CN1817940A - Process of continuously producing polyester polymer - Google Patents

Abstract

The present invention uses a reactor that combines devices having a special portion structure to solve the difficulty of uniform blending due to the reactants becoming highly viscous, the difficulty of heat removal, and the increase in pressure loss, thus leading to continuous production of a polyester-based polymer stably having excellent quality.

Description

The process for continuously producing of polyester polymer

The application is the Chinese invention patent application (applying date: on January 8th, 2003; Application number: 03802078.5; Denomination of invention: the dividing an application process for continuously producing of polyester polymer).

Technical field

The present invention is about a kind of process for continuously producing of polyester polymer, this method for making is to use by tower stirring mixer with 2 or 2 above stir shafts and the reaction unit that static mixer constituted that is connected in its outlet, makes polymkeric substance and one or more cyclic ester class with hydroxyl and/or ester bond carry out ring-opening polymerization and obtain multipolymer.

In addition, the present invention is about a kind of process for continuously producing of multipolymer, and this method for making is that the different static mixers with series combination are used for reactor, makes polymkeric substance with hydroxyl and/or ester bond and the cyclic ester class more than a kind or a kind carry out ring-opening polymerization.

Background technology

The dilactide of the intermolecular dehydration cyclic ester of use alcohol acid or diglycolide are as monomeric homopolymer, the lactone that uses the intramolecularly cyclic ester is as monomeric homopolymer, and these monomeric multipolymers (following abbreviate them as polyester polymer), decomposed by light, heat, ferment etc., be circulated to nature and can be reduced, therefore from security and antipollution viewpoint, as the Biodegradable polymer materials many research is arranged with it.

About the manufacture method of the homopolymer of dilactide or diglycolide, knownly roughly be divided into two kinds of manufacture method in the past.That is, in case by the hydroxycarboxylic acid of correspondence directly dewater polycondensation and make the method for polymkeric substance and the dehydration cyclic ester of synthesis of hydroxy acid after, make its ring-opening polymerization and make the method for polymkeric substance.

As direct polycondensation method by the former, be difficult to obtain molecular weight 4, polymkeric substance more than 000 or 4,000 (C.H.Halten work, " lactic acid " the 226th page, Veriag Chemie, 1971), also there is the operation condition of discussion to quantize, as sees special fair 2-52930 communique to seek polymer, molecular weight 20,000 degree are to be the limit.Therefore, in must making the situation of high molecular weight polymers more, be to use the ring-opening polymerization method of the latter's cyclic ester.

In addition, make the method for polyester polymer continuously about using these lactideses or lactone, the spy opens and has disclosed the method for continuous production that uses aromatic polyester and lactone in clear 61-281124,61-283619, the 61-287922 communique.

They are all at inside reactor has as the screw type of kneading machine or extrusion machine or the agitating vane of blade type, by using the stirring of dynamic agitation machine, and the stirring reaction system, and the polymkeric substance of content is added inlet by raw material in regular turn be transferred to the goods conveying end.These technology that disclosed can finish reaction at short notice.Yet, carry out mixture operation with such dynamic agitation machine, because the temperature that high viscosityization and can not preventing is sheared due to the heating rises, when reducing stirring velocity, the bad worry of mixing at initial stage is arranged at last stage reaction if avoid it on the contrary.In addition,, then must improve temperature of reaction as described in it for end reaction at short notice, the operation of maybe necessary increase catalytic amount etc., and except same problem is arranged, also can detrimentally affect be arranged to the water tolerance of polyester polymer.Moreover, cause evaporable cyclic ester class to leak to outside the system in order to prevent owing to heating or to shear heating, the stopping property of necessary raising stir shaft part, or in order to improve stopping property by resin itself, the high part of shear-stress must be set, so the suitable manufacture method of can not saying so.

In addition, about make the method for polyester polymer continuously by lactides, having disclosed several steel basin series connection in the Te Kaiping 5-93050 communique links to each other, by continuously to wherein supplying reaction raw materials, residence time with the extremely last reactive tank of initial reactive tank is carried out successive polymerization, promptly so-called CSTR method for continuous production as the reaction times.Yet, they are all the reaction unit that uses dynamic mixers, problem can take place when making the high-molecular weight polyester polymer continuously by lactides or lactone, make as high viscosityization to be difficult to evenly stir and be difficult to heat extraction, and also do not disclose or hint solves countermeasure for these problems owing to reactant.

Promptly, even the method that is disclosed in the above-mentioned various technology of revision test by lactides manufacturing polyester polymer, increase along with the molecular weight of the polymkeric substance that is generated, polymer viscosity rises to 10,000～hundreds thousand of pools and rises to very high range of viscosities, the stirring of general agitator is difficulty more and more, and be difficult to take out reaction content, in addition, promptly use powerful agitator, agitating wing is worked hard so that the stirring reaction system, but reaction content along with the rotation of agitating wing with near laminar flow move, the system that makes all is difficult to by uniform mixing.

In addition, because the heating that the ring-opening polymerization of cyclic ester is followed, high viscosityization is followed is difficult to even stirring, make the temperature control in the reactor become difficult, it is out of control to react, and occurrence temperature distributes in the polymkeric substance, owing to local heating causes quality variation.

As the spy open flat 7-26001 and special open put down in writing in the flat 7-149878 communique, in order to address these problems a little, bring into use the static mixer (SM) that is not the dynamic agitation machine, but by being fixed in the Immobile hybrid element in the pipe, owing to be to make fluid repeat to cut apart the structure that conversion is reversed, so the impedance of convection cell itself is very big.That is, the pressure-losses of reactive system becomes very big, and the design of reactor and pump is difficult.And, because its upper limit of pressure that spues makes throughput produce and reduces.

Again, in the situation of SM, because being fit to the control mixing is the movable part of shearing force, only optimal design is arranged at a certain specific operating condition, in the situation beyond it, under the promptly most operating condition, owing to can not control mixing, so usually there is to a certain degree above mixing bad, have to turn round having under the state of heat distribution in the same old way.

Moreover, in order to make the high pressure loss step-down, have the SM bore is the situation that the sectional area that passes through of fluid increases, very big but its mixing is bad and heat distribution becomes.Mix bad meeting and make by the running beginning elongatedly to the time of the article of discharging stable rerum natura, the residence time of reactivity that reaches target is elongated, and becomes goods character and the non-persistent reason of shape.

For fear of this kind situation, the situation that SM is used as the ring system continuous reaction apparatus is arranged.Can increase mixed effect though increase loop, only this part increases the residence time distribution in the reactor, and can not avoid because the painted quality badness of polymer unwinds due to being heated for a long time.Especially, when manufacturing has the multipolymer of the polymkeric substance of hydroxyl and/or ester bond and cyclic ester, it is wide that molecular weight distribution becomes, and because chain segment length's the homogeneity of each block that makes of transesterification reaction etc. reduces, they have the disadvantageous effect of widening for the peak crystallization that is recorded by DSC etc.Because the flow of loop portion increases, make hugeization of equipment, cost of equipment becomes very high, but unpractical.

On the other hand, for fear of the problem relevant with the mixing at initial stage, have and propose to use solvent etc. to prepare uniform solution in advance, or adopt stirring-type reactor to carry out prepolymerized method with stirrer, but making under solid or the treatment temp is under the polymer raw material and cyclic ester class blended situation of highly viscous liquid, must carry out long time treatment at heated condition, the carrying out of reaction can not avoid and the same problem of above-mentioned ring system continuous reaction apparatus.

Especially, be to have good Biodegradable by the polyester polymer of cyclic ester manufacturing, have the character that is subjected to acid, alkali or the hydrolysis of water institute easily but then and also easily because heat causes the character of molecular weight reduction.For example, at GUPTAM, C, Colloid Polym.Sol. (DEU) 260 (3) 308-311, in 1982, reported and passed through, the research example of the thermal decomposition rate of the homopolymer of dilactide in airborne intensification thermogravimetric analysis, but in the reaction vessel of sealing, the molecular weight that also takes place to quicken under the high temperature more than 250 ℃ or 250 ℃ reduces.

In addition, the homopolymer of this dilactide and multipolymer carry out character such as painted owing to being exposed to also to have in the high temperature.Promptly, in the known method for making of using these cyclic esters, because the high viscosityization of following the polymer of polymkeric substance to quantize, then hinder uniformly and mix, the result goes bad owing to part takes place local heating, therefore the problem that has the quality of causing to reduce all will seek better manufacture method in the experiment of small-scale research department or large-scale industrial production.

Therefore, when making polyester polymer, have because the high viscosityization of reactive system makes to be difficult to evenly stir thermolysis, painted etc. takes place, and the reduction that has the quality reduction or the high pressure-losses owing to the polymkeric substance that is generated to cause throughput.Owing to be to be difficult to mix with the cyclic ester class in initial reaction stage, and feasiblely have no alternative but become disadvantageous economically method for making as the polymkeric substance with hydroxyl and/or ester bond of raw material again.

The present invention, become the problem that productivity that mixed uniformly difficulty, high viscosity raw material and the mixed uniformly difficulty of low viscosity raw material, heat extraction difficulty and the high pressure-losses that the high viscosity of the reactant of problem causes cause descends when having solved industrial production high molecular weight polyesters type polymkeric substance, thereby a kind of manufacture method of continuous manufacturing high-quality polyester polymer is provided.

Summary of the invention

This case contrivers etc. in view of the above problems, attentively endeavour to having the polymkeric substance of hydroxyl and/or ester bond, the stirring mixing method of the polyester polymer of cyclic ester class and reaction product thereof, make method that the pressure-losses reduces with and found that of method for continuous production research, the tower stirring mixer and the reaction unit that static mixer constituted that is connected in its outlet that have the stir shaft more than 2 or 2 by use, even the viscosity height of polymer fluid then, also hybrid reaction content well, can remove heat of polymerization effectively, can be with the low pressure loss runs steadily, can be with high-quality, high-level efficiency and high productivity obtain not having decomposing or painted high-molecular weight polymer, so finished the present invention.

In addition, this case contrivers etc. in view of the above problems, also attentively endeavour to having the polymkeric substance of hydroxyl and/or ester bond, the stirring mixing method of the polyester polymer of cyclic ester class and reaction product thereof, make method that the pressure-losses reduces with and found that of method for continuous production research, by using by the continuous reaction apparatus of two or more different static mixers institute series combination at least, even the viscosity height of polymer fluid then, also hybrid reaction content well, can remove heat of polymerization efficiently, can be with the low pressure loss runs steadily, can be with high-quality, high-level efficiency and high productivity obtain not having decomposing or painted high-molecular weight polymer, so finished the present invention.

Promptly, the 1st process for continuously producing that provides a kind of polyester polymer of the present invention, it is characterized in that to by the tower stirring mixer with the stir shaft more than 2 or 2 be connected in the reaction unit that static mixer constituted of outlet, infeed polymkeric substance (A) with hydroxyl and/or ester bond and cyclic ester class (B) more than a kind or a kind continuously, make polymkeric substance (A) and cyclic ester class (B) carry out ring-opening polymerization and obtain multipolymer (C).

The 2nd method for making that provides as being put down in writing among the 1st of the present invention of the present invention, wherein polymkeric substance (A) is a crystalline aromatic polyester.

The 3rd method for making that provides as being put down in writing among the 2nd of the present invention of the present invention, wherein cyclic ester class (B) is a lactone.

The 4th method for making that provides as being put down in writing among the 3rd of the present invention of the present invention, wherein lactone is a 6-caprolactone.

The 5th of the present invention provides as each method for making of putting down in writing in the present invention the 1st～4, it is characterized in that after by tower stirring mixer with the stir shaft more than 2 or 2, before passing through static mixer, the reactivity of cyclic ester class (B) is 75 moles of % or 75 moles below the %, then is that 75 moles of % or 75 moles are more than the % after by static mixer.

The 6th process for continuously producing that provides a kind of polyester polymer of the present invention, this method is in the continuous reaction apparatus with static mixture, infeed polymkeric substance (A) with hydroxyl and/or ester bond and cyclic ester class (B) more than a kind or a kind continuously, make polymkeric substance (A) and cyclic ester class (B) carry out ring-opening polymerization and obtain the method for multipolymer (C), it is characterized in that, to be the static mixer (SM (i)) that used by initial reaction stage at least constituted with the static mixer (SM (e)) of the last stage reaction use different with SM (i) with SM (i) series combination and kind continuous reaction apparatus, and the value X (i: be more than 4 or 4 e) that is tried to achieve via following formula (1) than Zi and Ze and each inside diameter D i and De from each pressure-losses of SM (i) and SM (e)

X(i∶e)＝(Zi×De ⁴)/(Ze×Di ⁴) (1)

The 7th process for continuously producing that provides as being put down in writing among the 6th of the present invention, wherein X (i: be more than 10 or 10 e) of the present invention.

The 8th process for continuously producing that provides as being put down in writing among the present invention the 6th or 7 of the present invention is characterized in that the value Y (i) that is tried to achieve by following formula (2) than Z (i) and mixer length L (i) and inside diameter D (i) from the pressure-losses of SM (i) is 200～2,000,

Y(i)＝Z(i)×L(i)/D(i) (2)。

The 9th process for continuously producing that provides as being put down in writing among the 6th of the present invention of the present invention, wherein Y (i) is 500～1,000.

The 10th of the present invention provides as each process for continuously producing of putting down in writing in the present invention the 6th～9, wherein between SM (i) and SM (e), optionally is provided with the static mixer (SM (m)) that uses mid-term in reaction.

The 11st of the present invention provides as each process for continuously producing of putting down in writing in the present invention the 6th～10, wherein among SM (i), the SM (m) that optionally is provided with and the SM (e) one or more or constituted by several static mixers.

The 12nd of the present invention provides as each process for continuously producing of putting down in writing in the present invention the 6th～11, wherein for constituting SM (i), the SM (m) that optionally is provided with and total n the static mixer (SM (r) of SM (e), (r=1～n)), the total of the Yr that similarly tries to achieve with formula (2) (promptly, ∑ Yr=∑ Zr * Lr/Dr, (the total scope r=1 of ∑～n)) be below 5,000 or 5,000.

The 13rd of the present invention provides as each process for continuously producing of putting down in writing in the present invention the 6th～12, and wherein polymkeric substance (A) is a crystalline aromatic polyester.

The 14th of the present invention provides as each process for continuously producing of putting down in writing in the present invention the 6th～13, and wherein cyclic ester class (B) is a lactone.

The 15th of the present invention provides the 14th process for continuously producing of being put down in writing as the present invention, and wherein lactone is a 6-caprolactone.

Below, describe the present invention in detail.

The preferred plan that carries out an invention

In the present invention, multipolymer (C) is also referred to as polyester polymer (C) or only is called polymkeric substance (C).

At first, used reaction unit among the present invention 1 to 5 o'clock is described.The tower stirring mixer of being sayed among the present invention 1 to 5 with the stir shaft more than 2 or 2 (being called stirring mixer (1)) has the raw material supplying mouth at least, discharges the relief outlet that the molten state polymkeric substance is used, the stir shaft more than 2 or 2 that is provided with in the container of tubulose or combination in parallel with it respectively is connected in the power part of motor etc., the stir shaft device that to be each stir with equidirectional or different directions rotation.Its shapes etc. are not special to be limited, but can use the device of vertical, oblique or arranged transversely, can design to have the person of gas phase portion in the situation of arranged transversely.The agitating wing that is provided with blade etc. in the stir shaft is so that mix, and for example the gap of blade leading section and other stir shaft and tube wall is through tight adjustment person, and promptly so-called to have automatically cleaning ability person be preferable.

As the object lesson of stirring mixer (1), at first can enumerate the extruder more than 2 or 2, preferable 2 extruders, 2 extruders of equidirectional or different direction rotation.Te Jia is 2 extruders of engagement type of equidirectional rotation.The ratio L/D of spiro rod length of extruder (L) and diameter (D) etc. is to have no particular limits.Such extruder for example can be by the shaft portion and the fixing person of constituting who mediates the shaft portion of dish-type blade with several of standing screw type blade.The main task of screw type blade is for transferring the material in the footpath and having the mixing ability, mediates the dish-type blade and is according to mixing ability and situation and the solid state raw material is cut and had heating, a fused ability.Mediate the dish-type blade and be section with the axle right angle orientation for for example convex lens shape or like the polygon more than the trilateral, the flat blade of column or be added with the screw blade of some distortions according to circumstances.

As other object lesson, for example specifiable kneading mixing roll that has the Special Mixed function in essence just like made KRC kneader of chestnut ironworker etc.These mediate mixing rolls general with extruder similarly, by the screw type blade with mediate the dish-type blade and be combined into, mainly be combined into especially by kneading dish-type blade.These mediate mixing roll can add internal volume, and on the other hand, using L/D mostly is 20 or 20 following persons.At raw material is in the solid situation, is preferably the additional heat may fusion and is supplied to this device then.

As other object lesson, can use the poly-unit of Surface Renewal.As glass blade (glass blades) poly-unit, the grid blade poly-unit of Hitachi's manufacturing, Mitsubishi Heavy Industries Ltd make SCR, NewSCR particularly, and hundred pools that heavy-duty machine tool industry in Sumitomo is made draw storehouse (Bipolak) etc.

These stirring mixers (I) use with the state with gas phase portion usually, but among the present invention owing to worry the short circuit (short pass) of unreacted cyclic ester class (B), so operate with full liquid status, or as described later in the residence time of static mixer, shorten the shared residence time in the stirring mixer (I), and the influence of lowering it.In addition, also can use stirring mixer, eliminate near the method for the gas phase portion of relief outlet energetically originally as being obliquely installed.At raw material is in the solid situation, is preferably the additional heat may fusion and is supplied to this device then.

The said static mixer of the present invention is for the mixing device with dynamic agitation machine, does not have moving part, does not promptly have the static mixing device of dynamic agitation machine.More specifically, static mixer is generally pipe and the hybrid element that does not have moving part that is fixed in the pipe constitutes, and by cutting apart fluid, and changes flow direction or makes its counter-rotating, convection cell vertically, is laterally doing to cut apart the conversion counter-rotating, and with fluid blended device.According to the kind of static mixer, the person that possesses the chuck is also arranged, so that do heat exchange, the person that possesses the pipe is also arranged in addition, so that make thermal medium carry out heat exchange by hybrid element itself at the pipe peripheral part.

In the present invention the 1st to 5, stock liquid is to be supplied to static mixer via pump etc., uses the part of static mixer as reaction unit, uses it for the mixing of the polymkeric substance of raw material or generation in addition.Correspondingly thereto, in the present invention the 6th to 15, as described later, must use the major portion of the static mixer of several different sortses (with the different persons of shape of the static agitation wing that is called hybrid element, or same shape but internal diameter difference person) as reaction unit.

In the manufacturing of the present invention the 1st to 5 polyester polymer (C), if resin viscosity surpasses 10,000 the pool the high viscosity scope time, heat of polymerization is certain, owing to stir the heat of stirring fierceness that shear-stress took place, significant local pyrexia takes place in the mixing part when adopting dynamic agitation, so preferred use shear-stress is little and the static mixer of even action.

In addition, static mixer is generally tubulose, several static mixer series connection link, under inert gas environment, the low-molecular weight copolymer that is generated in atom and the stirring mixer (I) is without interruption by adding inlet, reactant moves in static mixer continuously, therefore can be continuously, and can with under outside atmosphere contacts not react fully.Therefore, from adding, react, reclaim the solvent of the unreacted monomer (B) that produces by the taking off low boiling point component of polymkeric substance or its oligopolymer or use optionally serially and only turn to the pill of polymkeric substance.

This be adopt batch formula reaction unit in the past manufacturing the advantage point, the particularly utmost point that can not obtain be suitable for making the method for making of the decomposability polymkeric substance that oxygen, moisture or polymkeric substance and light decomposes.Promptly, only stir dynamically, then for increasing full-bodied uniform mixing, must increase and stir power, more increase heat of stirring and also increase and stir thereupon, the result causes polymkeric substance to decompose, but the present invention is by using stirring mixer (I) and be connected in the static mixer (static mixer) of its outlet, and has solved this problem.

In addition, static mixer is to be provided with heat exchanger in the pipe outside, so the temperature in the may command reactor.Also have medium in the hybrid element of inside itself, to flow in addition, can obtain heat exchange area widely, thereby can control the temperature in the reaction unit more efficiently.

The preferable use of the object lesson of used static mixer Shi Lusha (Sulzer) formula static mixer, Kai Nikesi (Kenics) formula static mixer, Dong Lishi static mixer etc. among the present invention.When making high polymkeric substance of polymerization thermal value or especially full-bodied Biodegradable polyester polymer, be assembled with the SMR type static mixer of the Shi Lushashi of the required medium stream of heat exchange particularly preferably in the hybrid element of static mixer itself.

In addition, mixing efficiency and fluidic linear velocity are proportional.The number that obtains the required hybrid element of thorough mixing effect is the viscosity that depends on reaction solution, in this situation, and the reynolds number Re of the reaction solution in the static mixer=DU ρ/μ (D: bore (cm), U: velocity in pipes (cm/sec), ρ: density (g/m ³), μ: when general viscosity, be 10 viscosity (g/cmsec)) ³Or 10 ³More than.

Yet the present invention is important owing to be the polyreaction of very high viscosity so make the effect of fluid counter-rotating or conversion direction with static mixer, and the number of the hybrid element in the static mixer may not be set in Re several 10 ³Or 10 ³Above condition, but different with the form of employed static mixer.Therefore, used static mixer can be constituting of hybrid element among the present invention, and the sum of hybrid element is to have no particular limits, common 5～40 unit, and most situation is Unit 10～25.

Used reaction unit is made of tower stirring mixer with the stir shaft more than 2 or 2 (stirring mixer (I)) and static mixer among the present invention 1 to 5 o'clock.

Because static mixer itself does not have the handover ability, so the handover of material is the transport capacity with tower stirring mixer of the stir shaft more than 2 or 2, as required in reaction way, the handover of reacted reaction mixture, polyester polymer is the pump class that toothed gear pump, ram pump etc. must be arranged, or has the extruder of the stir shaft more than 1 or 2 or 2 of functions of heating and melting.

In addition, be in the solid situation at raw material, in the inner heating and melting of stirring mixer (I) (or with cyclic ester dissolving), or, be supplied to stirring mixer (I) by behind the other heating and meltings such as extruder.

Secondly, employed continuous reaction apparatus among the present invention 6 to 15 is described.

Employed continuous reaction apparatus only is made of static mixer among the present invention 6 to 15.Because static mixer itself do not have the handover ability, the adding of raw material, as required in the reaction way, the handover of reacted reaction mixture, polyester polymer is to use pump class or extruder.The example of pump class can be toothed gear pump, ram pump etc., can use the extruder of the stir shaft more than 1 or 2 or 2 with functions of heating and melting to add raw material and be the solid polymkeric substance.

Stirring-type reactive tank and connected static mixer constituted in batches-continuous reaction apparatus, or has a circulating continuous reaction apparatus of loop shape banded static mixer, in order to obtain the thorough mixing state of polymkeric substance (A) and cyclic ester class (B), must be in heated condition for a long time, then make high viscosityization or the residence time owing to reaction distributes extensively, and make the more obvious reduction of homogeneity, so be not preferred.

Among the present invention 6 to 15, different types of static mixer is meant the shape difference person of the static agitation blade that is called hybrid element, or same shape but inside diameter D difference person.Therefore, with regard to the static mixer of the static mixer of initial reaction stage and last stage reaction, use same agitating vane shape and, be not the present invention 6 to 15 method only by the method for placed in-line continuous polymerization unit more than 2 or 2 of the static mixer of same diameter.

Moreover, constitute each static mixer of the static mixer of same reaction period, for example SM (i ₁), SM (i ₂) ... etc., be to can be same kind or different sorts, but also can use whole same kinds, the i.e. identical or also identical person of internal diameter of the shape of static agitation blade.

Again, constitute each static mixer of the static mixer of each reaction period, begun to SM (m) and SM (e) by SM (i), only internal diameter similarly changes in regular turn.

The kind of the static mixer that these are different is in fact roughly divided into: the initial reaction stage of supply of polymer (A) out of the ordinary and cyclic ester class (B) is used; Reach the certain reaction rate of cyclic ester class (B), with what use as the last stage reaction before the handover step of main purpose beyond the multipolymer (C) that takes out reaction product or the ring-opening polymerization that continues cyclic ester class (B); And use if necessary in the reaction mid-term that is provided with between this static mixer of 2 types.

In the present invention 6 to 15, for employed static mixer SM of above-mentioned initial reaction stage (i) and the employed static mixer SM of above-mentioned last stage reaction (e), value X (the i: e) be necessary for more than 4 or 4, be preferably more than 10 or 10 that tries to achieve than the quadruplicate value of Zi and Ze and each inside diameter D i and De from each pressure-losses.

X(i∶e)＝(Zi×De ⁴)/(Ze×Di ⁴) (1)

If X (i: e) be lower than 4, so then the initial stage blended to improve reduction with the pressure-losses be to be difficult to and to deposit not preferred.X (i: maximum value e) is to have no particular limits, but if surpass at 100 o'clock, owing to each static mixer shape in appearance can differ widely, thus must be noted that in the design, and also because the rerum natura of raw materials mixed can improve all pressure-losseses.Therefore, be below 100 or 100, be more preferred from below 50 or 50.

In the present invention the 6th to 15, the static mixer SM (m) that optionally is used in reaction mid-term is arranged between SM (i) and the SM (e), the X that tries to achieve equally comparably with the context in the above-mentioned formula (1) (i: m) and X (m: e) for all more than 1 or 1.

X(i∶m)＝(Zi×Dm ⁴)/(Zm×Di ⁴)

X(m∶e)＝(Zm×De ⁴)/(Ze×Dm ⁴)

Preferably, make each static mixer that constitutes actual banded SM (i) and SM (e) belong to SM (i respectively ₁), SM (i ₂) ..., SM (e ₁), SM (e ₂) ..., the proper value Zi of the J of an initial reaction stage static mixer _j, Di _jAnd belong to the proper value Ze of k static mixer of last stage reaction _k, De _kX (the i that is tried to achieve _j: e _k) be preferably more than 1 or 1.

X(i _j∶e _k)＝(Zi _j×De _k ⁴)/(Ze _k×Di _j ⁴)(1′)

In the situation that static mixer SM (m) is set if necessary in reaction mid-term same relation is arranged also again.And, be SM (m being provided with several SM (m) ₁), SM (m ₂) ... situation in, same relation is also respectively arranged.

In the present invention the 6th to 15, the value Y (i) that is tried to achieve by following formula (2) than Z (i), mixer length L (i), inside diameter D (i) with the pressure-losses of the static mixer SM (i) that is used in initial reaction stage is more than 200 or 200, more than preferable 500 or 500.Maximum value is to have no particular limits, but is generally below 2,000 or 2,000, below preferable 1,000 or 1,000.It is worth then worries the pressure-losses when high influentially, must take time and energy on inferior design in outlet that the handover machine with pump etc. is arranged at this static mixer SM (i) or SM (m) etc.On the other hand, when if Y (i) is lower than 200, then may not fully carry out the mixing of initial reaction stage, because stability is had disadvantageous effect, so with the used static mixer SM (i) of initial reaction stage then in the design of banded static mixer SM (m) and SM (e), must the more early stage mixed uniformly design of consideration.

Y(i)＝Z(i)×L(i)/D(i)(2)

Among the present invention 6～15, constitute n the static mixer (SM (r) of SM (i), SM (e) and SM (m), (r=1～n) all with the total of the Yr that tries to achieve equally (promptly, ∑ Yr=∑ Zr * Lr/Dr, (till the total scope r=1～n of ∑)) be 5,000 or 5, below 000, below preferable 2,500 or 2,500.Then worry influentially when this value Yr is high, must design when near the handover machine with pump etc. is arranged at the outlet of each static mixer, waiting with taking time and energy the pressure-losses.

Moreover in the present invention the 6th to 15, between the static mixer of each reaction period, can be provided with the handover is the machines such as pump of purpose.

In the present invention the 6th to 15, the static mixer of each reaction period or the pressure-losses that constitutes its each static mixer are its static mixer inherent numerical value than Z, and are the pressure-losses value Δ P by static mixer _mWith the pressure-losses value Δ P under the situation of same fluid flow under the same flow condition in the blank pipe with internal diameter same with it ₀Than Δ P _m/ Δ P ₀Obtain (N.H arnby/ compiles, and high bridge is fortunately taken charge of/translated, liquid mixing technology, Nikkan Kogyo Shimbun).

Therefore, also can try to achieve pressure-losses ratio for the static mixer of not knowing pressure-losses ratio now by same method.For example, the loss of the pressure-losses of Kai Nikesi (Kenics) formula static mixer is than being 7, and the pressure-losses loss of the SMX of Shi Lusha company is than being 38, and the pressure-losses loss of the SMXL of Shi Lusha company is than being 7.8, and the pressure-losses ratio of Dong Lishi static mixer is 38.

Pressure-losses ratio for static mixer used in the present invention has no particular limits, and for example is 5～300, is typically 7～40.Initial reaction stage can be used high pressure-losses ratio, and last stage reaction can use low pressure-losses ratio.

The actual person that is provided with the hybrid element in using common piped static mixer, inside diameter D is the internal diameter for the static mixer pipe arrangement of transferring real liquid.Mixer length is the length of the componentry in the static mixer.

Secondly explanation is as the initial substance of method for making resulting polyester type polymkeric substance of the present invention (C), i.e. polymerization composition.

Used cyclic ester class (B) for example is the intermolecular cyclic ester and the lactone of hydroxycarboxylic acid among the present invention.

Lactone is meant to have intramolecularly cyclic ester constructor, be in particular 6-caprolactone, α, alpha-alpha-dimethyl-beta-propiolactone, 12 (carbon) alkane lactone, beta-propiolactone, butyrolactone, valerolactone, 3-alkyl valerolactone, β, the lactone of β-dialkyl group valerolactone, hydroxyl hexahydrobenzoic acid, Isocoumarin 〉97, tonka bean camphor, Hydroxycoumarin, 2-benzo [c] furanone etc.Wherein be preferably the use 6-caprolactone.

Also can use among the present invention and the same lactams of cyclic ester class (B), also can use the mixture of cyclic ester class (B) and lactams.Lactams is meant to have intramolecularly cyclic amide constructor.Be in particular ε-Ji Neixianan, δ-Valerolactim, butyrolactam, azetidinone etc.Wherein be preferably and use ε-Ji Neixianan, butyrolactam.

Can make cyclic ester class (B) or lactams ring-opening polymerization individually, and make polyester polymer, also can with the intermolecular cyclic ester copolymerization of hydroxycarboxylic acid more than a kind or a kind.In the case, the polymerization ratio of intermolecular cyclic ester and lactone is that various variations can be arranged along with subject polymer, but the various selections of the combination by intermolecular cyclic ester and lactone can add preferable character mutually.Be particularly useful in reduction, adjust the crystallinity of the cyclic ester class after the polymerization.

The dimolecular hydroxycarboxylic acid that the intermolecular cyclic ester of hydroxycarboxylic acid is meant identical or different kind intermolecular through dehydration ring-type esterification person.Representative example is following general formula 1 represented person.

General formula 1

In the formula, R ¹, R ², R ³, R ⁴Can be identical or differently each other, each represents hydrogen atom, methyl or ethyl.

The example of hydroxycarboxylic acid is that lactic acid, hydroxyethanoic acid, ethyl hydroxyethanoic acid, dimethyl hydroxyethanoic acid, Alpha-hydroxy valeric acid, Alpha-hydroxy isovaleric acid, Alpha-hydroxy caproic acid, Alpha-hydroxy isocaproic acid, HMV, Alpha-hydroxy enanthic acid, Alpha-hydroxy are sad, Alpha-hydroxy capric acid, Alpha-hydroxy tetradecanoic acid, Alpha-hydroxy stearic acid etc.

The example of the cyclic ester of identical hydroxycarboxylic acid is a diglycolide (promptly 1,4-dioxy-hexanaphthene-2, the 5-diketone, also abbreviate glycollide as), dilactide (promptly, 1,4-dioxy-3,6-dimethyl cyclohexane-2, the 5-diketone, also abbreviate rac-Lactide as), two (ethyl glycollide), two (diethyl glycollide), and L-lactic acid or D lactic acid each is intermolecular by the L-dilactide of ring-type esterification two, D-dilactide D, two molecules of L-lactic acid be by the D of ring-type esterification, the L-dilactide, each molecule of L-lactic acid or D lactic acid is by two lactideses of MESO-dilactide of ring-type esterification etc.

The example of the cyclic ester of different hydroxycarboxylic acids is methyl glycollide, α, alpha-alpha-dimethyl glycollide, trimethylammonium glycollide etc.

Used intermolecular cyclic ester is to select according to the characteristic of subject polymer among the present invention, can be used in combination two or more.For example, in using the situation of dilactide as the multipolymer of dilactide and diglycolide, not only use L-dilactide or D-dilactide as dilactide, and make and be selected from L-dilactide, D-dilactide, D more than 2 kinds or 2 kinds, the dilactide combination diglycolide of L-dilactide, MESO-dilactide, and, can realize the plasticity or the transparency, and better resin properties such as thermotolerance from the crystalline viewpoint of resin.

As the charging process of cyclic ester class (B), if aqueous then in room temperature or more than the room temperature, if solid then heating and melting use ram pump, toothed gear pump etc. that it is transplanted on reactor till the fluid temperature.

Can in can pre-heated groove, carry out the heating of cyclic ester class (B), also can use general used heat exchanger etc.For example, (A) has in the situation of fusing point or softening temperature at the aftermentioned polymkeric substance, is preferably to be heated to this temperature or this more than temperature, and good solubility is arranged, and do not take place in the solidified situation at polymkeric substance, also can implement than the temperature of low 30 ℃ of melting point polymer.Be in particular 125～300 ℃, better 150～250 ℃.

Cyclic ester class (B) through so heating also can be used static mixer or pipe arrangement etc. in 2 places that contain initial reaction stage, adds dispersedly.

Oxygen in the cyclic ester class, moisture are to keep dry state after removing in advance, being preferably removal, use methods such as decompression, rare gas element flushing, distillation, absorption to reduce oxygen and moisture content usually.

The used polymkeric substance with hydroxyl and/or ester bond (A) is meant polymkeric substance that has hydroxyl at least or the polymkeric substance that has ester bond at least among the present invention.

Polymkeric substance with hydroxyl for example is polyvinyl alcohol, starch, Mierocrystalline cellulose, ether of cellulose.Use that to obtain near grafting easily under their situation be the polymeric polymkeric substance, it is the polymeric polymkeric substance that polyoxyalkylene ether obtains near block easily.

The polymkeric substance that has ester bond and do not have a hydroxyl for example is polyvinyl acetate (PVA), vinyl acetate/ethylene copolymer, polyacrylic ester, polyacrylic ester analog copolymer, polycarbonate etc.

The polymkeric substance that the end that does not have a hydroxyl owing to have ester bond has a carboxyl for example can enumerate polyesteramide, aliphatic polyester, present cycloaliphatic polyesters, crystalline aromatic polyester, with crystalline aromatic as the polyester elastomer of principal constituent etc.

Do not have endways in the situation that hydroxyl exists, because speed of response is very slow, so be preferably interpolation in order to make the required micro-moisture of a part of ester hydrolysis or as the additive (alcohol etc.) (it is molecular weight adjustment agent described later that this additive can use) of promotor.

Polymkeric substance with hydroxyl and ester bond for example can enumerate partial esterification cellulose ester, polyesteramide, aliphatic polyester, present cycloaliphatic polyesters, crystalline aromatic polyester with crystalline aromatic as polyester based elastomers of principal constituent etc.

Can mix two or more that uses them.Wherein preferred especially crystalline aromatic polyester.

Crystalline aromatic polyester mainly is selected from terephthalic acid by one or more, m-phthalic acid, 2, the aromatic dicarboxylic acid of 6-naphthalene dicarboxylic acids etc., and/or 4-hydroxy-benzoic acid or 6-hydroxyl-2-naphthoic acid, be selected from ethylene glycol with one or more, propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, neopentyl glycol, cyclohexanedimethanol, the hydrogenation dihydroxyphenyl propane, xylyl alcohol, Diethylene Glycol, triethylene glycol, dipropylene glycol, dibutylene glycol, gather-1, the aliphatic diol of the polyalkylene glycol of 4-butyleneglycol etc. constitutes.Also can contain 4-amido phenylformic acid as minor constituent etc.

The fusing point of crystalline aromatic polyester or softening temperature are preferably more than 180 ℃ or 180 ℃.For example can enumerate polyethylene terephthalate, polybutylene terephthalate, PEN, PBN particularly and be the polyester based elastomers that constitutes of center etc. with these.

Again, can also use as the dicarboxylic acid composition, mole fraction in whole dicarboxylic acid compositions is no more than 10 moles of % scopes, selected aliphatic dicarboxylic acid from succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, Brazilian diacid, cyclohexane dicarboxylic acid, dipolymer acid.

Those crystalline aromatic polyesters are to be difficult to be melted in cyclic ester class or solvent based, and modulation required time of homogeneous solution is long especially, must at high temperature heat the method for the application of the invention and then can be improved.

Polymkeric substance involved in the present invention (A) can use these polymkeric substance or two or more these mixture of polymers, and has no particular limits.

The weight-average molecular weight (Mw) of polymkeric substance (A) is preferably 5,000～300,000, and better weight-average molecular weight is 10,000～200,000.

Especially, surpass at 20,000 o'clock,, can find that the present invention has bigger effect because the problem that the pressure-losses rises shows more significantly in weight-average molecular weight.

The fusing point viscosity of polymkeric substance (A) is preferably 5,000～500,000 pool under reinforced mixing condition (temperature, velocity of shear etc.), be more preferred from 10,000～200,000 pool.

From the intermiscibility viewpoint, cellulose ester is preferably 43～65% esterified persons of institute's hydroxyl.

Existing amount of hydroxyl groups such as the end of crystalline aromatic polyester, carboxylic acid amount or molecular weight can influence the block of resulting multipolymer.And, ring-opening polymerization and transesterification reaction are influenced by the terminal hydroxyl amount all can, because temperature of reaction dependency separately, the terminal hydroxyl orders of magnitude etc. are approaching, thus initial reaction stage and adjust latter stage the divided ring polymerization have big influence cyclic ester concentration method or to wait the method for adjusting by catalyst type be suitable.Therefore, have no particular limits.

The present invention also can implement in the presence of polymerizing catalyst.As polymerizing catalyst is the titanium sub-group compound of titanium chloride, tetrabutyl titanate, metatitanic acid orthocarbonate, tetraethyl titanate etc.; The tin based compound of tin protochloride, tin protobromide, tin protoiodide, 2 ethyl hexanoic acid tin etc.; Zn cpds, the aluminum compound of zinc chloride, zinc acetate, Zinc Stearate, zinc oxide, zinc carbonate, zinc subcarbonate, zinc ethyl etc.; Magnesium compound; Barium compound; Zirconium compounds; Germanium compounds etc. can be used alone or in combination them, and its addition is generally 0.001～1.0% with regard to regard to the weight ratio of the total of polymkeric substance (A) and cyclic ester class (B), is more preferred from 0.01～0.1% scope.

Polymkeric substance (A) adds the not special restriction of method in the reactor.Adding temperature is near temperature of reaction, particularly in the situation of solid state polymkeric substance, be to be selected from fusing point or softening temperature to than in the high 50 ℃ temperature range of fusing point or softening temperature, more preferably be selected from the temperature of the extremely high 20 ℃ temperature range of the temperature higher 5 ℃ than fusing point than fusing point, be in particular 125～300 ℃, be preferably 180～260 ℃.

Have 1 or 2 or 2 above stir shafts as device, and use the extruder etc. of the device can heat, transfer.In order more to improve charging precision, can toothed gear pump etc. be set in the extruder outlet.Again, can after the polyreaction just of the polymkeric substance (A) that other modes obtain, keep the original state of molten state, be transplanted on reactor.

Stock polymer (A) uses normally used drying machine etc., amount of moisture under decompression or ventilation in the resin, reduce to and be at least 1,000ppm or 1, below the 000ppm, be more preferred from 100ppm or below the 100ppm, moreover if necessary, be preferably to replace to lower oxygen concn and prevent the absorption again of moisture simultaneously with rare gas elementes such as nitrogen.

Viscosity ratio under the adding mixing condition of polymkeric substance (A)/cyclic ester class (B) surpasses at 100,000 o'clock, especially surpasses at 1,000,000 o'clock, and effect of the present invention shows significantly.Usually, mix more difficultly when viscosity ratio is big, and become full-bodied tendency, be difficult to and deposit so improve mixing efficiency in fact and reduce pressure to lose because the viscosity of resulting polyester type polymkeric substance (C) also has.The viscosity ratio that adds under the mixing condition is to consider velocity of shear, temperature etc., is tried to achieve by each viscosity of initial reaction stage.

Polymkeric substance (A) and the additional proportion of cyclic ester class (B) are along with the character of the copolymerization polymkeric substance of target and different, but in the copolymerization of cyclic ester class (B) and polymkeric substance (A), the part by weight of cyclic ester class (B)/polymkeric substance (A) is generally 99/1～1/99, be preferably 5/95～75/25, be more preferred from 10/90～50/50.

Polymeric reaction temperature is different along with used raw material, is 125～200 ℃, is more preferred from 150～190 ℃ but contain in the situation of cyclic ester in cyclic ester class (B).Is 150～300 ℃ at cyclic ester in only by the situation that lactone constituted, and is more preferred from 180～250 ℃.Again, in the temperature～high 50 ℃ temperature than low 15 ℃ of the melting point of polymkeric substance (A) or softening temperature, the preferably softening temperature of polymkeric substance (A) or fusing point～high 20 ℃ temperature.Be in particular 125 ℃～300 ℃, be more preferred from 150～260 ℃.Especially, in the situation of using crystalline aromatic polyester, be 180～300 ℃, be more preferred from 225～260 ℃.

The reactivity of cyclic ester class (B) can at random be set, the polymerization velocity of cyclic ester class (B) reduced when but this reactivity was high, on the other hand owing to carry out the reaction of transesterify etc., so especially when using crystalline aromatic polyester, must be noted that the variation of fusing point reduction etc. as polymkeric substance (A).Preferable reactivity is 75～99 moles of %, better 90～97.5 moles of %.

Residence time (reaction times) is to change along with the reactivity of used raw material and ratio, temperature of reaction, target, but is generally 0.2～10 hour, better 0.5～5 hour, and especially 0.5～2 hour.

Reaction pressure maximum in the system is 2～200kg/cm ², be preferably 2～50kg/cm ², be more preferred from 2～20kg/cm ²But, when in stirring mixer (I), not having the problem of content and volatile component leakage, can keep high pressure.

In addition, in the present invention the 1st to 5, especially after passing through stirring mixer (I), before passing through static mixer, the reactivity of cyclic ester class is preferably 75 moles of % or 75 moles below the %, is more preferred from 50 moles of % or 50 moles below the %, and especially 30 moles of % or 30 moles are below the %.Owing to the inner shearing of stirring mixer (I) causes heating, detrimentally affect is arranged when reactivity is high for the resin rerum natura.

On the other hand, in the present invention the 6th to 15, especially behind the static mixer that uses by initial reaction stage, the reactivity of cyclic ester class is preferably 75 moles of % or 75 moles below the %, be more preferred from 50 moles of % or 50 moles below the %, especially 30 moles of % or 30 moles are below the %.Owing to be used in the pressure-losses of the static mixer of initial reaction stage, and make device in running, problem be arranged when reactivity is high.

Employed polymer raw among the present invention is owing to have Biodegradable or water-disintegrable, so in order to suppress the decomposition of oxygen or moisture to polymer raw, the limit makes the polymer raw of the inert gas flow drying of nitrogen etc., and the limit is supplied to stirring mixer (I) with diverse ways separately.

Among the present invention, can under not the existing of solvent, make polymkeric substance (A) and cyclic ester class (B) carry out mass polymerization, but in order to adjust the viscosity of reaction solution, also can polyreaction is not had dysgenic solvent in the presence of react.

When adding solvent, owing to can reduce the viscosity of reactive system, so can seek more uniform mixing by the reduction of shear-stress, and owing to can reduce the number of employed hybrid element in the reaction unit, can reduce and mix required flow velocity, so can reduce pressure, so can force down all withstand voltage designs of reaction unit.

In the reactive system addible solvent be not can with the solvent of polymer raw and the polymer reaction that is generated, and polymer raw and the polymkeric substance that generated had good solubility, and a solvent of recycling easily.Object lesson should use toluene, dimethylbenzene, ethylbenzene etc.

Under the steady state of successive reaction, the quantity of solvent that is added in the reactive system is with regard to regard to polymer raw 100 weight parts, preferably uses 20 weight parts or below 20 weight parts, and the high viscosity that is preferably the reaction solution by the full response phase is adjusted at 50, below 000 pool or 50,000 is moored.If quantity of solvent in this scope, then can not have big influence to speed of response, also can not reduce the molecular weight of the polymkeric substance that is generated.

But, under the unsteady state of successive reaction, when for example successive reaction began, the quantity of solvent that is added in the reactive system was used the above amount of 20 weight parts or 20 weight parts with regard to respect to regard to polymerization composition 100 weight parts that monomer and/or polymkeric substance became of polymer raw.For the polyreaction that does not cause that it is fierce, begin reaction with the solvent cut reactive system, then, the limit sees that the state limit improves the ratio and the temperature of reaction of polymerization composition slowly, with the beginning polyreaction.

The interpolation of solvent can add the stage at raw material period, or the mixing ability of static mixer is splendid, because also easily full-bodied solution of uniform mixing and solvent, so in the reaction in the significant polymerization stage of thermal value, can be cooled to purpose and be added in the reactive system.

In addition, when the reaction later stage causes the reaction solution viscosity pole to increase owing to polymer quantizes to generate polymkeric substance, solvent can be added in the reactive system.And, when in the reaction solvent being added to the situation in the reactive system, can be added in the reactive system being dissolved with the monomer of polymer raw and/or the solvent of polymkeric substance, also other additive such as molecular weight can be adjusted agent, plasticizer, antioxidant etc. and be dissolved in the solvent and add in the reactive system.

The internal pressure of the polymerization reaction system when being added with solvent is different along with used polymer raw, but is generally 2～15kg/cm ², common 10kg/cm ²Or 10kg/cm ²Below, be generally 0.2～10 hour in the residence time (reaction times) of polymerization reaction system.

, because not having composition when axle envelope part etc. is leaked out, the device shape also can under the pressure more than above-mentioned or above-mentioned, operate in tower stirring mixer part with stir shaft.

Among the present invention, the reactivity of monomer (B) is preferably 75 moles of % or 75 moles more than the %, and the unreacted monomer beyond it is to be waited by the device that takes off low boiling point component to reclaim, once again as raw material.The starting monomer that is reclaimed can be sent continuously back to raw material and add groove, temporarily be stored in the dashpot, mix in groove with starting monomer and be used for reaction then.

Even reactivity is that 75 moles of % or 75 moles are more than the %, remaining monomer or oligopolymer still have reactivity, can influence stability in storage when remaining in the goods polymkeric substance, from security and the foul smell aspect to the people, being preferably does not have remaining monomer, oligopolymer, and wishes to remove them.

Therefore, in the present invention, in order to merge the recycling of unreacted monomer, and seek to improve the rerum natura of polymkeric substance, so in continuous reaction apparatus behind the polymeric polyester type polymkeric substance, in the device that takes off low boiling point component that is connected with continuous reaction apparatus, the residual monomer in the polymkeric substance that Separation and Recovery generated, oligopolymer or solvent.Institute's recovered solvent and the monomer separation that is reclaimed are stored in the storage tank, re-use as required.

As the not special restriction of the method for taking off low boiling point component, can be the generation polymkeric substance after heated polymerizable finishes, keeping under decompression state or the gas communication low boiling point component being rejected to method outside the system from the gas-bearing formation part.The concrete method of taking off low boiling point component be with preheater that reaction unit is connected in, the generation polymkeric substance after finishing for polyreaction at first gives polymkeric substance flowability fully, and gives low-boiling-point substance vaporization heat, dissolves with heating.At this moment, also can use setting type multi tube heat exchanger as heat exchanger or possess the static mixer of heat exchanger.

Be to use simple flash drum or the vertical low-boiling-point substance device that takes off as the device that takes off low-boiling-point substance, take off low-boiling-point substance with a stage, remaining monomer and/or solvent are taken off low boiling.More suitable ground is to take off low-boiling-point substance by the combination of taking off the low groove that boils of two-stage.That is, in the low device that boils of taking off of fs, take off low boiling in vacuum tightness 20～150mmHg, in the low device that boils of taking off of subordinate phase, in higher vacuum tightness, for example 0.1～20mmHg takes off low boiling, with the unreacted monomer of Separation and Recovery.Vacuum unit is usually spendable.For example, can use Flash Type to take off the low device that boils in the fs, can use film type to take off the low device that boils in the subordinate phase.

After taking off low boiling; take out polymkeric substance by toothed gear pump from taking off the low bottom of device of boiling, also can make its pillization, or by the exhaust extruder; extruded polymer is made several linear polymers of the bore of diameter 0.3～3mm, and be supplied to continuously to take off and low boil device to take off low-boiling-point substance.

Taking off the low polymkeric substance that boils when finishing is to be taken out by toothed gear pump, also its former state pillization optionally can be made it pillization by behind the mixed additives such as extrusion machine, static mixer.

Unreacted monomer is again via condenser cooling, reclaims and is supplied to reaction with new raw material once again.

The unreacted monomer that is reclaimed after successive reaction reaches steady state, is being circulated to raw material adding groove continuously, and is being used in reaction continuously.In addition, the solvent of institute's Separation and Recovery is stored in the solvent trough after cooling off recovery through condenser, is re-used as required.

In order to prevent that stock polymer (A) from remaining in the polyester polymer (C) that is generated, the adding of starting monomer thing (B) is than preferably more than stock polymer (A), and is recyclable, re-use unreacted monomer (B).By using these devices that takes off low-boiling-point substance continuously, can make monomer content remaining in the polyester based polymer (C) at 1 weight % or below the 1 weight %.

Depend on the weight-average molecular weight of stock polymer and the constituent ratio of raw material, the weight-average molecular weight of resulting polymkeric substance (C) is 5,000～500,000, is preferably 10,000～300,000.Especially, weight-average molecular weight is if surpass at 20,000 o'clock, because the problem that the pressure-losses rises is more remarkable, so effect of the present invention is more obvious.Melt viscosity under the operational condition of polymkeric substance (C) (temperature, velocity of shear) is 5,000～500, and 000 pool is preferably 10,000～200,000 pool.

And in the present invention, decide on purpose, adjust agent (chain-transfer agent), have and be selected from carboxyl, hydroxyl and other ester forming base compound more than 3 by the molecular weight that makes water, lactic acid, hydroxyethanoic acid and other alcohols or carboxylic acid etc., also can obtain low-molecular-weight polymkeric substance as the functional group.

Moreover, can add antioxidant as general other polymeric additive that uses, UV light absorber, softening agent etc. among the present invention, have no particular limits, they can be added in the reactive system with the form that is dissolved in the solvent in the reaction.

In addition, between successive reaction,, also can add isocyanates, acid anhydrides, epoxy compounds etc. more in addition among the present invention, so that the improvement polymer properties except above-mentioned copolymerizable composition.

The the 1st to 5 of the present invention is (to close in the reaction unit that machine and static mixer constitute to stir being mixed by the tower with the stir shaft more than 2 or 2, in addition, the the 6th to 15 of the present invention is in the continuous reaction apparatus that the static mixer series combination by two or more forms, in under the existence of solvent or under not existing, in reactant fully not with atmosphere in oxygen, under the moisture state of contact, cyclic ester class without interruption (B) and polymkeric substance (A), being preferably and making cyclic ester class (B) is reaction continuously more than 75% or 75% with the one way reactivity, and melt viscosity 500,000 pool or 500, following and the weight-average molecular weight 10 of 000 pool, the method for continuous production of the polyester polymer more than 000 or 10,000.

The present invention is particularly suitable for making block, the graft copolymer that is made of two or more component of polymer, the polymkeric substance of manufacturing can use as solubilizing agent, tackiness agent, elastomerics, shape memory resin, various shaping resin, and is used for multiple use.

Moreover the heated condition more than the fusing point of arbitrary raw material makes melting mixing in advance, or uses solvent etc., and after forming homogeneous solution, and the method that makes it to react is that polymkeric substance (A) is mixed with cyclic ester class (B).Since need for a long time and usually must be at heated condition, not only unfavorable economically, and the carrying out of the reaction in can not preventing from fully to dissolve, and become the unsettled reason of goods proterties.Even be suitable for continuation method, the degree of carrying out of the reaction in order will dissolve the time is maintained fixed and works hard, but can enlarge the residence time distribution with the long-time dissolving step of batch-type stirring-type reactive tank, so be unfavorable.

Embodiment

Embodiment

Below embodiment is shown and comparative example specifies the present invention, but the present invention is not limited by it.

Unless special record is arranged, otherwise % and part are all represented weight % and weight part.

Employed analysis, physical property measurement condition are as shown below.

(1) fusing point

With differential scanning calorimetry determinator (DSC),, as each fusing point, try to achieve fusing point and disperse with fusion peak temperature (Tpm), fusion beginning temperature (Tim) and fusion end temp (Tem) according to JIS K 7121.With regard to the resin after each polymerization of being put down in writing in embodiment and the comparative example, all do not observe low melting point peak from the block part of polycaprolactone homopolymer or polycaprolactone.

(2) unreacted lactone amount

The gas chromatograph GC-14A that uses Shimadzu Seisakusho Ltd. to make uses the glass tubing string through internal diameter 3.2mm, the length 2.1m of 10% of PEG 20M/excellent Buddhist nun's baud HPS institute filling.Correctly measure 0.5 gram sample and 0.1 gram as the phenyl ether of internal standard material, be dissolved in 20 and restrain in HFIP (hexafluoroisopropanol).Under 180 ℃ of steady temperatures, measure nitrogen as carrier, resulting result calculates by the internal standard method, and tries to achieve unreacted lactone amount (weight %).

(3) weight-average molecular weight

By GPC, convert and try to achieve with standard P MMA.Tubing string Shodex GPC HFIP-800P, HFIP-805P, HFIP-804P, HFIP-803P that the measurement of GPC is to use Showa Denko K. K to make, the RID-6A that analyzer uses Shimadzu Seisakusho Ltd. to make, elutriant uses HFIP, carries out with 50 ℃ of tubing string temperature, flow velocity 1.0 ml/min.

(4) raw material

Polymkeric substance (A): use polybutylene terephthalate (poly-plastic cement company (Port リ プ ラ ス チ Star Network ス society) system, 240 ℃, 10 seconds melt viscosity is 25,000 pools) in hopper dryer (using the air of 40 ℃ of dew points), be dried to below the moisture concentration 40ppm.

Cyclic ester class (B): 6-caprolactone.

(5) remaining monomer concentration

Beginning is to through the time point of the scheduled time behind the 6-caprolactone of supply specified amount, and per 30 minutes 5 times, resulting polyester type polymkeric substance is taken a sample, as remaining monomer concentration, show maximum value and minimum value with the mean value of separately monomer concentration.

(comparative example 1)

(internal diameter 32mm is L/D=42) as reactor for the engagement type extruder TEX30 of 2 equidirectional rotations that use JSW makes.

Using the screw feeder, with per hour 4.8 kilograms above-mentioned polybutylene terephthalate is supplied to above-mentioned reactor.Then, use ram pump, with per hour 3.2 kilograms with 6-caprolactone by the venting port supply.

With regard to the screw arrangement of reactor, under the polybutylene terephthalate supplying opening water screw, the right astern is the kneading disk oar, then 6-caprolactone is a water screw near supplying with venting port, after also disposing the kneading disk oar thereafter, disposes water screw at last.

Heating temperature is 190 ℃, 220 ℃ by beginning near the supplying opening place, and remaining barrel is all 230 ℃, and the screw rod rotation number is 100rpm, and reacts.Average retention time (adds painted mensuration by carbon black.Below same) be 7 minutes.Near the die head resin temperature is to rise to till 253 ℃.

Secondly, resulting polyester type polymkeric substance is flowed out pillization after water-cooled with the strand shape by die head.Pill is carried out the mensuration of various proterties, analysis, characteristic.The results are shown in the table 1.(supply with the time point that begins behind the 6-caprolactone through after 1 hour, carry out the sampling that remaining monomer is measured usefulness from predetermined amount.

(comparative example 2)

Except the screw rod rotation number is 50rpm, Heating temperature is 190 ℃, 230 ℃ by beginning near the supplying opening, similarly carries out with comparative example 1 in addition.Residence time is 10 minutes.Near the die head resin temperature is 238 ℃.Measurement result is shown in Table 1.

(comparative example 3)

(internal diameter 32mm L/D=28) as beyond the reactor, similarly carries out with comparative example 2 except the engagement type extruder TEX30 that uses 2 equidirectional rotations that JSW makes.

Residence time is 2.5 minutes.Near the die head resin temperature is 230 ℃.The reactivity of resulting polyester type polymkeric substance is low, can not take out with the strand shape, and measurement result is shown in Table 1.

(comparative example 4)

(internal diameter 501mm is L/D=9) as reactor for the KRC kneader S2 of this ironworker of use chestnut manufacturing.Use 1 extruder and the toothed gear pump of diameter 30mm, when resin temperature is 240 ℃, above-mentioned polybutylene terephthalate is supplied continuously by the raw material supplying mouth of above-mentioned reactor.On the other hand,, make the liquid temperature become 210 ℃, supply with by the venting port of above-mentioned reactor by the ram pump liquor charging and by the heat exchanger heats 6-caprolactone.Raw material supplying speed is 600 gram polybutylene terephthalates per hour, 400 gram 6-caprolactones per hour, catalyzer in being contained in polybutylene terephthalate not use.

With regard to screw arrangement, be water screw near raw material supplying mouth and the venting port, other is all platypelloid type kneading disk oar.Heating temperature is all 230 ℃, with the screw rod rotation number is to supply with continuously under the condition of 50rpm to carry out addition reaction.Average retention time is 40 minutes.Near the die head resin temperature is 235 ℃.Secondly, polymkeric substance is discharged with the strand shape by die head, after water cooling, cut, and obtain polyester polymer.Measurement result is shown in table 1.Time point after beginning through 3 hours after supplying with 6-caprolactone by predetermined amount carries out the sampling that remaining monomer is measured usefulness.

(comparative example 5)

Use Hitachi's system grid blade polymerization machine (6 liters of internal volumes) as reactor.Use 1 extruder and the toothed gear pump of diameter 30mm, when resin temperature is 240 ℃, above-mentioned polybutylene terephthalate is supplied continuously by the raw material supplying mouth.On the other hand,, make the liquid temperature become 210 ℃ by the ram pump liquor charging and by the heat exchanger heats 6-caprolactone, should by the raw material supplying confession.Raw material supplying speed is 5.4 kilograms of polybutylene terephthalates per hour, 3.6 kilograms of 6-caprolactones per hour, and catalyzer does not use in being contained in polybutylene terephthalate.

Heating temperature is all 230 ℃, carries out addition reaction to stir to supply with continuously under the condition that rotation number is 10rpm.Average retention time is 45 minutes.Near the die head resin temperature is stabilized in 230 ℃～231 ℃.Secondly, polymkeric substance is discharged with the strand shape by die head, after water-cooled, cut, and obtain polyester polymer.Measurement result is shown in Table 1.Time point being supplied with by predetermined amount after 6-caprolactone begins through 3 hours later on carries out the sampling that remaining monomer is measured usefulness.

(embodiment 1)

Use is connected in the system static mixer SMX (3 inches of internal diameters, length 1200mm) of Shi Lusha company (ス Le ザ one society) of the outlet of the extruder TEX30 identical with comparative example 1, as reactor.Use the screw feeder, with per hour 4.8 kilograms supply with above-mentioned polybutylene terephthalates.Use ram pump, with 3.2 kilograms of supplies 6-caprolactone thereafter per hour.

With regard to screw arrangement, be water screw under the polybutylene terephthalate supplying opening, the right astern is the kneading disk oar, then 6-caprolactone is a water screw near supplying with venting port, dispose the kneading disk oar more thereafter after, dispose water screw at last.Heating temperature is 190 ℃, 220 ℃ by beginning near the supplying opening place, and remaining barrel is all 230 ℃, and the screw rod rotation number is 50rpm, and carries out addition reaction.In addition, the Heating temperature of static mixer part is 230 ℃.The all average retention times of reactor are 43 minutes.Near the die head resin temperature is stabilized in 230 ℃～231 ℃.Secondly, polymkeric substance is discharged with the strand shape by die head, after water-cooled, cut, and obtain polyester polymer.Measurement result is shown in Table 1.Time point being supplied with by predetermined amount after 6-caprolactone begins through 3 hours later on carries out the sampling that remaining monomer is measured usefulness.

(embodiment 2)

Use on the kneader S2 identical as reactor, connect the static mixer SMX identical with embodiment 1 via toothed gear pump with comparative example 4.Use 1 extruder and the toothed gear pump of diameter 30mm, when resin temperature is 240 ℃, above-mentioned polybutylene terephthalate is supplied continuously by the supplying opening of kneader S2.On the other hand, by the ram pump liquor charging and by the heat exchanger heats 6-caprolactone, make the liquid temperature become 210 ℃.Venting port supply by kneader S2.Raw material supplying speed is 4.8 kilograms of polybutylene terephthalates per hour, 3.2 kilograms of 6-caprolactones per hour, and catalyzer does not use in being contained in polybutylene terephthalate.

With regard to screw arrangement, be water screw near raw material supplying mouth and the venting port, other is all has the spiral type kneading disk oar of carrying function.Heating temperature is all 230 ℃, carries out addition reaction to stir to supply with continuously under the condition that rotation number is 50rpm.The all average retention times of reactor are 45 minutes.Near the die head resin temperature is stabilized in 230～231 ℃.Secondly, polymkeric substance is discharged with the strand shape by die head, after water cooling, cut, and obtain polyester polymer.Measurement result is shown in Table 1.Time point being supplied with by predetermined amount after 6-caprolactone begins through 3 hours later on carries out the sampling that remaining monomer is measured usefulness.

Table 1

	Remaining monomer concentration (wt%)			Molecular weight (* 1000)		Fusing point Tpm (℃)	Fusing point dispersion Tem-Tim (℃)
								Mean value	Minimum value	Maximum value	Mn	Mw
	Embodiment 1	2.0	1.9	2.1	53								112	206	19
Embodiment 2						1.9	1.9	2.0	54	114	205	20
	Comparative example 1	8.8	8.0	9.9	42								105	215	18
Comparative example 2						7.2	6.5	7.7	45	109	211	22
	Comparative example 3	30.0	-	-	-								-	221	-
Comparative example 4						2.4	2.1	2.7	39	94	206	25
	Comparative example 5	3.3	3.0	3.9	39								110	204	28

(embodiment 3)

The static mixer of initial reaction stage is Shi Lusha corporate system SMX (pressure-losses is than 38), 1/2 inch of internal diameter (1.27 centimeters), length 68cm (using the 37cm and the 31cm unit of series combination), the static mixer of last stage reaction is Kai Nikesi (ケ ニ Star Network ス) formula static mixer (pressure-losses is than 7), 3/4 inch of internal diameter (1.91cm), the length 100cm 50cm unit of 2 series combination (use) links their series connection and as continuous polymerization unit.

(initial reaction stage: be 16.9 last stage reaction), Y (initial reaction stage) is 1,600, and all the Y aggregate value of static mixers is 1,930 to use the X that their actual inner diameter calculates.Represent X (initial reaction stage: last stage reaction), represent Y (initial reaction stage) with X in the following table 2 with Y.

Will be in hopper dryer (using the air of 40 ℃ of dew points) as polybutylene terephthalate (the poly-plastic cement corporate system of polymkeric substance (A), 240 ℃, 10/ second melt viscosity is 25,000 pool) after being dried to below the moisture concentration 40ppm, use 1 extruder and the toothed gear pump of diameter 30mm, when resin temperature is 240 ℃, the static mixer at supply response initial stage continuously.

On the other hand, use the 6-caprolactone of ram pump conveying as cyclic ester class (B), by heat exchanger heats liquid temperature to 210, the static mixer of giving initial reaction stage without interruption.

With regard to the adding ratio of raw material, polybutylene terephthalate is 300 grams per hour, and 6-caprolactone is 200 grams per hour, and catalyzer does not have use in being contained in poly-terephthalic acid fourth two phthaleins.Under 230 ℃ of temperature of reaction, carry out mass polymerization continuously.Near the resin temperature of die head that is arranged at the outlet of continuous polymerization unit is to be stabilized in 230～231 ℃.

Secondly, resulting polyester type polymkeric substance is discharged pillization after water-cooled with the strand shape by die head.Pill is carried out the mensuration of various proterties, analysis, rerum natura.The results are shown in the table 3.

Moreover, initial reaction stage begins with 1/10 of predetermined amount with the feed rate with 6-caprolactone, after then 6-caprolactone being adjusted to predetermined amount, make polybutylene terephthalate meet predetermined amount again, after making polybutylene terephthalate meet predetermined amount, a little while, the polymkeric substance of being discharged by die head can cut into the strand shape, remaining monomer concentration in the analyzing polymers of limit afterwards, its time till stable in error 10% scope is confirmed that as stabilizing take remaining monomer concentration is stable with 2.0 weight % after 1.3 hours.Begin later on to count from the polybutylene terephthalate of supplying with predetermined amount, carried out 5 sub-samplings in per 30 minutes, as remaining concentration, represent minimum and maximum value with the mean value of separately monomer concentration through the time after 3 hours.

(embodiment 4～12, comparative example 6～7)

Except respectively the static mixer shown in the table 2 being used for initial reaction stage, reaction mid-term and last stage reaction, carry out polymerization in addition similarly to Example 3, carry out the various mensuration of resulting polymkeric substance.The results are shown in the table 3.

The combination of the static mixer of each reaction period is to adjust volume in the total mode about equally of the residence time of each reaction period.The length of the static mixer of each reaction period of being put down in writing in the table 2 is identical with embodiment 3, shows the combined length of the static mixer that constitutes.

Moreover, in comparative example 7, behind the polybutylene terephthalate of setting predetermined amount,, the pressure-losses has to end running owing to rising slowly.

(comparative example 8)

(internal diameter 32mm L/D=42) replaces static mixer, as reactor to the engagement type extruder TEX30 of 2 equidirectional rotations that use JSW makes.

After the polybutylene terephthalate drying, use the screw feeder with per hour 4.8 kilograms of supplies.Use ram pump then, with per hour 3.2 kilograms supply with 6-caprolactone by venting port.

With regard to screw arrangement, polybutylene terephthalate supplying opening right astern is the kneading disk oar, and then 6-caprolactone is a water screw near supplying with venting port, and its rear disposes the kneading disk oar again, disposes water screw at last.

Heating temperature is 190 ℃, 220 ℃ by beginning near the supplying opening place, and remaining barrel is all 230 ℃, and the screw rod rotation number is 100rpm, and carries out addition reaction.Adding the painted average retention time that observes by carbon black is 7 minutes.Near the die head resin temperature is to rise to till 253 ℃.Secondly, resulting polyester type polymkeric substance is discharged pillization after water-cooled with the strand shape by die head.The results are shown in the table 3.

After supplying with the 6-caprolactone of predetermined amount, when analyzing remaining monomer concentration its time till stable in error 10% scope is confirmed that as stabilizing take remaining monomer concentration is stable with 8.8 weight % after 0.2 hour.

Begin later on to count from the 6-caprolactone of supplying with predetermined amount, carried out 5 sub-samplings in per 30 minutes, as monomer concentration, represent minimum and maximum value with the mean value of separately monomer concentration through the time after 1 hour.

(comparative example 9)

Except making the screw rod rotation number is 50rpm, and Heating temperature is similarly carried out with comparative example 8 by begin to be 190 ℃, 230 ℃ near the supplying opening place beyond.Residence time is 10 minutes, and near the resin temperature the die head is 238 ℃.The results are shown in the table 3.

Table 2

	Initial reaction stage		React mid-term		Last stage reaction		The X value	The Y value	The total of Y
										Kind	Length (cm)	Kind	Length (cm)	Kind	Length (cm)
	Embodiment 3	A	68	-	-	B										100	16.9	1600	1930
Embodiment 4							A	37	C	30	B	100	16.9	870	1330
	Embodiment 5	A	31	C	30	B										100	16.9	730	1190
Embodiment 6							A	19	C	30	B	100	16.9	450	910
	Embodiment 7	A	13	C	45	B										100	16.9	310	830
Embodiment 8							A	7	C	45	B	100	16.9	170	690
	Embodiment 9	A	68	C	30	D										50	8.3	1600	2430
Embodiment 10							A	68	-	-	E	100	14.1	1600	1980
	Embodiment 11	F	50	C	30	B										100	8.1	280	730
Embodiment 12							F	25	C	45	B	100	8.1	140	660
	Comparative example 6	C	60	-	-	B										100	3.1	260	590
Comparative example 7							A	68	-	-	G	93	2.6	1600	3330

The kind of static mixer

A:SMX, 1/2 inch diameter

B: Kai Nikesishi, 3/4 inch diameter

C: Kai Nikesishi, 1/2 inch diameter

D:SMX, 1 inch diameter

E:SMXL, 3/4 inch diameter

F: Kai Nikesishi, 3/8 inch diameter

G:SMX, 3/4 inch diameter

Table 3

	Stabilizing take (Hr)	Remaining depth-averaged value (wt%)	Remaining concentration minimum value (wt%)	Remaining concentration maximum value (wt%)	Mn (×1000)	Mw (×1000)	Fusing point Tpm (℃)	Fusing point dispersion Tem-Tim (℃)
									Embodiment 3	1.3	2.0	1.9	2.1	53	112	206	19
Embodiment 4	1.2	1.9	1.9	2.0	54	114	205	20
									Embodiment 5	1.3	2.0	1.9	2.2	53	112	206	19
Embodiment 6	1.4	2.1	2.0	2.2	54	113	206	20
									Embodiment 7	1.5	2.2	1.8	2.4	53	111	206	20
Embodiment 8	1.6	2.4	2.2	2.7	51	112	207	20
									Embodiment 9	1.3	2.0	1.9	2.1	58	115	206	19
Embodiment 10	1.3	2.1	1.9	2.2	53	111	206	20
									Embodiment 11	1.5	2.4	2.1	2.6	51	113	206	21
Embodiment 12	1.7	2.5	2.2	2.8	51	112	206	22
									Comparative example 6	2.2	3.5	2.9	4.3	49	113	207	24
Comparative example 7	-	-	-	-	-	-	-	-
									Comparative example 8	0.2	8.8	8.0	9.9	42	105	215	18
Comparative example 9	0.4	7.2	6.5	7.7	45	109	211	22

In comparative example 7,, the pressure-losses shuts down owing to rising.

Utilize possibility on the industry

According to the present invention, have the polymer (A) of hydroxyl and/or ester bond and cyclic ester class (B) more than a kind or a kind when making high molecular weight polyesters type polymer in continuous ring-opening polymerisation, can solve since the high viscosity of reactant cause be difficult to evenly mix and be difficult to heat extraction, and the rising that solves the pressure loss, can make continuously polyester polymer stable, fine quality.

Claims (10)

1. the process for continuously producing of a polyester polymer, this method for making is in the continuous reaction apparatus with static mixer, supply with continuously and have the polymkeric substance (A) of hydroxyl and/or ester bond and the cyclic ester class (B) more than a kind or a kind, make polymkeric substance (A) and cyclic ester class (B) carry out ring-opening polymerization and obtain the method for multipolymer (C), it is characterized in that, continuous reaction apparatus comprises the static mixer (SM (i)) that initial reaction stage is used at least, the static mixer (SM (e)) that uses with the last stage reaction different with SM (i) with SM (i) series combination and kind constitutes, and the value X (i: be more than 4 or 4 e) that is tried to achieve via following formula (1) than Zi and Ze and each inside diameter D i and De from each pressure-losses of SM (i) and SM (e)

X(i∶e)＝(Zi×De ⁴)/(Ze×Di ⁴) (1)。

2. according to the described process for continuously producing of claim 1, X (i: be more than 10 or 10 e) wherein.

3. according to the described process for continuously producing of claim 1, wherein the value Y (i) that is tried to achieve from following formula (2) than Z (i) and mixer length L (i) and inside diameter D (i) by the pressure-losses of SM (i) is 200～2,000,

Y(i)＝Z(i)×L(i)/D(i) (2)。

4. according to the described process for continuously producing of claim 3, wherein Y (i) is 500～1,000.

5. according to each described process for continuously producing in the claim 1～4, wherein between SM (i) and SM (e), be provided with as required and be used in the reaction static mixer (SM (m)) in mid-term.

6. according to each described process for continuously producing in the claim 1～4, wherein among SM (i), the SM (m) that is provided with as required and the SM (e) one or more or constituted by several static mixers.

7. according to each described process for continuously producing in the claim 1～4, this method for making is the total for total n static mixer SM (r) and the Yr that formula (2) is tried to achieve equally of SM (m) that constitutes SM (i), setting as required and SM (e), promptly, ∑ Yr=∑ Zr * Lr/Dr is the method below 5,000 or 5,000, about described static mixer SM (r), r=1～n, about the total ∑ Yr of described Yr, the total scope r=1～n of ∑.

8. according to each described process for continuously producing in the claim 1～4, wherein polymkeric substance (A) is a crystalline aromatic polyester.

9. according to each described process for continuously producing in the claim 1～4, wherein cyclic ester class (B) is a lactone.

10. according to the described process for continuously producing of claim 9, it is characterized in that lactone is a 6-caprolactone.