CN101693767B - Devolatilization method of soluble high molecular polymers and device thereof - Google Patents
Devolatilization method of soluble high molecular polymers and device thereof Download PDFInfo
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Abstract
The invention discloses a devolatilization method of soluble high molecular polymers and a devolatilization device for realizing the devolatilization method. The method and the device can realize devolatilization treatment for the soluble polymers in a continuous feeding and discharging mode under low-medium temperature, in a closed space and under the condition of vacuum or high vacuum. The invention is characterized by recovering solvents (or water) with the maximum, realizing devolatilization or drying under the condition that materials, the environment and operators are completely isolated in the devolatilization process, thereby reducing devolatilization time, increasing the efficiency, reducing the energy consumption, and enabling products to better meet the requirements specification of GMP in the production process. The invention mainly discloses the devolatilization method of soluble high molecular polymers and the device thereof.
Description
Technical field
The present invention relates to a kind of devolatilization device that under vacuum state, continuously soluble high molecular polymers is carried out method with this method of realization of devolatilization.
Background technology
The devolatilization technology of soluble high molecular polymers has a variety of modes up to now, if the soluble high molecular polymers of molecular weight between 8000～300,000 generally speaking, using the spraying drying way is a way the most general.U.S. Pat 4,794,167 and US4,892,932 have announced the related approaches of using the spraying drying way to come dry polymer.In addition, U.S. Pat 5252704 announced a kind of with PVP K120 as dispersing auxiliary to the spraying drying way of second-order transition temperature less than 50 ℃ redispersible dissolve polymer.
But spraying drying has more restriction for the composition of product, second-order transition temperature etc.Greater than the high molecular polymer more than 300,000, there is the atomizing difficulty in spraying drying for molecular weight, and too weak point can not be with the droplet drying duration of contact with warm air for droplet, and tough material adheres to problems such as accumulation in a large number at the drying tower inwall.Therefore in fact exist a lot of soluble polymers not carry out the exsiccant problem with the spraying drying way, simultaneous spray drying exists also that energy consumption is big, warm air consumes greatly, and organic solvent reclaims difficulty, and energy consumption is high, has problems such as air and sound pollution.
U.S. Pat 5; 394; 622 have announced a kind of technology of coming the thicker polymers soln of dry different temperature controlled region with subregion temperature key-course (band); Be characterized in that warm air with differing temps comes drying to be layered on coming dry polymer and preventing to contain solvent polymeric thing blistered problem in drying process of thicker polymer film on chassis or the transport tape, thus obtain a kind of uniformly, the bright and clean dry film of polymkeric substance of appearance.This technology can realize working continuously, but can not under vacuum condition, carry out, and therefore can not utilize the low-temperature evaporation under the condition of negative pressure, can not accomplish very desirable to the anti-pollution measure of material.
Drying for HMW, full-bodied water-soluble polymers polyvinylpyrrolidonesolution solution; Chinese patent CN1821690, Japanese Patent Laid are opened 2002-146033 and are disclosed on a kind of appearance heat-transfer surface that uses the extrusion roller aqueous solutions of polymers to be coated on rotary dryer and carry out drying, the dry way of with scraper plate dried polymeric film being peeled off then.The distinct disadvantage of this way is that drying is carried out in open operating space; The humidity of environment is very big for the exsiccant influence; Need very high temperature could the moisture in the superpolymer be got rid of; But higher temperature tends to cause molecular rupture for polymkeric substance, degradation problem under the polymerization degree, so the K value of Vinylpyrrolidone polymer has bigger decline before dry with after the drying; The moisture (steam) that ejects in the polymkeric substance has simultaneously got into operating environment, and can only solve removing of steam by operating environment; Open operation has also brought the mutual cross-contamination issue of material, operator, operating environment; And such problem can not be solved by individual's protection of the cleanliness factor that improves environment, improvement operator fully; Polymkeric substance such as sticking to the drying machine surface collapses from its surface after drying sometimes; Splash in ground or the air, can bring a lot of operations and managerial inconvenience thus.Simultaneously, for the soluble polymer that comprises other solvents beyond the water, because of this method can not reclaim solvent and the solvent contamination problem under open environment can't solve.Equally, this method also exists with the spray-drying process similar problem---heat energy efficiency is lower; Also have a significant disadvantages to be; If the thermo-sensitivity of polymkeric substance is higher; In non-pressurized open space, the time of certainly will require the medium temperature of drying or devolatilization higher, heating is longer, like this for some thermosensitive polymer; Will certainly cause the reduction of the polymerization degree and the generation of oxidizing reaction, and produce the problems such as variation on color, the smell.
Common intermittent type Vacuumdrier can only pass in and out material under normal pressure; Each input and output material must frequently be done negative pressure and non-pressurized conversion; Very loaded down with trivial details and most dependence manual operations; Working efficiency is low, for most of plant-scale soluble polymer products, can only be used to test or the production of pilot scale, can not be used for the production purpose of mass-producing.The possibility that also has the mutual crossed contamination between material, environment and operator simultaneously.
Therefore; Be necessary to invent a kind of devolatilization method of improved soluble polymer product; It can be in airtight space, under the condition of vacuum or high vacuum; With lower medium temperature, and the method for soluble polymer being carried out devolatilization with the mode of successive charging and discharging, the while is reclaimed material and the environment in solvent (or water), the devolatilization process, drying or the devolatilization under the complete isolation of operator to greatest extent.
Summary of the invention
Technical problem to be solved by this invention is to be implemented in successive under airtight vacuum or the high vacuum state carries out devolatilization or exsiccant method and this method of realization to soluble polymer devolatilization device; Reach simultaneously with relatively low temperature and carry out devolatilization to reduce the polymerization degree degraded of high temperature to polymkeric substance; At utmost reclaim solvent (or water) and realize material and the environment in the devolatilization process, devolatilization or the drying under the complete isolation of operator; Thereby reduce the devolatilization time, increase efficient, cut down the consumption of energy, and make process of producing product meet the code requirement of GMP better.If solvent is under the situation of water, can obtain moisture less than 5% dry polymer powder, if the polymers soln of solution common organic solvents then can obtain polymer powder or partical below 3%.
In order to solve the problems of the technologies described above, the present invention provides a kind of devolatilization method of soluble high molecular polymers and the devolatilization device of this method of realization, and wherein this devolatilization method carries out under vacuum state continuously, and this method may further comprise the steps:
Step 1, soluble polymer solution is inserted in the insulating container that can stir;
Step 2, soluble polymer solution is pressed in the distributor of continuous vacuum devolatilization machine in said insulating container with the metering-type pressure pump;
On step 3, the heating unit of said distributor with the continuous transmission in the soluble polymer solution uniform distribution vacuum devolatilization machine;
Soluble polymer after step 4, the said heating unit heating of process gets on the refrigerating unit of continuous transmission;
Step 5, the cooled dried soluble polymkeric substance of the said refrigerating unit of process get in the material receiving apparatus.
As a kind of preferred version; Described heating unit and refrigerating unit concentrate on the crawler belt in the vacuum devolatilization machine; Feed heating agent up and down between the aspect near said distributor crawler belt part and constitute heating unit, the other end of this crawler belt feeds refrigerant up and down and constitutes refrigerating unit between the aspect.
Further, said heat medium temperature scope is 25 ℃～150 ℃, and said refrigerant temperature scope is-10 ℃～10 ℃.
Further, said crawler belt is a hot spots near 4/5 part of distributor, and remaining 1/5 part of this crawler belt is a cooling segment.
As a kind of preferred version, the soluble high molecular polymers that this method is fit to is:
The synthesizing water-solubility high molecular polymer comprises: polyacrylamide (negatively charged ion, nonionic, zwitter-ion), Z 150PH, polyethylene glycols, Vinylpyrrolidone polymer, vinyl pyrrolidone/acetate ethylene copolymer, ROHM, methacrylate polymer, HPMA, alkyl vinyl ether/maleic acid (hydrolyzate of alkyl vinyl ether/maleic anhydride multipolymer), gather Sorbic Acid, polymine, polyoxyethylene, ZX-I, CMC 99.5, sodium carboxymethyl-cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and sodium salt thereof, ether of cellulose, water soluble polyurethane resin;
Water-soluble high molecular polymer comprises: carrageenin, gelatin, pectin, XG 550, gum arabic, sodium-alginate, guar gum, cycloheptaamylose, maltodextrin, water soluble starch and starch derivative;
Soluble high molecular polymer in volatile solvent; Comprise: polyacrylamide (negatively charged ion, nonionic, zwitter-ion), polyvinyl alcohol, polyethylene glycols, Vinylpyrrolidone polymer class, vinyl pyrrolidone/acetate ethylene copolymer, HPMA, alkyl vinyl ether/maleic acid (hydrolyzate of alkyl vinyl ether/maleic anhydride multipolymer), gather Sorbic Acid, polymine, polyoxyethylene, ZX-I, CMC 99.5, sodium carboxymethyl-cellulose, the solute of Vltra tears in alcohols, hydro carbons, ketone, lipid solvent; According to the dissolving situation of various polymerization thing in different solvents, the solid content of its solution can be from 0.5%～40%;
Inorganic high molecular weight water soluble polymer comprises: neusilin, lithium magnesium silicate, sodium magnesium silicate, wilkinite and modified alta-mud, hectorite and modified water pyroxene.
The devolatilization device of realization soluble high molecular polymers devolatilization method provided by the invention; This devolatilization device is made up of stirring-type insulating container, metering-type pressure pump, vacuum devolatilization machine and material receiver; The metering-type pressure pump connects insulating container and vacuum devolatilization machine; Part has heating zone and cooling zone in this vacuum devolatilization machine, and said material receiver is connected with the cooling zone of vacuum devolatilization machine.
Further; Inner heating zone of described vacuum devolatilization machine and cooling zone are distributed on the crawler belt; Be connected with heating agent up and down between the aspect at the anterior crawler belt of this vacuum devolatilization machine and form the heating zone, be connected with refrigerant up and down between the aspect at this vacuum devolatilization machine rear portion crawler belt and form the cooling zone.
Further, there is a distributor the anterior crawler belt of said vacuum devolatilization machine top.
Further, described insulating container is a stirring-type jacketed insulating container.
As a kind of preferred version; Condensing surface is introduced through outlet pipe in said vacuum devolatilization machine top; The other end of said condensing surface top is communicated with the vacuum unit, and described material receiver stirs cage by the recovering hopper of blank chopper, bottom and spiral discharging to be formed, and the material of cutting-out is through stirring the kibbler that cage is transported to vacuum devolatilization machine outside; Material through pulverizing gets into pipeline through a bottom screen cloth, and this pipeline links to each other with splice jug through a valve of opening.
Beneficial effect of the present invention is:
1, technical scheme of the present invention can enough relatively low temperature be carried out devolatilization to reduce the polymerization degree degraded of high temperature to polymkeric substance; The aqueous solution for water-soluble polymers; Can be from minimum 25 ℃; Dry polymer fast under the highest temperature that is no more than 80C, and farthest reduce degraded to the material polymerization degree.
2, technical scheme of the present invention can at utmost reclaim solvent (or water).
3, technical scheme of the present invention realizes material and the environment in the devolatilization process, devolatilization or the drying under the complete isolation of operator, thereby reduces the devolatilization time, increases efficient, cuts down the consumption of energy, and makes process of producing product meet the code requirement of GMP better.
4, the characteristics of technical scheme of the present invention are, if solvent is under the situation of water, can obtain moisture less than 5% dry polymer powder, if solvent is the polymers soln of common organic solvents, then can obtain polymer powder or partical below 3%.
5, the characteristics of technical scheme of the present invention are; The medium of its heating (heating agent) can be hot water, steam, thermal oil; Because of most of soluble polymers can be in the characteristics of low temperature devolatilization under the high vacuum condition; Can utilize the band waste heat of recovery steam condenses, utilize heat energy medium such as boiler afterheat regenerated hot water, thereby reduce carbon emission, reach the purpose of energy-conserving and environment-protective.
Figure of description
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is described in further detail.
Fig. 1 is an employed devolatilization apparatus structure synoptic diagram in the devolatilization method of the present invention.
Embodiment
Embodiment 1:
As shown in Figure 1, raw material: Vinylpyrrolidone polymer (PVP) K120 11% solution (Boai Xinkaiyuan Pharmacy stock Co., Ltd's production), viscosity: 7176mPa.s (25 ℃ of Brookfield RVT viscosmeters, 64# rotor, rotating speed 12rpm), K value: 122.Employed devolatilization method is described below:
The first, PVP solution is pumped in the container A of the jacketed insulation that can stir with closed conduit.
The second, PVP solution is pressed in the continuous vacuum devolatilization machine C with the speed of pressure pump according to 250kg/hr, solution is distributed on the crawler belt C2 of rotation uniformly by distributor C1.Through the heating coil C3 in hot water heating crawler belt middle layer, the temperature of the TP of control crawler belt top is at 55 ℃～80 ℃, crawler belt gait of march 400cm/hr; Said devolatilization machine devolatilization aspect length overall is 7500mm, and last 1500mm is cooling section C4, and logical 0～5 ℃ cold water makes the dry good PVP of devolatilization lower the temperature in the coil pipe.The water vapor that is evaporated in the devolatilization machine is pulled out outdoor by the vacuum machine, be introduced into condensing surface E, and refrigerant temperature is that the zero(ppm) water that condensation is got off is collected in the special-purpose storage tank at 3 ℃～5 ℃.
When three, dry good PVP foamed thin sheet arrives the other end of devolatilization machine; Be received the blank chopper (3 times/m) cutting-out of frequency of system; Get into the receiving vat of bottom; By the spiral cage that stirs in the groove, be transplanted on the outside kibbler of vacuum devolatilization machine, material is sent powder into splice jug by the material after pulverizing with end sieve (80 order).
When observing powder material in the splice jug and reach capacity state through the viewing window of splice jug; Close the valve that connects kibbler and splice jug; After the isolated vacuum system, splice jug is unloaded from body; And with the batch can of sky by after last, open vacuum valve, continue to receive powder material from kibbler.
The above-mentioned PVP K120 K120 powder that has obtained having better flowability; Its fugitive constituent (moisture content) is less than 3%, and the K value of powder is 120.4, changes less than 2; After powder-product reverts to the liquid of 11% solid content; Its viscosity is 7102mPa.s (25 ℃ of Brookfield RVT viscosmeters, 64# rotor, rotating speed 12rpm).Therefore, obtained the ideal powder-product after the polymkeric substance devolatilization (drying).
Devolatilization method provided by the invention meets the GMP production standard of pharmaceutical raw material, foodstuff additive, cosmetic field fully, can be used for the production of the raw material or the product of these industries.
Embodiment 2:
As shown in Figure 1, the devolatilization method of cycloheptaamylose solution is described below:
The first, cycloheptaamylose solution is pumped in the container A of the jacketed insulation that can stir with closed conduit.
The second, cycloheptaamylose solution is pressed in the continuous vacuum devolatilization machine C with the speed of pressure pump according to 270kg/hr, solution is distributed on the crawler belt C2 of rotation uniformly by distributor C1.Through the heating coil C3 in hot water heating crawler belt middle layer, the temperature of the TP of control crawler belt top is at 25 ℃～70 ℃, crawler belt gait of march 300cm/hr; Said devolatilization machine devolatilization aspect length overall is 7500mm, and last 1500mm is cooling section C4, and logical 0～5 ℃ cold water makes the dry good cycloheptaamylose of devolatilization lower the temperature in the coil pipe.The water vapor that is evaporated in the devolatilization machine is pulled out outdoor by the vacuum machine, be introduced into condensing surface E, and refrigerant temperature is that the zero(ppm) water that condensation is got off is collected in the special-purpose storage tank at 5 ℃～8 ℃.
When three, dry good cycloheptaamylose foamed thin sheet arrives the other end of devolatilization machine; Be received the blank chopper (3 times/m) cutting-out of frequency of system; Get into the receiving vat of bottom; By the spiral cage that stirs in the groove, be transplanted on the outside kibbler of vacuum devolatilization machine, material is sent powder into splice jug by the material after pulverizing with end sieve (80 order).
When observing powder material in the splice jug and reach capacity state through the viewing window of splice jug; Close the valve that connects kibbler and splice jug; After the isolated vacuum system, splice jug is unloaded from body; And with the batch can of sky by after last, open vacuum valve, continue to receive powder material from kibbler.
Embodiment 3:
As shown in Figure 1, the devolatilization method of polymaleic acid anhydride solution is described below:
The first, the polymaleic acid anhydride solution is pumped in the container A of the jacketed insulation that can stir with closed conduit.
The second, the polymaleic acid anhydride solution is pressed in the continuous vacuum devolatilization machine C with the speed of pressure pump according to 230kg/hr, solution is distributed on the crawler belt C2 of rotation uniformly by distributor C1.Through the heating coil C3 in hot water heating crawler belt middle layer, the temperature of the TP of control crawler belt top is at 100 ℃～150 ℃, crawler belt gait of march 400cm/hr; Said devolatilization machine devolatilization aspect length overall is 7500mm, and last 1500mm is cooling section C4, and logical 0～4 ℃ cold water makes the dry good HPMA of devolatilization lower the temperature in the coil pipe.The water vapor that is evaporated in the devolatilization machine is pulled out outdoor by the vacuum machine, be introduced into condensing surface E, and refrigerant temperature is that the zero(ppm) water that condensation is got off is collected in the special-purpose storage tank at 3 ℃～10 ℃.
When three, dry good HPMA foamed thin sheet arrives the other end of devolatilization machine; Be received the blank chopper (3 times/m) cutting-out of frequency of system; Get into the receiving vat of bottom; By the spiral cage that stirs in the groove, be transplanted on the outside kibbler of vacuum devolatilization machine, material is sent powder into splice jug by the material after pulverizing with end sieve (80 order).
When observing powder material in the splice jug and reach capacity state through the viewing window of splice jug; Close the valve that connects kibbler and splice jug; After the isolated vacuum system, splice jug is unloaded from body; And with the batch can of sky by after last, open vacuum valve, continue to receive powder material from kibbler.
As shown in Figure 1; Devolatilization device disclosed by the invention is made up of stirring-type jacketed insulating container A, metering-type pressure pump B, vacuum devolatilization machine C and material receiver D; Metering-type pressure pump B connects insulating container A and vacuum devolatilization machine C; Part has heating zone and cooling zone in this vacuum devolatilization machine C, and said material receiver D is connected with the cooling zone of vacuum devolatilization machine.Inner heating zone of described vacuum devolatilization machine C and cooling zone are distributed on the crawler belt C2; Be connected with hot water at the coil pipe C3 between the aspect about the anterior crawler belt C2 of this vacuum devolatilization machine and form the heating zone, the coil pipe about this vacuum devolatilization machine rear portion crawler belt C2 between the aspect is connected with cold water and forms cooling zone C4.The anterior crawler belt C2 of vacuum devolatilization machine C top has a distributor C1 evenly material to be distributed on the crawler belt C2.Said vacuum devolatilization machine C introduces condensing surface E through outlet pipe in the top, and the other end top of said condensing surface E is communicated with the vacuum unit.Described material receiver D stirs cage by the recovering hopper of blank chopper, bottom and spiral discharging and forms; The material that downcuts is transported to the outside kibbler of vacuum devolatilization machine through stirring cage; Material through pulverizing gets into pipeline through a bottom screen cloth, and this pipeline links to each other with splice jug through a valve of opening.
The foregoing description is the preferred version in the technical scheme of the present invention, but technology of the present invention is not limited to the foregoing description, and the every technology that technical scheme thought is done according to the present invention distortion all falls within protection scope of the present invention.
Claims (7)
1. the devolatilization method of a soluble high molecular polymers, it is characterized in that: this devolatilization method carries out under vacuum state continuously, and this method may further comprise the steps:
Step 1, soluble polymer solution is inserted in the insulating container that can stir;
Step 2, soluble polymer solution is pressed in the distributor of continuous vacuum devolatilization machine in said insulating container with the metering-type pressure pump;
On step 3, the heating unit of said distributor with the continuous transmission in the soluble polymer solution uniform distribution vacuum devolatilization machine;
Soluble polymer after step 4, the said heating unit heating of process gets on the refrigerating unit of continuous transmission;
Step 5, the cooled dried soluble polymkeric substance of the said refrigerating unit of process get in the material receiver;
Described heating unit and refrigerating unit concentrate on the crawler belt in the vacuum devolatilization machine, feed heating agent up and down between the aspect near said distributor crawler belt part and constitute heating unit, and the other end of this crawler belt feeds refrigerant up and down and constitutes refrigerating unit between the aspect; Said heat medium temperature scope is 25 ℃ ~ 150 ℃, and said refrigerant temperature scope is-10 ℃ ~ 10 ℃; Said crawler belt is a hot spots near 4/5 part of distributor, and remaining 1/5 part of this crawler belt is a cooling segment.
2. the devolatilization method of soluble high molecular polymers according to claim 1 is characterized in that, the soluble high molecular polymers that this method is fit to is:
The synthesizing water-solubility high molecular polymer, be selected from: the hydrolyzate of polyacrylamide, Z 150PH, polyethylene glycols, Vinylpyrrolidone polymer, vinyl pyrrolidone/acetate ethylene copolymer, ROHM, methacrylate polymer, HPMA, alkyl vinyl ether/maleic anhydride multipolymer, gather Sorbic Acid, polymine, ZX-I, CMC 99.5, sodium carboxymethyl-cellulose, Natvosol, hydroxypropylcellulose, Vltra tears and sodium salt thereof, ether of cellulose, water soluble polyurethane resin;
Water-soluble high molecular polymer, be selected from: carrageenin, gelatin, pectin, XG 550, gum arabic, sodium-alginate, guar gum, cycloheptaamylose, maltodextrin, water soluble starch and starch derivative;
Soluble high molecular polymer in volatile solventBe selected from: the hydrolyzate of polyacrylamide, polyvinyl alcohol, polyethylene glycols, Vinylpyrrolidone polymer class, vinyl pyrrolidone/acetate ethylene copolymer, HPMA, alkyl vinyl ether/maleic anhydride multipolymer, gather Sorbic Acid, polymine, ZX-I, CMC 99.5, sodium carboxymethyl-cellulose, the solute of Vltra tears in alcohols, hydro carbons, ketone, lipid solvent; According to the dissolving situation of various polymerization thing in different solvents, the solid content of its solution is 0.5% ~ 40%.
3. devolatilization device of realizing the said soluble high molecular polymers devolatilization method of claim 1; It is characterized in that: this devolatilization device is made up of stirring-type insulating container, metering-type pressure pump, vacuum devolatilization machine and material receiver; The metering-type pressure pump connects insulating container and vacuum devolatilization machine; Part has heating zone and cooling zone in this vacuum devolatilization machine, and said material receiver is connected with the cooling zone of vacuum devolatilization machine.
4. devolatilization device according to claim 3; It is characterized in that: inner heating zone of described vacuum devolatilization machine and cooling zone are distributed on the crawler belt; Be connected with heating agent up and down between the aspect at the anterior crawler belt of this vacuum devolatilization machine and form the heating zone, be connected with refrigerant up and down between the aspect at this vacuum devolatilization machine rear portion crawler belt and form the cooling zone.
5. the devolatilization device that is used for soluble high molecular polymers according to claim 4 is characterized in that: there is a distributor the anterior crawler belt of said vacuum devolatilization machine top.
6. devolatilization device according to claim 5 is characterized in that: described insulating container is a stirring-type jacketed insulating container.
7. according to described each devolatilization device of claim 3 to 6; It is characterized in that: condensing surface is introduced through outlet pipe in said vacuum devolatilization machine top; The other end top of said condensing surface is communicated with the vacuum unit; Described material receiver stirs cage by the recovering hopper of blank chopper, bottom and spiral discharging and forms; The material that downcuts is transported to the outside kibbler of vacuum devolatilization machine through stirring cage, gets into pipeline through the material of pulverizing through a bottom screen cloth, and this pipeline links to each other with splice jug through a valve of opening.
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| CN102675792B (en) * | 2012-05-04 | 2013-11-13 | 浦江县鑫平进出口有限公司 | Yellow semitransparent glue dots and preparation method thereof |
| CN103822461A (en) * | 2014-03-17 | 2014-05-28 | 无锡市海昌机械设备有限公司 | Improved structure of material distributing system for vacuum belt liquid continuous dryer |
| CN107311700B (en) * | 2017-06-30 | 2021-02-23 | 上海化工研究院有限公司 | Continuous production device for powder-particle polyphosphate fertilizer |
| CN107602909A (en) * | 2017-09-27 | 2018-01-19 | 王治民 | A kind of starch plastic degradation equipment |
| CN111359377B (en) * | 2018-12-26 | 2022-04-15 | 绍兴福膜新材料有限公司 | Devolatilization method and devolatilization system |
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| EP0283460A2 (en) * | 1987-03-16 | 1988-09-21 | Fina Research S.A. | "Process for removing the solvent from a solution of a polymer" |
| US6353088B1 (en) * | 1998-03-27 | 2002-03-05 | Nippon Steel Chemical Co., Ltd. | Method for removing volatile matter from polymer solution composition |
| CN201620117U (en) * | 2009-09-25 | 2010-11-03 | 博爱新开源制药股份有限公司 | Devolatilization device of soluble high molecular polymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283460A2 (en) * | 1987-03-16 | 1988-09-21 | Fina Research S.A. | "Process for removing the solvent from a solution of a polymer" |
| US6353088B1 (en) * | 1998-03-27 | 2002-03-05 | Nippon Steel Chemical Co., Ltd. | Method for removing volatile matter from polymer solution composition |
| CN201620117U (en) * | 2009-09-25 | 2010-11-03 | 博爱新开源制药股份有限公司 | Devolatilization device of soluble high molecular polymer |
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