CA1047195A - Block copolymer of poly(oxa-alkylene amide) and polyamide - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Novel block copolymer formed by melt blending a melt spinnable polyamide such as nylon 6 and a poly(oxa-amide) such as poly(4-oxaheptamethylene adipamide) (also known as 303-6) is disclosed. Said copolymer has utility as a fiber.
The fiber of copolymer, for example of nylon 6 and said poly-(oxa-amide) has superior absorption characteristics than that of nylon 6. Furthermore, resulting fiber still substantially maintains the other desirable properties of the major con-stituent, for example nylon 6.

Description

~V~a7195 CROSS REFERENCES TO RELATED APPLICATIONS

This application is related to Canadian Serial No.
213,649 filed same date by Robert M. Thompson and Richard S.
Stearns; title of the application is Copolymer of Blocks of Alternating Poly(Dioxa-~mide) and PolyamidLe. This application is also related to Canadian Serial Nos. 213,635 and 213,634 both filed same date by present inventor and titled Block Copolymer of Poly(Dioxa-Amide) and Polyamide, and Block Copolymer of Poly(Dioxa-Arylamide) and Polyamide, respect-ively. This application is also related to Canadian Serial No. 213,637, filed same date by Elmer J. Elollstein. Subject matter of this latter application relates to a method for the hydrogenation of a dinitrile, which is a precursor of a hydrophilic polymer disclosed within the aforementioned related applications.

BACKGROUND OF TEIE INVENTION

It is known that commercially important polyamides, such as nylon 6, has excellent physical properties in many respects. However, for certain textile applications fabrics and similar products prepared from such nylons are somewhat deficient in moisture absorption~ This characteristic is important because according to Encyclo~ia of Polymer Science Vol. 10, Section Polyamide Fibers, moisture absorpiton deter-mines rapid drying, comfort factors, 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 -i4 have been commercially successful to date.

Disclosed herein is a novel block copolymer which can be converted into a fiber having moisture absorption properties .~ superior to that of commercially used polyamide such as nylon 6.

,~ ~

1047~5 This novel block copolymer consists of a certain polyamide and a certain poly(oxa-amide). Surprisingly the incorporation of a certain poly(oxa-amide) into a certain polyamide does not adversely effect the many desirable fiber properties of the polyamide and yet materially improves its moisture absorption property. Also the copolymer can be formed into a desired shape by extrusion, injection molding and other well known thermoplastic forming methods.

H ~Generally, copolymers containing bhe amide function~
i.e., -N-C- can be ~ormed by melting two polyamides. Thus when two different polyamides are mixed and heated above their melting point copolymers are ~ormed. This process is also known as melt blending. However, the length of time the polymers are maintained at a temperature above -their melting points has a profound effect on -the resulting structure. As the mixing at the ~evated temperature begins the mass is a physical mixture of two different compounds. But gradually as the heating and mixing continues the mixture is converted into a copolymer characterized as a "block" copolymer. However, i~ the heating and mixing continues the length of the "blocks" decrease and sequences of "alternating" appear. If the heating and mixing occurs for a sufficient time most of the "bloc~s" disappear and mostly "alternating" sequences exist. At present there is no known direct way of determining chain sequence of such a polymer. But indirect methods exist and these are discussed in detail hereinafter. Controlled decomposition of such a copolymer will yield all identifiable components that make up the copolymer but will not indicate sequences.

As inferred from the previous discussion the terms "block" and "alternating" can easily be misapplied.

~J47~S
However, facilitating the characterizing of a polymer and/or copolymer is consideration of its starting materials and the methods used to prepare the polymers. Thus for example if caprolactam (C~O(C2H) ~ H is properly processed the resulting polymer is HOCCO(CH2)5NH]nH, or nylon 6 or a homopolymer. Thus the latter is a chainlike molecule composed of recurring units of low molecular weight species; it is not a l'block" and not an "alternating" polymer. By comparison a copolymer consists of two monomeric units, that is to say, each monomeric unit could by itself form a homopolymer. 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 t~e butadiene (a)-styrene (b) copolymer would have an alternating sequence. The sequence would be a "abababab-" structure. The latter has a regularly alternat~ng pattern. Other possible patterns of alternating copolymers are'~andom", i.e., -cdcdcddcccddcdcdcc-, and "short sequence"
i.e. -eefffeeffeeefffee- Examples of such alternating copolymers are as follows: Chemical Abstract 88764f, Vol. 70, 1969 (Japa-nese Patent 28,837(68) discloses an alternating copolymerhaving moisture retention properties prepared from (a) the salt of H2N(C~2)30(CH2)3N~I2 (also referred to as 303 diamine) and adipic acid and (b) the monomer caprolac-tam. Journal of Polymer Science, Vol. XXL, pages 237-250 (1956), Some Isomor-phous Copolyamides, by Cramer et al describes methods for preparing 303-6 polymer and its resulting properties.

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-tively long chains of a particular chemical composition, -the chains being separated by a polymer of different chemical 7~9S
composition, thus diagrammatically ~ A 1 ~ .
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 _ ¦ A~ Each o~ the aforementioned polymer chains i.e., A and/or B can be a homo-polymer or an alternating copolymer.

U. S. Patent, 3~514,L~98 also discloses a block (alter-natin~ copolymer prepared from two polymers i.e., (a) a polymer resulting from the salt of diamine of polyethylene oxide and adipic acid and ~-caprolactam and (b) poly- ~-capramide (nylon 6). U. S. Patent 3,549,72L~ also discloses a block (alternating) copolymer prepared from (a) polymer prepared from polyethylene oxLde diammonium adipate and ~-caprolactam and (b) nylon 6 or nylon 6,6. U. S. Patent 3,160,677 discloses a block copolymer prepared from (a) polymer prepared from dibutyl oxalate ((COOC4Hg)2) and a diamine and (b) polycapro-lactam.

Contrary to expectations based on the previously discussed art, it has now been found that it is possible to prepare a compositlon comprlsing a block copolymer of poly-amide and poly(oxa-amide) having excellent moisture uptake.
In additon fibers of the copolymer have overall fiber properties comparative to that of such nylons as nylon 6.

SUMMARY OF THE INV~NTION

Present invention resides in a novel composition.
It has utility as a fiber as well as other utilities. The composition is a block copolymer of a certain polyamide and a certain poly(oxa-amide). The polyamide portion of the ~47~L95 molecule is a bivalent radical of a melt spinnable polyamide.
The poly(oxa-amide) portion of this molecule contains both one oxygen linkage, e.g., -R -R -O-R - and amide linkage, e.e., -N-C-. The following repeating structural formula depicts the composition of this invention:

RlR R2R1 _ H 1 l2 1 1 ~ ll ll bivalent N-CH2-C C-O-C-C-CH2-N-C-Rl C radical of H 1 I H ~ melt spinnable 10R3 R3 Y polyamide l -wherein Rl, R2 and R3 is selected from the group consisting of H, Cl-C10 alkyls and C3-C1o isoalkyls; R~ is selected from the group consisting of CO-ClO alkylenes and C3-Clo isoalkylenes;
and ~ = 2-100 and z = 2-150. The molecular weight of the fore-golng ~lock copolymer is about 5,000 - 100,000.

DESCRIPTION

As stated heretofore one portion of the novel composi-tion is a melt spinnable polymer. Melt-~pinnable re~ers to a ~ process wherein the polymer, a polyamide, is heated to above its melting temperature and while molten forced through a spinneret.
The latter is a plate containing from one to many thousands orifices, through which the molten polymer is forced under pressure. The molten polymer is a continuous filament and depending on the number of orifices many filaments can be formed at the same time. The molten filaments are cooled, solidified, converged and ~inally collected on a bobbin. This technique is described in greater detail in Encyclopedia of Polymer Science & Technology7 Vol. 8, Man-Made Fibers~ Manufac-ture.

30If a single fiber is extruded as in the case when it is intended to be knitted into hosiery~ the product is called ~47~
a monofilament When the product is expected to be converted into a fabric by knitting or weaving, the number of monofilaments is in the range 10-100. Such a product is known as a multi-filament yarn. Yarns for industrial applications such as in the construction of the cords 7 usually cont;ains several hundred to a thousand or more filaments. When the fibers are used to make a spun yarn, i.e., a yarn formed by twisting short lengths of fibers together, as in the practice with cotton, the number of orifices can use 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 lnto spun yarn in the same manner as cotton. Polymer of present invention can be prepared into the aforementioned forms by the various methods described.

Also, the polymers of present invention can be used to prepare nonwovens. Nonwoven refers to a material such as 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 are described in detail in Manual of Nonwove~s, Prof. Depl-Ing and Dr. Radko Krema, Textile Trade Press, Manchester, England.

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 spinnable polyamides are as follows:
nylon 6,6 (also known as poly(hexamethylene adipamide)); nylon 6,10 (poly(hexamethylene sebacamide)); nylon 6 (poly(pentamethy-lene carbonamide)); nylon 11 (poly(decamethylene carbonamide));

MXD-6 (poly(metaxylene adipamide)); PACM-9(bis(paraamino-cyclohexyl) methane azelamide); PACM-10 (bis(paraaminocyclohexyl) ~47~95 methane sebacamide), and PAC~-12 (bis(paraaminocyclohexyl) methane dodecanoamide); others are listed in ncyclopedia of ~olymers Science & Technolog~, Vol. 10, Section Polyamide Fibers, table 12. Methods ~or preparing these polyamides are well known and described in nume~ous patents and trade journals.

The po~y(oxa-amide) portion o~ the composition can be prepared by the following generalized scheme:

(1) ~Rl JR2 RlR2 R2Rl N=C-C=C + H20- -~ N-C-C-C-O-C-C-CN
~R3 H I I H

(I) (II)

(2) (II)-~ H2~ NH2-CH2-C-C-O-~C-~CI-CH2-NH2 (III) ;

RlR2 R2 IRl +
20 (3) (III) + HOOCR4COOH -3(00CR4COO) (NH3CH2-C-C-O-C-C~CH2-NH3) (IV) (V) -- RlR2 R2Rl O
(4) (V)- ~ NH-CH2-C-l-o-l-c-cH2-N-c-R

(VI) Reaction (1) is o~ten re~erred to as cyanoethylation;
particularly wherein Rl=R2=R3=H; also these R's can be Cl-C10 alkyls or C3-C10 isoalkyls. Diamines o~ the type (II) are commercially available. Reaction (2) is a hydrogenation.
Reaction (3) is the reaction between a diacid and a diamine 1~7~95 resulting in a salt. R4 can be one of the following: CO-ClO
alkylenes and C3-C10 isoal~ylenes. Reaction (4) is often referred to as a condensation polymerization. Here the repeat-ing unit contains fewer atoms than the monomer and necessarily the molecular weight of the polymer so ~rmed is less than the sum of the molecular weights of all the original monomer units which were combined in the reaction to form the pol~mers chain.
Examples of Cl-C10 alkyls are methyl, propyl, butyl, pentyl, etc., examples of the C3-Clo isoalkyls are isopropyl, isobutyl, isopentyl, and the like.

Examples of Cl-C10 alkylenes are as follows: methylene, dimethylene, trimethylene and -the like, examples of C3-Clo iso-alkylenes are as follows: methyltrimethylene, methyl-2-tetra-methylene and the like. Examples o~ HOOCR~COOH of reaction (3) are as follows: oxallc, malonic, succinic, flutaric, adipic, pimelic, suberic, azelaic, sebacic, un~ecanedioic, ~,~-diethyl succinic and a-methyl-~-ethyl suberic.

Examples of poly(oxa-amide) polymers that can be prepared via the a~orementioned generalized scheme are the following:
O O

-NH-(CH2)3-0-(CH2)3-~ C (C 2)4 poly(4-oxaheptamethylene adipamide) also 303-6 -NH-cH2-c-cH2-o-cH2-c-cH2-N-c-(cH2)4-H H

poly(4-oxa-2,6-dimethylnonomethylene adipamide) O O
H U
-NH-(cH2)3-o-(cH2)3-N-c-(c~2)8 poly(4-oxaheptamethylene sebacamide) ~0~7~95 `
The polymers of present invention can also contain an antioxidant such as 1,3,5vtrimethyl-2,4,6-tris-(3~5-di-tertiary-butyl-4-hydroxybenzyl) benzene. Small amounts of antioxidant, e.g 0.5 weight percent, are satisfactory, however, as little as 0.01 weight percent can be used and as much as 2.0 weight percent also can be satisfactory. Antioxidants 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 stabilizers can also be in-corporated.

EXAMPLES

The following describes how the various novel polymers were prepared and the influence of certain varlables upon their properties. Also reported are results on comparative polymers.

1. Preparation of Poly(4-oxaheptamethylene adipamide) (33-6) Forty-four grams of adipic acid were dissolved in 200 milliliters of ethanol. Forty grams of purchased 4~oxahepta-methylene diamine (303) were dissolved in 200 milliliters of lsopropanol and the resulting mixture was added to the mixture of said acid and ethanol. An exothermic reaction occurred.
Upon cooling, a polymer salt crystallized out of the mixture of alcohols. The polymer salt was collected on a Buchner funnel and subsequently recrystallized from a solution of equal amounts of ethanol and isopropanol. About 80 grams of salt were obtained. A 1~ solution of the salt had a p~I=7.3. The salt itself had a melting point of 142.8C. The salt can be referred to as the salt of 303-6.

About L~o grams of the polymer salt were charged to a heavy walled glass polymer "D" tube. Then the neck of the tube was constricted for sealing and purged of air by evacuating and filling with nitrogen 5 times. Finally the tube was heated in an aluminum block for 2 hours at 200C. Af-ter cooling the tip of the tube was broken off and the remaining portion was ben~t over at a ~5 angle by heating and then colmected to a manifold and purged of air with nitrogen-vacuum cycles. The tubes were heated at 222C under nitrogen at atmospheric pressure for 6 hours using methyl salicylate vapor baths. On cooling, the tubes were broken and the polymer plug crushed to 1/8" size pieces. The resulting po~ymers had inherent viscosities rang-ing from 0.82 to 0.93 in a meta-cresol solution. One of the polymers had a melting point o~ 210C.

2. olymer Melt Blending Suitable amounts of dried 303-6 polymer 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 a nitrogen inlet. The container was purged of air, afterwards the nitrogen filled container was heated using a suitable liquid-vapor bath. The mixture of the two polymers was agi-tated with the helical stirrer powered by an air motor for the required time. Before allowing ~he molten polymer to cool the stirrer was lifted to drain the polymer. After solidi-fication the material was broken up and dried for spinning.

3. Polymer ~pinning and Drawing After the aforementioned melt blending the polymer was charged to micro spinning apparatus consisting of stainless 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 3L~47~S
the polymer. Generally, 245~ 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-form temperature had been reached (about 30 minutes) the nitro-gen pressure was increased by about 30 - 50 psig (depending on polymer melt viscosity) to extrude the poly~er.

The fiber as it left the tube was drawn on a series of rollers and wound up on a bobbin. The first roller or feed roll was traveling at 35 ft./min. The filament was wrapped 5 times around this. After crossing a hot pipe maintained at about 50~C the filament was wrapped around the second roller or a draw roll (5 times) which speed varied depending on the draw ratiol re~uired (130-175 ft./min. Unlike commercial draw rolls, the ~iber tended to abrade itsel~; that is the fiber coming off rubber against fiber coming on. This made higher araw ratios difficult to obtain. The third roll had a removable bobbin and was driven at a slightly lower speed than the draw roller.

Draw ratio refers to the ratio of the speed of the second roller or draw roll to the speed of the first roller or ~eed roll. Thus i~ 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. Stretching or drawing orientates the molecules, i.e., places them in a single plane running in the same direction as the fiber.

4. Results of Tests and ~omparative Runs Accompanying Table I shows the effect of melt blending's temperature and time on various block copolymers having different ~)47~95 proportions Or poly(oxa-amide) and polyamide. Also shown are comparative runs with alternating copol~mers (Runs 12-15), nylon 6 (Run l), and cotton (Run 2).

Comparison of Runs 5, 6 and 7 indicates that at 20~
of 303-6 in 303-6/6 an increase in blending time decreases the resulting polymer's melting point. This indicates a decrease in the amount of "blocks" and further indicates an increase in the amount of "alternating~

Comparison of Runs 7, 8, 9 indicates that at a con-stant percentage of 303-6 in 303-6/6 and at a constant blending time, as the temperature of ~lending increases substantial decreases occur in inherent viscosity and polymer melting point.
This decrease ln inherent ~iscosity, reflects decomposition of the macromolecule when the blending time is excessi~e.

Comparison of Run 12 with Runs 5, 6 and 7 demonstrate the difference between block and alternating copolymerS. Thus the alternating copolymer of Run 12 has a fiber melting point of 190C which is substantially lower than the 218C of the block copolymer of Run 5. Thus as the length of the "block"
copolymer decreases or the degree of "alternating" ~ncreases, i.e., Runs 6 and 7 the fiber melting point decreases.

Tensile, elongation (to rup-ture), and initial modulus (textile modulus) and the methods for obtaining such ~alues are defined and described in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Vol. 10, Textile Testing.

Accompanying Table II shows the moi.sture regain of block 303-6/6, nylon 6 and cotton. Comparison of Runs 3 and 1 indicates that the incorporation of 20~ of 303-6 into nylon 6 substantially impro~es the moisture regain of the nylon 6.

~C147~5 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 from desicators containing suitable saturated salt solutions (i.e., Na-N02=65~;
NaC1=75~; KC1G85~ Na2SO3-95~).

To determine moisture regain first the sample of the fiber was dried in a vacuum desicator over P2Q5. After a constant weight was obtained the sample was placed in one of the appropriate chambers. The chamber was then e~acuated to speed up equilibrium. The fiber remained in the chamber until a constant weight was obtained. The increase in weight of the sample o~er the dried sample was the amount of moisture regained.

Accompanying Table III shows the effect of boil off on moisture regain of nylon 6, block 303-6/6 and alterna-ting 303-6/6. The data indicates that boil off does increase moisture regain of both 303-6/6~S. The data also indica-tes that boil off has different influences on the a~ount of increase in moisture regain depending whether the polymer is block or alternating.

Boil of~ refers to the placement of the fiber in boiling water for a specified length of time. Afterwards the weight loss is determined. Also after following the procedure described for determining moisture regain the incremental increase in ~ moisture regain at 65~ relati~e humidity was determined. 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 be best understood by the following explana-tion. By placing the fiber in boiling water portions of the -1047:~95 ~iber relax. Thus the orientated amorphous sections tend to open up. Boiling o~ speeds up the relaxation o~ this unnatural state. This opening up permits the fiber to take up more mois~e than it otherwise would be capable of. Heating the ~iber, ~y other than placing in boiling water, will also relax the fiber.

Analagous results are obtained when nylon 6,6, nylon 6,10; nylon 11, MXD-6, PACM-12 are used in place o~
nylon 6 in the polymer melt blending step (2). Also anala-gous resuts are obtained when the adipic acid of step (1) is re-placed with one of the ~ollowing: oxalic, succinic, pimelic, oxelaic, and a,~-diethyl succinic.

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Claims (19)

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

1. A block copolymer having a molecular weight of about 5000-100,000 and the following repeating structural formula:

wherein R1, R2 and R3 is selected from the group consisting of H, C1-C10 alkyls and C3-C10 isoalkyls;
R4 is selected from the group consisting of CO-C10 alkylenes and C3-C10 isoalkylene;
and y = 2-100 z = 2-150.

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

3. A copolymer according to Claim 2 wherein the copolymer 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 consisting of nylon 6, nylon 6,6 and PACM 12.

5. A copolymer according to Claim 4 wherein the copolymer is hydrophillic.

6. A copolymer according to Claim 5 wherein the copolymer has a percent moisture regain of at least 4% at a relative humidity of 65%.

7. A copolymer according to Claim 6 wherein the bivalent radical polyamide is selected from the group consisting of nylon 6, nylon 6,6 and PACM 12.

8. A copolymer according to Claim 7 wherein R1, R2 and R3 are H and R4 is a C1-C10 alkylene.

9. A copolymer according to Claim 8 wherein the copolymer has a percent moisture regain of at least 4% at a relative humidity of 65%.

10. A copolymer according to Claim 8 wherein R4 is a C2 alkylene.

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

12. A fiber obtained by spinning the copolymer of Calim 8.

13. A fiber obtained by spinning the copolymer of Claim 10.

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

15. A fiber obtained by melt spinning the copolymer of Claim 8.

16. A fiber obtained by melt spinning the copolymer of Claim 10.

17. A monofilament obtained by extrusion of the copolymer of Claim 1.

18. A monofilament obtained by extrusion of the copolymer of Claim 8.

19. A monofilament obtained by extrusion of the copolymer of Claim 10.