CN118007276A - Bio-based polyamide carpet yarn and preparation method thereof - Google Patents
Bio-based polyamide carpet yarn and preparation method thereof Download PDFInfo
- Publication number
- CN118007276A CN118007276A CN202311845228.6A CN202311845228A CN118007276A CN 118007276 A CN118007276 A CN 118007276A CN 202311845228 A CN202311845228 A CN 202311845228A CN 118007276 A CN118007276 A CN 118007276A
- Authority
- CN
- China
- Prior art keywords
- polyamide
- bio
- carpet yarn
- heating
- tert
- 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.)
- Pending
Links
- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title description 7
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 55
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 239000006224 matting agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 37
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- 238000007664 blowing Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- 239000001361 adipic acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000004804 winding Methods 0.000 claims description 9
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001055 blue pigment Substances 0.000 claims description 4
- 239000001054 red pigment Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004595 color masterbatch Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 abstract description 25
- 229920002647 polyamide Polymers 0.000 abstract description 25
- 238000004043 dyeing Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000155 melt Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the technical field of polyamide products, and discloses a bio-based polyamide carpet yarn which comprises the following components in parts by weight: 5-20 parts of bio-based polyamide 56, 70-85 parts of polyamide 6, 10-15 parts of bio-based polyamide 56/polyamide 6 copolymer and additives, wherein the additives are selected from one or more of antioxidants, toners or matting agents, the antioxidants are 0.5-1.5 parts, the toners are 0.5-1 part, and the matting agents are 2-5 parts. The invention adopts the biological-based PA56 and the traditional polyamide 6 to be matched for producing the carpet yarn, and the obtained polyamide carpet yarn has good performance indexes, avoids the problem of price fluctuation caused by the carpet yarn manufactured by the biological-based PA56, and improves the performances of strength, dyeing and the like of the processed polymer material.
Description
Technical Field
The invention belongs to the technical field of polyamide products, and relates to a bio-based polyamide carpet yarn and a preparation method thereof.
Background
Polyamide (PA), commonly known as nylon, is a generic name of high polymers containing amide groups in the main chain repeat units of macromolecules, has good comprehensive properties, higher specific strength than metals, good mechanical properties, heat resistance, abrasion resistance, chemical resistance, flame retardance and self-lubricating property, is easy to process, has low friction factor, is suitable for filling reinforcing modification of glass fibers and other materials, and is widely applied to the aspects of electronics, electric parts, automobile parts, office supplies, household supplies and the like. The raw materials of the traditional polyamide production process are petroleum, and the polymerization is carried out by the polycondensation of diacid/diamine monomers and the ring-opening polymerization of amino acid polycondensation/lactam monomers. However, with the consumption of fossil energy and the enhancement of sustainable development concept, the development and application of biomass environment-friendly raw materials are hot spots of current research.
The bio-based poly (hexamethylene adipamide) (PA 56) is formed by condensing 1, 5-pentanediamine instead of hexanediamine and adipic acid, has excellent fluffiness, wear resistance, rebound resilience and flame retardance, and is an ideal raw material for high-end commercial carpets and household carpets. The biobased polyamide 56 has low monomer content and is not easy to generate gel after high-temperature melting, so that various polyamide 56 fibers can be prepared by adopting a melt direct spinning process. However, the application requirement of the bio-based PA56 on various polyamide products such as civil filaments, industrial filaments, short fibers, monofilaments and the like makes the price of carpet filaments produced by adopting pure bio-based PA56 easily fluctuated by the supply and demand of biological raw materials, and the production cost is not easy to control. Therefore, developing biobased PA56 to be used in combination with conventional polyamide 6, polyamide 66 to produce carpet filament to stabilize the product price is a highly desirable problem.
Disclosure of Invention
Aiming at the technical problems, the invention provides the bio-based polyamide carpet yarn and the preparation method thereof, which adopt the bio-based PA56 and the traditional polyamide 6 to be matched for producing the carpet yarn, and the obtained polyamide carpet yarn has good performance indexes, avoids the problem of price fluctuation caused by manufacturing the carpet yarn by adopting the bio-based PA56, and improves the performances of strength, dyeing and the like of the processed polymer material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the present invention provides a biobased polyamide carpet yarn comprising the following components in parts by weight: 5 to 20 parts of bio-based polyamide 56, 70 to 85 parts of polyamide 6, 10 to 15 parts of bio-based polyamide 56/polyamide 6 copolymer and additives, wherein the additives are selected from one or more of antioxidants, toner or matting agents, the antioxidants are 0.5 to 1.5 parts, the toner is 0.5 to 1 part, and the matting agents are 2 to 5 parts.
In the technical scheme of the invention, the bio-based polyamide 56 is formed by condensing 1, 5-pentanediamine prepared by biological fermentation and adipic acid, and the content of the bio-based polyamide 56 is 35-45%. The relative viscosity of the slices of the bio-based polyamide 56 is 2.0-3.6, the amino end content is 30-65 mmol/kg, and the water content is 350-450 ppm.
The preparation method of the bio-based polyamide 56/polyamide 6 copolymer in the technical scheme of the invention comprises the following steps: adding the bio-based polyamide 56 salt and caprolactam into a reaction kettle, wherein the mass ratio of the bio-based polyamide 56 salt to the caprolactam is 1: 10-20, stirring at a speed of 80-150 r/min, replacing air in the reaction kettle with nitrogen at a flow rate of 60-120 ml/min, heating, reacting for 3h when the temperature reaches 165 ℃, then heating to 170 ℃ for 1h, heating to 175 ℃ for 15min, heating to 200 ℃ for 30min, heating to 230 ℃ for 15min, and finally heating to 270 ℃ for 1h, wherein the crystallization temperature is controlled to be 100-220 ℃, so as to obtain the bio-based polyamide 56/polyamide 6 copolymer particles.
The preparation method of the bio-based polyamide 56 salt in the technical scheme of the invention comprises the following steps: according to the mass ratio of 1:2.5 to 3.5, adding adipic acid into absolute ethyl alcohol, setting the heating temperature to 65 ℃, and dripping bio-based pentanediamine after the adipic acid is dissolved, wherein the mol ratio of the bio-based pentanediamine to the adipic acid is 1:1, fully reacting adipic acid and pentanediamine, separating out white crystals after 6-8 min of reaction, and obtaining the bio-based polyamide 56 salt after 1h of reaction, suction filtration and drying.
The antioxidant in the technical scheme of the invention is selected from N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid N-octadecyl ester, tri [2, 4-di-tert-butylphenyl ] phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, 2-methylene-bis (4-ethyl-6-tert-butylphenol), 4-metabutylidene-bis- (6-tert-butyl m-cresol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; the toner is a red, yellow, blue or black polyamide 6 color master carrier; the delustrant is selected from titanium dioxide with purity of 99.0-99.9%, and is of anatase type with particle size of 150-300 nm.
The preparation method of the red, yellow, blue or black polyamide 6 color master batch carrier in the technical scheme of the invention comprises the following steps: respectively mixing a red pigment, a blue pigment, huang Seyuan pigment and a black pigment with a polyamide 6 matrix, and placing the mixture in a double-screw extruder for melt extrusion to prepare a red, yellow, blue or black polyamide 6 color master batch carrier; the mass ratio of the red pigment to the polyamide 6 matrix is 1: (65-70), the mass ratio of the blue pigment to the polyamide 6 matrix is 1: (55-68), huang Seyuan pigment and polyamide 6 matrix with a mass ratio of 1: (55-60), the mass ratio of the black pigment to the polyamide 6 matrix is 1: (75-80). Other colors can also be adjusted by using a red, yellow, blue or black polyamide 6 color master carrier according to the requirements of customers.
In a second aspect, the present invention provides a method for preparing bio-based polyamide carpet yarn, comprising the steps of:
a1, adding the dried bio-based polyamide 56, polyamide 6, a bio-based polyamide 56/polyamide 6 copolymer and additives into a hopper, and then performing melt extrusion in a screw through a screw extruder;
a2, pressurizing the extruded melt by a pressure pump, feeding the pressurized melt into a metering pump, filtering the pressurized melt by a spinning component, and spraying the filtered melt from a spinneret plate;
A3, cooling, oiling and winding the sprayed melt filaments by blowing to obtain the bio-based polyamide carpet filaments.
In the technical scheme of the invention, the screw extruder in the step A1 comprises 5 heating areas, the heating temperatures of the first area to the fifth area are all 250-300 ℃, and the rotating speed of the screw is 50-100 r/min.
In the technical scheme of the invention, the screw extruder in the step A1 comprises 5 heating areas, and the temperatures of the 5 heating areas are specifically as follows: first zone temperature: 250-280 ℃, and the temperature of a second zone: 250-280 ℃, and the temperature of a third zone: 270-300 ℃, and the temperature of a fourth zone: 280-300 ℃, and the temperature of a fifth zone: 280-300 ℃.
In the technical scheme of the invention, the air-blowing cooling in the step A3 adopts a side-blowing cooling mode, and the winding speed is 3000-4500 m/min.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts the biological-based PA56 and the traditional PA6 to be matched for producing the carpet yarn, and the obtained polyamide carpet yarn has good performance indexes, thereby avoiding the problem of price fluctuation caused by the manufacture of the carpet yarn by adopting the biological-based PA 56.
In the bio-based PA56/6 copolymer, the addition of the bio-based PA56 breaks the regularity of the PA6 chain, reduces the number of hydrogen bonds in the copolymer, and forms holes in the polymer, thereby increasing the activity of chain segments, effectively improving the melt fluidity of the PA6, and enabling the PA6 to obtain better fluidity at the same temperature; meanwhile, by controlling the content of the PA56, the ammonia end and the carboxyl end of the PA56/6 are in a relatively balanced state, and the strength, dyeing and other performances of the polymer material after being processed can be improved.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. The test methods in the following examples are conventional methods unless otherwise specified.
The following example uses a biobased polyamide 56 having a biobased content of 40% of the biobased polyamide 56, a relative viscosity of 2.78 for the slices of the biobased polyamide 56, an amino terminated content of 45mmol/kg, a water content of 400ppm, and a melting point of 254 ℃.
Example 1
Adding 14.6kg of adipic acid into 36.5kg of absolute ethyl alcohol, setting the heating temperature to 65 ℃, after the adipic acid is dissolved, dripping 10.2kg of bio-based pentanediamine to enable the adipic acid and the pentanediamine to fully react, separating out white crystals after 8 minutes of reaction, and obtaining the bio-based polyamide 56 salt after 1 hour of reaction, suction filtration and drying.
Example 2
Adding 20kg of biobased polyamide 56 salt and 300kg of caprolactam into a reaction kettle, stirring at a speed of 90r/min, replacing air in the reaction kettle with nitrogen at a flow speed of 70ml/min, heating, reacting for 3h when the temperature reaches 165 ℃, then heating to 170 ℃ for 1h, reacting for 15min at 175 ℃, reacting for 30min at 200 ℃ and reacting for 15min at 230 ℃, heating to 270 ℃ for 1h, and controlling the temperature of condensate water to 10 ℃ and the crystallization temperature to 152 ℃ to obtain the biobased polyamide 56/polyamide 6 copolymer particles.
Comparative example 1
Adding 20 kg bio-based polyamide 56 salt and 300 kg caprolactam into a reaction kettle, stirring at a speed of 90 r/min, replacing air in the reaction kettle with nitrogen at a flow speed of 70 ml/min, heating to 270 ℃ to react 6 h, controlling the condensed water temperature to 10 ℃, and controlling the crystallization temperature to 152 ℃ to obtain the bio-based polyamide 56/polyamide 6 copolymer particles.
Comparative example 2
Adding 20 kg polyamide 56 salt and 300 kg caprolactam into a reaction kettle, stirring at a speed of 90 r/min, replacing air in the reaction kettle with nitrogen at a flow speed of 70ml/min, heating, reacting for 3h when the temperature reaches 165 ℃, then heating to 170 ℃ for 1h, reacting at 175 ℃ for 15 min, reacting at 200 ℃ for 30min, reacting at 230 ℃ for 15 min, heating to 270 ℃ for 1h, reacting at 10 ℃ with condensed water, and controlling the crystallization temperature to 152 ℃ to obtain polyamide 56/6 copolymer particles.
The performance index of the polyamide copolymer obtained in example 2 and comparative examples 1 to 2 is shown in Table 1.
TABLE 1 Performance index of different Polyamide interpolymers
As can be seen from Table 1, the performance of the biobased polyamide 56/polyamide 6 interpolymer was comparable to that of the conventional polyamide 56/6 interpolymer, but the performance of the biobased polyamide 56/polyamide 6 interpolymer obtained by the staged reaction of the present invention was improved as compared to that of the biobased polyamide 56/polyamide 6 interpolymer obtained by the conventional temperature-rising reaction.
Example 3
The bio-based polyamide carpet yarn adopting the melt extrusion method specifically comprises the following steps:
(1) Dried 5 kg biobased polyamide 56, 85 kg polyamide 6, 10 kg biobased polyamide 56/polyamide 6 interpolymer, 0.5 kg of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.5 kg red polyamide 6 masterbatch carrier, 2 kg titanium dioxide were added to a hopper and then melt extruded in a screw by a screw extruder comprising 5 heating zones at the following temperatures in sequence: 255 ℃, 268 ℃, 275 ℃, 282 ℃, 285 ℃ and the rotation speed of the screw is 80 r/min.
(2) The extruded melt enters a metering pump after being pressurized by a pressure pump, and is sprayed out of a spinneret plate after being filtered by a spinning component.
(3) The sprayed melt filament is cooled by blowing, oiled and wound to obtain the bio-based polyamide carpet filament, and the blowing cooling adopts a side blowing mode for cooling, and the winding speed is 4000m/min.
Example 4
The bio-based polyamide carpet yarn adopting the melt extrusion method specifically comprises the following steps:
(1) 15kg of dried biobased polyamide 56, 80kg of polyamide 6, 13kg of biobased polyamide 56/polyamide 6 copolymer, 1kg of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.8kg of red polyamide 6 masterbatch carrier, 3kg of titanium dioxide were added to a hopper and then melt extruded in a screw by a screw extruder comprising 5 heating zones at the following temperatures in sequence: 255 ℃, 268 ℃, 275 ℃, 282 ℃, 285 ℃ and the rotation speed of the screw is 100r/min.
(2) The extruded melt enters a metering pump after being pressurized by a pressure pump, and is sprayed out of a spinneret plate after being filtered by a spinning component.
(3) The sprayed melt filament is cooled by blowing, oiled and wound to obtain the bio-based polyamide carpet filament, and the blowing cooling adopts a side blowing mode for cooling, and the winding speed is 4500m/min.
Comparative example 3
The bio-based polyamide carpet yarn adopting the melt extrusion method specifically comprises the following steps:
(1) 5kg of dried biobased polyamide 56, 85kg of polyamide 6, 10kg of polyamide 56/6 copolymer, 0.5kg of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.5kg of red polyamide 6 masterbatch carrier and 2kg of titanium dioxide are added into a hopper and then melt extruded in a screw extruder, the screw extruder comprising 5 heating zones, the temperature of the 5 heating zones being in sequence: 255 ℃, 268 ℃, 275 ℃, 282 ℃, 285 ℃ and the rotation speed of the screw is 80r/min.
(2) The extruded melt enters a metering pump after being pressurized by a pressure pump, and is sprayed out of a spinneret plate after being filtered by a spinning component.
(3) The sprayed melt filament is cooled by blowing, oiled and wound to obtain the bio-based polyamide carpet filament, and the blowing cooling adopts a side blowing mode for cooling, and the winding speed is 4000m/min.
Comparative example 4
The method for preparing the polyamide carpet yarn by adopting the melt extrusion method specifically comprises the following steps of:
(1) 5kg of dried polyamide 56, 85kg of polyamide 6, 10kg of polyamide 56/6 copolymer, 0.5kg of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.5kg of red polyamide 6 masterbatch carrier and 2kg of titanium dioxide are added into a hopper and then melt-extruded in a screw by a screw extruder comprising 5 heating zones at the following temperatures in sequence: 255 ℃, 268 ℃,275 ℃, 282 ℃,285 ℃ and the rotation speed of the screw is 80r/min.
(2) The extruded melt enters a metering pump after being pressurized by a pressure pump, and is sprayed out of a spinneret plate after being filtered by a spinning component.
(3) The sprayed melt filament is cooled by blowing, oiled and wound to obtain the bio-based polyamide carpet filament, and the blowing cooling adopts a side blowing mode for cooling, and the winding speed is 4000m/min.
Comparative example 5
The method for preparing the polyamide carpet yarn by adopting the melt extrusion method specifically comprises the following steps of:
(1) 10kg of dried bio-based polyamide 56, 90kg of polyamide 6, 0.5kg of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.5kg of red polyamide 6 masterbatch carrier and 2kg of titanium dioxide are added into a hopper and then melt extruded in a screw by a screw extruder, wherein the screw extruder comprises 5 heating zones, and the temperatures of the 5 heating zones are as follows in sequence: 255 ℃, 268 ℃, 275 ℃, 282 ℃, 285 ℃ and the rotation speed of the screw is 80r/min.
(2) The extruded melt enters a metering pump after being pressurized by a pressure pump, and is sprayed out of a spinneret plate after being filtered by a spinning component.
(3) The sprayed melt filament is cooled by blowing, oiled and wound to obtain the bio-based polyamide carpet filament, and the blowing cooling adopts a side blowing mode for cooling, and the winding speed is 4000m/min.
The performance index of the polyamide carpet yarn obtained in examples 3 to 4 and comparative examples 3 to 4 is shown in Table 2.
TABLE 2 Performance index of polyamide carpet yarn obtained from different components
| Performance index | Comparative example 3 | Comparative example 4 | Comparative example 5 | Example 3 | Example 4 |
| Line density specification (dtex/f) | 235/36 | 235/36 | 235/36 | 235/36 | 235/36 |
| Breaking strength (MPa) | 7.39 | 7.25 | 7.32 | 7.68 | 7.75 |
| Elongation at break (%) | 17.8 | 16.9 | 17.1 | 19.4 | 20.1 |
| Dry heat shrinkage (180 ℃ C. 2 min%) | 4.3 | 4.1 | 4.2 | 4.6 | 4.7 |
| Shrinkage in boiling water (%) | 6.8 | 6.4 | 6.5 | 7.4 | 7.5 |
| Initial modulus (cN/dtex) | 35.6 | 34.7 | 34.9 | 38.5 | 39.8 |
As can be seen from Table 2, the performance of the bio-based polyamide carpet yarn obtained by adding the bio-based polyamide 56 is better than that of the conventional polyamide carpet yarn, because the bio-based PA56 is added into the bio-based PA56/6 copolymer, the regularity of the PA6 chain is destroyed, the number of hydrogen bonds in the copolymer is reduced, holes are formed in the polymer, the activity of chain segments is further improved, the melt flowability of the PA6 is effectively improved, the PA6 can obtain better flowability at the same temperature, and the processability of the carpet yarn is further improved.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and other embodiments can be easily made by those skilled in the art through substitution or modification according to the technical disclosure in the present specification, so that all changes and modifications made in the principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A biobased polyamide carpet yarn characterized by comprising the following components in parts by weight: 5-20 parts of bio-based polyamide 56, 70-85 parts of polyamide 6, 10-15 parts of bio-based polyamide 56/polyamide 6 copolymer and additives, wherein the additives are selected from one or more of antioxidants, toners or matting agents, the antioxidants are 0.5-1.5 parts, the toners are 0.5-1 part, and the matting agents are 2-5 parts.
2. The biobased polyamide carpet yarn of claim 1 wherein the biobased polyamide 56 has a relative slice viscosity of 2.0 to 3.6, an amino terminated content of 30 to 65 mmol/kg and a moisture content of 350 to 450 ppm.
3. The biobased polyamide carpet yarn of claim 1 wherein said biobased polyamide 56/polyamide 6 interpolymer is prepared by the following process: adding the bio-based polyamide 56 salt and caprolactam into a reaction kettle, wherein the mass ratio of the bio-based polyamide 56 salt to the caprolactam is 1: 10-20, wherein the stirring speed is 80-150 r/min, firstly, replacing air in a reaction kettle with nitrogen with the flow rate of 60-120 ml/min, then starting heating, reacting for 3h when the temperature reaches 165 ℃, then, heating to 170 ℃ for 1h, heating to 175 ℃ for 15min, heating to 200 ℃ for 30min, heating to 230 ℃ for 15min, heating to 270 ℃ for 1h, and controlling the crystallization temperature to 100-220 ℃ to obtain the bio-based polyamide 56/polyamide 6 copolymer particles.
4. A biobased polyamide carpet yarn according to claim 3 wherein said biobased polyamide 56 salt is prepared by the process of: according to the mass ratio of 1: 2.5-3.5 adding adipic acid into absolute ethyl alcohol, setting the heating temperature to 65 ℃, and dripping bio-based pentanediamine after the adipic acid is dissolved, wherein the molar ratio of the bio-based pentanediamine to the adipic acid is 1:1, fully reacting adipic acid and pentanediamine, separating out white crystals after reaction for 6-8 min, and carrying out suction filtration and drying after reaction 1h to obtain the bio-based polyamide 56 salt.
5. A biobased polyamide carpet yarn according to claim 1 wherein said antioxidant is selected from the group consisting of N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecanol β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, 2-methylene-bis (4-ethyl-6-tert-butylphenol), 4-metabutylidene-bis- (6-tert-butyl m-cresol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; the toner is a red, yellow, blue or black polyamide 6 color master carrier; the matting agent is selected from titanium dioxide.
6. The bio-based polyamide carpet yarn of claim 5 wherein the toner is prepared by the following process: respectively mixing a red pigment, a blue pigment, huang Seyuan pigment and a black pigment with a polyamide 6 matrix, and placing the mixture in a double-screw extruder for melt extrusion to prepare a red, yellow, blue or black polyamide 6 color master batch carrier; the mass ratio of the red pigment to the polyamide 6 matrix is 1: (65-70), the mass ratio of the blue pigment to the polyamide 6 matrix is 1: (55-68), huang Seyuan pigment and polyamide 6 matrix with a mass ratio of 1: (55-60), the mass ratio of the black pigment to the polyamide 6 matrix is 1: (75-80).
7. The method for preparing the bio-based polyamide carpet yarn according to any one of claims 1 to 6, which is characterized by comprising the following steps:
a1, adding the dried bio-based polyamide 56, polyamide 6, a bio-based polyamide 56/polyamide 6 copolymer and additives into a hopper, and then performing melt extrusion in a screw through a screw extruder;
a2, pressurizing the extruded melt by a pressure pump, feeding the pressurized melt into a metering pump, filtering the pressurized melt by a spinning component, and spraying the filtered melt from a spinneret plate;
A3, cooling, oiling and winding the sprayed melt filaments by blowing to obtain the bio-based polyamide carpet filaments.
8. The method for preparing bio-based polyamide carpet yarn according to claim 7, wherein the screw extruder in the step A1 comprises 5 heating zones, the heating temperatures of the first zone to the fifth zone are all 250-300 ℃, and the rotating speed of the screw is 50-100 r/min.
9. The method of claim 7, wherein the screw extruder in step A1 comprises 5 heating zones, and the temperature of the 5 heating zones is as follows: first zone temperature: 250-280 ℃, and the temperature of a second zone: 250-280 ℃, and the temperature of a third zone: 270-300 ℃, and the temperature of a fourth zone: 280-300 ℃, and the temperature of a fifth zone: 280-300 ℃.
10. The method for preparing the bio-based polyamide carpet yarn according to claim 7, wherein the air-blowing cooling in the step A3 adopts a side-blowing cooling mode, and the winding speed is 3000-4500 m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311845228.6A CN118007276A (en) | 2023-12-29 | 2023-12-29 | Bio-based polyamide carpet yarn and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311845228.6A CN118007276A (en) | 2023-12-29 | 2023-12-29 | Bio-based polyamide carpet yarn and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118007276A true CN118007276A (en) | 2024-05-10 |
Family
ID=90945347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311845228.6A Pending CN118007276A (en) | 2023-12-29 | 2023-12-29 | Bio-based polyamide carpet yarn and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118007276A (en) |
-
2023
- 2023-12-29 CN CN202311845228.6A patent/CN118007276A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109957856B (en) | Parallel composite fiber and preparation method thereof | |
| CN111171312B (en) | Copolyamide 56/66 polymer and preparation method and application thereof | |
| TWI580830B (en) | Polyether polyamide fiber | |
| EP0558664B1 (en) | Polyamide pigment dispersion | |
| CN102471938B (en) | Polyamide fibers comprising stainable particles and method for the production thereof | |
| CN100349951C (en) | Solid phase polymerization process for preparing ethylene telephthalate and aromatic diamine copolymer | |
| KR20020016783A (en) | Method for condensing polyamides | |
| KR20110069789A (en) | Modified polyamide, method for preparing same, and article obtained from said polyamide | |
| CN112695390A (en) | High-elongation low-modulus para-aramid fiber and preparation method thereof | |
| CN109503829B (en) | Spinning-grade polyamide 66 resin for bright profiled yarn and preparation method thereof | |
| CN103469341B (en) | A kind of production method with high HEAT SETTING efficiency polyurethaneurea elastic fiber | |
| CN102666949B (en) | Yellowing-proof polyamide fiber and producing method thereof | |
| CN103173889B (en) | Wool-like polyester staple fiber and preparation method thereof | |
| CN118007276A (en) | Bio-based polyamide carpet yarn and preparation method thereof | |
| CN100537637C (en) | Method for the production of high-molecular polyamides | |
| CN111748092B (en) | Polyester amide, preparation method thereof and product fiber thereof | |
| CN116622065A (en) | Bio-based nylon containing furan ring structure and preparation method thereof | |
| CN109734899B (en) | Copolymerization type functional nylon 6 polymer and preparation method thereof | |
| CN114045562B (en) | High-stability bio-based polyamide 56 fiber and preparation process thereof | |
| US5389327A (en) | Polyamide pigment dispersion | |
| CN111876840B (en) | Preparation method of high-fluidity polyamide 56 fiber | |
| CN110387597B (en) | High-strength nylon 6 filament based on one-step drafting process and preparation method thereof | |
| KR102303209B1 (en) | Low-melting copolyamide and PREPARATION METHOD THEREOF | |
| TWI841925B (en) | A copolymer amide resin, fiber and preparation method and application thereof | |
| JPH0593063A (en) | Production of polyamide with increased content of terminal carboxyl group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |