CN102443147B - Preparation method of anti-ultraviolet anti-aging polyester slices - Google Patents
Preparation method of anti-ultraviolet anti-aging polyester slices Download PDFInfo
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Abstract
The invention relates to a preparation method of anti-ultraviolet anti-aging polyester slices. The preparation method comprises an esterification reaction working procedure and a polymerization reaction working procedure which are sequentially carried out, wherein in an esterification reaction, a third monomer with larger steric hindrance is introduced; after esterification reaction and before prepolymerization reaction, high-content titanium dioxide serving as a flatting agent, a hindered amine light stabilizer and a hindered phenol antioxidant are added; and after prepolymerization and before final polymerization in the polymerization reaction working procedure, an ultraviolet absorbent is added. The polyester fibers spun from the polyester slices prepared by the method provided by the invention have excellent anti-ultraviolet and anti-aging performances; and after the polyester fibers are knitted/woven into knitted/woven fabric, test shows that the fabric has the correlated technical index, namely not more than 5.0% of ultraviolet light transmittance, is suitable for outdoor sun perpendicular incidence conditions and has good shielding and anti-aging functions.
Description
Technical field
The present invention relates to a kind of preparation method of polyester slice, particularly the preparation method of a kind of uvioresistant, anti-aging polyester slice.
Background technology
Since the autopolyester fiber comes out, rely on its good intensity, good wrinkle resistance, draping property and wash and wear performance and be widely used in apparel textile, through the tremendous development of nearly decades, the PET trevira has become at present the synthesizing polyester kind that output is maximum in the world, range of application is the widest.But trevira is compared and also existed many deficiencies with various natural fibers: feel is hardened, water absorbability is poor, anti-ultraviolet property is poor, easily produce static, easily balling-up, be difficult to dyeing etc.Although, and natural fiber has ventilation property as cotton, real silk, hair, fiber crops etc. have good dyeing behavior, fabric, the absorbing sweat performance of keeping humidity is good, without static, characteristics that comfortableness is good, exist and easily wrinkle, lead the deficiencies such as wet and rapid-drying properties is poor.
Along with the progressively expansion of trevira range of application, from the seventies in last century, developed country is for the above-mentioned deficiency of trevira, the plurality of advantages of natural fiber of take is target, aspect the wearing comfort of fiber, from three aspects, improve the wear behavior of trevira.On the one hand: by the innovation of spinning technique technology, produce various differential fibre, progressively develop thin dawn, superfine Denier fibre spining technology, produce a series of differential spinning kinds such as sea-island fibre, tangerine lobe fiber, bicomponent composite fibre, modified cross-section fibre by composite spinning technology, make polyester fabric obtain rapid progress in function aspects such as flexibility, elasticity, Silks; On the other hand: by the co-blended spinning of different components, in the physical blending mode, produce the various fiber species with specific function, by the rear arrangement of fabric, also can give the function that fabric is brand-new; The third aspect: by copolyreaction, improve this body structure of polyester macromolecule chain, by introducing the copolymerization component group can improve the trevira fabric performance, permanently give fiber various properties.At present, comprise a series of functional polyalkylene ester fibers such as fire-retardant, cation-dyeable, high contraction, disperse dyeable, antistatic, uvioresistant, far infrared thermal insulation, trevira and fabric are segmented market and produced material impact.
The rapid progress of the chemical fibre market of China through reforming and opening up to the outside world in decades, in 68% level that has reached Gross World Product aspect the normal polyester fiber production, but the development and application field at the functional polyalkylene ester fiber, China is at present also in the starting stage, be limited at present the exploitation of single functional polyester and fiber more, as anti-ultraviolet polyester fiber, anti-static polyester fiber etc.And, for the exploitation with complex function, high added value functional fiber, also need the scientific research personnel badly and make a breakthrough in the multifunctional composite fiber field.
The Chinese invention patent that notification number is CN1204196C discloses a kind of uvioresistant zinc oxide complex polyester and preparation method thereof, at first the method prepares the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol, then after at the PET polyester, synthetic esterification stage finishes, before the rough vacuum polymerization, the suspension of anti ultraviolet agent intermediate zinc subcarbonate ethylene glycol is added, when polyreaction generates polyester, zinc subcarbonate decomposes generation zinc oxide, obtain uvioresistant zinc oxide complex polyester, wherein zinc oxide content is 0.1%～5% of polyester slice weight.In the method gained polyester, zinc oxide can keep less granularity, thereby absorb ultraviolet performance, strengthens.Yet, the method is in order to decompose zinc subcarbonate, must make to be aggregated in more than 285 ℃ and carry out, and zinc subcarbonate will resolve into carbonic acid gas, water and zinc oxide, and in whole collecting process, carbonic acid gas can affect vacuum tightness and cause section to contain a large amount of bubbles on the one hand, polycondensation final stage on the other hand, produces large quantity of moisture can produce DeR, have a strong impact on quality product, simultaneously, the zinc subcarbonate do not decomposed fully will continue to decompose in spinning process, the fiber spinnability variation, and breaking tenacity reduces.
The Chinese invention patent application that publication number is CN101864067A discloses a kind of preparation method with polyester of anti-ultraviolet function, and it comprises the manufacture of (1) compound anti ultraviolet agent: compound anti ultraviolet agent is comprised of inorganic uvioresistant screening agent and organic uv absorbers; The composition of inorganic uvioresistant screening agent is nano level TiO
2and Al
2o
3or SiO
2inorganic oxide; Organic uv absorbers is the benzotriazole category organic substance; The weight ratio of inorganic uvioresistant screening agent and organic uv absorbers is 1: 1, takes this compound anti ultraviolet agent and ethylene glycol and is made into slurries, then is placed in ball mill and disperses 0.5-1 hour; (2), the esterification operation: the terephthalic acid of melting and ethylene glycol, continuously or the intermittent entry esterifying kettle, 160～220 ℃ of temperature, carry out esterification under pressure 0.3Mpa, wait the water byproduct steamed reach theoretical amount 90% the time, esterification stops; (3) polyreaction operation: obtain terephthalic acid dihydroxyl ethyl ester monomer after the esterification operation, add compound anti ultraviolet agent, add catalyst acetic acid antimony simultaneously, send into polymerization process, in the terephthalic acid % by weight, the catalyzer add-on is 0.03-0.04%, and the add-on of compound anti ultraviolet agent is at 1.5-2.0%; Monomer first carries out prepolymerization in polymeric kettle under 215～225 ℃ of normal pressures, then in absolute pressure, is less than 150pa, at 285 ± 2 ℃ of temperature, carries out polymerization, impels reaction to reach certain polymerization degree, and the ethylene glycol of generation reclaims after condenser; (4), after condensation reaction finishes, material makes the uvioresistant polyester section through Cast Strip, cooling, pelletizing, drying.The deficiency of the method is: benzotriazole is organic phenolic compound, under hot conditions, as the protonic acid form, exists, and can destroy inorganic nanometer powder TiO
2and Al
2o
3or SiO
2surperficial organic agent, cause the reunion of inorganic nanometer powder in pre-collecting process.In addition, due to inorganic nanometer powder in polymerization process, continue the time of 4～6 hours under hot conditions, nanoparticle generation agglomeration is obvious, under the loose condition of low temperature oversubscription, the inorganic nano ion is to make light produce strong diffuse scattering effect through fabric the time with huge specific surface area, reach anti-ultraviolet purpose, but after long pyroreaction, inorganic nanometer powder is originally reunited in a large number and has been formed micro-size particles, diffuse scattering effect to light significantly reduces, in addition, the method adds the benzotriazole type organic before prepolymerization reaction, in the prepolymerization reaction process, can be drawn out of system because of a large amount of EG evaporations.
The Chinese invention patent that notification number is CN100503910C discloses a kind of Nano titanium nitride anti-ultraviolet polyester fiber, and it is by master batch method spinning uvioresistant fiber.The Chinese invention patent that notification number is CN1300246C discloses a kind of method of preparing uvioresistant polyester by nanometer titania generated in situ, though its ethylene glycol salt for preparing titanium carries out surface treatment through organic agent or silane coupling agent, but titanium ethylene glycolate is as polymerizing catalyst, the PET polyreaction is had to strong katalysis and side reaction Degradation, easily cause the PET hue of chip poor, molecular weight distribution is wide, in addition, the hydrolysis of polymerization process situ generates Nano titanium dioxide, the water molecules that the decomposition in polymerization later stage produces on the one hand has a strong impact on polyreaction, on the other hand, the Nano titanium dioxide that the method is made is good organic matter of sewage decomposing material, section is after long-time solar radiation, viscosity degradation, produce and decompose.The application for a patent for invention that publication number is CN101864067A, disclose anti-ultraviolet superfine terylene and preparation method thereof, is a kind of uvioresistant additive co-blended spinning technology of crossing through coupling agent treatment.The patent of invention that notification number is CN101735578B discloses a kind of fire-retardant uvioresistant matrix material and preparation method thereof, use be to take the inorganic nano ultraviolet ray-resistant material as ultraviolet scattering material, produce certain uvioresistant effect.
To sum up, thereby prior art is all mainly the huge specific surface area that relies on inorganic nanometer powder to have produces the uvioresistant effect for basis produces diffuse scattering to ultraviolet ray, stability and the efficiency of UVResistant effect are to be improved, this just need to start with from uvioresistant mechanism, the polyester that preparation has more excellent UVResistant effect and has good spinnability.In addition, also need exploitation badly when thering is anti-ultraviolet function, have other function for example resistance to deterioration, absorbing fast-drying concurrently, static resistance, the complex function polyester of anti-pilling.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and the preparation method of a kind of uvioresistant, anti-aging polyester slice is provided.
For solving above technical problem, the present invention takes following technical scheme:
The preparation method of a kind of uvioresistant, anti-aging polyester slice, comprise esterification operation and the polyreaction operation of carrying out successively, wherein:
Described esterification operation is implemented as follows: terephthalic acid, ethylene glycol and the 3rd monomer are joined in reaction kettle of the esterification, carry out esterification under 250 ℃～265 ℃, the molar ratio of described terephthalic acid, ethylene glycol is 1: 1.2～1.3, described the 3rd monomer is for being selected from m-phthalic acid, 1,4-cyclohexane cyclohexanedimethanodibasic, oreinol dioctyl phthalate, neopentyl glycol and 2, one or more in the 3-butyleneglycol, and its add-on is 0.3%～3.5% of terephthalic acid weight;
Described polyreaction operation is implemented as follows: after the esterification operation completes, at first add 0.5%～2.6% the titanium dioxide matting agent that weight is polyester slice weight, then add polymerizing catalyst, add the Hinered phenols antioxidant of the hindered amine light stabilizer of the 10～300ppm weight of polyester slice (take be benchmark) and 10～300ppm weight of polyester slice (take be benchmark) simultaneously, deliver to prepolymerization kettle after stirring and carry out prepolymerization reaction; Prepolymerization reaction is closed vacuum system, under nitrogen protection and negative pressure after finishing, the UV light absorber of liquid state or melting is injected, mixed, after the pre-polymerization strainer filters, enter terminal polymerization kettle, the add-on of described UV light absorber is 0.1%～2.0% of polyester slice weight; Finally, in terminal polymerization kettle, pressure 40～100pa, carry out the final polymerization reaction at 270 ℃～285 ℃ of temperature, and after final polymerization has reacted, the discharging pelletizing, obtain uvioresistant, anti-aging polyester slice.
According to the present invention, described the 3rd monomer is preferably the combination more than two kinds in m-phthalic acid, 1,4 cyclohexanedicarboxylic acid, oreinol dioctyl phthalate, neopentyl glycol and 2,3-butanediol, for example combination of m-phthalic acid and neopentyl glycol.
According to the present invention, described UV light absorber can be one or more the combination in the UV light absorber of following kind: Benzotriazole Ultraviolet Stabilizer:
326,
234,
350,
320,
328; The low volatility Benzotriazole Ultraviolet Stabilizer
360; The red shift Benzotriazole Ultraviolet Stabilizer
327; And
uV-P, the special UV light absorber CYASORB of cyanogen UV-3638F, triazine series UV light absorber UV-1577, the preferred add-on of UV light absorber is 0.15%～1.10% of polyester slice weight.Preferably, select one or more compound uses of following UV light absorber: Benzotriazole Ultraviolet Stabilizer:
234,
320,
328; The low volatility Benzotriazole Ultraviolet Stabilizer
360; The red shift Benzotriazole Ultraviolet Stabilizer
327; And
uV-P, the special UV light absorber CYASORB of cyanogen UV-3638F, triazine series UV light absorber UV-1577 etc.Particularly preferred, select one or more compound uses of the UV light absorber of following kind: Benzotriazole Ultraviolet Stabilizer:
234,
320,
328; And
uV-P, the special UV light absorber CYASORB of cyanogen UV-3638F.Add UV light absorber churning time afterwards to be preferably 3～8 minutes.
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
119FL, 770 pairs (2 of polymerized hindered amine photostabilizer Chimassorb944, Tinuvin 788 and photostabilizers, 2,6,6-tetramethyl-4-piperidyl) one or more in sebate, be preferably the composite light stabilizer that more than two kinds, photostabilizer mixes, be for example Tinuvin 788 with
119FL is the mixture of 1: 1 by weight.The add-on of described hindered amine light stabilizer is preferably 15～90ppm (take polyester slice 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 oxidation inhibitor more than two kinds mixes, for example Irganox1076 and Irganox 1010 was by weight the mixture of 1: 3.The add-on of Hinered phenols antioxidant is 30～250ppm (take polyester slice weight as benchmark).Preferably, the add-on of hindered amine light stabilizer is 35～60ppm, and the add-on of Hinered phenols antioxidant is 75～180ppm.A certain amount of hindered amine light stabilizer and Hinered phenols antioxidant can produce synergistic effect with UV light absorber as auxiliary component, have guaranteed that polyester has good photostabilization and antioxidant property.
According to the present invention, polymerizing catalyst can be known various polyester polymerizing catalysts.Particularly in the present invention, polymerizing catalyst is used antimony glycol, its add-on to be generally the 450～550ppm weight of polyester slice (take be benchmark).
The material chemical property of gained polyester slice according to the present invention, can be spun into polyester slice three leaves or the modified cross-section fibre such as cross special-shaped.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 trevira 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.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantage:
1, for uvioresistant in prior art, anti-aging copolyesters and fiber thereof are in exploitation and use procedure, use inorganic nano material, by increasing the specific surface area light reflection ultraviolet, reach anti-ultraviolet function, existing under the pyroreaction condition nanoparticle very easily reunite, the unsettled deficiency of product effect, the invention provides a kind of and anti-ultraviolet polyester fiber prior art has the uvioresistant mechanism of obvious difference aspect mechanism, be by process of polyester synthesizing, take UV light absorber as main, ultraviolet light in sunlight is converted to the light of other wavelength, and the auxiliary titanium dioxide matting agent with high-content reduces the penetrating amount of sunlight, further improved polyester uvioresistant effect.
2, from after esterification, added anti ultraviolet agent different in the past, the present invention is after prepolymerization reaction completes, poly-reaction adds the UV light absorber of liquid or melting before carrying out eventually, so, effectively reduce the residence time of UV light absorber, and significantly reduce the volatilization of UV light absorber, because melt kinematic viscosity after prepolymerization reaction completes is less, also guaranteed UV light absorber good dispersion effect in melt simultaneously.
3, the present invention adds a certain amount of photostabilizer and antioxidant, they and UV light absorber are collaborative, has improved the made fabric lining of the polyester ageing resistance under the direct sunlight condition out of doors.With anti-ultraviolet polyester in the past, compare, this product good spinnability in spinning process, intensity is high, even dyeing, row yielding is high.
4, the present invention adds the 3rd monomer with larger space steric hindrance, reduced the crystal property of trevira, prevent that out of doors under condition, the fiber predisposition is led the strength degradation that crystallization causes, fabric is eliminated because crystallization causes the impact of fabric strength decreased under the direct sunlight condition out of doors, improved the endurable performance of clothes.
5, the prepared polyester slice of the present invention can be spun into clothes trevira spring and summer, there is good uvioresistant, anti-aging function, the fiber that will be prepared by this polyester slice is made into knitting and woven fabric, its Specifications is after tested: uv transmittance≤5.0%, can be applicable to, under outdoor direct sunlight condition, thering is good protection and anti-aging function.As the various modified cross-section fibres of weaving, can give the hydroscopic fast-drying function that fiber is good, fabric after tested, measure wicking height >=120mm, vaporator rate >=0.20g/hr.
Embodiment
The present invention relates to the preparation method of uvioresistant, anti-aging polyester slice.In the process of synthetic polyethylene terephthalate, use a certain amount of UV light absorber as trevira uvioresistant additive major constituent, this UV light absorber comprises one or more compound uses that mainly are adapted to the polyester interpolation, and its add-on is 0.1～2.0% of polyester slice weight.For guaranteeing that polyester has good photostabilization and antioxidant property, UV light absorber and a certain amount of hindered amine light stabilizer and Hinered phenols antioxidant are used in conjunction with as auxiliary component, produce synergistic effect, make fabric have out of doors anti-aging function, such promoter addition is controlled at respectively 10～300ppm.Simultaneously, use m-phthalic acid, 1,4 cyclohexanedicarboxylic acid, neopentyl glycol etc. to have the diprotic acid of larger space steric hindrance or dibasic alcohol as reducing the fibre crystallinity modified component, add-on is 0.3～3.5% of terephthalic acid (PTA) weight; And adding high-content titanium dioxide matting agent, content is 0.5～2.6%, reduces light penetration when playing photoextinction, has further improved the anti-ultraviolet function of product.Can adopt the normal polyester production technique to be produced, special, UV light absorber with liquid state or molten state injected system, enters after filtering terminal polymerization kettle and completes polyreaction after prepolymerization reaction completes, and obtains uvioresistant, anti-aging polyester slice.This polyester slice spins three leaves or the trevira with good uvioresistant, absorbing fast-drying complex function such as cross special-shaped through spinning jet pre-crystallized, dry, that use particular design.
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.
Embodiment 1
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add in 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring; control 260 ℃～275 ℃ of temperature; open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes; close vacuum system, under nitrogen protection and negative pressure condition by 113g Benzotriazole Ultraviolet Stabilizer liquid or that melting is good
234, by the specific equipment injected system, after mixing 5 minutes, after filtering, the pre-polymerization strainer enters terminal polymerization kettle, open high vacuum, pressure is 40～100pa, carries out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, and its test result is in Table 1.
Embodiment 2
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg1, the 4-cyclohexane cyclohexanedimethanodibasic, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring; control 260 ℃～275 ℃ of temperature; open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes; close vacuum system, under nitrogen protection and negative pressure condition by 226g Benzotriazole Ultraviolet Stabilizer liquid or that melting is good
234, by the specific equipment injected system, after mixing 5 minutes, after filtering, the pre-polymerization strainer enters terminal polymerization kettle, open high vacuum, pressure is 40～100pa, carries out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, and its test result is in Table 1.
Embodiment 3
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260 ℃～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by 113g UV light absorber liquid or that melting is good
320, by the specific equipment injected system, after mixing 5 minutes, after filtering, the pre-polymerization strainer enters terminal polymerization kettle, open high vacuum, pressure is 40～100pa, carries out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, and its test result is in Table 1.
Embodiment 4
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg 1, the 4-cyclohexane cyclohexanedimethanodibasic, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2) polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260 ℃～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by 226g UV light absorber liquid or that melting is good
320, by the specific equipment injected system, after mixing 5 minutes, after filtering, the pre-polymerization strainer enters terminal polymerization kettle, open high vacuum, pressure is 40～100pa, carries out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, and its test result is in Table 1.
Embodiment 5
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.0% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260 ℃～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by liquid or melting is good 113g UV light absorber (
234 with
320 mixture, the ratio of the two weight is 1: 1), by the specific equipment injected system, mix after 5 minutes, enter terminal polymerization kettle after the pre-polymerization strainer filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, its test result is in Table 1.
Embodiment 6
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.0% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by liquid or melting is good 226g UV light absorber (
234 with
320 mixtures, the ratio of the two weight is 1: 1), by the specific equipment injected system, mix after 5 minutes, enter terminal polymerization kettle after the pre-polymerization strainer filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, its test result is in Table 1.
Embodiment 7
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add in 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.0% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
the 119FL weight ratio was mixed by 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3)).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260 ℃～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by liquid or melting is good 113g UV light absorber (
234 with the special UV light absorber CYASORB of cyanogen UV-3638F, the ratio of the two weight is 2: 1), by the specific equipment injected system, mix after 5 minutes, enter terminal polymerization kettle after the pre-polymerization strainer filters, open high vacuum, pressure is 40～100pa, carry out conventional polymerization under 270 ℃～285 ℃ conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain uvioresistant, anti-aging polyester slice 22.5kg, its test result is in Table 1.
Embodiment 8
The present embodiment provides the preparation method of a kind of uvioresistant, anti-aging polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250 ℃～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.0% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).Deliver to prepolymerization kettle intensification polymerization after stirring, control 260 ℃～275 ℃ of temperature, open vacuum pump; slowly be down to 2Kpa in 40 minutes; the rough vacuum polyreaction finishes, and closes vacuum system, under nitrogen protection and negative pressure condition by liquid or melting is good 226g UV light absorber (
234 with the mixture of the special UV light absorber CYASORB of cyanogen UV-3638F, the ratio of the two weight is 2: 1), by the specific equipment injected system, after mixing 5 minutes, after filtering, the pre-polymerization strainer enters terminal polymerization kettle, open high vacuum, pressure is 40～100pa, under 270～285 ℃ of conditions, carries out conventional polymerization, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes.Obtain uvioresistant, anti-aging polyester slice 22.5kg, its test result is in Table 1.
Comparative Examples 1
This Comparative Examples provides a kind of preparation method of polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).By 113g UV light absorber liquid or that melting is good
234, by the specific equipment injected system, after mixing 5 minutes, control 260～275 ℃ of temperature, open vacuum pump, slowly be down to 2Kpa in 40 minutes, the rough vacuum polyreaction finishes, and opens high vacuum, and pressure is 40～100pa, carry out conventional polymerization under 270～285 ℃ of conditions, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain polyester slice 22.5kg, its test result is in Table 1.
Comparative Examples 2
This Comparative Examples provides a kind of preparation method of polyester slice, and it comprises the steps:
(1), esterification operation: get 18kg pure terephthalic acid (PTA), 0.45kg m-phthalic acid, 0.05kg neopentyl glycol, 7.05kg ethylene glycol (EG) add 70 liters of reaction kettle of the esterification, after stirring, start to heat up and be forced into 0.3Mpa, carry out esterification, esterification temperature is controlled at 250～265 ℃, complete to the esterification water outlet, reply atmospheric pressure, finish to react to obtain polymerization single polymerization monomer.
(2), the polyreaction operation: after esterification completes, at first add the titanium dioxide matting agent, add-on is 1.5% of polyester slice weight, then adds polymerizing catalyst, and add the 1.125g composite light stabilizer (Tinuvin 788 with
119FL mixed by weight 1: 1), 3.375g composite antioxidant (Irganox 1076 mixes by weight with Irganox 1010 at 1: 3).By liquid or melting is good 113g UV light absorber (
234 with the mixture of the special UV light absorber CYASORBUV-3638F of cyanogen, the ratio of the two weight is 2: 1), by the specific equipment injected system, mix after 5 minutes, control 260～275 ℃ of temperature, open vacuum pump, slowly be down to 2Kpa in 40 minutes, the rough vacuum polyreaction finishes, open high vacuum, pressure is 40～100pa, under 270～285 ℃ of conditions, carries out conventional polymerization, to reaching regulation viscosity, stop polyreaction, discharging pelletizing after polyreaction completes, obtain polyester slice 22.5kg, and its test result is in Table 1.
The physical and chemical index of table 1 uvioresistant, anti-aging polyester slice
The quality index of the section by contrast above-described embodiment and Comparative Examples can be found out, polyester slice prepared by the present invention has kept the quality index of conventional PET polyester slice substantially, show that the preparation method is reasonable, and in Comparative Examples 1,2, due to adding of UV light absorber, caused the obvious flavescence of hue of chip, fusing point and second-order transition temperature raise, and show that the part UV light absorber takes system in the rough vacuum stage out of with a large amount of evaporations of ethylene glycol.
The polyester slice of above-described embodiment 1～8 and Comparative Examples 1～2 of take respectively is raw material, make trevira through pre-crystallized, dry, spinning, coiling, drawing and setting successively, different from common PET Direct-spinning of PET Fiber technique, this section is due to the titanium dioxide matting agent that adds modification UV light absorber, photostabilizer, oxidation inhibitor, the 3rd monomer and high-content, its section second-order transition temperature is lower, therefore must, through pre-crystallized, just can implement chip drying.
Above-mentioned preparation method is specific as follows: at first polyester slice is carried out pre-crystallizedly, it is 3～5 hours that pre-crystallized temperature is controlled 110 ℃～125 ℃, time.Then carry out drying, 130 ℃～145 ℃ of drying temperatures, the time is 3.5～5.0 hours.Carry out spinning after completing drying.Use the special crosssection spinning jets 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, be according to the fusing point of copolyester section, spinning and condition are adjusted, the condition of implementing spinning compares the common PET trevira, and each district's temperature of screw rod is lowered 8～15 ℃), POY fiber sprinning speed 2850m/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 40～111dtex/24～96f, have the low stretch network product of hydroscopic fast-drying function.Fiber quality is good.Finally, trevira is through the knitting and woven fabric of making, and the performance of fabric is in Table 2.
Table 2 trevira fabric performance
As seen from Table 2, the prepared fabric according to polyester of the present invention, its ultraviolet ray transmissivity significantly reduces, and anti-ultraviolet property is good.Generally speaking, uv transmittance≤5.0%, measure wicking height >=120mm, vaporator rate >=0.20g/hr, be particularly suitable for making spring, summer fashionable dress.
The fiber that polyester slice according to the present invention is spun into also can be used for making parasols, and curtain etc. have good result of use.
Above the present invention is described in detail, the equivalence that all spirit 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 a uvioresistant, anti-aging polyester slice, comprise esterification operation and the polyreaction operation of carrying out successively, it is characterized in that:
Described esterification operation is implemented as follows: terephthalic acid, ethylene glycol and the 3rd monomer are joined in reaction kettle of the esterification, carry out esterification under 250 ℃～265 ℃, the molar ratio of described terephthalic acid, ethylene glycol is 1:1.2～1.3, described the 3rd monomer is for being selected from m-phthalic acid, 1,4-cyclohexane cyclohexanedimethanodibasic, oreinol dioctyl phthalate, neopentyl glycol and 2, one or more in the 3-butyleneglycol, and its add-on is 0.3～3.5% of terephthalic acid weight;
Described polyreaction operation is implemented as follows: after the esterification operation completes, at first add 0.5%～2.6% the titanium dioxide matting agent that weight is polyester slice weight, then add polymerizing catalyst, add the Hinered phenols antioxidant that the weight of take hindered amine light stabilizer that the weight of polyester slice is benchmark 10～300ppm and take polyester slice is benchmark 10～300ppm simultaneously, deliver to prepolymerization kettle after stirring and carry out prepolymerization reaction; Prepolymerization reaction is closed vacuum system, under nitrogen protection and negative pressure after finishing, the UV light absorber of liquid state or melting is injected, mixed, after the pre-polymerization strainer filters, enter terminal polymerization kettle, the add-on of described UV light absorber is 0.1%～2.0% of polyester slice weight; Finally, in terminal polymerization kettle, pressure 40～100Pa, carry out the final polymerization reaction at 270 ℃～285 ℃ of temperature, and after final polymerization has reacted, the discharging pelletizing, obtain described uvioresistant, anti-aging polyester slice.
2. the preparation method of uvioresistant according to claim 1, anti-aging polyester slice is characterized in that: the combination of one or more in the UV light absorber that described UV light absorber is following kind: Benzotriazole Ultraviolet Stabilizer:
326,
234,
350,
320,
328; The low volatility Benzotriazole Ultraviolet Stabilizer
360; The red shift Benzotriazole Ultraviolet Stabilizer
327; And
uV-P, the special UV light absorber CYASORB of cyanogen UV-3638F, triazine series UV light absorber UV-1577.
3. the preparation method of uvioresistant according to claim 1 and 2, anti-aging polyester slice, it is characterized in that: the add-on of described UV light absorber is 0.15%～1.10% of polyester slice weight.
4. the preparation method of uvioresistant according to claim 1 and 2, anti-aging polyester slice is characterized in that: adding the mixing time after UV light absorber is 3～8 minutes.
5. the preparation method of uvioresistant according to claim 1, anti-aging polyester slice, 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) sebates of polymerized hindered amine photostabilizer Chimassorb944, Tinuvin788 and photostabilizer.
6. the preparation method of uvioresistant according to claim 5, anti-aging polyester slice, it is characterized in that: the add-on of described hindered amine light stabilizer is 15～90ppm.
7. the preparation method of uvioresistant according to claim 1, anti-aging polyester slice, it is characterized in that: described Hinered phenols antioxidant is Irganox1076, one or more in Irganox1010 and Irgafos168.
8. the preparation method of uvioresistant according to claim 7, anti-aging polyester slice, it is characterized in that: the add-on of described Hinered phenols antioxidant is 30～250ppm.
9. according to the preparation method of the described uvioresistant of any one claim, anti-aging polyester slice in claim 1,5 to 8, it is characterized in that: the add-on of described hindered amine light stabilizer is 35～60ppm, and the add-on of described Hinered phenols antioxidant is 75～180ppm.
10. according to the preparation method of the described uvioresistant of any one claim, anti-aging polyester slice in claim 1,5 to 8, it is characterized in that: described hindered amine light stabilizer is the composite light stabilizer that the photostabilizer more than two kinds mixes; Described Hinered phenols antioxidant is the composite antioxidant that the oxidation inhibitor more than two kinds mixes.
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| CN108950811B (en) * | 2018-08-24 | 2020-06-02 | 浙江蓝天海纺织服饰科技有限公司 | Crease-resistant soft tooling fabric and production process thereof |
| CN110055615B (en) * | 2019-04-25 | 2021-08-31 | 浙江恒冠化纤有限公司 | Production process of ultraviolet-resistant polyester low-stretch yarn |
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| CN101139435A (en) * | 2006-09-08 | 2008-03-12 | 东丽纤维研究所（中国）有限公司 | Polyester having excellent fire-retardancy and preparation method thereof |
| CN101857671A (en) * | 2009-04-08 | 2010-10-13 | 中国石油天然气股份有限公司 | High-shrinkage cationic normal-pressure easily-dyed polyester chip and preparation method thereof |
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| CN101041715A (en) * | 2006-03-21 | 2007-09-26 | 东丽纤维研究所（中国）有限公司 | Method and equipment for continuous production of ultraviolet resistant polyester |
| CN101139435A (en) * | 2006-09-08 | 2008-03-12 | 东丽纤维研究所（中国）有限公司 | Polyester having excellent fire-retardancy and preparation method thereof |
| CN101857671A (en) * | 2009-04-08 | 2010-10-13 | 中国石油天然气股份有限公司 | High-shrinkage cationic normal-pressure easily-dyed polyester chip and preparation method thereof |
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