CN100444947C - Lactide analog monomer continuous polymerization device and process - Google Patents
Lactide analog monomer continuous polymerization device and process Download PDFInfo
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- CN100444947C CN100444947C CNB2005100771749A CN200510077174A CN100444947C CN 100444947 C CN100444947 C CN 100444947C CN B2005100771749 A CNB2005100771749 A CN B2005100771749A CN 200510077174 A CN200510077174 A CN 200510077174A CN 100444947 C CN100444947 C CN 100444947C
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Abstract
The present invention relates to a device for the continuous polymerization of lactide monomers, which comprises a tubular polymerization reactor, a metering pump and a melting device which are orderly connected in series, wherein the tubular polymerization reactor is formed by connecting a plurality of tubular static mixers with gradually increased diameters in series, and the metering pump and the melting device are orderly connected to the minor diameter end of the tubular polymerization reactor in series. The present invention also relates to a technology for the continuous polymerization of lactide monomers, and the technical method comprises: the polymerization device is used for firstly adding materials into the melting device of the polymerization device in certain proportioning for melt and even mixture, and then the materials are filled into the minor diameter end of the tubular polymerization reactor in a certain speed rate by the metering pump so as to cause the materials to orderly pass through the static mixers with the gradual increased diameters, which are connected in series; after the materials react for some time, a polymer is extruded from the major diameter end of the polymerization reactor. The continuous polymerization device and the technology of the present invention have the advantages of high monomer conversion rate and good controllability of polymerization reaction and can largely enhance the quality and the yield of polymerization reaction products.
Description
Technical field
The present invention relates to a kind of device and technology of lactide analog monomer continuous polymerization, relate in particular to the device and the technology of a kind of poly-glycolide, polylactide and copolymer continuous polymerization thereof.
Background technology
Poly-glycolide, polylactide and copolymer thereof not only have characteristics such as good mechanical performance, easy processing, and have excellent biological compatibility and biodegradability, and catabolite is nontoxic to human body, nothing is put aside, can be absorbed by tissue.Now be widely used in fields such as suture for surgery, bone fracture internal fixation material, slow releasing carrier of medication, at aspects such as environmentally conscious materials, organizational projects good prospects for application arranged also in addition.
The preparation of this base polymer has two kinds of approach at present, and the one, be the direct polycondensation method of raw material with glycolic, lactic acid, the method polymer molecular weight is on the low side, and range of application is very limited; The 2nd, lactic acid, glycolic are made lactide earlier, after carry out the body ring-opening polymerisation and obtain the method for heavy polymer, it is the most effective preparation approach that widely adopts at present.
The method that the body ring-opening polymerisation of lactide is implemented is based on batchwise polymerization, as patent US3839297, US5041529, US3442871 etc. finish polymerization in the enclosed system relatively with raw material, and the state of polymer can be a solid phase in the polymerization process, also can be to finish under the molten condition, though this method can realize production in batches, there are shortcomings such as the controllability of polymer homogeneity, reappearance, polymerization is relatively poor, the productive rate of polymer is also lower.
Continuous polymerization just can overcome the shortcoming of batchwise polymerization, but the research of relevant this respect is less.
German patent DE 3936188A1 has reported the method for producing polyactide with double-screw reactor continuously, after monomer and initator mixed, under blanket of nitrogen, directly add double-screw reactor, just can obtain the product of polyactide after reaction a period of time, this method have the reaction time short, output big, polymerisation is easy to advantages such as control, but have also that polymerization reaction time lacks that monomer conversion is lower, in the polymerization process because of the excessive polymer of shearing force shortcoming such as may degrade.
Application number is the continuous producing method that 96117710.1 Chinese patent discloses a kind of raw-silastic continuously, polymer reactor in this method is connected in series 2 to 3 motionless mixers that diameter increases gradually, constitute polyplant by this polymer reactor and preheater series connection again, during use, each material is entered the preheater preheating after mixed in proportion, enter polymer reactor then and stopped 0.5 to 2 hours, can obtain the HMW raw-silastic continuously.The polymer reactor that the motionless mixer that the present invention owing to adopted is increased gradually by diameter is connected in series, production capacity is big, power consumption is low, equipment is simple, investment is little.But still there is following problem:
1, this invention only is the technological design at polysiloxane, so some processes, technological parameter of being given in the invention etc. can not be used in the continuous polymerization of poly-glycolide, polylactide and copolymer thereof certainly.
2, this invention realize an important prerequisite of its effect be to guarantee material the pressure of each section motionless mixer fall all in a reasonable range and the reaction temperature that will control each section all in a zone of reasonableness, and this invention does not provide effective control device, and the controllability of polymerisation is not high.
The present invention will select suitable technological parameter, process and control device at the characteristics of poly-glycolide, polylactide and copolymer thereof, guarantee polymerisation efficiently finishing in static mixer.
Summary of the invention
The object of the present invention is to provide the device and the process of continuous polymerizations such as a kind of poly-glycolide, polylactide and copolymer thereof, this device and process can make lactide analog monomer conversion ratio height, polymerisation controllability good, significantly improve polymeric reaction product quality and yield.
For solving the problems of the technologies described above, the process of lactide analog monomer continuous polymerization of the present invention is: the tubular static mixer that is increased gradually by a plurality of diameters tubular polymerization reactor that is in series is connected in series a measuring pump and a melter in succession in its smaller diameter end again; Constitute the continuous polymerization unit of lactide analog monomer; Material is added melter with certain proportioning, fusion also mixes the back enters tubular polymerization reactor by measuring pump with certain speed smaller diameter end, and successively through each static mixer that is serially connected and diameter increases gradually, after the reaction of a period of time, polymer is extruded by the larger diameter end of tubular polymerization reactor.
Because produce a large amount of polymerization reaction heats in the polymerization process of poly-glycolide, polylactide and copolymer thereof, and fluid viscosity height (the polymerization later stage surpasses 1,000,000 centipoises), heat transfer rate is slow, often with the hot-spot phenomenon, product quality is worsened.Adopt static mixing reactor, utilize its inner mixed cell element, heat of polymerization can pass quickly, each component of reaction also can rapid mixing, dispersion, each component and fluid temperature (F.T.) are evenly distributed in the pipe, fluid reduces the unusual delay of fluid near plug flow simultaneously, can increase substantially polymeric reaction product quality and yield.
As the further improvement of process of the present invention, described static mixing reactor can all adopt the mixed cell of patterns such as SV, SK, SMX or in conjunction with the mixed cell that adopts these several patterns, its series connection number is 2-8;
As the further improvement of process of the present invention, the melt temperature of described melter is higher than the fusing point of monomer, and its excursion is between 80 ℃～180 ℃;
As the further improvement of process of the present invention, the reaction temperature of described polymer reactor raises piecemeal, and its excursion is between 120 ℃～280 ℃, and polymerization reaction time is between 0.5 hour～4 hours; As the further improvement of this method, the outer surface of described each static mixer all has the reaction temperature in the heater control polymer reactor.
Further improvement as process of the present invention, add a kind of initator in the described polymerisation, this initator can be wherein any of proton acid type, halide type, anionic, organo-aluminum compound, pink salt class, rare earth compound, and the mole proportioning of itself and raw material is 0.1%～0.0001%.
The preferred pink salt class of initator.
The present invention also provides a kind of process unit, and it comprises tubular polymerization reactor, measuring pump and melter, and the three is serially connected successively; Wherein tubular polymerization reactor is in series by the tubular static mixer that a plurality of diameters increase gradually, and measuring pump and melter successive bursts are connected on the smaller diameter end at tubular polymerization reactor.
As the further improvement of process unit of the present invention, described static mixing reactor can all adopt the mixed cell of patterns such as SV, SK, SMX or the mixed cell that these several patterns are adopted in combination; Its series connection number is 2-8; The parameter of its static mixing reactor also can further be optimized for: the barrel diameter scope is between 10～100mm; The scope of cylindrical shell length is between 2～10 meters.
Further improvement as process unit of the present invention, the outer surface of described each static mixer all has heater, these heaters are formed a jacket heating system: this heating system is divided into 4～16 thermals treatment zone, and the temperature of each thermal treatment zone is controlled by temperature control instrument respectively.
The setting of heating system and control instrument is controlled in the best range of reaction temperature reaction temperature of static mixing reactor.
Its heating system has several optimal ways: directly electric jacket is set or establishes the electrical heating cover again or be provided with a chuck at the outer surface of tubular reactor after the tubular reactor outer surface is established the layer of aluminum cover at the tubular reactor outer surface, conduction oil and electrically heated rod are set in the chuck again.
As the further improvement of process unit of the present invention, the larger diameter end of described tubular polymerization reactor is provided with a gear pump, by this gear pump polymer is evenly extruded from the larger diameter end of tubular polymerization reactor.
Melter in the process unit of the present invention can be the container of stirred autoclave and other thawings.
Of the present invention this overlaps continuous polyplant and technology and can be used for producing the binary of poly-glycolide, polylactide, polycaprolactone and their different proportionings or terpolymer etc., and the monomer of polymerization is glycolide, lactide, caprolactone and other cyclic ester etc.Advantage such as continuous polymerization unit of the present invention and technology have the monomer conversion height, the polymerisation controllability is good, polymerized production capacity is big, the simple small investment of equipment, power consumption are low.
Below in conjunction with the drawings and specific embodiments process of the present invention and process unit are described in further detail.
Description of drawings
Fig. 1 is the work schematic diagram of process unit of the present invention.
The specific embodiment
As shown in Figure 1, process unit of the present invention comprises tubular polymerization reactor 1, measuring pump 4 and melter 2, and the three is serially connected successively; Wherein tubular polymerization reactor 1 is in series by the tubular static mixer 3 that a plurality of diameters increase gradually, and measuring pump 4 and melter 2 successive bursts are connected on the smaller diameter end 11 of tubular polymerization reactor 1.
As a further improvement on the present invention, this process unit also comprises:
---gear pump 5, this gear pump 5 is arranged on the larger diameter end of polymer reactor 1, by this gear pump 5 polymer is evenly drawn from the larger diameter end 12 of tubular polymerization reactor 1; This device is also established a die head 6 as drawing mechanism behind gear pump 5 in addition.
---a jacket heating system 7, form by the heater 71 that is located at the static mixer outer surface, be divided into into 4～16 thermals treatment zone 72, each thermal treatment zone is accurately controlled by accurate temperature control instrument respectively.This jacket heating system can adopt multiple mode of heating, as: can be directly electric jacket is set or after the tubular reactor outer surface is established the layer of aluminum cover, establishes the electrical heating cover again or be provided with a chuck, conduction oil and electrically heated rod or the like are set in the chuck again at the outer surface of tubular reactor at the tubular reactor outer surface.The heating principle of this heating system is same as prior art, repeats no more here.
---static mixing reactor 1 of the present invention can all adopt the mixed cell of patterns such as SV, SK, SMX or the mixed cell that these several patterns are adopted in combination; Its series connection number is 2-8; The barrel diameter scope of each hybrid cell is between 10～100mm; The scope of cylindrical shell length is between 2～10 meters.
---the melter 2 in the process unit of the present invention can be stirred autoclave or other thawing containers.
---be inflow, the outflow of the material in the further control polymer reactor, between the arrival end 11 of polymer reactor 1 and the port of export 12 and measuring pump 4 and melter 2, a valve 8 be set all.
Specify process of the present invention and process unit further combined with following examples more below, but scope of the present invention is not limited to the following example.
Embodiment one
Produce object and be poly-glycolide PGA
1, material proportion: raw material is a glycolide, and initator adopts stannous octoate, and both proportionings are: stannous octoate/glycolide=0.005% (mol ratio);
2, process unit comprises: tubular polymerization reactor 1, melter 2, measuring pump 4, gear pump 5, heating system 7:
A: tubular polymerization reactor 1 is in series by the tubular static mixer 3 of three SK types, and the diameter of these three motionless mixers increases successively by the direction that fluid flows, and their specification is as follows respectively:
The barrel diameter of static mixer I is 20mm, long 1400mm, and interior dress diameter 20mm, the SK type static mixing unit of high 20mm is divided into three thermals treatment zone, and temperature is respectively 180 ℃, and 190 ℃, 205 ℃;
The barrel diameter of static mixer II is 25mm, long 1000mm, and interior dress diameter 25mm, the SK type static mixing unit of high 25mm is divided into two thermals treatment zone, and temperature is respectively 220 ℃, 235 ℃;
The barrel diameter of static mixer III is 32mm, long 960mm, and interior dress diameter 32mm, the SK type static mixing unit of high 32mm is divided into two thermals treatment zone, and temperature is respectively 235 ℃, 230 ℃.
B: the mode of heating of heating system adopts tubular reactor 3 outsides to add layer of aluminum cover and electrical heating cover.
C: melter adopts the 50L stirred autoclave, and melt temperature is controlled at 130 ℃.
3, technical process is: mixed material joins melter 2 in proportion, the temperature that guarantees melter 2 is at 130 ℃, when material enters static mixer I, II, III by measuring pump 4 with the charging rate of 1.1L/h successively after melter 2 melts and mixes, reaction time is about 1.5 hours, extrude granulation by gear pump 5, die head 6 at last.
The weight average molecular weight of this kind embodiment resulting polymers is 6.2 ten thousand, and the conversion ratio of monomer is 98.9%.
Embodiment two
Producing object is polylactide PLA
1, material proportion: raw material is the L-lactide, and initator adopts stannous octoate, and both proportionings are: stannous octoate/L-lactide=0.01% (mol ratio);
2, process unit comprises: tubular polymerization reactor 1, melter 2, measuring pump 4, gear pump 5, heating system 7.
A: tubular polymerization reactor is in series by the tubular static mixer 3 of SV, SK type, and their serial connection order is a SK type behind the first SV, and the diameter of these 4 motionless mixers increases successively by the direction that fluid flows, and their specification is as follows:
The barrel diameter of static mixer I is 15mm, long 1200mm, and interior dress diameter 15mm, the SV type static mixing unit of high 15mm is divided into two thermals treatment zone, and temperature is respectively 160 ℃, 170 ℃;
The barrel diameter of static mixer II is 20mm, long 1000mm, and interior dress diameter 20mm, the SV type static mixing unit of high 20mm is divided into two thermals treatment zone, and temperature is respectively 175 ℃, 180 ℃;
The barrel diameter of static mixer III is 25mm, long 1250mm, and interior dress diameter 25mm, the SK type static mixing unit of high 25mm is divided into two thermals treatment zone, and temperature is respectively 190 ℃, 200 ℃;
The barrel diameter of static mixer IV is 32mm, long 1280mm, and interior dress diameter 32mm, the SK type static mixing unit of high 32mm is divided into two thermals treatment zone, and temperature is respectively 210 ℃, 205 ℃;
B: the mode of heating of heating system is that tubular reactor 3 outsides add one deck chuck, and the inside is provided with conduction oil and electrically heated rod.
℃: melter 2 adopts the 50L stirred autoclave, and melt temperature is controlled at 125 ℃.
3. technical process is: mixed material joins melter 2 in proportion, the temperature that guarantees melter 2 is at 125 ℃, when material enters static mixer I, II, III, IV by measuring pump 4 with the charging rate of 0.8L/h successively after melter 2 melts and mixes, reaction time is about 2.5 hours, extrude granulation by gear pump 5, die head 6 at last.
The weight average molecular weight of this kind embodiment resulting polymers is 8.8 ten thousand, and the conversion ratio of monomer is 97.2%.
Embodiment three
Produce object and be poly-different lactide PGLA (90/10)
1, material proportion: raw material adopts glycolide/lactide=90/10 (mol ratio), and initator adopts stannous octoate, and the mol ratio of itself and raw material glycolide/lactide is 0.005%.
2, process unit comprises: tubular polymerization reactor 1, melter 2, measuring pump 4, gear pump 5, heating system 7:
A: tubular polymerization reactor is that the tubular static mixer 3 by two SK types is in series, and the diameter of these two motionless mixers increases successively by the direction that fluid flows, and their specification is as follows:
The barrel diameter of static mixer I is 20mm, long 1600mm, and interior dress diameter 20mm, high 20mmSK type static mixing unit is divided into three thermals treatment zone, and temperature is respectively 180 ℃, and 195 ℃, 215 ℃;
The barrel diameter of static mixer II is 25mm, long 1500mm, and interior dress diameter 25mm, the SK type static mixing unit of high 25mm is divided into three thermals treatment zone, and temperature is respectively 225 ℃, and 233 ℃, 233 ℃;
B: the mode of heating of heating system adopts the tubular reactor outside to add layer of aluminum cover and electrical heating cover.
C: melter adopts the 50L stirred autoclave, and melt temperature is controlled at 135 ℃.
3, technical process is: mixed material joins melter 2 in proportion, the temperature that guarantees melter 2 is at 135 ℃, when material enters static mixer I, II by measuring pump 6 with the charging rate of 0.8L/h successively after melter 2 melts and mixes, reaction time is about 1.5 hours, extrude granulation by gear pump 5, die head 6 at last.
The weight average molecular weight of this kind embodiment resulting polymers is 5.8 ten thousand, and the conversion ratio of monomer is 98.2%.
Here be noted that, initator in the foregoing description is not limited to giving an example among the embodiment, they can be in proton acid type, halide type, anionic, organo-aluminum compound, pink salt class, the rare earth compound any, and wherein proton acid type initator can be to toluene naphthenic acid, carboxylic acid etc.; The anionic initator can be butyl lithium, sodium alkoxide, potassium alcoholate etc., and halide type initator can be ZnCl2, AlCl3 etc.
Claims (11)
1. the process of a lactide analog monomer continuous polymerization, it is characterized in that: the tubular static mixer series connection that is increased gradually by a plurality of diameters constitutes tubular polymerization reactor, be connected in series a measuring pump and a melter in succession in its smaller diameter end again, constitute the continuous polymerization unit of lactide analog monomer; Material is added melter with certain proportioning, fusion also mixes the back enters tubular polymerization reactor by measuring pump with certain speed smaller diameter end, make it successively through each static mixer that is serially connected and diameter increases gradually, after the reaction of a period of time, polymer is extruded by the larger diameter end of tubular polymerization reactor.
2. process as claimed in claim 1 is characterized in that: described static mixing reactor is one or more the combination in the tubular static mixer of SV, SK and SMX type, and its series connection number is 2-8.
3. process as claimed in claim 1 is characterized in that: the melt temperature of material is higher than the fusing point of monomer in the described melter, between 80 ℃～180 ℃.
4. process as claimed in claim 1 is characterized in that: the reaction temperature of described polymer reactor raises piecemeal, and its scope is between 120 ℃～280 ℃, and polymerization reaction time is between 0.5 hour～4 hours.
5. process as claimed in claim 4 is characterized in that: the outer surface of described each static mixer all has the reaction temperature in the heater control polymer reactor.
6. as the described arbitrary process of claim 1 to 5, it is characterized in that: add a kind of initator in the described polymerisation, this initator can be wherein any of proton acid type, halide type, anionic, organo-aluminum compound, pink salt class, rare earth compound, and the mole proportioning of itself and raw material is 0.1%～0.0001%.
7. process unit that is used for claim 1, it is characterized in that: comprise tubular polymerization reactor, measuring pump and melter, the three is serially connected successively; Wherein tubular polymerization reactor is in series by the tubular static mixer that a plurality of diameters increase gradually, and measuring pump and melter successive bursts are connected on the smaller diameter end of tubular polymerization reactor; The outer surface of each static mixer all has a cover heater, and these heaters are formed a jacket heating system, and this heating system is divided into 4-16 the thermal treatment zone, and the temperature of each thermal treatment zone is controlled by temperature control instrument respectively.
8. process unit as claimed in claim 7 is characterized in that: the larger diameter end of described tubular polymerization reactor is connected with a gear pump, by this gear pump polymer is evenly extruded from the larger diameter end of tubular polymerization reactor.
9. process unit as claimed in claim 8, it is characterized in that: described heating system is provided with conduction oil and electrically heated rod again for directly electric jacket is set or establishes the electrical heating cover again or be provided with a chuck at the outer surface of tubular reactor after the tubular reactor outer surface is established the layer of aluminum cover at the tubular reactor outer surface in the chuck.
10. as the arbitrary described process unit of claim 7 to 10, it is characterized in that: described static mixing reactor is one or more the combination in the tubular static mixer of SV, SK and SMX type, and the number of its series connection is 2-8.
11. process unit as claimed in claim 10 is characterized in that: described static mixing reactor barrel diameter scope is between 10～100mm; The scope of cylindrical shell length is between 2～10 meters.
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| EP2030679A1 (en) * | 2007-09-03 | 2009-03-04 | Uhde Inventa-Fischer GmbH | Polymerisation reactor, polymerisation device, method for manufacturing biodegradable polyester and applications |
| CN110394143B (en) * | 2019-08-21 | 2024-06-07 | 兖矿能源集团股份有限公司 | Tubular reaction device is cleared up to coal |
| CN111804218A (en) * | 2020-03-23 | 2020-10-23 | 杭州普力材料科技有限公司 | Industrial continuous production equipment for polycarbonate polyether polyol |
| CN115505107B (en) * | 2021-06-22 | 2024-08-27 | 上海浦景化工技术股份有限公司 | Preparation method of granular polyglycolic acid |
| CN115677986A (en) * | 2021-07-27 | 2023-02-03 | 上海浦景化工技术股份有限公司 | Preparation method of thermal aging-resistant degradable aliphatic polyester |
| CN115672214A (en) * | 2021-07-27 | 2023-02-03 | 上海浦景化工技术股份有限公司 | Device and method for preparing polyglycolic acid through low-temperature polymerization |
| CN115090185A (en) * | 2022-07-15 | 2022-09-23 | 中国科学院青岛生物能源与过程研究所 | Continuous polymerization method for preparing high-viscosity branched butadiene-isoprene rubber and preparation device thereof |
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