DE1669532C - Method of making elastic threads - Google Patents

Description

High demands are made on elastic threads which are to be used for industrial purposes placed. In particular, they have a high tensile strength and a high elongation at break together iii with low permanent elongation and high resistance to corrosive agents, such as light, ozone or oxygen.

Up to now have been used as the base materials for manufacture such threads of natural rubber and polyurethanes are used, from which. materials Under the usual spinning conditions, threads can be obtained which, depending on the starting file used ta! have different properties.

xo The German Auslegeschrift 1 645 241 describes a method using special systems, in which polymers are obtained, which, as has now been found, for the production of elastic threads are particularly suitable.

The aim of the present invention is to create elastic threads from the polymer can be obtained, which are the contents of the aforementioned patent. Generally printed there is an object of the present invention in the reu

ao position of elastic threads, which are obtained from polymers that graze after vulcanization Have the property that they can be crystallized under tensile stress.

The inventive method of manufacturing

»5 saturated of elastic threads made of vulcanized copolymers and unsaturated epoxides is characterized in that a solution or melt of a polymerization product, which consists of at least one alkylene oxide with at least one saturated ¹ unsaturated alkylene oxide at temperatures between -20 and 100 ° C in the presence of the inert diluents benzene, toluene or aliphatic and cycloaliphatic hydrocarbons and a catalyst consisting of an inorganic aluminum compound of the al! common η formula AIHXYZ used, optionally in combination with the chelating agents acetylacetone, diacetone monoxym, dimethylglyoxime and acetonylacetone and / or water, where X and Y are the same or different and represent hydrogen, halogen or residues of secondary aliphatic or aromatic amines and Z is a compound of the type a Lewis base, ie ether or a tertiary amine, which may be absent if X and / or Y is a secondary amine radical, has been obtained and which product can be crystallized after vulcanization with stretching, together with a vulcanizing agent, per se more known way spun, vulcanized the threads in a known manner and, if necessary, then stretched.

The threads according to the invention can be made from the polymerization products of ethylene oxide, propylene oxide, butylene oxide or epichlorohydrin and butadiene monoxide, Vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylates, Glycidyl methacrylates and the like.

The known methods (British patent specification 898 306 and British patent specification 1 000 222) for Production of the polymers of these compounds does not provide any material that can be used to produce elastics Threads is suitable, which have the characteristics required for industrial purposes.

The relative amounts of the comonomers in the polymer can be within a wide range vary, the olefin oxide in any case being present in a larger amount while the other is present Monomers is used in a smaller amount, preferably in an amount of about 10% or less.

3 f 4

The production of the threads according to the invention by means of which contain 0 to 70 percent by volume of solvent

includes the following levels: use.

The temperature of the coagulation bath can be

a) Preparation of a polymer solution or melt vary within a wide range. Preferably together with hardening agents; ₅ i _{IEGT they zw} i _sc hen 0 and 100 ° C, with temperatures

b) Spinning the solution or melt by means of between 35 and 60 ^° C. are particularly preferred, suitable spinnerets which are provided with one or more holes; between 3 and 35%, depending on the molecular

z) when using solutions, remove the weight of the polymer and the type of polymer used

Solvent by coagulation in ₁₀ SITUATE solvent.

Neten Koaguiierungsbädern or by comparison £ _s j _st h _AUC possible, the polymers of the

steam; Spin melt. In such a case

d) Vulcanization of the thread at a suitable one using the vulcanizing agents

Temperature, for example at 100 to 170 ° C. suitable mixing devices added, whereupon the

15 paste thus obtained at a temperature

During the preparation of the polymer solution, the exudation that is lower than the vulcanization

Addition of the vulcanization agent takes place at this temperature; connect ^ the thread obtained

could of course also be subjected to the vulcanization process during any other.

Process stage are carried out. In stage a) The following examples illustrate the invention,

it is also possible to use reinforcing agents, pigments ao without restricting them,
as well as generally adding any additive,

which the thread depending on its use Example 1

7 gives the desired properties. 100 g of a propylene oxide-AIlylglycidyläther-Co-

Stage c) consists in that the solvent polymerisats (which contains 6% allyl glycidyl ether and

by evaporation or by introducing the threads as has an intrinsic viscosity of 11.5)

is removed in suitable baths. were in 1250 g of methyl alcohol at a temperature

The vulcanization stage can be carried out at 40 ^° C. in this way. The polymer solution were vulcanized

be that the threads are added in a known manner beispieis- nisationsmittel, which in the following amounts in

due to the action of hot air, hot liquid methyl alcohol had been predispersed:

Opportunities steam, 1R rays, molten salts 30 copolymer 100 parts

od ^ like. to be exposed · _Ste £ _ri J _{sälire 0} .5 parts

This process stage can be continuous or zinc oxide 5 parts

be carried out in batches ^ Tetramethylthiuram disulfide ''.'.'.'.'. 1.5 parts

The threads obtained have better mechanical mercaptobenzothiazole 0.5 parts

and physical properties as the filament from 35 sulfur 1 5 parts

natural rubber. In addition, the

mechanical properties of the threads practically until the solution provided with the additives

to achieve the properties of polyurethane for 2 hours ^ stirred, whereupon it deaerates and in the

fibers are improved by the threads after the device, as shown in the drawing (F i g. 1).

Vulcanization can be stretched by 100 to 400%. 40 forms is, was wet spun.

With this method, the permanent deformation is achieved. 1 means 1 a solution container, 2

mation reduced in a noticeable way, with the pulling a small gear metering pump (1.68 ecm per

strength is doubled. Rotation), 3 a candle filter, 4 a spinneret

The filaments obtained according to the invention have a retainer, 5 a spinneret, 6 a coagulation bath,

In addition, in contrast to the threads made of natural 45 7, a device for immersing the threads,

Rubber good dyeing properties, which with those 8 a thread drive device, 9 and 11 rollers,

of polyurethane fibers are comparable. 10 a wash bath, 12 an equipment bath (the one

The most suitable dyes are dispersed and aqueous 10% talc dispersion contains), 13 dry

pre-metallized dyes (2: 1). When using rollers, 14 a winder; 15 a container

these dyes will have a good color intensity as well as 5 ° for the coagulating solution and 16jine circulation pump,

achieved good lightfastness. The solution contained in the container 1 is through

To produce the spinning solution, many applications of nitrogen pressure can be added to the pump 2.

Solvents can be used. leads where ^r on it after filtration through a

Examples of such solvents are: acetone, 20,000 mesh / cc ^ 3 stainless steel sieve

Methyl alcohol, ethyl alcohol, benzyl alcohol, Dime- SS spinneret 5, the 48 holes (Dufchmes-

ethylformamide, dioxane, ethyl acetate, chloroform, Ben- ser 165 μ) possesses. The thread is in the coagulation

Zol, toluene, carbon tetrachloride or the like., The bath 6 coagulates, in which water with a

Selection of the solvent from the applied temperature of 40 ⁰ C is located, which by a

Temperature (between 15 and 100 ⁰ C) depends. Pump 16 is circulated.

This solution can be made using conventional methods. 60 The thread is placed in the coagulation bath with a

can be spun dry or wet. Length of 180 cm inserted and by means of the winding

In the case of wet spinning, each dissolving device 9 can be wound up.

medium, provided that it is with the The thread forms turns and is then in the

Coagulant is miscible. Bath 10 washed with water.

In any case, it is preferable to use the polymer as the 85 Then the thread in the bath 12 with

Compounds which can be mixed with solvents and water, such as an aqueous talc dispersion, were washed.

Acetone or methyl alcohol and as a coagulation on it in the device 13 and dried by means of

means of water or water-solvent mixtures, device 14 is wound up.

Which vulcanized for 30 seconds using hot air at a temperature of 150 ° C Thread has the properties given in the table (thread A).

Example 2

100 of a propylene oxide-allyl glycidyl ether-co-polymer g (4% allyl glycidyl ether, intrinsic viscosity 12.5) were dissolved in 1550 grams of methyl alcohol at 40 ⁰ C.

The solution was admixed with vulcanizing agents and according to that described in the previous example Way vresponnen. The characteristic properties of the vulcanized threads are in the Table summarized (thread B).

B e 1 s ρ 1 e 1 3

The thread described in the previous example was subjected to two different treatments:

1. The thread was stretched 400% after vulcanization and heated for 30 minutes Air kept at 40 ° C under stretching conditions.

2. The thread was stretched 400% after vulcanization and heated for 30 minutes Air kept at a temperature of 25 ° C under the stretching conditions.

After 30 minutes, the threads were relaxed, whereupon their mechanical properties were determined. These properties are summarized in the table, the threads as C (drawn at 40 ° C) and D (stretched at 25 ° C).

B e 1 s ρ ι e 1 4

The solution of Example 1 was through a spinneret with ten holes with a diameter of 80 μ, which is at the upper end of a spinning chamber with a length of 2 m, which by means of circumferential Water with a temperature of 80 ° C is heated, with a gentle stream of nitrogen with a temperature of 55 ° C is introduced at the bottom of the spinning chamber and strokes through the spinning chamber, attached is spun.

The solution from the container 17 was filtered through a disk filter 18 by applying nitrogen pressure and pressed through a spinneret 19. The thread obtained after evaporation of the solvent possessed had good strength and could be wound using a winder frame.

. -ic example D

Using a mixer for rubber, a mixture of the copolymer was made Propylene oxide and allyl glycidyl ether of Example 2 and prepared from vulcanizing agents. The mix consisted of:

was charged by means of a hydraulic piston, which is located in a heated chamber, which the copolymer contained, moved.

The Extrusionstemperalur was heated to 95 to 10C ^- kept C, ie on a temperature value measured under _13-J H, (j vulcanization _he is.

A polymer was obtained which, after vulcanization, showed physical-mechanical properties which were comparable to those of the threads obtained by a Na / Spinning process.
". . .

An 8% methyl alcohol solution of a propylene oxide-AHylglycidyläther copolymer was described using the same apparatus and using the same process conditions as Example 1 j _m, was obtained.

The copolymer had an intrinsic viscosity (at 30 ° C. in toluene) of 8.30 and an Allyl- ™> glycidyl ether content of 2.76%.

. ^A methyl alcohol dispersion from vulcanization

1Ζ * * ^E.

2 parts

Stearic acid 2 parts

j _o 5 _Te ji _e

Mercartobenzothiazöl ''. '.'. ". '.'. '.'. '. '. 1 part Tetr _a m ^r eth _y .thiuramdi3 _U , nd 1 part

The copolymer was through a spinneret provided with a hole 0.3 mm in diameter Spun from the melt, using the spinneret

100 parts copolymer

^as stearic acid 1 part '

ZnO 5 parts

Mercaptobenzothiazoi 1 part

Tetramethylthiuram disulfide 2 parts

Sulfur 2 parts

The solution was then through a spinneret with 30 holes with a diameter of 125 μ was provided, wet spun in the manner described in Example 1.

The table shows the properties of the threads _{designated as E ^ 5} Mj utes long vulcanized in molten salts at 160 ° C.) and F (vulcanized for 30 minutes in an autoclave with steam at 4 atmospheres).

. . .

Comparative example 1

A propylene oxide-allyl glycidyl ether copolymer,

this using a catalyst system

Diethyl zinc / water and 4% AUyI-

glycidyl ether was dissolved in methyl alcohol.

After the addition of the vulcanizing agents in the manner described in Example 2, the result was: the copolymer also vulcanized and spun in the manner described in Example 2.

The characteristic properties of the vulcanized thread (thread M) are arge in the table give

Comparative example II

A propylene oxide-allyl glycidyl ether copolymer using a catalyst system made from aluminum triisobutyl and acetylacetone and contained 4% allyl glycidyl ether, was dissolved ii methyl alcohol.

^After ^ V ** ^{of the} vulcanizing agent as copolymer was vulcanized by the method described in the foregoing manner and Beispii verspönnet ¹ J g ^ f ^{d (V ls} ^ fj ichneten fader

can be improved by making sure that the thread section is as close as possible approaching circular section.

table

Padcn A. Titcr tensile strenght Elongation at break Permanent deformation 200 ° / o 8.4 Permanent ones
strain B. (the) g / den 7o ! 00% 7th 6.2 400 per cent C. 550 0.40 690 3 9 0 12th D. 180 0.46 690 4th 2: 5 0 11th E. 120 0.72 500 3 '. 6th 0.4 8th F. 140 0.55 560 1.2 2.3 10 G (comparison) 114 0.37 715 2.8 8th 16 H (comparison) 118 0.43 703 0 4 \ 5 12.3 1 (comparison) 700 0.18 560 0 0 L (comparison) 2080 0.27 630 0 0 M (comparison) 2850 0.20 630 0.6 1.5 N (comparison) 70 0.84 600 3.5 6.5 200 0.12 620 2 9.5 170 0.14 640 11th

The samples designated as G, H and I are handds- (iblichc Natural rubber thread; sample L is a polyurethane-based thread.

The mechanical and elastic properties of the threads were determined using an Instrom dynainometer. The permanent set was determined by subjecting the samples to a hysteresis cycle, ie elongations of 100, 200 and 400%. a suitable sample length of 5 cm and a pulling speed of 10 cm / 1 'were used. After stretching to the predetermined value, the samples were held under tension for 1 minute, after which they were returned to their original length at the same speed and then stretched again to the predetermined value after 5 minutes. The permanent set is built from the flat part (without stress) of the curve obtained during the second stretch.
The permanent deformation is given as a percentage of the predetermined elongation.

Here 1 sheet of drawings

Claims (4)

Patent claims: 1. Process for the manufacture of elastic threads from vulcanized copolymers saturated and unsaturated epoxies, characterized in that a solution or a melt of a polymerisation product, which consists of at least one saturated alkylene oxide with at least one unsaturated alkylene oxide, at temperatures between -20 and 100 ° C in the presence of the inert diluents benzene, toluene or aliphatic and cycloaliphatic Hydrocarbons and a catalyst consisting of an inorganic aluminum compound of the general formula AlHXY · / used, optionally in combination with de.ι chelating agents acetylacetone, Diacetone monoxym, dimethylglyoxium; ind acetonylacetone and / or water, where X and Y are the same ί or different and are hydrogen, Halogen or radicals of secondary aliphatic or aromatic amines and Z represent a compound is the rtrt of a Lewis base, d. H. Ether or a tertiary amine, which may be absent when X and / or Y is a secondary amine residue, and this product after vulcanization unl-T stretching is crystallizable, together with a vulcanizing agent, spun in a manner known per se, the threads in per se vulcanized in a known manner and, if necessary, then stretched. 2. The method according to claim 1, characterized in that one polymerization products from ethylene oxide, propylene oxide, butylene oxide or epichlorohydrin and butadiene monoxide, vinyl glycidyl ether, Allyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate are used. 3. The method according to claim 2, characterized in that there is a polymerization product Propylene oxide and allyl glycidyl ether used, which contains 1.5 to 10% allyl glycidyl ether units. 4. The method according to claim 1, characterized in that a 5 to 30% solution of a propylene oxide-alkylglycidyl & ether copolymer in methyl alcohol, ethyl alcohol, dimethylformamide, dioxane, chloroform, carbon tetrachloride or benzene, to which vulcanizing agents have been added, is spun dry or wet , a coagulation bath of water or a water / solvent mixture containing 0 to 70% solvent is used in wet spinning and the temperature of the coagulation bath is kept between 0 and IuO ⁰ C, the threads obtained in this way at a temperature of 100 to 17O ⁰ C vulcanized, then subjected to a stretching treatment at 100 to 500 ⁰ C. and maintained under the Verstrekkungsbedingungen at a temperature between 10 and 120 ⁰ C.