DE2454118A1 - BLOCKCOPOLYMERES - Google Patents

Description

Block copolymer
Priority: November 14, 1973 No. 418 524 USA

The invention relates to a new block copolymer obtained by melt blending a melt-spinnable polyamide, such as nylon-6, and a poly (dioxa-amide), such as poly (4,7 ~ dioxadecamethylene adipamide), is formed. This polymer is useful for making fibers that have similar good moisture absorption properties like cotton.

It is known that industrially important polyamides such as nylon-6 have excellent physical properties in many respects to have. For certain textile uses, such as fabrics and similar products made from such types of nylon, however, have been found to be unsatisfactory ! have moisture absorption. This property is important as according to publication in Encyclopedia of Polymer. Science and Technology, Volume 10, Section Polyamide Fibers, the Moisture absorption is decisive for quick drying, for comfort factors, lightness and economy a coloring and for the handle of the fabric. In order to eliminate this poor moisture absorption, have already been Numerous attempts were made, which, however, are still technical today

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O / C / 11

were unsuccessful.

The invention "therefore relates to a new block copolymer which can be converted into a fiber ₉ whose moisture absorption properties correspond to those of cotton, the current technical comparison standard." This new block copolymer "consists of a" certain polyamide and a certain poly (dioxa-amide) Surprisingly, the introduction of a certain poly (dioxa-amide) into a particular polyamide does not detract from the many desirable fiber properties of the polyamide and still improves its moisture absorption properties deformed to the desired shape.

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ORIGINAL! NSPECTED

2A541T8

In general, copolymers containing the amide function, i.e. H. have the group H 0 by melting two polyamides

-N-C-

are formed. Therefore, when two different polyamides are mixed and heated to a temperature above their melting points, they form copolymers; This process is also known as melt blending. The duration during which the polymers Maintained at a temperature above their melting points, however, has a pronounced effect on the resulting Structure. When mixing begins at the elevated temperature, the mass is a physical mixture of two different ones Links. However, as the heating continues, the mixture is gradually converted into a copolymer known as. "Block copolymer" can be characterized. However, if the mixing and heating is continued, it will decrease length of the blocks and there are sequences of alternating copolymers on. If the mixing and heating is carried out for a sufficient period of time, all of the blocks and disappear there are only alternating sequences. There is currently no direct way of determining the chain sequences such polymers are known. However, there are indirect methods which are explained in detail below. The controlled decomposition of such a copolymer gives all identifiable ones Components that make up the copolymer, however, it indicates: not the sequences.

As can be seen from the preceding explanation, it is easily possible to use the terms "block" copolymer or "alternating" Incorrect use of copolymer.

However, characterization of a polymer and / or copolymer is made easier by considering its starting materials and the methods used to make the polymers. If, for example, caprolactam [CO (CH ₂ ), - EHJ is reacted in a suitable manner, the polymer obtained is HO [CO (CHp) ₅ IInI H

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2 5/4 113

or nylon-6. This latter polymer can be referred to as a homopolymer. It thus represents a chain-like molecule that is formed from recurring monomer units. In comparison, a copolymer consists of two monomer units, that is to say of two different units, of which each monomer unit could itself form a homopolymer. For example, a butadiene-styrene copolymer consists of butadiene, which could form a butadiene homopolymer, and styrene, which could form a styrene homopolymer. In addition, the butadiene (a) -styrene (b) copolymer could show alternating sequence. The sequence would result in a "-abababab-" structure. This structure shows a regularly alternating scheme. Other possible attachment schemes of alternating copolymers are "random" (random), i. E. -cdcdcddcccddcdcdcc or a short sequence scheme, d. h "-eefffeeffeeefffee-. Examples of such alternating copolymers are given below. In "Chemical Abstract" 88764 f, volume 70, 1969 (Japanese patent application 28 837/68) an alternating copolymer with moisture retention properties is described, which is obtained by combining (a) a salt of bis (o6-aminopropoxy) ethane (also known as . 30203) and adipic acid and (b) the monomer caprolactam is produced. GB-PS 1 169 276 describes an alternating copolymer with improved hydrophilic properties, which is obtained by combining (a) a salt (I) of H ₂ N (CH ₂ ) ₅ -O-CH ₂ -C (CH ₅ ) ₂ -CH ₂ -O- (CH ₂ UNH ₂ and adipic acid is formed with (b) monomeric caprolactam, as well as an alternating copolymer of the above-mentioned salt (I) with hexamethylene _{diammonium adipate (H 5} ⁺ N (CH ₂ ) ^ NHCO (CH ₂ ) , COO) ", also known as nylon 6-6 salt.

From "Chemical Abstract" 4514 h, Volume 49, 1955, an alternating copolymer is known which is composed of (a) a salt (II) of HpN (CH 0- (CH ₂ UO- (CH ₂ ), - NH ₂ and Adipic acid and (b) nylon 6-6 salt The salt (II) forms an off-white material on heating, this discoloration impairs its usefulness when freedom from color is required. US Patent 3,522,329 describes an alternating copolymer , the

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from (a) a salt of the diamine of polyethylene oxide (HOCH ₂ CHp (O-CHpCHp) OH and adipic acid and (b) ε-caprolactam (also referred to simply as "caprolactam"). US Pat. No. 3,514,498 is a alternating copolymer "known, which was prepared from (a) the salt of the diamine of polyethylene oxide and adipic acid and ^ -Caprolactam.

A block copolymer can be formed when a mixture of the Polymer A and polymer B, both of which contain amides, is reacted in a suitable manner. The resulting block copolymer thus contains relatively long chains of a certain chemical composition, these chains being made up of a polymer of a different chemical composition and can be represented schematically as follows:

A. A block copolymer can also be relative

contain long chains of a certain chemical composition, however, in this type the chains are separated from one another by a low molecular weight coupling group. This block copolymer can be represented schematically by the following formula:

Inside each of the prominent ones

The polymer chains mentioned, namely A and / or B, can be a homopolymer or an alternating copolymer is present. Examples of some of these polymers are given below. In the above-mentioned US-PS 3,514,498 is also a block copolymer (alternating copolymer) made from two polymers, (a) one from the salt of the diamine of polyethylene oxide and adipic acid and f-Caprolac tarn formed polymers and (b) poly-ε-carboxamide (nylon-6). U.S. Patent -3,549,724 a block copolymer (with blocks with an alternating sequence) is also called, which is made from (a) one of polyethylene oxide diammonium adipate and ^ -caprolactam formed polymers and (b) nylon-6 or nylon-6,6 was obtained. In US-PS 3,160,677 a Block copolymer described, which consists of (a) one of dibutyl oxalate

(COOC.Hq) ₂ and a diamine formed polymer and (b) polycaprolactam was produced.

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In contrast to what would have been expected on the basis of the state of the art explained above, it has now been established that that it is possible to produce a block copolymer from blocks of polyamide and poly (dioxa-amide), its moisture absorb is equivalent to that of cotton copolymers according to the invention fibers could be produced, • whose overall fiber properties are otherwise practically equivalent to the properties of nylon fibers, such as Mylon-6.

The invention relates to the opposite, a new block copolymer that _s suitable for the production of fibers, as well as for other applications. The copolymer according to the invention is a block copolymer of a "certain polyamide and a certain poly (dioxa-amide). The polyamide part of the molecule is the divalent radical of a melt-spinnable polyamide. The poly (dioxa-amide) part of the molecule contains both a double oxygen linkage, namely the group ■ -RORO = R-, as well as an amide linkagej namely the "group H 0

The subject of the invention is thus a block copolymer with a molecular weight of about 5000 to 100 00O ₉ which is characterized by a structure of recurring units of the formula '■'

R _n R ₉ R ₀ R ₁ "0 0

'N-CH ₉ -CCOR.-0-CC-CH ₉ -NC-Rc-C 2ii 4 ι ι 2 5

H-R ö TT

IW iW AA

A-

In the R, _s Rp ₉ R ^ hydrogen atoms, C ₁ to C-, Q-alkyl groups or Cz to C ₁ Q-isoalky groups

R. a C ₁ to C., Q-alkylene group or a C ^ to G-, Q-isoalkylene group,

R _{5 is} a Cq to G ₁₀ = alkylene group or C ₃ to C- ^ Q isoalkylene group,

A is the divalent residue of a co-spinnable polyamide.

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/ 454 HB - 7 -

th, and

y represent a number from 2 to 100 and ζ represent a number from 2 to 150.

As already explained, there is a part of the inventive new block copolymers made from a melt-spinnable polymer. • The term 'melt-spinnable' refers to a process in which the polymer, a polyamide, is heated to a temperature above its melting temperature and in the molten state is squeezed out through a spinning nozzle. This spinneret consists of a plate with one to several thousand openings through which the molten polymer is pressed out under pressure will. The molten polymer is converted into a continuous ■ filament and depending on the number numerous filaments can be formed at the same time of the openings. The melted threads are cooled, solidified, brought together and finally wound onto a spool. This procedure is described in greater detail in "Encyclopedia of Polymer Science and Technology ", Volume 8, Kan-Made Fibers, Manufacture.

When a single fiber is extruded, as in the case in which If this fiber is intended for knitting into hosiery, the product obtained is called a monofilament. If that If the product is to be converted into a fabric by knitting or weaving, the number of monofilaments is in the range from 10 to 100. 'One such product is called multifilament yarn known. Yarns for technical purposes, such as Composition of tire cords, usually contain several hundred to 1000 or more filaments. When the fibers are used to make a spun Yarn can be used, namely a yarn formed by twisting short lengths of fiber, as in use of cotton is common, the number of openings can be increased to tens of thousands. The extruded material will cut into pieces about one to four inches long to make staple fiber to manufacture. This staple fiber is produced in the same way as tree

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wool transferred into spun yarn. The polymer according to the invention can be processed into the shapes described above using the various methods described.

The polymers of the invention can also be used to make nonwoven materials or nonwovens. Fleece is a material used as a fabric made without weaving. These fleeces contain in particular textile fibers, which are bonded or laminated to one another with the aid of an adhesive resin, rubber or plastic, or which are to one another under pressure are matted. Many of these methods are detailed in "Manual of Nonwovens", Prof. Dipl.-Ing. Dr. Radko Krema, Textile Trade Press, Manchester, England.

The invention therefore also relates to fibers or monofilaments or yarns of several twisted fibers made from the invention. Block copolymers, as well as from such fibers, monofilaments woven, knitted or knitted fabrics or non-woven fabrics obtained from yarns.

Polyamides that are crystallizable and between their melting point and the temperature at which the molten polymer undergoes decomposition have a difference of at least 30 ° C, can be melt spun. Examples of melt-spinnable Polyamides include the following polymers: nylon-6,10 (poly (hexamethylene sebacamide)); Nylon-6 (poly-cpentamethylene carbonamide)); Nylon-6,6 (hexamethylene adipamide); Nylon-11 (poly (decamethylene carbonamide)); MXD-6 (poly (metaxylene adipamide)); PACM-9 (bis (paraaminocyclohexyl) methane azelaic acid amide); PACM-IO (bis (paraaminocyclohexyl) methane sebacic acid amide); and PACM-12 (bis (paraaminocyclohexyl) methane dodecanoic acid amide). Other melt-spinnable polyamides are in Encyclopedia of Polymer Science and Technology, Volume 10, Polyamide Fibers Section, Table 12. Process for making these polyamides are well known and described in numerous patents, corporate publications, and publications.

The poly (dioxa-amide) part of the block copolymers according to the invention can be made according to the following general scheme:

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Rl R ₂

• /

(1) N = C-C = ^ C + KO-fy-OH λ R3

(2) (III) + H ₂

R. 1 ^R 2 (IV) ) R.
/ ? ^{2 R} l II \ ^
R ₃ \
H ^ 3 \
H (in: Ζ ¹ R ₂ 1 »
H \
^R 3 * 3 CH;

R ₁ R ₂ Ro Ri (3) (IV) + HOOCR ₅ COOH- ^ (00CR ₅ COO) (NH ₃ ⁺ CHp-CCO-RIi-OC

HR ₃ Rq U

R ₁ R? Rp Ri OO -H ₂ O * / »/ - ¹ κ» »

(V) [NHCH ₂ -CC ^ -o-Rii-OCC-CHp-RC-Rp-C ^

H ^ ^s > R ₃ R ₃ H

Reaction 1 is often referred to as cyanoethylation, especially when R ₁ = Rp = R ^ = H. The radicals R-, "to R, can also mean / alkyl groups with 10 carbon atoms or isoalkyl groups with 3 to 10 carbon atoms. R. can represent an alkylene group with 1 to 10 carbon atoms or an isoalkylene group with 3 to 10 carbon atoms. The reaction 2 is a hydrogenation reaction. Reaction 3 is the reaction between a dicarboxylic acid and a diamine to form a salt. R, - can be a C _Q to C _1Q alkylene group

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or a C1 to C3 isoalkylene group. -Reaction 4 is often referred to as condensation polymerization. Here the repeating unit contains fewer atoms than the monomer and necessarily the molecular weight of the polymer formed is lower than that. Sum of the molecular weights of all monomer units originally used, which were combined in the reaction to form the polymer chain. Examples of C, to C, Q-alkyl groups include the methyl, propyl, butyl, pentyl group and the like; Examples of the C_ to C ₁₀ -Isoalkylgruppen are isopropyl, isobutyl, isopentyl and the like. Examples of C to C ₁₀ alkylene groups are methylene, dimethylene, trimethylene groups and the like; Examples of C1 to C3 isoalkylene groups are methyltrimethylene, 2-methyltetramethylene and the like.

Variants of preparation reactions 1 and 2 are also in Chemical Abstracts 3935K, Volume 71 (1969) and "in ZA-PS 6 704 described.

Examples of the diol HO-R.OH in reaction 1 are ethylene glycol, propylene glycol and irimethylene glycol. Examples of dicarboxylic acids HOOCRc-COOH in reaction 3 include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebecanedioic acid, «F, β -diethylsuccinic acid and oc -methyl-cG-ethyl-suberic acid.

For examples of poly (dioxa-amide) polymers prepared according to the above The following polymers can be produced:

Poly- (4f7-dioxadecamethylene-adipamide), also 30203-6

■ [kh- (ch ₂ ) ₃ -o- (ch ₂ ) ₂ -o- (ch ₂ ) ₃ 4-c- (ch ₂ ) ₈ -cJ-

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- li -

Poly- (4,7-dioxadecamethylene-sebacamide), also 30203-10 - (CH ₂ ) ₃ -0- (CH ₂ ) ₄ -0- (CH ₂ J ₃ -NC- (CH ₂ ) ₄ -c |

Poly (4,9-dioxadecamethylene adipamide), also 30403-6

ti CH, Tr O 0

■ [n- (CH ₂ ) 5-0-CH ₂ -C-CH ₂ -O- (CH ₂ ) ₃ -NC ^ CH ₂ ) ₄ -cl

CH ₃

Poly (4,8-dioxa-6,6-dimethyl-undecamethylene-adipamide)

0 0

ΓΗ CH ₃ CH _{3 H} 0 0

4N-CH ₂ -CH -CH ₂ -O- (CH ₂ ) 2-0-CH ₂ -CH-CH ₂ -RC- (CH ₂ ) ₄ -8l ·

Poly (4,7-dioxar2, S-dimethyl-dodecamethylene-adipamide) .υ υ 0 CH, O ₇

• jN- (CH ₂ ) 5-0- (CH ₂ ) ₂ -0- (CH ₂ ) ₃ -ir-C-CH ₂ -CH-CH ₂ -CH ₂ -Cf-poly (4,7-dioxadecamethylene -2-methyladipamide)

The polymers according to the invention can also be an antioxidant, such as 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tertiary-butyl-4-hydroxybenzyl) -benzene, contain. Small amounts of the antioxidant, e.g. B. 0.5 wt .- ^, are satisfactory however, amounts as small as 0.01% by weight can also be used or high proportions, such as 2.0 wt .- ^, can also be satisfactory be. Antioxidants other than the above-mentioned compound can also be used. Using of an antioxidant, this will generally be. in combination with the two polymers prior to melt blending mixed. Other conventional additives for polyamides, such as matting agents and / or light stabilizers, can also be mixed in will.

Examples

Below is the preparation of various new polymers and their predecessors. In addition, the influence of certain variables on their properties is examined. To-

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In addition, results are shown which were obtained with comparative polymers.

1 .. Production of 1,2-bis (ß-cyanoethoxyethane) (NC- (CH ₂ ) ₂ O- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -CN)

930 g (15 mol) of ethylene glycol and 45.6 g of 40% aqueous KOH solution were placed in a double-walled (for water cooling) 5 liter glass reactor with a bottom outlet and stopcock. About 1620 g (30.6 mol) of acrylonitrile (NC-CH = CHp) were then added dropwise with stirring at a rate such that the temperature was kept below 35 ° C. After the addition was complete, the mixture was stirred for an additional hour and then allowed to stand overnight. The mixture was then neutralized to pH 7 by adding 6 molar HCl. After washing three times with saturated NaCl solution, the product was separated from the aqueous layer, _{dried over CaCl 2} and passed through an Al ₂ O, column to ensure that all basic materials were removed The yield was 90 rh of theory.

2Preparation of 4,7-dioxadecamethylenediamine (MH ₂ (CH ₂ ) ₃ -0- (OH ₂ ) ₂ -0- (CHg) ₃ -MH ₂ )

150 g of 1,2-bis (/? - cyanäthyloxyäthan), 230 ml of dioxane and about 50 g of Raney cobalt were added. After displacing the air, the reactor was filled with hydrogen Brought to a pressure of 140.6 kg / cm and heated to 110 ° C. While the hydrogen was being consumed, additional was added Hydrogen supplied so that the pressure remained constant. After cooling, the pressure was relieved and the catalyst was filtered. The dioxane was removed by distillation at atmospheric pressure. The remaining mixture was made with the help

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distilled on a 91.4 cm rotating belt distillation unit. That Diamine distilled at 123 to 124 ° C / 3.75 mm Hg. About 98 g of a 99 »95% pure material were obtained. The material can be referred to as diamine 30203.

3. Production and polymerization of poly (4 »7-dioxadecamethylene-adipamide) (30203-6)

To a solution of 41.50 g of adipic acid in a mixture of 250 ml of isopropanol and 50 ml of ethanol, 50 g were added with stirring des diamine 30203, dissolved in 200 ml of isopropanol, was added. An exothermic reaction occurred. Crystallized on cooling a polymer salt from the solution. The salt was obtained on a Buchner funnel and then from a mixture of 400 ml of ethanol and 300 ml of isopropanol recrystallized. The product was dried in vacuo at 60 ° C. overnight. It then had a melting point of 182 C and the pH value of one

n solution was 6.9. 85 g (yield 92 % of theory) of the salt were obtained.

About 40 grams of the polymer salt was placed in a thick walled polymerization tube ("D" tube) made of glass. The neck of the tube was then narrowed to seal and the tube was passed through five times evacuating and filling with nitrogen freed of air. Finally, the tube was in for two hours at 200 ° C heated by an aluminum block. After cooling, the tip of the tube was broken off and the remaining part was removed by heating bent at an angle of 45 ° and then with a. Piping system connected and with the help of nitrogen-vacuum cycles freed from air. The tubes were heated to 222 ° C under nitrogen at atmospheric pressure for six hours, taking methyl salicylate vapor baths were used. After cooling, the tubes were broken and the polymer plug formed into pieces crushed to a size of 1.25 mm. The resulting polymers had inherent viscosities ranging from 0.9 to 1.1 in metacresol solution.

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4. Melt blending the polymers

Appropriate proportions of the dried 30203-6 polymer and nylon-6 were placed in a large test tube with two openings in the rubber stopper. The openings were intended for a spiral stirrer and a nitrogen inlet tube. The vessel was purged of air. Thereafter the vessel filled with nitrogen was heated with the aid of a suitable liquid-vapor bath. The mixture of the two Polymer was turned on with the spiral mixer for the required time stirred, which was operated with an air motor. Before when the molten polymer was allowed to cool, the stirrer was raised to drain the polymer. After solidification the material was broken up and dried for spinning.

5. Spinning and drawing the polymer

After melt-blending, carried out as above, the polymer was introduced into a micro-spinning device which consisted of a stainless steel tube (0.625 cm outer diameter χ 30.5 cm) with a capillary of 0.094 cm. The tube was heated in a steam bath to the temperature appropriate for the polymer. Generally a temperature of about 245 ° C was used. Nitrogen was bubbled through the polymer until the polymer melted and the capillary closed. After the polymer had completely melted, and after a uniform temperature was reached (about 30 minutes), the nitrogen pressure was increased by about 3.11 to 4.52 kg / cm ² (30 to 50 psig) (depending on the , Melt viscosity of the polymer to extrude the polymer.

Due to its design, this device could not be equipped with a filter system to remove particles from the polymer melt to remove. This made it difficult to continuously spin polymers that lead to the formation of gel particles tend to like nylon-6,6.

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Immediately after exiting the tube, the fiber was drawn on a series of rollers and wound onto a spool. The first roller or the feed roller had a running speed of 10.67 m / min. The thread was wrapped around the roller five times. After the yarn had been passed through a bath maintained at about 50 ⁰ C hot pipe, it was about the second roller or drawing roller (five times) is wound, - the speed-· speed varied depending on the desired stretch ratio (39.62 to 53, 34 m / min). Unlike industrial draw rolls, the fiber had a tendency to "rub against itself", that is, the unwound fiber rubbed against the fiber coming on the roll. This made it difficult to achieve high draw ratios. The third roll had a removable spool and was made operated at a slightly slower speed than the pull roller.

The draw ratio is the ratio of the speed of the second roll or the draw roll to the speed of the first roller or feed roller. Therefore, if the second roller at a speed of 53 »34 m per minute and the first roller was operated at 10.67 meters per minute, the draw ratio was 5 (53.34 / 10.67). Because of this difference in speed between the rollers the fiber is drawn. By stretching or stretching the molecules are oriented, d. H. arranged in a single plane running in the same direction as the fiber.

6. Results of tests and comparative tests

In Table 1 below is the effect of temperature and time of melt blending on various properties some block copolymers are shown, which consist of different proportions of poly (dioxa-amide) and polyamide. Furthermore comparative results are listed.

A comparison of tests 1, 3 and 5 shows that the addition is more important at relatively low temperatures and with a short mixing time Amounts of polymer 3020-6 to nylon-6 have the melting point

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of the resulting polymer 3020-6 / 6 is not significantly reduced. Decreases in tensile strength and initial modulus are found, while an increase in elongation occurs.

A comparison of tests 5, 6 and -7 shows that if the mixing time is increased at constant temperature, there is a decrease the melting point occurs. This indicates a decrease in the amount of the blocks and also gives an increase in the proportion the alternating structure.

It was found indirectly that the crystallinity of a Block copolymers decrease as the proportion of alternating sequences increases. Properties based on crystallinity, such as melting point and tensile strength, therefore, decrease as the alternating structure increases.

The fact that inherent viscosity, a measure of molecular weight, increases, means that the molecular weight is increased, so that the degradation is the reason for the change in Melting point is turned off. The increase in the mixing time also causes a decrease in tensile strength, elongation and the initial module,

A comparison of runs 7, 8 and 9 indicates that if maintained a constant mixing time, but with an increase in the mixing temperature, a reduction in the inherent viscosity and the melting point occurs «, In addition, the tensile strength and the initial modulus decreased.

The tensile strength, elongation (elongation at break) and the initial modulus (textile modulus) as well as methods of determining these values are in Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Volume 20, Textile Testing, defined and described.

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Tabel. 1

'' Influence of melt blending on the properties of the block copolymer made of poly (dioxa-amide) and polyamide (30203-6,6)

Try Polymer Percent

30203-6

cn
ο
co
co
ro
σ

1
2
3
4th
5
6th

7th
8th

10
, 11

Nylon-6
30203-6
30203-6.6

If
Il
Il
Il
Il
Il

100
10
10
20th
20th
20th
20th
20th
25th
30th

Melt Mixing Inherent Melt Tensile Strength Elongation Initial Mo ·

Temgera- Mmu- viscosi- _Ώ ν, _η ν + ^Ο η ^ ° ^ speed ^ ^b ^ tur ^e C ten _{+ y +} (c) ^{pure C lceit}

did'

282
282
282
282
282
295
305
295
295

15th
180

15th

180

360

360

360

30th

30th

1.10 0.89 1.15 1.18 1.03 1.04 1.10 0.73 0.68 1.05 1.03

219 182 219 215 218 213 205 195 193 214 220

3.7

2.6 3.5 2.9 3.0 2> 3 1.9 1.4 2.2 2.1

45

11.5

43 OO 12.0 60 12.0 68 9.0 66 8.0 59 7.0 59 7.0 64
64 5.5
6.3 65 7, .2

(a) Probably not a representative sample

-. ± o -

(b) draw ratio 3.7, ambient relative humidity, however, at different values of the relative humidity

- humidity no significant differences observed; .40 monofilaments twisted together, average 7 or 8 samples per test.

(c) fiber

Table 2 below shows the moisture absorption of several block copolymers in different proportions of poly (dioxa-amide) and polyamide. Comparative results obtained with nylon-6 and cotton are also shown became.

A comparison of tests 1 to 6 (Table 2) shows that when the proportion of poly (dioxa-amide) in the block copolymer is increased, the moisture absorption is significantly increased in comparison with the moisture absorption of nylon-6 at various relative humidities. A comparison of Runs 7 and 6 also indicates that the block copolymer containing 30 % 30203-6 shows better moisture pick-up than cotton at 95 % and 85% relative humidity and nearly the same moisture pick-up at lower relative humidity levels 65 and 65% 75 # ^:

Moisture uptake means the amount of moisture that a dried fiber sample will take up in an atmosphere of constant relative humidity. This property was measured using a series of moisture chambers made from desiccators containing suitable saturated salt solutions (65 % UaNO ₂ ; 75 % NaCl; 85% KCl; 95%

To determine the moisture absorption, a sample of the fiber was first dried _{over P 2} O _{5 in a vacuum desiccator.} After reaching constant weight, the sample was placed in one of the suitable chambers. The chamber became the faster one

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Table 2

attempt Moisture absorption of the block copolymer of Monofilament, after cooking) Polyamide and poly (dioxa-amide) 7 c at ptl ν D, (30203-6.6, ) 2454 ' 65 # RH ^ Percent poly- (dioxa- • 4.5 4.1 1 material amide), in the material 95 t RH ^(b) 5.9 4.5. 2 0 7.6 Moisture absorption Nylon-6 10 • ίο; O op % Kxi 6.3
7.2 5.2 3
4th 30203-6 / 6 5.8 7.3 5.4 cn 5 15th
20th 11.7
12.2 7.4 8.6 6.0 09820/1 6th Il 25th 13.0 061 It ■ 30 15.5 8.2
9.2 It 10.0 12.1

cotton

14.5

11.8

(a) Melt blended at 295 ° C for 30 minutes, draw ratio 3.7

(b) $> RH = percent relative humidity

'9.5

Evacuated reaching equilibrium. The fiber stayed in the chamber until constant weight was achieved. The weight increase of the sample over the dried sample was the Amount of moisture absorbed.

The attached table 3 shows the influence of boiling on the moisture absorption of various block copolymers shown, which were produced with different mixing temperatures and durations. Also shown are the weight losses, that occurred during cooking. In addition, comparative data for nylon-6 are given.

Boiling means soaking the fiber in boiling water for a set period of time. The weight loss was then determined. Even after the procedure described for determining the moisture absorption, the increase in the percentage moisture absorption at 65 % relative humidity was determined. Cooking can be considered equivalent to dyeing treatment.

The increase in moisture uptake as a result of cooking is believed to be best explained by the discussion below becomes understandable. When the fiber is placed in boiling water, parts of the fiber relax. The oriented amorphous Sections tend to open up. Cooking accelerates the relaxation of this unnatural state. This opening allows the fiber to absorb more moisture than it otherwise could. By heating the fiber by other methods, than by soaking in boiling water, relaxation of the fiber also takes place. The comparison of weight loss in experiments 3, 2 and 1 again indicates that the polymer becomes more alternating with an increase in the miso duration.

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Table 5

Effect of cooking on moisture absorption of block copolymers of Pol.y- (dioxa-amia) and .

Polyamide (soaking in boiling water for 15 minutes)

Try material percent 50205-6 im

Material mixing conditions ■

cn
ο 1 Fylon-6 CD
approx 2 50205-6 / 6 O 5 Il 1061 4th
5 Il
Il 6th Il 7th It

20th

Il Il

H Il

25th

Temperature C Duration, min. Weight
loss, .f ^K ' Increase in pro
centual damp
activity would take up
at 65 t · RH N? - - 1.4 0.5 1.8 9 ¹ 282. 360 1.8 0.7 ** 282 15th 5.9 _ ♦ 295 60 5.5 - 295 30th 5.4 - 295 15th 5.4 295 60

(a)

Weight before - weight close to weight before

Tabel Influence of the draw ratio on the properties of the block copolymer of poly (dioxa-amide)

and polyamide (30203-6 / 6)

Experiment # 30203-6 in tensile ratio- moisture absorption tensile- - expansion- initial-

30203-6 / 6 nis ^ ^a) 95 % RH ^{Cb J} 85 # RH ^ 75 * RH ^{(b )} 65 # RH ^ sti gkeit aung

13.0 10.0 14.2 10.1 15.5 11.7 14.0 11.8

7.3 5.4 7.4 5.2 9.6. 6.0 7.8 5.7

oil 25 3.7

oo 2 "4.5

ο 3 "5.0

Ξ 4 30 3.7

- * 5 "4.5 -

6 "5.0

(a): Ratio of the speed of the second roller to the speed of the first roller.

(b) Percent RH: percent relative humidity.

(c) monofilament. <

(d) 40 monofilaments twisted together; an average of 7 or 8 samples per test

(e) Mix at 295 ° C for 30 minutes

2.2 64 6.3 « * 2.8 40 13.0 K? 2.9 24 15.0 2.1
2.8. 65
59 7.2
8.6 3.7 52 16.2

Table 5
Influence of the percentage content of poly (dioxa-amide) in the block copolymer on dye uptake

O CO OO K>

attempt

1 2 3

Percent 30203-6 in 30203-6 / 6

O '10

15 20 30

(; a) Directly ge Ib 28 ,. 6 χ ΙΟ "" ⁵ g / ml

(b) Melt blending for 30 minutes at 295 ° C, draw ratio 3.7

Dye absorption moles / gram of fiber 10

1.00 1.65 1.90 2.15 2.70

N)

CO

In "the attached Table 4, the influence of various Tensile ratios on moisture absorption, tensile strength, elongation and the initial modulus of various block copolymers of poly (ether amide) and polyamide shown.

The data indicate that with an increase in the draw ratios in general the moisture absorption decreased, except at a relative humidity of $ 95. With an increase the tensile ratios also increased the tensile strength and the initial modulus; however, the elongation decreased.

In the accompanying Table 5 the influence of the percentage of 30203-6 in 30203-6 / 6 on the dye uptake is shown. The data indicate that increasing the proportion of 30203-6 in 30203-6 / 6 increases dye uptake. in the Compared to water molecules, dyes have larger molecules and cannot penetrate the crystalline structure of the nylon fiber; the dye uptake can therefore with the proportion amorphous areas in the fiber.

The amount of dye uptake was measured in the following manner. The pre-weighed fibers were dyed in suitable containers at room temperature. The concentration of the direct yellow dye 28 in the aqueous dye solution was determined spectrophotometrically before and after the dyeing process. The staining was; considered complete when no reduction in the dye concentration was observed over a period of several hours. Before dyeing, it was found that the initial concentration of the dye in the bath was more than 5.8 10 g / ml had to, so that the measured dye absorption independent of the initial dye concentration was.

509820/1061

.-lab e'l 1 e

Relative oxidative degradation of block copolymers made from poly (dioxa-amide) 'and polyamide (30203-6 / 6; Twisted threads)

attempt material (' cn
O 1 Nylon-6 30203-6 / 6 ^ CD ti OO It NJ 2 NyIon-6 antioxidant O
«V, and 30203-6 O 3 Il Il cn ti - * 4th 5 · 6th ■ 7 8th 9

.Duration at

ο n (e)

O 1 2

O 1 2

Percentage of original toughness retained

108 98

87 70

101 108

■ P *

(a) Untreated old material has a basic tenacity (tear: length) of 100; a value greater than 100 therefore means an increase of less than 100 x a decrease.

2454 Π 8

(b) The ratio of 30203-6: 6 is 30/70.

(c) 0.5 fi Ethyl Antioxidant 330 is added prior to melt blending.

(d) melt blending for 30 minutes at 295 ° C; Draw ratio 3.7.

(e) hours

Table 6 explains the relative oxidative degradation of a block copolymer of poly (dioxa-amide) and polyamide. The data indicate that polymer 30203-6 / 6 suffers loss of toughness when exposed to air at elevated temperature; this can be seen from the comparison of tests 4, 5 and 6. However, the data also indicate that the addition of a small amount of an antioxidant such as 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene at least prevents loss of toughness
and sometimes also the toughness increased, which a comparison of tests 8 and 5.9 and 6 shows. In addition, the relative
Stability of nylon-6 shown. It is assumed that the
Increase in toughness of nylon-6 in Comparative Experiment 2 _; the annealing is due.

Surprisingly, according to experiment 5, there was practically no discoloration although a loss of toughness was observed.

In experiments 7, 8 and 9 the indicated antioxidant was used added before melt blending in an amount of 0.5 wt .- ^.

The data in Table 6 were obtained in the following manner.
The fibers indicated in the table were placed in a drying cabinet maintained at 120 ° C. with forced ventilation for the period indicated. After a sufficient time had passed, the samples were taken out and the change in their toughness was determined.

- Analogous results are obtained when nylon-6,10; Nylon-11,

509820/1061

MXD-6 * PACM-12 and other materials instead of nylon-6 in the stage of melt blending (4) the polymer is used will" '

Similar results are also achieved if, in step (3), adipic acid is replaced by one of the following acids: Oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undeeandioic acid, c (,, A -Eiäthy! Succinic acid or (X-methyl-QC-ethyl-suberic acid. If in stage (1) ethylene glycol by one of the glycols Trimethyle.n-, If propylene or tetramethylene glycol is replaced, similar results are also achieved.

509820/10 61

Claims (8)

Claims 1. Block copolymer with a molecular weight of about 5000 up to 100,000, characterized by recurring Units of the following structure: ττ tin Λ «Λρ« ■■) A-CH ₉ -CCOR.-0-CC-CH ₉ - ² η, ⁴ ι . * ² 0 0 κ η -C-Rt-Cf in which A denotes the divalent radical of a spinnable polyamide, Rj, R «and R, hydrogen atoms, alkyl groups with 1 to 10 carbon atoms or isoalkyl groups with 3 to 10 carbon atoms, R. alkylene groups with 1 to 10 carbon atoms and isoalkylene groups with 3 up to 10 carbon atoms, and Rc is alkylene groups with 0 to 10 carbon atoms or isoalkylene groups with 3 to 10 carbon atoms, and y is 2 to 100 and ζ is 2 to 150 _o 2. Copolymer according to claim I _8, characterized in that it is hydrophilic. 3. Copolymer according to claim 2, characterized in that it shows a percentage moisture absorption of at least 4 # at a relative humidity of 65 % . 4. Copolymer according to any one of claims 1 to 3, characterized in that that the recurring unit A d: en 6.9820 / 1061 means divalent radical of nylon-6 or PACM-12. 5. Copolymer according to one of claims 1 "to 4, characterized in that it has as radicals R- ,, R ₂ and R, hydrogen atoms and as radicals R. and Rj- alkylene groups with 1 to 10 carbon atoms * 6. Copolymer according to claim 5 »characterized in that R. is a Cp-alkylene group and R ₁ - is a C.-alkylene group". 7. Paser obtained by spinning the copolymer after fine of claims 1 "to 6. 8. fiber obtained by melt spinning the copolymer according to any one of claims 1 to 6. 509820/1061