CN104031252B - The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer - Google Patents
The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer Download PDFInfo
- Publication number
- CN104031252B CN104031252B CN201410258922.2A CN201410258922A CN104031252B CN 104031252 B CN104031252 B CN 104031252B CN 201410258922 A CN201410258922 A CN 201410258922A CN 104031252 B CN104031252 B CN 104031252B
- Authority
- CN
- China
- Prior art keywords
- flame
- continuous polymerization
- pet copolymer
- fast
- polymerization preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to PET copolymer field, specifically, relate to the continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer. On the continuous polymerization production line of flexible modified poly ester; adopt the novel short flow process continuous polymerization unit of an esterifying kettle, a preshrunk still, a whole polycondensation vessel; continuous production goes out fast crystallization, Flame-retardant PET copolymer; preparation process energy consumption is low; output is large; quality stability is good, easily large-scale industrial production, and product has the very strong market competitiveness.
Description
Technical field
The present invention relates to PET copolymer field, specifically, relate to the continuous polymerization system of a kind of fast crystallization, Flame-retardant PET copolymerPreparation Method.
Background technology
Polyester relies on its special structure and good physical and chemical performance, obtains extensive use in fields such as weaving, films. ByMore intense in polyester molecule chain rigidity, when it is used as engineering plastics moulding crystallization slow, be not easy moulding, forImprove this point and often need to add crystallization nucleating agent and nucleation accelerating agent etc., as CN201310239570.1, preparation technology's ratioTrouble, cost is also higher. Often limit its extensive use in engineering plastics field.
The polyester fibers such as PET belong to inflammable macromolecular material, apply many occasions require it to have good resistance as engineering plasticsCombustion property, is necessary it to carry out fire-retardant. Fire-retardant to it is at present mainly to add brominated halogen flame by the method for blendRealize, the research of the Flame-retardant PET carrying out as people such as Xu Xiaonan, along with the raising gradually of people's environmental consciousness, gradually fire-retardant at presentTo non-halogen future development.
In order to overcome these shortcomings, the present invention, on the continuous polymerization production line of flexible modified poly ester, adopts the online polyethers that addsImprove polyester molecule chain flexibility, accelerate the rapid crystallization ability of polyester, the online phosphorous flame-retardant monomer adding carries out copolymerizationWhen realizing its rapid crystallization, also give polyester and have the characteristic of halogen-free flameproof. Flow process is the short flow process polymerization work of three still flow processsSkill, continuous production goes out to have fast crystallization property halogen-free antiflaming polyester section.
In production reality, adopt the method for the short flow process continuous polymerization of three still flow processs to carry out the halogen-free flame-proof copolymerized thing of fast crystallization propertyThe preparation of polyester slice, on the one hand, continuously production can ensure the steady quality of product, avoided batch and batch between propertyThe difference of energy index, also can relatively carry out large-scale industrial production on the other hand, effectively reduces the cost of product, enters oneStep improves the competitiveness of product in market.
CN200910312669 relates to a kind of quickly crystallized polyester engineering plastic and preparation method thereof, by following raw material components at two spiral shellsIn bar extruder, extrude and make: modification fast crystallization polyester A100 weight portion, crystallization nucleating agent B0.05～5 weight portion, glassFiber C10～40 weight portion, fire retardant D10～30 weight portion, flexibilizer E1～15 weight portion and antioxidant F0.01～3Weight portion.
ZL201110174664.6 discloses a kind of PBT composite and preparation method thereof, PBT composite percentage by weightThan composed of the following components: PBT resin 20～60%, PBN resin 10-30%, nucleator 0.3～1%, bromide fire retardant 5～15%, fire retarding synergist 2～6%, flexibilizer 2～5%, antioxidant 0.1～1%, lubricant 0.1～2%, glass fibre 10-50%.
Patent application 201210545807.4 provides a kind of continuous polymerization method of flame retardant polyester copolymer, but fire-resistant copolyestersThing does not but have the characteristic of fast crystallization, if that injection mo(u)lding also needs to carry out is crystalline modified soon.
In order to overcome defect of the prior art, special proposition the present invention directly directly synthesizes and has continuously in the short flow process of three stillsThe modified PET of fast crystallization flame-retarding characteristic, can directly be injection molded into parts and use.
Summary of the invention
Goal of the invention of the present invention has been to propose the continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer.
In order to realize object of the present invention, the technical scheme of employing is:
The present invention, in the short flow process of three stills, adds the monomer that flame-retardant monomer and fast crystallization promote online, and then continuous polymerization becomes a kind ofFast crystallization, Flame-retardant PET copolymer, comprise the steps:
(1) terephthalic acid (TPA) and ethylene glycol are put into making beating still, add nucleator to pull an oar together simultaneously, put slurry charging-tank 1 into;The addition of nucleator is 0.3～0.8% of terephthalic acid (TPA) and ethylene glycol gross mass, preferably 0.2～0.6%;
(2) slurry of step (1) gained is pumped into the first reaction kettle of the esterification, carry out esterification, coutroi velocity, makes byAfter one esterifying kettle, esterification yield reaches 90～96%, and preferably 91～93%; Pump into pipeline, successively through syringe 1 and noteEmitter 2;
(3) PEG or PTMG are melted in melting kettle, add antioxidant simultaneously, after stirring, pump in charging-tank 2, by noteEmitter 1 is added online; The addition of PEG or PTMG is 5～10% of terephthalic acid (TPA) and ethylene glycol gross mass,Preferably 6～8%;
(4) mixed slurry of preparation fire retardant monomer and solvent, puts into charging-tank 3, adds online by syringe 2; InstituteThe addition of the fire retardant monomer of stating is 10～15% of terephthalic acid (TPA) and ethylene glycol gross mass, preferably 10～12%;
(5) will mix through static mixer through the carboxylate of syringe 1 and syringe 2;
(6) control melt liquid level and enter successively precondensation still, whole polycondensation vessel, carry out polycondensation reaction, through online test point, treat that characteristic is stickyAfter number is 0.7～0.85dL/g, carries out discharging pelletizing and prepare fast crystallization, fire-retardant, antistatic copolymer particle.
The first optimal technical scheme of the present invention is: in step (6), while entering precondensation still, melt liquid level flow velocity is 210～300Kg/h, in precondensation still, melt liquid level is 500～550mm.
The second optimal technical scheme of the present invention is: in precondensation still, melt temperature is 270～275 DEG C; Vacuum is 2500～3000Pa, preferably 2600～2800Pa.
The 3rd optimal technical scheme of the present invention is: in step (6), in whole polycondensation vessel, melt liquid level is 100～150mm;Vacuum is 100～300Pa, preferably 100～250Pa.
The 4th optimal technical scheme of the present invention is: in step (6), in whole polycondensation vessel, melt temperature is 275～285 DEG C,Preferably 278～282 DEG C.
The 5th optimal technical scheme of the present invention is: in step (1), described nucleator agent is 4000～10000 order talcumsPowder, preferably 4000～6000 orders; Beating time is 30～50 minutes, preferably 35～40 minutes. Wherein, preferred, rightPhthalic acid and ethylene glycol mol ratio are 1:1.15.
The 6th optimal technical scheme of the present invention is: in step (2), esterification temperature is 250～265 DEG C, preferably 255～258 DEG C.
The 7th optimal technical scheme of the present invention is: in step (3), PEG molecular weight is 800～2000, preferred molecular weightBe 1000; The temperature of melting kettle is 50～80 DEG C, preferably 55～75 DEG C; Described antioxidant is selected from antioxidant 1010, antioxidant1098 or antioxidant 1076 at least one, preferred antioxidant 1010, addition is terephthalic acid (TPA) and ethylene glycol gross mass0.05～0.15%, preferably 0.1～0.15%; Antioxidant adds rear stirring 20～30 minutes, preferably 23～27 minutes.
The 8th optimal technical scheme of the present invention is: in step (4), and fire retardant list in fire retardant monomer and solvent slurryThe mass percentage content of body is 70～80%, the described preferred 2-ethoxy of fire retardant monomer phenyl phosphinic acids, described solventPreferably ethylene glycol.
The 9th optimal technical scheme of the present invention is: the structural formula of the copolymer preparing is:
-(CO-C6H4-COORO-)n-(-CH2CH2O)m-(CO-C6H4-COORO-C9H9O3P)k-；
Wherein R is-(CH2)2，15＜m＜20，1＜n＜250，1＜k＜10。
Below technical scheme of the present invention is made further explanation.
The present invention relates to a kind ofly on the continuous polymerization production line of flexible modified poly ester, add comonomer, directly continuous production is providedThere is the method for the poly-polyester copolymer polyester slice of fast crystallization property halogen-free flameproof. The present invention is prepared and is had fast knot by continuous polymerizationBrilliant characteristic halogen-free antiflaming polyester section raw material, is directly used in the injection mo(u)lding of follow-up halogen-free antiflaming polyester plastics.
The object of the present invention is to provide a kind of preparation method with fast crystallization property halogen-free flameproof polyarylene block copolymer polyester continuous polymerization,The method is on the continuous polymerization production line of flexible modified poly ester, adopts an esterifying kettle, a preshrunk still, a final minification to gatherThe new type of continuous polyplant of still (the short flow process of three stills), adopts the method for continuous polymerization to prepare fast crystallization, Flame-retardant PET copolymerizationThing, preparation process energy consumption is low, and output is large, and quality stability is good, easily large-scale industrial production, product has Hen Qiang cityField competitiveness.
The present invention the PET molecular skeleton of copolymer on contain poly-second diether (PEG) structure, this copolymer has following knotStructure formula:
-(CO-C6H4-COORO-)n-(-CH2CH2O)m-(CO-C6H4-COORO-C9H9O3P)k-；
Wherein R is-(CH2)2-，15＜m＜20，1＜n＜250，1＜k＜10。
The main chain of this copolymer by glycol ester segment, with low molecular polyether (PEG or PTMG) unit and polyphenyl diformazanAcid glycol ester segment and 2-ethoxy phenyl phosphinic acids unit random arrangement composition, in polymerization process, the end group of polyethers and rightPhthalic acid glycol ester or prepolymer carry out copolycondensation, end group and the terephthalic acid (TPA) second two of 2-ethoxy phenyl phosphinic acidsAlcohol ester or prepolymer carry out copolycondensation, synthetic flame-retardant and anti-static polyphenyl dioctyl phthalate glycol ester copolymer. 2-hydroxyl in strandEthylphenyl phosphinic acids embody anti-flaming function.
The intrinsic viscosity of PET copolymer of the present invention is 0.70～0.80dL/g, and hot strength is 50～80MPa, extension at breakRate is 60～150%, and hardness is at 50～80A; The fusing point of copolymer only has one, and melting range is at 240～260 DEG C.
The synthetic preparation of polyester copolymer normally in polymerization reaction kettle intermittently polymerization prepare. Due to every in Batch ProcessCriticize and there are differences between every batch, the stability of quality also can some fluctuation. The present invention establishes at the short flow process polyester continuous polymerization of three stillsA kind of method of modified polyesters continuous polymerization is provided on standby basis. The present invention is in order further to improve the anti-flammability of productCan, improving the addition of fire retardant, its addition is polyester raw material 10～15%,, in the present invention, is also added with into meanwhileThe components such as core agent, and under the higher condition of auxiliary material content, macromolecular material polymerization difficulty, is difficult to aggregate into being total to of HMWPolymers. Therefore, the present invention is by controlling in the condition of precondensation still and whole polycondensation vessel, by controlling melt liquid level and vacuumDegree, thus reach the HMW scope of copolymer of the present invention, and if melt liquid level height is not controlled preparationThe material molecule amount obtaining is low, poor performance.
The copolymer of preparing of the copolymer that the method for copolymer continuous polymerization provided by the present invention is prepared and batchwise polymerizationAdvantage is:
1, overcome the difference in the same reactor of intermittent polyreaction. Discharging due to reactor in batchwise polymerization method is wanted conventionallyFor some time, tend to cause the intrinsic viscosity of the prepared copolymer of same reactor material different, as intermittently poly-in a stillClose reaction:
The intrinsic viscosity of the discharging material of 5 minutes: 0.70dl/g
The intrinsic viscosity of the discharging material of 20 minutes: 0.72dl/g
Discharging finishes the intrinsic viscosity of first 5 minutes material: 0.74dl/g
Often same reactor material, the molecular weight of material can be variant, and subsequent applications is had a negative impact.
And continuous polymerization is continuous dynamic operation, so just can ensure that the intrinsic viscosity of controlling material is all at 0.70dl/g, with a collection ofBetween defective material, there will not be difference.
2. overcome the difference between batchwise polymerization still and still, in intermittent polyreaction, finished after the first still reaction, often notCan wash immediately still, but and then carry out the second still reaction, because on the still wall due to the first still reaction, often residual amount is manyThe polymer of the first still, these residual polymer will, in the polymerization process of the second still, stand certain thermal degradation, makeBecome the quality of the polymer of the second still to tend to the quality lower than the first still, section color burn, shows in the index of section to be:
The content of carboxyl end group of the copolymer of the first still: 15mol/t, form and aspect b value: 10;
The content of carboxyl end group of the copolymer of the second still: 19mol/t, form and aspect b value: 12;
The increase of the increase of content of carboxyl end group and form and aspect b value, can cause chipping qualities to decline.
The increase of form and aspect b value in addition, can cause product quality to decline.
And the content of carboxyl end group of modified copolymer prepared by continuous polymerization can be very stable be controlled at 15mol/t, form and aspect b value stabilizationBe controlled at 10, more stable.
Adopt continuous production technique of the present invention, the copolymer crystallization rate preparing is fast, is the bar of 55 DEG C in mold temperatureUnder part, the demoulding smoothly, and mechanical strength is high, (the Injection hold pressure time is 6～10S, and mold temperature is soon in injection mo(u)ldingUnder the condition of 55 DEG C, stripping forming smoothly), demoulding at low temperatures, and product is indeformable; And product has veryHigh fire resistance.
Brief description of the drawings
Fig. 1 is the process flow diagram of copolymer continuous polymerization of the present invention.
Be below the specific embodiment of the present invention, described embodiment is in order to further describe the present invention instead of to limit thisBright.
Detailed description of the invention
Embodiment 1
Daily output 5 tons of small flexible modified poly ester continuous polycondensation polycondensation process units on, by terephthalic acid (TPA), ethylene glycol with mol ratioFor 1:1.15 puts into making beating still, add nucleator 4000 order talcum powder to pull an oar together simultaneously, beating time is 40 pointsClock, puts slurry charging-tank 1 into after making beating finishes; The addition of nucleator is 0.5% of terephthalic acid (TPA) and ethylene glycol gross mass;
2. the slurry of step 1 gained is pumped into the first reaction kettle of the esterification, carry out esterification, esterification temperature is 258 DEG C; Coutroi velocity,Make by after the first esterifying kettle, esterification yield reaches 92%; Pump into pipeline, pass through successively syringe 1 and syringe 2;
3. the PEG that is 1000 by molecular weight melts in melting kettle, and fusion temperature is 80 DEG C, adds antioxidant 1010 simultaneously, stirsMix after 25 minutes and pump in charging-tank 2, add online by syringe 1; The addition of PEG is terephthalic acid (TPA)With 6% of ethylene glycol gross mass; Antioxidant 1010 addition is 0.15% of terephthalic acid (TPA) and ethylene glycol gross mass;
4. the mixed slurry of preparation 2-ethoxy phenyl phosphinic acids and ethylene glycol, puts into charging-tank 3, is undertaken online by syringe 2Add; The addition of 2-ethoxy phenyl phosphinic acids is 10% of terephthalic acid (TPA) and ethylene glycol gross mass; 2-ethoxy phenylThe mass percentage content of the middle 2-ethoxy phenyl phosphinic acids of phosphinic acids slurry is 80%;
5. will mix through static mixer through the carboxylate of syringe 1 and syringe 2;
6. control melt liquid level enters precondensation still successively, whole polycondensation vessel carries out polycondensation reaction: while entering precondensation still, and melt liquid level streamSpeed is 300Kg/h, and in precondensation still, melt liquid level is 550mm; Melt temperature is 275 DEG C; Vacuum is 3000Pa;In whole polycondensation vessel, melt liquid level is 150mm; Control vacuum at 200Pa, melt temperature is 280 DEG C; Through online inspectionMeasuring point, after intrinsic viscosity is 0.75dL/g, carries out discharging pelletizing and obtains copolymer, through underwater cutpellet, and dry preparingCarry out discharging pelletizing and prepare fast crystallization, Flame-retardant PET particle.
The intrinsic viscosity of the modified copolyester of preparing is all 0.75g/dl all the time, constant product quality, and content of carboxyl end group is also stabilized in15mol/t, form and aspect b value stabilization is controlled at 10, is better than discontinuous polycondensation copolymer product. Product limiting oxygen index determination value is 38, moltenMelt 265 DEG C of temperature, mold temperature is that under the condition of 55 DEG C, (mold temperature of common PET will reach stripping forming smoothly95～130 DEG C), there are good fast crystallization property and good anti-flammability, tensile strength of material is 67MPa, elongation at break is80%, hardness is at 75A, and copolymer fusing point, can be for the preparation of some electronic apparatus parts, as transformer bone at 248 DEG CFrame, electrical connector etc.
Embodiment 2
Daily output 5 tons of small flexible modified poly ester continuous polycondensation polycondensation process units on, by terephthalic acid (TPA), ethylene glycol with mol ratioFor 1:1.15 puts into making beating still, add nucleator 6000 order talcum powder to pull an oar together simultaneously, beating time is 50 pointsClock, puts slurry charging-tank 1 into after making beating finishes; The addition of nucleator is 0.3% of terephthalic acid (TPA) and ethylene glycol gross mass;
2. the slurry of step 1 gained is pumped into the first reaction kettle of the esterification, carry out esterification, esterification temperature is 265 DEG C, coutroi velocity,Make by after the first esterifying kettle, esterification yield reaches 91%; Pump into pipeline, pass through successively syringe 1 and syringe 2;
3. the PEG that is 2000 by molecular weight melts in melting kettle, and fusion temperature is 80 DEG C, adds antioxidant 1010 simultaneously, stirsMix after 27 minutes and pump in charging-tank 2, add online by syringe 1; The addition of PEG is terephthalic acid (TPA)With 8% of ethylene glycol gross mass; Antioxidant 1010 addition is 0.10% of terephthalic acid (TPA) and ethylene glycol gross mass;
4. the mixed slurry of preparation 2-ethoxy phenyl phosphinic acids and ethylene glycol, puts into charging-tank 3, is undertaken online by syringe 2Add; The addition of described fire retardant monomer is 12% of terephthalic acid (TPA) and ethylene glycol gross mass; 2-ethoxy phenylThe mass percentage content of the middle 2-ethoxy phenyl phosphinic acids of phosphonic acids slurry is 70%;
5. will mix through static mixer through the carboxylate of syringe 1 and syringe 2;
6. control melt liquid level enters precondensation still successively, whole polycondensation vessel carries out polycondensation reaction: while entering precondensation still, and melt liquid level streamSpeed is 210Kg/h, and in precondensation still, melt liquid level is 500mm; Melt temperature is 275 DEG C; Vacuum is 2500Pa;In whole polycondensation vessel, melt liquid level is 100mm; Control vacuum at 200Pa, melt temperature is 278 DEG C; Through online inspectionMeasuring point, after intrinsic viscosity is 0.75dL/g, carries out discharging pelletizing and obtains copolymer, through underwater cutpellet, and dry preparingCarry out discharging pelletizing and prepare fast crystallization, Flame-retardant PET particle.
The intrinsic viscosity of the modified copolyester of preparing is all 0.75g/dl all the time, constant product quality, and content of carboxyl end group is also stabilized in15mol/t, form and aspect b value stabilization is controlled at 10, is better than discontinuous polycondensation copolymer product. Product limiting oxygen index determination value is 39, moltenMelt 265 DEG C of temperature, mold temperature is under the condition of 55 DEG C, can smoothly demoulding type (mold temperature of common PET will reach 95～130 DEG C), there are good fast crystallization property and good anti-flammability, tensile strength of material is 65MPa, elongation at break is 80%,Hardness is at 75A, and copolymer fusing point is at 248 DEG C, can be for the preparation of some electronic apparatus parts, and as transformer framework,Electrical connector etc.
Embodiment 3
Daily output 5 tons of small flexible modified poly ester continuous polycondensation polycondensation process units on, by terephthalic acid (TPA), ethylene glycol with mol ratioFor 1:1.15 puts into making beating still, add nucleator 5000 order talcum powder to pull an oar together simultaneously, beating time is 35 pointsClock, puts slurry charging-tank 1 into after making beating finishes; The addition of nucleator is 0.4% of terephthalic acid (TPA) and ethylene glycol gross mass;
2. the slurry of step 1 gained is pumped into the first reaction kettle of the esterification, carry out esterification, esterification temperature is 255 DEG C, coutroi velocity,Make by after the first esterifying kettle, esterification yield reaches 91%; Pump into pipeline, pass through successively syringe 1 and syringe 2;
3. the PEG that is 800 by molecular weight melts in melting kettle, and fusion temperature is 75 DEG C, adds antioxidant 1010 simultaneously, stirsMix after 23 minutes and pump in charging-tank 2, add online by syringe 1; The addition of PEG is terephthalic acid (TPA)With 8% of ethylene glycol gross mass; Antioxidant 1010 addition is 0.12% of terephthalic acid (TPA) and ethylene glycol gross mass;
4. the mixed slurry of preparation 2-ethoxy phenyl phosphinic acids and ethylene glycol, puts into charging-tank 3, is undertaken online by syringe 2Add; The addition of 2-ethoxy phenyl phosphinic acids is 15% of terephthalic acid (TPA) and ethylene glycol gross mass; 2-ethoxy phenylThe mass percentage content of the middle 2-ethoxy phenyl phosphinic acids of phosphinic acids slurry is 75%;
5. will mix through static mixer through the carboxylate of syringe 1 and syringe 2;
6. control melt liquid level enters precondensation still successively, whole polycondensation vessel carries out polycondensation reaction: while entering precondensation still, and melt liquid level streamSpeed is 250Kg/h, and in precondensation still, melt liquid level is 525mm; Melt temperature is 273 DEG C; Vacuum is 2800Pa;In whole polycondensation vessel, melt liquid level is 120mm; Control vacuum at 250Pa, melt temperature is 282 DEG C; Through online inspectionMeasuring point, after intrinsic viscosity is 0.75dL/g, carries out discharging pelletizing and obtains copolymer, through underwater cutpellet, and dry preparingCarry out discharging pelletizing and prepare fast crystallization, fire-retardant, antistatic PET particle.
The intrinsic viscosity of the modified copolyester of preparing is all 0.75g/dl all the time, constant product quality, and content of carboxyl end group is also stabilized in15mol/t, form and aspect b value stabilization is controlled at 10, is better than discontinuous polycondensation copolymer product. Product limiting oxygen index determination value is 40; MoltenMelt 265 DEG C of temperature, mold temperature is that under the condition of 55 DEG C, (mold temperature of common PET will reach stripping forming smoothly95～130 DEG C), there are good fast crystallization property and good anti-flammability, tensile strength of material is 63MPa, elongation at break is80%, hardness is at 75A, and copolymer fusing point, can be for the preparation of some electronic apparatus parts, as transformer bone at 248 DEG CFrame, electrical connector etc.
Experimental example 1
Prepare modified PET polyester material according to the condition of embodiment 1 and method, difference is only, in step (6), rightThe conditions such as vacuum change, and actual conditions is as shown in table 1:
Table 1:
Being prepared according to above-mentioned condition the parameter that obtains product is:
Table 2:
Experimental example 2
Prepare modified PET polyester material according to the condition of embodiment 1 and method, difference is only, in step (6), rightThe conditions such as vacuum change, and actual conditions is as shown in table 3:
Table 3:
Being prepared according to above-mentioned condition the parameter that obtains product is:
Table 4:
Claims (22)
1. a continuous polymerization preparation method for fast crystallization, Flame-retardant PET copolymer, is characterized in that, described preparation method comprise asLower step:
(1) terephthalic acid (TPA) and ethylene glycol are put into making beating still, add nucleator to pull an oar together simultaneously, put slurry charging-tank 1 into;The addition of nucleator is 0.3～0.8% of terephthalic acid (TPA) and ethylene glycol gross mass;
(2) slurry of step (1) gained is pumped into the first reaction kettle of the esterification, carry out esterification, coutroi velocity, makes byAfter one esterifying kettle, esterification yield reaches 90～96%; Pump into pipeline, pass through successively syringe 1 and syringe 2;
(3) PEG or PTMG are melted in melting kettle, add antioxidant simultaneously, after stirring, pump in charging-tank 2, by noteEmitter 1 is added online; The addition of PEG or PTMG is 5～10% of terephthalic acid (TPA) and ethylene glycol gross mass;
(4) mixed slurry of preparation fire retardant monomer and solvent, puts into charging-tank 3, adds online by syringe 2; InstituteThe addition of the fire retardant monomer of stating is 10～15% of terephthalic acid (TPA) and ethylene glycol gross mass;
(5) will mix through static mixer through the carboxylate of syringe 1 and syringe 2;
(6) control melt liquid level and enter successively precondensation still, whole polycondensation vessel, in precondensation still, melt temperature is 270～275 DEG C;Vacuum is 2500～3000Pa; In whole polycondensation vessel, melt temperature is 275～285 DEG C, and melt liquid level is 100～150mm;Vacuum is 100～300Pa; Carry out polycondensation reaction, through online test point, after intrinsic viscosity is 0.7～0.85dL/g,Carry out discharging pelletizing and prepare fast crystallization, fire-retardant, antistatic copolymer particle.
2. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that nucleationThe addition of agent is 0.2～0.6% of terephthalic acid (TPA) and ethylene glycol gross mass.
3. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, in stepSuddenly in (2), esterification yield reaches 91～93%.
4. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that PEGOr the addition of PTMG is 6～8% of terephthalic acid (TPA) and ethylene glycol gross mass.
5. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, described inThe addition of fire retardant monomer be 10～12% of terephthalic acid (TPA) and ethylene glycol gross mass.
6. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, in stepSuddenly in (6), while entering precondensation still, melt liquid level flow velocity is 210～300Kg/h, in precondensation still, and melt liquid levelBe 500～550mm.
7. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, in stepSuddenly in (6), in precondensation still, vacuum is 2600～2800Pa.
8. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, in stepSuddenly in (6), in whole polycondensation vessel, vacuum is 100～250Pa.
9. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that, in stepSuddenly in (6), in whole polycondensation vessel, melt temperature is 278～282 DEG C.
10. the continuous polymerization preparation method of fast crystallization according to claim 1, Flame-retardant PET copolymer, is characterized in that,In step (1), described nucleator agent is 4000～10000 order talcum powder; Beating time is 30～50 minutes.
The continuous polymerization preparation method of 11. fast crystallizations according to claim 10, Flame-retardant PET copolymer, is characterized in that, slidingStone flour is 4000～6000 orders.
The continuous polymerization preparation method of 12. fast crystallizations according to claim 10, Flame-retardant PET copolymer, is characterized in that, beatsThe slurry time is 35～40 minutes.
The continuous polymerization preparation method of 13. fast crystallizations according to claim 1, Flame-retardant PET copolymer, is characterized in that,In step (2), esterification temperature is 250～265 DEG C.
The continuous polymerization preparation method of 14. fast crystallizations according to claim 13, Flame-retardant PET copolymer, is characterized in that esterChanging temperature is 255～258 DEG C.
The continuous polymerization preparation method of 15. fast crystallizations according to claim 1, Flame-retardant PET copolymer, is characterized in that,In step (3), PEG molecular weight is 800～2000, and the temperature of melting kettle is 50～80 DEG C; Described antioxidant is selected from antioxygenIn agent 1010, antioxidant 1098 or antioxidant 1076 at least one, addition is terephthalic acid (TPA) and ethylene glycol gross mass0.05～0.15%; Antioxidant adds rear stirring 20～30 minutes.
The continuous polymerization preparation method of 16. fast crystallizations according to claim 15, Flame-retardant PET copolymer, is characterized in that, moltenThe temperature of changing still is 55～75 DEG C.
The continuous polymerization preparation method of 17. fast crystallizations according to claim 15, Flame-retardant PET copolymer, is characterized in that instituteState antioxidant and be selected from antioxidant 1010.
The continuous polymerization preparation method of 18. fast crystallizations according to claim 15, Flame-retardant PET copolymer, is characterized in that, anti-Oxygen agent addition is 0.1～0.15% of terephthalic acid (TPA) and ethylene glycol gross mass.
The continuous polymerization preparation method of 19. fast crystallizations according to claim 15, Flame-retardant PET copolymer, is characterized in that, anti-Oxygen agent adds rear stirring 23～27 minutes.
The continuous polymerization preparation method of 20. fast crystallizations according to claim 1, Flame-retardant PET copolymer, is characterized in that,In step (4), in fire retardant monomer and solvent slurry, the mass percentage content of fire retardant monomer is 70～80%.
The continuous polymerization preparation method of 21. fast crystallizations according to claim 20, Flame-retardant PET copolymer, is characterized in that instituteThe fire retardant monomer of stating is selected from 2-ethoxy phenyl phosphinic acids, and described solvent is selected from ethylene glycol.
22. according to the continuous polymerization preparation method of the fast crystallization described in claim 1～21 any one, Flame-retardant PET copolymer, itsBe characterised in that, the structural formula of the copolymer preparing is:
-(CO-C6H4-COORO-)n-(-CH2CH2O)m-(CO-C6H4-COORO-C9H9O3P)k-；
Wherein R is-(CH2)2-，15＜m＜20，1＜n＜250，1＜k＜10。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410258922.2A CN104031252B (en) | 2014-06-11 | 2014-06-11 | The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410258922.2A CN104031252B (en) | 2014-06-11 | 2014-06-11 | The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104031252A CN104031252A (en) | 2014-09-10 |
| CN104031252B true CN104031252B (en) | 2016-05-11 |
Family
ID=51462262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410258922.2A Active CN104031252B (en) | 2014-06-11 | 2014-06-11 | The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104031252B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585701B (en) * | 2014-10-22 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of polyether-modified copolyesters continuous preparation method |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN105985514B (en) * | 2015-03-03 | 2018-11-30 | 东丽纤维研究所（中国）有限公司 | A kind of preparation method of flame-retardant polyester composition |
| CN104804177B (en) * | 2015-04-09 | 2016-05-11 | 中国纺织科学研究院 | A kind of high tenacity amorphous modified PET copolymer and preparation method thereof |
| CN107383839A (en) * | 2017-08-22 | 2017-11-24 | 安徽悦尔伟塑料机械有限公司 | Fire-retardant mechanical arm of high impact properties and preparation method thereof |
| CN113512278B (en) * | 2021-06-15 | 2023-04-28 | 山东贝润防水材料有限公司 | Toughening type polyester carcass film for waterproof coiled material and preparation method thereof |
| CN113563698B (en) * | 2021-09-23 | 2021-12-10 | 苏州宝丽迪材料科技股份有限公司 | Reactive functional polyester master batch and preparation method thereof |
| CN115197549B (en) * | 2022-06-27 | 2023-12-29 | 山东道恩合复新材料有限公司 | Rapid crystallization PET resin of nano attapulgite copolymerized PEG and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020766A (en) * | 2009-09-23 | 2011-04-20 | 四川富尔新纺织阻燃材料有限公司 | Method for preparing flame-retardant copolymerized and modified polyester |
| CN102617837B (en) * | 2012-03-27 | 2014-04-02 | 中国纺织科学研究院 | Quickly-crystallized PET (polyester) chip capable of being marked by laser and preparation method for same |
| CN103724605B (en) * | 2013-12-24 | 2016-03-09 | 中国纺织科学研究院 | A kind of continuous polymerization preparation method of flame-retardant and anti-static PTT polyester and the polyester of preparation |
-
2014
- 2014-06-11 CN CN201410258922.2A patent/CN104031252B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104031252A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104031252B (en) | The continuous polymerization preparation method of a kind of fast crystallization, Flame-retardant PET copolymer | |
| TWI705094B (en) | Recycle pet foaming material and method for manufacturing the same | |
| Zhang et al. | Enhancing the melt strength of poly (lactic acid) via micro-crosslinking and blending with poly (butylene adipate-co-butylene terephthalate) for the preparation of foams | |
| CN105440315A (en) | Polymer material, production method thereof | |
| JP2011510116A (en) | Extruded blow molded article | |
| Xu et al. | Cellulose acetate thermoplastics with high modulus, dimensional stability and anti-migration properties by using CA-g-PLA as macromolecular plasticizer | |
| CN112745493B (en) | Heat-resistant polyester resin and preparation method thereof | |
| CN103788587B (en) | A kind of high viscosity easily processes ethylene glycol terephthalate and preparation method thereof | |
| CN112898785B (en) | Thermoplastic elastomer material and preparation method and application thereof | |
| CN112469760B (en) | Integrated preparation method for producing polyglycolic acid product | |
| CN103951822A (en) | Modified polyesteramide and preparation method thereof | |
| CN104974337A (en) | Degradable branched polyester and preparation method thereof | |
| CN114773810A (en) | High-performance polylactic acid-based 3D printing wire rod and preparation method thereof | |
| US4382138A (en) | Polyamide containing 4,4'-diamino-2,2', 6,6'-tetramethylbiphenyl moieties | |
| CN112876828A (en) | Degradable electronic film and preparation method thereof | |
| CN104862813A (en) | Flame retardation PTT polyester fiber and preparation method therefor | |
| JPH024608B2 (en) | ||
| JP2010083957A (en) | Method for production of polybutylene terephthalate | |
| CN108752835A (en) | A kind of plastics resistant to chemical etching | |
| CN114605633B (en) | Bulk flame-retardant nylon and preparation method and application thereof | |
| JPH07196782A (en) | Production of polyester having high polymerization degree and production of polyester molding having high polymerization degree | |
| CN109825057B (en) | Modified PET/PC alloy with high anti-reflection and good ultraviolet resistance and preparation method thereof | |
| CN114369213B (en) | PET tackifier, PET foaming material and preparation method thereof | |
| CN114656756B (en) | Liquid crystal polyester composition and preparation method and application thereof | |
| CN114891324B (en) | Flame-retardant modified material with cross-linked grid structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |