CA1099431A - Copolymer of poly (4,7-dioxadecamethylene adipamide) - polycaprolactam containing terephthalic acid - Google Patents

Abstract

Thompson S-76-054 INVENTOR: ROBERT M. THOMPSON
2313 Berwyn Road Wilmington, New Castle County State of Delaware 19803 TITLE OF THE INVENTION: "COPOLYMER OF POLY (4,7-DIOXADECAMETHYLENE
ADIPAMIDE) - POLYCAPROLACTAM CONTAINING
TEREPHTHALIC ACID"

ABSTRACT OF THE DISCLOSURE

Fibers of block copolymer of poly (4,7-dioxade-camethylene adipamide) - polycaprolactam, i.e. N-30203-6//6, have the tendency to fuse when scoured in boiling water. By replacing between from about 3 to about 13 weight % of the adipic acid present in the N-30203-6 portion of the block copolymer with terephthalic acid the fusion is eliminated.
The resulting novel composition consists of blocks of random N-30203-6 and N-30203-T with nylon-6 blocks. The composition maintains its good hydrophilic properties.

Description

1~943~

BACKGROUND OF THE INVENTION

Field of the Invention This invention is directed to a novel composition of matter. The composition is a particular nylon copolymer having utility as a fiber.

Description of the Prior A _ The poly(4,7-dioxadecamethylene adipamide)-polycaprolactam block copolymer, referred to hereinafter as N-30203-6//6, is disclosed in my U.S. Patent 4,130,602, issued December 19, 1978.
~iethod for making such a polymer is also disclosed therein. The block copolymer N-30203-6//6 has utility as a hydrophilic fiber.
While it also has other favorable properties sueh as tenacity, elongation and initial modulus, it can have a fusion problem as deseribed hereinafter.

To form a fabric from a block copolymer N-30203-6//6, the eopolymer is spun into a fiber by known means. While spinning the fiber, a lubrieating finish is applied to the fiber to faeilitate subsequent processing steps. After the copolymer is spun, it is drawn and then annealed to stabilize the drawning.
The resulting fiber is knitted into a tube and then, to wash off the finish applied earlier, it is placed in boiling water.
During this washing off in the boiling water, the copolymer fibers have a tendency to fuse together. (The washing off in boiling water is referred to as scouring.) This fusion causes the knitted fabric to become stiff which is unacceptable to a wearer.

l~q9431 SU~RY

It has been discovered that if a small portion of the adipic acid in the N-30203-6 portion of the block copolymer N-30203-6//6 is replaced with terephthalic acid (hereinafter referred to as T), the aforementioned fusion problem is eliminated. Surprisingly the resulting copolymer maintains the desirable hydrophillic tenacity, elongation and initial modulus properties of N-30203-6//6.

DESCRIPTION

The copolymer of my discovery has the following structural formula:
1S l~r-(CH2)3-O-(CH2)2-o-(cH2)3-N-c x t ~cH2~s Y Z

wherein x is between from about 97 weight % to about 93 weight % of the bivalent radical -(CH2)4-, and the balance is para-phenylene and y = 4-200 z = ~-200 and the copolymer has a molecular weight of within the range of about 5000 - 100,000.

lO~g4~

The ether-amide portion of the copolymer can be prepared by the following scheme:

H H H H H
N-C-CH + HO(CH2)2OHN-C-C-C-O-(CH2)2O-C-C-C-N (l) (I) (II) (III) FI H HH
O (CH ) O-CC-C-N + 4H2-~ NH2-(CH2)3 ( 2 2 2 (III) (IV) NH2-(CH2)3-O-~CH2~2-O-(CH2)3-NH2 + HOC-(CH2)4-C-OH (3) O O
(IV) (V) ( 3 (CH2)3 (CH2)2 O(CH2)3-NH3 ) (OC-(CH2)4-C-O) O O
(4) (VI) 3 ( 2)3 (CH2)2-O-(CH2)3-NH3 )(OC- ~ -C-O) O O
(VII) H H H
) tCH ) -N-~-(CH2)4-C-)(-N (C~2)3 2 2 O O O O
(VIII) ~09943~

Aforementioned reaction (:L) is often referred to as cyanoethylation; it is between acrylonitrile, I, and ethylene glycol, II, and results in 1,2-bis ( -cyanoethoxyethane), III.
Reaction (2) is the hydrogenation of compound III to the diamine (i.e., 4,7-dioxadecamethylenediamine), IV. The diamine, IV, is reacted with adipic acid, V, to form the salt, VI, in reaction (3). To prepare the analogous terephthalic salt, the afore-mentioned reactions (1) - (3) can be duplicated except that in reaction (3) in place of adipic acid, terephthalic acid is used. Then the two salts, i.e., VI and VII, are polymerized by heating to form the random copolymer, VIII. The latter contains N-30203-6 and N-30203-T. Thus the random copolymer can be represented as N-30203-6/T.

The amount of adipic acid used to prepare the afore-mentioned salt VI is such that it constitutes between about 97 weight % to about 87 weight $ of the total diacid that could be used to react with the diamine IV. The balance of the acid used is T and amounts to between about 3 weight % to about 13.5 weight %. If less than about 3 weight % of T is used, the fusion problem is not corrected whereas if much more than about 13 weight % of T is used, then the other properties may deteriorate too much.

The other portion of the copolymer of present invention I H
is L-N-(CH2)5-C- which is also known as a bivalent radical of nylon-6 or N-6. The latter is available commercially and methods for preparing it are well known and abundantly disclosed in numerous publications.

!~ :

3~

As indicated, the aforementioned portions of N-30203-6/T
and N-6 each can contain as few as 4 repeating units within the copolymer of present invention. Thus, both x and y can equal 4.
As reported in my previously referred to application, 4 represents the lowest value that the components can be present and still retain its own particular properties without substantially degrading the properties of the other repeating units. To minimize loss of properties, the preferred minimum values for y and z are 8 and more preferred values are 10. While values of z of 200 are operative, preferred maximum values of y and z are 175 and 185 with values of 150 and 160 more preferred.

The process used to prepare the copolymer involves a process known as melt blending. In melt blending two different polyamides are mixed together and heated to a temperature which ranges from above both their melting points to below both their decomposition temperatures. The length of time the mixture is maintained within the temperature range has a profound effect on the resulting structure. As the mixing with the aforementioned temperature range 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, if the heating and mixing continues, the length of the "blocks" decreases and sequences of "random" copolymers appear. If the heating and mixing occurs for a sufficient time, most of the "blocks" disappear and mostly "random" sequences form as evidenced by deterioration of its physical properties, including melting point. Use of a higher temperature within the aforementioned range reduces the time necessary to~ achieve the desired amount of block formation at a lower temperature. At present there is no known direct way of determining chain sequence of such a polymer. But indirect methods exist, and these are known to those skilled in the art.
Controlled decomposition of such a copolymer will yield all identifiable components that make up the copolymer but will not indicate sequences.

Melt Blending can be used to prepare N-30203-6/T//6.
Desired amounts of N-30203-6/T are blended with suitable amounts of N-6. The resulting mixture is heated to a temperature which ranges from above the melting point of each to below the decomposition temperature of each. While within this temperature range, the mixture is mixed until the desired amount of blocks are formed. The time for mixing at the elevated temperature depends upon how much material is present, the amount of mixing occurring, the type of equipment used, and the like.

The copolymer of the invention can also contain an antioxidant, delusterant, light stabilizer, and other such additives.
The additives can be incorporated, e.g. prior to the melt blending or during the melt blending or afterwards.

The following examples illustrate further my invention.

EXAMPLES

A random N-30203-6/T, containing by weight 80% of N-30203-6 and 20% of N-30203-6/T, was prepared in the following manner. Eight grans of N-30203-T salt were mixed with 32 grams of N-30203-6 salt. Both salts were prepared by the previously discussed scheme, i.e. reactions 1-3. The resulting mixture of the two salts were changed to a heavy walled polymer tube. In addition 0.04 grams of benzoic acid were changed to the tube.
Its function was to control the polymer's molecular weight as represented by the resulting viscosity; its use is optional.

~0~$~431 In addition 0.04 grams of H3PO3 were changed to the tube. Its function is to serve as a catalyst, against its use is optional.
After purging the tube with a nitrogen-vacuum cycle the tube was evacuated and sealed. The tube was placed in an aluminl~m heating block and the tube's temperature raised to 190C. It was maintained at that level for 2 hours. The tube was then opened and while an atmosphere of nitrogen was maintained its temperature was raised to 245C and maintained at that level for half an hour. Then while the sample was still at 245C the nitrogen was removed and while in a vacuum the temperature was maintained for another hour. A sealed tube was used initially to prevent any monomer from distilling off. The lower temperature was used to slowly build up the molecular weight until a higher temperature could be used. After the final heating at 245C
the material was cooled, chopped and dried for the subsequent melt blending step.

A second random N-30203-6/T, containing by weight 60% of N-30203-6 and 40% of N-30203-T, was prepared in an analogous manner except that the amounts of the salts used were different. A third random N-30203-6-T was prepared containing 20% of N-30203-6 and 80% of N-30203-T.

The first prepared N-30203-6/T copolymer was melt blended in the following manner. Seventy three grams of the polymer (80%
of 6 and 20% of T) was mixed with 170.3 grams of N-6 and then dried by heating to 80C. The resulting dried mixture was charged to a suitable lass tube containing a stainless steel helical stirrer.
The tube was purged of air with nitrogen and heated to 282C using a vapor bath of dimethyl phthalate and stirred for 30 minutes. Upon cooling the resulting N-30203-6/T/6 was removed from the tubes, chopped and dried. In this copolymer the -(CH2)4- bivalent radical amounts to 97% of the x defined in Claim 1.

The second prepared N-30203-6/T copolymer was melt blended as previously described except that 75 grans of the N-30203-6/T copolymer (60% of 6 and 40% of T) and 175 grams of N-6 were used. In the resulting copolymer of N-30203-6/T//6 the -(CH2)4- bivalent radical amounts to 93.5% of the "x" defined in Claim 1.

The third prepared N-30203-6/T was melt blended as previously described except that 60 grams of N-30203-6/T (20%
of 6 and 80% of T) were used. In the resulting copolymer of N-30203-6/T//6 the -(CH2)4- bivalent radical amounts to 87.5% of the "x" defined in Claim 1.

A comparative N-30203-6//6 sample was also prepared by heating and mixing at 282C for 26 minutes.

Samples of the three N-30203-6/T//6 copolymers along with the N-30203-6//6 were individually spun into a fiber using a ram-extruder. The samples were spun through a spinneret having 7 orifices 12 mils in diameter and 24 miles in length. The dried samples, about 50 grams, were changed to the extruder and allowed 25 minutes to melt and reach an equilibrium temperature i.e., about 230C. Then the samples were forced through screen filters, 40 mesh and 250 mesh stainless steel screens and the spinneret by a motor-driven ram. The samples of N-30203-6//6 were melt spun at a suitable feed rate. The samples of N-30203-6/T//6 were spun at a feed rate of about 1.6 cm /min. The yarns were passed from the spinneret through guides and were collected on paper tubes at a take-up speed of 138 ft./min. A spin finish, which is commercially available and which had been dissolved in heptane, was applied to each yarn as it passed over an applicator. The applicator was a nylon felt saturated with a spin finish and was attached to the ~`

.~

3~

yarn guide located about 4 feet below the spinneret. During each of the spinning steps the block temperature of the extruder was about 225C while the ram pressure for the sample containing 3% T
was 400 psig whereas it was 535 psig for the sample containing 6.5% T. The pressure for the 12.5% T sample was 670 psig and the temperature was 232C.

After the fiber spun was drawn and then annealed to stabilize the drawing the resulting stabilized fiber was knitted into a tube, and placed in boiling water. After cooling the tube was deknitted. During the deknitting step no fiber fusion was found for any of the three N-30203-6/T//6 samples.

Samples of the three N-30203-6/T//6 copolymers were tested as to water retention (LA. Welco, H.M. Zufle and A.W. McDonald, Textile Research Journal, 22, 261 (1952)). The amount of water retention versus the amount of T in the copolymer is as follows:

%T % Water Retention 3.5 26 6.5 23 12.5 19 In contrast during the deknitting step for the tube made of N-30203-6//6 polymer a small number of fibers were found fused together. While the amount of fusion was labeled small, the amount was sufficient to make it unacceptable as a commercial fabric.

'~g

Claims (2)

THE INVENTION CLAIMED IS:

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

wherein x is between the range from about 97 weight % to about 87 weight % of the bivalent radical of -(CH2)4- and the balance is para-phenylene;
and y = 4-200 z = 4-200.

2. A method for producing a copolymer of poly (4,7-dioxadecamethyleneadipamide)-polycaprolactam containing terephthalic acid comprising:

a. mixing salts of both and b. heating the salts to form a random copolymer; and c. melt blending the random copolymer and poly-caprolactam to form a copolymer having a molecular weight of about 5000-100,000 and the following repeating structural formula:

wherein X is between the range from about 97 weight % to about 87 weight % of the bivalent radical of -(CH2)4- and the balance is para-phenylene:
and y = 4-200 z = 4-200.