Inherent light and heat stabilised polyamide, method thereof, the threads obtained his high-speed molding, and paintings obtained from threads

 

(57) Abstract:

Describes a method of producing polyamides by polymerization or polycondensation of monomers, whereby as the monomers used caprolactam or adipic acid and hexamethylenediamine were or their salt, and a polymerization or polycondensation of the monomers is carried out in the presence of triacetonediamine formula (I) used in the amount of at least 0,03 mol. % based on 1 mol carboxamide groups in the resulting polyamide. Obtained by this method polyamides are light and thermally stabilized and used for receiving sutures by means of high-speed molding, and paintings. 4 C. and 3 h.p. f-crystals, 7 PL.

The invention relates to the technology of polyamides, in particular to inherent light and heat stabilised polyamide, the method thereof, the threads obtained his high-speed molding, and paintings derived from thread.

A known method of producing polyamides by polymerization or polycondensation of monomers of different kinds, which can be processed into thread, of which you can get the canvas (see F. fourne. Synthetic fibers, Moscow, Chemistry, 1970, page 51).

The problem is solved in a method of producing polyamides by polymerization or polycondensation of monomers due to the fact that, as the monomers used caprolactam or adipic acid and hexamethylenediamine were or their salt, and a polymerization or polycondensation of the monomers is carried out in the presence of triacetonediamine formula

< / BR>
used in the amount of at least 0,03 mol.% in terms of 1 mol carboxamide groups in the resulting polyamide.

A further object of the invention is obtained by the proposed method inherent light and depletability polyamide characterized chemically bound to the polymer chain triacetonediamine the above formula.

The polymerization or polycondensation of the original monomers in the presence of triacetonediamine preferably carried out with known methods. Thus, the polymerization of caprolactam in the presence of triacetonediamine can be done, for example, described in the application DE N 1495198 and 2558480 continuous ways. Polymerization of salt hypertension in the presence of triacetonediamine you can make a standard discontinuous way (see "Polymerization Processes", pages 424 - 467, in particular, pages 444 - 446, Interscience, new yo what s can be fed into the reactor separately or as a mixture. Preferably triacetonediamine served according to a given program number/time.

According to a preferred form of execution of the proposed method triacetonediamine add to the original monomers in the maximum amount of 0.8 mol. %, preferably in an amount of 0.06 to 0.4 mol.%, in terms of 1 mol of acid amide groups of the polyamide. In case of use of the diamine salt (salt AG) a specified number of triacetonediamine relates to 0.5 mol of salt hypertension. It was found that when amounts less than 0.03 mol.% do not achieve sufficient stabilization of the obtained polyamide, and in quantities of more than 0,8 mol. % do not reach the desired degree of polymerization due to the inhibitory effect of triacetonediamine.

Triacetonediamine can be combined with at least one standard inhibitor of polymerization. Suitable polymerization inhibitors are, for example, monocarboxylic acids such as acetic acid, propionic acid and benzoic acid. This combination of inhibitors of polymerization and used the number to choose, among other things, in accordance with the desired content of terminal amino groups of the final product and the desired stability of the melt. Content to the yarn to dyeing. The stability of the melt depends on the practical needs in the processing of products, in particular in forming them.

In the case of use as a monomer caprolactam process can be carried out in the presence of a polymerization inhibitor dicarboxylic acids, preferably selected from the group comprising alkalicarbonate acid with 4 to 10 carbon atoms, such as, in particular, adipic acid, azelaic acid, sabotinova acid and dodecadienol acid, cycloalkylcarbonyl acid with 5-8 carbon atoms, such as, in particular, cyclohexane-1,4-dicarboxylic acid, and benzylcarbamoyl and naphthalenesulphonate acid, such as, in particular, isophthalic acid, terephthalic acid and naphthalene-2,6-dicarboxylic acid. Dicarboxylic acids preferably used in the amount of 0.06 to 0.6 mol.%, preferably in an amount of 0.01 to 0.5 mol.%, in terms of 1 mol of acid amide groups of the polyamide. In particular, in the case of polyamide 6 (polycaprolactam) such products along with the necessary stability of the melt, the desired ability of the yarn to dyeing and good light and heat stability has, in addition, increased strength policenew polymerization in combination with the connection of triacetonediamine dicarboxylic acid may be identical with used as dicarboxylic acids And dicarboxylic acids or may be different from them. They are preferably chosen from alkalicarbonate acids with 4 to 10 carbon atoms, such as, in particular, adipic acid, azelaic acid, sabotinova acid and dodecadienol acid, cycloalkylcarbonyl acids with 5 to 8 carbon atoms, such as, in particular, cyclohexane-1,4-dicarboxylic acid, and from benzylcarbamoyl and naphthalenesulphonic acids, such as, in particular, isophthalic acid, terephthalic acid and naphthalene-2,6-dicarboxylic acid. Preferably the dicarboxylic acid is used in the amount of 0.06 to 0.6 mol.%, preferably in an amount of 0.01 to 0.5 mol.%, in terms of 1 mol of acid amide groups of the polyamide.

According to preferred feature of the proposed method the polymerization or polycondensation is carried out in the presence of at least one pigment. Preferred pigments are titanium dioxide or inorganic or organic coloring compounds. The pigments are preferably added in an amount up to 5 weight.h., in particular 0.02 to 2 weight.h., based on 100 weight.h. polyamide. The pigments can be fed into the reactor together with the initial substances or separately. The use of triacetonediamine (also as a component of the inhibitor reconsider pigment.

Another object of the invention are those derived from fibres obtained by molding the polyamide according to the invention at speeds not lower than 4000 m/min. Specified in the following examples, the preferred upper limit on the number of triacetonediamine about 4500 m/min are not included in the claims, as it does not affect the solution of the above tasks. Exceeding it just means that a product with any degree of polymerization is not possible.

The following examples explain the invention.

General notes examples

The relative viscosity of the polyamides (granules and threads) determined in 1% solution (1 g/100 ml) in concentrated 96 weight. % sulfuric acid at 25oC. Content of end groups is determined by acidimetric titration. Terminal amino titrate with perchloric acid in the form of a solution in a mixture of phenol and methanol in a weight ratio of 70:30. Carboxyl end groups is titrated with a solution of caustic potash in the form of a solution in benzyl alcohol.

The content of triacetonediamine and, if necessary, dicarboxylic acid polyamides can be determined after hydrolysis of the sample in dilute mineral acid carrying out analerotic polyamide filaments is carried out in the conditions, which largely correspond to the conditions in the heat-setting processes at the stages of further processing, such as thermal stabilization of high volume complex threads or stabilization of textile fabrics in the drying and tentering machine. Otmachivajut coils 5 g of extruded filaments, together with samples for comparison quickly serve their carrier in a pre-heated up to 185oC circulating the drying chamber and leave them for another 120 seconds after the re-attainment of air temperature, measured in the immediate vicinity of the sample. Then immediately remove the sample and allow to cool in air at room temperature 20oC. Threads that compare with each other, handle together.

As a measure of damages (compared with untreated breakdown of the same thread) determine the decrease in relative viscosity and the content of amino groups, as well as the increase in the content of carboxyl groups.

The absolute reduction in major groups with the purpose of appropriate assessment practice then converted to percent reduction compared with untreated break yarn.

Elongation at maximum tensile strength was determined by measuring 200 mm, and in the case of extruded and textured filament yarn - 500 mm test Time before breaking threads is (20 2)C. In the case of pre-oriented yarns pre-tension force is 0.025 cH/dtex, in the case of elongated thread - 0,05 cH/dtex.

Referred to the unit of linear density maximum tensile force RHdetermined according to the equation RH= FH/Ttvwhile FHmeans the maximum tensile force in cH, a, Ttv- the initial linear density in dtex. For maximum tensile force take the maximum value when measuring the strain at maximum tensile force.

Tensile EHwhen the maximum tensile strength is defined as the ratio of the change in length l when the maximum tensile force to the original length lvthe test sample according to the equation EH= l 100%/lvwhile the value of l is calculated from the difference between the length of the sample at maximum tensile force lHand the original length lv.

Example 1

As the polymerization reactor using a tubular reactor for continuous polymerization according to the application EP N 20946 stainless steel, material N 1.454 EU.h. molten caprolactam, 0.5 weight.h. water and 0.33 weight.h. terephthalic acid under stirring continuously served the top of the first reaction zone of the tubular reactor. At the same time continuously served 55 ml/h triacetonediamine in a separate thread in the first reaction zone of the tubular reactor. Thus, the concentration of triacetonediamine is 0,087 mol.%, and the concentration of terephthalic acid - 0,23 mol.% accordingly, calculated on 1 mole of caprolactam. The temperature in the first reaction zone is 266oC; the pressure in the vapor phase above the first reaction zone is 1.5 bar abs. Polycaprolactam taken from the bottom of the tubular reactor, is transferred to the granulated material is extracted with hot water and dried. Get the dried polymer with a relative viscosity 2,70, the content of terminal amino groups 39 mEq/kg and a content of terminal carboxyl groups 65 mEq/kg

The product at a melt temperature of 275oC is subjected to high-speed spinning pre-oriented yarn to foster spinning disks on the experimental spinning device company EMC Inventa at 23 grams per minute and the die plate of the die with a hole diameter of 0.2 mm and a length of spunbond channel 0.6 mm

the g-Kraft 4500 m/min

Under villeroi filament is cooled by an air stream temperature of 20oC, relative humidity of 65% and a speed of 0.4 m/s in the blasting mine firm Barmag with the panel in the transverse direction. Preparation perform the standard drug of 0.65% of Limanowa E 100 company Shill & Seilacher on the thread through the metering pump and ceramic butter dish in the blasting mine. Pre-oriented yarns have the following characteristics: elongation at maximum tensile force 72%, referred to the unit of linear density maximum tensile strength of 4.1 cH/dtex, rowdata in Uster (standard test) U% = 0,6.

Then perform additional pulling in cold condition on the torsion handling machine of the type 14's company Zinser with a stretching ratio of 1: 1,363 and with the speed of 820 m/min to thereby obtain filaments with a tensile maximum tensile force in 37%, referred to the unit of linear density maximum tensile force 5.2 cH/dtex and rownameu on Uster U% (standard test) of 0.7. The titer equal to 43.1 f 12 dtex.

The relative viscosity of 2.70, the concentration of terminal amino groups to 35 mEq/kg, and the concentration of terminal carboxyl groups - 63 mEq/to the conventional polyamide 6 with a relative viscosity 2,67 without triacetonediamine. Received pre-oriented yarns have the following characteristics: elongation at maximum tensile force 73%, referred to the unit of linear density maximum tensile strength of 4.0 cH/dtex, rowdata in Uster (standard test) U% = 0,6.

Then perform additional stretching in the cold state with a stretching ratio of 1: 1,336. So get strands with tensile maximum tensile force in 43%, referred to the unit of linear density maximum tensile force 4.8 cH/dtex and rownameu on Uster U% (standard test) 0.5. The title is 43.8 f 12 dtex. The relative viscosity is 2,66, the content of terminal amino groups of 32 mEq/kg, and the content of terminal carboxyl groups 53 mEq/kg

Threads within 120 is subjected to heat treatment in air at a temperature of 185oC. They have the figures shown in the table. 1.

From table 1 it is evident that the proposed polyamides 6 after heat treatment show less strong decrease in relative viscosity and the content of terminal amino groups, as well as less strong increase in the content of carboxyl groups than the polyamide of comparative example 1 and the sama is in the same tubular reactor, as in example 1, with the addition of 0.38 mol.% terephthalic acid, of 0.20 mol.% triacetonediamine, 0.5 wt.% water and 0.3 wt.% titanium dioxide (as a matting agent). The polymerization is carried out at a flow rate of 25 kg/h and 255oC in the first reaction zone under atmospheric pressure. In the rest of the process is identical to example 1. The dried product has a relative viscosity of 2.37, the content of terminal amino groups in 45 mEq/kg, and the content of terminal carboxyl groups in 79 mEq/kg

The product is melted in a single screw extruder firm Barmag and a melt temperature of 270oC is fed to the molding system of the type SP 42 firm Barmag. When applying to 22.6 grams per minute and the die plate, and also when using nozzles with 12 holes with capillary holes with a diameter of 0.20 mm and a length of 0.60 mm at a speed of winding of 4500 m/min receive titer molding (MON) 52 f 12 dtex. After passing through the blowing shaft with a transverse blowing in 0.40 m/s and spooling 0,60 - 0,65% of the standard drug (liminal E 100 company Shill & Seilacher in the form of an 8% solution) thread off with two foster spinning disks with a speed 4510 or 4535 m/min as the winding head is used winding device firm Barmag Kraft th density maximum tensile force 4.6 cH/dtex and shrinkage of 9% while boiling.

Pre-oriented yarn is subjected to torsion with pulling in cold condition with the speed of 748 m/min on the torsion exhaust machine type J5/10a firm Riter. The tension in the area of pre-stretching is 0.8%, and the total stretching ratio is 1:1,298.

Extruded filaments have an elongation at maximum tensile force in 36%, related to the unit linear density of the maximum tensile strength of 5.2 cH/dtex, title 44 f 12 dtex and roveto on Uster U% (standard test) 0.7.

Establish the relative viscosity of 2.41, the content of terminal amino groups in 42 mEq/kg and a content of terminal carboxyl groups in 74 mEq/kg

Comparative example 2

Standard polyamide 6 with a relative viscosity 2,39, not containing triacetonediamine, ekstragiruyut described in example 2. Cooling and preparation of threads is done according to the above description. Wound without receiving a spinning disk with a speed of 4500 m/min PONT have an elongation at maximum tensile force in 62%, related to the unit linear density of the maximum tensile strength of 4.2 cH/dtex and a shrinkage in boiling 9%.

Previously intended the Deposit in this case is 1:1,279. Extruded filaments have an elongation at maximum tensile force in 34%, related to the unit linear density of the maximum tensile force 4.6 cH/dtex, the titer in 43,6 f 12 dtex and roveto on Uster U% (standard test) in 0.9.

Establish the relative viscosity of threads 2.41, the content of terminal amino groups at 25 mEq/kg and a content of terminal carboxyl groups in 65 mEq/kg

The thread is subjected to the appropriate process textile stabilization in drying and tentering installation conditions (185oC hot air, 120 C) and measure the following indicators (see table. 2).

Table 2 shows, the polymerized in polyamide 6 in the presence of triacetonediamine caprolactam has better thermal stabilization than the polyamide of comparative example 2 not containing triacetonediamine.

Example 3

Obtained according to example 2, but without the addition of titanium dioxide, the polyamide is subjected to high-speed molding according to example 2. PONT have an elongation at maximum tensile force in 64%, related to the unit linear density of the maximum tensile force 4.7 cH/dtex and a shrinkage in boiling 10%.

The stretching is carried out in the conditions, p is the power in 37%, related to the unit linear density of the maximum tensile strength of 5.4 cH/dtex, a shrinkage in boiling in 14%, roveto on Uster U% (standard test) in 0.8 and title 44 f 12 dtex.

The relative viscosity is 2,40, the content of terminal amino groups 42 mEq/kg, the content of terminal carboxyl groups - 74 mEq/kg

Comparative example 3A/3B

Two types of standard polyamide 6 with a relative viscosity of 2.40 (3A) and 2,44 (3B) is subjected to high-speed molding according to example 2. The molding temperature is 275oC, the speed of the two foster spinning disks - 4510 4520 or m/min.

According to table 3 of the proposed polyamide 6 has a better thermal stabilization than polyamide 6 comparative examples.

Example 4

Caprolactam is subjected to polymerization in the same tubular reactor as in example 1, with the addition of 0.55 wt.% (0,375 mol.%) terephthalic acid, 0.33 weight. % (0,239 mol.%) triacetonediamine, 0.5 wt.% water and 0.3 wt.% titanium dioxide. The polymerization is carried out at a flow rate of 25 kg/h and 255oC in the first reaction zone under atmospheric pressure. The technological process in the rest corresponds to example 1. The dried product has a relative viscosity in the s extractable components is 0,38 %.

Subjected to molding without the help of foster spinning disk with a speed of 4500 m/min, respectively comparative example 2, and then pull in a cold state when the stretching ratio 1:1,229 and with a speed of 600 m/min.

PONT have a linear density in 52 f 12 dtex, elongation at maximum tensile force in 59% and related to the unit linear density of the maximum tensile strength of 4.1 cH/dtex.

When testing on the device for determining defects (slit width 45 m) average set to 0.5 blemish/100 km.

After pulling establish elongation at maximum tensile force in 36% and related to the unit linear density of the maximum tensile strength of 4.3 cH/dtex. The title is 46 f 12 dtex.

Comparative example 4

Caprolactam is subjected to polymerization in the same tubular reactor as in example 4, with the addition of 0.53 wt.% (0,361 mol.%) terephthalic acid, 0.5 wt.% water and 0.3 wt.% titanium dioxide. The polymerization is carried out at 255oC in the first reaction zone. The technological process in the rest corresponds to example 4. The dried product has a relative viscosity of 2.39, the content of terminal amino groups in 27 mEq/kg and the content is

50 kg of the above chips of polyamide-6 put 165 g triacetonediamine (TAD) (0.33 wt.%) in the liquid state by a two-hour mixing in a drum mixer.

Thus crumb contains the same amount of mixed TAJ and almost the same amount of terephthalic acid (introduced by polymerization), as described above, the product of example 4, except for the additive method TAJ both products are identical.

Applied with a drum mixer TAD not (completely) absorbed into the crumbs. She is wet from the TAJ and highlights the intense smell of amine. These properties are very negative when applying, in addition, necessary measures for security, as TAD has a corrosive effect.

If during your stay in a spinning system in example 4, the viscosity normally increases, in comparative example 4 it decreases sharply. Predominant are also relatively minor changes in the content of amino groups and extractable components in example 4 (definition: 16 hours extraction with methanol; the process is carried out under reflux) and the fact that it produces much less smoke in the area of the nozzle when p is x in example 4 conditions. PONT have a linear density in 52 f 12 dtex, elongation at maximum tensile force in 54% and related to the unit linear density of the maximum tensile strength of 3.8 cH/dtex. When testing on the device for determining defects set in the middle of 7.5 lesions (nodules, the cliffs of filaments, loops) per 100 km

After pulling establish elongation at maximum tensile force in 35 % and related to the unit linear density of the maximum tensile strength of 4.2 cH/dtex.

As can be seen from table 5 of the proposed polyamide 6 example 4 in all stages of processing has a lower number of defects than polyamide 6 comparative example 4, in which the polyamide mix TAD.

Example 4 TAD more completely/firmly attached to the polyamide, than in comparative example 4. Thus, when the processes of extraction (such as colour) less Amina enters the liquid phase.

After one hour of extraction wound without spooling PONT boiling water under reflux establish the following chemical characteristics (see tab. 6).

As can be seen from table 6, the number of terminal amino groups in the proposed polyamide set less terminal amino groups. Thus, the extraction of the proposed less polyamide amine enters the liquid phase.

Comparative example 5

Standard, frosted 0.3% of titanium dioxide polyamide 6 with a relative viscosity 2,39, not containing triacetonediamine, is subjected to molding as described in comparative example 2 method.

PONT have a linear density in 51 f 12 dtex, elongation at maximum tensile force in 57% and related to the unit linear density of the maximum tensile strength of 3.8 cH/dtex.

Irradiation and measurement of the strain at maximum tensile strength and maximum tensile strength exercise together with example 5. The results are summarized in table 7.

Example 5

Caprolactam is subjected to polymerization in example 4 conditions (with the same initial substances and quantities), and apply the same type of titanium dioxide, as in comparative example 5. The dried polyamide has a relative viscosity in 2,43, the content of terminal amino groups in 44 mEq/kg and a carboxyl end groups in 71 IEC/kg. Content of extractable components is 0.36%.

Shaping is done is described in a comparative note is, asthenia at maximum tensile force in 61% and related to the unit linear density of the maximum tensile strength of 4.3 cH/dtex.

After pulling in a cold state with a stretching ratio of 1: 1,244 set are summarized in the following table 7 characteristics of the raw sample.

Then the yarn is wound on a tentering frame, 28 days is irradiated in a device of the type Xenotest 450 firm Heraus, , Hanau, and measure the residual elongation at maximum tensile strength and maximum residual tensile strength according to DIN 53834 when the length of the clip 100 mm on the device for carrying out the tensile test type UPM 1425 company Zwick. The results are summarized in table 7.

Table 7 shows clearly that obtained in the presence of triacetonediamine and titanium dioxide polyamide (example 5) has a substantially higher resistance compared with the comparative polymer (comparative example 5) containing only titanium dioxide and not triacetonediamine.

Example 6

The process is carried out in an autoclave. Of the 50% aqueous solution of the salt of adipic acid and a diamine containing 0.25% by weight of salt AG triacetonediamine, distilled water up to its pressure. This sets a pressure of 18 bar. Next heated to 275oC, and the pressure is kept at 18 bar due to reset. Then the pressure dropped to atmospheric, the reaction mixture is kept still at 275oC for a further 60 min, after which by using nitrogen melt is released through the bottom valve of the autoclave and cooled.

The obtained polyamide 6.6 processed into yarn as in example 1, which properties are not inferior to the product of example 1.

The same results are obtained if instead of salt AG use adipic acid and hexamethylenediamine were.

Example 7

Filaments of examples 1 to 6 are processed in chloroarsine blade length of 1 m and a diameter of 10 cm circular knitting machine company Losen - Hemphill with 380 needles. The resulting paintings have the same characteristics by light and thermal stability, the original thread.

1. The method of producing polyamides by polymerization or polycondensation of monomers, characterized in that the monomers used caprolactam or adipic acid and hexamethylenediamine were or their salt, and a polymerization or polycondensation of the monomers is carried out in the presence of triacetonediamine formula

< / BR>
used in >/P>2. The method according to p. 1, characterized in that the polymerization or polycondensation is carried out in the presence of at least one pigment.

3. Inherent light and heat stabilised polyamide-based caprolactam or adipic acid and a diamine or their salts, characterized chemically bound to the polymer chain amine radical of the formula

< / BR>
in the amount of at least 0,03 mol.% in terms of 1 mol carboxamide groups in the polyamide obtained by the method according to p. 1.

4. The polyamide under item 3, characterized in that it contains at least one pigment.

5. The polyamide under item 3 or 4, characterized in that it contains 0.06 to 0.4 mol. % the specified amine radical in terms of 1 mol carboxamide groups of the polyamide.

6. The filament obtained by the high-speed molding of polyamide, characterized in that the polyamide used polyamide under item 3 if the speed reading is not below 4000 m/min.

7. Cloth, obtained from threads on p. 6.

Priority points:

15.04.94 on PP.1, 2, 4 to 7 and 3, concerning heat stabilised polyamide.

17.08.94 under item 3, which relates to light-stabilized polyamide.

 

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