CN104629027A - Polyethylene glycol terephthalate copolymer and preparation method thereof - Google Patents
Polyethylene glycol terephthalate copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyethylene glycol terephthalate copolymer and a preparation method thereof. The method comprises the following steps: step S1, mixing terephthalic acid, isosorbide, glycol and a first catalyst, carrying out an esterification reaction to obtain a first product system; step S2, mixing ethylene naphthalate, glycol and a second catalyst, carrying out a transesterification reaction to obtain a second product system; step S3, carrying out a prepolycondensation reaction on the first product system and the second product system to obtain a prepolycondensation product; step S4, carrying out a final polycondensation reaction on the prepolycondensation product to obtain the polyethylene glycol terephthalate copolymer. The polyethylene glycol terephthalate copolymer prepared by the method disclosed by the invention is good in heat resistance, relatively low in preparation cost and more suitable for industrial large-scale production. Meanwhile, the preparation method provided by the invention can be used for directly producing the polyethylene glycol terephthalate copolymer which satisfies the viscosity requirements even by adopting a continuous process, and is more advantageous in process.
Description
Technical field
The present invention relates to organic polymer preparing technical field, in particular to a kind of pet copolymer and preparation method thereof.
Background technology
Polyethylene terephthalate is a kind of common saturated polyester, can be used for manufacturing many fields such as fiber, film, bottle, engineering plastics, therefore about the synthesis of polyethylene terephthalate, properity and application have caused scientific research personnel's research enthusiasm greatly.Poly-2,6-(ethylene naphthalate) is a kind of homology polyester of novel polyethylene terephthalate, there is excellent performance, as mechanical property, resistance toheat, barrier property etc., but due to its cost ratio polyethylene terephthalate costly, polyethylene glycol 2，6-naphthalene dicarboxylate range of application is made to have limitation.In order to make full use of the excellent properties of polyethylene glycol 2，6-naphthalene dicarboxylate, solve its expensive problem, people adopt the two copolymerization and/or blended method usually, show fully to make both superiority simultaneously.Such as, the polyethylene glycol 2，6-naphthalene dicarboxylate adding l0% in polyethylene terephthalate can make the heat resisting temperature of body bring up to 90 DEG C.
In existing preparation method, usually ethylene glycol, NDA and terephthalic acid are directly mixed, adopt interrupter method to carry out polycondensation to prepare the multipolymer of polyethylene terephthalate and polyethylene glycol 2，6-naphthalene dicarboxylate.The introducing of 2,6-naphthalene two formyl unit adds multipolymer macromole chain rigidity, thus makes the pet copolymer of modification show more excellent thermal stability, and 2,6-naphthalene nucleus unit content is larger, and thermal stability is better.But in heat resistant type pet copolymer preparation process, need the NDA adding high-content, obtained product just can have good thermotolerance.And practical situation are: because synthetic technology is not also very ripe, highly purified NDA is difficult to produce in enormous quantities, and expensive, and this has raised the preparation cost of heat resistant type pet copolymer largely.If but do not introduce naphthalene ring unit the thermotolerance of obtained pet copolymer can be caused again to improve.
In addition, in the preparation method of existing modified poly ester, the intrinsic viscosity of the multipolymer obtained after polycondensation terminates does not reach necessary requirement usually.Therefore after above-mentioned polycondensation terminates, need above-mentioned multipolymer to carry out pelletizing, then will cut the modified copolyester particle transport that obtains and improve to solid-state polymerization device the intrinsic viscosity of product, thus obtain meeting viscosity requirement and gather modified copolyester.If China Patent Publication No. is 1869096.But there is operation steps complexity in this intermittent type preparation technology, high in cost of production defect.
For these reasons, be necessary to develop a kind of with low cost and preparation method of the pet copolymer of product excellent heat resistance.
Summary of the invention
Main purpose of the present invention is to provide a kind of pet copolymer and preparation method thereof, to solve the problem of the high or product poor heat resistance of existing preparation method's cost.
To achieve these goals, according to an aspect of the present invention, provide a kind of preparation method of pet copolymer, it comprises the following steps: S1, after terephthalic acid, Isosorbide, ethylene glycol and the first catalyst mix, carry out esterification, obtain the first product system; S2, to after naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyst mix, will carry out transesterification reaction, obtains the second product system; S3, carries out prepolymerization reaction by the first product system and the second product system, obtains precondensation product; And S4, precondensation product is carried out whole polycondensation, obtains pet copolymer.
Further, above-mentioned preparation method comprises the following steps: S1, the first reactant system is obtained by after terephthalic acid, Isosorbide, ethylene glycol and the first catalyst mix, through the first volume pump, the first reactant system is pumped in reaction kettle of the esterification, carry out esterification, obtain the first product system; S2, will obtain the second reactant system to after naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyst mix, and pump in ester interchange vessel, carry out transesterification reaction, obtain the second product system through the second volume pump by the second reactant system; S3, pumps into prepolymerization kettle by the first product system through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, carries out prepolymerization reaction, obtains precondensation product; And S4, precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump and carries out whole polycondensation, obtain pet copolymer.
Further, step S3 comprises: S31, and the first product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, after homogenizing mixing, obtains melted blend; S32, pumps into melted blend in prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; Preferably, prepolymerization kettle is upflowing prepolymerization kettle.
Further, in step S4, carry out in the process of whole polycondensation, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
Further, in step S1, the mol ratio of terephthalic acid and ethylene glycol is 1:1.15 ~ 1:1.20, and the mol ratio of terephthalic acid and Isosorbide is 1:0.02. ~ 1:0.08 Preferably, the mol ratio of terephthalic acid and ethylene glycol is 1:1:1.15 ~ 1:1.18, and the mol ratio of terephthalic acid and Isosorbide is 1:0.04. ~ 1:0.06.
Further, in step S2, be 1:2.2 ~ 1:2.4 to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol.
Further, in step S3, the weight ratio of the first product system and the second product system is 1:0.1 ~ 1:0.5.
Further, in step S1, the catalyzer of esterification is antimony glycol, one or more in antimonous oxide and Cobaltous diacetate; And/or in step S2, the catalyzer of transesterification reaction is one or more in zinc acetate, magnesium acetate and manganese acetate; And/or in step S3, in prepolymerization reaction process, simultaneously adding stablizer to prepolymerization reaction system, stablizer is one or more in trimethyl phosphite 99, triphenylphosphate and methyl phosphite.
Further, in step S1, the molar weight of the catalyzer of esterification is 0.03 ~ 0.05% of terephthalic acid molar weight, is preferably 0.03 ~ 0.04%; And/or in step S2, the molar weight of the catalyzer of transesterification reaction is to naphthalene diformic acid dimethyl ester molar weight 0.03 ~ 0.05%, be preferably 0.03 ~ 0.04%; And/or in step S3, the molar weight of the stablizer added in prepolymerization reaction process is 0.02 ~ 0.05% of terephthalic acid molar weight, be preferably 0.02 ~ 0.04%.
Further, in step S1, the temperature of reaction of esterification is 245 ~ 255 DEG C, is preferably 250 ~ 255 DEG C; And/or in step S2, the temperature of reaction of transesterification reaction is 165 ~ 215 DEG C, be preferably 175 ~ 200 DEG C; And/or in step S3, the temperature of reaction of prepolymerization reaction is 280 ~ 285 DEG C, and the reaction times is 20 ~ 40min; And/or in step S4, the temperature of reaction of whole polycondensation is 285 ~ 290 DEG C.
Further, in step S1, control the first volume pump, make the charging flow velocity of the first reactant system be 180 ~ 190Kg/h, be preferably 185 ~ 190Kg/h; And the liquid level controlled in reaction kettle of the esterification is at 800 ~ 900mm; In step S2, control the second volume pump, make the charging flow velocity of the second reactant system be 60 ~ 90Kg/h, be preferably 65 ~ 80Kg/h; And the liquid level controlled in transesterification reactor is 300 ~ 400mm; In step S3, the liquid level controlled in prepolymerization kettle is 240 ~ 300mm; Vacuum tightness is 1000 ~ 2000Pa, preferably 1200 ~ 1500Pa; And in step S4, the liquid level controlled in whole polycondensation vessel is 100 ~ 250mm; Vacuum tightness is 100 ~ 300Pa, is preferably 110 ~ 130Pa.
According to a further aspect in the invention, provide a kind of pet copolymer, obtained by above-mentioned preparation method.
Application the present invention in technical scheme, with terephthalic acid, Isosorbide, ethylene glycol and to naphthalene diformic acid dimethyl ester for raw material, esterification and transesterification reaction are separately carried out.Then by esterification products and ester exchange offspring mixing, sequentially precondensation is carried out and whole polycondensation obtains pet copolymer.Isosorbide, as one of reactant, is conducive to the thermotolerance improving product.Transesterification reaction simultaneously by carrying out separately can obtain the NDA diethyl ester of higher degree, and this just can be avoided, and use is originated not easily, expensive NDA, thus is conducive to the economy improving whole technique.The pet copolymer that the reason of above-mentioned several respects makes the present invention obtain has good thermotolerance, and preparation cost is lower, industrialization scale operation preferably.In addition, for polymer raw and the technique of uniqueness, even if make the preparation method of this pet copolymer provided by the present invention adopt continuous processing, also direct production can go out meet the pet copolymer of viscosity requirement, have more advantage compared to traditional intermittent type preparation technology.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the process flow diagram of preparation method provided by the invention; And
Fig. 2 shows the another kind of process flow diagram of preparation method provided by the invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
As described by background technology part, there is the problem of the high or product thermal stability difference of cost in the preparation method of existing pet copolymer.In order to address this problem, the invention provides a kind of preparation method of pet copolymer, comprise the following steps: S1, after terephthalic acid, Isosorbide, ethylene glycol and the first catalyst mix, carry out esterification, obtain the first product system; S2, to after naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyst mix, will carry out transesterification reaction, obtains the second product system; S3, carries out prepolymerization reaction by the first product system and the second product system, obtains precondensation product; And S4, precondensation product is carried out whole polycondensation, obtains pet copolymer.
In preparation method provided by the invention, with terephthalic acid, Isosorbide, ethylene glycol and to naphthalene diformic acid dimethyl ester for raw material, esterification and transesterification reaction are separately carried out.Then by esterification products and ester exchange offspring mixing, sequentially precondensation is carried out and whole polycondensation obtains pet copolymer.In this preparation method, in reaction system, add Isosorbide.Isosorbide, as one of reactant, can increase the fragrant heterocycle structure in multipolymer macromolecular main chain, thus rotatable singly-bound number in main chain is reduced relatively, and the kindliness of chain declines, and then can improve the thermotolerance of product.The more important thing is, in preparation method of the present invention, esterification and transesterification reaction are separately carried out, be conducive to avoiding Isosorbide and terephthalic acid participate in transesterification reaction and produce by product.Meanwhile, can be obtained the NDA diethyl ester of higher degree by the transesterification reaction of carrying out separately, this just can be avoided, and use is originated not easily, expensive NDA, thus is conducive to the economy improving whole technique.The pet copolymer that the reason of above-mentioned several respects makes the present invention obtain has good thermotolerance, and preparation cost is lower, industrialization scale operation preferably.In addition, for polymer raw and the technique of uniqueness, even if make the preparation method of this pet copolymer provided by the present invention adopt continuous processing, also direct production can go out meet the pet copolymer of viscosity requirement, have more advantage compared to traditional intermittent type preparation technology.
In preparation method provided by the invention, as long as adopt above-mentioned raw materials and technique, just can prepare heat resistant type pet copolymer, and production cost is relatively low.In a preferred embodiment, as shown in Figure 1, preparation method provided by the invention comprises the following steps: S1, the first reactant system is obtained by after terephthalic acid, Isosorbide, ethylene glycol and the first catalyst mix, through the first volume pump, the first reactant system is pumped into reaction kettle of the esterification from the first reactant system charging-tank, carry out esterification, obtain the first product system; S2, the second reactant system will be obtained to after naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyst mix, through the second volume pump, the second reactant system is pumped into ester interchange vessel from the second reactant system charging-tank, carry out transesterification reaction, obtain the second product system; S3, pumps into prepolymerization kettle by the first product system through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, carries out prepolymerization reaction, obtains precondensation product; And S4, precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump and carries out whole polycondensation, obtain pet copolymer.
In the preparation process in accordance with the present invention, adopt above-mentioned continuous production technique can improve the stability of reaction, thus improve the quality stability of pet copolymer product.Meanwhile, compared to traditional intermittent reaction technique, this continuous production technique also helps enhances productivity, industrialization large-scale application preferably.More particularly, adopting above-mentioned continuous processing, without the need to carrying out extra solid state polymerization process after whole polycondensation terminates, the pet copolymer that intrinsic viscosity is higher can be obtained.
In the preparation process in accordance with the present invention, according to above-mentioned instruction, those skilled in the art can select the concrete technology in step S3.In a preferred embodiment, as shown in Figure 2, step S3 comprises: S31, first product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, after homogenizing mixing, obtain melted blend; S32, pumps into melted blend in prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; Preferably, prepolymerization kettle is upflowing prepolymerization kettle.Adopt above-mentioned process advan more even in what make esterification products and ester exchange offspring mix, and adopt upflowing prepolymerization kettle to be conducive to improving the transformation efficiency of reaction, thus improve product yield.
In the preparation process in accordance with the present invention, according to the above-mentioned instruction of invention, those skilled in the art can select the concrete technology in step S4.In a preferred embodiment, in step S4, carry out in the process of whole polycondensation, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.By monitoring the intrinsic viscosity of reaction system, the polymerization degree of product can be controlled more accurately.Controlled by intrinsic viscosity in above-mentioned scope, the resistance toheat of product is more excellent, and overall mechanical property is better simultaneously.
In the preparation process in accordance with the present invention, those skilled in the art can select the mol ratio of para Toluic Acid and ethylene glycol in step S1.In a preferred embodiment, in step S1, the mol ratio of terephthalic acid and ethylene glycol is 1:1.15 ~ 1:1.20, and the mol ratio of terephthalic acid and Isosorbide is 1:0.02. ~ 1:0.08.Terephthalic acid and ethylene glycol controlled, in above-mentioned scope, can improve the productive rate of ethylene glycol terephthalate with magnitude relation, and then improves the productive rate of target product.And terephthalic acid and Isosorbide controlled in above-mentioned scope with magnitude relation, in target product, more appropriate fragrant heterocycle structure can be introduced by Isosorbide, thus improve thermotolerance and other over-all propertieies of product further.
In the preparation process in accordance with the present invention, those skilled in the art can select the mol ratio to naphthalene diformic acid dimethyl ester and ethylene glycol in step S2.In a preferred embodiment, in step S2, be 1:2.2 ~ 1:2.4 to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol.Control in above-mentioned scope by the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol, be conducive to improving the transformation efficiency to transesterification reaction, and then be conducive to improving the productive rate to naphthalic acid diethyl ester.
In the preparation process in accordance with the present invention, as long as select above-mentioned reaction raw materials and processing method just can obtain the thermotolerance of the good pet copolymer of thermotolerance.In a preferred embodiment, in step S3, the weight ratio of the first product system and the second product system is 1:0.1 ~ 1:0.5.The weight ratio of the first product system and the second product system is controlled in above-mentioned scope, be conducive to the ratio controlling naphthalene nucleus and fragrant heterocycle in product main chain, thus improving the main chain rigidity of product, this can make the second-order transition temperature of product raise, and namely can improve the thermotolerance of product further.
In preparation method provided by the invention, those skilled in the art can select catalyzer conventional in above-mentioned esterification and transesterification reaction.In a preferred embodiment, in step S1, the catalyzer of esterification is antimony glycol, one or more in antimonous oxide and Cobaltous diacetate; And/or in step S2, the catalyzer of transesterification reaction is one or more in zinc acetate, magnesium acetate and manganese acetate; And/or in step S3, in prepolymerization reaction process, adding stablizer to prepolymerization reaction system, stablizer is one or more in trimethyl phosphite 99 triphenylphosphate and methyl phosphite.Above-mentioned catalyzer is adopted to be conducive to improving the speed of reaction of each step of reaction, Reaction time shorten.
In preparation method provided by the invention, the catalyst choice conventional amount used of above-mentioned esterification, transesterification reaction and prepolymerization reaction.In step S1, the molar weight of the catalyzer of esterification is 0.03 ~ 0.05% of terephthalic acid molar weight, is preferably 0.03 ~ 0.04%; And/or in step S2, the molar weight of the catalyzer of transesterification reaction is to naphthalene diformic acid dimethyl ester molar weight 0.03 ~ 0.05%, be preferably 0.03 ~ 0.04%; And/or in step S3, the molar weight of the stablizer added in prepolymerization reaction process is 0.02 ~ 0.05% of terephthalic acid molar weight, be preferably 0.02 ~ 0.04%.The consumption of catalyzer and stablizer is controlled in above-mentioned scope, process costs can be reduced while raising speed of reaction.
In preparation method provided by the invention, those skilled in the art can select the concrete technology condition in above-mentioned esterification, transesterification reaction, precondensation and whole polycondensation.In a preferred embodiment, in step S1, the temperature of reaction of esterification is 245 ~ 255 DEG C, is preferably 250 ~ 255 DEG C; And/or in step S2, the temperature of reaction of transesterification reaction is 165 ~ 215 DEG C, be preferably 175 ~ 200 DEG C; And/or in step S3, the temperature of reaction of prepolymerization reaction is 280 ~ 285 DEG C, and the reaction times is 20 ~ 40min; And/or in step S4, the temperature of reaction of whole polycondensation is 285 ~ 290 DEG C.Temperature of reaction and reaction times are controlled in above-mentioned scope, be conducive to the transformation efficiency improving each step of reaction.And be conducive to the polymerization degree of product being controlled in suitable scope, to obtain the better pet copolymer product of the over-all propertieies such as thermotolerance, mechanical property and processibility.
In preparation method provided by the invention, those skilled in the art can select charging flow velocity, the operating procedure such as liquid level and vacuum tightness of each reactor in esterification, transesterification reaction, precondensation and whole polycondensation.In a preferred embodiment, in step S1, control the first volume pump, make the charging flow velocity of the first reactant system be 180 ~ 190Kg/h, be preferably 185 ~ 190Kg/h; And the liquid level controlled in reaction kettle of the esterification is at 800 ~ 900mm; In step S2, control the second volume pump, make the charging flow velocity of the second reactant system be 60 ~ 90Kg/h, be preferably 65 ~ 80Kg/h; And the liquid level controlled in transesterification reactor is 300 ~ 400mm; In step S3, the liquid level controlled in prepolymerization kettle is 240 ~ 300.mm; Vacuum tightness is 1000 ~ 2000Pa, preferably 1200 ~ 1500Pa; And in step S4, the liquid level controlled in whole polycondensation vessel is 100 ~ 250mm; Vacuum tightness is 100 ~ 300Pa, is preferably 110 ~ 130Pa.By charging flow velocity in esterification, transesterification reaction and precondensation and whole polycondensation, liquid level and vacuum tightness three process parameter controls are in above-mentioned scope, be conducive to making esterification, transesterification reaction and precondensation and whole polycondensation have better continuity, thus the stability of improving the quality of products further.
As long as adopt above-mentioned preparation method and processing parameter just can prepare the good pet copolymer of thermotolerance.In one preferably embodiment, in step sl, after terephthalic acid, Isosorbide, ethylene glycol and the first catalyzer being mixed in the first making beating still, carry out slurrying, mixing time is 30 ~ 50min, is then delivered in the first slurry charging-tank; And/or in step s 2, after mixing in the second making beating still naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyzer, carry out slurrying, mixing time will be 30 ~ 50min, then be delivered in the second slurry charging-tank.Reaction-ure mixture carries out the pulping process of 30 ~ 40min, can the granularity of reactant grind less, thus be conducive to above-mentioned reactant is mixed more uniformly, and reaction is also more thorough.Preferably, in step S1, mixing time is 35 ~ 40min; In step S2, mixing time is 35 ~ 40min.
In addition, in a kind of preferred embodiment, preparation method provided by the invention also comprises the step to carrying out raw materials recovery in prepolymerization reaction, whole polycondensation and pelletizing process.Carry out the step of raw materials recovery, be conducive to cost-saving further, improve the economy of whole technique.
The present invention additionally provides a kind of pet copolymer on the other hand, and it is obtained by above-mentioned preparation method.This pet copolymer has good resistance toheat and mechanical property.
Be described in further detail the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as restriction the present invention scope required for protection.
Comparative example 1
By terephthalic acid, NDA, Isosorbide, ethylene glycol and catalyst glycol antimony, after mixing, obtain the first reactant system; Wherein, the mol ratio of terephthalic acid and ethylene glycol is 1:1.15, and the mol ratio of terephthalic acid and Isosorbide is 1:0.02, and antimony glycol accounts for 0.03% and 10%2,6-naphthalic acid (accounting for terephthalic acid) of terephthalic acid molar weight.Through the first volume pump, with charging flow velocity for 180kg/h, pump in reaction kettle of the esterification by the first reactant system, tank level control, at below 900mm, carries out esterification at 246 DEG C, obtains the first product system, at 230 DEG C, carry out esterification;
In above-mentioned esterification products system, add account for terephthalic acid molar weight 0.02% trimethyl phosphite 99, at 270 DEG C, carry out prepolymerization reaction, obtain precondensation product; At 275 DEG C, precondensation product is carried out polycondensation, obtain pet copolymer.
Comparative example 2
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.15, Cobaltous diacetate accounts for the proportionlity of 0.03% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, ethylene glycol and Cobaltous diacetate being mixed, through the first volume pump, with charging flow velocity for 180kg/h, pump in reaction kettle of the esterification by the first reactant system, tank level control is at below 800mm, carry out esterification at 245 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.2, zinc acetate accounts for the proportionlity to 0.03% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 60kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 300mm, carry out transesterification reaction at 165 DEG C, obtain the second product system;
First product system is pumped into prepolymerization kettle through the first melt metering pump, control reaction liquid level at below 240mm, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.02% triphenylphosphate, under vacuum tightness is 1000MPa, first product and the second product, with weight ratio 1:0.1, carry out prepolymerization reaction at 280 DEG C, obtain precondensation product; And
Pump in whole polycondensation vessel by precondensation product through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control, at 100MPa, is carried out whole polycondensation at 285 DEG C, is obtained pet copolymer.
Embodiment 1
With the mol ratio of terephthalic acid and ethylene glycol for 1:0.9, the mol ratio of terephthalic acid and Isosorbide is 1:0.02, Cobaltous diacetate accounts for the proportionlity of 0.025% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, Isosorbide, ethylene glycol and antimony glycol being mixed, through the first volume pump, with charging flow velocity for 170kg/h, first reactant system is pumped in reaction kettle of the esterification, tank level control is at below 750mm, carry out esterification at 230 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2, zinc acetate accounts for the proportionlity to 0.025% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 55kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 280mm, carry out transesterification reaction at 160 DEG C, obtain the second product system;
First product system is pumped into prepolymerization kettle through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.015% trimethyl phosphite 99, by tank level control at below 230mm under vacuum tightness is 1000MPa, first product and the second product are with weight ratio 1:1, carry out prepolymerization reaction at 270 DEG C, obtain precondensation product; And
Pump in whole polycondensation vessel by precondensation product through the 3rd melt metering pump, control reaction liquid level at below 90mm, vacuum degree control, at 98MPa, is carried out whole polycondensation at 275 DEG C, is obtained pet copolymer.
Embodiment 2
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.15, the mol ratio of terephthalic acid and Isosorbide is 1:0.02, antimonous oxide accounts for the proportionlity of 0.03% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate being mixed, through the first volume pump, with charging flow velocity for 180kg/h, first reactant system is pumped in reaction kettle of the esterification, tank level control is at below 800mm, carry out esterification at 245 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.2, manganese acetate accounts for the proportionlity to 0.03% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 60kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 300mm, carry out transesterification reaction at 165 DEG C, obtain the second product system;
First product system is pumped into prepolymerization kettle through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.02% triphenylphosphate, by tank level control at below 240mm under vacuum tightness is 2000MPa, first product and the second product are with weight ratio 1:0.2, carry out prepolymerization reaction at 280 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control is at 100MPa, whole polycondensation is carried out at 285 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
Embodiment 3
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.20, the mol ratio of terephthalic acid and Isosorbide is 1:0.08, Cobaltous diacetate accounts for the proportionlity of 0.05% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate being mixed, through the first volume pump, with charging flow velocity for 182kg/h, first reactant system is pumped in reaction kettle of the esterification, tank level control is at below 900mm, carry out esterification at 246 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.4, magnesium acetate accounts for the proportionlity to 0.05% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 90kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 400mm, carry out transesterification reaction at 215 DEG C, obtain the second product system;
First product system is pumped into prepolymerization kettle through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.05% methyl phosphite, by tank level control at below 300mm under vacuum tightness is 1100MPa, first product and the second product are with weight ratio 1:0.2, carry out prepolymerization reaction at 245 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control is at 300MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
Embodiment 4
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.2, the mol ratio of terephthalic acid and Isosorbide is 1:0.08, the molar weight of catalyst glycol antimony accounts for the proportionlity of 0.05% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, Isosorbide, ethylene glycol, antimonous oxide and Cobaltous diacetate being mixed, through the first volume pump, with charging flow velocity for 182kg/h, first reactant system is pumped in reaction kettle of the esterification, tank level control is at below 900mm, carry out esterification at 247 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.4, zinc acetate accounts for the proportionlity to 0.05% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 85kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 350mm, carry out transesterification reaction at 210 DEG C, obtain the second product system;
First product system is pumped into prepolymerization kettle through the first melt metering pump, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.05% trimethyl phosphite 99, by tank level control at below 245mm under vacuum tightness is 1100MPa, first product and the second product are with weight ratio 1:0.3, carry out prepolymerization reaction at 285 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 105mm, vacuum degree control is at 250MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
Embodiment 5
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.16, the mol ratio of terephthalic acid and Isosorbide is 1:0.03, antimony glycol and Cobaltous diacetate molar weight account for the proportionlity of 0.03% of terephthalic acid molar weight, the first reactant system is obtained after terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate being mixed, through the first volume pump, with charging flow velocity for 185kg/h, first reactant system is pumped in reaction kettle of the esterification, tank level control is at below 800mm, carry out esterification at 250 DEG C, obtain the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.3, zinc acetate accounts for the proportionlity to 0.03% of naphthalene diformic acid dimethyl ester molar weight, the second reactant system will be obtained to after the mixing of naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, through the second volume pump, with charging flow velocity for 65kg/h, pump in ester interchange vessel by the second reactant system, tank level control is at below 300mm, carry out transesterification reaction at 175 DEG C, obtain the second product system;
First product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, the first product obtains melted blend after mixing with weight ratio 1:0.4 homogenizing with the second product; S32, pumps into melted blend in upflowing prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; First product system is pumped into prepolymerization kettle through the first melt metering pump, control reaction liquid level at below 240mm, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.02% trimethyl phosphite 99, under vacuum tightness is 1200MPa, carry out prepolymerization reaction at 280 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control is at 110MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
Embodiment 6
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.17, the mol ratio of terephthalic acid and Isosorbide is 1:0.04, the molar weight of antimony glycol, antimonous oxide and Cobaltous diacetate accounts for the proportionlity of 0.03% of terephthalic acid molar weight, terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate are mixed, carry out slurrying, mixing time is 35min, obtains the first reactant system.First reactant system is delivered in the first slurry charging-tank.Then through the first volume pump, with charging flow velocity for 185kg/h, pump in reaction kettle of the esterification by the first reactant system, tank level control, at below 900mm, carries out esterification at 250 DEG C, obtains the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.3, zinc acetate accounts for the proportionlity to 0.03% of naphthalene diformic acid dimethyl ester molar weight, will mix, and carry out slurrying to naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, mixing time is 35min, obtains the second reactant system.Second reactant system is delivered in the second slurry charging-tank.Then through the second volume pump, with charging flow velocity for 80kg/h, pump in ester interchange vessel by the second reactant system, tank level control, at below 400mm, carries out transesterification reaction at 175 DEG C, obtains the second product system;
First product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, the first product and the second product carry out after homogenizing mixes, obtaining melted blend with weight ratio 1:0.5; Melted blend is pumped in upflowing prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; First product system is pumped into prepolymerization kettle through the first melt metering pump, control reaction liquid level at below 240mm, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.02% trimethyl phosphite 99, under vacuum tightness is 1500MPa, carry out prepolymerization reaction at 280 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control is at 300MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
In addition, also raw materials recovery has been carried out to prepolymerization reaction, whole polycondensation and pelletizing process.
Embodiment 7
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.18, the mol ratio of terephthalic acid and Isosorbide is 1:0.05, the molar weight of antimony glycol, antimonous oxide and Cobaltous diacetate accounts for the proportionlity of 0.04% of terephthalic acid molar weight, after terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate are mixed, carry out slurrying, mixing time is 40min, obtains the first reactant system.First reactant system is delivered in the first slurry charging-tank.Then through the first volume pump, with charging flow velocity for 190kg/h, pump in reaction kettle of the esterification by the first reactant system, tank level control, at below 800mm, carries out esterification at 255 DEG C, obtains the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.3, zinc acetate accounts for the proportionlity to 0.04% of naphthalene diformic acid dimethyl ester molar weight, will mix, and carry out slurrying to naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, mixing time is 40min, obtains the second reactant system.Second reactant system is delivered in the second slurry charging-tank.Through the second volume pump, with charging flow velocity for 80kg/h, pump in ester interchange vessel by the second reactant system, tank level control, at below 401mm, carries out transesterification reaction at 200 DEG C, obtains the second product system;
First product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, the first product and the second product carry out after homogenizing mixes, obtaining melted blend with weight ratio 1:0.5; Melted blend is pumped in upflowing prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; First product system is pumped into prepolymerization kettle through the first melt metering pump, control reaction liquid level at below 300mm, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.05% trimethyl phosphite 99, under vacuum tightness is 1200MPa, carry out prepolymerization reaction at 285 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 250mm, vacuum degree control is at 110MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
In addition, also raw materials recovery has been carried out to prepolymerization reaction, whole polycondensation and pelletizing process.
Embodiment 8
With the mol ratio of terephthalic acid and ethylene glycol for 1:1.18, the mol ratio of terephthalic acid and Isosorbide is 1:0.06, the molar weight of antimony glycol, antimonous oxide and Cobaltous diacetate accounts for the proportionlity of 0.04% of terephthalic acid molar weight, terephthalic acid, Isosorbide, ethylene glycol and Cobaltous diacetate are mixed, carry out slurrying, mixing time is 38min, obtains the first reactant system.First reactant system is delivered in the first slurry charging-tank.Then through the first volume pump, with charging flow velocity for 190kg/h, pump in reaction kettle of the esterification by the first reactant system, tank level control, at below 900mm, carries out esterification at 255 DEG C, obtains the first product system;
With to the mol ratio of naphthalene diformic acid dimethyl ester and ethylene glycol for 1:2.4, zinc acetate accounts for the proportionlity to 0.04% of naphthalene diformic acid dimethyl ester molar weight, will mix, and carry out slurrying to naphthalene diformic acid dimethyl ester, ethylene glycol and zinc acetate, mixing time is 38min, obtains the second reactant system.Second reactant system is delivered in the second slurry charging-tank.Then through the second volume pump, with charging flow velocity for 80kg/h, pump in ester interchange vessel by the second reactant system, tank level control, at below 402mm, carries out transesterification reaction at 200 DEG C, obtains the second product system;
First product system is pumped into homogenizing mixers through the first melt metering pump, and the second product system is pumped into homogenizing mixers through the second melt metering pump, the first product and the second product carry out after homogenizing mixes, obtaining melted blend with weight ratio 1:0.5; Melted blend is pumped in upflowing prepolymerization kettle through the 4th melt metering pump and carries out prepolymerization reaction; First product system is pumped into prepolymerization kettle through the first melt metering pump, control reaction liquid level at below 300mm, and the second product system is pumped into prepolymerization kettle through the second melt metering pump, and add account for terephthalic acid molar weight 0.05% trimethyl phosphite 99, under vacuum tightness is 1500MPa, carry out prepolymerization reaction at 290 DEG C, obtain precondensation product; And
Precondensation product is pumped in whole polycondensation vessel through the 3rd melt metering pump, control reaction liquid level at below 100mm, vacuum degree control is at 130MPa, whole polycondensation is carried out at 290 DEG C, when intrinsic viscosity is 0.80 ~ 0.82dL/g, carry out discharging, through pelletizing, obtain pet copolymer.
In addition, also raw materials recovery has been carried out in prepolymerization reaction, whole polycondensation and pelletizing process.
Carry out performance test to pet copolymer obtained in embodiment 1 to 9, method is as follows:
Tensile strength: the tensile strength being tested product by ASTM D638 standard method, tensile strength shows that more greatly the molecular chain rigidity of product is stronger.
Elongation at break: by ASTM D638 standard method, test the elongation at break of product, elongation at break shows that more greatly the toughness of product is better..
Hardness: by ASTM D2240 standard method, test the hardness of product, hardness shows that more greatly the rigidity of product is stronger..
Thermotolerance: by ISO75 standard method, tests the heat resisting temperature of product, and heat resisting temperature is higher shows that the resistance toheat performance of product is better.
Test result is in table 1.
Table 1
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect: have employed intermittent preparing process in comparative example 1, and the viscosity of product is the viscosity of the product that 0.35mpa.s adopts continuous production technique to obtain well below the present invention; Simultaneously, on the basis of embodiment 2, Isosorbide is not added in comparative example 2, the heat resisting temperature of therefore obtained in comparative example 2 product is only 60 DEG C, this is also lower than the heat resisting temperature 73 DEG C of the product in embodiment in the present invention 2, and the thermotolerance added for product of visible Isosorbide has very important effect; In addition, compared to other embodiments of the invention, the processing parameter in embodiment 1 have employed the numerical value outside scope.Although the over-all properties of product obtained in the embodiment of the present invention 1 is worse than other embodiments, but still is better than comparative example 1 and comparative example 2.It can thus be appreciated that the raw material that the present invention adopts, preparation method and the over-all properties of processing parameter to pet copolymer have very important effect.
With terephthalic acid, Isosorbide, ethylene glycol and to naphthalene diformic acid dimethyl ester for raw material, esterification and transesterification reaction are separately carried out.Then by esterification products and ester exchange offspring mixing, sequentially precondensation is carried out and whole polycondensation obtains pet copolymer.Isosorbide, as one of reactant, is conducive to the thermotolerance improving product.Transesterification reaction simultaneously by carrying out separately can obtain the NDA diethyl ester of higher degree, and this just can be avoided, and use is originated not easily, expensive NDA, thus is conducive to the economy improving whole technique.The pet copolymer that the reason of above-mentioned several respects makes the present invention obtain has good thermotolerance, and preparation cost is lower, industrialization scale operation preferably.
In addition, for polymer raw and the technique of uniqueness, even if make the preparation method of this pet copolymer provided by the present invention adopt continuous processing also just direct production can go out meet the pet copolymer of viscosity requirement without the need to carrying out extra polymerization process, have more advantage compared to traditional intermittent type preparation technology.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a preparation method for pet copolymer, is characterized in that, described preparation method comprises the following steps:
S1, after terephthalic acid, Isosorbide, ethylene glycol and the first catalyst mix, carries out esterification, obtains the first product system;
S2, to after naphthalene diformic acid dimethyl ester, ethylene glycol and the second catalyst mix, will carry out transesterification reaction, obtains the second product system;
S3, carries out prepolymerization reaction by described first product system and described second product system, obtains precondensation product; And
S4, carries out whole polycondensation by described precondensation product, obtains described pet copolymer.
2. preparation method according to claim 1, is characterized in that, described preparation method comprises the following steps:
S1, the first reactant system is obtained by after described terephthalic acid, described Isosorbide, described ethylene glycol and described first catalyst mix, through the first volume pump, described first reactant system is pumped in reaction kettle of the esterification, carry out described esterification, obtain described first product system;
S2, described second reactant system is obtained to after naphthalene diformic acid dimethyl ester, described ethylene glycol and described second catalyst mix by described, through the second volume pump, described second reactant system is pumped in ester interchange vessel, carry out described transesterification reaction, obtain described second product system;
S3, pumps into prepolymerization kettle by described first product system through the first melt metering pump, and described second product system is pumped into described prepolymerization kettle through the second melt metering pump, carries out described prepolymerization reaction, obtains described precondensation product; And
S4, pumps into described precondensation product in whole polycondensation vessel through the 3rd melt metering pump and carries out described whole polycondensation, obtain described pet copolymer.
3. preparation method according to claim 2, is characterized in that, described step S3 comprises:
S31, pumps into homogenizing mixers by described first product system through described first melt metering pump, and described second product system is pumped into described homogenizing mixers through described second melt metering pump, after homogenizing mixing, obtains melted blend;
S32, pumps into described melted blend in described prepolymerization kettle through the 4th melt metering pump and carries out described prepolymerization reaction; Preferably, described prepolymerization kettle is upflowing prepolymerization kettle.
4. preparation method according to claim 3, is characterized in that, in described step S4, carry out, in the process of described whole polycondensation, when described intrinsic viscosity is 0.80 ~ 0.82dL/g, carrying out discharging, through pelletizing, obtain described pet copolymer.
5. preparation method according to any one of claim 1 to 4, it is characterized in that, in described step S1, the mol ratio of described terephthalic acid and described ethylene glycol is 1:1.15 ~ 1:1.20, and the mol ratio of described terephthalic acid and described Isosorbide is 1:0.02. ~ 1:0.08; Preferably, the mol ratio of described terephthalic acid and described ethylene glycol is 1:1:1.15 ~ 1:1.18, and the mol ratio of described terephthalic acid and described Isosorbide is 1:0.04. ~ 1:0.06.
6. preparation method according to any one of claim 1 to 4, is characterized in that, in described step S2, the described mol ratio to naphthalene diformic acid dimethyl ester and described ethylene glycol is 1:2.2 ~ 1:2.4.
7. preparation method according to any one of claim 1 to 4, is characterized in that, in described step S3, the weight ratio of described first product system and described second product system is 1:0.1 ~ 1:0.5.
8. preparation method according to any one of claim 1 to 4, is characterized in that,
In described step S1, the catalyzer of described esterification is antimony glycol, one or more in antimonous oxide and Cobaltous diacetate; And/or
In described step S2, the catalyzer of described transesterification reaction is one or more in zinc acetate, magnesium acetate and manganese acetate; And/or
In described step S3, in described prepolymerization reaction process, simultaneously add stablizer to prepolymerization reaction system, described stablizer is one or more in trimethyl phosphite 99, triphenylphosphate and methyl phosphite.
9. preparation method according to claim 8, is characterized in that,
In described step S1, the molar weight of the catalyzer of described esterification is 0.03 ~ 0.05% of described terephthalic acid molar weight, is preferably 0.03 ~ 0.04%; And/or
In described step S2, the molar weight of the catalyzer of described transesterification reaction be described to naphthalene diformic acid dimethyl ester molar weight 0.03 ~ 0.05%, be preferably 0.03 ~ 0.04%; And/or
In described step S3, the molar weight of the described stablizer added in described prepolymerization reaction process is 0.02 ~ 0.05% of described terephthalic acid molar weight, is preferably 0.02 ~ 0.04%.
10. preparation method according to any one of claim 1 to 4, is characterized in that,
In described step S1, the temperature of reaction of described esterification is 245 ~ 255 DEG C, is preferably 250 ~ 255 DEG C; And/or
In described step S2, the temperature of reaction of described transesterification reaction is 165 ~ 215 DEG C, is preferably 175 ~ 200 DEG C; And/or
In described step S3, the temperature of reaction of described prepolymerization reaction is 280 ~ 285 DEG C, and the reaction times is 20 ~ 40min; And/or
In described step S4, the temperature of reaction of described whole polycondensation is 285 ~ 290 DEG C.
11. preparation methods according to any one of claim 2 to 4, is characterized in that,
In described step S1, control described first volume pump, make the charging flow velocity of described first reactant system be 180 ~ 190Kg/h, be preferably 185 ~ 190Kg/h; And the liquid level controlled in described reaction kettle of the esterification is at 800 ~ 900mm;
In described step S2, control described second volume pump, make the charging flow velocity of described second reactant system be 60 ~ 90Kg/h, be preferably 65 ~ 80Kg/h; And the liquid level controlled in described transesterification reactor is 300 ~ 400mm;
In described step S3, the liquid level controlled in described prepolymerization kettle is 240 ~ 300mm; Vacuum tightness is 1000 ~ 2000Pa, preferably 1200 ~ 1500Pa; And
In described step S4, the liquid level controlled in described whole polycondensation vessel is 100 ~ 250mm; Vacuum tightness is 100 ~ 300Pa, is preferably 110 ~ 130Pa.
12. 1 kinds of pet copolymers, is characterized in that, the preparation method according to any one of claim 1 to 11 obtains.
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