CN103232594A - Cationic dyeable propylene glycol polyterephthalate continuous polymerization preparation method - Google Patents
Cationic dyeable propylene glycol polyterephthalate continuous polymerization preparation method Download PDFInfo
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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, and the structure that it is special and good physical and chemical performance make it in the acquisition widespread use of fields such as weaving, engineering plastics, film." strange carbon effect " that be different from PET and PBT that causes owing to three methylene radical that exist on the PTT macromolecular chain, make the PTT trevira can overcome the rigidity of PET and the flexibility of PBT simultaneously, and have the advantage of PET and PA concurrently, as rebound resilience, workability, easy dyeing and the fluffiness etc. of excellence.Therefore it is at clothes, carpet, and family the field such as spins and is widely used,
Though ptt fiber has good performance, but its molecular structure is tightr, the problem that does not have close dye groups in the molecular chain causes ptt fiber to dye with dispersed dye, and compares with cationic dyestuff, dispersed dye exist environment protecting poor, chromatogram is incomplete, and coloured light is not gorgeous, and dispersed dye require high to dyeing installation, shortcomings such as cost of investment height have limited the application of PTT on fiber to a certain extent.
The Cha Lilili of Donghua University " preparation of cation-dyeable PTT polyester and the research of performance " discloses a kind of intermittently method of copolymerization cation-dyeable ptt fiber of little reactor of using.And its performance carried out detailed research.
Chinese patent application CN200510054950.3 discloses a kind of modification Poly(Trimethylene Terephthalate) fiber that can use cation stain at normal temperatures and pressures, has following structure, n=100-150 wherein, x=25-100, y=1-4, this application is to be properties-correcting agent with dimethyl isophthalate-5-sodium sulfonate, is embedded in the poly terephthalic acid propylene glycol through the fusion copolymerization process, and formation can have adsorbing adsorption group to do to cationic dyestuff to dye seat.
At present the preparation method of cation-dyeable PTT polyester copolymer adopts normally that polymerization prepares in polymerization reaction kettle intermittently.Because there are differences between every batch and every batch in the batch production, the stability of quality quality also can some fluctuation.And the method preparation of the poly-continuous polymerization of present conventional polyester and modified poly ester, most of batchwise polymerization device has all stopped operation and has produced owing to can't adopt the technical process competition of Colaesce with the most of preparation of successive polymerization.Given this, special proposition the present invention.
Summary of the invention
The continuous polymerization preparation method that the purpose of this invention is to provide a kind of cation-dyeable Poly(Trimethylene Terephthalate), the stable performance of the modification Poly(Trimethylene Terephthalate) that this method obtains, the energy consumption of preparation process is low, easily extensive chemical industry production.
For realizing purpose 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 are to carry out esterification under 250-260 ℃ the condition in temperature, obtain esterification yield and reach esterification products more than 92%;
(2) with the temperature control of the esterification products of step (1) at 225～235 ℃; The propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is joined in the esterification products, enter homogenizing mixing tank, the melt that obtains mixing then together;
(3) the gained melt enters first polycondensation vessel, second polycondensation vessel and the 3rd polycondensation vessel successively, carry out polycondensation, through online check point, after treating that intrinsic viscosity is 0.83～0.86dL/g, carry out the discharging pelletizing and obtain cation-dyeable Poly(Trimethylene Terephthalate) multipolymer, through underwater cutpellet, drying is prepared cation-dyeable propylene glycol ester terephthalate copolymer pellet.
Wherein, step (1) is titanium compound at the catalyzer that carries out the esterification employing, preferred tetrabutyl titanate or isopropyl titanate.
Catalyst consumption is the 0.03-0.05% of reactant total mass in the step (1), and sorrow selects 0.04%.
Preferably, the control of the temperature of the esterification products of step (1) is at 228～232 ℃.
Terephthalic acid and propylene glycol are 1:1.6 – 1:1.8 by the ratio of amount of substance in the step (1).
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, preferred 4～6%.The control melt flow time makes its sluggish flow, makes its melt temperature slowly reach 250 ℃.
The preparation method of the propylene glycol solution of described m-phthalic acid propylene glycol ester-5-sodium sulfonate comprises the steps: dimethyl isophthalate-5-sodium sulfonate; propylene glycol; esterifying catalyst; sodium acetate, anhydrous and trimethyl phosphite 99 mix; it is 180 ℃ in temperature; carry out transesterification reaction under the condition of nitrogen protection; reach the 92-95% of theoretical amount when the amount of steaming of methyl alcohol; finish 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, and 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 is 1:2.5 with the amount of substance ratio of propylene glycol.
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.
Adopt the temperature of interchanger control esterification products in step (2), described interchanger carries out hot oiling by heating agent, makes deep fat enter the control of heat exchanger entrance temperature at 190～205 ℃, preferred 195～200 ℃.
Described interchanger links to each other with reaction kettle of the esterification at reaction kettle of the esterification discharge nozzle place.
In step (3), melt enters first polycondensation vessel, 245～255 ℃ of control melt temperatures, 20～40 minutes time; Enter second polycondensation vessel, the control melt temperature arrives 255～260 ℃, 30～40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature is controlled at 260～270 ℃.
Wherein, also add polycondensation catalyst in described the 3rd polycondensation vessel, described polycondensation catalyst is titanium compound, and its preferred tetrabutyl titanate, its addition are the 0.03-0.05% of total reactant quality, and it is preferred 0.04% years old.
Described m-phthalic acid propylene glycol ester-5-sodium sulfonate is added by volume pump control dosage, and the rotating speed control of volume pump is at 10～50rpm.
Contain 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 formed by p-poly-phenyl dioctyl phthalate propylene glycol ester segment, 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 dye polyphenyl dioctyl phthalate propylene glycol ester multipolymer.
The intrinsic viscosity of the cation-dyeable polyphenyl dioctyl phthalate propylene glycol ester 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%, the multipolymer fusing point is at 220-230 ℃, 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 synthetic preparation of cation-dyeable polyphenyl dioctyl phthalate propylene glycol ester multipolymer normally in polymerization reaction kettle intermittently polymerization prepare.Because there are differences between every batch and every batch in the batch production, quality of stability also can some fluctuation.The present invention is in the method for stay in grade cation-dyeable PTT successive polymerization.
Because the continuous polymerization technique of the polymerization characteristics of polyphenyl dioctyl phthalate propylene glycol ester multipolymer itself and conventional polyester there is some difference property, in conjunction with the polymerization characteristics of multipolymer of the present invention, need do some corresponding adjustment and changes to the continuous polymerization unit of common polyester.
Common polyester esterification at 250-260 ℃, the melt temperature of conventional polyester also is in this temperature range, the successive polymerization of conventional polyester can continue the polycondensation of back on the basis of this temperature, and the application's modified polyesters is because the polymerization characteristics of itself, melt temperature need be dropped to 225-235 ℃, preferably be reduced to 228-232 ℃.
The present invention is in above-mentioned steps 2) in esterification reaction product is carried out heat exchange by an interchanger that links to each other with reaction kettle of the esterification, melt temperature can be controlled at 230 ± 2 ℃ after the heat exchange.
For realizing above-mentioned technology, interchanger of the present invention links to each other with reaction kettle of the esterification at reaction kettle of the esterification discharge nozzle place, is preferably linking to each other with reaction kettle of the esterification for about 1.5 meters from the reaction kettle of the esterification discharge nozzle.
Among the present invention, the distance limit of described interchanger and reaction kettle of the esterification junction is not very strict, but must connect in the reaction kettle of the esterification back.
Interchanger described in the present invention carries out hot oiling by heating agent, and the temperature that makes deep fat enter heat exchanger entrance is controlled at 190～205 ℃, controls at 230 ± 2 ℃ thereby can control through the melt temperature of interchanger.
Among the present invention, SIPT solution is metered into by a volume pump control that links with its solution still, and the rotating speed control of volume pump is at 10～50rpm, is 4～6% with the amount that realizes containing in the multipolymer copolymerization units.
Among the present invention, the temperature of control solution still mainly is for solution is kept mixing state, mainly is to keep the interior melt of volume pump to keep a certain amount of and certain pressure and control its rotating speed, is convenient to be metered into.
The advantage of the cation-dyeable polyphenyl dioctyl phthalate propylene glycol ester multipolymer of preparing of the stay in grade cation-dyeable polyphenyl dioctyl phthalate propylene glycol ester 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, and the intrinsic viscosity that so just can guarantee to control material difference can not occur all at 0.94dl/g between the same batch material, keeps the stay in grade of product.And the difference in the same reactor of intermittent polyreaction, discharging owing to reactor in the cation-dyeable batchwise polymerization method usually will be for some time, tend to cause the intrinsic viscosity of the prepared multipolymer of same reactor material different, as a still intermittent polyreaction:
The intrinsic viscosity of 5 minutes material of discharging: 0.83dl/g
The intrinsic viscosity of 20 minutes material of discharging: 0.84dl/g
Discharging finishes the intrinsic viscosity of preceding 5 minutes material: 0.86dl/g
Same reactor material often, the molecular weight of material can be variant, and subsequent applications is had a negative impact.
The content of carboxyl end group of the modified copolymer of successive polymerization preparation can be very stable control below 18mol/t, form and aspect b value stabilization is controlled below 8, and is more stable, and stay in grade.And the difference between batchwise polymerization still and the still, in intermittent polyreaction, after finishing the reaction of first still, often can not wash still immediately, but and then carry out the reaction of second still, because the polymkeric substance of many first still of residual amount often on the still wall of first still reaction, these residual polymkeric substance will stand certain thermal destruction in the polymerization process of second still, cause the quality of the polymkeric substance of second still to tend to be lower than the quality of first still, the section color burn shows on the index of section to be:
The content of carboxyl end group of the multipolymer of first still: 20mol/t, form and aspect b value: 8
The content of carboxyl end group of the multipolymer of second still: 25mol/t, form and aspect b value: 10
The increase of the increase of content of carboxyl end group and form and aspect b value can cause chipping qualities to descend, and the increase of form and aspect b value in addition can cause quality product to descend.
Description of drawings
Fig. 1 is the process flow diagram of continuous polymerization of polymer of the present invention;
Embodiment
Below be the specific embodiment of the present invention, described embodiment is in order to further describe the present invention rather than restriction the present invention.
The preparation method of the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate:
With dimethyl isophthalate-5-sodium sulfonate; propylene glycol; esterifying catalyst; sodium acetate, anhydrous and trimethyl phosphite 99 mix; it is 180 ℃ in temperature; carry out transesterification reaction under the condition of nitrogen protection; when the amount of steaming of methyl alcohol reaches 95% of theoretical amount; finish 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, and 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 3 tons of small-sized low temperature short process continuous polycondensation polycondensation production equipments of daily output, terephthalic acid (PTA) and propylene glycol (PDO) in temperature are under 255 ℃ the condition, catalyzer is the 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%;
The esterification products temperature is controlled at 235 ℃, the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is added in the esterification products by volume pump control dosage, the rotating speed control of volume pump is at 10rpm, guarantee that propylene glycol ester-5-sodium sulfonate add-on is 4% of total reactant quality to m-phthalic acid, mixes at the homogenizing mixing tank;
With mixed melt first polycondensation vessel, control 255 ℃ of melt temperatures, 20 minutes time afterwards; Enter second polycondensation vessel, the control melt temperature arrives 260 ℃, 40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature is controlled at 270 ℃, and the intrinsic viscosity of the cation-dyeable PTT multipolymer of the stay in grade of preparing all is 0.85g/dl all the time.Constant product quality, content of carboxyl end group also are stabilized in 16mol/t, and form and aspect b value stabilization is controlled 6, be better than the 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 3 tons of small-sized low temperature short process continuous polycondensation polycondensation production equipments of daily output, terephthalic acid (PTA) and propylene glycol (PDO) in temperature are under 250 ℃ the condition, catalyzer is the 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%;
The esterification products temperature is controlled at 225 ℃, the propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is added in the esterification products by volume pump control dosage, the rotating speed control of volume pump is at 30rpm, guarantee that propylene glycol ester-5-sodium sulfonate add-on is 6% of total reactant quality to m-phthalic acid, mixes at the homogenizing mixing tank;
With mixed melt first polycondensation vessel, control 245 ℃ of melt temperatures, 40 minutes time afterwards; Enter second polycondensation vessel, the control melt temperature arrives 255 ℃, 30 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature is controlled at 260 ℃, and the intrinsic viscosity of the cation-dyeable PTT multipolymer of the stay in grade of preparing all is 0.84g/dl all the time.Constant product quality, content of carboxyl end group also are stabilized in 17mol/t, and form and aspect b value stabilization is controlled 7, be better than the 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 (10)
1. the continuous polymerization preparation method of a cation-dyeable Poly(Trimethylene Terephthalate) comprises the steps:
(1) terephthalic acid and propylene glycol are to carry out esterification under 250-260 ℃ the condition in temperature, obtain esterification yield and reach esterification products more than 92%;
(2) with the temperature control of the esterification products of step (1) at 225～235 ℃; The propylene glycol solution of m-phthalic acid propylene glycol ester-5-sodium sulfonate is joined in the esterification products, enter homogenizing mixing tank, the melt that obtains mixing then together;
(3) the gained melt enters first polycondensation vessel, second polycondensation vessel and the 3rd polycondensation vessel successively, carry out polycondensation, through online check point, after treating that intrinsic viscosity is 0.83～0.86dL/g, carry out the discharging pelletizing and obtain cation-dyeable Poly(Trimethylene Terephthalate) multipolymer, through underwater cutpellet, drying is prepared cation-dyeable propylene glycol ester terephthalate copolymer pellet.
2. preparation method according to claim 1 is characterized in that, the temperature control of the esterification products of step (1) is at 228～232 ℃.
3. preparation method according to claim 1 and 2 is characterized in that, in the step (1), the time of esterification is 20～60 minutes.
4. preparation method according to claim 1 and 2 is characterized in that, described m-phthalic acid propylene glycol ester-5-sodium sulfonate add-on is 2～8% of total reactant quality, preferred 4～6%.
5. according to each described preparation method of claim 1-4; 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: dimethyl isophthalate-5-sodium sulfonate; propylene glycol; esterifying catalyst; sodium acetate, anhydrous and trimethyl phosphite 99 mix; it is 180 ℃ in temperature; carry out transesterification reaction under the condition of nitrogen protection; reach the 92-95% of theoretical amount when the amount of steaming of methyl alcohol; finish 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, and the addition of esterifying catalyst is the 0.03-0.05% of total reactant quality.
6. preparation method according to claim 5 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.
7. preparation method according to claim 1, it is characterized in that adopt the temperature of interchanger control esterification products in step (2), described interchanger carries out hot oiling by heating agent, make deep fat enter the control of heat exchanger entrance temperature at 190～205 ℃, preferred 195～200 ℃.
8. preparation method according to claim 1 is characterized in that, in step (3), melt enters first polycondensation vessel, 245～255 ℃ of control melt temperatures, 20～40 minutes time; Enter second polycondensation vessel, the control melt temperature arrives 255～260 ℃, 30～40 minutes time; Enter the 3rd polycondensation vessel again, proceed polymerization, improve its molecular weight, temperature is controlled at 260～270 ℃.
9. preparation method according to claim 8 is characterized in that, also adds polycondensation catalyst in described the 3rd polycondensation vessel, described polycondensation catalyst is titanium compound, its preferred tetrabutyl titanate, its addition are the 0.03-0.05% of total reactant quality, and it is preferred 0.04% years old.
10. 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 dosage, and the rotating speed control of volume pump is at 10～50rpm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031251A (en) * | 2014-06-11 | 2014-09-10 | 中国纺织科学研究院 | Continuous polymerization preparation method of easily dyed and antistatic PTT copolymer of cationic dyes |
| CN109438292A (en) * | 2018-11-16 | 2019-03-08 | 青岛中科荣达新材料有限公司 | A kind of method of three monomer process Waste water concentrating material production modifying agent SIPP |
| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
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| CN101130603A (en) * | 2006-08-22 | 2008-02-27 | 东丽纤维研究所（中国）有限公司 | Modified poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same |
| CN101376703A (en) * | 2008-09-23 | 2009-03-04 | 江苏中鲈科技发展股份有限公司 | Preparation method of cationic dyeable PTT |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101130603A (en) * | 2006-08-22 | 2008-02-27 | 东丽纤维研究所（中国）有限公司 | Modified poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same |
| CN101376703A (en) * | 2008-09-23 | 2009-03-04 | 江苏中鲈科技发展股份有限公司 | Preparation method of cationic dyeable PTT |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031251A (en) * | 2014-06-11 | 2014-09-10 | 中国纺织科学研究院 | Continuous polymerization preparation method of easily dyed and antistatic PTT copolymer of cationic dyes |
| CN104031251B (en) * | 2014-06-11 | 2016-10-05 | 中国纺织科学研究院 | A kind of cation dye chromophil, the continuous polymerization preparation method of anlistatig PTT copolymer |
| CN109438292A (en) * | 2018-11-16 | 2019-03-08 | 青岛中科荣达新材料有限公司 | A kind of method of three monomer process Waste water concentrating material production modifying agent SIPP |
| CN109438292B (en) * | 2018-11-16 | 2021-08-10 | 青岛中科荣达新材料有限公司 | Method for producing modifier SIPP (selected p-phenylene terephthalamide) by using three-monomer process wastewater concentrate |
| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
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