DE1817782C3 - - Google Patents

Description

RK) R) _n OH

in which / 1 for an integer between 3 and 90 and in which R 'is hydrogen, a straight chain or branched alkyl group having 1 to 20 carbon atoms, an aryl or alkylaryl group and R is a Ethylene and or 1,2-propylene radical means, and / or of these bis- and monohalohydrin ethers derived Bis- and Monoglycidyliither or Bis * and Monoaminohydrinäther used.

In the above formula, (OR) _{n represents} the homopolymer of ethylene oxide or propylene oxide or the statistically distributed or the block copolymer of ethylene oxide and propylene oxide. In this case the molar ratio of ethylene oxide to propylene oxide can be within the range of 100/0 to 40/60 IiC

nan ι ο £.

R 'can include a phenyl, tolyl or Be xylyl group.

The bishalohydrin ethers and monohalohydrin ethers used in the present invention include those obtained by adding epichlorohydrin or epibromohydrin to the following djol-like or monool-like compounds of the formula

RZ (OR) _n OH

have been received:

Polyethylene glycol, polypropylene glycol, and random or block copolymers of ethylene oxide and propylene oxide, addition products of aliphatic alcohols such as isopropyl alcohol, n-butyl alcohol, n-Hexyl alcohol 2-Ethyihexyl alcohol, n-Octyl alcohol, Nonyl alcohol, decyl alcohol, lauryl alcohol, Tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, Octadecyl alcohol and oleyl alcohol, as well as addition products of phenols, such as η-butyl, isobutyl, Amyl, dibutyl, diamyl, tripropyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tetradecyl, Cetyl, oleyl, octadecylphenol and cresol, dihexylphenol, Trihexylphenol, Diisoheptylphenol, Dioctylphenol, Dinonylphenol, Dioctyl-p-cresol, Dioctylo-kreso !, Didecyl-phenol, didecyl-p-cresol and didodecylphenol, and from ethylene oxide and / or propylene oxide, ethylene oxide and propylene oxide also Can form block segments.

The polyether glycol derivatives used according to the invention are used in amounts of 0.5 to 20%, in particular 1 to 10%, based on the weight of the polyamide, are used. Keeping these amounts down very good * and permanent hydrophilic properties are given to the polyamide without the good properties that are inherent in polyamide, such as strength, elongation, elasticity after stretching and the ability to absorb paint, deteriorated to a noticeable extent will.

Examples of polyamide-forming monomers are-caprolactam, t- aminocaproic acid, hexamethylenediamine, metaxylylenediamine, piperazine, terephthalic acid, isophthalic acid, adipic acid and sebacic acid.

In the method according to the invention, known additives, such as matting agents, Pigments, dyes, light stabilizers, heat stabilizers and plasticizers are also used will. The hydrophilic polyamides produced according to the invention can be used in a known manner another thermoplastic polymer, such as a polyamide of the same or different composition, which does not contain any additive used according to the invention, a polyester. Polyether ester. Polyether or polyolefin.

The polyether glycol derivatives used are in the polyamides produced according to the invention evenly distributed. They are connected to the polyamide and will be washed repeatedly In contrast, with hot water or with warm water that contains a detergent, not washed out to polyether glycols themselves and their previously known, used for the same purpose Derivatives that are separated out.

The polyamides produced by the process according to the invention thus have permanent hydrophilic properties; fibers made from them avoid this otherwise synthetic fibers clinging uncomfortable feeling and have a similar grip as it Own natural fibers. Further technical advantages unexpectedly achieved by the process according to the invention can be seen from the comparison tests.

In the examples, the information relating to the parts and the percentage composition, unless otherwise stated, by weight.

a) Production of the starting material

Jn a ReaktionsgefaU 400 parts PoIyäth} englykol having an average MoIe- - weight of from 4000 at 80 ⁰ C is melted and added with portions 47% sodium boron trifluoride etherate!. The resulting mixture was stirred thoroughly and 18.8 parts of epichlorohydrin were then added dropwise over the course of one hour. After the addition was complete, stirring was continued at the same temperature for 1 hour. The catalyst and the unreacted components were then distilled off in a boiling water bath. The polyethylene glycol bischlorohydrin ether obtained was dissolved in 2.5 times the amount of methanol and the solution obtained was brought into contact with an anion exchanger of the OH type. After the complete ion exchange, the solution was separated from the exchange resin, whereupon the methanol was distilled off. The purified polyethylene glycol bischlorohydrin ether contained 1.68% chlorine.

example 1

Certain amounts of the polyethylene glycol bischlorohydrin ether obtained under a), 100 parts of t -caprolactam, were placed in an autoclave. 3TeJ! ·: Brought water and 0.3 part of titanium oxide and heated under nitrogen for 3 hours at a pressure of 1.5 kg / cm ² to 260 ° C. and then at the same temperature for 2 hours at atmospheric pressure. Then it became 5 hours

. polycondensed under a reduced pressure of 300 mm Hg and then extruded.

For comparison, a mixture of 100 parts of f-caprolactam, 3 parts of water, 0.3 part of titanium oxide and 0.18 parts of acetic acid in the same manner and under the same conditions as above polycondensation

5 «sated.

Cutlet of the polyamide according to the invention and the comparative material were washed to remove water-soluble components 20 times with hot water at 8O ⁰ C and then

j ;; at 80 ° C and a reduced pressure of 0.1 mm Hg dried down to a water content of 0.069%.

To determine the properties, the dried chips, after being left in the molten state for 40 minutes, were extruded through a die using a hot-mesh p-type melt spinning machine, whereupon the obtained undrawn filaments were wound on bobbins at 259 d / 18 f and 20 hours at 20 ^° C

6f | And left to stand at a relative humidity of 65%. Thereupon they increased to 3.69 times stretched to the original length, Table I shows the properties.

Table I.

Salary of the PaIy Polymer water soluble
Components strength Fuden Absorbed water content
(%) 100% RH Ethylene glycol bis
cblorhydrin ethers (%) (g / d) strain 80% RH 9.0 -Cresol 10.7 5.3 (%) 5.0 10.1 0 *) 1.2 10.1 5.5 29.8 5.1 13.7 0.2 *) 1.3 10.4 4.9 28.3 5.5 14.6 0.5 1.1 10.0 5.2 36.2 5.6 15.8 1 1.1 9.8 5.1 29.8 5.8 16.2 2 1.0 8.9 5.2 27.6 6.0 17.0 5 1.2 10.5 5.0 30.1 6.1 19.4 10 1.1 12.6 4.1 32.0 6.8 21.5 15th 0.9 13.1 3.7 40.5 7.2 20th 0.9 15.2 that was spinning 42.8 - 25 *) 0.6 not possible -

*) Comparison test.

The above-mentioned drawn threads were boiled in pure water for 1 hour and then boiled a semi-textured garment which had been dried for its hygroscopicity ches sprayed with a detergent and examined with water. The repeated measurements gave the washed and dried. On the horizontal following results, Stretched garment was dropped from a height of 2 cm of water and used for spreading into a circle with a diameter of 4 cm 30 necessary time determined. This time was known as the "sweat absorption rate". the Results obtained are shown in Table II.

Table III

Table II Sweat absorption Content of polyethylene glycol speed (lake) Bischlorohydrin ethers (%) 250 0 *) 12th 0.2 *) 8th 0.5 5 1 4th 2 3 10 *) Comparison test.

Amount of water absorbed at 100 rh (%)

Number ^{1 of} the cooking processes

16.2

16.0

16.1

15.8

b) Production of the starting material

Furthermore, the thread was made from the invention with the addition of 5% of the polyethylene glycol bischlorohydrin ether Manufactured polyamide after

As under a), polyethylene glycols were used with different average molecular weights with epichlorohydrin in a molar ratio of 1 to 2 in the presence of 47% boron trifluoride etherate (molar ratio of polyethylene glycol OH groups / BFj = 1 / 0.075) implemented. The obtained polyethylene glycol bischlorohydrin ether were purified by treatment with ion exchangers.

Example 2

In each case 5% of the polyethylene glycol bischlorohydrin ether obtained under b) were converted to F-caprolactam before polymerization, under the same conditions as was carried out in Example 1, given.

Table IV

Average molecular weight of the polyethylene glycol used

No addition of polyethylene glycol bischlorohydrate *) ........

100 *),

■ 200 *),. ,,

600

2000 ,,,

*) Comparative comparison

Polymer

(.,) at 30 C in m-cresol

0.8 0.9 1.0 U

water soluble components

10.7 13.8 12.1 10.5 9.5

strength
(g / d)

5 * 3

3.6
4.5
4.8
5.0

strain

thread

Content of absorbed. water

29.8
46.5
37.3
32.8
31.6

80% RH

5.0 5.2 5.4 5.8 5.7

100% RH

9.0 10.8 13.9 15.3 15.8

continuation

Average molecular weight of the one used
Polyethylene glycol

4000 ..
10000 ..
20,000 *).
40000 *)

(.,) at 30 C
in m-cresol

l'polymeres

water soluble components

1%)

1.2
U
1.0

8.9
10.5
12.8
14.0

strength
(g / d)

*) Comparative example.

From Table IV it can be seen that with an average molecular weight of the polyethylene glycol part from 600 to 10000 the f-caprolactam without

lialtenc polymers and the threads from it handy have the same properties as the urimodified Polyamide, but also have excellent hygroscopicity.

c) Production of the starting material

Using polyethylene glycol with an average molecular weight of 1000, polyethylene glycol bischlorohydrin ether was prepared in the same way as under a). 300 parts of an n-NaOH solution were added to a solution of 119 parts of the product obtained in five times the amount of benzene, and the resulting mixture was at 5.2
5.1
4.8
5.0

strain

thread

Content of all absorbed water

30.1
29.6
32.7
30.2

80% RH

6.0
5.8
5.6
5.1

100% RH

16.2
15.1
Π.8
9.5

Room temperature stirred for 1 hour. After standing, the reaction mixture separated into two Layers on. The benzene layer was removed

Polyethylene glycol bisglycidyl ether with an epoxy equivalent of 1.7 meq / g was obtained.

Example 3

4% of the polyethylene glycol bisglycidyl ether obtained under c) were converted to f-caprolactam before Polymerization carried out under the same conditions as in Example 1 was given.

For ver £ (Jeich was added F-caprolactam polymerized from 4% polyethylene glycol with an average molecular weight of 1000, what happened under the same conditions as above. The properties were determined as described in Example 1; Table V contains the results.

Table V

Additive

No*)

Polyethylene glycol *)

Polyethylene glycol bisglycidyl ether

Polymer

{/,) at 30 ° C
in m-cresol

1.2
1.0

1.1

water soluble components

10.7

13.1
10.5

strength

*) Comparison test.

strain

thread

Absorbed water content

29.8
32.1

30.6

80% RH

5.0
5.2

6.1

100% RH

9.0
11.3

16.5

Each of the above threads was knitted into a garment, its sweat absorption speed was determined. When polyethylene glycol was used alone, the sweat absorption rate was 68 seconds, however, when using the polyethylene glycol bisglycidyl ether 7 seconds.

d) Production of the starting material

A copolymer of ethylene oxide and propylene oxide in a molar ratio of 70/30 with a random distribution and an average molecular weight of 800 as described under c) in the corresponding Bisglycidylatlier converted 50 parts of this Bisglycidyläthers were with 50 parts of water and 250 parts of ethylenediamine reacted under reflux for 5 hours. The water and the excess ethylenediamine were distilled off, whereby the corresponding bisaminohydrin ether was obtained.

Example 4

F-caprolactam was made with 6% of this bisaminohydrin ether in the same way as in Example 1 polymerized

The properties were given as in example i and are given in Table VI below.

Table Vl

Additive

Polyethylene glycol bisaminohydrin ether ...

Polymer

(.,) at .10 C in m-KresoI

1.0

water soluble components

! 1,2

strength

4.8

strain

thread

Content of absorbed
water

31.5

80% RH

5.9

100%
RH

15.9

Coloring

affinity *) door

acidic dyes

98

*) For control thread made of nylon: 45.

Even with repeated washing of the threads, there was no change in the properties described above on.

Example 5 300 parts nylon-66 (in the form of fine chips) mil

ciücf ΐΓίίΠΠ51ί> \ iäKOäitüt (f /) VOH ί, ΐ ΪΠ ΓΠ-tvrCSOi at 30 ° C and with 45 meq / kg terminal amino groups were melted in an autoclave under nitrogen for 3 hours with stirring at 285 ° C. Thereupon, based on the nylon 66, 5% of a polyethylene glycol bisglycidyl ether, the underlying polyethylene glycol of which had an average molecular weight of 2000, or 5% of a mixture of 20% polyethylene glycol bishlorohydrin ether and 80% polyethylene glycol bisglycidyl ether, both of which were derivatives the polyethylene glycol also had an average molecular weight of 2000 was added. The mixture obtained was stirred at 290 ° C. for 2 hours and then extruded and cut into chips. The latter were washed with hot water, dried and converted into threads in the same way as in Example 1 to determine the properties.

Table VII contains the results.

Table VII

Additive

No*)

Polyethylene glycol bisglycidyl ether, polyethylene glycol bischlorohydrin ether / polyethylene glycol bisglycidyl ether

*) Comparison test.

Polymeric water-soluble components

0.1 U3

1.8

Properties of the thread

Strength elongation (g / d)

18.9
20.3

21.5

Hydrophilic properties of the thread

Sweat

absorption

speed

Content of absorbed
water

80% RH

5.2
6.1

5.9

100% RH

10.1
16.5

15.8

(Sec.)

320
15th

21

Even after repeatedly washing the thus obtained nylon 66 hydrophilic filaments and those therefrom There was no significant change in the properties of the fabric produced.

e) Production of the starting material

50 parts of monochlorohydrin ether, according to a) from the monoethyl ether of a polyethylene glycol with an average molecular weight of 10,000 were made with 50 parts Water and 100 parts of ethylenediamine reacted under reflux for 3 hours. The water and the excess Ethylenediamine was distilled off and the reaction product was dissolved in 300 parts of methanol and brought into contact with an OH type anion exchange resin. After the ion exchange has ended the methanol was distilled off from the separated solution, whereby a purified monoaminohydrin ether was obtained.

Example 6

3% of the monoaminohydrin ether obtained under e) became F-caprolactam before the polymerization, which was carried out under the same conditions as in Example 1, given. To determine In terms of properties, the chips obtained were washed with water, dried and spun and cold drawn. The drawn filament properties are given in Table VIII.

Table VIII Additive

Polymer

(,;) at 30-C in m-cresoI

water soluble components

strength

strain

thread

Content of absorbed water

80% RH

100% RH

Coloring

affinity *) for

acidic dyes

Monoaminohydrin ether 1.1

*) For the nylon control thread 6:45.

9.7 5.0

29

5.8

14.8

73

Comparative experiments

Using fully dried polyethylene glycol (Molecular weight 4000) the following derivatives were produced:

A. Seiii Bischlorhydfinäthef according to a).

B. The polyethylene glycol was first cyanoethyl and then in a conventional manner for Hydrogenated diamine derivative.

C. 5 parts of ί-caprolactam, 1 part of ω-aminocaproic acid and 1 part of adipic acid were ^{copolymerized at 260 °} C. under nitrogen for 8 hours. The low molecular weight polyamide obtained was dissolved in ten times the amount of ε-caprolactam at 9O ⁰ C and then poured with stirring into a large quantity of ice water, thereby obtaining a fine powder of the polyamide having a molecular weight of from 980th 141 parts of this powder, 46 parts

g vuii juu iciicn

ι uiu ^ iGiiunauu ^ anai uuu uic g

Polyethylene glycol in 500 parts of benzene were combined and the mixture at 75 ° C for 5 hours Stirring Implemented.

Then benzene was distilled off under reduced pressure and then the temperature was all ·

gradually increased to 250 ° C. This temperature was held for a further 2 hours and then cooled and pulverized.

In each case 2 parts of one of the above polyethylene glycol derivatives were mixed with 98 parts of nylon 66 cut

cells (i; = 1.1 in rri-Kresöl at 30 ° C) in a dryer of the rotation type thoroughly mixed. The resulting mixture was then put into a melt spinning machine introduced with a nozzle of 20 mm 0 at 285 ° C and from this to non-stretched strings

from 230 d / 18 f extruded, wound on spools of yarn became. The residence time of the molten polymer in the machine was between 15 and 20 minutes. The unstretched strings were cut to 3.3 times their length on a hot nadei

ίο stretched at 90 ⁰ C.

On the threads thus obtained
of the following Table IX. various parameters were measured, the results being Table IX

additive

According to the present
Invention A

According to British patent specification 1062547 B

According to German interpretation 1224031 C

Spin

Spinnable wedge

Well

Well

normal verslreckbarkcit

Well
small amount
small amount

string

with hot

water

cxlrahier-

cash share

1.0
1.0
0.9

0.2
1.5
0.7

Giirnquulilät

Strength

(g / d)

4.5
4.2
3.9

strain

18.2 19.3
20.2

Amount of water absorbed (%)

80% RH

5.7 5.5 5.4

100% RH

The strings were washed with water containing a customary detergent for 30 minutes at 40 ^° C. with movement, rinsed with running water for 30 minutes, then dried and examined for their hygroscopicity. The results obtained are summarized in Table X below.

Table X

According to the invention A

According to British patent specification 1062 547 B

According to German interpretation 1224031 C

80% RH
100% RH

80% RH
100% RH

80% RH
100% RH 5.7
14.0

5.5
13.5

5.4
13.2

Amount of water absorbed Number of washes

3 5 10

5.6

13.8

5.3
11.4

5.3
11.8

5.5
13.7

5.1
11.0

5.2
11.5

5.6 13.8

5.2 11.1

5.2 11.6

5.7 13.8

5.1 11.0

5.1 11.4

These comparative experiments show that the process according to the invention is better for hydrophilic products Processability leads. In the case of the polyamides produced according to the invention, the hydrophilicity is particularly important more durable than with modified polyamides, which are manufactured according to the known state of the art.

Claims (1)

Claim; Process for the production of hydrophilic polyamides by adding derivatives of Polyether glycols made from ethylene oxide and / or propylene oxide, the polyether glycol part being an average Molecular weight between 600 and 10,000, in amounts of 0.5 to 20%, based on the weight of the polyamide, before or during the polycondensation of salts from diamines and dicarboxylic acids, uj-aminocarboxylic acids and / or lactams to polyamides or, after polycondensation, to give molten polyamides from the monomers mentioned, thereby characterized in that the derivatives of the polyether glycols are bishalohydrin ethers or monohalohydrin ethers of compounds of the general formula R '! OR) "OH in which η is an integer between 3 and 90 and in which R 'is hydrogen, a straight-chain or branched alkyl group with 1 to 20 carbon atoms, an aryl or alkylaryl group and R is an ethylene and / or 1,2-propylene radical , and / or bis- and monoglycidyl ethers or bis- and monoaminohydrin ethers derived from these bis- and monohalohydrin ethers. 33 Polyamides are produced on a large scale and used in the form of fibers. These are in Extremely hydrophobic compared to natural fibers, which is a certain disadvantage as the fibers are hydrophobic have a waxy feel and have difficulty adapting to the skin. About that In addition, they easily leave stains with oil that cannot be easily removed. Furthermore can These fibers become electrically charged when rubbing, thereby adsorbing dust and an unpleasant one Result in carrying feeling. These deficiencies are closely related to the hydrophobic properties of the polyamides. A number of measures have already been taken to improve the hydrophilic properties of polyamides known. Japanese patent 193 864 describes the polymerization of > -C'aprolactam in the presence of polyethylene glycol. However, it is difficult to completely polymerize the polyethylene glycol with the caprolactam, so that unreacted polyethylene glycol remains in the polyamide obtained, which adversely affects the spinnability and the stretchability and the yarn quality is deteriorated. In Japanese patent specification 274 616 a method is described * in which caprolactam in the presence of an oxidation product of poly (5 ethylene glycol is polymerized. As in the treatment of polyethylene glycol with an oxidizing agent the polyethylene glycol is quite heavily depolymerized, the degree of polymerization is so modified polyethylene glycol so unevenly that a regulation of the viscosity of the Polymerization of the caprolactam obtained polymer can hardly take place. According to Belgian patent 697 891, antistatic polyamides contain oxyalkylation products of alcohols, while according to British Patent 1,062,547 and British Patent 948 507 an improvement in the hydrophilicity and a reduction in the electrostatic chargeability can be achieved by incorporating polyalkylene glycol diamines into polyamides. From the German exposition 1 224031 is known for this purpose polyamides with free carboxyl and / or amino groups with polyether glycols or with isocyanate-modified polyether glycols made from ethylene and / or propylene oxide to implement. Finally, from British patent specification 880 897, mono- and bis-chlorohydrin ethers are known from PolyalkWenoxidsn, like the ^ eni ^ en from Äth ^ len- and / or propylene oxide, mono- and bis-glycidyl ethers of these polyalkylene oxides or monochlorohydrin ethers or monoglycidyl ethers of alkoxyated alcohols with organic di- or polyamines to form water-soluble ones To implement resins, to apply them to hydrophobic materials, such as fibers made of polyamides, and then fix by heating. This surface treatment increases the electrostatic chargeability of hydrophobic substances is reduced. The durability of such a surface treatment However, the antistatic effect achieved is small. A process has been found which allows the production of polyamides with improved hydrophilic Properties permitted and inadequacies occurring in known processes avoided. The inventive method for production of hydrophilic polyamides by adding derivatives of polyether glycols from ethylene oxide and / or propylene oxide, the polyether glycol portion having an average molecular weight between 600 and 10,000, in amounts of 0.5 to 20%, based on the weight of the polyamide, before or during the polycondensation of salts from diamines and dicarboxylic acids, (»-aminocarboxylic acids and / or lactams to polyamides or, after polycondensation, to molten polyamides the monomers mentioned is characterized in that the derivatives of the polyether glycols are bishalohydrin ethers or monohalohydrin ethers of compounds of the general formula