CN105013196B - For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method - Google Patents
For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method Download PDFInfo
- Publication number
- CN105013196B CN105013196B CN201510239541.4A CN201510239541A CN105013196B CN 105013196 B CN105013196 B CN 105013196B CN 201510239541 A CN201510239541 A CN 201510239541A CN 105013196 B CN105013196 B CN 105013196B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- raw material
- concentration
- production method
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyamides (AREA)
Abstract
The invention provides a kind of raw material enrichment facility for being used to prepare polyamide, including the preheating device for preheating raw material to be concentrated, for be concentrated by evaporation preheating after raw material evaporation concentration device, and for condensation evaporation enrichment facility evaporate discharge gas condensing unit.Present invention also offers a kind of raw material method for concentration and a kind of polyamide 5X production equipment and production method.The raw material enrichment facility that the present invention is provided can effectively reclaim the raw material lost in evaporation process, moreover it is possible to recycle vapours, reduce heat-energy losses, can substantially reduce production cost.The polyamide 5X production equipments and production method that the present invention is provided can produce the polyamide 5X products of polytypic particularly for polyamide 5X, can expand production and the application of polyamide 5X products.
Description
Technical field
The present invention relates to field of polyamides, and in particular to a kind of to be used to prepare the device of polyamide, raw material method for concentration, bag
Include the polyamide production equipment of described device, and a kind of production method of polyamide.
Background technology
In the prior art, the polymerization of polyamide generally can be divided into heating polycondensation or interface polycondensation.For example：(Bacon
Ke,A.W.Sisko,Differential thermal analysis of high polymers.III.Polyamides,
Journal of Polymer Science the 153rd phases of volume 50, page 87-98, in March, 1961) heating condensation methods are described,
However, for root is it is reported that heat condensation methods compared to interface polycondensation, obtained polyamide fusing point is low and heat resistance is deteriorated
(J.Polym.Sci.50,87,1961；Macromolecules,30,8540,1998).And interface polycondensation process is very multiple
It is miscellaneous, it is difficult to be industrially applicable.Above-mentioned technique is all short distance polymerization technique, no matter which kind of technique all has certain defect, and system
The polyamide obtained, the particularly polyamide 5X degree of polymerization is not high, and commercial Application is very restricted.
With continuing to develop for polymerization technique, continuous polymerization technique is arisen at the historic moment, and short distance is compensate for a certain extent and is gathered
The defect of conjunction.Main continuous polymerization technique specifically mainly includes following link in the world at present：Concentration → high pressure pre-polymerization
→ flash distillation → normal pressure or vacuum polycondensation.E.I.Du Pont Company is as polyamide manufacturer well-known in world wide, to polyamide 66
Continuous polymerization technique is improved, and its unique continuous polymerization technique mainly includes following link：High pressure concentrates pre-polymerization → sudden strain of a muscle
Steaming → normal pressure polycondensation.
In continuous polymerization technique, by the collective effect of each group equipment, by heat apply to reactant mixture and by water by
Gradually remove, to drive reaction balance towards polyamide, until polymer reaches required length range, extrude granulating again afterwards
Material, is spun into fiber or is processed as other shapes.Whole continuous polymerization technique needs substantial amounts of heat, to cause condensation reaction to send out
Life simultaneously removes water from reactant mixture.
In the prior art, for the concentration of polyamide raw materials polyamide salt solution, most common method is evaporation, i.e.,：Profit
Different with boiling point, the heating aqueous solution makes the moisture evaporation in solution, so that concentrate solution is with the polyamide salt concentration needed for reaching.
Japanese real public clear 49-42658 publications disclose a kind of inwall for making liquid under gravity with film-form along heat-transfer pipe
Under surface current, the film downward flow type evaporation concentration device for concentrating the liquid evaporation.But in the film downward flow type evaporation concentration device,
The treatment fluid supplied to each heat-transfer pipe is not mixed with the treatment fluid of other heat-transfer pipes, is difficult in addition to each heat-transfer pipe uniformly dispersing,
Therefore there is film in the apparatus to disconnect the dry heat-transfer area of generation or cross concentration, incrustation scale attachment and can not obtain and design
The problem of consistent thermal efficiency.Japanese Patent Publication 33-6314 publications disclose one kind and flowed liquid into evaporator, and make
Hot water evaporator heat-transfer pipe interior circulation so that liquid heating evaporation, with the dip tube formula evaporation concentration device concentrated.
In the dip tube formula evaporation concentration device, with the nucleateboiling heat transfer by tube surface.Therefore, exist in the apparatus and pass
The thermal efficiency is relatively low, incrustation scale is attached to tube surface causes the problem of thermal conductivity factor is reduced.
The content of the invention
To overcome the defect that raw material enrichment facility is present in existing polyamide production technology, it is an object of the invention to carry
For a kind of device for being used to prepare polyamide.
Second object of the present invention is to provide a kind of raw material method for concentration for being used to prepare polyamide.
Third object of the present invention is to provide a kind of polyamide 5X production equipment.
Fourth object of the present invention is to provide a kind of polyamide 5X production method.
It is raw material enrichment facility provided by the present invention for the device for preparing polyamide, including：
Preheating device, the raw material to be concentrated for preheating；
Evaporation concentration device, is connected with the preheating device, for the raw material being concentrated by evaporation after preheating；And
Condensing unit, is connected with the evaporation concentration device, for condensing the evaporation concentration device evaporation discharge
Gas.
In device of the present invention, the preheating device is heat exchanger.
In device of the present invention, the evaporation concentration device includes boil-off gas and exported and phegma entrance, point
It is not connected with the condensing unit, the gas of the evaporation concentration device evaporation discharge enters institute by boil-off gas outlet
State in condensing unit, phegma obtained by after condensation is by the phegma inlet return into the evaporation concentration device.
In device of the present invention, the evaporation concentration device is evaporator with central downcomer, an including central tube
And around some tube banks of the central tube, raw material to be concentrated is heated concentration in the central tube and the tube bank.
In device of the present invention, the length of the tube bank is 1~2m, a diameter of 30~75mm, draw ratio is 20~
40。
In device of the present invention, the sectional area of the central tube is the 1~10% of the total sectional area of the tube bank.
In device of the present invention, the condensing unit is also connected with the preheating device, wherein gained after condensation
Gas is used to heat the preheating device as thermal source.
It is provided by the present invention for the raw material method for concentration for preparing polyamide：Using described in above any one of technical scheme
Device carry out raw material concentration process.
The production equipment for the polyamide 5X that the present invention is provided includes：The raw material enrichment facility that is sequentially connected, pre-polymerization device, subtract
Pressure device, Moisture separation device and polycondensation device, wherein, the raw material enrichment facility is described in above any one of technical scheme
Device.
The production method for the polyamide 5X that the present invention is provided is：Using foregoing production equipment, with the polyamide salt aqueous solution
For initiation material, raw material concentration step, prepolymerization step, depressurization steps, moisture separating step and condensation polymerization step system are sequentially passed through
Obtain the polyamide 5X.
In production method of the present invention, the mass percent concentration of the polyamide salt aqueous solution initiation material is
More than 50%, preferably 50~65%.
In production method of the present invention, in the raw material concentration step, the tube side pressure of the raw material enrichment facility
For 0.005~0.35MPa, preferably 0.05~0.35MPa, tube side temperature is 60~200 DEG C, preferably 80~160 DEG C；And/or
Shell side pressure is 0~2.0MPa, and uneven shell-side temperature is less than 250 DEG C, preferably less than 212 DEG C；And/or
The mass percent concentration of the polyamide salt aqueous solution after concentration is 50~80%, preferably 70~80%.
In production method of the present invention, the temperature of the prepolymerization step is 200~300 DEG C, preferably 220~280
DEG C, more preferably 230~260 DEG C；And/or
The pressure of the prepolymerization step is below 3.0MPa, more preferably preferably below 2.0MPa, 1.0~1.8Mpa；
And/or
The prepolymerization step terminate the mass percentage content of the polymer of rear gained for 80~100%, preferably 85~
95%.
In production method of the present invention, in the depressurization steps, in the depressurization steps, temperature is the polyamide
Temperature more than 5X fusing points, more preferably preferably 200~300 DEG C, 230~260 DEG C.
In production method of the present invention, in the moisture separating step, temperature is 250~320 DEG C, preferably 250
~300 DEG C.
In production method of the present invention, the temperature of the condensation polymerization step is 250~320 DEG C, preferably 250~300
℃；And/or
The condensation polymerization step is carried out under normal pressure or vacuum condition, carries out using inert gas shielding during polycondensation under normal pressure,
Pressure is 0~760mmHgA, preferably 150~250mmHgA when polycondensation is carried out under vacuum condition.
In production method of the present invention, the polyamide 5X is polyamide 56.
The raw material enrichment facility that the present invention is provided includes preheating device, evaporation concentration device and condensing unit, by cold
Solidifying device can effectively reclaim the raw material lost in evaporation process, and the vapours discharged in evaporation process can also be reclaimed for original
Material preheating, reduces heat-energy losses, can substantially reduce production cost, and raw material enrichment facility number of devices of the invention is few, operation
Easy, stable, convenient maintenance is with changing.
Raw material method for concentration that the present invention is provided is stable, significant loss is few, and concentrating degree is easily-controllable, and heat energy facilitates back
Receive, so as to ensure that the integrality and high efficiency of bulk polymerization technique.
The polyamide 5X production equipments that the present invention is provided employ the raw material enrichment facility that the present invention is provided, it is ensured that wherein
Raw material concentration production link, be especially suitable for polyamide 5X production.
The polyamide 5X production methods that the present invention is provided provide the technique for polyamide 5X, can produce the poly- of polytypic
Acid amides 5X products, can expand production and the application of polyamide 5X products, very with industrial value.
Brief description of the drawings
Fig. 1 is the structural representation of raw material enrichment facility of the present invention；
Fig. 2 is the structural representation of polyamide 5X production equipments of the present invention；
Wherein, description of reference numerals is as follows：0th, into salt device；1st, raw material enrichment facility；2nd, pre-polymerization device；3rd, decompression dress
Put；4th, Moisture separation device；5th, polycondensation device；11st, preheating device；12nd, evaporation concentration device；13rd, condensing unit；121st, center
Pipe；122nd, restrain；123 boil-off gas are exported；124th, phegma entrance.
Embodiment
One aspect of the present invention provides a kind of raw material enrichment facility for being used to prepare polyamide, as shown in figure 1, the original
Material enrichment facility includes：For preheating the preheating device 11 of raw material to be concentrated, the evaporation for being concentrated by evaporation raw material to be concentrated
Enrichment facility 12, it is connected with preheating device 11, and the condensing unit 13 being connected with evaporation concentration device 12, condensation dress
Putting 13 is used for the gas that condensation evaporation enrichment facility 12 evaporates discharge.
When above-mentioned raw materials enrichment facility works, as shown in figure 1, raw material (the polyamide salt aqueous solution of low concentration) to be concentrated
A is initially entered to be preheated in preheating device 11, and the solution B after heating is discharged into evaporation concentration device by preheating device 11
In 12, the raw material C after being concentrated after the evaporation of evaporation concentration device 12 is discharged into downstream life by evaporation concentration device 12
Produce unit.The gas D that evaporation concentration device 12 is evaporated is due to being mingled with a small amount of raw material (especially lower boiling diamines), therefore palpus
Reclaimed, into condensing unit 13, condensed wherein.
The diamines boiling point for forming polyamide salt is not generally high, and the boiling points of especially 1,5- pentanediamines only has about 180 DEG C, and
And, 1,5- pentanediamine has fabulous hydrophily, easily because high temperature action gasifies with water evaporation during evaporation and concentration,
Suppress the loss of diamines it is therefore necessary to take measures, to ensure rubbing between follow-up polymerization later stage Amino End Group and end carboxyl
You keep balance.Therefore, raw material enrichment facility of the invention is provided with condensing unit 13, is connected with evaporation concentration device 12,
Containing raw materials such as diamines in the steam that evaporation concentration device 12 is produced in evaporation process, carried out together into condensing unit 13 cold
Solidifying, the raw material formation phegma being mingled with steam is back to evaporation concentration device 12, thus the raw material in recyclable steam.
In an embodiment of the raw material enrichment facility according to the present invention, raw material enrichment facility of the invention is applicable
In common polyamide 6 X series, such as nylon66 fiber is equally applicable to polyamide 5X series, such as polyamide 56.It is excellent at one
In the embodiment of choosing, raw material enrichment facility of the invention is especially adapted for use in polyamide 5X production fields.
In an embodiment of the raw material enrichment facility according to the present invention, in the case of some needs, downstream preshrunk
Polyamide salt solution in poly- unit such as needs concentration, can also return into evaporation concentration device 12 and be located through supply pump
Reason.
In an embodiment of the raw material enrichment facility according to the present invention, preheating device 11 can be common for this area
The heat exchanger of type, the thermal source of heat exchanger can be external source, or be produced in prepolymerization process or polyamide production technology
Raw heat.
In an embodiment of the raw material enrichment facility according to the present invention, evaporation concentration device 12 includes boil-off gas
Outlet 123 and phegma entrance 124, is connected with condensing unit 13 respectively, the gas D that evaporation concentration device 12 is evaporated by
Boil-off gas outlet 123 is discharged into condensing unit 13, and gained condensate liquid E is back to steaming by phegma entrance 124 after condensation
Send out in enrichment facility 12.In one preferred embodiment, it can be set in the middle of evaporation concentration device 12 and condensing unit 13
There is supply pump, for condensate liquid E to be delivered in evaporation concentration device 12.
In an embodiment of the raw material enrichment facility according to the present invention, evaporation concentration device 12 can be this area
The evaporator with central downcomer of common type, it includes a central tube 121 and some tube banks 122 around central tube 121,
Raw material to be concentrated is heated in central tube 121 and tube bank 122.During heating evaporation, the nylon salt gas-liquid mixed in tube bank 122
The density of thing causes nylon salt gas-liquid mixture in tube bank 122 upwards much smaller than the density of nylon salt in central tube 121,
In the natural flowing that central tube 121 is downward.The top of evaporator with central downcomer should have sufficiently large space, it is ensured that have and fill
The evaporating space divided, while keeping the droplets of feed taken away by steam minimum.
In one preferred embodiment, the length of tube bank 122 can be 1~2m, and diameter can be 30~75mm, long
Footpath ratio can be 20~40.
In one preferred embodiment, the sectional area of central tube 121 is the 1~10% of the total sectional area of tube bank 122.
In one preferred embodiment, heating tube heat transfer coefficient can be 600~3000w/ (m. DEG C).
In an embodiment of the raw material enrichment facility according to the present invention, the polyamide salt from preheating device 11 is molten
Liquid is fed from the solution inlet port of the lower side of evaporation concentration device 12, it is concentrated after from the concentrated solution outlet of evaporation concentration device 12
Outflow.
According to the present invention raw material enrichment facility an embodiment in, condensing unit 13 also with the phase of preheating device 11
Connection, the gas F of gained after condensation is used to as thermal source to heat preheating device 11, the gas G discharges after heat exchange.
In an embodiment of the raw material enrichment facility according to the present invention, the heat source H for evaporation concentration device 12
Can be external source, or the heat produced in prepolymerization process or polyamide production technology, the gas H ' rows after heat exchange
Go out.
In an embodiment of the raw material enrichment facility according to the present invention, the raw material to be concentrated in preheating device 11
Inlet amount, the condensate liquid capacity of returns of the material solution liquid level in evaporation concentration device 12 and condensing unit 13 should form dynamic
State equilibrium relation, to maintain the stable operation of raw material enrichment facility.
The second aspect of the invention provides a kind of raw material method for concentration for being used to prepare polyamide, and it uses above skill
Raw material enrichment facility described in art any one of scheme carries out concentration process.
The third aspect of the invention provides a kind of polyamide 5X production equipment, as shown in Fig. 2 including being sequentially connected
Raw material enrichment facility 1, pre-polymerization device 2, decompressor 3, Moisture separation device 4 and polycondensation device 5, wherein, raw material concentration dress
It is the raw material enrichment facility described in above any one of technical scheme to put 1.
In an embodiment of the production equipment according to the present invention, the upstream of raw material enrichment facility 1 can also be connected
There is into salt device 0, for forming base polyamide salt, as shown in Figure 2.
Pre-polymerization device of the present invention, decompressor, Moisture separation device and polycondensation device can use existing polyamides
Any type of amine production field, the present invention is not particularly limited, and can all coordinate with raw material enrichment facility of the present invention makes
With.
Pre-polymerization device available for production equipment of the present invention can be a tubular reactor, and body is arranged in serpentine, including
Some straight sections and bent portion of connection, monomer material are conveyed and are heated in body, and thus polycondensation forms prepolymer.Pre-polymerization
Device can further include one or more, preferably more than three heating jackets, for heated Tube reactor.Pre-polymerization
Device can also further include one or more heating agent evaporators, for providing heating agent to heating jacket.Pre-polymerization device makes
Heating agent can be the organic heating agent of liquid phase, and the gas phase heating medium for heating side that liquid phase conveying is evaporated on the spot is overheated using organic heating agent
Formula, using gas phase heating medium for heating tubular reactor, the heating agent lime set after use sends heating agent evaporator circulating-heating profit back to after reclaiming
With.
Decompressor available for production equipment of the present invention can be a horizontal flash vessel, an including kettle, be set in kettle
There is snakelike material coil pipe, the internal diameter of material coil pipe increases successively by entrance.Material after pre-polymerization is in material coil inlet
Place's pressurization (generally 20~25kg/cm2), material flows in coils, because internal diameter becomes larger, and adds material and coil pipe pipe
The drag effect that wall rubs, pressure is reduced rapidly, is down to exit close to normal pressure, the moisture in material reduce because of pressure and
Rapid expansion vaporization at high temperature, material is in coil pipe inwall film flow at high speed annular in shape, and vapor then flow through in coils by centre,
Polymer in coil outlet material is up to 99%, while pressure energy is kinetic energy, makes the mixture of material and water at a high speed
Into follow-up Moisture separation device.
Available for production equipment of the present invention Moisture separation device can be this area any type, including normal pressure or add
The separator of pressure.For example, the separator of normal pressure can be directly entered from decompressor by being entrained with the prepolymer of a large amount of vapor
It is interior, vapor is separated with prepolymer in the device, temperature preferably 250~320 DEG C, more preferably 250~300 of separating step
℃.The kettle of separator 4 can overheat the gas phase heating medium for heating mode that liquid phase conveying is evaporated on the spot using organic heating agent.From heating agent
The overheat liquid phase heating agent that stove heat comes out is transported in the flash vessel at heating scene and carries out vacuum flashing under pressure, dodges
The gas phase heating medium for heating separator being steamed out, heating agent lime set after use by liquid trap after the reception of matchmaker's condensate liquid recycling can,
Send heating medium for heating stove circulating-heating back to heat medium circulation pump.The squeeze cylinder of separator uses liquid phase heating medium for heating.
Polycondensation device available for production equipment of the present invention can be any type of this area, including normal pressure or pressurization
Separator.For example, the liquid material (predominantly prepolymer) after being handled through Moisture separation device is in polycondensation unit feeding pump
Effect is lower to enter polycondensation device, and prepolymer passes through further polymerization generation molecular weight larger end in the polycondensation vessel of polycondensation device
Polymers.The polymer generated in polycondensation device can be pumped into end of extruded band via melt and carry out extruding pelletization, or deliver to screw rod
Extruder is modified granulation, or delivers to straight spinning.The kettle of polycondensation device can on the spot be steamed using the overheat liquid phase conveying of organic heating agent
The gas phase heating medium for heating mode of hair.It is existing that the overheat liquid phase heating agent come out from heating agent stove heat is transported to heating under pressure
Flashed in the flash vessel of field, the kettle of the gas phase heating medium for heating polycondensation device flashed off, the heating agent lime set after use is led to
Liquid trap is crossed after the receiving of matchmaker's condensate liquid recycling can, heating medium for heating stove circulating-heating is sent back to heat medium circulation pump.Polycondensation device
Squeeze cylinder can use liquid phase heating medium for heating.
The fourth aspect of the invention provides a kind of polyamide 5X production method, and the production provided using the present invention is set
It is standby, using the polyamide salt aqueous solution as initiation material, sequentially pass through raw material concentration step, prepolymerization step, depressurization steps, moisture separation
The polyamide 5X is made in step and condensation polymerization step.
In an embodiment in accordance with the present production process, the quality hundred of the initiation material polyamide salt aqueous solution
It can be more than 50% to divide specific concentration, preferably can be 50~65%.
In an embodiment in accordance with the present production process, in raw material concentration step, tube side pressure can be
0.005~0.35MPa, preferably 0.05~0.35MPa, tube side temperature can be 60~200 DEG C, preferably 80~160 DEG C；Shell
Stroke pressure can be 0~2.0MPa, and uneven shell-side temperature can be less than 250 DEG C, preferably less than 212 DEG C；Gained is poly- after concentration
The mass percent concentration of acid amides saline solution can be 50~80%, preferably 70~80%.
In an embodiment in accordance with the present production process, in prepolymerization step, the temperature of pre-polymerization can be 200
~300 DEG C, more preferably preferably 220~280 DEG C, 230~260 DEG C；The pressure of pre-polymerization can be below 3.0MPa, be preferably
Below 2.0MPa, more preferably 1.0~1.8Mpa.
In an embodiment in accordance with the present production process, prepolymerization step terminates the polymer quality of rear gained
Degree can be 80~100%, preferably 85~95%.
In an embodiment in accordance with the present production process, depressurization steps can be carried out using flash vessel, flash distillation
Temperature and pressure in device is to be adapted to polyamide 5X and any condition of moisture flash separation, and the temperature of decompression can be polyamide
Temperature more than 5X fusing point, more preferably preferably 200~300 DEG C, 230~260 DEG C.
In an embodiment in accordance with the present production process, the temperature in moisture separating step can be 250
~320 DEG C, preferably can be 250~300 DEG C.
In an embodiment in accordance with the present production process, condensation polymerization step is entered under normal pressure or vacuum condition
OK, carry out protecting using inert gas (such as nitrogen) during polycondensation under normal pressure, pressure can be 0 when carrying out polycondensation under vacuum condition
~760mmHgA, preferably 150~250mmHgA, the temperature of condensation polymerization step can be 250~320 DEG C, preferably can for 250~
300℃。
In an embodiment in accordance with the present production process, polyamide 5X is preferably polyamide 56.
Polyamide production equipment and production method of the present invention be applied to polyamide continuous polymerization technique and
Batch polymerization processes, the continuous polymerization technique for the polyamide that is particularly suitable for use in.
Polyamide 5X of the present invention refers to the polyamides that 1,5- pentanediamines are formed with organic dibasic acid by polycondensation reaction
Amine series matter.
Polyamide 5X produced by the present invention formic acid relative viscosity is preferably 45~100, and terminal amino group content is preferably 10~
Side reaction easily occurs again at high temperature for 100mol/ton, more preferably 20~60mol/ton, the Amino End Group of too high amount.
Polyamide 5X narrow molecular weight distributions produced by the present invention, are represented with the polydispersity coefficient d of conventional molecular weight distribution
Mw/Mn；Mw represents the average weight-molecular mass using weight as statistical weight：
Mn represents the equal relative molecular mass of number using quantity as statistical weight：
Polyamide 5X produced by the present invention d values are less than 2.5.
Polyamide 5X made from the apparatus and method that the present invention is provided can jointly make with other polymer and/or additive
Into the polyamide of various uses.In general, polyamide 5X amount can account for more than the 80% of polyamide quality.
Additive can for antioxidant, heat-resisting stabilizing agent, weather resisting agent, pigment, gloss enhancer, dyestuff, crystal nucleating agent,
Any one or a few combination in delustering agent, plasticizer, antistatic additive, fire retardant, metal and metal salt.
Wherein, heat-resisting stabilizing agent can be the existing any type in this area, include but is not limited to the change based on hindered phenol
Compound, the compound based on quinhydrones, the compound based on thiazole, the compound (such as phenyl-phosphonic acid) based on phosphorus, based on imidazoles
Compound (such as 2-mercaptobenzimidazole) and its substitution product, copper halide and iodine compound.
Weather resisting agent can be the existing any type in this area, including but not limited to resorcinol, salicylate, benzo three
Azoles, benzophenone and hindered amine etc..
Pigment can be the existing any type in this area, including but not limited to cadmium sulfide, phthalocyanine and carbon black etc..
Gloss enhancer can be the existing any type in this area, including but not limited to titanium oxide, calcium carbonate etc..
Dyestuff can be the existing any type in this area, including but not limited to Ni Gehei and nigrosine etc..
Crystal nucleating agent can be the existing any type in this area, including but not limited to talcum, silica, kaolin
With clay etc..
Plasticizer can be the existing any type in this area, include but is not limited to oxybenzoic acid monooctyl ester and N- butyl benzenes
Sulfonamide etc..
Antistatic additive can be the existing any type in this area, and including but not limited to alkyl sulphate type anionic resists
Oxidant, quaternary ammonium salt cationic type antistatic additive, non-ionic antistatic agent (such as polyoxyethylene sorbitol acid anhydride monostearate
Ester) and both sexes antistatic additive based on glycine betaine etc..
Fire retardant can be the existing any type in this area, including but not limited to melamine cyanurate, hydroxide
Thing (such as magnesium hydroxide or aluminium hydroxide), ammonium polyphosphate, brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated
Oxygen tree fat, the combination being made up of any fire retardant based on bromine and antimony oxide etc..
Other polymer include but is not limited to following polymer：(1) other polymer, which can contain, is derived from following component
Construction unit：Aliphatic carboxylic acid (such as oxalic acid, malonic acid, butanedioic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid), fat
Ring race dicarboxylic acids (such as cyclohexyl dicarboxylic acid) or aromatic dicarboxylic acid (such as terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid, two
Phenyl dicarboxylic acids, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenoxyethanedicarboxylic acid, diphenylethane dicarboxyl
Acid, 1,4 cyclohexane dicarboxylic acid, 5- sodiosulfoisophthalic acids, 5- 4-butyl-phosphonium M-phthalic acids etc.).
(2) other polymer can contain the construction unit derived from following component：Fat in addition to 1,5- pentanediamines
Race's diamines (such as ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutanes, 1,6- diamino hexanes, 1,7- diaminoheptanes,
1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- diamino decanes, 1,11- diamino undecanes, 1,12- diaminourea ten
Dioxane, 1,13- diaminourea tridecane, the 1,14- diaminourea tetradecane, 1,15- diaminourea pentadecane, 1,16- diaminourea hexadecane,
1,17- diaminourea heptadecane, 1,18- diaminourea octadecane, 1,19- diaminourea nonadecane, 1,20- diaminourea eicosane or 2- first
Base -1,5- pentanediamines), alicyclic diamine (such as cyclohexanediamine or double-(4- Aminohexyls) methane) or aromatic diamine (such as benzene two
Methylamine).
(3) other polymer can contain the construction unit derived from following component：Aromatic series, aliphatic or alicyclic two
Alcoholic compound (such as ethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, 1,4- cyclohexanedimethanols, neopentyl glycol, quinhydrones,
Benzenediol, dihydroxybiphenyl, naphthalene glycol, anthracene glycol, luxuriant and rich with fragrance glycol, 2,2- double (4- hydroxy phenyls) propane, 4,4 '-dihydroxy hexichol
Base ether or bisphenol S).
(4) other polymer can contain the construction unit derived from following component：Aromatic series with hydroxyl and carboxylic acid
Compound, aliphatic compound or cycloaliphatic hydroxyl group carboxylic acid compound.Wherein, cycloaliphatic hydroxyl group carboxylic acid includes but is not limited to breast
Acid, 3- hydroxy propionates, 3-hydroxybutyrate ester, 3-hydroxybutyrate ester-valerate, hydroxybenzoic acid, hydroxyl naphthalene-carboxylic acid, hydroxyl anthracene
Carboxylic acid, hydroxyl phenanthrene carboxylic acid, (hydroxy phenyl) vinyl carboxylic acid.
(5) other polymer can contain the construction unit derived from following component：Amino acid (such as 6-aminocaprolc acid, 11-
Amino undecanoic acid, 12 amino dodecanoic acid or PAMBA) or lactams (such as epsilon-caprolactams or ε-ten two
Lactams).
(6) other polymer can be for can be with 1,5- pentanediamines and the copolymerization list of aliphatic long carbochain biatomic acid copolymerization
Body, the comonomer includes but is not limited to amino acid, lactams, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxyl
Acid, aromatic diol, aliphatic diol, alicyclic diol, aromatic diamine, aliphatic diamine, alicyclic diamine, aromatic series hydroxyl
Yl carboxylic acid, aliphatic hydroxyl carboxylic acid, cycloaliphatic hydroxyl group carboxylic acid, and the respective derivative of above-mentioned comonomer.Wherein, it is above-mentioned common
The respective derivative of polycondensation monomer includes the product of above-mentioned any two kinds of comonomers reaction, for example, the one of a molecule diamines
Product of one carboxyl reaction of individual amino and a molecule dicarboxylic acids into salt.
Below by embodiment, the present invention is described in detail, so that the features and advantages of the present invention become apparent from.But should
This points out that embodiment is used for the design for understanding the present invention, and the scope of the present invention is not limited only to reality listed herein
Apply example.
Such as it is not particularly illustrated, concentration of the present invention is mass percent concentration.
The polyamide initiation material that embodiment is used be the polyamide salt aqueous solution, the polyamide salt by bio-based 1,5- penta
Diamines is formed with aliphatic dibasic acid.
[1,5- pentanediamine]
1,5- pentanediamine (abbreviation pentanediamine, also known as 1., 5- 1,5-DAP), also referred to as cadaverine, it is a kind of polyamines, is raw
The nitrogenous base with bioactivity being widely present in object, is that lysine occurs in the presence of decarboxylase when protein is corrupt
Decarboxylic reaction is generated.Industrial pentanediamine can also by chemical method, such as after the ethanol solution of glutaronitrile is boiled, with
Faster speed adds metallic sodium, adds water after having reacted, ethanol is steamed, remaining reactant is distilled with superheated steam, then
Acidifying is neutralized, and the method for distillation is obtained.Discovered in recent years pentanediamine can be by hafnia alvei (Hafnia.Alvei)
Lysine decarboxylase (L-lysine decarboxylase, EC 4.1.1.18) act on the bioanalysis of lysine and obtain.This
1, the 5- pentanediamines of inventive embodiments can be prepared from by bioanalysis, can also be prepared from by chemical method, and can be contained
There is the organic carbon for the renewable source for meeting ASTM D6866 standards.
[aliphatic dibasic acid]
Aliphatic dibasic acid, including adipic acid and aliphatic long carbochain biatomic acid.Aliphatic long carbochain biatomic acid can also
It is prepared from by bioanalysis or chemical method, and the bio-based organic carbon for meeting ASTM D6866 standards can also be contained.
Aliphatic long carbochain biatomic acid can be decanedioic acid, DC11, SL-AH, 13 carbon binary
Acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 and △ 9-1,
Any one or a few combination in 18- octadecylene binary acid, preferably decanedioic acid or SL-AH.
The continuous flow procedure of polyamide is as follows：
(1) preparation of polyamide salt solution
1, the 5- pentanediamines of high concentration are diluted to the deionized water of degasification under the protection of nitrogen certain density molten
Liquid (30%~50%).Aliphatic dibasic acid and 1, the 5- pentanediamines diluted are simultaneously continuously added in reactor, it is cold
But reaction heat when water removes neutralization reaction in time.The pH value of solution is constantly detected in N-process, makes two in reactor
The mol ratio of first amine/binary acid is slightly below after 1, stabilization, and this gained salting liquid is transferred in the reactor connected below and (can gone here and there
Lian Duotai, but be usually no more than 3), with the further fractional neutralization of two amine aqueous solutions and adjust the mol ratio of diamine/binary acid
With the mass concentration of salt, the flow of two amine aqueous solutions is controlled with the pH data detected.Until being eventually fabricated mass percent concentration
For 50~65% salting liquid, it is stored in stand-by in salt holding vessel.
(2) enrichment facility and its reaction
Using mass percent concentration be 50~65% the 5X polyamide salts aqueous solution as initiation material, by filter mistake
Filter, sends into measuring tank, the common additives that a certain amount of different size can be added in measuring tank (are usually no more than polyamides in batches
Amine salt quality 5%), be made polyamide salt mixed solution, it is agitated it is well mixed after, be admitted in the middle of second under measuring tank
Groove.Polyamide salt mixed liquor in second medial launder is continuously supplied to dense by salt supply pump by salt filter, salt preheater
In compression apparatus.In enrichment facility, polyamide salt solution concentration is set to be concentrated to 70~80% by 50~65%.
(3) pre-polymerization device and its reaction
Concentrate reactor supply in enrichment facility is pumped into pre-polymerization device.
Prepolymerization reaction is with continuous flowed through in tubular reactor of polyamide saline solution under controllable HTHP
Gradually occur.The pressure of this present invention device is automatically controlled, and tubular reactor is divided into more than three sections independent heatings, preceding 2/
In 3 sections of tubular reactor still based on concentration, solution concentration is concentrated to about 90% by 70~80% and (suitably carries out polymerisation
Concentration), final stage is to carry out based on prepolymerization, and polymer content can reach 85~95% in the material of outlet.
(4) decompressor and its reaction
Pressure reducer (flash vessel) is continuously given with pressure reducer pump by prepolymer made from tubular reactor.Material leads to rapidly
Pressure reducer is crossed, pressure is continuously reduced and close to atmospheric pressure, so the dissolving water in prepolymer gasifies rapidly in prepolymer, formed
The mixture of material, moisture.
Additive is also provided with pipeline between pressure reducer pump and pressure reducer and adds mouth, according to the use of PA5X resins
Way determines the species and addition of additive, such as delustering agent TiO2Suspension etc., mouth is added by additive, can be at this
The individual stage is continuously and quantitatively injected into prepolymer, and material, moisture and additive are ultimately formed after being depressurized by decompressor
Mixture.
(5) separator and its reaction
Material continuously enters water-separator after pressure reducer.The water for gasifying out from pressure reducer in separator
Divide and remove, further improve the degree of polymerization of prepolymer.
(6) poly- device and its reaction eventually
The material by separator is sent into poly- device (terminal polymerization kettle) eventually with pump altogether, in poly- device eventually, in negative pressure
Under the conditions of remove Residual water and the water that further polymerization is produced in polymer, obtain being adapted to granulation or it is modified or directly spin it is high-quality
Weight polymers.In order to prevent separator, the oxidation of terminal polymerization kettle material, it is preferred to use nitrogen-sealed.
It is the embodiment for preparing PA56 below：
Embodiment 1
Polyamide 56 salting liquids of the pH for 7.95 65% concentration is configured, by production equipment of the present invention by table 1
Process conditions are polymerize, terminal polymerization kettle pressure 210mmHg A, obtain the section that relative viscosity is 68.9, and its terminal amino group content is
40.4。
Embodiment 2
Polyamide 56 salting liquids of the pH for 8.05 65% concentration is configured, embodiment is pressed by production equipment of the present invention
1 process conditions are polymerize, but the pressure of terminal polymerization kettle is adjusted to by force 180mmHg A, and load improves 20% than embodiment 1,
The section that relative viscosity is 69.7 is obtained, its terminal amino group content is 40.1.
Embodiment 3
In addition to the pressure change in terminal polymerization kettle is 216mmHg A, other conditions are same as Example 2, and load is same,
The section that relative viscosity is 56.1 is obtained, its terminal amino group content is 42.6.
Table 1
Above example is the explanation to technical scheme, and the limitation to the technology of the present invention is not constituted.The technology of this area
Personnel according to professional knowledge, can be realized by the raw material proportioning and process conditions adjusted in preparation process different end group content and
The polyamide of relative viscosity.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is not used to limit the scope of the invention merely for exemplary purpose,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the invention is not restricted to
Above-mentioned embodiment, and be only defined by the claims.
Claims (22)
1. a kind of device for being used to prepare polyamide, it is characterised in that described device is raw material enrichment facility, including：
Preheating device, the raw material to be concentrated for preheating；
Evaporation concentration device, is connected with the preheating device, for the raw material being concentrated by evaporation after preheating；And
Condensing unit, is connected with the evaporation concentration device, the gas for condensing the evaporation concentration device evaporation discharge；
Wherein, the evaporation concentration device is evaporator with central downcomer, including a central tube and around the central tube
Some tube banks, raw material to be concentrated is heated concentration, the sectional area of the central tube in the central tube and the tube bank
For the 1~10% of the total sectional area of the tube bank；
The evaporation concentration device includes boil-off gas and exported and phegma entrance, is connected respectively with the condensing unit,
The gas of the evaporation concentration device evaporation discharge is entered in the condensing unit by boil-off gas outlet, gained after condensation
Phegma is by the phegma inlet return into the evaporation concentration device.
2. device according to claim 1, it is characterised in that the preheating device is heat exchanger.
3. device according to claim 1, it is characterised in that the length of the tube bank is 1~2m, a diameter of 30~
75mm, draw ratio is 20~40.
4. device according to claim 1, it is characterised in that the condensing unit is also connected with the preheating device,
Gained gas is used to heat the preheating device as thermal source after wherein condensing.
5. a kind of raw material method for concentration for being used to prepare polyamide, it is characterised in that using described in claim any one of 1-4
Device carries out raw material concentration process.
6. a kind of polyamide 5X production equipment, it is characterised in that including the raw material enrichment facility being sequentially connected, pre-polymerization device,
Decompressor, Moisture separation device and polycondensation device, wherein, the raw material enrichment facility is described in claim any one of 1-4
Device.
7. a kind of polyamide 5X production method, it is characterised in that using the production equipment described in claim 6, with polyamide
Saline solution is initiation material, sequentially passes through raw material concentration step, prepolymerization step, depressurization steps, moisture separating step and contracting
The polyamide 5X is made in poly- step.
8. production method according to claim 7, it is characterised in that the quality of the polyamide salt aqueous solution initiation material
Percent concentration is more than 50%.
9. production method according to claim 8, it is characterised in that the quality of the polyamide salt aqueous solution initiation material
Percent concentration is 50~65%.
10. production method according to claim 7, it is characterised in that in the raw material concentration step, the raw material concentration
The tube side pressure of device is 0.005~0.35MPa, and tube side temperature is 60~200 DEG C；And/or
Shell side pressure is 0~2.0MPa, and uneven shell-side temperature is less than 250 DEG C；And/or
The mass percent concentration of the polyamide salt aqueous solution after concentration is 50~80%.
11. production method according to claim 10, it is characterised in that in the raw material concentration step, the raw material is dense
The tube side pressure of compression apparatus is 0.05~0.35MPa, and tube side temperature is 80~160 DEG C；And/or
Uneven shell-side temperature is less than 212 DEG C；And/or
The mass percent concentration of the polyamide salt aqueous solution after concentration is 70~80%.
12. production method according to claim 7, it is characterised in that the temperature of the prepolymerization step is 200~300 DEG C；
And/or
The pressure of the prepolymerization step is below 3.0MPa；And/or
The mass percentage content that the prepolymerization step terminates the polymer of rear gained is 80~100%.
13. production method according to claim 12, it is characterised in that the temperature of the prepolymerization step is 220~280
℃；And/or
The pressure of the prepolymerization step is below 2.0MPa；And/or
The mass percentage content that the prepolymerization step terminates the polymer of rear gained is 85~95%.
14. production method according to claim 13, it is characterised in that the temperature of the prepolymerization step is 230~260
℃；And/or
The pressure of the prepolymerization step is 1.0~1.8Mpa.
15. production method according to claim 7, it is characterised in that in the depressurization steps, temperature is the polyamide
Temperature more than 5X fusing points.
16. production method according to claim 15, it is characterised in that in the depressurization steps, temperature is 200~300
℃。
17. production method according to claim 7, it is characterised in that in the depressurization steps, temperature is 230~260
℃。
18. production method according to claim 7, it is characterised in that in the moisture separating step, temperature is 250~
320℃。
19. production method according to claim 18, it is characterised in that in the moisture separating step, temperature is 250~
300℃。
20. production method according to claim 7, it is characterised in that the temperature of the condensation polymerization step is 250~320 DEG C；
And/or
The condensation polymerization step is carried out under normal pressure or vacuum condition, carries out using inert gas shielding, vacuum during polycondensation under normal pressure
Under the conditions of carry out polycondensation when pressure be 0~760mmHgA.
21. production method according to claim 20, it is characterised in that the temperature of the condensation polymerization step is 250~300
℃；And/or
It is 150~250mmHgA that the condensation polymerization step carries out pressure during polycondensation under vacuum.
22. the production method according to claim any one of 7-21, it is characterised in that the polyamide 5X is polyamide
56。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510239541.4A CN105013196B (en) | 2015-05-12 | 2015-05-12 | For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510239541.4A CN105013196B (en) | 2015-05-12 | 2015-05-12 | For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105013196A CN105013196A (en) | 2015-11-04 |
| CN105013196B true CN105013196B (en) | 2017-07-28 |
Family
ID=54403715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510239541.4A Active CN105013196B (en) | 2015-05-12 | 2015-05-12 | For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105013196B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107029442A (en) * | 2017-06-21 | 2017-08-11 | 江苏北松健康产业有限公司 | A kind of redistillation system and production system for drug extract |
| CN111518269B (en) * | 2019-02-02 | 2023-06-30 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin capable of crystallizing rapidly and preparation method thereof |
| CN111450559B (en) * | 2020-05-13 | 2023-09-26 | 南京工业大学 | Continuous evaporation desalination device for 1, 5-pentanediamine and application method thereof |
| CN111715159B (en) * | 2020-06-30 | 2021-06-04 | 华峰集团上海工程有限公司 | Continuous reaction system of polyamide |
| CN111821714B (en) * | 2020-07-27 | 2021-07-20 | 华峰集团上海工程有限公司 | Polyamide is with continuous concentrated system of refined salt |
| CN111821715B (en) * | 2020-07-27 | 2021-07-30 | 华峰集团上海工程有限公司 | Continuous concentration process of refined salt for polyamide |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008089484A1 (en) * | 2007-01-20 | 2008-07-24 | Dais Analytic Corporation | Multi-phase selective mass transfer through a membrane |
| CN102317351B (en) * | 2008-12-12 | 2013-12-11 | 巴斯夫欧洲公司 | Process for continuously preparing copolyamides from lactams and salts of diamines and dicarboxylic acids |
| CN101885842B (en) * | 2010-07-09 | 2012-03-21 | 北京三联虹普新合纤技术服务股份有限公司 | Continuous polymerization production technology for polyamide fibre 6 |
| EP2460839A1 (en) * | 2010-12-02 | 2012-06-06 | Stamicarbon B.V. acting under the name of MT Innovation Center | Method of making Polyamide 66 |
| ES2535741T3 (en) * | 2012-10-23 | 2015-05-14 | Uhde Inventa-Fischer Gmbh | Continuous procedure to prepare polyamide 6 and devices for it |
| CN104129880B (en) * | 2013-05-01 | 2018-11-23 | 英威达纺织（英国）有限公司 | For the method and system from polyamide synthesis technology recycle-water |
| CN204779449U (en) * | 2015-05-12 | 2015-11-18 | 上海凯赛生物技术研发中心有限公司 | Polyamide 5X's production facility |
| CN204767455U (en) * | 2015-05-12 | 2015-11-18 | 上海凯赛生物技术研发中心有限公司 | A production facility for preparing device and polyamide 5X of polyamide |
-
2015
- 2015-05-12 CN CN201510239541.4A patent/CN105013196B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105013196A (en) | 2015-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105013196B (en) | For preparing the device of polyamide, the production equipment of raw material method for concentration and polyamide, production method | |
| CN105885037B (en) | A kind of production equipment and method of polyamide 5X | |
| CA1216993A (en) | Continuous preparation of nylons | |
| CN204768734U (en) | A production facility for preparing device and polyamide of polyamide | |
| US20100144986A1 (en) | Continuous production of polyamides | |
| CN105013205B (en) | For preparing the device of polyamide, the production equipment of decompression method and polyamide, production method | |
| CN204767455U (en) | A production facility for preparing device and polyamide 5X of polyamide | |
| US20120245308A1 (en) | Process for preparing polyamides | |
| CN101528811B (en) | Application of coil tube evaporators for the production of polyamides | |
| CN105885038A (en) | Method for preparing polyamide | |
| CN102311545A (en) | Method for producing polyamide | |
| CN110156984A (en) | A kind of semiaromatic branched polyamide block copolymer and preparation method thereof | |
| CN105885040B (en) | It is used to prepare the device of polyamide, the production equipment of Prepolymerizing process and polyamide, production method | |
| CN110918018A (en) | Combined heat removal method for kettle type slurry polyethylene reactor | |
| CN104724728A (en) | Catholyte heat recovery evaporator and method of use | |
| CN105085904B (en) | It is a kind of to be used to prepare polyamide 5X device, eventually poly- method and polyamide 5X production equipment, method | |
| CN204779449U (en) | Polyamide 5X's production facility | |
| JP2016511781A (en) | Reactor with vertical condensing tube and process for polymerizing polyamide in such reactor | |
| JP2008081634A (en) | Polyamide prepolymer and method for producing polyamide | |
| US6759505B2 (en) | Single-phase or multi-phase continuous polyamide polymerization processes | |
| TW201938641A (en) | Process for preparing polymers | |
| BG64392B1 (en) | Polyamide production process | |
| JP2008080267A (en) | Composite heat exchange type reactor and production method of polycaproamide prepolymer using it | |
| US9062204B2 (en) | Process for the manufacture of a polyamide | |
| CN105885041B (en) | Production equipment, the method for a kind of device being used to prepare polyamide 5X, separation method and polyamide 5X |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190416 Address after: Fourth Floor, Building 5, No. 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Co-patentee after: CIBT American Company Patentee after: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. Address before: 201203 Shanghai Pudong New Area Zhangjiang hi tech park, Cai Lun Road, No. 5, 5 building, 4 floor. Co-patentee before: Cathay Industrial Biotech Co., Ltd. Patentee before: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190611 Address after: Fourth Floor, Building 5, No. 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Co-patentee after: CIBT American Company Patentee after: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. Co-patentee after: Victory (Wusu) biological materials Co., Ltd. Address before: 201203 Shanghai Pudong New Area Zhangjiang hi tech park, Cai Lun Road, No. 5, 5 building, 4 floor. Co-patentee before: CIBT American Company Patentee before: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP03 | Change of name, title or address |
Address after: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Co-patentee after: CIBT American Company Patentee after: Shanghai Kaisai Biotechnology Co., Ltd. Co-patentee after: Kaisai (Wusu) Biomaterials Co., Ltd. Address before: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 1690 Building 5 Floor 4 Co-patentee before: CIBT American Company Patentee before: Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. Co-patentee before: Kaisai (Wusu) Biomaterials Co., Ltd. |
|
| CP03 | Change of name, title or address |