CN108560074A - A kind of preparation method of ageing-resistant polyamide fibre - Google Patents
A kind of preparation method of ageing-resistant polyamide fibre Download PDFInfo
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- CN108560074A CN108560074A CN201810509957.7A CN201810509957A CN108560074A CN 108560074 A CN108560074 A CN 108560074A CN 201810509957 A CN201810509957 A CN 201810509957A CN 108560074 A CN108560074 A CN 108560074A
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- acid
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- proline
- ageing
- polyamide fibre
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 62
- 229920002647 polyamide Polymers 0.000 title claims abstract description 62
- 239000000835 fiber Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000032683 aging Effects 0.000 title claims abstract description 23
- 239000004970 Chain extender Substances 0.000 claims abstract description 56
- 239000002105 nanoparticle Substances 0.000 claims abstract description 50
- 238000009987 spinning Methods 0.000 claims abstract description 49
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 238000002074 melt spinning Methods 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 230000006837 decompression Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000004677 Nylon Substances 0.000 claims description 18
- 229920001778 nylon Polymers 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000502 dialysis Methods 0.000 claims description 14
- 230000004224 protection Effects 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 15
- 230000000996 additive effect Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 10
- 230000000379 polymerizing effect Effects 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- KJBJPJYEPGYTJX-ZBRNBAAYSA-N (2s)-2-aminobutanedioic acid;(2s)-pyrrolidine-2-carboxylic acid Chemical compound OC(=O)[C@@H]1CCCN1.OC(=O)[C@@H](N)CC(O)=O KJBJPJYEPGYTJX-ZBRNBAAYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 229940024606 amino acid Drugs 0.000 description 9
- 235000001014 amino acid Nutrition 0.000 description 9
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 235000003704 aspartic acid Nutrition 0.000 description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 6
- 229960002989 glutamic acid Drugs 0.000 description 5
- 239000004220 glutamic acid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 241000432767 Asparagus setaceus Species 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 150000001279 adipic acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000013930 proline Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 150000003442 suberic acids Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000002268 wool Anatomy 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to fibers to synthesize field, discloses a kind of preparation method of ageing-resistant polyamide fibre, step is：A) it polymerize：There are aspartic acid proline glutamic nano-particle, antioxidant, anti ultraviolet agent and the water of chain extender to be uniformly mixed caprolactam, inorganic acid catalyst, binary acid, load, 170 180 DEG C of 30 50min of pre-polymerization are first heated to, 230 250 DEG C of 3 5h of reaction are then heated to；The water in system is taken away in decompression, waits for that product is in sticky shape postcooling, slices of caprone is made after purified, slice, drying；B) melt spinning；C) hot-stretch；D) boundling oils；E) it is wound into cylinder.The method of the present invention just adds function additive in polymerizing polyamide in advance, and the compatibility of function additive and polyamide substrate is good, is influenced on the spinnability of spinning solution smaller, the processing parameter setting of spinning process is required more loose, controllability is strong.
Description
Technical field
The present invention relates to fiber synthesis field more particularly to a kind of preparation methods of ageing-resistant polyamide fibre.
Background technology
Nylon fibre can be divided into two major classes：One kind is the PA 66 obtained by diamines and diacid polycondensation, this kind of
The relative molecular weight of polyamide fibre is generally 17000-23000.It is different with the carbon atom number of binary acid according to diamine used, it can obtain
To different polyamide fibre products, and can be distinguished by being added in the number after polyamide fibre, wherein last digit is the carbon atom number of diamine,
Latter number is the carbon atom number of binary acid.Such as polyamide fibre 66, illustrate that it is made by hexamethylene diamine and adipic acid polycondensation；Polyamide fibre
610, illustrate that it is made by hexamethylene diamine and decanedioic acid.It is another kind of to be obtained by caprolactam polycondensation or ring-opening polymerisation.
The most prominent advantage of polyamide fibre is that wearability is higher than other all fibres, 10 times higher than cotton wearability, higher than wool
20 times, some polyamide fibres are slightly entered in blended fabric, are greatly improved its wearability；When being stretched to 3-6%, elastic recovery rate
Up to 100%；Foldings up to ten thousand time are amenable to scratch and not broken.
But simultaneously the shortcomings that polyamide fibre it is also obvious that its heat resistance and light resistance are poor, under high temperature or long-time illumination,
Amido bond on polyamide molecule is easily broken off so that and strand shortens, and molecular weight reduces, so that polyamide fibre is easy aging,
Seriously affect fibre strength.
In order to solve the above-mentioned technical problem, people add all kinds of antioxidants in polyamide fibre melt spinning, UV resistance agent, expand
Chain agent etc..But since the dispersibility of above-mentioned function additive and polyamide, compatibility are generally poor, above-mentioned substance can not be short
In the case of being fully fully compatible with spinning melt in time, the spinnability of spinning solution can be influenced by adding a large amount of function additive,
To influence the quality of polyamide fibre product again, it is therefore necessary to strictly control technological parameter in spinning process to solve above-mentioned technology
Problem.
Invention content
In order to solve the above technical problem, the present invention provides a kind of preparation methods of ageing-resistant polyamide fibre.The method of the present invention
Just add function additive in advance in polymerizing polyamide, the time of fusion of function additive and polyamide substrate is long, and compatibility is more preferable,
Therefore smaller on the influence of the spinnability of spinning solution, more loose for the processing parameter setting requirement of spinning process, controllability is strong.
In spinning technique the dispersibility and compatibility of function additive are improved without additional step is increased.
The specific technical solution of the present invention is：A kind of preparation method of ageing-resistant polyamide fibre, steps are as follows：
A) it polymerize：Caprolactam, inorganic acid catalyst, binary acid, load are had to aspartic acid-proline-of chain extender
It is uniformly mixed in glutamic nano-particle, antioxidant, anti ultraviolet agent and water input reaction kettle, under nitrogen protection first
It is heated to 170-180 DEG C of pre-polymerization 30-50min, is then heated to 230-250 DEG C of reaction 3-5h；The water in system is taken away in decompression, waits for
Product is in sticky shape postcooling, and slices of caprone is made after purified, slice, drying, spare.
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning is carried out to spinning solution, polyamide fibre list is made
Silk.
C) hot-stretch：Hot-stretch is carried out to nylon monofilament.
D) boundling oils：To the side-blown air cooling of nylon monofilament, then boundling oils.
E) it is wound into cylinder.
Compared with the prior art adds function additive during melt spinning, process that the present invention is synthesized in materials of the synthetic fibre
In just function additive is compound in polyamide material, its advantage is that：The interaction time of function additive and polyamide material
It is long, there is the sufficient time to be merged, compatibility is more preferable, therefore smaller on the influence of the spinnability of spinning solution, for spinning process
Processing parameter setting require it is more loose, controllability is strong.In addition it is improved in spinning technique without additional step is increased
The dispersibility and compatibility of function additive.
On the other hand, include chain extender in function additive of the invention, in the prior art, the effect of chain extender be
Reaction is directly participated in polymerization process, improves the molecular weight of polyamide to improve product strength and resistance to ag(e)ing.But molecular weight
Excessively high viscosity of polyamides is excessively high, poor fluidity, is unfavorable for subsequent spinning.And in the present invention, the effect of chain extender is not
It is reaction to be participated in polymerization, but the resistance to ag(e)ing of polyamide fibre is improved after polyamide fibre product is made.When polyamide fibre encounters high temperature or length
When time illumination, a degree of degradation can occur for molecular weight, and long chain is cracked into multistage small molecule chain, at this time in high temperature
Or under illumination, chain extender can reconnect the polyamide molecule chain of cracking, prevent the aging of product.
But chain extender can react in advance in polymerizing polyamide, and if addition not only needs to change in spinning
Spinning process, it is more inconvenient, and the spinnability of spinning solution can be influenced again.Therefore it is crucial for how preventing chain extender from consuming in advance
Place.For this purpose, the present invention loads chain extender using special aspartic acid-proline-glutamicacid copolymer nano particle.It
Winter propylhomoserin-proline-glutamicacid copolymer nano particle is triblock polymer, according to aspartic acid, proline, glutamic acid three
The property of the specific collocation amino acid of kind, the polymer have following characteristic：When environment pH is less than 3 or less, three of polymer
Block is all positively charged, and due to the principle that identical charges repel each other, strand is in extended configuration；When environment pH is in 3-6, it is located at molecule
The aspartic acid segment and glutamic acid segment at chain both ends are negatively charged, and the proline positioned at interlude is still negatively charged, therefore
The block at both ends is close to interlude under electrostatic interaction, and strand is " rolling up " state at this time；When environment is neutral or alkalinity
When, the block at both ends is still negatively charged, and proline section also transitions into neutral (pH is 7 or so) or negatively charged (alkali at this time
Property), both ends block repels each other at this time, and whole strand is in extended configuration.The present invention is exactly the above-mentioned characteristic using the polymer, will
After chain extender load, adds in polymerizing polyamide, since polymerizing polyamide environment is weakly acidic (pH is about 5-6), gather at this time
Adduct molecule chain is in " rolling up " shape, and strand tightly coats chain extender, and chain extender is difficult to participate in reaction under its barrier.Work as system
After standby finished product, product is under neutral environment, and polymer molecule chain-unfolding, chain extender is released, in high temperature or solarization condition
Small chain extender, which can be reacted, reconnects the polyamide molecule segment of cracking, plays the role of ageing-resistant.
Select amino acid copolymer as carrier, it is close with polyamide property, compatibility is good, to the spinnability of spinning solution
Influence can almost be ignored.In addition, after product is made, amino acid copolymer also can slowly be sent out under long-time with polyamide
Raw crosslinking, reaction, further increase polyamide fibre intensity.
Further, step B) in, spinning temperature is 235-250 DEG C, spinning speed 4500-5000m/min.
Further, step C) in, hot-stretch draw ratio is 1.1-1.3.
Further, step D) in, side-blown wind velocity is 0.5-1.0m/s.
Further, step A) in, the inorganic acid catalyst be 80-90wt% the concentrated sulfuric acid or 80-90wt% it is dense
Phosphoric acid；The dosage of inorganic acid catalyst is the 1-3wt% of caprolactam.
Further, step A) in, the binary acid is selected from least one of adipic acid, suberic acid, Kui diacid；Binary acid
Dosage be caprolactam 3-5wt%.
Further, step A) in, the chain extender Wei bisoxazolines or polymethyl methacrylate.
Further, step A) in, it is described to load the aspartic acid-proline-glutamicacid copolymer nano for having chain extender
The preparation method of particle is：
1) by L-Aspartic acid-N- carboxyls-ring inner-acid anhydride, nickel chelate catalyst in mass ratio 100:1-3 is added to N,
In dinethylformamide, 8-16h is stirred to react at nitrogen protection, 30-35 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring
Inner-acid anhydride continues insulated and stirred and reacts 12-24h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, it is anti-to continue insulated and stirred
Answer 8-16h；It is most precipitated afterwards through n-hexane and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Its
It is sour in middle L-Aspartic acid-N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring
The molar ratio of acid anhydride is 0.8-1.2:1-1.5:0.8-1.2.
2) chain extender is added in the ethanol solution that pH is 8-14 and is stirred evenly, it is chain extender 8-12 then to add quality
Simultaneously ultrasonic disperse is uniform for aspartic acid-proline-glutamicacid copolymer nano particle again, after standing adsorption 1-3h, adjusts body
Be pH it is 4-6, most obtaining after dialysis load afterwards has aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
Amino acid classes in the amino acid copolymer of the present invention are according to polymerizing polyamide environment of the present invention and product
Use environment and targetedly strictly screen, the property of different aminoacids is different, the amino acid copolymer of not arbitrary combination
Previously described technique effect (may be completely opposite) can be played.Correspondingly, the pH of load chain extender is controlled in step 2)
It is to be designed completely according to the characteristic of amino acid copolymer of the present invention.Chain extender could be only realized within the scope of above-mentioned pH
Payload.
When preparing amino acid copolymer, need strictly to control the ratio between each block, in the case of intermediate segment is longer,
Load factor can be effectively improved.
Further, step A) in, it is described to load the aspartic acid-proline-glutamicacid copolymer nano for having chain extender
The dosage of particle is the 4-6wt% of caprolactam.
Further, step A) in, the dosage of the antioxidant is the 0.01-0.5wt% of caprolactam, the anti-purple
Outer dose of dosage is the 0.01-0.5wt% of caprolactam.
It is compared with the prior art, the beneficial effects of the invention are as follows：
1, the method for the present invention just adds function additive in polymerizing polyamide in advance, and function additive and polyamide substrate are melted
The conjunction time is long, and compatibility is more preferable, therefore smaller on the influence of the spinnability of spinning solution, and the processing parameter setting of spinning process is wanted
Ask more loose, controllability is strong.In spinning technique the dispersibility and phase of function additive are improved without additional step is increased
Capacitive.
2, contain chain extender in polyamide fibre of the invention, the polyamide molecule chain of cracking can be rebuild and be connected, effectively improved
The resistance to ag(e)ing of polyamide fibre.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1
Load has the preparation of aspartic acid-proline-glutamicacid copolymer nano particle of chain extender：
1) 100 parts of L-Aspartic acid-N- carboxyls-ring inner-acid anhydrides, 2 parts of nickel chelate catalyst are added to 80 parts of N, N- bis-
In methylformamide, 12h is stirred to react at nitrogen protection, 32 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring inner-acid anhydride, after
Continuation of insurance temperature is stirred to react 18h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 12h；Most pass through afterwards
N-hexane precipitates and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Wherein L-Aspartic acid-
The molar ratio of N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride is
1:1.3:1。
2) 10 parts of chain extenders are added in the ethanol solution that 2000 parts of pH are 12 and are stirred evenly, then add 100 parts of days
Simultaneously ultrasonic disperse is uniform for winter propylhomoserin-proline-glutamicacid copolymer nano particle, and after standing adsorption 2h, regulation system pH is 5,
Most obtaining load after dialysis afterwards has aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
The preparation of ageing-resistant polyamide fibre：
A) it polymerize：100 parts of caprolactams, the concentrated sulfuric acid of 2 parts of 85wt%, 4 parts of adipic acids, 5 parts of loads there is into poly- methyl-prop
The aspartic acid of e pioic acid methyl ester-proline-glutamicacid copolymer nano particle, 0.3 part of antioxidant, 0.02 part of anti ultraviolet agent and
It is uniformly mixed in 30 parts of water input reaction kettles, is first heated to 175 DEG C of pre-polymerization 40min under nitrogen protection, is then heated to 240 DEG C
React 4h；The water in system is taken away in decompression, waits for that product is in sticky shape postcooling, and polyamide fibre, which is made, after purified, slice, drying cuts
Piece, it is spare.
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning, spinning temperature are being carried out to spinning solution
It is 240 DEG C, spinning speed 4800m/min, nylon monofilament is made.
C) hot-stretch：Hot-stretch, draw ratio 1.2 are carried out to nylon monofilament.
D) boundling oils：To the side-blown air cooling of nylon monofilament, side-blown wind velocity is 0.8m/s, and then boundling oils.
E) it is wound into cylinder.
Embodiment 2
Load has the preparation of aspartic acid-proline-glutamicacid copolymer nano particle of chain extender：
1) 100 parts of L-Aspartic acid-N- carboxyls-ring inner-acid anhydrides, 2.5 parts of nickel chelate catalyst are added to 60 parts of N, N-
In dimethylformamide, 12h is stirred to react at nitrogen protection, 32 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring inner-acid anhydride,
Continue insulated and stirred and reacts 14h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 12h；Finally
It is precipitated through n-hexane and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Wherein L- asparagus ferns ammonia
The molar ratio of acid-N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride
It is 1:1.1:1.
2) 10 parts of chain extenders are added in the ethanol solution that 2000 parts of pH are 11 and are stirred evenly, then add 90 parts of asparagus ferns
Simultaneously ultrasonic disperse is uniform for propylhomoserin-proline-glutamicacid copolymer nano particle, and after standing adsorption 2.5h, regulation system pH is
5.5, most obtaining load after dialysis afterwards has aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
The preparation of ageing-resistant polyamide fibre：
A) it polymerize：By 100 parts of caprolactams, the concentrated phosphoric acid of 1.5 parts of 90wt%, 4.5 parts of suberic acids, 5 parts of bis- Evil of load You
The aspartic acid of oxazoline-proline-glutamicacid copolymer nano particle, 0.01 part of antioxidant, 0.5 part of anti ultraviolet agent and 35 parts
Water puts into reaction kettle and is uniformly mixed, and is first heated to 175 DEG C of pre-polymerization 45min under nitrogen protection, is then heated to 245 DEG C of reactions
4h；The water in system is taken away in decompression, waits for that product is in sticky shape postcooling, and slices of caprone is made after purified, slice, drying, standby
With.
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning, spinning temperature are being carried out to spinning solution
It is 245 DEG C, spinning speed 4600m/min, nylon monofilament is made.
C) hot-stretch：Hot-stretch, draw ratio 1.25 are carried out to nylon monofilament.
D) boundling oils：To the side-blown air cooling of nylon monofilament, side-blown wind velocity is 0.8m/s, and then boundling oils.
E) it is wound into cylinder.
Embodiment 3
Load has the preparation of aspartic acid-proline-glutamicacid copolymer nano particle of chain extender：
1) 100 parts of L-Aspartic acid-N- carboxyls-ring inner-acid anhydrides, 1 part of nickel chelate catalyst are added to 50 parts of N, N- bis-
In methylformamide, 8h is stirred to react at nitrogen protection, 30 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring inner-acid anhydride, after
Continuation of insurance temperature is stirred to react for 24 hours；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 8h；Most pass through afterwards
N-hexane precipitates and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Wherein L-Aspartic acid-
The molar ratio of N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride is
0.8:1.5:0.8。
2) 10 parts of chain extenders are added in the ethanol solution that 2000 parts of pH are 14 and are stirred evenly, then add 90 parts of asparagus ferns
Simultaneously ultrasonic disperse is uniform for propylhomoserin-proline-glutamicacid copolymer nano particle, and after standing adsorption 3h, regulation system pH is 4, most
There is aspartic acid-proline-glutamicacid copolymer nano particle of chain extender by load is obtained after dialysis.
The preparation of ageing-resistant polyamide fibre：
A) it polymerize：100 parts of caprolactams, the concentrated sulfuric acid of 1 part of 90wt%, 3 parts of Kui diacid, 4 parts of loads there is into poly- methyl-prop
The aspartic acid of e pioic acid methyl ester-proline-glutamicacid copolymer nano particle, 0.5 part of antioxidant, 0.01 part of anti ultraviolet agent and
It is uniformly mixed in 10 parts of water input reaction kettles, is first heated to 170 DEG C of pre-polymerization 50min under nitrogen protection, is then heated to 230 DEG C
React 5h；The water in system is taken away in decompression, waits for that product is in sticky shape postcooling, and polyamide fibre, which is made, after purified, slice, drying cuts
Piece, it is spare.
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning, spinning temperature are being carried out to spinning solution
It is 235 DEG C, spinning speed 4500m/min, nylon monofilament is made.
C) hot-stretch：Hot-stretch, draw ratio 1.1 are carried out to nylon monofilament.
D) boundling oils：To the side-blown air cooling of nylon monofilament, side-blown wind velocity is 0.5m/s, and then boundling oils.
E) it is wound into cylinder.
Embodiment 4
Load has the preparation of aspartic acid-proline-glutamicacid copolymer nano particle of chain extender：
1) 100 parts of L-Aspartic acid-N- carboxyls-ring inner-acid anhydrides, 3 parts of nickel chelate catalyst are added to 100 parts of N, N-
In dimethylformamide, 16h is stirred to react at nitrogen protection, 35 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring inner-acid anhydride,
Continue insulated and stirred and reacts 16h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 16h；Finally
It is precipitated through n-hexane and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Wherein L- asparagus ferns ammonia
The molar ratio of acid-N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride
It is 0.9:1:0.9.
2) 10 parts of chain extenders are added in the ethanol solution that 2000 parts of pH are 14 and are stirred evenly, then add 120 parts of days
Simultaneously ultrasonic disperse is uniform for winter propylhomoserin-proline-glutamicacid copolymer nano particle, and after standing adsorption 1-3h, regulation system pH is
6, most obtaining load after dialysis afterwards has aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
The preparation of ageing-resistant polyamide fibre：
A) it polymerize：100 parts of caprolactams, the concentrated phosphoric acid of 3 parts of 80wt%, 5 parts of adipic acids, 6 parts of loads there is into poly- methyl-prop
The aspartic acid of e pioic acid methyl ester-proline-glutamicacid copolymer nano particle, 0.3 part of antioxidant, 0.2 part of anti ultraviolet agent and
It is uniformly mixed in 50 parts of water input reaction kettles, is first heated to 180 DEG C of pre-polymerization 30min under nitrogen protection, is then heated to 250 DEG C
React 3h；The water in system is taken away in decompression, waits for that product is in sticky shape postcooling, and polyamide fibre, which is made, after purified, slice, drying cuts
Piece, it is spare.
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning, spinning temperature are being carried out to spinning solution
It is 250 DEG C, spinning speed 5000m/min, nylon monofilament is made.
C) hot-stretch：Hot-stretch, draw ratio 1.3 are carried out to nylon monofilament.
D) boundling oils：To the side-blown air cooling of nylon monofilament, side-blown wind velocity is 1.0m/s, and then boundling oils.
E) it is wound into cylinder.
Comparative example 1
Load has the preparation of Aspartic acid-Arginine-glutamic nano-particle of chain extender：
1) 100 parts of L-Aspartic acid-N- carboxyls-ring inner-acid anhydrides, 2 parts of nickel chelate catalyst are added to 80 parts of N, N- bis-
In methylformamide, 12h is stirred to react at nitrogen protection, 32 DEG C；It is subsequently added into L-arginine-N- carboxyls-ring inner-acid anhydride, after
Continuation of insurance temperature is stirred to react 18h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 12h；Most pass through afterwards
N-hexane precipitates and passes through dialysis legal system Aspartic acid-Arginine-glutamic nano-particle；Wherein L-Aspartic acid-
The molar ratio of N- carboxyls-ring inner-acid anhydride, L-arginine-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride is
1:1.3:1。
2) 10 parts of chain extenders are added in the ethanol solution that 2000 parts of pH are 12 and are stirred evenly, then add 100 parts of days
Simultaneously ultrasonic disperse is uniform for winter propylhomoserin-arginine-glutamic acid copolymer nano particle, and after standing adsorption 2h, regulation system pH is 5,
Most obtaining load after dialysis afterwards has Aspartic acid-Arginine-glutamic nano-particle of chain extender.
Chain extender release test
By the load obtained of embodiment 1 have chain extender aspartic acid-proline-glutamicacid copolymer nano particle (under
Load, which is made, with comparative example 1 in literary abbreviation nano-particle a) Aspartic acid-Arginine-glutamic nanoparticle of chain extender
(hereinafter referred nano-particle b) carries out chain extender release test to son, and method is as follows：
1g nano-particles a and 1g nano-particle b is respectively divided into the second for the 80wt% that three groups are put into 100mL by pH environment
In alcoholic solution, chain extender release rate is detected at a temperature of 25 DEG C.
First group, adjust after ethanol solution pH is 5,60min, the chain extender release rate of nano-particle a be 0.5-1.5% it
Between, the chain extender release rate of nano-particle b is between 0.5-1%；
Second group, adjust after ethanol solution pH is 7,60min, the chain extender release rate of nano-particle a be 40-50% it
Between, the chain extender release rate of nano-particle b is between 1-2%；
Third group is adjusted after ethanol solution pH is 12,60min, the chain extender release rate of nano-particle a be 50-60% it
Between, the chain extender release rate of nano-particle b is between 35-45%.
From the foregoing, it will be observed that the nano-particle b of comparative example 1 can not almost discharge chain extender under neutral environment, it must be in pH
It could be discharged in the case of more than 11, therefore not be suitable for the present invention.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (10)
1. a kind of preparation method of ageing-resistant polyamide fibre, it is characterised in that steps are as follows：
A) it polymerize：Caprolactam, inorganic acid catalyst, binary acid, load are had to aspartic acid-proline-paddy ammonia of chain extender
It is uniformly mixed in acid copolymer nano-particle, antioxidant, anti ultraviolet agent and water input reaction kettle, first heats under nitrogen protection
To 170-180 DEG C of pre-polymerization 30-50min, it is then heated to 230-250 DEG C of reaction 3-5h；The water in system is taken away in decompression, waits for product
In sticky shape postcooling, slices of caprone is made after purified, slice, drying, it is spare；
B) melt spinning：Slices of caprone is heated and is melted, spinning solution is made；Spinning is carried out to spinning solution, nylon monofilament is made；
C) hot-stretch：Hot-stretch is carried out to nylon monofilament；
D) boundling oils：To the side-blown air cooling of nylon monofilament, then boundling oils；
E) it is wound into cylinder.
2. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step B) in, spinning temperature
It is 235-250 DEG C, spinning speed 4500-5000m/min.
3. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step C) in, hot-stretch is led
It stretches than for 1.1-1.3.
4. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step D) in, side-blown wind speed
Degree is 0.5-1.0m/s.
5. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step A) in, it is described inorganic
Acid catalyst is the concentrated sulfuric acid of 80-90wt% or the concentrated phosphoric acid of 80-90wt%；The dosage of inorganic acid catalyst is caprolactam
1-3wt%.
6. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step A) in, the binary
Acid is selected from least one of adipic acid, suberic acid, Kui diacid；The dosage of binary acid is the 3-5wt% of caprolactam.
7. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step A) in, the chain extension
Agent Wei bisoxazolines or polymethyl methacrylate.
8. a kind of preparation method of ageing-resistant polyamide fibre as claimed in claim 1 or 7, which is characterized in that step A) in, it is described negative
The preparation method for being loaded with aspartic acid-proline-glutamicacid copolymer nano particle of chain extender is：
1) by L-Aspartic acid-N- carboxyls-ring inner-acid anhydride, nickel chelate catalyst in mass ratio 100:1-3 is added to N, N- bis-
In methylformamide, 8-16h is stirred to react at nitrogen protection, 30-35 DEG C；It is subsequently added into L-PROLINE-N- carboxyls-ring sour
Acid anhydride continues insulated and stirred and reacts 12-24h；Then Pidolidone-N- carboxyls-ring inner-acid anhydride is added, continues insulated and stirred and reacts 8-
16h；It is most precipitated afterwards through n-hexane and passes through dialysis legal system aspartic acid-proline-glutamicacid copolymer nano particle；Wherein L-
Aspartic acid-N- carboxyls-ring inner-acid anhydride, L-PROLINE-N- carboxyls-ring inner-acid anhydride and Pidolidone-N- carboxyls-ring inner-acid anhydride
Molar ratio is 0.8-1.2:1-1.5:0.8-1.2；
2) chain extender is added in the ethanol solution that pH is 8-14 and is stirred evenly, it is 8-12 times of chain extender then to add quality
Simultaneously ultrasonic disperse is uniform for aspartic acid-proline-glutamicacid copolymer nano particle, after standing adsorption 1-3h, regulation system pH
For 4-6, most obtaining load after dialysis afterwards has aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
9. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step A) in, the load
It is the 4-6wt% of caprolactam to have the dosage of aspartic acid-proline-glutamicacid copolymer nano particle of chain extender.
10. a kind of preparation method of ageing-resistant polyamide fibre as described in claim 1, which is characterized in that step A) in, the antioxygen
The dosage of agent is the 0.01-0.5wt% of caprolactam, and the dosage of the anti ultraviolet agent is the 0.01- of caprolactam
0.5wt%.
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| CN111732845A (en) * | 2020-06-12 | 2020-10-02 | 福建通海镍业科技有限公司 | Self-repairing anticorrosive coating for waste gas recovery pipeline |
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| CN105669969A (en) * | 2016-02-01 | 2016-06-15 | 东华大学 | Nylon 6 polymerization method and direct spinning method of melt of polymer obtained with nylon 6 polymerization method |
| CN106400156A (en) * | 2016-08-31 | 2017-02-15 | 义乌华鼎锦纶股份有限公司 | Method for preparing high-tenacity low-elongation polyamide 6 fiber |
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| US7736702B1 (en) * | 2009-02-19 | 2010-06-15 | Milliken & Company | Method of making a coated airbag |
| CN101787120A (en) * | 2010-03-04 | 2010-07-28 | 中国科学院宁波材料技术与工程研究所 | Triblock polyamino acid and hydrogel thereof |
| CN105669969A (en) * | 2016-02-01 | 2016-06-15 | 东华大学 | Nylon 6 polymerization method and direct spinning method of melt of polymer obtained with nylon 6 polymerization method |
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