CN101367916A - Suspending solid phase polymerization method for polyester with high molecular weight - Google Patents
Suspending solid phase polymerization method for polyester with high molecular weight Download PDFInfo
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Abstract
The invention discloses a method for suspension solid-phase polymerization of high-molecular polyester. The polyester prepolymers are suspended in liquid inert medium in powder or particle for solid-phase polymerization, the temperature of polymerization drops within the temperature of vitrification transformation and the melting point of the polyester prepolymers. The method is capable of overcoming the problems that polymerization heat and crystallization heat are not easy to diffuse, and particle or powder is easy to agglomerate. The polyester products achieved by the method have the advantaged of high molecular, nice color, excellent performance, and the like.
Description
Technical field
The present invention relates to a kind of polymerization process for preparing high molecular weight polyesters.
Background technology
Polyester
Polyester is meant in the molecular backbone chain and contains-a resinoid general name of [O-COR]-chain link.By whether containing aromatic group in the molecular backbone chain structure, polyester can be divided into two big classes: aromatic polyester and aliphatic polyester.The representative of aromatic polyester is polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
Polyethylene terephthalate (PET) is polymerized by pure terephthalic acid (PTA) and ethylene glycol (EG). at present, be mainly used in bottle level polyester (being widely used in the especially packing of soda pop of various beverages), polyester film (being mainly used in wrapping material, film and tape etc.) and chemical fibre terylene.
The polyester process route has direct esterification method (PTA method) and ester-interchange method (DMT method).The PTA method has advantages such as raw material consumption is low, the reaction times is short, and oneself becomes the main technique and the one preferred technique route of polyester from the eighties.
Polybutylene terephthalate has another name called poly terephthalic acid four methyne esters, is called for short PBT.It is terephthalic acid and 1, the polycondensate of 4-butyleneglycol.Can be made through polycondensation by ester-interchange method or direct esterification method, development trend is from now on produced for the direct esterification method.The PBT main chain is to be the saturated line style molecular composition that rigidity phenyl ring and flexible Fatty Alcohol(C12-C14 and C12-C18) couple together by each repeating unit, the height geometrical regularity of molecule and rigid element make polymkeric substance have high physical strength, outstanding chemical reagent resistance, thermotolerance and good electrical property; Do not have side chain in the molecule, symmetrical configuration satisfies the requirement of closely piling up, thereby makes this polymkeric substance that the crystallinity and the high-melting-point of height be arranged.
The representative of aliphatic polyester is poly(lactic acid) (PLA), poly butylene succinate (PBS).Poly(lactic acid) (PLA) is to be the new polyester material of raw material production with organic acid lactic acid, be decided to be the most rising new packaging material of new millennium by industrial community, be a star of environment-friendly package material, to be expected to replace materials such as polyethylene, polypropylene, polystyrene to be used for plastics in future, have a extensive future.
Have by lactic acid system PLA preparation technology: (1) direct polycondensation method, the polycondensation of under vacuum, dewatering.(2) non-solvent method makes lactic acid generate the cyclic dimer rac-Lactide, and the open loop polycondensation becomes PLA again.The direct polymerization method is difficult to the poly(lactic acid) of synthetic macromolecule amount and the manufacturing purifying technique complexity of rac-Lactide in the open loop method.
Poly butylene succinate (PBS) is internationally recognized fully biodegradable polymkeric substance.Realize industrialization, annual production 3000t by Japanese SHOWA HIGHPOLYMER company at present.PBS is with petrochemical material Succinic Acid and 1, and the 4-butyleneglycol is produced.Usually utilize MALEIC ANHYDRIDE to obtain Succinic Acid and 1,4-butyleneglycol.PBS not only can be applicable to disposable products such as wrapping material, food and drink articles for use, mulch film, also has application prospect in dress with aspects such as fiber, paint, ink, medical material, drug matrices.
Polyester generally gets by melt condensation polymerization.But, be difficult to obtain the high-molecular weight polyester by melt condensation polymerization because the equilibrium constant of pet reaction is less.On the other hand, the product tone of long-time melt condensation polymerization is relatively poor.For addressing these problems, now generally adopt solid phase polymerization method to improve the molecular weight of polyester.In this polymerization technique, behind the polyester prepolyer powder crystallization, obtained the high-molecular weight polyester under the temperature below the fusing point, carrying out solid state polymerization under inert gas or the vacuum.The advantage of this method is to obtain the superior high-molecular weight product of color and luster excellent properties.Shortcoming is that prepolymer powder easily bonds, and causes the instability of production technique and the deterioration of product quality.Improve powder diameter caking is alleviated, can slow down polymerization velocity but improve particle diameter.
Suspension polymerization
Suspension polymerization is by the brute force stirring and under the effect of dispersion agent, and monomer is dispersed into the polyreaction that countless little liquid pearls suspends in water and undertaken by the oil-soluble initiator initiation.
Suspension polymerization system generally comprises four kinds of basal components: monomer, initiator, water, suspension agent.Wherein monomer is water insoluble or be slightly soluble in water, and initiator is dissolved in monomer.Suspension agent is that a class can be dispersed in oil-soluble monomer the material that forms stable suspension in the water, is generally water-soluble high-molecular substance or water-fast inorganics.What suspension polymerization obtained is granular resin, and particle diameter is in 0.01～5mm scope.
Suspension polymerization system is a thermodynamic unstable system, needs to borrow stirring and dispersion agent to keep stable.Stirring under the shearing action, the monomer that is dissolved with initiator is dispersed into small droplets, and initiated polymerization suspends in water.Monomer droplet is equivalent to the little reactor of mass polymerization, and polymerization mechanism is identical with mass polymerization.But when polymerisation conversion was 15%～50%, polymkeric substance-monomer droplet viscosity increased, and the granulated danger of mutual bonding is arranged.Except that stirring, must be with suitable dispersion agent insulation blocking.Final resulting polymers particle diameter is about 0.001～5mm, and this is relevant with stirring intensity, suspension system character.
The advantage of suspension polymerization is: (1) system is an external phase with water, and viscosity is low, conducts heat easily and controls; Heat of polymerization easily spreads, and polymeric reaction temperature is easy to control, the polymer molecular weight narrowly distributing; (2) polymerisate is the solid bead particle, and is easily separated, drying; (3) production investment and expense are few; Product is than the purity height of letex polymerization.Its shortcoming is: there is automatic booster action in (1); (2) must use dispersion agent, and after polymerization is finished, be difficult to from polymerisate, remove, can influence the performance (as outward appearance, aging resistance etc.) of polymerisate; (3) the polymerisate particle can contain small amounts of monomer, and is difficult thoroughly clear, the impact polymer performance; (4) be difficult to adopt continuous processing production.
Suspension polymerization mostly is radical polymerization at present, but very wide in industrial application.The suspension polymerization process is adopted in production 75% as polyvinyl chloride, and polymeric kettle also gradually maximizes; Polystyrene and styrol copolymer mainly also adopt suspension polymerization production; Other also have Vinyl Acetate Copolymer, polyacrylate(s), fluoro-resin etc.
Solid phase polymerization method
Solid state polymerization is to be lower than the fusing point of prepolymer at polymerization temperature and to be higher than its second-order transition temperature and a kind of polymerization process of carrying out.
The mechanism of solid state polymerization is: in low-molecular-weight performed polymer (section, powder etc.), a part (often being most of) molecule segment " is freezed " to form crystallizing field, and thereby functional group's terminal group, small molecule monomer and catalyzer are ostracised and are had certain motor capacity in the pars amorpha and can further polyreaction take place by diffusion generation effective collision adjacent to each other.By vacuum or rare gas element small molecule by-product in the reaction system is taken away, molecular balance moves to positive dirction, thereby makes that molecular chain continues to increase, and obtains the product of higher molecular weight.The molecule segment of these lengthenings again can be coalescent in the crystalline region, and part meeting crystallization makes crystallinity of polymer increase.Solid state polymerization speed depends on the competition of chemical reaction and physical diffusion two aspects simultaneously, and the small molecules product diffuses into vacuum or atmosphere of inert gases on every side from intraparticle diffusion to particle surface and then from particle surface.According to low speed decision principle, the speed of reaction of whole polyreaction is by the slowest above-mentioned step decision.Polymerization time, polymerization temperature, catalyzer, vacuum tightness (or nitrogen flow), performed polymer degree of crystallinity, performed polymer geometrical shape etc. all will influence the process of solid-phase polymerization.
Owing to generally can not being present in the crystalline region, functional group's terminal group and catalyzer cause terminal group and catalyzer in the solid state polymerization in the amorphous domain enrichment.Such as, when degree of crystallinity was 50wt%, catalyzer was 2 times of bulk concentration in the concentration of amorphous domain; During 80wt%, be 5 times of bulk concentration; During 90wt%, be 10 times of bulk concentration.Because in the solid state polymerization, degree of crystallinity usually reaches 70-90wt%, so terminal group and catalyzer are quite remarkable at the enrichment degree of amorphous domain.Thisly be enriched with the raising that is beneficial to polymerization velocity.On the other hand, because the mobility of terminal group can be subjected to the restriction of crystalline region, cause activity to descend, and this can cause polymerization velocity to descend.
Prepolymer generally carries out solid state polymerization with section or powder type, and its particle diameter is generally between tens microns to several millimeters.This little size of particles (liquid that is equivalent to melt polymerization is dark) is to help the diffusion of small molecule by-product and remove, thereby driving a reaction carries out to positive dirction.On the other hand, because the existence of crystalline region, can suppress the diffusion of small molecule by-product again and remove in the fit particle of solid polycondensation.
The advantage of solid state polymerization: (1) because of solid phase polymerization temperature is lower, can obviously reduce Yin Gaowen and the generation of the side reaction that causes, thereby generally only produce linear macromolecule.Some polymkeric substance are owing to very easily degrade during high temperature, are difficult to when adopting the high-temperature fusion polymerization even may obtain the high-molecular weight product.The high molecular weight product for preparing these polymkeric substance, solid state polymerization have just become unique selection.(2) by the same token, the general color and luster of the product of solid state polymerization is better, and rerum natura is also more excellent than the melt polymerization product.(3) on the other hand, solid state polymerization can improve the residual monomer transformation efficiency greatly and reduce the content of monomer in polymerisate, so no longer need after the polymerization polymkeric substance is made further purification process.(4) simultaneously, owing to do not use solvent in the polymerization process, thereby comparatively friendly to environment.(5) be easy to realize the serialization industrial production.The shortcoming of solid state polymerization is a solid phase particles, the less particle of particle diameter particularly, and caking causes stirring and flow difficulties easily in crystallization or polymerization process.Cause the reason of luming may be mainly from three aspects: (1) degree of crystallinity be too small, and particularly upper layer degree of crystallinity is too small; (2) non-uniform temperature, local superheating cause local temperature to surpass the fusing point of prepolymer; (3) crystallization velocity is too fast, and heat of crystallization is emitted in a large number.
At present, solid phase polycondensation generally is used for polymer manufacture and productions such as polyester, nylon, polyester, can obtain high-molecular weight polyester, nylon, polyester etc. by solid state polymerization.
Summary of the invention
The object of the present invention is to provide a kind of caking that can effectively prevent particle or powder, the suspending solid phase polymerization method of the high molecular weight polyesters that polymerization effect is good.
Technical solution of the present invention is:
A kind of suspending solid phase polymerization method of high molecular weight polyesters is characterized in that: polyester prepolyer is suspended in the form of powder or particle carries out solid state polymerization in the liquid inert medium, polymerization temperature is between the second-order transition temperature and fusing point of polyester prepolyer.
Particle all is in solid-state in whole polymerization process.
The temperature (Ts) of general suspending solid phase polymerization is between the second-order transition temperature (Tg) and fusing point (Tm) of prepolymer:
Tg<Ts<Tm (1)
Be lower than second-order transition temperature, reaction can not be carried out.Being higher than fusing point then no longer is solid state polymerization.Because temperature is low, polymerization velocity is also low.Be to guarantee to improve polymerization temperature under the situation that particle or powder do not melt generally speaking as far as possible.Under prerequisite greater than second-order transition temperature, preferably the temperature range of suspending solid phase polymerization be fusing point following 40 ℃ between the fusing point:
Tm-40≤Ts<Tm (2)
Better the temperature range of suspending solid phase polymerization be fusing point following 20 ℃ between the fusing point:
Tm-20≤Ts<Tm (3)
The temperature range of best suspending solid phase polymerization be fusing point following 10 ℃ between the fusing point:
Tm-10≤Ts<Tm (4)
Because polymerization system molecular weight in polymerization process constantly increases, general degree of crystallinity also can improve constantly, so the fusing point of system also can constantly change in polymerization process.Fusing point also can improve constantly generally speaking, and often is to improve comparatively fast at the initial stage, and the middle and later periods raising is slower even almost constant.So in polymerization process, polymeric temperature T s can keep constant; Also can constantly change along with polymerisation run; Also can in the early stage Ts be set in lower temperature, remain on moderate temperature mid-term and the later stage remains on comparatively high temps; Also can according to polymerisation run the Ts continuous adjustment later stage then be constant at a certain fixed temperature or the like in the early stage.
Because high molecular polymolecularity, high molecular fusion has certain temperature range.So be necessary above-mentioned fusing point (or melt temperature) Tm is done an explanation.On the other hand, also be appreciated that polymer fusing point and the periodic heat-up rate of survey have certain relation.Tm among the present invention is meant (10～20 ℃/the melt initiation temperature degree min) measured down of medium heat-up rates.
It is can crystalline that the suspending solid phase polymerization method of polyester of the present invention requires prepolymer.Degree of crystallinity do not had any special restriction.Can before being suspended in inert media, carry out crystallization treatment and also can after being suspended in inert media, carry out crystallization treatment them.
The suspending solid phase polymerization method of polyester of the present invention requires the initiator prepolymer to be suspended in the inert media with powder or particle shape.Size to powder and particle does not have any restriction.Consider the diffusion of the small molecule by-product that is produced in the difficulty or ease of suspension and the polymerization process and remove speed, particle diameter is unsuitable excessive, generally is advisable to be not more than 10mm.
The suspending solid phase polymerization method of polyester of the present invention requires suspension medium to the initiator prepolymer, and intermediate polymer and final polymkeric substance are inert.Just require liquid medium not with initiator prepolymer, intermediate polymer, catalyzer and initiator and final polymkeric substance generation chemical reaction; Liquid medium is for the initiator prepolymer, and intermediate polymer and final polymkeric substance are non-solvent or slightly soluble agent.The boiling point of the suspending solid phase polymerization method liquid towards inert media of polyester of the present invention has certain limitation, requires under polymerization pressure, and the boiling point of liquid medium is not less than polymerization temperature.Liquid inert medium is in liquid state under polymerization temperature and pressure.
In the suspending solid phase polymerization method of polyester of the present invention liquid inert medium can be organic solvent, ionic liquid, at the micromolecular compound that is in liquid non-organic solvent under polymerization temperature and the pressure, under polymerization temperature and pressure, be in the polymer of molten state one or more.
The present invention can effectively prevent the caking of particle or powder, and polymerization effect is good.
The suspending solid phase polymerization that the present invention adopts be a kind of of suspension polymerization also be a kind of of solid state polymerization; Meanwhile, suspending solid phase polymerization is a kind of extension of classical suspension polymerization and a kind of extension and the expansion that expansion also is solid state polymerization.The main difference of suspending solid phase polymerization and classical suspension polymerization is: (1) is in solid-state in the suspending solid phase polymerization process always as the prepolymer of initiator or monomer, and in classical suspension polymerization, its initial monomers is in liquid state; (2) in the suspending solid phase polymerization system, generally do not contain suspension agent, and in classical suspension polymerization system, generally contain suspension agent; (3) suspending solid phase polymerization method is applicable to condensation polymerization and classical suspension polymerization is not suitable for condensation polymerization.The main difference of suspending solid phase polymerization and general solid state polymerization is: in suspending solid phase polymerization solids or powder suspension in inert media and in the general solid state polymerization solids or powder accumulation react together.With respect to general solid state polymerization, the advantage of suspending solid phase polymerization is that heat of polymerization and heat of crystallization easily spread, and temperature is easy to control, can effectively prevent the caking of particle or powder.Even so the solid state polymerization of micro mist (～1-100 μ m), polymerization also can be carried out reposefully when adopting suspension method.
The invention will be further described below in conjunction with embodiment.
Embodiment
Below will be with PLA, PET, PBS, PBT is polymerized to example, describes the suspending solid phase polymerization method of polyester of the present invention in detail.But this does not illustrate that the present invention only limits to the polymer quantification of these four kinds of polyester, and the present invention is applicable to that the polymer of crystallizable polyester of all its prepolymers and polyester copolymer quantizes.
Embodiment 1:
Initiator: lactic acid prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=10k, melting enthalpy Δ Hm=60J/g, fusing point Tm=158 ℃, glass transition temperature Tg=45 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180 ℃ under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g lactic acid prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 155 ℃ and be to keep 24 hours under the 200Pa at 155 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly(lactic acid) white powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 22g poly(lactic acid), productive rate is 88%; Mw is 150,000,175 ℃ of fusing points.
Embodiment 2:
Initiator: lactic acid prepolymer powder, powder diameter D ≈ 500um, molecular weight Mw=10k, melting enthalpy Δ Hm=60J/g, fusing point Tm=158 ℃; Glass transition temperature Tg=45 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180 ℃ under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g lactic acid prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 155 ℃ and be to keep 24 hours under the 200Pa at 155 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly(lactic acid) white powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 23g poly(lactic acid), productive rate is 92%; Mw is 110,000,174 ℃ of fusing points.
Embodiment 3:
Initiator: lactic acid prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=20k, melting enthalpy Δ Hm=58J/g, fusing point Tm=160 ℃; Glass transition temperature Tg=47 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180 ℃ under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g lactic acid prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 158 ℃ and be to keep 24 hours under the 200Pa at 158 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly(lactic acid) white powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 22.6g poly(lactic acid), productive rate is 90%; Mw is 170,000,176 ℃ of fusing points.
Embodiment 4:
Initiator: lactic acid prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=10k, melting enthalpy Δ Hm=60J/g, fusing point Tm=158 ℃; Glass transition temperature Tg=45 ℃
Liquid inert medium: refined wax
The 250ml refined wax is put into the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask is put into oil bath, be warming up to and begin after the paraffin fusion to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 30g lactic acid prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 157 ℃ and be to keep 24 hours under the 200Pa at 157 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly(lactic acid) white powder, with 100ml hexanaphthene washing 5 times, vacuum-drying, weigh the 26g poly(lactic acid), productive rate is 87%; Mw is 160,000,175 ℃ of fusing points.
Embodiment 5:
Initiator: lactic acid prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=10k, melting enthalpy Δ Hm=60J/g, fusing point Tm=158 ℃; Glass transition temperature Tg=45 ℃
Liquid inert medium: 1-ethyl-3-methyl imidazolium tetrafluoroborate ([EMIM]
+[BF
4]
-)
250ml 1-ethyl-3-methyl imidazolium tetrafluoroborate is injected the there-necked flask that 500ml is placed with magneton, and replace nitrogen three times.Under nitrogen atmosphere, 30g lactic acid prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 155 ℃ and be to keep 24 hours under the 200Pa at 155 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly(lactic acid) white powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 27g poly(lactic acid), productive rate is 90%; Mw is 130,000,173 ℃ of fusing points.
Embodiment 6:
Initiator: polyethylene terephthalate prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=11k, melting enthalpy Δ Hm=29J/g, fusing point Tm=253 ℃; Glass transition temperature Tg=67 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180 ℃ under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.Four-hole boiling flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g polyethylene terephthalate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 230 ℃ and be to keep 15 hours under the 200Pa at 230 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the polyethylene terephthalate powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 22g polyethylene terephthalate, productive rate is 88%; Mw is 2.5 ten thousand, 264 ℃ of fusing points.
Embodiment 7
Initiator: polybutylene terephthalate prepolymer powder, powder diameter D ≈ 500um, molecular weight Mw=9k, melting enthalpy Δ Hm=37J/g, 209 ℃ of fusing points; Glass transition temperature Tg=45 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180 ℃ under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.Four-hole boiling flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g polybutylene terephthalate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 200 ℃ and be to keep 15 hours under the 200Pa at 200 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the polybutylene terephthalate powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 23g polybutylene terephthalate, productive rate is 92%; Mw is 2.1 ten thousand, 220 ℃ of fusing points.
Embodiment 8
Initiator: polytrimethylene terephthalate prepolymer powder, powder diameter D ≈ 500um, molecular weight Mw=10.1k, melting enthalpy Δ Hm=32J/g, 211 ℃ of fusing points, glass transition temperature Tg=57 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180oC under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.Four-hole boiling flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g polytrimethylene terephthalate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 205 ℃ and be to keep 15 hours under the 200Pa at 205 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the polytrimethylene terephthalate powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 22.5g polytrimethylene terephthalate, productive rate is 90%; Mw is 2.05 ten thousand, 227 ℃ of fusing points.
Embodiment 9
Initiator: polyethylene terephthalate prepolymer powder, powder diameter D ≈ 200um, molecular weight Mw=11k, melting enthalpy Δ Hm=29J/g, 253 ℃ of fusing points; Glass transition temperature Tg=67 ℃
Liquid inert medium: refined wax
The 250ml refined wax is put into the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask is put into oil bath, be warming up to and begin after the paraffin fusion to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 30g polyethylene terephthalate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 254 ℃ and be to keep 24 hours under the 200Pa at 254 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the polyethylene terephthalate powder, with 100ml hexane wash 5 times, vacuum-drying, weigh the 26g polyethylene terephthalate, productive rate is 87%; Mw is 20,000,264 ℃ of fusing points.
Embodiment 10
Initiator: poly butylene succinate prepolymer powder, powder diameter D ≈ 250um, molecular weight Mw=13k, melting enthalpy Δ Hm=40J/g, 100 ℃ of fusing points, glass transition temperature Tg=-41 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180oC under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g poly butylene succinate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 95 ℃ and be to keep 24 hours under the 200Pa at 95 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly butylene succinate powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 22g poly butylene succinate, productive rate is 88%; Mw is 160,000,125 ℃ of fusing points.
Embodiment 11
Initiator: poly butylene succinate prepolymer particle, particle diameter D ≈ 4mm, molecular weight Mw=13k, melting enthalpy Δ Hm=40J/g, fusing point are 100 ℃ of glass transition temperature Tg=-41 ℃
Liquid inert medium: phenyl silicone oil (boiling point is not less than 180oC under the 200Pa)
The 250ml phenyl silicone oil is injected the there-necked flask that 500ml is placed with magneton.There-necked flask connects nitrogen flatly, connects vacuum system flatly, inserts thermocouple thermometer flatly.There-necked flask put into begin after the oil bath to stir, open vacuum, and displacement nitrogen three times.Under nitrogen atmosphere, 25g poly butylene succinate prepolymer powder is slowly joined in the there-necked flask.After opening vacuum pressure being reduced to 200Pa, be warming up to 95 ℃ and be to keep 48 hours under the 200Pa at 95 ℃ of polymerization temperature Ts and polymerization temperature pressure P.In whole process, particle is in the state of wandering about as a refugee, and caking phenomenon do not occur.The gained suspension filtered is obtained the poly butylene succinate powder, with 100ml washing with acetone 5 times, vacuum-drying, weigh the 23g poly butylene succinate, productive rate is 92%; Mw is 140,000,125 ℃ of fusing points.
Claims (6)
1. the suspending solid phase polymerization method of a high molecular weight polyesters, it is characterized in that: polyester prepolyer is suspended in the form of powder or particle carries out solid state polymerization in the liquid inert medium, polymerization temperature is between the second-order transition temperature and fusing point of polyester prepolyer.
2. the suspending solid phase polymerization method of high molecular weight polyesters according to claim 1 is characterized in that: described liquid inert medium be not with the liquid medium of prepolymer, final polymkeric substance, catalyzer and initiator and final polymkeric substance generation chemical reaction.
3. the suspending solid phase polymerization method of high molecular weight polyesters according to claim 1, it is characterized in that: liquid inert medium is the non-solvent or the slightly soluble agent of polyester.
4. the suspending solid phase polymerization method of high molecular weight polyesters according to claim 1, it is characterized in that: prepolymer is the crystallinity prepolymer.
5. the suspending solid phase polymerization method of high molecular weight polyesters according to claim 1, it is characterized in that: the boiling point of liquid inert medium has certain limitation, requires under polymerization pressure, and the boiling point of liquid inert medium is not less than polymerization temperature.
6. the suspending solid phase polymerization method of high molecular weight polyesters according to claim 1 is characterized in that: liquid inert medium is organic solvent, ionic liquid, be in the micromolecular compound of liquid non-organic solvent under polymerization temperature, be in the polymer of molten state one or more under polymerization temperature.
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| CNA2007100260526A CN101367916A (en) | 2007-08-15 | 2007-08-15 | Suspending solid phase polymerization method for polyester with high molecular weight |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019202A (en) * | 2010-09-30 | 2011-04-20 | 南京工业大学 | Sulfonic acid dual-core ion liquid catalyst and method using same for synthesizing polydiethylene glycol sebacate |
| CN112210073A (en) * | 2020-10-26 | 2021-01-12 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
-
2007
- 2007-08-15 CN CNA2007100260526A patent/CN101367916A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019202A (en) * | 2010-09-30 | 2011-04-20 | 南京工业大学 | Sulfonic acid dual-core ion liquid catalyst and method using same for synthesizing polydiethylene glycol sebacate |
| CN112210073A (en) * | 2020-10-26 | 2021-01-12 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
| CN112210073B (en) * | 2020-10-26 | 2021-11-16 | 浙江大学 | Preparation method of crystalline polyester and product thereof |
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