods used to prepare the polymers. Thus, ~or example, if caprolactam [CO(CH2)5NH] is properly processed, the resulting polymer is HO[CO~CH2)5NHn]H or alternatively nylon-6. The latter can be designated a homopolymer. Thus the latter is a chainlike molecule composed of recurring units (monomeric).
By comparison a copolymer consists of two monomeric units, that is to say, each monomeric unit could by itself form a homopoly-mer. Thus, for example, a butadiene-styrene copolymer consists of butadiene which could form a butadiene homopolymer and styrene which could form a styrene homopolymer And the butadiene(a)-styrene(b) copolymer would have an alternating sequence. The sequence would be a "-abababab-" structure. The latter has a regularly alternatlng pattern. Other possible patterns of alternating copolymers are "random", i.e., cdcdcdcccddcdcdcc-;
and "short sequence", i.e., -eefffeeffeeefffee-. Examples of such alternating copolymers are as ~ollows: Chemical Abstract 88764f, vol. 70, 1969 (Japanese Patent 28,837/68) discloses a copolymer prepared from the combination of (a) salt of bis ~-aminopropoxy) ethane (also referred to as 30203) and adipic acid and (b) the monomer caprolactam. British patent 1,169,276 discloses an alternating copolymer having improved hydrophylic properties prepared from the combination of (a) salt (I) of H2N(CH2)3-0-CH2-c(cH3)2-cH2o-(cH2)3 2 adipic acid and (b) the monomer caprolac~am, also an alternat-ing copolymer of the aforemention salt (I) and hexamethylene diammonium adipate ~H3 N(CH2)6NHCO(CH2)6CO-] also referred to as nylon-6,6 salt. Chemical ~bstract 451L~h, vol. 49, 1955 3o discloses an alternating oopolymer prepared from the (a) salt (II) of H2N(CH2)3-0-(CH2)3-NH2 and the adipic acid and (b) ~47~96 nylon-6,6 salt. Salt (II) upon heating ~orms a cream-colored material; such discoloration detracts Irom its utility where clarity is required. U. S. Patent 3,522,329 discloses an alternating copolymer prepared fr~m the (a) salt o:f diamine of polyethylene oxide CHOC~I2CH2(0-CH2CH2)n~ and adipic acid and (b) ~ -caprolactam (also called caprolactam).

U. S. Patent 3,514,498 discloses an alternating copolymer prepared ~rom the (a) salt o:E diamine of polyethylene oxide and adipic acid and (b)~ -caprolactam.

A block copolymer can result when a mixture of polymer "A" and polymer "B", both of which contain amides is properly processed. Thus the resulting block copolymer contains rela-tl~ely long chains OI a particular chemical composition~ the chalns being separated by a polymer o:~ di:E:Eerent chemical composition; -thus diagrammatically ¦ A L B ¦ A ¦ .
A block copolymer can also contain relatively long chains of a particular chemical composition but in this type the chains are separated by a low molecular weight "coupling group";
thus diagrammatically ¦ A B A 1. Each of the 20 a:~orementioned polymer chains, i.e., A and/or B can be homopolymer or an alternating copolymer. Examples of some o~
these polymers are as :Eollows. The pre~iously mentioned U. S.
Patent 3,514,498 also discloses a block (alternating) copolymer prepared :~rom two polymers: (a) polymer resulting from the salt of diamine o~ polyethylene oxide and adipic acid and ~-caprolactam and (b) poly-~-capramide (nylon-6). U. S.
Patent 3,549,724 also discloses a block (alternating) copolymer prepared from (a) polymer prepared ~rom polye-thylene oxide diammonium adipate and ~ -caprolactam and (b) nylon-6 or nylon-6,6. U. S Patent 3,160,677 discloses a block copolymer 1047~
prepared from (a) a polymer prepared from dibutyl oxalate [(COOC4Hg)2] and a diamine and (b) polycaprolactam.

Contrary to expectations based on the previously discussed arb it has no~ been found that i-t is possible to prepare a composition comprising a copolymer of blocks of polyamide and alternating poly(dioxa-amide) having moisture uptake equivalent to that of cotton. In addition, fibers of the copolymer have overall fiber properties substantially equi~alent to that of such nylons as nylon-6.

SUMMARY OF THE INVENTION

Present invention resides in a novel composition. It has utLlity as a fiber in addition to other utilities. The composition is a copolymer of blocks o~ a certain polyamide and blocks of certain alternating poly(dioxa-amide). The polyamide portion o~ the molecule is a bivalent radical of a melt spin~able polyamide. The poly(dioxa-amide) portion o~ this molecule contains both a double oxygen linkage, i.e., -R-O-R-O-R-and amide linkage, H O
t ll i.e., -N-C-. The following repeating structural formula depicts the composition o~ this invention:

(a) an alternating component consisting of:

H ~Rl~R2 1R21Rl H
~N-CH2-C-C-O-R4-0-C-C-CH2-N~n and Il 11 ~C _ Rs - C~ m and one of the following:

~0~7i~6 ~I H
~C - (;R6! N~p H
~ N - R7 - N~q wherein the relative proportions of each are n- 1-10, m= 1-10, q= 0-10, and if p= O then n + q = m;
and ~herein R1, R2, R3 is selected from the group consisting of H, Cl - C10 alkyls and C3 - C10 isoalkyls, R4 is selected from the group consisting of Cl - Clo alkylenes and C3 - C10 isoalkylenes;
R5 is selected from the group consisting of CO - C10 alkylenes and C3 - C10 isoalkylenes;
R6 and R7 is selected from the group consisting o~
C5 - Cl1 alkyleneS;
(b) and a block component consisting o~

bivalent radical of _ L
_ ~ melt spi~able polyamide i and wherein the weight ratio of components (a) and (b) is SUC~l that a/b = 0.05-1.5. The copolymer has a molecular weight o~
about 5,000-100,000.
DESCRIPTION

As stated heretofore, one portion of the novel compo-sition is a melt spi~able polymer. Melt spi~le refers to a process wherein the polymer, a polyamide, is heated to above its melting temperature and whilemolten forced through a spinneret. The latter is a plate containing from one to many thousand orifices, through which the molten polymer is forced ~ 04'7~ 6 under pressure. The molten polymer is a continuous filament and depending on the number of orifices many filàments can be formed at the same time. The molten filaments are cooled, solidified, converged and finally collected on a bobbin. This technique is described in greater detail in Encyclopedia of Polymer Science & Technology, vol. 8 Man-Made Fibers, Manufac-ture.

If a single fiber is extruded, as in the case when it is intended to be knitted into hosiery,the product is called a monofilament. When the product is expected to be converted into a fabric by knitting or weaving, the number of mono~ilaments is in the range of 10-100. Such a product is known as a multi-filament yarn. Yarn for industrial application, such as in the construction of tire cord, usually contain several hundred to a thousand or more fLlaments. When the fibers are used to make spun yarn, i.e., a yarn formed by twisting short lengths of fibers together, as is the practice with cotton, the number of orifices can rise to tens of thousands. The extruded material is cut into pieces in the range of 1-5 inches long to produce "staple" fiber. This staple fiber is converted in-to spun yarn in a similar manner as cotton. Polymer of present invention can be prepared lnto the aforementioned forms by the various methods disclosed.

Also, the polymers of present invention can be used to prepare nonwovens. Nonwoven refers to a material used as a fabric made without weaving, and in particular having textile fibers bonded or laminated together by adhesive resin, rubber or plastic or felted together under pressure. Many such methods ~jpI~

are described in detail in Manual of Nonwovens, Pro~. D~Fl-I~
~" - K~
and Dr. Radko ~ro~, Textile Trade Press, Manchester, England.

1047~9~, Polyamides which are crystallizable and have at least a 30C difference between melting point and the temperature at which the molten polymer undergoes decomposition can be melt spun. Examples of melt sp~le polyamides are as follows:
nylon~6,6 [also known as poly(hexamethylene adipamide)]; nylon-6,10 [poly(hexamethylene sebacamide)]; nylon-6 ~poly(pentamethylene carbonamide)]; nylon-ll [poly(decamethylene carbonamide)]; MXD-6 [poly(meta-xylene adipamide)]; PACM-9 [bis(paraaminocyclo-hexyl) methane azelamide], and PACM-10 [bis(paraaminocyclo-hexyl) methane sebacamide], and PACM-12 [bis(paraaminocyclo-hexyl)methane dodecanoamide]. Others are listed i~ Encyclo-pedia of Polymer Science &.Technology, vol. 10, Section Polyamide Fibers, table 12. Methods ~or preparing these polyamides are well known and described in numerous well known patents and trade journals.

The poly(dioxa-amide) portion of the composition can be prepared by the following generalized scheme:

/Rl,R2 IRllR2 llIR2 (1) N-C-C=C + HO-R4-OH- 3 N--C-C-C-C-O-C-C-C--N
I H I I H

(I) (II) (III) RlR2 ~1 ~R2

(2) 2 2 2 H I ~ I H

(IV) ~Rl ~R2 ~R2 ~Rl

(3) (I~) + HOCR5cOOH---~(OOcR5coo~I) (NH3cH2-c-c-o~R~-ola-c-o~NH-3~) (V) 10 ~ 7 ~ 9 6

(4) (~) + CO(CH2)5NH H2o RlR R2R1 1 l2 1 I H 11 11 H 11 ~NH-cH2-c-c-o-R~-o-c-c-cH2N-c-R5-c-N-(cH2)5-3 (VI) Another generalized scheme, replaci~g steps 3 and ~ would beas follows:

(5) (IV) + H2NR6NH2 + HOOCR5COOH~ SALT
(VII) (VIII)

(6) (VIII) ~ ~lternating copolymer Reaction (l) is o~ten referred to as cyanoethylation, particularly wherein Rl = ~2 = R3 = H; also these R's can be C1 - ClO alkyls or C3 - ClO isoalkyls. R4 can be one o~ the ~ollowing: Cl - ClO alkylene and C3 - ClO isoalkylene. Re-action (2) is a hydrogenation. Reactions (3) and (5) is a reaction between a diacid and diamine resulting in a salt.
R5 can ~e one of the following: C0 - C10 alkylene and C3 - C10 isoalkylene. Reactions (4) and (6) are often referred to as condensation polymerization. R6 can be one of the ~ollo~ing C2 - ClO alkylene and C3 ~ C10 isoalkylene- In the a~orementioned condensation polymerization, the repeating unit contalns fewer atoms than the monomer, and necessarily, the molecular weight of the polymer as formed is less than the sum o~ the molecular weights of all the original monomer units which were combined in the reaction to form the polymer chain.
Examples of Cl - ClO alkyls are methyl, propyl, butyl, pentyl, etc.: examples o~ the C3 - ClO isoalkyls are isopropyl, iso-butyl, isopentyl and the like. Examples of Cl - C10 isoalkylenes are the following: methyltrime-thylene, 1,2-methyltetramethylene and the like.

~47196 A variation of preparation reactions (1) and (2) are also disclosed in Chemical Abstracts 3935K~ vol. 71 (1969) S. African Patent 6,704,646.

Examples of HOR40R of reaction (:L) are &S follows:
ethylene glycol, propylene glycol and trimethylene glycol.
Examples of HOOCR5COOH of reaction (3) are as follows: oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, ~ diethyl~s~cGinic-a~d ~-methyl-~-ethyl suberic.

The polymers of present invention can also contain an antioxidant such as 1,3,5 -trimethyl-2,4,6-tris-(3,5-ditertiary-butyl-l~-hydroxybenzyl) benzene. Small amounts of antioxidant e.g., 0.5 weight percent can be used or as much as 2.0 weight perc0nt also can be satisfactory. Antloxidants other than the aforementioned one can be used. The antioxidant generally would be mixed in combination with the two polymers prior to melt blending. Other usual additives for polyamides such as delustrants and/or light stabili~ers can also be incorporated.

EXA~PLES

The followin~ describes how the various novel polymers and their precursors were prepared, and the :Ln~luence of certain variable upon their properties. Also reported as results on comparative polymers.

1. Preparation of 1,2-bis~ cyanoethoxyethane) (Nc-(cH2)2o--~c-H2l2-o(cH2l2-cN

To a 5 liter double walled (for water cooling) glass reactor with a bottom drain and stopcock ~as charged 930 grams (15 moles) of ethylene glycol and 1~5.6 grams of ~0~ aqueous ~0~7~6 KOH solution. Some 1620 grams (2006 moles) of acrylonitrile (NC-CH=CH2) were then added dropwise with stirring at such a rate that the temperature was kept below 35C. After the addition was completed the mixture was stirred an additional hour and then allowed to stand overnight. The mixture was then neutralized to a pH of 7 by the addition of 6 molar HCl. After washing with saturated NaCl solution three times, the product was separated from the aqueous layer, dried over CaC12 and ~ passed through an A1203 column to insure that all basic 10 materials had been removed. The yield obtained was 90~ of theoretical.

2. Preparation of 4,7-dioxadecamethylenediamine ~ NH2 ( CH.2 ) 3~2 ) 2 - ( CH2 ) 3 N~I2 ~, In an 800 mllliliter hydrogena-tion reactor was charged 150 grams of 1,2-bis-(~ -cyanoethyloxyethane), 230 milliliters of dioxane and about 50 grams of Raney Co. After purging the air, the reaction was pressurized with hydrogen up to 3,000 psi and heated to 110C. As the hydrogen was consumed additional hydrogen was added until pressure remained constant. Upon cooling, the pressure was released and the catalyst was fil-tered. The dioxane was removed by atmospheric distilla-tion.
The remaining mixture was distilled by a 3 ~t. spinning band distillation unit. About 98 grams of 99.95~ pure material was obtained. The materials can be referred to as 30203 diamine.

3. Preparation of 4,7-dioxadecamethylene adipamide 0203-6 salt) To a solution of 41.50 grams of adipic acid dissolved in a mixture of 250 milliliters of isopropanol and 50 milli-liters of ethanol was added, with stirring, 50 grams of the ~047~6 30203 diamine dissolved in 200 milliliters o~ isopropanol. An exothermic reaction occurred. Upon cooling, a polymer salt crystallized out of solution. The salt was collected on a Buchner ~unnel and subsequently recrystalli~ed ~rom a mixture o~ 400 milliliters o~ ethanol and 300 milliliters of iso-propanol solution. The product dried i vacuo overnight at 60~, had a melting point of 182C and the pH of a 1~
solution was 6.9. 85 grams (92~ yield of theortical) of the salt was obtained.

4. Preparation of 50/50 Alternating Component About 27 grams o~ caprolactam, 27 grams o~ 30203-6 salt, 0.5 grams of water and 0.1 grams of acetic acid were charged to a heavy walled polymer tube. The latter was purged o~ air, sealed and then heated at 250C for about 6 hours.
Afterwards the tube was broken at the tip and a long glass tube inserted for a nitrogen purge. The ~illed tube was heated at 255C in a biphenyl vapor bath ~or 2 hours. During the latter heating nitrogen was passed through the glass tube.
After heating ~or 2 hours, the tube was broken and the alternat-ing polymer removed. The so~tening point o~ the polymer waslow so that it had to be cut by hand because machine cutting created too much heat. The polymer had an inherent viscosity o~ o.78 in a meta-cresol solution at 100C.

The low melting points indicated that this component was amorphous. Amorphous polymers do not exhibit structural order among the chains. There are not regular repeating spacing or distances between the molecules. These polymers are usually made up of molecules that are irregular in shape, that cannot pack in an ordered fashion and that may be thought of as a mass of cooked spaghetti. By comparison crystalline polymers 10~7196 are characterized by the capability o~ their molecules or, more correctly, segments in these molecules to form three-dimensionally ordered arrays exhibiting characteristic inter-or intra-molecular spacings. Increases in crystallinity generally increase strength.

5. _olymer Melt Blending Suitable amounts of dried alternating component and nylon-6 were charged to a large test tube having two openings in the rubber stopper. The openings were for a helical stirrer and an nitrogen inlet. The container was purged of air. After-wards, the nitrogen filled container was heated using a suitable liquid-vapor bath. The mixture of the two polymers was agitated with a helical stirrer powered by an air motor ~or the required tlme. Before allowing the molten polymer to cool the stirrer was lifted to drain the polymer. After solidification the material was broken up and dried for spinning.

6. Polymer Spinning and Drawing After the aforementioned melt blending the polymer was charged to a micro spinning apparatus consisting of stain-less steel tube (5/8" O.D. x 12") with a .037" capillary. The tube was heated with a vapor bath to the temperature consistent with the polymer. Generally about 2~5~ was used. Nitrogen was swept through the polymer until the polymer melted and sealed the capillary. After the polymer was completely melted and a uni~orm temperature had been reached (about 30 minutes) the nitrogen pressure ~as increased by about 30-50 psig (de-pended on polymer melt viscosity) to extrude the polymer.

The fiber as it lef-t the tube was drawn on a series of rollers and wound up on a bobbin. The first roller or feed ~L04~:196 roll was traveling at 35 ft./min. The filament was wrapped 5 times around this. After crossing a hot pipe maintained at about 50C the filament was wrapped around the second roller or a draw roll (5 times) which speed varied depending on the draw ra-tio required (130-175 ft./min.). Unlike commercial draw rolls~ the fiber tended to abrade itself; that is, the fiber coming off rubbed against the fiber coming on. This made high draw ratios difficult to obtain. The third roll had a removable bobbin and was driven at a slightly lower speed than the draw roller. The differences in speeds caused the fiber to be stretched.

Stretching or drawing orientates the molecules, i.e., places them in a single plane running in the same direction as the fiber. Draw ratios refers -to the ratio of the speed of the second roller or draw roll to the speed of the first roller or feed roll. Th~s if the second roller was traveling at 175 feet per minute and the first roller at 35 feet per minute the draw ratio is 5 (175/35). This difference in speeds of the rollers stretches the fiber.

7. Results of Tests and Comparative Runs The accompanying Table I shows the fiber proper-ties of various copolymers of alternating poly(dioxa-amide) and blocks of polyamide as well as comparative data for nylon-6 and cotton.

Comparison of runs 2-4 with run 1 indicates that as the amount of alternating 30203-6 incorporated with nylon-6 increases the moisture regain at various relative humidities increases. Same comparison of runs indicates that increasing the proportion of 30203-6 in the copolymer does not adversely il0~7~96 influence the tensile, elongation, and initial modulus properties of nylon-6.

Comparison of runs 3-5 with run 6 indicates that as the amount of poly(dioxa-amide) incorporated with nylon-6 increases, the moisture regain approaches that of cot-ton.
Thus indicating that the novel copolymer has excellen-t moisture regain properties while still maintaining the other excellent physical properties of nylon-6.

Tensile, elongation (elongation -to rupture), and initial modulus (textile modulus) and the methods of obtaining such values are defined and described in Kirk-Othmer, Encyclo-o~ Chemical Technology, 2nd Edition, vol. 20, Textile Testing.

Moisture regain refers to the amount of moisture a dried sample of fiber picks up in a constant relative humidity atmosphere. Measurement of this property was carried using a series of humidity chambers made ~rom desicators containing suitable saturated salt solutions (i.e., NaN02-65~;
NaCl-75~; ~C1-~5~; Na2S03-95~)-To de-termine moisture regain first a sample of the fiber was dried in a vacuum desicator over P205. After a constant weight was obtained the sample was placed in one of the appropriate chambers. The chamber was then evacuated to speed up equilibrium. The fiber remained in the chamber until a constant weight was obtained. The increase in weight of the sample over the dried sample was the amount of moisture re-gained.

Table II discloses the weight loss during boil off incurred by the novel copolymer compared to nylon-6. The data ~04~9ti of Table III indicates that boil of~ increases the moisture regain of the alternating copolymer as well as that of nylon-6.

Boil off refers to placing the fiber in boiling water for a specified length o~ time. Afterwards the weight loss was determined. Also after following the procedure described for determining moisture regain the incremen-tal increase in ~
moisture regain at 65~ relative humidity was de-termined. Boil off can be considered as akin to a dye treatment.

The increase in moisture regain as a result of boil off is thought to best be understood by the following explana-tion. By placing the fiber in boiling water portions of the fiber relax, thus the orientated amorphous sections tend to open lIp. Boiling off speeds up the relaxatlon o~ the unnatural state. This opening up permits the ~iber to take up more moisture than it otherwise would be capable of. Heating the fiber, by other than placing in boiling water, will also relax the fi~er.

Accompanying Table IV shows the effect of percent o~
30203-6 in 30203-6~6 on dye uptake. The data indicates that ; 20 as the percent of 30203-6 in 30203-6~6 increases dye uptake increases. Compared to water molecules, dyes are larger molecules and cannot penetrate the crystalline structure of nylon fiber, thus dye uptake can be related to the amount of amorphous regions in the fiber.

The amount o~ dye uptake was measured in the follow-ing manner. The preweigh~d fibers were dyed in suitable containers at room temperature. The concentration of the "direct yellow 28" in the a~ueous dye solution was measured before and after spectrophotometrically. The dyeing was ~C~47~6 considered complete when no decrease in dye concentration was observed over several hours. Prior -to dyeing ~t ~as de-termined that the initial concentration of the dye in the bath had to be greater than 5.8 x 10-5 gra.ms/milliliter so that the measured dye absorption was independent of the initial dye concentration.

Analogous results are obtained when nylon-6,6, nylon-6,10, nylon-11, MXD-6, PACM-10, PACM-12 are used in place of nylon-6 in the polymer melt blending s-tep (~). Also analogous results are obtained within step (3), adipic acid is replaced with one of the following acids: oxalic, malonic, succinic, glutaric, pimelic, suberic, azelaic, sebacic, undecanedioic ~ diethylsuccinic, and ~-methyl ~-ethyl suberic. When the ethylene glycol o~ s-tep (1) is replaced with one o~ the following glycols: trime-thylene propylene and tetramethylene and the like, analogous results are obtained.

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Claims (23)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DFINED AS FOLLOWS:

1. A copolymer of block of alternating poly(dioxa-amide) and polyamide having a molecular weight of about 5,000-100,000 and the following two components:
(a) an alternating component consisting of:

and and one of the following wherein the relative proportions of each are n = 1-10, m = 1-10, q = 0-10, p = 0-10, and if p = 0 then n + q = m; and wherein R1, R2, R3 is selected from the group consisting of H, C1-C10 alkyls and C3-C10 isoalkyls;
R4 is selected from the group consisting of C1-C10 alkylenes and C3-C10 isoalkylenes;

R5 is selected from the group consisting of CO-C10 alkylenes and C3-C10 isoalkylenes;

R6 and R7 are selected from the group consisting of C5-C11 alkylenes;

(b) and a block component consisting of:

and wherein the weight ratio of components (a) and (b) are such that a/b = 0.05-1.5.

2. A copolymer according to Claim 1 wherein the polymer is hydrophilic.

3. A copolymer according to Claim 2 wherein the polymer has a percent moisture regain of at least 4% at a relative humidity of 65%.

4. A copolymer according to Claim 1 wherein the bivalent radical polyamide is selected from the group consist-ing of the following: nylon-6, nylon-6/6, and PACM-12.

5. A copolymer according to Claim 4 wherein the weight ratio of components (a) and (b) is such that a/b =
0.10-1.25.

6. A copolymer according to Claim 5 wherein the polymer is hydrophilic.

7. A copolymer according to Claim 6 wherein the polymer has a percent moisture regain of at least 4% at a relative humidity of 65%.

8. A copolymer according to Claim 7 wherein R1, R2, and R3 are selected from the group consisting of H and C1-C5 alkyls.

9. A copolymer according to Claim 8 wherein R4 is a C1-C5 alkylene.

10. A copolymer according to Claim 9 wherein R5 and R6 are C5-C8 alkylenes.

11. A copolymer according to Claim 10 wherein the melt spinnable polyamide is nylon-6.

12. A fiber obtained by spinning the copolymer of Claim 1.

13. A fiber obtained by spinning the copolymer of Claim 3.

l4. A fiber obtained by spinning the copolymer of Claim 9.

15. A fiber obtained by spinning the copolymer of Claim 11.

16. A fiber obtained by melt spinning the copolymer of Claim 1.

17. A fiber obtained by melt spinning the copolymer of Claim 3.

18. A fiber obtained by melt spinning the copolymer of Claim 9.

19. A fiber obtained by melt spinning the copolymer of Claim 11.

20. A monofilament obtained by extruding the copolymer of Claim 1.

21. A monofilament obtained by extruding the copolymer of Claim 3.

22. A monofilament obtained by extruding the copolymer of Claim 9.

23. A monofilament obtained by extruding the copolymer of Claim 11.