CN101735430B - Method for continuously preparing modified polyester - Google Patents
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- CN101735430B CN101735430B CN2009103124594A CN200910312459A CN101735430B CN 101735430 B CN101735430 B CN 101735430B CN 2009103124594 A CN2009103124594 A CN 2009103124594A CN 200910312459 A CN200910312459 A CN 200910312459A CN 101735430 B CN101735430 B CN 101735430B
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Abstract
The invention relates to a method for continuously preparing modified polyester, comprising the following steps: conveying PET AND EG to an esterification autoclave from a feed port for esterification reaction, so as to obtain terephthalic acid ethylene glycol low polymer; then inputting the low polymer melt to a polycondensation autoclave through a pipeline for polymerization reaction with SIPM or multi-simplexes and addition agent, thus obtaining modified polyester melt and then carrying out granulation or direct spinning; wherein the two ends of the pipeline are respectively connected with the esterification autoclave and the polycondensation autoclave, when the low polymer melt flows through the pipeline, ethylene glycol solution of the SIPM or multi-simplexes and addition agent are added to the pipeline and mixed evenly with the low polymer melt in the pipeline, meanwhile the later-stage esterification reaction is carried out, and the mixture enters the polycondensation autoclave for polymerization reaction. With the method of the invention adopted, continuous industrialized production is realized, production cost is greatly reduced; in addition the SIPM or multi-simplexes with special groups are evenly distributed on the backbone of the polyester, as a result, high quality modified polyester products can be obtained for sure in the later stage.
Description
Technical field
The present invention relates to the preparation method of multiple modified poly ester, a kind of serialization of specific design prepares the method for modified poly ester.
Background technology
In recent years, along with the kind of polyester modification increases gradually, the continuous development of fabricating technology, the market share occupation rate of modified poly ester product is increasing, has formed the stable market requirement.This wherein the kind of large usage quantity mainly contain: cation dyeable polyester, acid-dyeable polyester, full-dull polyester, water-soluble polyester, low-melting point polyester, flame retardant polyester etc.Yet because high-crystallinity, high-orientation and the higher performances such as second-order transition temperature of polyethylene terephthalate (PET) fiber itself, the material of various dyestuffs or property is difficult to be diffused in the PET molecule and goes in the presence of the normal pressure carrier free, brought difficulty for the preparation technology of dyeing or property polyester, therefore in order to obtain high performance modified poly ester, the technology of following adopted often will be carried out under High Temperature High Pressure and the severe condition that have carrier to exist, but these method cost height, contaminate environment.For solving above-mentioned problems, use in the market is that the third method of employing promptly adds the 3rd monomer or many monomers carry out modification by copolymerization more widely, promptly introducing the 3rd monomer or many monomers make it and its formation segmented copolymer (being called copolyesters again) or blend in the macromolecular chain of PET, this the 3rd monomer or many monomers contain the functional group of property, can with cationic dyestuff, matching stain generation chemical reaction, make dyestuff be easy to fix, it is fire-retardant also to give it, original liquid coloring, the good rerum natura of disappearing property of light, thereby fundamentally change the dyeing of section, fire-retardant, many performances such as water-soluble, and can not park or use owing to the time is long and fade, problems such as property forfeiture.In addition, adopt the modified poly ester product that adds three monomers or the preparation of many monomer methods much higher on cost performance, thereby the existing market demand is increasing with the modified poly ester product that adopts traditional blending modification method preparation.
As the bigger field of market demand, the preparation of modified poly ester all the time is in the interrupter method production phase, though this method has the advantage of the handiness of production, the product lack of homogeneity that it is produced is all to be in tangible inferior position on cost, quality or output.The increase of particularly nearest domestic polyester raw material cost, market competition are fierce day by day, in order to guarantee product low cost, high quality, force enterprise to open up the competitive edge that new approach improves the modified poly ester product that forms scale by every means.Very fast in conjunction with the engineering development of current domestic Large Scale and Continuous polyester, how intermittently the Flexible Production of the small-sized apparatus for continuous polycondensation of part is a good approach, promptly solve the stable mass production of realization on apparatus for continuous polycondensation of sophisticated modified poly ester kind success.Can predict from the transformation process of present stage continuous polycondensation engineering construction and some devices, what modified poly ester was produced in serialization will replace the intermittenceization production model gradually.So the technological development that small-sized apparatus for continuous polycondensation is produced modified poly ester has bigger advantage and good market outlook.
Therefore, based on the consideration of above-mentioned each side, the present invention develops the continuous process flow process to adapt to serialization production in enormous quantities, in the hope of obtaining steady quality, the modified poly ester product of good uniformity.
Summary of the invention
The purpose of this invention is to provide the method that a kind of serialization prepares modified poly ester, this method has realized industrial continuous production, greatly reduce production cost, the modified poly ester of preparing can make three monomers or many monomers specific functional groups of giving its performance relatively be evenly distributed on the polyester backbone, make the various performance homogeneity of polyester after its modification good, and the phenomenon of loss of performance does not take place in long-time placement.
For realizing purpose of the present invention, a kind of serialization prepares the method for modified poly ester, comprises the steps:
Raw material terephthalic acid and ethylene glycol join from opening for feed and carry out esterification in the esterifying kettle; obtain oligoterephthalic acid glycol ester; the oligoterephthalic acid glycol ester melt is input in the polycondensation vessel with three monomers or many monomers and additive by pipeline and carries out polyreaction afterwards; follow-up pelletizing or the direct fabrics of carrying out of modified poly ester melt that reaction obtains; it is characterized in that; the two ends of described pipeline link to each other with polycondensation vessel with esterifying kettle respectively; in the oligopolymer melt-flow during through this pipeline; the ethylene glycol solution of three monomers or many monomers and additive joins in the pipeline; mix in pipeline with the oligopolymer melt; carry out the reaction in esterification later stage simultaneously, enter then and carry out polyreaction in the polycondensation vessel.
The method that mixes in pipeline is by high-shear homogenizing pump or/and mix in the homogenizer, and it preferably mixes by high-shear homogenizing pump and homogenizer.
Utilize these dynamic mixers of high-shear homogenizing pump and homogenizer or motionless mixer and the dynamically combination of mixer, oligomer solution and three monomers or many monomers are mixed, homogenizer also provides high pressure and has increased the residence time simultaneously, thereby guarantees mixture homogeneous phase, plug flow and fully reaction within it.Make the group that has various characteristics be evenly distributed on the main chain of polyester, guaranteed that the later stage obtains high-quality modified poly ester product
Described pipeline is provided with injected system, humidity control system and high-shear homogenizing pump and/or homogenizer, and its preferred pipeline is provided with injected system, humidity control system, high-shear homogenizing pump and homogenizer.
Modified poly ester comprises cation dyeable polyester, anionic dyestuff dyeable polyester, water-soluble polyester, low-melting point polyester, high-contraction polyester, full-dull polyester, original liquid coloring polyester or flame retardant polyester etc.
Described additive comprises catalyzer or stablizer, and wherein catalyzer comprises magnesium compounds, manganese compounds, titanium compound, antimony compounds or germanium compounds, its preferred antimony compounds, more preferably antimony glycol, antimony acetate or ANTIMONY TRIOXIDE SB 203 99.8 PCT; Described stablizer comprises trimethyl phosphite 99 ((CH
3O)
3PO
4).
When the above-mentioned modified poly ester of preparation, can add this area three monomers or many monomers commonly used, the present invention has enumerated some concrete various modified poly esters three monomers or many monomers commonly used respectively:
Three monomers that the preparation process of described cation dyeable polyester adds comprise dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described anionic dyestuff dyeable polyester adds are Macrogol 2000, its solution quality percentage concentration is 40%-70%, four monomers are dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described water-soluble polyester adds are m-phthalic acid, its solution quality percentage concentration is 60%-80%, four monomers are Macrogol 2000 or hexanodioic acid, its solution quality percentage concentration is 40%-70%, five monomers are dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described low-melting point polyester adds are m-phthalic acid, and its solution quality percentage concentration is 60%-80%, and four monomers are glycol ether, and its quality percentage composition is 100%;
Three monomers that the preparation process of described high-contraction polyester adds are m-phthalic acid, and its solution quality percentage concentration is 60%-80%, and four monomers are glycol ether, its quality percentage composition 100%;
Three monomers that the preparation process of described full-dull polyester adds are titanium dioxide, and its solution quality percentage concentration is 10%-30%;
Three monomers that the preparation process of described original liquid coloring polyester adds are carbon black, and its solution quality percentage concentration is 5%-30%;
Three monomers that the preparation process of described flame retardant polyester adds are hydroxyethyl phenyl phosphoric acid, and its solution quality percentage concentration is 20%-50%.
Described pipe temperature is 230-265 ℃, and pressure is 0.1-1MPa, oligopolymer melt in pipeline residence time 10-50 minute.
In the oligopolymer melt-flow during through pipeline, the ethylene glycol of flowing through successively adds pipeline, three monomers or how monomeric ethylene glycol solution and adds pipeline and additive solution interpolation pipeline, three monomers or many monomer solutions add the 1%-30% that fashionable flow is the oligopolymer flow, the flow that additive solution adds is the 1%-5% of oligopolymer flow, and ethylene glycol adds the 4%-10% that fashionable flow is the oligopolymer flow.
Described polyreaction is to carry out in two or more polycondensation vessels successively, its preferred polymeric reaction is carried out in two polycondensation vessels successively, described two polycondensation vessels are respectively precondensation still, whole polycondensation vessel, and the precondensation product is input in the terminal polymerization kettle after filtering.
Described being filtered into through the aperture is the strainer or the filtering membrane of 10-25 micron.
For further detailed explanation technical scheme of the present invention and the technique effect that reaches, below adopt the continuous production method of cation dyeable polyester to describe.
The mass percent concentration that cation dyeable polyester prepares the ethylene glycol solution of described dimethyl isophthalate-5-sodium sulfonate (SIPM) or ethylene isophthalate-5-sodium sulfonate (SIPE) is 15-30%, and the mass percent concentration of its preferred solution is 15%-25%.
Phthalic acid glycol ester-5-sodium sulfonate can directly use commercially available product, also can pass through the preparation of dimethyl isophthalate-5-sodium sulfonate and ethylene glycol generation transesterification reaction, its preparation method is as follows: ethylene glycol, SIPM and transesterification catalyst are mixed, after stirring, be to carry out transesterification reaction under 220-240 ℃ the condition in temperature, reaction times is 10-12 hour, and reaction finishes the back spent glycol ester exchange offspring is diluted to the solution that mass percent concentration is 15-30%.
Wherein ethylene glycol is 1.05-1.3 with the ratio of the amount of substance of SIPM: 1, and catalyst consumption is the 2.5-3.5% of reactant total mass.
The catalyzer that the present invention adds in pipeline is antimony glycol, antimony acetate or ANTIMONY TRIOXIDE SB 203 99.8 PCT, and catalyst solution is that described catalyzer is dissolved in the ethylene glycol, is made into the ethylene glycol solution that mass percent concentration is 2.5%-3.5%.
Above-mentioned catalyst solution also can add for example trimethyl phosphite 99 ((CH of a spot of stablizer
3O)
3PO
4) or other additives.
The injection of every kind three monomer or many monomers and additive all has corresponding metering system to control among the present invention, injects the temperature or the pressure of additive and can regulate by corresponding temperature or pressure regulating system.
The present invention is provided with a high-shear pump dynamic mixer or the two chambers homogenizer static mixer or the system and device of dynamic mixer and static mixer combination on pipeline, the uniform mixing means of three monomeric dispersions and many materials are provided, homogenizer provides high pressure and has increased the residence time simultaneously, thereby guarantee each material homogeneous phase within it, plug flow, fully reaction, make three monomers of the oligopolymer of glycolysis and online interpolation and catalyst solution at transport pipe, carry out the esterification late phase reaction in high-shear pump and the homogenizer, and because reaction is to carry out under well-mixed situation, thereby three monomer in oligopolymer, disperse more evenly, oligopolymer and three monomer reactions are more abundant more even.
Described polyreaction is to carry out in two or more polycondensation vessels successively, its preferred polymeric reaction is carried out in two polycondensation vessels successively, described two polycondensation vessels are respectively precondensation still, whole polycondensation vessel, carry out prepolymerization reaction, the poly-reaction of final minification in above-mentioned two reactors, the precondensation product is input in the terminal polymerization kettle after filtering.Described being filtered into through the aperture is the strainer or the filtering membrane of 10-25 micron.
When oligopolymer was flowed through pipeline, the ethylene glycol solution that the ethylene glycol of flowing through successively adds pipeline, dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate added pipeline and catalyst solution interpolation pipeline.
Oligopolymer enters pipeline after esterifying kettle comes out, in the pipeline near one section of esterifying kettle, utilize reversed liquid to stir temperature is 45-60 ℃, and ethylene glycol joins the pipeline from adding pipeline, and oligopolymer is dissolved in the ethylene glycol rapidly.
Ducted pressure is controlled at 400-600kPa, under this high pressure, can avoid ducted ethylene glycol vaporization, can allow oligopolymer, SIPM or SIPE well be dissolved in the ethylene glycol.
The temperature of the ethylene glycol solution of described dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate is 80-100 ℃.Stir above-mentioned solution is joined in the pipeline adding fashionable preferred employing reversed liquid, this adding mode can be rapidly mixes oligomer solution and SIPM solution or SIPE solution, guaranteed that in the precondensation still, sodium group is evenly distributed on the main chain of polycondensate.
In pipeline, dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate solution adds the 8%-10% that fashionable flow is the oligopolymer flow, the flow that catalyst solution adds is the 1%-2% of oligopolymer flow, and ethylene glycol adds the 5%-7% that fashionable flow is the oligopolymer flow.
In the preparation process of cation dyeable polyester, what later stage fiber dyeability was played decisive step is that the 3rd monomer adds and mixes link with oligopolymer, the temperature of carboxylate for the polymerization degree that guarantees carboxylate and when injecting three monomers, simultaneously, guarantee that the carboxylate that esterifying kettle comes out can be dissolved in the ethylene glycol in a short period of time, make it can be with three monomers rapid and thorough mixing is even, just must make two process segmentations and to carry out in the minimum relatively volume, the ethylene glycol that in pipeline, adds successively of the present invention, the mode of the 3rd monomer solution is just well mixed oligopolymer all with three monomers.
The temperature of esterification of the present invention is controlled at 240-270 ℃, when the mean polymerisation degree of oligopolymer reaches 3-8, when esterification yield reaches 90%-92%, with this oligopolymer output esterifying kettle.
Pressure in the esterifying kettle is normal pressure.
Described terephthalic acid is 1 with the amount of substance ratio of ethylene glycol: 1-2.
The temperature of prepolymerization reaction of the present invention is controlled at 250-275 ℃, and when the product degree of polymerization of prepolymerization reaction reached 10～28, esterification yield reached more than 99%, was entered in the whole polycondensation vessel.
During prepolymerization reaction, pressure is 150-200KPa.
The temperature of the poly-reaction of final minification of the present invention is controlled at 275-285 ℃, when the product degree of polymerization of the poly-reaction of final minification reaches 100-103, and termination reaction.
During prepolymerization reaction, pressure is 50-150KPa.
The mensuration of the polymerization degree of above-mentioned polymkeric substance is all judged according to power of agitator.The time of controlling each reaction by experience in industrial production gets final product.
Serialization provided by the invention prepares the method for modified poly ester than prior art, and outstanding advantage is:
At first,, be fed to the discharging of intermediate reaction and the finished product, realized continuous industry production from raw material from whole process flow, and compared with existing serialization production technology, the short parking technology of the three still low temperature that the energy consumption of employing is lower.
Secondly, mass analysis from the finished product, the 3rd monomer that adopts among the present invention or many monomers adding technology fully take into account the reaction of homogeneous phase plug flow, in the 3rd monomer or the adding of many monomers, adopt the mode that adds solution, the amount, temperature, the pressure that add all have the corresponding online Controlling System to be regulated, and according to the difference of solvability and concentration parameter, select for use to the 3rd monomer or many monomers solvability preferably EG as solvent; Add oligopolymer and three monomers short shortcoming of the residence time in pipeline in order to overcome pipeline in addition, guarantee three monomers or many monomers and the sufficient mixing time of oligopolymer, high-shear homogenizing pump dynamic mixer or homogenizer static mixer or both combinations on pipeline, have been added, thereby making entire reaction nearly all is at homogeneous phase, carry out under the situation continuously, EG in the various adding solution still keeps liquid state not vaporize under the high pressure that homogenizer provides when having impelled pure dissolved oligopolymer and three monomers to mix, realize the more abundant of homogeneous phase plug flow reaction, make the group that has various characteristics be evenly distributed on the main chain of polyester, guaranteed that the later stage obtains high-quality modified poly ester product.And traditional batch process prepares modified poly ester, be oligopolymer and the 3rd monomer reaction that in second esterifying kettle, obtains by esterification in first esterifying kettle, because the material that adds is vaporized easily, make that oligopolymer is not a homogeneous reaction with the reaction that added for the 3rd monomer generation esterification later stage in this still, and with the present invention in plug flow reacting phase ratio, complete mixing flow reaction in second esterifying kettle, cause the dispersion of three monomers in oligopolymer inhomogeneous, the amount of reaction is also uncontrollable, thereby influences the quality of subsequent product.
Description of drawings
The process flow diagram that Fig. 1 carries out in two reactors for the inventive method polyreaction.
Fig. 2 is the synoptic diagram of three kinds of modes of the 3rd monomer adding technology unique among the present invention
Fig. 3 is the 3rd a monomer adding technology of traditional batch device
Embodiment
Below in conjunction with specific embodiment content of the present invention is described in detail, so that to its better understanding, technical process total among the embodiment is as accompanying drawing 1, shown in 2, in accompanying drawing 1, raw material PTA, the EG slurry flows in the esterifying kettle, oligopolymer enters pipeline afterwards, three monomers or catalyst solution inject from add pipeline, with the oligopolymer mixing, enter the precondensation still after the mixing successively, carry out polyreaction in the whole polycondensation vessel, shown in Figure 2 is that oligopolymer is when flowing through pipeline, add EG, three monomeric process flow sheets add EG earlier, and then add three monomer solutions, enter two chambers homogenizer afterwards, it is mixed.
Embodiment 1
With raw material terephthalic acid and ethylene glycol respectively with 6250kg/h, the flow velocity of 3125kg/h joins in the esterifying kettle, be to carry out esterification or polyreaction under 270 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches 3, esterification yield is 91% o'clock, being 3 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 455kg/h being 45 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 100 ℃ concentration be 25% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 607kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 400KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 151kg/h 2.5% antimonous oxide solution from adding pipeline; The ducted final mixture that flows to the precondensation still is that 260 ℃, pressure are that 160KPa carries out polycondensation in temperature in the precondensation still, reach 18 in the precondensation product degree of polymerization, esterification yield reaches more than 99%, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, in temperature is that 275 ℃, pressure are to carry out the poly-reaction of final minification under the condition of 100KPa, 102, import final product at polymkeric substance from discharge port.
Embodiment 2
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 90 ℃ concentration be 20% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 675kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 3
With raw material terephthalic acid and ethylene glycol respectively with 6250kg/h, the flow velocity of 1875kg/h joins in the esterifying kettle, be to carry out esterification or polyreaction under 240 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches 8, esterification yield is 92% o'clock, being 8 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 379kg/h being 60 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 80 ℃ concentration be 15% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 758kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 550KPa, the mixture of this pipeline enters the liquid homogenizer through high-shear homogenizing pump mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 76kg/h 3.5% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is that 250 ℃, pressure are that 200KPa carries out polycondensation in temperature in the precondensation still, reach 28 in the precondensation product degree of polymerization, esterification yield reaches more than 99%, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, in temperature is that 285 ℃, pressure are to carry out the poly-reaction of final minification under the condition of 50KPa, 103, import final product at polymkeric substance from discharge port.
Embodiment 4
With raw material terephthalic acid and ethylene glycol respectively with 6250kg/h, the flow velocity of 4000kg/h joins in the esterifying kettle, be to carry out esterification or polyreaction under 262 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches 5, esterification yield is 90% o'clock, being 5 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 455kg/h being 55 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 90 ℃ concentration be 25% SIPM solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 607kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 600KPa, is 3.% antimony acetate solution with the flow velocity implantation concentration of 151kg/h from adding pipeline; The ducted final mixture that flows to the precondensation still is that 270 ℃, pressure are that 150KPa carries out polycondensation in temperature in the precondensation still, reach 25 in the precondensation product degree of polymerization, esterification yield reaches more than 99%, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, in temperature is that 280 ℃, pressure are to carry out the poly-reaction of final minification under the condition of 120KPa, 100, import final product at polymkeric substance from discharge port.
Embodiment 5
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 2860kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 7 o'clock, and acid number is 40mgKOH/g; Being 7 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 80 ℃ concentration be 30% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 614kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 450KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 120kg/h 2.7% antimony glycol solution from adding pipeline; The ducted final mixture that flows to polycondensation vessel is that 280 ℃, pressure are that 110KPa carries out polycondensation in temperature in polycondensation vessel, reaches 101 in the precondensation product degree of polymerization, and esterification yield reaches more than 99%, from discharge port input final product.
Embodiment 6
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 2981kg/h respectively, are to carry out esterification or polyreaction under 270 ℃ the condition in temperature, reach at 6 o'clock at the mean polymerisation degree of esterification products, and esterification yield is 91%; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 400kg/h being 60 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 90 ℃ concentration be 15% SIPM solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 675kg/h from this pipeline, it is 400KPa that the temperature of pipeline remains on 230 ℃, pressure, is 3% antimony acetate solution with the flow velocity implantation concentration of 103kg/h from adding pipeline subsequently; The ducted final mixture that flows to the precondensation still is 275 ℃ in the inherent temperature of precondensation still (1), pressure is to carry out polycondensation under the condition of 110KPa, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, with the flow velocity input precondensation still (2) inherent 270 of its product with 6894kg/h, pressure is to carry out polycondensation under the condition of 120KPa, reach 42 in the precondensation product degree of polymerization, esterification yield is more than 99%, temperature is 270 ℃ and carries out polycondensation the flow velocity of precondensation product with 7605kg/h is being input in the whole polycondensation vessel, at pressure is 150KPa, temperature is to carry out the poly-reaction of final minification under 282 ℃ the condition, 103, import final product at polymkeric substance from discharge port.
Embodiment 7
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 3760kg/h respectively, are to carry out esterification or polyreaction under 265 ℃ the condition in temperature, reach at 8 o'clock at the mean polymerisation degree of esterification products, and esterification yield reaches 92%; Being 8 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 490kg/h being 60 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 90 ℃ concentration be 20% SIPM solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 675kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 118kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is that 275 ℃, pressure are that 120KPa carries out polycondensation in temperature in the precondensation still, reach 16 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, is 10 micron strainer filter after to be input to whole polycondensation vessel in the flow velocity of 7605kg/h through the aperture with the precondensation product, at pressure is that 130KPa, temperature are to carry out the poly-reaction of final minification under 278 ℃ the condition, 101, import final product at polymkeric substance from discharge port.
Embodiment 8
The preparation of SIPE solution:
Is mixing in 1.1: 1 with ethylene glycol, SIPM with the ratio of amount of substance, adding 3% the antimony glycol that quality is the reactant total mass, after stirring, be to carry out transesterification reaction under 230 ℃ the condition in temperature, reaction times is 10 hours, reaction finishes the back spent glycol, and ester exchange offspring is diluted to mass percent concentration is 25% solution, adds a spot of trimethyl phosphite 99 ((CH again
3O)
3PO
4), promptly obtain SIPE solution.
The preparation of cation dyeable polyester:
With raw material terephthalic acid and ethylene glycol respectively with 6250kg/h, the flow velocity of 3760kg/h joins in the esterifying kettle, be to carry out esterification or polyreaction under 261 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches 4, esterification yield is 92% o'clock, being 4 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 437kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, is that 90 ℃ concentration be 25% the above-mentioned SIPE solution for preparing apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 627kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, is 3.5% antimony acetate solution with the flow velocity implantation concentration of 140kg/h from adding pipeline; The ducted final mixture that above-mentioned mixed solution flows to the precondensation still through high-shear homogenizing pump is that 260 ℃, pressure are that 170KPa carries out polycondensation in temperature in the precondensation still, reach 20 in the precondensation product degree of polymerization, esterification yield reaches more than 99%, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, in temperature is that 275 ℃, pressure are to carry out the poly-reaction of final minification under the condition of 70KPa, 100, import final product at polymkeric substance from discharge port.
Embodiment 9
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 50% Macrogol 2000 solution with the flow velocity implantation temperature of 500kg/h, is that 90 ℃ concentration be 20% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 675kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 10
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 70% m-phthalic acid solution with the flow velocity implantation temperature of 500kg/h, is that 90 ℃ of concentration are 45% Macrogol 2000 solution from the interpolation pipeline that is right after this pipeline with the flow velocity implantation temperature of 500kg/h, is that 90 ℃ concentration be 12% SIPE solution apart from the nearer interpolation pipeline of precondensation still with the flow velocity implantation temperature of 675kg/h from this pipeline, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 11
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 70% m-phthalic acid solution with the flow velocity implantation temperature of 500kg/h, 's 90 ℃ glycol ether from this pipeline apart from the nearer interpolation pipeline of precondensation still, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 12
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 80% m-phthalic acid solution with the flow velocity implantation temperature of 500kg/h, 's 90 ℃ glycol ether from this pipeline apart from the nearer interpolation pipeline of precondensation still, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 13
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of reinforced concentration are 20% titania solution with the flow velocity implantation temperature of 500kg/h, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 14
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 20% carbon black solution with the flow velocity implantation temperature of 500kg/h, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 15
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 30% carbon nanomaterial solution with the flow velocity implantation temperature of 500kg/h, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the dispersion of liquid high-shear homogenizing pump and mixes, entering homogenizer then mixes it to carry out the esterification afterreaction, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Embodiment 16
Raw material terephthalic acid and ethylene glycol are joined in the esterifying kettle with the flow velocity of 6250kg/h, 4202kg/h respectively, be to carry out esterification or polyreaction under 260 ℃ the condition in temperature, mean polymerisation degree at esterification products reaches at 6 o'clock, and acid number is 40mgKOH/g; Being 6 esterification products oligopolymer with the polymerization degree is transported to a pipeline with the flow velocity of 7588kg/h, by from this pipeline with the flow velocity implantation temperature of 530kg/h being 50 ℃ ethylene glycol apart from the nearer interpolation pipeline of esterifying kettle, from this pipeline and then the interpolation pipeline of ethylene glycol be that 90 ℃ of concentration are 45% poly-hydroxy phenyl phosphoric acid solution with the flow velocity implantation temperature of 500kg/h, the temperature of pipeline remains on 230 ℃, pressure is 500KPa, the mixture of this pipeline enters the liquid homogenizer mixes it, flow to the precondensation still from homogenizer through a pipeline afterwards, in the pipeline that flows to the precondensation still, with the flow velocity implantation concentration of 103kg/h 3% antimony glycol solution from adding pipeline; The ducted final mixture that flows to the precondensation still is 275 ℃ in temperature and carries out polycondensation in the precondensation still, reach 15 in the precondensation product degree of polymerization, when acid number reaches 1mgKOH/g, the flow velocity of precondensation product with 7605kg/h is input in the whole polycondensation vessel, at pressure is that 150KPa, temperature are to carry out the poly-reaction of final minification under 282 ℃ the condition, 100, when holding the carboxyl value, import final product at polymkeric substance from discharge port less than 25mol/t.
Should be appreciated that above narration only is an example and illustrative for the present invention who sets forth as claim, is limited it.The of the present invention content disclosed according to this paper, other embodiment of the present invention is conspicuous for a person skilled in the art.Should be noted that this specification sheets and embodiment only should be regarded as is example, and actual range of the present invention and spirit should be determined by claim.
Claims (12)
1. a method for preparing modified poly ester continuously comprises the steps:
Raw material terephthalic acid and ethylene glycol join from opening for feed and carry out esterification in the esterifying kettle, obtain oligoterephthalic acid glycol ester, the oligoterephthalic acid glycol ester melt is input in the polycondensation vessel with three monomers or many monomers and additive by pipeline and carries out polyreaction afterwards, follow-up pelletizing or the direct fabrics of carrying out of modified poly ester melt that reaction obtains, it is characterized in that, the two ends of described pipeline link to each other with polycondensation vessel with esterifying kettle respectively, in the oligopolymer melt-flow during through this pipeline, the ethylene glycol solution of three monomers or many monomers and additive joins in the pipeline, mix in pipeline with the oligopolymer melt, carry out the reaction in esterification later stage simultaneously, enter then and carry out polyreaction in the polycondensation vessel; The method that mixes in pipeline is or/and mix in the homogenizer by high-shear homogenizing pump.
2. method according to claim 1 is characterized in that, the method that mixes in pipeline is by mixing in high-shear homogenizing pump and the homogenizer.
3. method according to claim 1 is characterized in that, described pipeline is provided with injected system, humidity control system and high-shear homogenizing pump and/or homogenizer.
4. method according to claim 3 is characterized in that, described pipeline is provided with injected system, humidity control system, high-shear homogenizing pump and homogenizer.
5. method according to claim 1, it is characterized in that modified poly ester comprises cation dyeable polyester, anionic dyestuff dyeable polyester, water-soluble polyester, low-melting point polyester, high-contraction polyester, full-dull polyester, original liquid coloring polyester or flame retardant polyester.
6. method according to claim 5, it is characterized in that, three monomers that the preparation process of described cation dyeable polyester adds comprise dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described anionic dyestuff dyeable polyester adds are Macrogol 2000, its solution quality percentage concentration is 40%-70%, four monomers are dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described water-soluble polyester adds are m-phthalic acid, its solution quality percentage concentration is 60%-80%, four monomers are Macrogol 2000 or hexanodioic acid, its solution quality percentage concentration is 40%-70%, five monomers are dimethyl isophthalate-5-sodium sulfonate or ethylene isophthalate-5-sodium sulfonate, and the mass percent concentration of its solution is 15%-30%;
Three monomers that the preparation process of described low-melting point polyester adds are m-phthalic acid, and its solution quality percentage concentration is 60%-80%, and four monomers are glycol ether, and its quality percentage composition is 100%;
Three monomers that the preparation process of described high-contraction polyester adds are m-phthalic acid, and its solution quality percentage concentration is 60%-80%, and four monomers are glycol ether, its quality percentage composition 100%;
Three monomers that the preparation process of described full-dull polyester adds are titanium dioxide, and its solution quality percentage concentration is 10%-30%;
Three monomers that the preparation process of described original liquid coloring polyester adds are carbon black, and its solution quality percentage concentration is 5%-30%;
Three monomers that the preparation process of described flame retardant polyester adds are hydroxyethyl phenyl phosphoric acid, and its solution quality percentage concentration is 20%-50%.
7. according to each described method of claim 1-6, it is characterized in that the temperature in the described pipeline is 230-265 ℃, pressure is 0.1-1MPa, oligopolymer melt in pipeline residence time 10-50 minute.
8. according to each described method of claim 1-6, it is characterized in that in the oligopolymer melt-flow during through pipeline, the ethylene glycol of flowing through successively adds that pipeline, three monomers or how monomeric ethylene glycol solution add pipeline and additive solution adds pipeline.
9. method according to claim 8, it is characterized in that, three monomers or many monomer solutions add the 1%-30% that fashionable flow is the oligopolymer flow, and the flow that additive solution adds is the 1%-5% of oligopolymer flow, and ethylene glycol adds the 4%-10% that fashionable flow is the oligopolymer flow.
10. according to each described method of claim 1-6, it is characterized in that described polyreaction is to carry out successively in two or more polycondensation vessels.
11. method according to claim 10 is characterized in that, described polyreaction is carried out in two polycondensation vessels successively, and described two polycondensation vessels are respectively precondensation still, whole polycondensation vessel, and the precondensation product is input in the terminal polymerization kettle after filtering.
12. method according to claim 11 is characterized in that, described being filtered into through the aperture is the strainer or the filtering membrane of 10-25 micron.
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| CN102409428B (en) * | 2011-09-19 | 2013-04-17 | 江苏中鲈科技发展股份有限公司 | Preparation method for polyester fiber with composite ultraviolet resisting and cationic dyeing functions |
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