CN103570922A - Continuous production process of high-viscosity PTT (polytrimethylene terephthalate) polyester - Google Patents
Continuous production process of high-viscosity PTT (polytrimethylene terephthalate) polyester Download PDFInfo
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Abstract
The invention provides a continuous production process of a high-viscosity PTT (polytrimethylene terephthalate) polyester, which comprises five major procedures (esterification, prepolycondensation, final polycondensation, liquid phase tackifying and molten mass post processing) and specifically comprises the following steps: esterifying 1,3-propanediol and terephthalic acid used as raw materials, performing prepolycondensation, performing final polycondensation to prepare a PTT polyester molten mass, performing liquid phase tackifying to prepare a high-viscosity PTT polyester molten mass, and performing molten mass post processing on the high-viscosity PTT polyester molten mass to obtain a industrial yarn or polyester chip. The esterification is performed by using a double-chamber automatic boosting external cycle esterification reactor; then, the prepolycondensation and the final polycondensation are performed through a tower type prepolycondensation reactor and a basket type film-drawing final polycondensation reactor respectively; the liquid phase tackifying is performed by using a liquid phase tackifying reaction kettle having a self-cleaning function, the in-kettle vacuum degree is 20-100Pa, the temperature is 240-265 DEG C, and the retention time of the molten mass is 30-120 minutes; and after the liquid phase tackifying, the viscosity of the molten mass can be up to 0.90-1.20dl/g. According to the invention, the process is simple and flexible in operation, saves energy, reduces consumption and can effectively achieve the purpose of producing the high-viscosity PTT polyester through a one-step method.
Description
Technical field
The invention belongs to PTT production of polyester technical field, be specifically related to a kind of continuous production processes of high viscosity PTT polyester.
Background technology
Poly trimethylene terephthalate (PTT), belongs to a kind of novel organic polymer aromatic polyester product of same series of polymers with PET and PBT.PTT, as a kind of novel polyester product, has good characteristic.PTT has the stability of good processing characteristics, electric property, mechanical property and size.Ptt fiber has kept good crease resistance and the chemical resistant properties of PET fiber, and intensity meets weaving requirement.Excellent dyeing behavior has great magnetism to the dyeing and finishing processing of fiber textile, is conducive to increase economic efficiency and environmental benefit.In addition, it also has good flexibility, anti-Japanese photosensitiveness, resistance to soiling, low static behaviour, low water absorption etc.New composite fibre materials and engineering plastics that PTT resin is made, its application prospect is boundless.In man-made fiber Application Areas, ptt fiber combines the flexibility (and having better colour fastness) of polyamide fibre, the fluffiness of acrylic fibers (and having avoided liability fraying), the conformality of terylene (but having possessed good feel), in addition there is good elasticity, static resistance and pollution resistance, the good wear behavior of various fibers is integrated in one, becomes one of popular macromolecular material of recent development on current world market.
The viscosity of PTT polyester has very large impact to post-treatment such as its performance and spinning, and therefore, the PTT polyester that need to obtain polymerization carries out further tackify.At present, the production method of high viscosity PTT polyester fondant is mainly solid phase polycondensation tackify.
Solid-phase tack producing (SSP) is the polycondensation that the polyester slice of pelletizing is carried out under solid state, specifically the estrodur performed polymer with certain molecular weight is heated to the following second-order transition temperature of its fusing point above (being generally following 10～40 ℃ of fusing point), by vacuumize or rare gas element (as N
2, CO
2, He etc.) protection and take away small molecules product, make the viscosity rise of polyester slice.Above process is called the two-step process that polyester slice with high viscosity is produced.Solid phase polycondensation is due to the advantage of its mild condition, good product quality, become the polyester tackify industrial process of current widespread use, but the production technique time of solid phase polycondensation long (more than 30 hour), needs to consume a large amount of rare gas elementes, and elapsed time and energy are all higher.
Melt phase polycondensation, also referred to as liquid-phase tackifying, referring at the polycondensation vessel rear of general polycondensation production equipment and increase a reactor, by reducing the modes such as pressure, raising fusant reaction temperature and devolatilization area, realize melt tackify, is the new polycondensating process that obtains high-viscosity polyester.The advantages such as efficient, energy-conservation and constant product quality in view of liquid-phase tackifying technology, have at present broad research at home and abroad, but only have several major companies to succeed in developing and realized industrial applications, and liquid-phase tackifying is used on the technics of enhancing viscosity of PTT polyester fondant and does not see especially, based on this, the present invention has carried out deep analysis to the continuous production processes of PTT polyester and technics of enhancing viscosity, has proposed practicable terms of settlement.
Summary of the invention
The object of the present invention is to provide a kind of continuous production processes that adopts the high viscosity PTT polyester of liquid-phase tackifying technology, adopt this technique can realize the target of the high sticky PTT polyester of One-step production.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
A kind of continuous production processes of high viscosity PTT polyester, this technique comprises that esterification, precondensation, final minification are poly-, liquid-phase tackifying, the large operation of melt post-treatment five, production process is: raw material 1, ammediol and terephthalic acid make PTT polyester fondant through esterification, precondensation, whole polycondensation step (three stills or four stills or five stills), through liquid-phase tackifying operation, prepare high viscosity PTT polyester fondant afterwards, the high viscosity PTT polyester fondant obtaining obtains industrial yarn or polyester slice through melt post-treatment operation again.
Described esterification step, adopt esterifier (preferably adopting two chamber automatic boosting outer circulation esterifiers), raw material 1, ammediol is chemical method or Biological preparation, and the mol ratio of raw material 1,3-PD and terephthalic acid (being acid-alcohol ratio) is 1.3-2.0:1, preferred 1.5-1.9:1, esterification temperature is 225-265 ℃, and preferably 235-255 ℃, reacts and obtain propylene glycol ester terephthalate's monomer.
Melt after described esterification enters in the lump Oligomer pipeline (additive is metered into pipeline via pipeline syringe) with additive, then enters Prepolycondensating reactor after being pressurizeed by oligopolymer pump; The two ends of described Oligomer pipeline are connected with Prepolycondensating reactor with esterifier respectively.Additive adds pipeline can realize oligopolymer by pipeline syringe to mix with additive, has overcome and in still, has mixed technological difficulties uneven and that cause subsequent product performance to reduce in the past.
Described additive types changes according to the difference of subsequent production finished product, while producing PTT polyester product, adds catalyzer, thermo-stabilizer, can add if desired matting agent and the toning agent of certain content.
Described precondensation operation, adopts the tower Prepolycondensating reactor being comprised of precondensation well heater, tower conversion zone and gas-liquid segregation section, and heater temperature is 235-275 ℃; Body temperature is: 235-275 ℃.
Described whole polycondensation step, adopts cage basket formula membrane net dish reactor.
Described liquid-phase tackifying operation, adopts the liquid-phase tackifying reactor with self-cleaning function, and in still, vacuum tightness is 20-100Pa, and temperature is 240-265 ℃, and melt residence time is 30min-120min, and after liquid-phase tackifying, melt viscosity can reach 0.90-1.20dl/g.
Described process melt post-treatment operation obtains industrial yarn or polyester slice, both can, via spinning process manufacture silk, also can obtain high viscosity PTT polyester slice through blank operation.
The continuous production processes of a kind of high viscosity PTT polyester provided by the invention, according to the finished product type and performance requriements, this technique comprises esterification, precondensation, final minification is poly-, liquid-phase tackifying, several large operations of melt post-treatment, production process is: raw material 1, ammediol and terephthalic acid (comprise esterification through the low temperature short process technique of autonomous innovation, precondensation, whole polycondensation step) make PTT polyester fondant, the liquid-phase tackifying technique with leading technology level through autonomous innovation prepares high viscosity PTT polyester fondant afterwards, the high viscosity PTT polyester fondant obtaining obtains industrial yarn or polyester slice through melt post-treatment operation again.The technical process of this processing method as shown in Figure 1.
Beneficial effect of the present invention:
Technique provided by the present invention is simple, and flexible operation is energy-saving and cost-reducing, can effectively realize the target of the high sticky PTT polyester of One-step production.The present invention adopts liquid-phase tackifying Technology leading in the world to prepare high viscosity PTT polyester, compare with domestic traditional solid phase polycondensation process, not only flow process is short, reduced operation link, and centre does not have melt cooling granulation and the heating process again of cutting into slices, both reduce equipment number of units, reduced again energy consumption.
The poly-device of final minification that technique of the present invention has realized at existing normal polyester device picks out PTT polyester fondant, through liquid-phase tackifying, obtains high sticky PTT polyester fondant.
Accompanying drawing explanation
Fig. 1 is the continuous production processes schema of a kind of high viscosity PTT polyester of the present invention.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described; by contributing to, the advantage of technical scheme of the present invention and effect are had to further understanding; embodiment does not limit protection scope of the present invention, and protection scope of the present invention is decided by claim.
Embodiment 1
Raw material 1, ammediol and terephthalic acid are with acid-alcohol ratio 1.3:1, 265 ℃ of esterification temperatures, esterification time 200min, by direct esterification, prepare carboxylate BHPT, the carboxylate obtaining enters precondensation still and carries out prepolymerization reaction, temperature of reaction is 235 ℃, reaction vacuum tightness 2kPa, reaction times 60min, prepare prepolymer, prepolymer enters follow-up whole polycondensation vessel and carries out whole polycondensation, 255 ℃ of the poly-temperature of reaction of final minification, reaction times 240min, preparing limiting viscosity is the PTT melt of 0.72dl/g, (in still, vacuum tightness is 100Pa to the liquid-phase tackifying reactor of melt by independent research afterwards, temperature is 265 ℃, melt residence time is 30min) carry out after liquid-phase tackifying, preparing viscosity is the PTT polyester fondant of 1.00dl/g, finally by crossing blank operation, obtain the PTT polyester slice that viscosity is 1.00dl/g.
Embodiment 2
Raw material 1, ammediol and terephthalic acid are with acid-alcohol ratio 1.6:1, 240 ℃ of esterification temperatures, esterification time 220min, by direct esterification, prepare carboxylate BHPT, the carboxylate obtaining enters precondensation still and carries out prepolymerization reaction, temperature of reaction is 250 ℃, reaction vacuum tightness 2kPa, reaction times 40min, prepare prepolymer, prepolymer enters follow-up whole polycondensation vessel and carries out whole polycondensation, 260 ℃ of the poly-temperature of reaction of final minification, reaction times 210min, preparing limiting viscosity is the PTT melt of 0.85dl/g, (in still, vacuum tightness is 80Pa to the liquid-phase tackifying reactor of melt by independent research afterwards, temperature is 260 ℃, melt residence time is 60min) carry out after liquid-phase tackifying, preparing viscosity is the PTT polyester fondant of 1.18dl/g, finally by crossing blank operation, obtain the PTT polyester slice that viscosity is 1.18dl/g.
Embodiment 3
Raw material 1, ammediol and terephthalic acid are with acid-alcohol ratio 1.9:1, 235 ℃ of esterification temperatures, esterification time 200min, by direct esterification, prepare carboxylate BHPT, the carboxylate obtaining enters precondensation still and carries out prepolymerization reaction, temperature of reaction is 250 ℃, reaction vacuum tightness 2kPa, reaction times 40min, prepare prepolymer, prepolymer enters follow-up whole polycondensation vessel and carries out whole polycondensation, 255 ℃ of the poly-temperature of reaction of final minification, reaction times 210min, preparing limiting viscosity is the PTT melt of 0.82dl/g, (in still, vacuum tightness is 60Pa to the liquid-phase tackifying reactor of melt by independent research afterwards, temperature is 250 ℃, melt residence time is 90min) carry out after liquid-phase tackifying, preparing viscosity is the PTT polyester fondant of 1.10dl/g, finally by crossing blank operation, obtain the PTT polyester slice that viscosity is 1.10dl/g.
Embodiment 4
Raw material 1, ammediol and terephthalic acid are with acid-alcohol ratio 2.0:1, 225 ℃ of esterification temperatures, esterification time 300min, by direct esterification, prepare carboxylate BHPT, the carboxylate obtaining enters precondensation still and carries out prepolymerization reaction, temperature of reaction is 275 ℃, reaction vacuum tightness 10kPa, reaction times 40min, prepare prepolymer, prepolymer enters follow-up whole polycondensation vessel and carries out whole polycondensation, 260 ℃ of the poly-temperature of reaction of final minification, reaction times 240min, preparing limiting viscosity is the PTT melt of 0.78dl/g, (in still, vacuum tightness is 20Pa to the liquid-phase tackifying reactor of melt by independent research afterwards, temperature is 240 ℃, melt residence time is 120min) carry out after liquid-phase tackifying, preparing viscosity is the PTT polyester fondant of 1.06dl/g, finally by crossing blank operation, obtain the PTT polyester slice that viscosity is 1.06dl/g.
Embodiment 5
Raw material 1, ammediol and terephthalic acid are with acid-alcohol ratio 1.5:1, 255 ℃ of esterification temperatures, esterification time 220min, by direct esterification, prepare carboxylate BHPT, the carboxylate obtaining enters precondensation still and carries out prepolymerization reaction, temperature of reaction is 255 ℃, reaction vacuum tightness 6kPa, reaction times 50min, prepare prepolymer, prepolymer enters follow-up whole polycondensation vessel and carries out whole polycondensation, 265 ℃ of the poly-temperature of reaction of final minification, reaction times 220min, preparing limiting viscosity is the PTT melt of 0.83dl/g, (in still, vacuum tightness is 50Pa to the liquid-phase tackifying reactor of melt by independent research afterwards, temperature is 250 ℃, melt residence time is 100min) carry out after liquid-phase tackifying, preparing viscosity is the PTT polyester fondant of 1.15dl/g, finally by crossing blank operation, obtain the PTT polyester slice that viscosity is 1.15dl/g.
Claims (9)
1. the continuous production processes of a high viscosity PTT polyester, it is characterized in that: this technique comprises that esterification, precondensation, final minification are poly-, liquid-phase tackifying, the large operation of melt post-treatment five, production process is: raw material 1, ammediol and terephthalic acid make PTT polyester fondant through esterification, precondensation, whole polycondensation step, through liquid-phase tackifying operation, prepare high viscosity PTT polyester fondant afterwards, the high viscosity PTT polyester fondant obtaining obtains industrial yarn or polyester slice through melt post-treatment operation again.
2. the continuous production processes of high viscosity PTT polyester according to claim 1, it is characterized in that: described esterification step, adopts two chamber automatic boosting outer circulation esterifiers, raw material 1, the mol ratio of ammediol and terephthalic acid is 1.3-2.0:1, and esterification temperature is 225-265 ℃.
3. the continuous production processes of high viscosity PTT polyester according to claim 2, is characterized in that: the mol ratio of raw material 1,3-PD and terephthalic acid is 1.5-1.9:1, and esterification temperature is 235-255 ℃.
4. according to the continuous production processes of the high viscosity PTT polyester described in claim 1,2 or 3, it is characterized in that: after the melt after described esterification is pressurizeed by oligopolymer pump, enter in the lump Oligomer pipeline with the additive that is metered into pipeline by pipeline syringe, then enter Prepolycondensating reactor; The two ends of Oligomer pipeline are connected with precondensation still with esterifier respectively.
5. the continuous production processes of high viscosity PTT polyester according to claim 4, is characterized in that: described additive comprises catalyzer, thermo-stabilizer, matting agent, toning agent, according to the requirement of subsequent production finished product is different, changes.
6. the continuous production processes of high viscosity PTT polyester according to claim 5, it is characterized in that: described precondensation operation, the tower Prepolycondensating reactor that employing is comprised of precondensation well heater, tower conversion zone and gas-liquid segregation section, heater temperature is 235-275 ℃; Body temperature is: 235-275 ℃.
7. the continuous production processes of high viscosity PTT polyester according to claim 6, is characterized in that: described whole polycondensation step, adopts cage basket formula membrane net dish reactor.
8. the continuous production processes of high viscosity PTT polyester according to claim 7, it is characterized in that: described liquid-phase tackifying operation, employing has the liquid-phase tackifying reactor of self-cleaning function, in still, vacuum tightness is 20-100Pa, temperature is 240-265 ℃, melt residence time is 30min-120min, and after liquid-phase tackifying, melt viscosity can reach 0.90-1.20dl/g.
9. the continuous production processes of high viscosity PTT polyester according to claim 8, it is characterized in that, described process melt post-treatment operation obtains industrial yarn or polyester slice is: via spinning process manufacture silk, or, through blank operation, obtain high viscosity PTT polyester slice.
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| CN201310431894.5A CN103570922A (en) | 2013-09-22 | 2013-09-22 | Continuous production process of high-viscosity PTT (polytrimethylene terephthalate) polyester |
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Cited By (2)
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| CN104530396A (en) * | 2015-01-05 | 2015-04-22 | 福建省鑫东华实业有限公司 | Polyethylene glycol terephthalate preparation method |
| CN107057048A (en) * | 2017-02-15 | 2017-08-18 | 山东大学 | A kind of poly- phthalic acid propanediol copolyesters of high intrinsic viscosity poly trimethylene co and preparation method thereof |
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| CN1491933A (en) * | 2002-10-24 | 2004-04-28 | 中国石油化工股份有限公司 | Continuous esterification device for preparing terephthalate of dihydric alcohol |
| CN101544750A (en) * | 2009-04-22 | 2009-09-30 | 无锡国能新材料科技有限公司 | Method for preparing polyethylene glycol terephthalate by adopting anchoring agent |
| CN101643946A (en) * | 2009-09-14 | 2010-02-10 | 江苏鹰翔化纤股份有限公司 | Poly terephthalic acid 1, 2-propylene glycol ester fiber |
| CN102942688A (en) * | 2012-08-31 | 2013-02-27 | 上海聚友化工有限公司 | Single-shaft/shaft-free high-viscosity polyester continuous production device |
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2013
- 2013-09-22 CN CN201310431894.5A patent/CN103570922A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1417247A (en) * | 2001-11-08 | 2003-05-14 | 中国石化上海石油化工股份有限公司 | Production process of polypropylene glycol terephthalate |
| CN1491933A (en) * | 2002-10-24 | 2004-04-28 | 中国石油化工股份有限公司 | Continuous esterification device for preparing terephthalate of dihydric alcohol |
| CN101544750A (en) * | 2009-04-22 | 2009-09-30 | 无锡国能新材料科技有限公司 | Method for preparing polyethylene glycol terephthalate by adopting anchoring agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530396A (en) * | 2015-01-05 | 2015-04-22 | 福建省鑫东华实业有限公司 | Polyethylene glycol terephthalate preparation method |
| CN107057048A (en) * | 2017-02-15 | 2017-08-18 | 山东大学 | A kind of poly- phthalic acid propanediol copolyesters of high intrinsic viscosity poly trimethylene co and preparation method thereof |
| CN107057048B (en) * | 2017-02-15 | 2019-04-09 | 山东大学 | A kind of poly- phthalic acid propanediol copolyester of high intrinsic viscosity poly trimethylene-co- and preparation method thereof |
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