CN103204989B - Method for preparing nylon 6 for fibers from hindered amine prepolymerization unit - Google Patents
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Abstract
The invention relates to a method for preparing nylon 6 for fibers from a hindered amine prepolymerization unit. The nylon 6 for fibers is formed by polymerizing caprolactam and the hindered amine prepolymerization unit in the mass ratio of 1000:(0.5-10). The hindered amine prepolymerization unit is generated by pre-condensing a piperidine derivative with a steric-hinerance effect and 6-aminocaproic acid in the presence of a catalyst, wherein the molar ratio of the piperidine derivative with the steric-hinerance effect to 6-aminocaproic acid to the catalyst is equal to 2:1:(0.1-0.3); the reaction temperature is 125-270 DEG C; and the reaction time lasts for 0.5-20 hours. By the method, the problems of nylon fiber yellowing and unstable quality can be effectively solved, and the obtained anti-yellowing nylon 6 for fibers is uniform in molecular weight distribution, good in viscosity stability, free of oxidization and ageing, and suitable for processing high-quality nylon fibers.
Description
Technical field
The present invention relates to a kind of preparation method of fiber nylon 6, particularly relate to a kind of by the method for hindered amine pre-polymerization unit style for fiber nylon 6.
Background technology
Along with the continuous expansion in China's tynex market, particularly by the promotion that superfine denier fiber demand increases rapidly, to the production capacity of polymeric amide and the quality of synthesis, especially polyamide molecular weight distribution is had higher requirement.
Yellow is the important technical problem of tynex one of existing in manufacture and usage process, traces it to its cause and mainly contains following influence factor: light, heat cause that polymeric amide is aging, oxidation, cause chain rupture to be decomposed, thus cause yellowing; Oxynitrides in air causes the amino group of polymeric amide, generates yellow substance, causes yellowing; Yellowing is caused under meta-alkalescence condition.
In order to solve the problems of the technologies described above, mainly take following measures in practice at present: in order to avoid alkaline condition, adopt citric acid as anti-yellow treatment agent; Generating nitro-compound to prevent the oxynitrides in air from causing the amino group of polymeric amide, being combined by the positively charged ion of phenol xanthochromia agent on polymeric amide, close its cation group, prevent the yellow substance precipitation generated; In order to suppress photooxidation droping to react, adopting and adding hindered amine as the method for photostabilizer, suppressing photooxidation droping to react by catching the number of ways such as the energy of free radical, hydroperoxide decomposition and transmission excited state molecule.
Chinese invention patent ZL200510122192.4 discloses nylon 6/ poly methylene imine molecular composite material and preparation method thereof.This inventive features for this matrix material be adopt para-amino benzoic acid phenyl ester or Toluene-2,4-diisocyanate, 4-vulcabond carries out end-blocking to poly methylene imine and is prepared into macromole activator, then cause ε-caprolactam anionic ring-opening polymerization, obtain triblock copolymer and nylon 6/ poly methylene imine molecular composite material.This molecular composite material is due to the employing of block copolymerization technology, improve the consistency of poly methylene imine and nylon-6 matrix body, improve the dispersion effect of poly methylene imine in nylon 6, material mechanical performance is greatly improved, and when tensile strength 85MPa, shock strength is 26.21kJ/m2.
Chinese invention patent application 201110114496.1 discloses a kind of nylon 6 slices for superfine sea-island fibers and manufacture method thereof.This invention is polymerized by hexanolactam and auxiliary agent, and the ratio of hexanolactam and auxiliary agent is 100:7-10, and described auxiliary agent is obtained in 3-6:40-60:3-6:10-40 ratio by binary acids end-capping reagent, water, amine end-capping reagent, isophthaloyl piperylhydrazine.
Chinese invention patent ZL200410011153.2 discloses a kind of high impact strength nylon alloy and preparation method thereof.Nylon alloy composition described in this invention has nylon resin 60-85 weight part, Polyurethane Thermoplastic Elastomer 15-40 weight part, polymeric plasticizer 0.5-5 weight part.Preparation method, after each component being mixed in proportion, adds in Twin screw extruder; Controlling screw zones temperature is 150-250 DEG C, controls screw speed within the scope of 10-100rpm; Said polymeric plasticizer is the multipolymer that the polyamide 1010 of hydroxy-end capped polyethylene glycol adipate and carboxy blocking reacts obtained.
Chinese invention patent ZL03115279.1 discloses the preparation method of ultra-tough, high visocity nylon 6 resin.The method comprises the following steps: (1) carries out vacuum hydro-extraction to hexanolactam and catalyzer, obtain the caprolactam monomer that water content is less than 300ppm, (2) promotor is added, after mixing, open loop pre-polymerization is carried out to caprolactam monomer, obtain prepolymer, (3) carry out mass polymerization to prepolymer, after polymerization completely, add end-blocking auxiliary agent, described mass polymerization carries out continuous bulk polymerization with successive reaction extrusion molding to prepolymer.
Chinese invention patent ZL200810020776.4 discloses a kind of preparation method of original position PI modified nylon composite material, step is: the first step: prepare polyimide preformed polymer, dianhydride/the diamine monomer with ehter bond group is dissolved in polar solvent by 1-1.6:1 in molar ratio, and at room temperature stirring reaction, then solvent refluxing cyclisation is added, moisture in removing system, add isocyanic ester, be obtained by reacting isocyanate-terminated PI macromole, add hexanolactam blocked isocyanate group, add methanol extraction and go out PI, washing and drying is for subsequent use afterwards, the amount accounting for caprolactam monomer weight percent 5%-15% by PI adds in hexanolactam melt, maintenance system viscosity 0.02-1Pas, second step: laid in a mold by carbon fiber by 50%-85% volume fraction, preheating, by NaOH, primary antioxidant, auxiliary antioxidant in proportion, injects mould situ polyreaction after mixing obtain FRP sheet material at 90 DEG C-120 DEG C with the performed polymer of the first step manufacture.
Chinese invention patent application 201210091705.X discloses a kind of high temperature resistant nylon and has the nylon composite materials of good fracture toughness property.This high temperature resistant nylon is prepared by 100 parts of aromatic dicarboxylic acids, 100-102 part aliphatie diamine, 2-4 part end-capping reagent and 1-2 part phosphorus-containing catalyst; Aromatic dicarboxylic acid is wherein made up of the terephthalic acid of 80-95% and the naphthalic acid of 5-20%; The nylon composite materials of this invention is prepared by 70-85 part high temperature resistant nylon, 15-25 part ethylene-octene copolymer and 0.5-13 part auxiliary agent.This invention by the proportion optimization of phthalic acid and naphthalic acid in nylon building-up process and the formulation content of modified nylon process elastomer preferred, prepare a kind of large modified nylon materials of initial impact energy of rupture, effectively can keep long-term operational characteristics and the life-span of material.
Chinese invention patent application 201010564494.8 discloses a kind of high temperature resistant semi-aromatic nylon and preparation method thereof, by 75-95 part nylon salt, 0.2-0.8 part end-capping reagent, 0.1-0.6 part catalyzer, 0.5-1 part oxidation inhibitor, 0.1-0.5 part lubricant, 30-50 part deionized water joins and stirs in polymermaking autoclave, the high temperature resistant nylon prepolymer synthesized in high-pressure stirring reactor, this prepolymer is successively passed twice through twin screw extruder melt extrude, improve devolatilization efficiency, shorten the thickening time, the smooth discharging of the high-viscosity polymer in reactor can be made simultaneously, successively adopt different extrusion temperatures, prevent the high temperature degradation of prepolymer.
Chinese invention patent application 201080035261.7 discloses a kind of nylon and method of improvement, this disclosure of an invention relates to polymkeric substance as nylon66 fiber, it has low yellowing and outstanding retention of whiteness, the increase in its middle-molecular-weihydroxyethyl be unfavorable melt extrusion and injection-molded in application.This polymkeric substance is the phosphorus compound inclusion of the amount adopting 150 to 300ppm by weight, and such as, prepared by sodium hypophosphite inclusion." end-blocking " additive added when being polymerized initial is as being selected from the existence of the additive of acetic acid, propionic acid, phenylformic acid or succsinic acid, and effectively alleviating unfavorable molecular weight increases.
Hindered amine as light stabilizer (HALS) is the additive of the very efficient polymeric material of a class, is most study in all kinds of photostabilizer, kind with fastest developing speed.20 century 70s are total to company's development by Japan three mid-term, and its light stabilising effect is 2 ~ 4 times of ordinary light stablizer, and hindered amine light stabilizer is nontoxic, raw material is easy to get, and synthesizes easy, has good consistency with many resins.
Chinese invention patent ZL201010600090.X discloses a kind of electric wire and cable jacket special-purpose nylon matrix material, the mass percentage of component contained by it and each component is as follows: nylon 8 6%-96%, primary antioxidant 0.1%-2.0%, auxiliary antioxidant 0.1%-2.0%, lubricant releasing agent 0.1-2.0%, photostabilizer 0.1-2.0%, lubricant 0.1-2.0%, nucleator 0.1-2.0%, tackifier 0.3-2.0%, described primary antioxidant selects phenolic antioxidant, described auxiliary antioxidant selects thio-2 acid dibasic acid esters or phosphorous acid ester, described lubricant releasing agent is selected from calcium stearate, described photostabilizer is selected from hindered amine light stabilizer, the two ammonium stearate of ethylene selected by described lubricant, silicone powder or its composition, nanomete talc powder selected by described nucleator, the nylon 6 containing reactive group selected by described tackifier.Formula is simple, and each component used is cheap and easy to get, and cost is lower, termite-proof, the anti-mouse of the electric wire and cable jacket prepared with this nylon composite materials, wear-resisting, corrosion-resistant.
Chinese invention patent ZL92114759.7 discloses a kind of method for making being used as the multipolymer containing hindered amine side base of photostabilizer, with 2 on the side chain of this photostabilizer, 2,6, the preparation method of the multipolymer of 6-tetramethyl-piperidyl (hindered amine) is by 4-(methyl) acryloxy-2,2,6,6-tetramethyl piperidine and α-vinyl monomer precipitate process for copolymerization by free radical and obtain.Owing to instead of aromatic organic solvent with acyclic straight or naphthenic hydrocarbon in copolymerization, not only eliminate the pollution of aromatic hydrocarbons, and simplify technique, improve yield.
Current hindered amine is usually taked to mix the method for adding at article formulations as a kind of auxiliary agent and is used.Although hindered amine has various advantages as photostabilizer in the polymer, but because its consumption is few, mixing is certainly led to uneven in melt-mixing, still free blended state is in polymkeric substance, so, dispersion must be caused uneven, and assemble and the defect of generation owing to producing this additive, and then reduce the performance of polymkeric substance and limit its light stabilization.
For the polymeric amide xanthochromia of above-mentioned existence, and the pursuit to high-quality tynex, the invention discloses a kind of by the method for hindered amine pre-polymerization unit style for fiber nylon 6, so that it is good to obtain light fastness, product molecular weight distribution is even, good quality, is conducive to the fiber nylon 6 of processing superfine dawn silk.
Summary of the invention
The object of the invention is in exploitation a kind of by the method for hindered amine pre-polymerization unit style for fiber nylon 6, solve the nylon fiber yellow and quality instability problem that exist in prior art, obtain even molecular weight distribution simultaneously, viscosity stability is good, polymeric amide can be prevented to be oxidized, aging, be suitable for the anti-yellow fiber nylon 6 processing high-quality tynex.
The present invention adopts following technical scheme:
By hindered amine pre-polymerization unit style for a method for fiber nylon 6, it is characterized in that:
(1) by the piperidine derivative of space steric effect and 6-aminocaprolc acid with mol ratio be the ratio of 2:1, add in reactor and mix, and add mol ratio for (0.1 ~ 0.3) catalyzer, under 125 DEG C ~ 270 DEG C temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour ~ 20 hours, make hindered amine pre-polymerization unit.
(2) by hexanolactam with hindered amine pre-polymerization unit with mass ratio l000:(0.5 ~ 10) ratio mix, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 250 DEG C ~ 270 DEG C, under the condition that main polymerization temperature is 230 DEG C ~ 250 DEG C, through polymerization in 2 hours ~ 17 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
The piperidine derivative of described space steric effect is 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethvl, 2,2,6, one or more mixture in 6-tetramethyl--4-piperidine alcohols and 1,2,2,6,6-pentamethyl--4-piperidine alcohols.
Described catalyzer is one or more the mixture in acetic acid, propionic acid, hydrochloric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, Zeo-karb.
The present invention compared with prior art, has significant technical progress and obvious positively effect:
1, hindered amine is the organic amine compound that a class has steric restriction.The photooxidation droping reaction of hindered amine to superpolymer and organic compound has good inhibition.Hindered amine is different from the mode of action of UV stabilizer, but suppresses photooxidation droping to react by number of ways such as the energy of catching free radical, hydroperoxide decomposition and transmission excited state molecule.The molecular weight of hindered amine initial production is little, its thermotolerance and resistance to extractibility all poor.
By itself and 6-aminocaprolc acid condensation, can by the 4-amino-2,2 of band amino, 6,6-tetramethyl piperidine or 4-amino-1,2,2,6, carboxyl condensation in 6-pentamethvl and 6-aminocaprolc acid molecule, generates amido linkage, encloses this carboxyl, obtain the amino dissociated, be conducive to follow-up polymerization process and grow to single direction; In like manner, 2,2,6,6-tetramethyl--4-piperidine alcohols or 1, carboxyl condensation in 2,2,6,6-pentamethyl--4-piperidine alcohols and 6-aminocaprolc acid molecule, generate ester bond, enclose this carboxyl, obtain the amino dissociated, be also conducive to follow-up polymerization process and grow to single direction.Therefore, the hindered amine pre-polymerization unit made, can improve the molecular weight of hindered amine, and then improve its performance.On the other hand, hindered amine pre-polymerization unit is added in hexanolactam reaction system, as the center of chain reaction, in series reaction process, the homogeneity of the molecular weight distribution improving polymeric amide can be conducive to.
2, owing to all connecting hindered amine end group on the termination of each nylon 6 molecular chain, therefore, the problem of the issuable two-way extension of condensation polymerization process can be limited, the polymerization degree of product can be designed according to feed ratio.
3, according to the nylon 6 of the present invention's synthesis, owing to the termination of each molecular chain all having connected the end group of hindered amine, therefore, its distributing homogeneity can have been improved, the ununiformity that the light that produces under admixture is stable can have been improved.
In sum, the present invention, by adopting above production technique, effectively can solve nylon fiber yellow and quality instability problem, obtain even molecular weight distribution, viscosity stability is good, nylon can be prevented to be oxidized, aging, is suitable for the anti-yellow fiber nylon 6 processing high-quality nylon fiber.
Specific embodiments
Below in conjunction with embodiment, the present invention is further described:
Embodiment 1
(1) by 2 parts of 4-amino-2,2,6,6-tetramethyl piperidine adds in reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.3 part of acetic acid, under 125 DEG C of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 20 hours, make hindered amine pre-polymerization unit.
(2) hexanolactam is mixed with the ratio of mass ratio l000:3 with hindered amine pre-polymerization unit, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 250 DEG C, under the condition of main polymerization temperature 230 DEG C, through polymerization in 5 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
Embodiment 2
(1) by 2 parts of 4-amino-2,2,6,6-tetramethyl piperidine adds in reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.1 part of sulfuric acid, under 150 DEG C of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 1 hour, make hindered amine pre-polymerization unit.
(2) hexanolactam is mixed with the ratio of mass ratio l000:10 with hindered amine pre-polymerization unit, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 250 DEG C, under the condition of main polymerization temperature 250 DEG C, through polymerization in 2 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
Embodiment 3
(1) just 2 part 2,2,6,6-tetramethyl--4-piperidine alcohols adds in reactor with 1 part of 6-aminocaprolc acid and mixes, and add 0.1 part of Phenylsulfonic acid, under 270 DEG C of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour, make hindered amine pre-polymerization unit.
(2) hexanolactam is mixed with the ratio of mass ratio l000:0.5 with hindered amine pre-polymerization unit, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 270 DEG C, under main polymerization temperature 230 DEG C of conditions, through polymerization in 14 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
Embodiment 4
(1) by 2 part 1,2,2,6,6-pentamethyl--4-piperidine alcohols adds in reactor with 1 part of 6-aminocaprolc acid and mixes, and adds 0.3 part of Zeo-karb, under 125 DEG C of temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 15 hours, make hindered amine pre-polymerization unit.
(2) hexanolactam is mixed with the ratio of mass ratio l000:1 with hindered amine pre-polymerization unit, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 270 DEG C, under main polymerization temperature 230 DEG C of conditions, through polymerization in 17 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
Claims (4)
1. one kind by hindered amine pre-polymerization unit style for the method for fiber with nylon 6, it is characterized in that: described is be polymerized by hexanolactam and hindered amine pre-polymerization unit by hindered amine pre-polymerization unit style for fiber nylon 6, the mass ratio of hexanolactam and hindered amine pre-polymerization unit is l000:(0.5 ~ 10)
Described hindered amine pre-polymerization unit is by having the piperidine derivative of space steric effect and 6-aminocaprolc acid under catalyzer exists, generate through precondensation, the piperidine derivative of described space steric effect: 6-aminocaprolc acid: the mol ratio of catalyzer is 2:1:(0.1 ~ 0.3); Temperature of reaction is 125 DEG C ~ 270 DEG C; Reaction times is 0.5 hour ~ 20 hours.
2. according to claim 1 by hindered amine pre-polymerization unit style for the method for fiber nylon 6, it is characterized in that, the piperidine derivative of described space steric effect is 4-amino-2,2,6,6-tetramethyl piperidine, 4-amino-1,2,2,6,6-pentamethvl, 2,2,6,6-tetramethyl--4-piperidine alcohols and 1,2,2, one or more mixture in 6,6-pentamethyl--4-piperidine alcohols.
3. according to claim 1 by the method for hindered amine pre-polymerization unit style for fiber nylon 6, it is characterized in that, described catalyzer is one or more the mixture in acetic acid, propionic acid, hydrochloric acid, sulfuric acid, Phenylsulfonic acid, tosic acid, methylsulfonic acid, Zeo-karb.
4. according to claim 1 by hindered amine pre-polymerization unit style for the method for fiber nylon 6, it is characterized in that, successively through following steps:
(1) by the piperidine derivative of space steric effect and 6-aminocaprolc acid with mol ratio be the ratio of 2:1, add in reactor and mix, and add mol ratio for (0.1 ~ 0.3) catalyzer, under 125 DEG C ~ 270 DEG C temperature of reaction, make the piperidine derivative condensation of 6-aminocaprolc acid and space steric effect, after reacting 0.5 hour ~ 20 hours, make hindered amine pre-polymerization unit;
(2) by hexanolactam with hindered amine pre-polymerization unit with mass ratio l000:(0.5 ~ 10) ratio mix, conveying is measured by volume pump, after static mixer mixing, add pressurization prepolymerization-normal pressure main polymerization successive polymerization reactor and carry out polyreaction: prepolymerization temperature 250 DEG C ~ 270 DEG C, under the condition that main polymerization temperature is 230 DEG C ~ 250 DEG C, through polymerization in 2 hours ~ 17 hours, obtain the described fiber Nylon 6 standby by hindered amine pre-polymerization unit style, then polymer melt extrudes tape continuously through melt metering pump, through pelletizing, continuous extraction, after nitrogen successive drying, obtain anti-yellow fiber nylon 6 slice.
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| DE102018220616B3 (en) * | 2018-11-20 | 2019-05-29 | Thyssenkrupp Ag | Process for the preparation of polyamide 6 |
| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN114349957B (en) * | 2020-10-13 | 2023-10-03 | 华峰集团有限公司 | Preparation method of weather-resistant polyamide resin |
| CN115125727A (en) * | 2022-07-25 | 2022-09-30 | 南通大学 | Yellowing-resistant fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618909A (en) * | 1995-07-27 | 1997-04-08 | Alliedsignal Inc. | Light stabilized polyamide substrate and process for making |
| JP2001261819A (en) * | 2000-03-14 | 2001-09-26 | Unitika Ltd | Nylon 6 or copolymer thereof, and process for preparation thereof |
| CN1537139A (en) * | 2001-06-14 | 2004-10-13 | Light-stabilized polymers cmprising light-stabilizing moieties, articles therefrom and method of making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618909A (en) * | 1995-07-27 | 1997-04-08 | Alliedsignal Inc. | Light stabilized polyamide substrate and process for making |
| JP2001261819A (en) * | 2000-03-14 | 2001-09-26 | Unitika Ltd | Nylon 6 or copolymer thereof, and process for preparation thereof |
| CN1537139A (en) * | 2001-06-14 | 2004-10-13 | Light-stabilized polymers cmprising light-stabilizing moieties, articles therefrom and method of making the same |
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