US3839496A - Manufacture of filaments or fibers of polyamides - Google Patents
Manufacture of filaments or fibers of polyamides Download PDFInfo
- Publication number
- US3839496A US3839496A US00290321A US29032172A US3839496A US 3839496 A US3839496 A US 3839496A US 00290321 A US00290321 A US 00290321A US 29032172 A US29032172 A US 29032172A US 3839496 A US3839496 A US 3839496A
- Authority
- US
- United States
- Prior art keywords
- filaments
- polyamide
- fibers
- polyamides
- alkoxylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 45
- 229920002647 polyamide Polymers 0.000 title claims abstract description 45
- 239000000835 fiber Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000003951 lactams Chemical class 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 5
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 3
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000001408 amides Chemical class 0.000 claims abstract 4
- 229920002292 Nylon 6 Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical class NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical class OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical class NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical class NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- -1 octolactam Chemical compound 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 208000003028 Stuttering Diseases 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009732 tufting Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- This invention relates to a process for the manufacture of filaments or fibers containing alkoxylated polyamides.
- This object is achieved by a method of making filaments or fibers of filament-forming synthetic linear polyamides containing alkoxylated polyamides in an amount of from 2 to 15%, on the weight of the filaments or fibers, Wherein a molten mixture of the filament-forming synthetic linear polyamides and alkoxylated polyamides is subjected to thorough mixing so that the alkoxylated polyamides are present in the finished filaments in the form; of particles having a diameter of not more than 0.1,u., and the molten mixture is filtered at least once through a filter having a pore width of not more than 2071, the mixture is converted to chip form if desired, and the mixture is melt spun, the molten mixture being maintained at temperatures of up to not more than 290 C. for a total period of not more than 30 minutes.
- filament-forming synthetic linear polyamides of high molecular weight we mean those having recurring amide groups in the backbone.
- Suitable filament-forming or fiber-forming synthetic linear polyamides are, for example, the polycondensates of lactams having from 4 to 12 carbon atoms, such as e-caprolactam, octolactam, dodecanolactam or mixtures of said lactams, and the polycondensates of salts of diamines and dicarboxylic acids having from 4 to 12 carbon atoms, such as the salts of adipic acid, suberic acid or sebacic acid, and hexamethylene diamine, octamethylene diamine or dodecamethylene diamine or mixed condensates of said polyamide-forming materials.
- Particularly suitable are polycaprolactam; and polyhexamethylene adipamide.
- the filament-forming or fiber-forming polyamides may contain an excess of Basic groups or they may have a content of sulfo groups or alkali metal sulfonate groups. Conveniently, the polyamides to be modified ha've relative viscosities in the range 1.5 to 2.9.
- Polyamides alkoxylated with 1,2-alkylene oxides may be manufactured by known processes, for example by the method described in Belgian Pat. 665,018 comprising the reaction of 1,2-alkylene oxides, for example ethylene oxide and/ or 1,2-propylene oxide, with polyamides under pressure and at elevated temperatures, in particular at temperatures ranging from 60 to C.
- the reaction may be carried out in the presence or absence of organic solvents and/or reducing or oxidizing agents, the alkylene oxides being reacted with the polyamides preferably in a ratio of from 2 to 5:1 by weight. It has been found advantageous to use alkoxylated polyamides having a total molecular weight of at least 10,000 and in particular from 20,000 to 80,000.
- Suitable polyamides from which the alkoxylated polyamide antistatic agents may be manufactured are for example conventionally produced polycondensates of lactams having from 4 to 12 carbon atoms, such as e-caprolactam, octolactam, dodecanolactam or mixtures of said lactams, the polycondensates of salts of diamines and dicarboxylic acids having from 4 to 12 carbon atoms, such as the salts of adipic acid, suberic acid or sebacic acid, and hexamethylene diamine, octamethylene diamine or dodecamethylene diamine or copolyamides of said polyamide-forming materials.
- Particularly suitable are all those polyamides which have low crystallinity, for example copolyamides or polyamides which have been prepared by quenching the polymer melt, for example molten polycaprolactam.
- the amount of alkoxylated polyamides used is conveniently from 2 to 15% and in particular from 4 to 10% w./w. of the weight of the filaments or fibers. It is possible to use larger proportions, but this leads to changes in the properties of the filaments or fibers.
- the solid components i.e. the filament-forming polyamides and the alkoxylated polyamides, may be melted separately or together.
- the components may be mixed in a conventional single-worm or twin-worm extruder, of which one or both of the worms may be axially displaceable if desired.
- Static mixers having stationary conducting elements may also be used to advantage. Adequate mixing is usually obtained using static mixers having 15 or more elements. Static mixers of this kind are described for example in US. Pats. 3,286,992 and 3,404,689 and German Published Application 1,178,404.
- Conditions should be such as to achieve such thorough mixing that the alkoxylated polyamides, which form a separate phase in the filaments after cooling and drawing, have a particle diameter of not more than 0.1 4.
- the degree of mixing required to achieve this end may be previously found by simple experiment.
- the length of the separate particles of alkoxylated polyamides in the filaments after drawing is generally a multiple of their diameter, for example about 111 or more. It is an important feature of the process of the invention that filtration of the molten mixture of components is carried out at least once through filters having pore widths or not more than 201L- Examples of suitable filters are metal sieves or, in particular, sintered metal filters such as sintered metal plates or sintered metal tubelets.
- the molten mixture may, if desired, be converted to chips and subsequently melt-spun to filaments or fibers.
- the molten mixture may be thoroughly mixed and filtered and immediately melt-spun to filaments or fibers without intermediate conversion to chip form.
- Another alternative is to carry out mixing and filtration in the spinning apparatus by using a spinning extruder capable of providing thorough mixing and placing a filter having a pore width of less than 20g immediately downstream of the spinning nozzle, which filter is advantageously an appropriate sintered metal filter.
- the molten mixture of filamentforming polyamide and alkoxylated polyamide is maintained at temperatures of not more than 290 C. and generally at from 250 to 290 C. for a total period of not more than 30 minutes including the melt-spinning time.
- the time during which the mixture may be in chip form in a colder state is, of course, not included.
- the filaments are made using conventional spinning systems wherein, of course, the conditions usually observed in the manufacture of polyamide filaments, such as the exclusion of oxygen and the use of certain low moisture contents, must be met.
- the filaments or fibers produced by melt-spinning may have a round crosssection or a profiled cross-section such as a trilobate or tetralobate cross-section.
- the filaments may be in the form of two-component filaments with other filamentforming materials.
- the filaments or fibers of the invention are stretched, for example at a draw ratio of from 1:2.5 to 1:4.5.
- the filaments or fibers may also be texturized, for example by the false-twist or stutter-box method or by texturizing in moving gas media.
- the filaments or fibers may incorporate conventional additives such as pigments, for example titanium dioxide, or light stabilizers, heat stabilizers, and stabilizers to prevent the degradation of polyether chains.
- pigments for example titanium dioxide, or light stabilizers, heat stabilizers, and stabilizers to prevent the degradation of polyether chains.
- the filaments or fibers produced by the method of the invention are distinguished by their greatly reduced tendency to build up electrostatic charges. This good antistatic behavior remains after repeated washing.
- Electrostatic build-up on textile articles may be determined by the method proposed by Heyl & Liittgens (Kunststoife, Vol. 56, 1966, p. 51).
- a suitable method as regards carpets is the stroll test (Test Method for Determining the Static Propensity of Carpets, Report American Carpet Institute, Aug. 19, 1968).
- the process of the invention is distinguished in that the yields produced in spinning and drawing are high as compared with unmodified polyamides, which means that the number of defects found in the subsequent stages of warping and knitting is low.
- the quality of the filaments is tested by the conventional technological tests on mechanical properties and dyeability.
- the values found for the filaments produced by the invention hardly differ from those provided by the corresponding unmodified polyamides. Indeed, the filaments modified by the present invention can usually by dyed deeper and more level shades a frequently desirable feature. Since the streak-free dyeing of conventional polyamides remains a problem, the above improvement as concerns dyeability is particularly advantageous.
- the filaments made in accordance with the present invention may be woven or knitted to textile articles such as underwear and shirts with advantageous results.
- the quality required in such articles is particularly high and the measures of the invention are therefore especially efiective for this application.
- Filaments made in the manner proposed by the present invention may also be used successfully in carpets, both in the form of continuous filaments and as staple fibers. A distinct improvement in the quality of the filaments is achieved as compared with prior art modifying processes for the manufacture of twophase antistatic fibers.
- a filter unit which is heated at 25 0 C. and is fitted with metal sieves of 17 mesh.
- the filtered molten mixture is extruded in four strands which are cooled in a water bath and then granulated.
- the granules are dried to a water content of less than 0.1% and then melt-spun to filaments 144 f 10 dtex. using an extruder provided with a sintered metal filter having an average pore width of about 18
- the residence time of the molten mixture in the spinning system is about 15 minutes.
- the resulting filaments are then stretched at a draw ratio of 113.28 to form filaments 44 f 10 dtex.
- the drawing yield is 96% based on cops weighing 1 kg.
- the ethoxylated polycaprolactam is present in the filaments as a separate phase in the form of very small rods having a diameter of not more than 0.1 4.
- knitted material made from the filaments of the invention and which has been washed five times has a field strength of only 60 volts/ cm. when measured at 50% relative humidity after being rubbed for 4 minutes against a knitted fabric of unmodified polycaprolactam.
- Unmodified polycaprolactam in the form of knitted fabric which has been washed five times shows a field of strength of 2,400 volts/cm. when measured under similar conditions.
- Knitted fabric made from the filaments of the invention shows very uniform affinity for acid dyes as well as disperse dyes and also shows a distinctly higher color yield than unmodified polycaprolactam material.
- a process for the manufacture of antistatic polyamide filaments which comprises: forming a molten mixture of (a) a. filament-forming synthetic linear aliphatic polyamide having recurring amide groups in the backbone and having a relative viscosity in the range of 1.5 to 2.9, measured as a 1% w./w. solution in 98% H 80 at 20 C.,
- an alkoxylated polyamide manufactured by reaction of a polyamide selected from the group consisting of the polycondensates of lactams of 4 to 12 carbon atoms and polycondensates of the salts of diamines and dicarboxylic acids of 4 to 12 carbon atoms with a 1,2-alkylene oxide in a weight ratio of from 1:2 to 1:5 and to provide a total molecular weight of 10,000 to 80,000,
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2146885A DE2146885B2 (de) | 1971-09-20 | 1971-09-20 | Verfahren zum Herstellen von Fäden oder Fasern aus Polyamiden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3839496A true US3839496A (en) | 1974-10-01 |
Family
ID=5820059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00290321A Expired - Lifetime US3839496A (en) | 1971-09-20 | 1972-09-19 | Manufacture of filaments or fibers of polyamides |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3839496A (fr) |
| BE (1) | BE789019A (fr) |
| CH (1) | CH530480A (fr) |
| DE (1) | DE2146885B2 (fr) |
| GB (1) | GB1394835A (fr) |
| IT (1) | IT963885B (fr) |
| NL (1) | NL7212728A (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932340A (en) * | 1973-08-21 | 1976-01-13 | Daicel Ltd. | Nylon coating composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2217527C3 (de) * | 1972-04-12 | 1980-02-14 | Basf Ag, 6700 Ludwigshafen | Aus der Schmelze geformte, ein Antistatikum enthaltende Fäden oder Fasern aus Polyamiden sowie ein Verfahren zu deren Herstellung |
-
0
- BE BE789019D patent/BE789019A/fr unknown
-
1971
- 1971-09-20 DE DE2146885A patent/DE2146885B2/de not_active Ceased
-
1972
- 1972-08-10 IT IT28069/72A patent/IT963885B/it active
- 1972-09-04 CH CH1299772A patent/CH530480A/de not_active IP Right Cessation
- 1972-09-19 GB GB4325872A patent/GB1394835A/en not_active Expired
- 1972-09-19 US US00290321A patent/US3839496A/en not_active Expired - Lifetime
- 1972-09-20 NL NL7212728A patent/NL7212728A/xx not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932340A (en) * | 1973-08-21 | 1976-01-13 | Daicel Ltd. | Nylon coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2146885B2 (de) | 1974-01-17 |
| DE2146885A1 (de) | 1973-03-29 |
| GB1394835A (en) | 1975-05-21 |
| BE789019A (fr) | 1973-03-20 |
| NL7212728A (fr) | 1973-03-22 |
| IT963885B (it) | 1974-01-21 |
| CH530480A (de) | 1972-11-15 |
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