CN102433605B - Preparation method of antistatic, anti-balling, and ordinary pressure cation dyeable polyester chip - Google Patents
Preparation method of antistatic, anti-balling, and ordinary pressure cation dyeable polyester chip Download PDFInfo
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- CN102433605B CN102433605B CN 201110277246 CN201110277246A CN102433605B CN 102433605 B CN102433605 B CN 102433605B CN 201110277246 CN201110277246 CN 201110277246 CN 201110277246 A CN201110277246 A CN 201110277246A CN 102433605 B CN102433605 B CN 102433605B
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Abstract
The invention relates to a preparation method of an antistatic, anti-balling, and ordinary pressure cation dyeable polyester chip, comprising the following steps: a primary esterification reaction step, an ester exchange reaction step, a secondary esterification reaction step, and a polymerization reaction step, wherein, a ternary-monomer is added in the ester exchange reaction step, hindered anime light stabilizers, hindered phenol antioxygens and hydroxyl silicone oil are added after the ester exchange reaction and before a prepolymerization reaction, and an antistatic agent is added after the prepolymerization of the polymerization reaction step and before a final polymerization. Fabrics prepared from polyester fibers produced by using the polyester chips disclosed herein have good antistatic behavior and good anti-balling behavior, and have unlimited dyeing possibilities by using the ordinary pressure cation dyeability, thus the uniform requirements of present high-grade spring and summer clothes for functionality and colors can be satisfied. The obtained fibers can be dyed with wool together, and the blending of the fibers with wool has good dress effect. The polyester chips and fibers disclosed herein are an important supplement of present cation dyeable polyester fiber market, and have a wide market prospect.
Description
Technical field
the present invention relates to a kind of preparation method of polyester slice, particularly the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section.
Background technology
in recent years, along with the develop rapidly of domestic polymerization technique, the functional polyester synthetic technology of China has obtained rapid progress, and domestic cation dyeable polyester has formed the scale of nearly 400,000 tons, and its differentiation kind emerges in an endless stream.Present the impetus that both production and marketing thrive, but, we also should see, there are sizable gap in the cationic polyester synthetic technology of China and range of application and developed country, the main application fields of China's cationic dyeable polyester fiber is decorative fabric and clothes filler rod, the original intention that this and cation dyeable polyester are developed has very large distance, requirement with current western developed country to the decorative fabric safe, in fact, the cation dyeable polyester fabric, owing to containing a large amount of sodium groups, ionizes the accelerated combustion process under hot conditions when burning.Long-range seeing, along with China's living standards of the people and whole people's awareness of safety raising, at present the Application Areas of cationic polyester fiber maximum can progressively be replaced by fire-retardant polyester fibre, the cationic polyester fiber will progressively recover its Application Areas originally.Along with the exploitation of various functional cation dyeable polyesters, the cationic-dyeable fiber color beautiful with it becomes the top grade material of clothes spring and summer.
since the autopolyester fiber comes out, rely on good intensity, good wrinkle resistance, draping property and wash and wear performance and be widely used in apparel textile, through tremendous development in recent decades, the PET polyester fiber has become at present the synthesizing polyester kind that output is maximum in the world, range of application is the widest.But, compare and also exist many deficiencies with various natural fabrics, its feel is hardened, hygroscopicity is poor, anti-pilling property is poor, easily produce static, easily balling-up, be difficult to the shortcoming such as dyeing.Natural fabric has gas permeability as cotton, real silk, hair, fiber crops etc. have good dyeability, fabric, the absorbing sweat performance of keeping humidity is good, without static, characteristics that comfortableness is good.But, also there is easy wrinkle in natural fabric material, leads the shortcoming wet, that rapid-drying properties is poor.
cationic dyeable polyester fiber is owing to being mainly used in Fashion Design use spring and summer, therefore when giving the beautiful color of fabric, for sun-drenched characteristics spring and summer, can develop consciously the cation dyeable polyester new varieties of the complex function with permanent ANTIPILLING function, when meeting colourful requirement, owing to possessing certain ANTIPILLING function, make fabric there is new bright spot.But yet there are no so far, the relevant report of the polyester fiber and preparation method thereof of, ANTIPILLING antistatic about having, normal atmosphere cation-dyeable complex function.
Summary of the invention
technical problem to be solved by this invention is to provide the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, by the polyester slice of the method gained can spin there is antistatic, ANTIPILLING, the polyester fiber of normal atmosphere cation-dyeable complex function.
for solving above technical problem, the present invention takes following technical scheme:
the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, it specifically comprises the steps:
(1), an esterification operation: terephthalic acid (TPA), ethylene glycol are joined in reaction kettle of the esterification 1:1.2～1.3 in molar ratio, carry out an esterification and generate the two hydroxyl glycol esters of terephthalic acid (TPA) under 255 ℃～260 ℃;
(2), ester exchange reaction operation: after a described esterification completes, add ethylene glycol cooling depolymerization, at 220～245 ℃ of temperature, keep 0.4～1.0 hour, control the two hydroxyl glycol ester mass content of terephthalic acid (TPA) in material and reach 55%～80%, then add three monomer solutions, after stirring, progressively be warming up to 255 ℃～260 ℃, carry out ester exchange reaction, going out methyl alcohol to esterification completes, wherein, the ester exchange rate that described three monomer solutions are Sodium Dimethyl Isophthalate-5-sulfonate and ethylene glycol generation ester exchange reaction gained under ester exchange catalyst exists is 60%～90%, the solution that ethylene isophthalate-5-sodium sulfonate mass content is 35%～45%, wherein, 0.5%～3.5% of the amount of substance that the amount of substance of the Sodium Dimethyl Isophthalate-5-sulfonate used is terephthalic acid (TPA),
(3), secondary esterification operation: in the system after completing to step (2) ester exchange reaction, add ethylene glycol, make system be cooled to 230 ℃～235 ℃, under inert gas shielding, add polyethylene glycol that number-average molecular weight is 600～6000 as the 4th monomer, the addition of the 4th monomer is 1.0%～6.5% of polyester slice weight, then add the seasoning liquid of the hindered amine light stabilizer that mass concentration is 2%～5% and the seasoning liquid of the Hinered phenols antioxidant that mass concentration is 2%～5%, take polyester slice weight as benchmark, the addition of described hindered amine light stabilizer and Hinered phenols antioxidant is respectively 10～300ppm, the seasoning liquid of described hindered amine light stabilizer be hindered amine light stabilizer be dispersed in solvent ethylene glycol and add acetic acid after the gained pH value solution that is 4～5, the seasoning liquid of described Hinered phenols antioxidant be Hinered phenols antioxidant be dispersed in solvent ethylene glycol and add acetic acid after the gained pH value solution that is 4～5, after adding, stir, reactor starts to heat up, slowly add the hydroxy silicon oil that hydroxyl value is 0.5%～8.0%, carry out the secondary esterification, finish to the esterification water outlet, the addition of wherein said hydroxy silicon oil is 0.1%～1.2% of polyester slice weight,
(4), polymerisation operation: after the secondary esterification finishes, add polymerization catalyst, after stirring, deliver in prepolymerization kettle, carry out prepolymerization reaction, the prepolymerization reaction temperature is controlled at 255 ℃～270 ℃, pressure is 0.6～2.0kpa, after prepolymerization reaction finishes, close vacuum system, under nitrogen protection and negative pressure, the antistatic additive that melting is good is injected, stir, deliver to terminal polymerization kettle after being filtered, carry out the final polymerization reaction, eventually poly-reaction condition is: 275～280 ℃ of temperature, pressure: 40～100pa, time: 2～4 hours, eventually after poly-the reaction, the pressurization pelletizing, make antistatic, ANTIPILLING, the cation dyeable polyester section, wherein, the addition of described antistatic additive is 0.5%～4.5% of polyester slice weight.
according to the present invention, the preparation process of described three monomer solutions is: Sodium Dimethyl Isophthalate-5-sulfonate (SIPM), ethylene glycol are fed intake 1:5.0～8.5 in molar ratio, add ester exchange catalyst, carry out ester exchange reaction at 135 ℃～185 ℃ of temperature, the ester exchange reaction rate is 60%～90%, after reaction finishes, add rapidly ethylene glycol to be cooled to 80 ℃～110 ℃, described ester exchange catalyst is one or more the combination in sodium acetate, calcium acetate, lithium acetate, zinc acetate and manganese acetate.Control ester exchange rate and can effectively prevent from forming the cationic salts self-aggregate.
according to the present invention, the number-average molecular weight of the described polyethylene glycol as the 4th monomer is preferably 1500～3000, and addition is preferably 1.5%～4.0% of polyester slice weight.
according to the present invention, when polyester slice is used for spinning polyester staple fiber, in polymerization process, the use amount of hydroxy silicon oil is wanted a little higher than long filament grade polyester chip, mainly will pass through steam-heated stretching process and heat-setting process in the short fiber spinning process, certain thermal degradation of fiber under the condition of high temperature in winding process, in stretching and HEAT SETTING process, the contact high-temperature steam, in macromolecular chain, the estersil bonding further ruptures, producing secondary viscosity falls, its fiber final response viscosity is: 0.54 ± 0.012, the fibrous fracture strength control exists: 3.0 ± 0.2, meet processing and taking intensity simultaneously, give the anti-pilling property that fiber is good.When polyester slice is used for spinning polyester filament, in polymerization process, the use amount of hydroxy silicon oil is slightly lower than the high comfortable copolyester section of staple fibre level, but add relatively the 4th monomer polyethylene glycol of a large amount, so that in the situation that in spinning process for once viscosity fall, low-fiber fracture strength is effectively fallen.Its fiber final response viscosity is: 0.58 ± 0.012, and the fibrous fracture strength control exists: 2.6 ± 0.2, meeting processing and taking intensity simultaneously, give the anti-pilling property that fiber is good.Concrete scheme is: when for the preparation of staple fibre, the addition of hydroxy silicon oil is preferably 0.6%～1.2% of polyester slice weight.When the long filament for the preparation of polyester fiber, the addition of hydroxy silicon oil is preferably 0.1%～0.8% of polyester slice weight.
according to the present invention, described hindered amine light stabilizer can be for being selected from non-polymeric type high molecular weight hindered amine light stabilizer CHIMASSORB 119FL, 770 pairs (2 of polymerized hindered amine light stabilizer Chimassorb 944, Tinuvin 788 and light stabilizers, 2,6,6-tetramethyl-4-piperidyl) one or more in sebacate, being preferably the composite light stabilizer that more than two kinds, light stabilizer mixes, is for example Tinuvin 788 and the mixture of CHIMASSORB 119FL by weight 1:1.The addition of described hindered amine light stabilizer is preferably 15～90ppm(and take the polyester gross weight as benchmark).Described Hinered phenols antioxidant can be Irganox 1076, one or more in Irganox 1010 and Irgafos168, be preferably the composite antioxidant that the antioxidant more than two kinds mixes, for example Irganox 1076 and the mixture of Irganox 1010 by weight 1:3.The addition of Hinered phenols antioxidant is that 30～250ppm(be take the polyester gross weight as benchmark).Preferably, the addition of hindered amine light stabilizer is 35～60ppm, and the addition of Hinered phenols antioxidant is 75～180ppm.Adding of a certain amount of hindered amine light stabilizer and Hinered phenols antioxidant, guaranteed that polyester has good light resistance and antioxygenic property.
according to the present invention, polymerization catalyst can be known various polyester polymerization catalysts.Particularly in the present invention, polymerization catalyst use antimony glycol, its addition to be generally 450～550ppm(to take the weight of polyester slice be benchmark).
the material chemical characteristic of gained polyester slice according to the present invention, can be spun into polyester the fiber of circle or odd-shaped cross section shape.Compare with conventional PET polyester to some extent and descend according to its fusing point of polyester slice of gained of the present invention, in spinning process, spinning condition is adjusted, implement the more common PTT polyester fiber of condition of spinning, each district's temperature of screw rod is lowered 8～15 ℃.Corresponding drawing and setting temperature also will be lowered.Those skilled in the art can adjust corresponding spinning condition according to the fusing point of concrete polyester slice.According to a concrete aspect of the present invention, spinning temperature is controlled at 255 ℃～278 ℃, and draft temperature is 142 ℃～150 ℃, and heat setting temperature is 110 ℃～135 ℃.
according to the present invention, prepared antistatic, ANTIPILLING, cation easily dye polyester chip, owing to having added multiple modified component, the more conventional PET polyester of its section vitrification point has decline in various degree, easily cause bonding in the spinning chips dry run, before spinning, at first carry out pre-crystallized can effectively avoiding and bond.A concrete scheme is: before spinning process, antistatic, ANTIPILLING, cation dyeable polyester section are successively carried out to pre-crystallized and dry step, wherein, it is that 110 ℃～125 ℃, time are 3～5 hours that pre-crystallized temperature is controlled, dry first at 130 ℃～145 ℃ of temperature, carry out 3.5～5.0 hours, then carry out 5～8 hours under 140 ℃～155 ℃.
due to the utilization of technique scheme, the present invention compared with prior art has following advantage:
1, by adding three monomers, the 4th monomer is given the fiber cationic dye normal temperature and pressure and is easily dyed function, can dye various beautiful colors, in conjunction with it, has permanent ANTIPILLING function, is the selection that other style is provided of dress shell fabric spring and summer.In the ester exchange reaction operation, to the control of BHET content and to the control of the ester exchange rate of three monomer solutions that add, effectively stop the SIPE self-polymeric reaction, guaranteed polyester cationic-dyeable, chromatophilia energy.
2, by add antistatic additive mid-term in polymerization, and use and to there is good hygroscopic polyethylene glycol as the 4th monomer, can keep, on section key property basis, obtaining good antistatic property, especially be applicable under spring, the autumn north dry climatic condition needs that clothes static is eliminated.Adding of the 4th monomer also is beneficial to the anti-pilling property that reduces fibrous fracture intensity and improve fiber.And make fiber obtain good softness, the gained fiber can be realized and the wool co-bathing dyeing, the blended yarn of itself and wool has antistatic, ANTIPILLING effect, can substitute now widely used acrylic and polyamide staple fibre on a large scale, has better wearing comfort.
3, the present invention adds hydroxy silicon oil in secondary esterification operation, and in forming the macromolecular chain process, hydroxy silicon oil participates in polymerisation, and on the one hand, the hydroxy silicon oil reaction activity is low, is conducive to accelerate polymerization rate; On the other hand, bonding after itself and carboxylic acid reaction belongs to weak bond, easy fracture is heated in spinning process, can make polyester fondant produce evenly and larger viscosity is fallen, so, by controlling addition and the spinning condition of hydroxy silicon oil, can produce on the one hand the section kind that is applicable to staple fibre and the different spinning requirement of long filament, different according to staple fibre and continuous yarn spinning technique on the other hand, can control polyester viscosity during spinning silk winding and drawing and setting falls, effectively reduce fibre strength, thereby make fiber there is good anti-pilling property.
4,, by adding a certain amount of hindered amine light stabilizer and Hinered phenols antioxidant, guaranteed that polyester has good light resistance and antioxygenic property; Hindered amine light stabilizer and Hinered phenols antioxidant first are dispersed in acetic acid and ethylene glycol and add, can under the prerequisite that does not affect product quality, (flash distillation can occur rapidly in acetic acid in the prepolymerization reaction process, the discharge system), effectively suppress hindered amine light stabilizer at high temperature react with Hinered phenols antioxidant and the follow-up hydroxy silicon oil added (be the Bronsted acid with some strength under hydroxy silicon oil high temperature, can at high temperature produce and react with hindered amine light stabilizer and Hinered phenols antioxidant).
5, for being applicable to clothes characteristics spring and summer, especially summer clothes requires hygroscopicity, poisture-penetrability, the requirement of the pleasant performance such as rapid-drying properties, giving the resistant fiber balling-up, antistatic, in the time of the normal atmosphere cation-dyeable ability, also can be by using the odd-shaped cross section spinnerets in the process by this polyester slice spinning fibre, produce the hydroscopic fast-drying fiber of all size, circular and three leaves of 40～111dtex/24 of its production～96f specification, cross, the various profiled fibres such as five leaves, through knitting, woven one-tenth fabric, its Specifications is after tested: anti-pilling property>=4 grade, fiber volume fraction resistance≤10
10
Ω .cm, evaporation rate>=0.20g/hr.
The specific embodiment
below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.
three monomer solutions that use in following examples are ester exchange rate is 60～90%, ethylene isophthalate-5-sodium sulfonate (SIPE) content is 40wt% solution.
in following examples, all adopt that the pH value is 4～5, (solvent is ethylene glycol to the seasoning liquid of the composite light stabilizer of mass concentration 2%, and use the vinegar acid for adjusting pH value), and the pH value is 4～5, the seasoning liquid (solvent is ethylene glycol, and uses the vinegar acid for adjusting pH value) of the composite antioxidant of mass concentration 2%.Wherein, composite light stabilizer is comprised of by weight 1:1 Tinuvin 788 and CHIMASSORB 119FL; Composite antioxidant is comprised of by weight 1:3 Irganox 1076 and Irganox 1010.
in addition, for adapting to different spinning process requirements, it is 0.590 ± 0.012 that short fiber grade polyester chip inherent viscosity is controlled; 245 ± 1 ℃ of fusing points; 72 ± 1 ℃ of vitrification points; It is 0.600 ± 0.012 that long fine grade polyester chip inherent viscosity is controlled; 247 ± 1 ℃ of fusing points; 73 ± 1 ℃ of vitrification points.
embodiment 1
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 2500 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 160g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by melting is good 226g antistatic additive 102 injected systems, mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, discharging pelletizing after polymerisation completes, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 2
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 2500 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 120g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by 339g antistatic additive 103 injected systems of having melted, mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the discharging pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 3
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 3000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 160g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by 226g antistatic additive 102 injected systems of having melted, continue to mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the discharging pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 4
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 3000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 120g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition, by 339g antistatic additive 103 injected systems of having melted, mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the pressurization pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 5
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 4000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 160g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by 226g antistatic additive 102 injected systems of having melted, continue to mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, the pressurization pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 6
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 4000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 120g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by 339g antistatic additive 103 injected systems of having melted, mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the discharging pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 7
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 2000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 180g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by the 275g antistatic additive that melted (being formed by weight 1:1 by antistatic additive 103 and antistatic additive 102) injected system, mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the discharging pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
embodiment 8
the present embodiment provides the preparation method of a kind of antistatic, ANTIPILLING, normal pressure cation dyeable polyester section, and it comprises the steps:
(1), an esterification operation: get 18kg p-phthalic acid (PTA), 7.05kg ethylene glycol (EG), add 70 liters of polyester experimental provisions, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 255～260 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish reaction.
(2), ester exchange reaction operation: after an esterification completes, add ethylene glycol cooling depolymerization, temperature is controlled 220～245 ℃, 0.4～1.0 hour time, then add 1400g tri-monomer solutions, after stirring, be warming up to 255 ℃, carry out ester exchange reaction, make unreacted completely SIPM complete ester exchange reaction.
(3), secondary esterification operation: after ester exchange reaction completes; at first add ethylene glycol; make temperature of reaction kettle be down to 230～235 ℃, the polyethylene glycol that is then 2000 by the 450g number-average molecular weight that heating and melting is good adds reactor under nitrogen protection, stirs.Then add the 1.125g composite light stabilizer with above-mentioned seasoning liquid form, with above-mentioned seasoning liquid form, add the above-mentioned composite antioxidant of 3.375g.After adding, stir.Reactor starts to heat up, and slowly adds the hydroxy silicon oil that the 120g hydroxyl value is 5.5%, carries out the secondary esterification, reaches 260 ℃ to temperature of reaction kettle.The water outlet of hydroxy silicon oil secondary esterification completes, and esterification column backs down the cooling of beginning.
(4), polymerisation operation: after the secondary esterification completes, add polymerization catalyst, deliver to prepolymerization kettle intensification polymerization, control 255～270 ℃ of temperature, open vavuum pump, slowly be down to 2Kpa in 40 minutes, the low vacuum polymerisation finishes, close vacuum system, under nitrogen protection and negative pressure condition by the 275g antistatic additive that melted (being formed by weight 1:1 by antistatic additive 103 and antistatic additive 102) injected system, continue to mix 2 minutes, the reactor pressurization, the pre-polymerization melt enters terminal polymerization kettle after the pre-polymerization filter filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～280 ℃ conditions, to reaching regulation viscosity, stop polymerisation, the pressurization pelletizing, obtain antistatic, ANTIPILLING, cation dyeable polyester section 23.8kg, its test result is in Table 1.
table 1 is antistatic, ANTIPILLING, normal pressure cation dyeable polyester section physical and chemical index
as known from Table 1, that prepared by method of the present invention is antistatic, ANTIPILLING, normal pressure cation dyeable polyester section physical and chemical index are good, shows that the preparation method is reasonable.
the polyester slice of embodiment 1,3,5,7 of take respectively is raw material, prepare as follows there is antistatic, ANTIPILLING, normal atmosphere cation-dyeable complex function polyester staple fiber: at first by polyester slice, undertaken pre-crystallized, 110 ℃～125 ℃ of pre-crystallized temperature controls, time are 3～5 hours, then carry out drying, first at 130 ℃～145 ℃ of temperature dry 3.5～5.0 hours, under 140 ℃～155 ℃ dry 5～8 hours again, carry out spinning after completing drying.Use the odd-shaped cross section spinneretss such as three leaves, cross, five leaves.At first on the short fiber spinning production line, produce through reeling, oiling process is made the short fiber tow, spinning speed 850m/min, spinning temperature is controlled at 255 ℃～278 ℃, (because a large amount of modified additives are used in this section, the section melting point depression, in spinning process, will be according to the fusing point of copolyester section, spinning and condition are adjusted, the condition of implementing spinning compares the common PET polyester fiber, each district's temperature of screw rod is lowered 8～15 ℃), then, the short fiber tow is through falling barrel balance after 24 hours, then boundling is stretched, the steam heat setting process, draft temperature is 142 ℃～150 ℃, 110 ℃～135 ℃ of heat setting temperatures, then after the carrier bar drying process, cut off, fixed heavy, finished fiber is made in packing.Product specification is 1.56dtex/38mm, and its fiber volume fraction resistance is about 0.85 * 10
10
Ω .cm.This fiber, through spinning (50s), is made into knitting and woven fabric, and its Specifications is in Table 2 after tested.
the polyester slice of embodiment 2,4,6,8 of take respectively is raw material, prepare as follows there is antistatic, ANTIPILLING, the normal atmosphere cation-dyeable composite functional polyester fiber: at first by polyester slice, undertaken pre-crystallized, 110 ℃～125 ℃ of pre-crystallized temperature controls, time are 3～5 hours, then carry out drying, first at 130 ℃～145 ℃ of temperature dry 3.5～5.0 hours, under 140 ℃～155 ℃ dry 5～8 hours again, carry out spinning after completing drying.Use the odd-shaped cross section spinneretss such as three leaves, cross, five leaves.At first to spin the pre-oriented yarn (POY) of corresponding product, spinning temperature is controlled at 255 ℃～278 ℃, (because a large amount of modified additives are used in this section, the section melting point depression, in spinning process,, according to the fusing point of copolyester section, spinning and condition are adjusted, the condition of implementing spinning compares the common PET polyester fiber, and each district's temperature of screw rod is lowered 8～15 ℃.), POY fibre spinning speed 2680m/min.The POY fiber of spinning is through after 24 hours balances, then stretches and texturing craft through corresponding, and draft temperature is 142 ℃～150 ℃, prepares corresponding drawing and setting temperature and also will lower.The preparation specification is the low stretch network product that 83.3dtex/36f has the hydroscopic fast-drying function, and its fiber volume fraction resistance is about 0.92 * 10
10
Ω .cm.Fiber quality is good, and fiber is through the knitting and woven fabric of making, and after tested, the fabric performance index is in Table 2.
that table 2 has is antistatic, ANTIPILLING, cationic-dyeable composite functional polyester fiber fabric performance
as seen from Table 2, by the polyester fiber of polyester slice of the present invention spinning made fabric antistatic, anti-pilling good, utilize its atmospheric cation dyestuff performance can dye various beautiful colors, current top grade clothes spring and summer have been met to functional and unified requirement color, simultaneously, this fiber also can with the wool co-bathing dyeing, with wool blended acquisition good take effect.Gained fiber that polyester slice spins of the present invention is to an important supplement in the current cationic dyeable polyester fiber of China market, has wide market prospects.
above the present invention is described in detail, the equivalence that all Spirit Essences according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. the preparation method of antistatic a, ANTIPILLING, normal pressure cation dyeable polyester section, it is characterized in that: described preparation method specifically comprises the steps:
(1), an esterification operation: terephthalic acid (TPA), ethylene glycol are joined in reaction kettle of the esterification 1:1.2～1.3 in molar ratio, carry out an esterification and generate the two hydroxyl glycol esters of terephthalic acid (TPA) under 255 ℃～260 ℃;
(2), ester exchange reaction operation: after a described esterification completes, add ethylene glycol cooling depolymerization, at 220～245 ℃ of temperature, keep 0.4～1.0 hour, control the two hydroxyl glycol ester mass content of terephthalic acid (TPA) in material and reach 55%～80%, then add three monomer solutions, after stirring, progressively be warming up to 255 ℃～260 ℃, carry out ester exchange reaction, going out methyl alcohol to esterification completes, wherein, the ester exchange rate that described three monomer solutions are Sodium Dimethyl Isophthalate-5-sulfonate and ethylene glycol generation ester exchange reaction gained under ester exchange catalyst exists is 60%～90%, the solution that the M-phthalic acid binaryglycol ester-5-sodium sulfonate mass content is 35%～45%, wherein, 0.5%～3.5% of the amount of substance that the amount of substance of the Sodium Dimethyl Isophthalate-5-sulfonate used is terephthalic acid (TPA),
(3), secondary esterification operation: in the system after completing to step (2) ester exchange reaction, add ethylene glycol, make system be cooled to 230 ℃～235 ℃, under inert gas shielding, add polyethylene glycol that number-average molecular weight is 600～6000 as the 4th monomer, the addition of the 4th monomer is 1.0%～6.5% of polyester slice weight, then add the seasoning liquid of the hindered amine light stabilizer that mass concentration is 2%～5% and the seasoning liquid of the Hinered phenols antioxidant that mass concentration is 2%～5%, take polyester slice weight as benchmark, the addition of described hindered amine light stabilizer and Hinered phenols antioxidant is respectively 10～300ppm, the seasoning liquid of described hindered amine light stabilizer be hindered amine light stabilizer be dispersed in solvent ethylene glycol and add acetic acid after the gained pH value solution that is 4～5, the seasoning liquid of described Hinered phenols antioxidant be Hinered phenols antioxidant be dispersed in solvent ethylene glycol and add acetic acid after the gained pH value solution that is 4～5, after adding, stir, reactor starts to heat up, slowly add the hydroxy silicon oil that hydroxyl value is 0.5%～8.0%, carry out the secondary esterification, finish to the esterification water outlet, the addition of wherein said hydroxy silicon oil is 0.1%～1.2% of polyester slice weight,
(4), polymerisation operation: after the secondary esterification finishes, add polymerization catalyst, after stirring, deliver in prepolymerization kettle, carry out prepolymerization reaction, the prepolymerization reaction temperature is controlled at 255 ℃～270 ℃, pressure is 0.6～2.0KPa, after prepolymerization reaction finishes, close vacuum system, under nitrogen protection and negative pressure, the antistatic additive that melting is good is injected, stir, deliver to terminal polymerization kettle after being filtered, carry out the final polymerization reaction, eventually poly-reaction condition is: 275～280 ℃ of temperature, pressure: 40～100Pa, time: 2～4 hours, eventually after poly-the reaction, the pressurization pelletizing, make antistatic, ANTIPILLING, the cation dyeable polyester section, wherein, the addition of described antistatic additive is 0.5%～4.5% of polyester slice weight.
2. according to claim 1 antistatic, ANTIPILLING, the preparation method of normal pressure cation dyeable polyester section, it is characterized in that: the preparation process of described three monomer solutions is: by Sodium Dimethyl Isophthalate-5-sulfonate, ethylene glycol 1:5.0～8.5 in molar ratio feeds intake, add ester exchange catalyst, carry out ester exchange reaction at 135 ℃～185 ℃ of temperature, the ester exchange reaction rate is 60%～90%, after reaction finishes, add rapidly ethylene glycol to be cooled to 80 ℃～110 ℃, described ester exchange catalyst is sodium acetate, calcium acetate, lithium acetate, the combination of one or more in zinc acetate and manganese acetate.
3. the preparation method of antistatic, ANTIPILLING according to claim 1, normal pressure cation dyeable polyester section, it is characterized in that: described hindered amine light stabilizer is for being selected from non-polymeric type high molecular weight hindered amine light stabilizer
119FL, one or more in 770 pairs of (2,2,6,6-tetramethyl-4-piperidyl) sebacates of polymerized hindered amine light stabilizer Chimassorb944, Tinuvin788 and light stabilizer.
4. the preparation method of antistatic, ANTIPILLING according to claim 3, normal pressure cation dyeable polyester section is characterized in that: the weight of polyester slice of take is benchmark, and the addition of described hindered amine light stabilizer is 15～90ppm.
5. the preparation method of antistatic, ANTIPILLING according to claim 1, normal pressure cation dyeable polyester section, it is characterized in that: described Hinered phenols antioxidant is Irganox1076, one or more in Irganox1010.
6. the preparation method of antistatic, ANTIPILLING according to claim 5, normal pressure cation dyeable polyester section is characterized in that: the weight of polyester slice of take is benchmark, and the addition of described Hinered phenols antioxidant is 30～250ppm.
7. according to the preparation method of described antistatic, the ANTIPILLING of any one claim in claim 1 to 6, normal pressure cation dyeable polyester section, it is characterized in that: the addition of described hindered amine light stabilizer is 35～60ppm, and the addition of described Hinered phenols antioxidant is 75～180ppm.
8. according to the preparation method of described antistatic, the ANTIPILLING of any one claim in claim 1 to 6, normal pressure cation dyeable polyester section, it is characterized in that: described hindered amine light stabilizer is the composite light stabilizer that the light stabilizer more than two kinds mixes; Described Hinered phenols antioxidant is the composite antioxidant that the antioxidant more than two kinds mixes.
9. according to the preparation method of described antistatic, the ANTIPILLING of any one claim in claim 1 to 6, normal pressure cation dyeable polyester section, it is characterized in that: when described polyester slice is used for spinning filament yarn, the addition of described hydroxy silicon oil is 0.1%～0.8% of polyester slice weight; When described polyester slice is used for spinning staple fibre, the addition of described hydroxy silicon oil is 0.6%～1.2% of polyester slice weight.
10. according to the preparation method of described antistatic, the ANTIPILLING of any one claim in claim 1 to 6, normal pressure cation dyeable polyester section, it is characterized in that: described antistatic additive is one or more the combination in antistatic additive 102, antistatic additive 103, antistatic additive 105 and antistatic additive 308, and its addition is 0.65%～2.5% of described polyester slice weight.
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| CN109320440A (en) * | 2018-11-20 | 2019-02-12 | 上海炼升化工股份有限公司 | A method of synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate |
| CN113668092B (en) * | 2021-10-25 | 2022-02-08 | 苏州宝丽迪材料科技股份有限公司 | Polyester fiber and method for producing same |
| CN114149574B (en) * | 2021-12-02 | 2022-09-13 | 浙江佳人新材料有限公司 | Process for producing normal-pressure easily-dyed cationic polyester chips by chemical cyclic regeneration method |
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