WO2022257462A1 - 一种聚酰胺树脂及其制备方法、组合物和纤维制品 - Google Patents

一种聚酰胺树脂及其制备方法、组合物和纤维制品 Download PDF

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Publication number
WO2022257462A1
WO2022257462A1 PCT/CN2022/071923 CN2022071923W WO2022257462A1 WO 2022257462 A1 WO2022257462 A1 WO 2022257462A1 CN 2022071923 W CN2022071923 W CN 2022071923W WO 2022257462 A1 WO2022257462 A1 WO 2022257462A1
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Prior art keywords
polyamide
acid
polyamide resin
water
fiber
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PCT/CN2022/071923
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English (en)
French (fr)
Inventor
秦兵兵
孙朝续
高源艳
刘修才
Original Assignee
上海凯赛生物技术股份有限公司
Cibt美国公司
凯赛（金乡）生物材料有限公司
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Application filed by 上海凯赛生物技术股份有限公司, Cibt美国公司, 凯赛（金乡）生物材料有限公司 filed Critical 上海凯赛生物技术股份有限公司
Priority to EP22819070.8A priority Critical patent/EP4353768A1/en
Priority to JP2023575942A priority patent/JP2024521432A/ja
Priority to US18/567,921 priority patent/US20240270906A1/en
Publication of WO2022257462A1 publication Critical patent/WO2022257462A1/zh

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    • 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C08G69/04—Preparatory processes
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • 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
    • C08G69/46—Post-polymerisation treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/34—Yarns or threads having slubs, knops, spirals, loops, tufts, or other irregular or decorative effects, i.e. effect yarns
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/04—Heat-responsive characteristics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to a polyamide resin and its preparation method, composition and fiber product.
  • Polyamides have been widely used as clothing materials, industrial materials, fibers, or general-purpose engineering plastics due to their excellent characteristics and ease of melt molding, and thus have attracted much attention.
  • Polyamide 5X is a linear long-chain macromolecule synthesized from bio-based pentamethylenediamine and a series of dibasic acids. The amide bond is easy to form a hydrogen bond. Therefore, the polyamide 5X fiber has high strength and good hygroscopicity.
  • the polymer macromolecular chain will be broken into two segments when the intrachain amylase exchange reaction occurs, or the linear low molecular weight will be dehydrated directly, resulting in low molecular weight polymerization. things.
  • water extractables are low-molecular polymers ranging from monomers to decamers, such as dimers and trimers, including linear and cyclic.
  • water extractables in the polyamide 5X melt will form "weak points" in the fibers. Under the action of external forces (such as stretching), these places are easy to break and cause difficulties in spinning. In addition, water extractables are also easy to precipitate on the surface of the silk, resulting in the increase of wool, floating filaments and broken single filaments during stretching, the decrease in the strength of the finished silk, and the low production rate.
  • one of the objectives of the present invention is to provide a polyamide resin.
  • the structural units of the polyamide include diamine structural units and dibasic acid structural units, more than 90 mol% of the dibasic acid structural units are from adipic acid, and more than 90 mol% of the dibasic amine structural units are from 1,5-pentamethylenediamine, the polyamide resin contains water extractables with a number average molecular weight of less than 2000, and the content of the water extractables in the polyamide resin is less than 0.7 wt%.
  • the content of the water extractables is less than 0.6 wt%, further less than 0.5 wt%.
  • the water extractables are mainly oligomers produced from monomers during the polymerization stage.
  • the number average molecular weight of the polyamide resin is above 28000, further 30000-45000, further 30000-40000.
  • the content (wt%) of the water extractables is within the above-defined range, the anti-yellowing performance of the obtained polyamide resin and the resin composition described below is improved.
  • the scraping cycle of the components during the spinning process is greatly increased, and the production efficiency is greatly improved.
  • the content (wt%) of the water extractables when the content (wt%) of the water extractables is within the above-defined range, there will be less broken filaments and less fluff during the spinning process, and the strength of the polyamide fiber will be high.
  • the content (wt%) of the water extractables when the content (wt%) of the water extractables is within the above-defined range, the boiling water shrinkage of the fiber is low, and the dimensional stability of the polyamide fiber is improved.
  • the content (wt%) of the water extractables when the content (wt%) of the water extractables is within the above-defined range, the unevenness of the polyamide fiber is low and the dyeing effect is good.
  • the content (wt%) of the water extractables when the content (wt%) of the water extractables is within the above-defined range, the yield of the polyamide resin spinning process is high, and the dyeing rate is high.
  • the content of water extractables in the polyamide resin is above 0.05wt%, further above 0.1wt%, further above 0.2wt%.
  • the content of water extractables is lower than the above-mentioned limited range, the performance of the polyamide fiber is reduced.
  • the content of water extractables in the polyamide resin is extracted by heating in deionized water (for example, using water at 97°C to 100°C to extract the polyamide resin for 24 hours), and the components that can be extracted into water after the extraction process account for The mass percent of the polyamide resin before treatment.
  • the water extractable content (%) (mass m 1 of polyamide resin before water extraction-mass m 2 of polyamide resin after water extraction)/mass m 1 of polyamide resin before water extraction*100%.
  • the extraction condition is, for example, to extract the polyamide resin with water at 97°C-100°C for 24 hours, and the mass ratio of the polyamide resin to water is 1:48-51, for example, 1:50.
  • test method for the content of water extractables is as follows: dry the polyamide sample in a blast oven at 130°C for 7 hours, then put it in an aluminum-plastic bag, seal it, put it in a desiccator to cool, and then weigh it accurately
  • the polyamide sample is about 2 g, and the actual mass (m 1 ) of the polyamide sample is recorded.
  • the melt is introduced into an airtight container, and after cooling, samples are taken for testing according to the above method.
  • the number average molecular weight of the water extractables is 500-2000.
  • the water extractables include one or both of the following structures:
  • n1 and n2 are respectively selected from the integers of 1 to 8, preferably, n1 and n2 are respectively selected from the integers of 1 to 6, more preferably, n1 and n2 are respectively selected from the integers of 1 to 5, further preferably, n1 is 2, 3 or 4; n2 is 2, 3, 4 or 5; m1 is 4 and m2 is 4.
  • the pentamethylenediamine in the polyamide resin may be pentamethylenediamine derived from chemical sources or biomass, and further be 1,5-pentanediamine derived from biomass.
  • more than 95 mol%, preferably more than 97 mol%, of the diamine structural units in the polyamide resin are derived from 1,5-pentanediamine.
  • the diamine structural unit in the polyamide resin also includes one or more of butanediamine, hexamethylenediamine, decanediamine, and dodecanediamine structural unit.
  • more than 95 mol%, preferably more than 97 mol%, of the dibasic acid structural units in the polyamide resin are derived from adipic acid.
  • the dibasic acid structural unit in the polyamide resin also includes succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, Alkanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, heptadecandioic acid and octadecanedioic acid, and terephthalic A structural unit of one or more of formic acid, isophthalic acid, and phthalic acid.
  • the content of the polyamide (main polymer) composed of diamine structural units and dibasic acid structural units in the polyamide resin is more than 90wt%, further more than 95wt%, further more than 95wt%. 97 wt% or more, further 99 wt% or more.
  • the diamine structural unit and the dibasic acid structural unit meet the above definition.
  • the polyamide resin contains additives.
  • the additives include, but are not limited to, any one or a combination of blocking agents, nucleating agents, antioxidants, defoamers, and flow modifiers.
  • the capping agents include lauric acid, stearic acid, benzoic acid, and acetic acid.
  • the additives include but are not limited to lauric acid, stearic acid, benzoic acid, acetic acid, sodium hypophosphite, calcium hypophosphite, phosphorous acid, silicone defoamer, caprolactam, carbon black, nano calcium carbonate, titanium dioxide, And any one or a mixture of several phthalocyanine compounds.
  • the content of additives in the polyamide resin is less than or equal to 10wt%, preferably less than or equal to 5wt%, more preferably less than or equal to 3wt%, more preferably less than or equal to 1wt%.
  • the polyamide resin is polyamide 56 resin.
  • the polyamide 56 content in the polyamide 56 resin is above 90wt%, further above 95wt%, further above 97wt%, further above 99wt%.
  • the moisture content of the polyamide resin is 200-2000 ppm, preferably 250-1200 ppm, more preferably 300-1000 ppm.
  • the content of terminal amino groups of the polyamide resin is 10-100 mol/ton, preferably 20-90 mol/ton, more preferably 30-80 mol/ton.
  • the relative viscosity of the polyamide resin is 1.8-4.0, preferably 2.2-3.5, more preferably 2.4-3.3.
  • pressures mentioned in the present invention refer to gauge pressures.
  • the second object of the present invention is to provide a method for preparing the above-mentioned polyamide resin.
  • the method includes the following steps:
  • step S1 the molar ratio of 1,5-pentanediamine and dibasic acid used in preparing the nylon salt solution is (1-1.1):1.
  • step S2 the temperature of the reaction system is 232-260° C. after the pressure holding process is completed.
  • step S2 the temperature of the reaction system after the depressurization process is 240-295°C, further 243-288°C.
  • step S2 the temperature of the reaction system after vacuuming is 250-290°C, further 252-285°C.
  • step S2 the time for maintaining the vacuum degree after vacuuming is 11-75 minutes.
  • step S3 the granulation is carried out in water, and the water temperature is 15-50°C. After strand cutting described in step S3, polyamide slices or polyamide pellets are obtained.
  • the method also includes the following steps:
  • the reactor is a reactor capable of forming a closed environment.
  • the reactor may be, for example, a continuous extraction tower or a batch reactor.
  • step S4 the method for replacing the air in the reactor is to vacuumize with a vacuum pump and then fill with an inert gas.
  • the operation of replacing the air in the reactor described above may be repeated two or more times.
  • the water is deionized water, further deionized water after oxygen removal treatment, wherein the oxygen removal treatment can be thermal oxygen removal, ultrasonic oxygen removal, vacuum oxygen removal, chemical oxygen removal, One or more combinations of analytical oxygen removal or other arbitrary oxygen removal methods; in some preferred embodiments, the content of dissolved oxygen in the deionized water after the oxygen removal treatment is less than or equal to 0.5mg/L, Further less than or equal to 0.1mg/L.
  • the mass of the deionized water is more than 1 times the mass of the polyamide pellets, further more than 2 times, for example, 1 to 12 times, 1 to 10 times, 2 to 10 times, 2 to 6 times, 1.5 times times, 2.3 times, 2.5 times, 3 times, 5 times, or 8 times.
  • the inert gas is selected from one or more of nitrogen, argon, helium, etc., and is further preferably one of high-purity nitrogen, high-purity argon, and high-purity helium or several.
  • step S4 during the air replacement operation, the vacuum is evacuated to a vacuum degree of -0.1MPa ⁇ -0.001MPa (gauge pressure), maintained for 5-20min, and then filled with an inert gas, more preferably , Repeat the air replacement operation 5 to 15 times, further 8 to 10 times.
  • the heating time is 4-50 hours, further 8-45 hours.
  • the heating temperature is 80-140°C, further 85-120°C.
  • step S5 the rinsing is performed with hot water at a temperature of 50°C to 100°C.
  • the drying is selected from one or more of vacuum drying, freeze drying, airflow drying, microwave drying, infrared drying and high frequency drying.
  • the method for preparing polyamide resin comprises the following steps:
  • polyamide chips are mixed with water and placed in a reactor, and an inert gas is used to place the air in the reactor;
  • the polyamide chips described in step (1) are commercially available polyamide chips, polyamide chips prepared according to the above methods including S1-S3, or polyamide chips prepared by other methods.
  • the reactor is selected from a continuous extraction tower and a batch reactor.
  • the operation method for replacing the air in the reactor includes vacuumizing the reactor with a vacuum pump and then filling the reactor with inert gas. The operation of replacing the air in the reactor was repeated two or more times.
  • the water is deionized water, further deionized water after oxygen removal treatment.
  • the quality of the water is more than 1 times the mass of the polyamide pellets, further more than 2 times, such as 1 to 12 times, 2 to 10 times, 2 to 6 times, such as 3 times, 5 times, 8 times, or 10 times times.
  • the inert gas is selected from one or more of nitrogen, argon, helium and the like.
  • the heating time is 4 to 50 hours, further 8 to 45 hours; the heating temperature is 80 to 140°C, further 85 to 120°C; the washing is performed at a temperature of 50°C to Washing with hot water at 100°C; the drying is selected from one or more of vacuum drying, freeze drying, airflow drying, microwave drying, infrared drying and high frequency drying.
  • the third object of the present invention is to provide a resin composition, which includes the polyamide resin described in any one of the above.
  • the fourth object of the present invention is to provide a fiber, which is prepared by using the polyamide resin described in any one of the above as raw materials.
  • the breaking strength of the fiber is 3.3-10.0 cN/dtex, further 3.5-9.0 cN/dtex, further 4.0-8.5 cN/dtex, 3.0-7.0 cN/dtex, 4.0-10.0 cN /dtex, or 4.0 ⁇ 6.0cN/dtex, such as 5cN/dtex, 6cN/dtex, or 7cN/dtex.
  • the elongation at break of the fiber is 10%-90%, further 15%-80%, further 18%-55%, such as 20%, 25%, 35%, 40% , or 47%.
  • the boiling water shrinkage of the fiber is 1.0%-13.8%, further 3.0%-12.0%, 3.0%-10.0%, or 3.0%-7.0%, such as 4.5%, 5%, 6.5%. , 7%, or 8%.
  • the fiber has a linear density of 11-2330 dtex, further 33.0-933 dtex, 44.0-555 dtex, 30-100 dtex, or 30-60 dtex, such as 130 dtex, 220 dtex, 300 dtex, or 400 dtex.
  • the unevenness of the fibers is ⁇ 1.5%, further ⁇ 1.3%, further ⁇ 1.2%, and further ⁇ 1.0%.
  • the fabrication rate of the fibers is 96% or more, further 97% or more, and further 98% or more.
  • the dyed M rate of the fiber is 96% or more, further 97% or more, further 98% or more, further 98.5% or more, and further 99% or more.
  • the number of yarn breakages of the fibers is ⁇ 2 (times/24h), further ⁇ 1 (times/24h), and further ⁇ 0 (times/24h).
  • the number of filaments of the fiber is ⁇ 3 (unit/9 kg package), further ⁇ 2 (unit/9 kg package), further ⁇ 1 (unit/9 kg package) ).
  • the fifth object of the present invention is to provide a method for preparing the above-mentioned fibers, the method comprising the steps of:
  • the post-processing includes cooling, and/or stretching, and/or winding, and/or setting treatment.
  • the component scraping period is ⁇ 3 (times/24h), further is ⁇ 2 (times/24h), and is further ⁇ 1 (times/24h).
  • the fibers obtained in step (c) include pre-oriented yarns (POY), medium-oriented yarns (MOY), highly-oriented yarns (HOY), textured yarns (DTY), fully drawn yarns FDY , industrial yarn (IDY), continuous bulked filament (BCF), staple fiber, and monofilament fiber.
  • POY pre-oriented yarns
  • MOY medium-oriented yarns
  • HOY highly-oriented yarns
  • DTY textured yarns
  • FDY fully drawn yarns
  • IDY industrial yarn
  • BCF continuous bulked filament
  • staple fiber and monofilament fiber.
  • the implementation of the present invention has at least the following advantages:
  • the preparation method of the polyamide resin of the present invention is simple, and the process parameters are easy to control, without the assistance of large-scale instruments, and are convenient for quantitative production;
  • the polyamide resin of the present invention has less water extractables in the spinning process, longer component shoveling cycle, fewer broken filaments, and the obtained polyamide fiber has less wool and low fiber evenness. , Less dyed dark lines, good dyeing effect, and the fiber has excellent elongation at break, breaking strength and low shrinkage in boiling water. The yield of spinning and dyeing is higher.
  • Ubbelohde viscometer concentrated sulfuric acid method Accurately weigh 0.5 ⁇ 0.0002g of the dried polyamide sample, add 50mL concentrated sulfuric acid (98%) to dissolve, measure and record the concentrated sulfuric acid flow time t0 and The polyamide solution flows for a time t.
  • t flow time of polyamide solution
  • t 0 flow time of concentrated sulfuric acid solvent
  • the melt When testing the content of water extractables in the polyamide resin melt, the melt is introduced into a closed container, and after cooling, samples are taken for testing according to the above method.
  • Number of broken yarns (times/24h): manual statistics. Fewer yarn breaks are considered to represent better spinnability.
  • Production rate (weight of finished fiber prepared/total weight of input resin) ⁇ 100%.
  • the dyeing uniformity method (ASTMZ7667-B999) was used to measure the dyeing uniformity of the polyamide fiber prepared by the above preparation method, and the dyeing M rate was measured by a 5-level color judgment standard method.
  • M rate (the number of fibers whose dyeing uniformity is ⁇ 4.5)/the total number of all dyed fibers) ⁇ 100%.
  • the number of filaments is judged manually.
  • the shovel cycle adopts manual statistics.
  • step (3) Discharging the melt obtained in step (2), cutting the strands into pellets to obtain slices of polyamide 56; the pelletizing is carried out in water, and the water temperature is 20°C.
  • step (3) Discharging the melt obtained in step (2), cutting the strands into pellets to obtain polyamide slices; the pelletizing is carried out in water, and the water temperature is 21°C.
  • step (3) discharging the melt obtained in step (2), and cutting the strands into pellets.
  • step (4) Put N2 protection into the reaction kettle in step (4), heat at 96°C for 46h, then filter, separate the slices from water, rinse the slices with water at 95°C, and dry them in vacuum at 105°C for 15h to obtain Polyamide 56 resin.
  • step (3) The melt obtained in step (2) is discharged, and the strands are cut into pellets.
  • the pelletization is carried out in water, and the water temperature is 20°C.
  • the polyamide 56 resin prepared in Example 1-A was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly through single-screw heating, and the temperature of the spinning box was 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide 56 resin prepared in Example 1-A was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 1-A was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.2mm, the length is 0.6mm, and the number of holes is 51.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 83%
  • the wind speed is 0.4m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning tunnel to obtain pre-oriented yarn (POY).
  • the winding speed is 4200m/min, and it is made into polyamide 56 pre-oriented wire.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the polyamide 56 resin prepared in Example 3 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide 56 resin prepared in Example 3 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 3 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.2mm, the length is 0.6mm, and the number of holes is 51.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 83%
  • the wind speed is 0.4m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning tunnel to obtain pre-oriented yarn (POY).
  • the winding speed is 4200m/min, and it is made into polyamide 56 pre-oriented wire.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the polyamide 56 resin prepared in Example 4 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide 56 resin prepared in Example 4 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 4 was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt, and the spinneret aperture is 0.2mm, the length is 0.6mm, and the number of holes is 51. After being cooled and formed by the side blowing device, the wind temperature of the side blowing device is 22°C, the rheumatism is 83%, and the wind speed is 0.4m/s. The cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning tunnel to obtain pre-oriented yarn (POY).
  • POY pre-oriented yarn
  • the winding speed is 4200m/min, and it is made into polyamide 56 pre-oriented wire.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the polyamide 56 resin prepared in Example 7-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide 56 resin prepared in Example 7-A was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 7-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 7-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.2mm, the length is 0.6mm, and the number of holes is 51.
  • the wind temperature of the side blowing device is 22°C, the rheumatism is 83%, and the wind speed is 0.4m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning tunnel to obtain pre-oriented yarn (POY).
  • the winding speed is 4200m/min, and it is made into polyamide 56 pre-oriented wire.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the polyamide resin prepared in Example 1-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide resin prepared in Example 1-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon fully drawn filament (FDY).
  • the polyamide resin prepared in Example 1-B was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.2mm, the length is 0.6mm, and the number of holes is 51.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 83%
  • the wind speed is 0.4m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning shaft to obtain pre-oriented yarn (POY), and the winding speed is 4200m/min to make polyamide pre-oriented yarn. Oriented filaments.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the polyamide 56 resin prepared in Example 7-C is fed into the spinning equipment through a feeder, heated by a single screw and evenly distributed into the spinning assembly, and the temperature of the spinning box is 280°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.25mm, the length is 0.75mm, and the number of holes is 48.
  • the wind temperature of the side blowing device is 22°C
  • the rheumatism is 85%
  • the wind speed is 0.45m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roller and the second godet roller after the spinning shaft, and wound into a silk cake on the winder at a winding speed of 4300m/min to obtain a pre-oriented Silk (POY).
  • POY pre-oriented Silk
  • the polyamide 56 resin prepared in Example 7-C was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to become a thin stream of melt.
  • the spinneret hole diameter is 0.22mm, the length is 0.605mm, and the number of holes is 36.
  • the wind temperature of the side blowing device is 21°C
  • the rheumatism is 90%
  • the wind speed is 0.43m/s.
  • the cooled and formed tow is oiled and drawn to the first pair of hot rollers and the second pair of hot rollers after the spinning shaft.
  • the winding speed is 4800m/min, the draft ratio is 1.5, and the setting temperature is 155°C. into nylon 56 fully drawn filament (FDY).
  • the polyamide 56 resin prepared in Example 7-C was fed into the spinning equipment through a feeder, and evenly distributed into the spinning assembly after being heated by a single screw, and the temperature of the spinning box was 283°C. It is sprayed out through the spinneret to form a thin stream of melt.
  • the spinneret hole diameter is 0.2mm, the length is 0.6mm, and the number of holes is 51.
  • the wind temperature of the side blowing device is 22°C, the rheumatism is 83%, and the wind speed is 0.4m/s.
  • the cooled and formed tow is oiled and drawn to the first godet roll and the second godet roll after the spinning tunnel to obtain pre-oriented yarn (POY).
  • the winding speed is 4200m/min, and it is made into polyamide 56 pre-oriented wire.
  • the pre-oriented yarn is stretched, twisted, shaped and networked on a texturing machine to obtain a texturized yarn (DTY).
  • the processing speed is 550m/min, the draw ratio is 1.28, the D/Y ratio is 1.65, and the temperature of the hot box is 185°C.
  • the content of water extractables in the polyamide resin of the present invention is small, and the fiber prepared from the polyamide resin has excellent properties such as elongation at break, breaking strength, low boiling water shrinkage and unevenness, and the spinning process
  • the number of broken yarns is less, and the scraping cycle of the components is longer; the unevenness of the fibers obtained by spinning is lower, the dyeing uniformity is improved, and the dyeing rate is high.
  • the resin with less water extractables reduces the precipitation and condensation of water extractables under the spinneret during the spinning process, avoiding the excessive precipitation of water extractables that will affect the floating filaments, broken filaments and components during the spinning process Frequent shoveling and other phenomena further increase the fiber production rate.

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Abstract

本发明提供一种聚酰胺树脂及其制备方法、组合物和纤维制品。所述聚酰胺的结构单元包括二元胺结构单元和二元酸结构单元，所述二元酸结构单元中90mol％以上来自于己二酸，所述二元胺结构单元中90mol％以上来自于1,5-戊二胺，所述水可萃取物在聚酰胺树脂中的含量为0.7wt％以下。所述水可萃取物的数均分子量为2000以下。本发明的聚酰胺树脂的制备方法简单，工艺参数易于控制，无需大型仪器协助，便于进行量化生产。本发明的聚酰胺树脂在纺丝过程中组件铲板周期长、断丝次数较少，得到的纤维的毛丝少、条干不均率低、染色暗纹少、染色效果好，且具有优异的断裂伸长率、断裂强度和较低的沸水收缩率。纺丝和染色的成品率较高。

Description

一种聚酰胺树脂及其制备方法、组合物和纤维制品 技术领域
本发明属于高分子材料领域，具体涉及一种聚酰胺树脂及其制备方法、组合物和纤维制品。
背景技术
聚酰胺由于其优异的特性和熔融成型的容易程度，已被广泛用作衣料、产业材料、纤维、或通用的工程塑料中，因而受到广泛关注。聚酰胺5X是由生物基戊二胺和系列二元酸合成的线型长链大分子，酰胺键容易形成氢键，因此，聚酰胺5X纤维的强度高，吸湿性好。而在聚酰胺5X聚合的过程中，由于发生环化反应，链内酰胺基交换反应发生时聚合物大分子链会断成两段，或者线状低分子物直接脱水反应，而产生低分子聚合物。一般来说，水可萃取物是一聚体到十聚体的低分子聚合物，例如二聚体、三聚体，包括线状和环状。
通常，水可萃取物无法单独加工成型，并且，大量的水可萃取物如果随切片进入纺丝工段，不仅会对纺丝工艺造成严重的后果，同时也是对原料的极大浪费。如果树脂中二聚体、三聚体的含量偏高，将影响切片的分子量分布，从而造成原丝的强度降低、废丝率增加等一系列负面影响。在熔融纺丝过程中，这些化合物会从熔融体中蒸发出来变成气体，增加聚酰胺5X熔体中的气泡，蒸发出的气体再凝固后还会恶化纺丝环境，缩小纺丝组件铲板周期。而且聚酰胺5X熔体中的水可萃取物会在纤维中形成“弱点”，在外力(如拉伸)作用下，这些地方就容易断裂，给纺丝造成困难。此外，水可萃取物也易在丝的表面析出，从而造成拉伸时毛丝、飘丝和断单丝增加、成品丝的强力下降、制成率低等不良现象。
因此，如何改善聚酰胺5X在纺丝过程中的铲板周期短、飘丝、断单丝与制成率低等不良现象，是现有技术领域中亟待解决的问题。
发明内容
为解决现有技术和产品的不足，本发明目的之一在于提供一种聚酰胺树脂。
所述聚酰胺的结构单元包括二元胺结构单元和二元酸结构单元，所述二元酸结构单元中90mol％以上来自于己二酸，所述二元胺结构单元中90mol％以上来自于1,5-戊二胺，所述聚酰胺树脂中含有数均分子量为2000以下的水可萃取物，且所述水可萃取物在聚酰胺树脂中的含量为0.7wt％以下。
根据本发明的一些实施方式，所述水可萃取物的含量为0.6wt％以下，进一步为0.5wt％以下。所述水可萃取物主要为单体在聚合阶段产生的低聚物。
根据本发明的一些实施方式，所述聚酰胺树脂的数均分子量为28000以上，进一步为30000～45000，进一步为30000～40000。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，所得聚酰胺树脂及后述的树脂组合物的抗黄变性能提高。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，纺丝过程中组件铲板周期大大增加，生产效率大大提高。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，纺丝过程中断丝少、毛丝少，聚酰胺纤维的强度高。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，纤维沸水收缩率低，聚酰胺纤维尺寸稳定性提高。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，聚酰胺纤维的条干不均率低，染色效果好。
在本发明一些优选实施方式中，所述水可萃取物的含量(wt％)在上述限定的范围时，聚酰胺树脂的纺丝过程成品率高、染色M率高。
在本发明一些优选实施方式中，所述聚酰胺树脂中水可萃取物的含量为0.05wt％ 以上，进一步为0.1wt％以上，进一步为0.2wt％以上。当水可萃取物的含量低于上述限定范围时，所述聚酰胺纤维的性能有所降低。
所述聚酰胺树脂中水可萃取物含量为在去离子水中加热进行萃取处理(例如使用97℃～100℃的水萃取聚酰胺树脂24h)，萃取处理后能够被萃取到水中的组分占萃取处理前的聚酰胺树脂的质量百分比。
所述水可萃取物含量(％)＝(水萃取前聚酰胺树脂的质量m 1-水萃取后聚酰胺树脂的质量m 2)/水萃取前聚酰胺树脂的质量m 1*100％。
萃取条件例如为使用97℃～100℃的水萃取聚酰胺树脂24h，聚酰胺树脂与水的质量比为1:48～51，例如1:50。
进一步的，所述水可萃取物含量的测试方法如下：将聚酰胺样品在鼓风烘箱中于130℃干燥7小时，然后放入铝塑袋密封后放入干燥器中冷却，然后准确称量聚酰胺样品约2g，记录聚酰胺样品实际质量(m 1)。将聚酰胺样品置于250mL圆底烧瓶中，加入100mL去离子水，在97℃～100℃加热回流24小时，取水萃取后的聚酰胺样品用去离子水清洗三遍，再将聚酰胺样品在130℃鼓风烘箱中干燥7小时，然后转移至事先称重的铝塑袋中，封口后放入干燥器中冷却，称量铝塑袋与聚酰胺样品总重与铝塑袋重量，两者相减，得到水萃取后聚酰胺样品的重量(m 2)。通过对比聚酰胺样品水萃取前、后重量差，计算出水可萃取物含量。水可萃取物含量(％)＝(m 1-m 2)/m 1*100％。
进一步地，当进行聚酰胺树脂熔体中水可萃取物含量检测时，将熔体导入密闭容器中，冷却后取样按上述方法进行检测。
根据本发明的一些实施方式，所述水可萃取物的数均分子量为500～2000。
例如所述水可萃取物包括以下结构中的一种或两种：
Figure PCTCN2022071923-appb-000001
其中，n1和n2分别选自1～8的整数，优选地，n1和n2分别选自1～6的整数，更优选地，n1和n2分别选自1～5的整数，进一步优选地，n1为2、3或4；n2为2、3、4或5；m1为4，m2为4。
根据本发明的一些实施方式，所述聚酰胺树脂中的戊二胺可以为化学来源或者生物物质来源的戊二胺，进一步为生物物质来源的1,5-戊二胺。
根据本发明的一些实施方式，所述聚酰胺树脂中的二元胺结构单元中95mol％以上，优选97mol％以上来自于1,5-戊二胺。
根据本发明的一些实施方式，所述聚酰胺树脂中的二元胺结构单元还包括来自于丁二胺、己二胺、癸二胺、和十二碳二元胺中的一种或多种的结构单元。
根据本发明的一些实施方式，所述聚酰胺树脂中的二元酸结构单元中95mol％以上，优选97mol％以上来自于己二酸。
根据本发明的一些实施方式，所述聚酰胺树脂中的二元酸结构单元还包括来自于丁二酸、戊二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸和十八烷二酸、以及对苯二甲酸、间苯二甲酸、和邻苯二甲酸中的一种或多种的结构单元。
根据本发明的一些实施方式，所述聚酰胺树脂中由二元胺结构单元和二元酸结构单元构成的聚酰胺(主聚合物)的含量在90wt％以上，进一步为95wt％以上，进一步为97wt％以上，进一步为99wt％以上。所述二元胺结构单元和二元酸结构单元符合以上的限定。
根据本发明的一些实施方式，所述聚酰胺树脂中含有添加剂。
所述添加剂包括但不限于封端剂、成核剂、抗氧剂、消泡剂、和流动改性剂中任意一种或几种的组合。所述封端剂包括月桂酸、硬脂酸、苯甲酸、和乙酸。
所述添加剂包括但不限于月桂酸、硬脂酸、苯甲酸、乙酸、次亚磷酸钠、次亚 磷酸钙、亚磷酸、硅酮类消泡剂、己内酰胺、炭黑、纳米碳酸钙、二氧化钛、和酞菁类化合物中任意一种或几种的混合物。
在本发明一些优选实施方式中，所述聚酰胺树脂中添加剂的含量为小于或等于10wt％，优选小于或等于5wt％，更优选小于或等于3wt％，更优选小于或等于1wt％。
根据本发明的一些实施方式，所述聚酰胺树脂为聚酰胺56树脂。所述聚酰胺56树脂中聚酰胺56的含量在90wt％以上，进一步为95wt％以上，进一步为97wt％以上，进一步为99wt％以上。
在本发明一些实施方式，所述聚酰胺树脂的含水率为200～2000ppm，优选250～1200ppm，进一步优选为300～1000ppm。
在本发明的一些实施方式，所述聚酰胺树脂的端氨基含量为10～100mol/ton，优选20～90mol/ton，进一步优选为30～80mol/ton。
在本发明的一些实施方式中，所述聚酰胺树脂的相对粘度为1.8～4.0，优选2.2～3.5，进一步优选为2.4～3.3。
除非另有说明或者明显矛盾，本发明所述压力均指表压。
本发明的目的之二在于提供制备上述聚酰胺树脂的方法。
根据本发明的一些实施方式，所述方法包括以下步骤：
S1:惰性气体氛围下，制备尼龙盐溶液；
S2:将所述尼龙盐溶液加热，使所述尼龙盐溶液反应体系的压力升至0.5～2.5MPa，排气保压0.5～4h，然后降压使所述反应体系内的压力降至0～0.7MPa(表压)，之后抽真空使所述反应体系内的真空度为-0.05～-0.08MPa，得到聚酰胺熔体；
S3:将所得熔体出料，拉条切粒，得聚酰胺切片。
其中，步骤S1中，制备尼龙盐溶液所用1,5-戊二胺和二元酸的摩尔比为(1～1.1)：1。
步骤S2中，保压过程结束后所述反应体系的温度为232～260℃。
步骤S2中，降压过程结束后所述反应体系的温度为240～295℃，进一步为243～288℃。
步骤S2中，抽真空后所述反应体系的温度为250～290℃，进一步为252～285℃。
步骤S2中，抽真空后维持所述真空度的时间为11～75min。
步骤S3中，所述切粒在水中进行，水温为15～50℃。经过步骤S3所述的拉条切粒，得到聚酰胺切片或聚酰胺切粒。
根据本发明的一些实施方式，所述方法还包括以下步骤：
S4:将聚酰胺切片与水混合置于反应器中，利用惰性气体置换反应器内的空气；
S5:惰性气体氛围下，加热，过滤，冲洗，干燥，即得到所述聚酰胺树脂。
步骤S4中，所述反应器为可以形成密闭环境的反应器。步骤S4中，所述反应器例如可以为连续萃取塔或间歇反应釜。
优选地，步骤S4中，所述置换反应器内的空气的方法为真空泵抽真空后再充入惰性气体。上述的置换反应器内的空气的操作可以重复二次以上。
步骤S4中，所述水为去离子水，进一步为经过除氧处理后的去离子水，其中，所述的除氧处理可以为热力除氧、超声除氧、真空除氧、化学除氧、解析除氧或其他任意的除氧方式中的一种或几种的组合；在一些优选实施方式中，所述除氧处理后的去离子水中溶解氧的含量为小于或等于0.5mg/L，进一步为小于或等于0.1mg/L。
步骤S4中，所述去离子水的质量为聚酰胺切粒的质量1倍以上，进一步为2倍以上，例如1～12倍、1～10倍、2～10倍、2～6倍、1.5倍、2.3倍、2.5倍、3倍、5倍、或8倍。
步骤S1、S4和步骤S5中，所述惰性气体选自氮气、氩气、氦气等中的一种或几种，进一步优选高纯度氮气、高纯度氩气、高纯度氦气中的一种或几种。
根据本发明的一些实施方式，步骤S4中，所述置换空气操作过程中抽真空至真空度-0.1MPa～-0.001MPa(表压)，维持5～20min后，再充入惰性气体，进一步优选，重复置换空气操作5～15次，进一步为8～10次。
根据本发明的一些实施方式，步骤S5中，所述加热的时间为4～50h，进一步为8～45h。
根据本发明的一些实施方式，步骤S5中，所述加热的温度为80～140℃，进一步为85～120℃。
根据本发明的一些实施方式，步骤S5中，所述的冲洗为用温度50℃～100℃的热 水进行冲洗。
根据本发明的一些实施方式，步骤S5中，所述的干燥选自真空干燥、冷冻干燥、气流干燥、微波干燥、红外线干燥和高频率干燥中的一种或几种。
根据本发明的一些实施方式，制备聚酰胺树脂的方法包括以下步骤：
(1)将聚酰胺切片与水混合置于反应器中，利用惰性气体置反应器内的空气；和
(2)惰性气体氛围下，加热，过滤，冲洗，干燥，即得到所述聚酰胺树脂。
步骤(1)所述的聚酰胺切片为市售的聚酰胺切片、按照以上包括S1～S3的方法制备得到的聚酰胺切片或其他方法制备的聚酰胺切片。步骤(1)中，所述反应器选自连续萃取塔和间歇反应釜。所述置换反应器内的空气的操作方法包括用真空泵将反应器抽真空后再充入惰性气体。置换反应器内的空气的操作为重复二次以上。所述水为去离子水，进一步为经过除氧处理后的去离子水。所述水的质量为聚酰胺切粒的质量1倍以上，进一步为2倍以上，例如1～12倍，2～10倍，2～6倍，例如3倍、5倍、8倍、或10倍。步骤(1)和步骤(2)中，所述惰性气体选自氮气、氩气、氦气等中的一种或几种。
步骤(2)中，所述加热的时间为4～50h，进一步为8～45h；所述加热的温度为80～140℃，进一步为85～120℃；所述的冲洗为用温度50℃～100℃的热水进行冲洗；所述的干燥选自真空干燥、冷冻干燥、气流干燥、微波干燥、红外线干燥和高频率干燥中的一种或几种。
本发明的目的之三在于提供一种树脂组合物，所述树脂组合物包括以上任一项所述的聚酰胺树脂。
本发明的目的之四在于提供一种纤维，所述纤维采用以上任一项所述的聚酰胺树脂为原料制备。
在一些实施方式中，所述纤维的断裂强度为3.3～10.0cN/dtex，进一步为3.5～9.0cN/dtex，更进一步为4.0～8.5cN/dtex、3.0～7.0cN/dtex、4.0～10.0cN/dtex、或4.0～6.0cN/dtex，例如5cN/dtex、6cN/dtex、或7cN/dtex。
在一些实施方式中，所述纤维的断裂伸长率为10％～90％，进一步为15％～80％，更进一步为18％～55％，例如20％、25％、35％、40％、或47％。
在一些实施方式中，所述纤维的沸水收缩率为1.0％～13.8％，进一步为3.0％～12.0％、3.0％～10.0％、或3.0％～7.0％，例如4.5％、5％、6.5％、7％、或8％。
在一些实施方式中，所述纤维的线密度为11～2330dtex，进一步为33.0～933dtex，44.0～555dtex，30～100dtex，或30～60dtex，例如130dtex、220dtex、300dtex、或400dtex。
在一些实施方式中，所述纤维的条干不均率为≤1.5％，进一步为≤1.3％，进一步为≤1.2％，更进一步为≤1.0％。
在一些实施方式中，所述纤维的制成率为96％以上，进一步为97％以上，更进一步为98％以上。
在一些实施方式中，所述纤维的染色M率为96％以上，进一步为97％以上，更进一步为98％以上，更进一步为98.5％以上，更进一步为99％以上。
在一些实施方式中，所述纤维的断纱次数≤2(次数/24h)，进一步为≤1(次数/24h)，更进一步为≤0(次数/24h)。
在一些实施方式中，所述纤维的毛丝个数≤3(个/9公斤卷装)，进一步为≤2(个/9公斤卷装)，更进一步为≤1(个/9公斤卷装)。
本发明的目的之五在于提供一种制备上述纤维的方法，所述方法包括如下步骤：
(a)将聚酰胺树脂加热至熔融状态，形成聚酰胺熔体；
(b)将所述聚酰胺熔体进行纺丝，形成初生丝；和
(c)对所述初生丝进行后处理，得到聚酰胺纤维。
所述后处理包括冷却，和/或拉伸，和/或卷绕，和/或定型处理。
根据本发明的一些实施方式，所述纤维制备过程中组件铲板周期≤3(次/24h)，进一步为≤2(次/24h)，更进一步为≤1(次/24h)。
根据本发明的一些实施方式，步骤(c)中得到的纤维包括预取向丝(POY)、 中取向丝(MOY)、高取向丝(HOY)、加弹丝(DTY)、全牵伸丝FDY、工业丝(IDY)、连续膨体长丝(BCF)、短纤维、和单丝纤维。
与现有技术相比，本发明的实施，至少具有以下优势：
1、本发明的聚酰胺树脂的制备方法简单，工艺参数易于控制，无需大型仪器协助，便于进行量化生产；
2、本发明的聚酰胺树脂在纺丝过程中的水可萃取物少、组件铲板周期长、断丝次数较少，得到的聚酰胺纤维的毛丝少、纤维的条干不均率低、染色暗纹少、染色效果好，且纤维具有优异的断裂伸长率、断裂强度和较低的沸水收缩率。纺丝和染色的成品率较高。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
1、相对粘度ηr的检测方法
乌氏粘度计浓硫酸法：准确称量干燥后的聚酰胺样品0.5±0.0002g，加入50mL浓硫酸(98％)溶解，在25℃恒温水浴槽中测量并记录浓硫酸流经时间t 0和聚酰胺溶液流经时间t。
相对粘度计算公式：
相对粘度ηr＝t/t 0
其中：t：聚酰胺溶液的流经时间；t 0：浓硫酸溶剂的流经时间。
2、含水率
取1g树脂样品，利用卡尔费休水分测定仪测定，检测温度200℃，检测时间20min。
3、端氨基含量测定
利用三氟乙醇溶解样品后，分别用盐酸标准液和氢氧化钠标准液滴定，并计算。
4、数均分子量(单位：g/mol)的检测
通过凝胶渗透色谱(简称为GPC)测试得到。
5、聚酰胺树脂中水可萃取物含量的测试
将聚酰胺样品在鼓风烘箱中于130℃干燥7小时，然后放入铝塑袋密封后放入干燥器中冷却，然后准确称量聚酰胺样品约2g，记录聚酰胺样品实际质量(m 1)。将聚酰胺样品置于250mL圆底烧瓶中，加入100mL去离子水，在97℃～100℃加热回流24小时，取水萃取后的聚酰胺样品用去离子水清洗三遍，再将聚酰胺样品在130℃鼓风烘箱中干燥7小时，然后转移至事先称重的铝塑袋中，封口后放入干燥器中冷却，称量铝塑袋与聚酰胺样品总重与铝塑袋重量，两者相减，得到水萃取后聚酰胺样品的重量(m 2)。通过对比聚酰胺样品水萃取前、后重量差，计算出水可萃取物含量。水可萃取物含量(％)＝(m 1-m 2)/m 1*100％。
当进行聚酰胺树脂熔体中水可萃取物含量检测时将熔体导入密闭容器中，冷却后取样按上述方法进行检测。
6、线密度
按照GB/T 14343-2008测定。
7、沸水收缩率
按照GB/T 6505-2008测定。
8、断纱次数
断纱次数(次数/24h)：人工统计。较少的断纱次数被认为是代表更好的可纺性。
9、条干不均率
按GB/T 14346-93方法进行测定。
10、纤维制成率
制成率＝(制备的成品纤维重量/总共投入树脂重量)×100％。
11、染色M率
采用染色均匀度方法(ASTMZ7667-B999)测定上述制备方法制备得到的聚酰胺纤维的染色均匀度，并采用5级判色标准方法测定染色M率。
M率＝(染色均匀度≥4.5级的纤维数量)/所有染色纤维总数量)×100％。
12、毛丝个数
毛丝个数采用人工判定。
13、断裂强度、断裂伸长率
参考GB/T 14344-2008化学纤维纤维拉伸性能试验方法；施加0.05±0.005cN/dtex预张力，夹持距离500mm，拉伸速度500mm/min。
14、铲板周期
铲板周期采用人工统计。
制备例1
(1)氮气条件下，将1,5-戊二胺、己二酸和水混合均匀，其中，1,5-戊二胺、己二酸的摩尔比例为1.08:1，制得60wt.％的尼龙盐溶液，所述百分比为占尼龙盐溶液的质量百分比；将尼龙盐溶液取样并稀释至浓度为10wt.％时，pH值为7.85。
(2)将上述溶液加热，反应体系内压力升至2.3MPa，用时1小时30分钟，排气保压，保压结束时反应体系的温度为245℃，保压用时3小时，然后降压使反应体系内压力降至0.003MPa(表压)，降压结束后反应体系的温度为273℃，降压用时1小时。抽真空维持在-0.06MPa，抽真空时间32min，真空后反应体系的温度为272℃，得到聚酰胺56熔体。
(3)将步骤(2)所得熔体出料，拉条切粒，得聚酰胺56切片；所述切粒在水中进行，水温为20℃。
制备例2
(1)氮气条件下，将1,5-戊二胺、己二酸、癸二酸(占己二酸重量的3％)和水混合均匀，其中1,5-戊二胺的摩尔数与己二酸、癸二酸的摩尔数之和的比值为1.06：1，制得62wt.％的尼龙盐溶液，所述百分比为占尼龙盐溶液的质量百分比；将尼龙盐溶液取样并稀释至浓度为10wt.％时，pH值为8.4。向尼龙盐溶液中加入2％的己内酰胺，400ppm乙酸，600ppm苯甲酸，消泡剂10ppm，和次亚磷酸钠18ppm；
(2)将上述溶液加热，反应体系内压力升至2.1MPa，用时1小时30分钟，排气保压，保压结束时反应体系的温度为245℃，保压用时3小时，再降压，压力下降至0.5MPa时，加入配置好的TiO 2水溶液(TiO 2水溶液中TiO 2的含量为15wt％)，使加入的二氧化钛的重量占尼龙盐重量比例0.3％，继续使反应体系内压力降至0.004MPa(表压)，降压结束后反应体系的温度为276℃，降压用时1小时。抽真空维持在-0.07MPa，抽真空时间30min，真空后反应体系的温度为273℃，得到聚酰胺熔体。
(3)将步骤(2)所得熔体出料，拉条切粒，得聚酰胺切片；所述切粒在水中进行，水温为21℃。
实施例1-A
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比是1:6；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.08MPa(表压)，维持12min后充入氮气， 重复置换9次。
(b)在N 2氛围下，在98℃加热45h，然后过滤，将切片与水分离，再用94℃热水冲洗切片，103℃真空干燥18h，即得到聚酰胺56树脂。
实施例1-B
(a)在反应釜中加入制备例2所制得的聚酰胺切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比是1:6；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.08MPa(表压)，维持11min后充入氮气，重复置换9次。
(b)在N 2氛围下，在98℃加热45h，然后过滤，将切片与水分离，再用95℃热水冲洗切片，103℃真空干燥18h，即得到聚酰胺树脂。
实施例2
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比是1:6；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.09MPa(表压)，维持10min后充入氮气，重复置换9次。
(b)在氮气氛围下，在90℃加热32h，然后过滤，将切片与水分离，再用95℃水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例3
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比为1:3；利用氮气进行置换空气， 具体操作方法：真空泵抽真空，真空度-0.07MPa(表压)，维持10min后充入氮气，重复置换5次。
(b)在氮气氛围下，在96℃加热48h，然后过滤，将切片与水分离，再用95℃水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例4
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比是1:6；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.08MPa(表压)，维持10min后充入氮气，重复置换10次。
(b)在氮气氛围下，在95℃加热35h，然后过滤，将切片与水分离，再用60℃水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例5
(1)氮气条件下，将1,5-戊二胺、己二酸和水混合均匀，其中，1,5-戊二胺、己二酸的摩尔比例为1:1，制得70wt.％的尼龙盐溶液，所述百分比为占尼龙盐溶液的质量百分比；将尼龙盐溶液取样并稀释至浓度为10wt.％时，pH值为7.96。
(2)将上述溶液加热，反应体系内压力升至2.0MPa，用时1小时30分钟，排气，在2.40MPa保压，保压结束时反应体系的温度为243℃，保压用时3小时，再降压使反应体系内压力降至0.005MPa(表压)，降压结束后反应体系的温度为290℃，降压用时1小时。抽真空维持在-0.08MPa，抽真空时间30min，真空后反应体系的温度为290℃，得到聚酰胺56熔体。
(3)将步骤(2)所得熔体出料，拉条切粒。
(4)在反应釜中加入聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比是1:6；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.07MPa(表压)，维持10min后充入氮气，重复置换10次。
(5)将步骤(4)中的反应釜中通入N 2保护，在96℃加热46h，然后过滤，将切片与水分离，再用95℃水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例6
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比为1:12；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.09MPa(表压)，维持10min后充入氮气，重复置换10次。
(b)将步骤(a)中的反应釜通入N 2保护，在95℃加热50h，然后过滤，将切片与水分离，再用95℃热水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例7-A
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比为1:20；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.09MPa(表压)，维持10min后充入氮气，重复置换10次。
(b)在氮气氛围下，在95℃加热50h，然后过滤，将切片与水分离，再用95℃热水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例7-B
(a)在反应釜中加入制备例1所制得的聚酰胺56切片，加入无氧处理后的去离子水，所述切片与无氧处理后的去离子水的质量比为1:40；利用氮气进行置换空气，具体操作方法：真空泵抽真空，真空度-0.09MPa(表压)，维持10min后充入氮气，重复置换10次。
(b)在氮气氛围下，在95℃加热50h。
然后过滤，将切片与水分离，将分离的切片作为原料，按照步骤(a)～(b)的操作条件重复三次，再用95℃热水冲洗切片，105℃真空干燥15h，即得到聚酰胺56树脂。
实施例7-C
(1)氮气条件下，将1,5-戊二胺、己二酸和水混合均匀，其中，1,5-戊二胺与己二酸的摩尔比例为1.05:1，制得60wt.％的尼龙盐溶液，所述百分比为占尼龙盐溶液的质量百分比；将尼龙盐溶液取样并稀释至浓度为10wt.％时，pH值为7.98。
(2)将上述溶液加热，反应体系内压力升至2.0MPa，用时1小时30分钟，排气保压，保压结束时反应体系的温度为243℃，保压用时3小时，再降压使反应体系内压力降至0.005MPa(表压)，降压结束后反应体系的温度为290℃，降压用时1小时。抽真空维持在-0.08MPa，抽真空时间30min，真空后反应体系的温度为290℃，得到聚酰胺56熔体。
(3)将步骤(2)所得熔体出料，拉条切粒，所述切粒在水中进行，水温为20℃。
(4)105℃真空干燥15h，即得到聚酰胺56树脂。
实施例8
用实施例1-A制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆 加热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例9
用实施例1-A制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例10
将实施例1-A制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为4200m/min，制成聚酰胺56预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
实施例11
用实施例3制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例12
用实施例3制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例13
将实施例3制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为 4200m/min，制成聚酰胺56预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
实施例14
用实施例4制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例15
用实施例4制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例16
将实施例4制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷 丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为4200m/min，制成聚酰胺56预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
实施例17
用实施例7-B制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例18-A
用实施例7-A制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例18-B
用实施例7-B制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例19
将实施例7-B制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为4200m/min，制成聚酰胺56预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
实施例20
用实施例1-B制得的聚酰胺树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺 丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例21
用实施例1-B制得的聚酰胺树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙全拉伸长丝(FDY)。
实施例22
将实施例1-B制得的聚酰胺树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为4200m/min，制成聚酰胺预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
实施例23
用实施例7-C制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加 热均匀分配到纺丝组件中，纺丝箱温度为280℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.25mm，长度为0.75mm，孔数为48孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿85％，风速0.45m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，在卷绕机上卷绕成丝饼，卷取速度为4300m/min，得到预取向丝(POY)。
实施例24
用实施例7-C制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.22mm，长度为0.605mm，孔数为36孔。经过侧吹风装置冷却成型，侧吹风装置的风温21℃，风湿90％，风速0.43m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一对热辊与第二对热辊，卷绕速度为4800m/min，牵伸倍数为1.5，定型温度为155℃，制成尼龙56全拉伸长丝(FDY)。
实施例25
将实施例7-C制得的聚酰胺56树脂通过加料器加入纺丝设备中，经过单螺杆加热均匀分配到纺丝组件中，纺丝箱温度为283℃。经喷丝板喷出而成为熔体细流，喷丝板孔径为0.2mm，长度为0.6mm，孔数为51孔。经过侧吹风装置冷却成型，侧吹风装置的风温22℃，风湿83％，风速0.4m/s。冷却成形的丝束经过上油，纺丝甬道后，被牵引到第一导丝辊与第二导丝辊，得到预取向丝(POY)，卷绕速度为4200m/min，制成聚酰胺56预取向丝。预取向丝在加弹机上进行拉伸加捻定型加网络得到加弹丝(DTY)，加工速度550m/min，拉伸比1.28，D/Y比为1.65，热箱温度185℃。
表1聚酰胺树脂性能测试结果表
Figure PCTCN2022071923-appb-000002
表2 POY纤维性能测试结果表
Figure PCTCN2022071923-appb-000003
表3 FDY纤维测试结果表
Figure PCTCN2022071923-appb-000004
Figure PCTCN2022071923-appb-000005
表4 DTY纤维测试结果表
Figure PCTCN2022071923-appb-000006
表1～4可知：
本发明聚酰胺树脂中水可萃取物含量少，聚酰胺树脂制备的纤维具有优异的断裂伸长率、断裂强度、具有较低的沸水收缩率与不匀率等性能，并且，纺纱过程中 的断纱次数较少，组件铲板周期长；纺丝得到的纤维的条干不均率较低，染色均匀度提高，染色M率高。水可萃取物少的树脂在纺丝过程中，减少了喷丝板下方的水可萃取物析出凝结，避免了水可萃取物析出过多会影响纺丝过程中飘丝、断单丝与组件频繁铲板等现象，进一步提高纤维制成率。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (15)

  1. 一种聚酰胺树脂，其特征在于，所述聚酰胺的结构单元包括二元胺结构单元和二元酸结构单元，所述二元酸结构单元中90mol％以上来自于己二酸，所述二元胺结构单元中90mol％以上来自于1,5-戊二胺，所述聚酰胺树脂中水可萃取物含量为0.7wt％以下。
  2. 如权利要求1所述的聚酰胺树脂，其特征在于，
    所述聚酰胺树脂的数均分子量为28000以上，进一步为30000～45000，进一步为30000～40000；和/或，
    所述水可萃取物的含量为0.6wt％以下，进一步为0.5wt％以下；和/或，
    所述水可萃取物的含量为0.05wt％以上，进一步为0.1wt％以上，进一步为0.2wt％以上；和/或，
    所述聚酰胺树脂的二元胺结构单元中95mol％以上，优选97mol％以上来自于1,5-戊二胺；和/或，
    所述聚酰胺树脂的二元胺结构单元还包括来自于丁二胺、己二胺、癸二胺、和十二碳二元胺中的一种或多种的结构单元；和/或，
    所述聚酰胺树脂的二元酸结构单元中95mol％以上，优选97mol％以上来自于己二酸；和/或，
    所述聚酰胺树脂的二元酸结构单元还包括来自于丁二酸、戊二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸和十八烷二酸、以及对苯二甲酸、间苯二甲酸、和邻苯二甲酸中的一种或多种的结构单元；和/或，
    所述聚酰胺树脂中由二元胺结构单元和二元酸结构单元构成的聚酰胺的含量在90wt％以上，进一步为95wt％以上，进一步为97wt％以上，进一步为99wt％以上；和/或，
    和/或，所述聚酰胺树脂中添加剂的含量为小于或等于10wt％，优选小于或等于 5wt％，更优选小于或等于3wt％，更优选小于或等于1wt％。
  3. 如权利要求1或2所述的聚酰胺树脂，其特征在于，所述水可萃取物包括以下结构中的一种或两种：
    Figure PCTCN2022071923-appb-100001
    其中，n1和n2分别选自1～8的整数，优选地，n1和n2分别选自1～6的整数，更优选地，n1和n2分别选自1～5的整数，进一步优选地，n1为2、3或4；n2为2、3、4或5；m1和m2为4；和/或，
    所述水可萃取物的数均分子量为500～2000；和/或，
    所述聚酰胺树脂为聚酰胺56树脂，所述聚酰胺56树脂中聚酰胺56的含量为90wt％以上，进一步为95wt％以上，进一步为97wt％以上，进一步为99wt％以上。
  4. 如权利要求2所述的聚酰胺树脂，其特征在于，
    所述添加剂包括但不限于封端剂、成核剂、抗氧剂、消泡剂、和流动改性剂中任意一种或几种的组合；和/或，
    所述添加剂包括月桂酸、硬脂酸、苯甲酸、乙酸、次亚磷酸钠、次亚磷酸钙、亚磷酸、硅酮类消泡剂、己内酰胺、炭黑、纳米碳酸钙、二氧化钛、和酞菁类化合物中任意一种或几种的混合物。
  5. 如权利要求1或2所述的聚酰胺树脂，其特征在于，所述聚酰胺树脂的含水率为200～2000ppm，优选250～1200ppm，进一步优选为300～1000ppm；和/或，
    所述聚酰胺树脂的端氨基含量为10～100mol/ton，优选20～90mol/ton，进一步优选为30～80mol/ton；和/或，
    所述聚酰胺树脂的相对粘度为1.8～4.0，优选2.2～3.5，进一步优选为2.4～3.3。
  6. 一种制备如权利要求1～5中任意一项所述的聚酰胺树脂的方法，其特征在于，所述方法包括以下步骤：
    S1:惰性气体氛围下，制备尼龙盐溶液；
    S2:将所述尼龙盐溶液加热，使所述尼龙盐溶液反应体系的压力升至0.5～2.5MPa，排气保压0.5～4h，然后降压使所述反应体系内的压力降至0～0.7MPa，之后抽真空使所述反应体系内的真空度为-0.05～-0.08MPa，得到聚酰胺熔体；
    S3:将所得熔体出料，拉条切粒，得聚酰胺切片。
  7. 如权利要求6所述的方法，其特征在于，
    步骤S1中，制备尼龙盐溶液所用1,5-戊二胺和二元酸的摩尔比为(1～1.1)：1；和/或，
    步骤S2中，保压过程结束后所述反应体系的温度为232～260℃；和/或，
    步骤S2中，降压过程结束后所述反应体系的温度为240～295℃；和/或，
    步骤S2中，抽真空后所述反应体系的温度为250～290℃；和/或，
    步骤S2中，抽真空后维持所述真空度的时间为11～75min；和/或，
    步骤S3中，所述切粒在水中进行，水温为15～50℃。
  8. 如权利要求7所述的方法，其特征在于，还包括以下步骤：
    S4:将聚酰胺切片与水混合置于反应器中，并且利用惰性气体置换反应器内的空气；
    S5:惰性气体氛围下，加热，过滤，冲洗，干燥，即得到所述聚酰胺树脂。
  9. 如权利要求8所述的方法，其特征在于，
    步骤S4中，所述反应器选自连续萃取塔和间歇反应釜；和/或，
    步骤S4中，所述置换反应器内的空气的操作方法包括用真空泵将反应器抽真空后再充入惰性气体；和/或，
    步骤S4中，置换反应器内的空气的操作为重复二次以上；和/或，
    步骤S4中，所述水为去离子水，进一步为经过除氧处理后的去离子水；和/或，
    步骤S4中，所述水的质量为聚酰胺切片的质量的1倍以上，进一步为2倍以上，例如1～12倍，2～10倍，2～6倍；和/或，
    步骤S4和步骤S5中，所述惰性气体选自氮气、氩气、氦气等中的一种或几种；和/或，
    步骤S5中，所述加热的时间为4～50h，进一步为8～45h；和/或，
    步骤S5中，所述加热的温度为80～140℃，进一步为85～120℃；和/或，
    步骤S5中，所述的冲洗为用温度50℃～100℃的热水进行冲洗；和/或，
    步骤S5中，所述的干燥选自真空干燥、冷冻干燥、气流干燥、微波干燥、红外线干燥和高频率干燥中的一种或几种。
  10. 一种制备如权利要求1～5中任意一项所述的聚酰胺树脂的方法，其特征在于，所述方法包括以下步骤：
    (1)将聚酰胺切片与水混合置于反应器中，利用惰性气体置换反应器内的空气；和
    (2)惰性气体氛围下，加热，过滤，冲洗，干燥，即得到所述聚酰胺树脂。
  11. 一种树脂组合物，所述树脂组合物的组分包括如权利要求1-5中任一项所述的聚酰胺树脂。
  12. 一种纤维，其特征在于，所述纤维采用如权利要求1-5中任一项所述的聚酰胺树脂或权利要求11所述的树脂组合物为原料制备。
  13. 如权利要求12所述的纤维，其特征在于：
    所述纤维包括预取向丝、中取向丝、高取向丝、加弹丝、全牵伸丝、工业丝、 连续膨体长丝、短纤维、和单丝纤维；和/或，
    所述纤维的断裂强度为3.3～10.0cN/dtex，进一步为3.5～9.0cN/dtex，更进一步为4.0～8.5cN/dtex；和/或，
    所述纤维的断裂伸长率为10％～90％，进一步为15％～80％，更进一步为18％～55％；和/或，
    所述纤维的沸水收缩率为1.0％～13.8％，进一步为3.0％～12.0％，更进一步为4.0％～10.0％；和/或，
    所述纤维的线密度为11～2330dtex，进一步为33.0～933dtex，更进一步为44.0～555dtex；和/或，
    所述纤维的条干不均率为≤1.5％，进一步为≤1.3％，进一步为≤1.2％，更进一步为≤1.0％；和/或，
    所述纤维的断纱次数≤2(次数/24h)，进一步为≤1(次数/24h)，更进一步为0(次数/24h)；和/或，
    所述纤维的毛丝个数≤3(个/9公斤卷装)，进一步为≤2(个/9公斤卷装)，更进一步为≤1(个/9公斤卷装)；和/或，
    所述纤维的制成率为96％以上，进一步为97％以上，更进一步为98％以上；和/或，
    所述纤维的染色M率为96％以上，进一步为97％以上，更进一步为98.5％以上。
  14. 一种制备如权利要求12或13所述的纤维的方法，其特征在于，所述方法包括如下步骤：
    (a)将聚酰胺树脂加热至熔融状态，形成聚酰胺熔体；
    (b)将所述聚酰胺熔体进行纺丝，形成初生丝；和
    (c)对所述初生丝进行后处理，得到聚酰胺纤维。
  15. 如权利要求14所述的方法，其特征在于，所述纤维制备过程中组件铲板周期≤3(次/24h)，进一步为≤2(次/24h)，更进一步为≤1(次/24h)。
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