CN103232594B - Cationic dyeable propylene glycol polyterephthalate continuous polymerization preparation method - Google Patents
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Abstract
The invention relates to a cationic dyeable propylene glycol polyterephthalate continuous polymerization preparation method comprising the steps that: terephthalic acid and propylene glycol are subjected to an esterification reaction under a temperature of 250-260 DEG C, such that an esterification product with an esterification rate higher than 92% is obtained; the temperature of the esterification product is controlled at 225-235 DEG C; a propylene glycol solution of propylene glycol isophthalate-5-sodium sulfonate is added into the esterification product, such that a uniformly mixed melt is obtained; the obtained melt is sequentially delivered into a first polycondensation kettle, a second polycondensation kettle, and a third polycondensation kettle, such that a polycondensation reaction is carried out; through an on-line detection point, when intrinsic viscosity is 0.83-0.86dL/g, discharging and dicing are carried out, such that a cationic dyeable propylene glycol polyterephthalate copolymer is obtained; underwater dicing and drying are carried out, such that cationic dyeable propylene glycol polyterephthalate copolymer particles are prepared. With the method, the obtained modified propylene glycol polyterephthalate has stable properties. Energy consumption during a preparation process is low, and large-scale industrial production is easy.
Description
Technical field
The present invention relates to a kind of preparation method of cation-dyeable Poly(Trimethylene Terephthalate), concrete, relate to a kind of preparation method of successive polymerization of cation-dyeable Poly(Trimethylene Terephthalate).
Background technology
Poly(Trimethylene Terephthalate) (PTT) is a kind of new polyester of excellent performance, its special structure and excellent physical and chemical performance, makes it to obtain widespread use in fields such as weaving, engineering plastics, films." the strange carbon effect " that be different from PET and PBT that cause due to three methylene radical that PTT macromolecular chain exists, make PTT trevira can overcome the rigidity of PET and the flexibility of PBT simultaneously, and have the advantage of PET and PA concurrently, as the rebound resilience of excellence, workability, easy dyeing and fluffiness etc.Therefore it is at clothes, carpet, and family the field such as to spin and is widely used,
Although ptt fiber has excellent performance, but its molecular structure is tightr, there is no the problem of close dye groups in molecular chain, cause ptt fiber can only dye with dispersed dye, and compared with cationic dyestuff, there is environment protecting difference in dispersed dye, chromatogram is incomplete, and coloured light is not gorgeous, and dispersed dye require high to dyeing installation, the shortcomings such as cost of investment is high, limit the application of PTT on fiber to a certain extent.
The Cha Lilili " research of the preparation and property of cation-dyeable PTT polyester " of Donghua University discloses and a kind ofly uses little reactor batch copolymerisation to prepare the method for cation-dyeable ptt fiber.And its performance is studied in detail.
Chinese patent application CN200510054950.3 discloses a kind of modification PTT fiber can using cation stain at normal temperatures and pressures, there is following structure, wherein n=100-150, x=25-100, y=1-4, this application take Sodium Dimethyl Isophthalate-5-sulfonate as properties-correcting agent, is embedded in poly terephthalic acid propylene glycol through melting copolymerization process, and formation can have adsorbing adsorption group to do dye seat to cationic dyestuff.
The preparation method of current cation-dyeable PTT polyester copolymer normally adopts to be polymerized in the polymerization reaction kettle of interval and prepares.There are differences between often criticizing in batch production and often criticizing, the stability of quality also can some fluctuation.And the method preparation of the poly-continuous polymerization of current conventional polyester and modified poly ester, most of batchwise polymerization device has adopted the technical process of Colaesce to compete owing to cannot prepare with successive polymerization major part, all stopped to run and has produced.Given this, special proposition the present invention.
Summary of the invention
The object of this invention is to provide a kind of continuous polymerization preparation method of cation-dyeable Poly(Trimethylene Terephthalate), the stable performance of the modification Poly(Trimethylene Terephthalate) that the method obtains, the energy consumption of preparation process is low, easy large-scale industrial production.
For realizing object of the present invention, a kind of continuous polymerization preparation method of cation-dyeable Poly(Trimethylene Terephthalate), comprises the steps:
(1) terephthalic acid and propylene glycol carry out esterification under temperature is the condition of 250-260 DEG C, obtain the esterification products that esterification yield reaches more than 92%;
(2) temperature of the esterification products of step (1) is controlled at 225 ~ 235 DEG C; The propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is joined in esterification products, then enters homogenizing mixers together, obtain the melt mixed;
(3) gained melt enters the first polycondensation vessel, the second polycondensation vessel and the 3rd polycondensation vessel successively, carry out polycondensation, through on-line checkingi point, be after 0.83 ~ 0.86dL/g until intrinsic viscosity, carry out discharging pelletizing and obtain cation-dyeable Poly(Trimethylene Terephthalate) multipolymer, through underwater cutpellet, cation-dyeable propylene glycol ester terephthalate copolymer pellet is prepared in drying.
Wherein, step (1) is titanium compound at the catalyzer carrying out esterification employing, preferred tetrabutyl titanate or isopropyl titanate.
In step (1), the consumption of catalyzer is the 0.03-0.05% of reactant total mass, and sorrow selects 0.04%.
Preferably, the temperature of the esterification products of step (1) controls at 228 ~ 232 DEG C.
In step (1), terephthalic acid and propylene glycol are 1:1.6 – 1:1.8 by the ratio of amount of substance.
The time of esterification is 20 ~ 60 minutes.
Described m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 2 ~ 8% of total reactant quality, preferably 4 ~ 6%.Control melt flow time, make its sluggish flow, make its melt temperature slowly reach 250 DEG C.
The preparation method of the propylene glycol solution of described m-phthalic acid propylene glycol ester-5-sodium sulfonate comprises the steps: Sodium Dimethyl Isophthalate-5-sulfonate, propylene glycol, esterifying catalyst, sodium acetate, anhydrous and trimethyl phosphite 99 mixing, it is 180 DEG C in temperature, transesterification reaction is carried out under the condition of nitrogen protection, when the amount of steaming of methyl alcohol reaches the 92-95% of theoretical amount, terminate this reaction, obtain the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate, wherein, the addition of sodium acetate, anhydrous is the 0.03-0.04% of total reactant quality, the dosage of trimethyl phosphite 99 is the 0.03-0.04% of total reactant quality, the addition of esterifying catalyst is the 0.03-0.05% of total reactant quality.
Preferably, m-phthalic acid propylene glycol ester-5-sodium sulfonate and the amount of substance of propylene glycol are than being 1:2.5.
Described esterifying catalyst is titanium compound, its preferred tetrabutyl titanate.
Preferably, the addition of sodium acetate, anhydrous is 0.02% of total reactant quality.
Preferably, the dosage of trimethyl phosphite 99 is 0.02% of total reactant quality.
In step (2), adopt interchanger to control the temperature of esterification products, described interchanger carries out hot oiling by heating agent, makes deep fat enter recuperator inlet temperature and controls at 190 ~ 205 DEG C, preferably 195 ~ 200 DEG C.
Described interchanger is connected with reaction kettle of the esterification at reaction kettle of the esterification discharge nozzle place.
In step (3), melt enters the first polycondensation vessel, controls melt temperature 245 ~ 255 DEG C, 20 ~ 40 minutes time; Enter the second polycondensation vessel, control melt temperature and arrive 255 ~ 260 DEG C, 30 ~ 40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature controls at 260 ~ 270 DEG C.
Wherein, also add polycondensation catalyst in described 3rd polycondensation vessel, described polycondensation catalyst is titanium compound, its preferred tetrabutyl titanate, and its addition is the 0.03-0.05% of total reactant quality, and it is preferably 0.04% years old.
Described m-phthalic acid propylene glycol ester-5-sodium sulfonate is added by volume pump control dose, and the rotating speed of volume pump controls at 10 ~ 50rpm.
Containing m-phthalic acid propylene glycol ester-5-sodium sulfonate (SIPT) structure on the PTT molecular skeleton of the multipolymer that aforesaid method obtains, this multipolymer has following structural formula:
-(CO-C
6h
4-COORO-) n-(-SIPT)-; Wherein R is-CH
2cH
2cH
2-; 1 < n < 250.
The main chain of this polymkeric substance is by p-poly-phenyl naphthalate segment, form with m-phthalic acid propylene glycol ester-5-sodium sulfonate random arrangement, in polymerization process, the end group of m-phthalic acid propylene glycol ester-5-sodium sulfonate and propylene glycol ester terephthalate or prepolymer carry out copolycondensation, and synthesizing cationic can contaminate polytrimethylene phthalate multipolymer.
The intrinsic viscosity of the cation-dyeable polytrimethylene phthalate multipolymer of stay in grade of the present invention is 0.83 ~ 0.86dL/g, tensile strength is 40 ~ 80MPa, elongation at break is 20 ~ 40%, multipolymer fusing point is at 220-230 DEG C, use cationic red X-LGL, boiling dyeing at normal pressure 60 minutes, dye uptake reaches 20-80%, can reach the requirement of cationic dyeable polyester fiber.
The synthesis preparation of cation-dyeable polytrimethylene phthalate multipolymer is normally polymerized and prepares in the polymerization reaction kettle of interval.There are differences between often criticizing in batch production and often criticizing, the stability of quality also can some fluctuation.The present invention is in the method for stay in grade cation-dyeable PTT successive polymerization.
Due to the continuous polymerization technique of the polymerization feature of polytrimethylene phthalate multipolymer itself and conventional polyester there is some difference property, in conjunction with the polymerization feature of multipolymer of the present invention, need to do some corresponding adjustment and changes to the continuous polymerization unit of common polyester.
Common polyester esterification at 250-260 DEG C, the melt temperature of conventional polyester is also in this temperature range, the successive polymerization of conventional polyester can continue polycondensation below on the basis of this temperature, and the modified polyesters of the application is due to the polymerization feature of itself, need melt temperature to drop to 225-235 DEG C, be preferably reduced to 228-232 DEG C.
The present invention is in above-mentioned steps 2) in esterification reaction product is carried out heat exchange by an interchanger be connected with reaction kettle of the esterification, after heat exchange, melt temperature can control at 230 ± 2 DEG C.
For realizing above-mentioned technique, interchanger of the present invention is connected with reaction kettle of the esterification at reaction kettle of the esterification discharge nozzle place, is preferably being connected from reaction kettle of the esterification discharge nozzle about 1.5 meters with reaction kettle of the esterification.
In the present invention, the distance limit of described interchanger and reaction kettle of the esterification junction is not very strict, but must connect after reaction kettle of the esterification.
Interchanger described in the present invention carries out hot oiling by heating agent, and the temperature making deep fat enter heat exchanger entrance controls at 190 ~ 205 DEG C, thus can control to control at 230 ± 2 DEG C through the melt temperature of interchanger.
In the present invention, the volume pump that SIPT solution is connected with its solution still by controls to be metered into, and the rotating speed of volume pump controls at 10 ~ 50rpm, to realize containing in multipolymer the amount of copolymerization units for 4 ~ 6%.
In the present invention, control the temperature of solution still mainly in order to be kept mixing state by solution, and control its rotating speed and mainly keep melt in volume pump to maintain a certain amount of and certain pressure, be convenient to be metered into.
The advantage of the cation-dyeable polytrimethylene phthalate multipolymer prepared of the stay in grade cation-dyeable polytrimethylene phthalate multipolymer that the method for continuous polymerization of polymer provided by the present invention is prepared and batchwise polymerization is:
Successive polymerization is continuous dynamic operation, so just can ensure that the intrinsic viscosity controlling material is all at 0.94dl/g, there will not be difference between same batch material, keep the stay in grade of product.And the difference in the same reactor of intermittent polyreaction, because the discharging of reactor usually will be for some time in cation-dyeable batch polymerization process, often cause the intrinsic viscosity of the multipolymer prepared by same reactor material different, as a still intermittent polyreaction:
The intrinsic viscosity of the discharging material of 5 minutes: 0.83dl/g
The intrinsic viscosity of the discharging material of 20 minutes: 0.84dl/g
Discharging terminates the intrinsic viscosity of first 5 minutes material: 0.86dl/g
Often same reactor material, the molecular weight of material can be variant, has a negative impact to subsequent applications.
The content of carboxyl end group of modified copolymer prepared by successive polymerization can be very stable control at below 18mol/t, form and aspect b value stabilization controls below 8, more stable, and stay in grade.And the difference between batchwise polymerization still and still, in intermittent polyreaction, after terminating the first still reaction, often can not wash still immediately, but and then carry out the second still reaction, due to the polymkeric substance of often the first still that residual amount is many on the still wall of the first still reaction, these residual polymkeric substance in the polymerization process of the second still, will stand certain thermal destruction, cause the quality of the polymkeric substance of the second still often lower than the quality of the first still, section color burn, the index showing section is:
The content of carboxyl end group of the multipolymer of the first still: 20mol/t, form and aspect b value: 8
The content of carboxyl end group of the multipolymer of the second still: 25mol/t, form and aspect b value: 10
The increase of content of carboxyl end group and the increase of form and aspect b value, can cause chipping qualities to decline, in addition the increase of form and aspect b value, and quality product can be caused to decline.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of Inventive polymers successive polymerization;
Embodiment
Be below the specific embodiment of the present invention, described embodiment is to further describe the present invention instead of restriction the present invention.
The preparation method of the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate:
By Sodium Dimethyl Isophthalate-5-sulfonate, propylene glycol, esterifying catalyst, sodium acetate, anhydrous and trimethyl phosphite 99 mixing, it is 180 DEG C in temperature, transesterification reaction is carried out under the condition of nitrogen protection, when the amount of steaming of methyl alcohol reaches 95% of theoretical amount, terminate this reaction, obtain the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate, wherein, the addition of sodium acetate, anhydrous is 0.04% of total reactant quality, the dosage of trimethyl phosphite 99 is 0.04% of total reactant quality, the addition of esterifying catalyst is 0.05% of total reactant quality, m-phthalic acid propylene glycol ester-5-sodium sulfonate is 1:2.5 with the amount of substance ratio of propylene glycol.
Embodiment 1
On daily output 3 tons small-sized low temperature short process continuous polycondensation polycondensation production equipment, terephthalic acid (PTA) and propylene glycol (PDO) in temperature are under the condition of 255 DEG C, catalyzer is tetrabutyl titanate esterification, the amount of substance of phthalic acid and propylene glycol is than being 1:1.6, catalyst levels is reactant total mass 0.04%, and esterification yield reaches more than 92%;
Esterification products temperature is controlled at 235 DEG C, the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate adds in esterification products by volume pump control dose, the rotating speed of volume pump controls at 10rpm, ensure that m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 4% of total reactant quality, mix at homogenizing mixers;
Afterwards by blend melt first polycondensation vessel, control melt temperature 255 DEG C, 20 minutes time; Enter the second polycondensation vessel, control melt temperature and arrive 260 DEG C, 40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature controls at 270 DEG C, and the intrinsic viscosity of the cation-dyeable PTT multipolymer of the stay in grade prepared is all 0.85g/dl all the time.Constant product quality, content of carboxyl end group is also stabilized in 16mol/t, and form and aspect b value stabilization controls 6, be better than discontinuous polycondensation copolymer product, use cationic red X-LGL, boiling dyeing at normal pressure 60 minutes, dye uptake reaches 60%, can reach the requirement of cationic dyeable polyester fiber.
Embodiment 2
On daily output 3 tons small-sized low temperature short process continuous polycondensation polycondensation production equipment, terephthalic acid (PTA) and propylene glycol (PDO) in temperature are under the condition of 250 DEG C, catalyzer is tetrabutyl titanate esterification, the amount of substance of phthalic acid and propylene glycol is than being 1:1.8, catalyst levels is reactant total mass 0.03%, and esterification yield reaches more than 92%;
Esterification products temperature is controlled at 225 DEG C, the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate adds in esterification products by volume pump control dose, the rotating speed of volume pump controls at 30rpm, ensure that m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 6% of total reactant quality, mix at homogenizing mixers;
Afterwards by blend melt first polycondensation vessel, control melt temperature 245 DEG C, 40 minutes time; Enter the second polycondensation vessel, control melt temperature and arrive 255 DEG C, 30 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature controls at 260 DEG C, and the intrinsic viscosity of the cation-dyeable PTT multipolymer of the stay in grade prepared is all 0.84g/dl all the time.Constant product quality, content of carboxyl end group is also stabilized in 17mol/t, and form and aspect b value stabilization controls 7, be better than discontinuous polycondensation copolymer product, use cationic red X-LGL, boiling dyeing at normal pressure 60 minutes, dye uptake reaches 70%, can reach the requirement of cationic dyeable polyester fiber.
Claims (11)
1. a continuous polymerization preparation method for cation-dyeable Poly(Trimethylene Terephthalate), comprises the steps:
(1) terephthalic acid and propylene glycol carry out esterification under temperature is the condition of 250-260 DEG C, obtain the esterification products that esterification yield reaches more than 92%;
(2) temperature of the esterification products of step (1) is controlled at 225 ~ 235 DEG C; The propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is joined in esterification products, then homogenizing mixers is entered together, obtain the melt mixed, described m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 2 ~ 8% of total reactant quality;
(3) gained melt enters the first polycondensation vessel, the second polycondensation vessel and the 3rd polycondensation vessel successively, carry out polycondensation, through on-line checkingi point, be after 0.83 ~ 0.86dL/g until intrinsic viscosity, carry out discharging pelletizing and obtain cation-dyeable Poly(Trimethylene Terephthalate) multipolymer, through underwater cutpellet, cation-dyeable propylene glycol ester terephthalate copolymer pellet is prepared in drying;
Melt enters the first polycondensation vessel, controls melt temperature 245 ~ 255 DEG C, 20 ~ 40 minutes time; Enter the second polycondensation vessel, control melt temperature and arrive 255 ~ 260 DEG C, 30 ~ 40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature controls at 260 ~ 270 DEG C.
2. preparation method according to claim 1, is characterized in that, the temperature of the esterification products of step (1) controls at 228 ~ 232 DEG C.
3. preparation method according to claim 1 and 2, is characterized in that, in step (1), the time of esterification is 20 ~ 60 minutes.
4. preparation method according to claim 1 and 2, it is characterized in that, the preparation method of the propylene glycol solution of described m-phthalic acid propylene glycol ester-5-sodium sulfonate comprises the steps: Sodium Dimethyl Isophthalate-5-sulfonate, propylene glycol, esterifying catalyst, sodium acetate, anhydrous and trimethyl phosphite 99 mixing, it is 180 DEG C in temperature, transesterification reaction is carried out under the condition of nitrogen protection, when the amount of steaming of methyl alcohol reaches the 92-95% of theoretical amount, terminate this reaction, obtain the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate, wherein, the addition of sodium acetate, anhydrous is the 0.03-0.04% of total reactant quality, the dosage of trimethyl phosphite 99 is the 0.03-0.04% of total reactant quality, the addition of esterifying catalyst is the 0.03-0.05% of total reactant quality.
5. preparation method according to claim 4, is characterized in that, m-phthalic acid propylene glycol ester-5-sodium sulfonate is 1:2.5 with the amount of substance ratio of propylene glycol; The addition of sodium acetate, anhydrous is 0.02% of total reactant quality; The dosage of trimethyl phosphite 99 is 0.02% of total reactant quality.
6. preparation method according to claim 1, it is characterized in that, in step (2), adopt interchanger to control the temperature of esterification products, described interchanger carries out hot oiling by heating agent, makes deep fat enter recuperator inlet temperature and controls at 190 ~ 205 DEG C.
7. preparation method according to claim 6, is characterized in that, deep fat enters recuperator inlet temperature and controls at 195 ~ 200 DEG C.
8. preparation method according to claim 1, is characterized in that, also add polycondensation catalyst in described 3rd polycondensation vessel, described polycondensation catalyst is titanium compound, and its addition is the 0.03-0.05% of total reactant quality.
9. preparation method according to claim 1, is characterized in that, described m-phthalic acid propylene glycol ester-5-sodium sulfonate is added by volume pump control dose, and the rotating speed of volume pump controls at 10 ~ 50rpm.
10. preparation method according to claim 1, is characterized in that, described m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 4 ~ 6% of total reactant quality.
11. preparation methods according to claim 8, is characterized in that, described polycondensation catalyst is tetrabutyl titanate, and its addition is 0.04% of total reactant quality.
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