CN114573735B - Integrated device for preparing epoxidized natural rubber, method and application thereof - Google Patents
Integrated device for preparing epoxidized natural rubber, method and application thereof Download PDFInfo
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- CN114573735B CN114573735B CN202011370898.3A CN202011370898A CN114573735B CN 114573735 B CN114573735 B CN 114573735B CN 202011370898 A CN202011370898 A CN 202011370898A CN 114573735 B CN114573735 B CN 114573735B
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Abstract
The invention relates to an integrated device for preparing epoxidized natural rubber, a method and application thereof, wherein the device comprises a reaction tank body and a multi-module double-screw extruder; the multi-module double-screw extruder is connected with a discharge port of the reaction tank body. The device has good corrosion resistance and temperature control effects, has the functions of steam flocculation, water washing, drying and the like, can control the reaction temperature within +/-3 ℃ of a set temperature, and can realize quick solidification and drying after the reaction is finished to obtain a final dry rubber product.
Description
Technical Field
The invention relates to the field of rubber preparation, in particular to an integrated device for preparing epoxidized natural rubber, a method and application thereof.
Background
The natural rubber has high elasticity, high stretching strength, good insulativity, plasticity, tear resistance and wear resistance, can generate better adhesive force with other materials, has the characteristic of 'stretching crystallization', and has various advantages to determine that the natural rubber becomes an elastomer with excellent comprehensive performance, is widely used in various industries such as transportation, national defense and military industry, medical and health, aerospace and the like, and is the most widely applied and green renewable general rubber. However, natural rubber is a rubber with a nonpolar structure, which results in poor solvent resistance, aging resistance, wet skid resistance, air tightness and the like, and further limits the wide application thereof. The double bonds on the molecular chain are modified by a chemical method, so that the performance of the natural rubber can be effectively improved, the application of the natural rubber is expanded, and the added value of the product is increased.
Among various modification methods of natural rubber, epoxidation modification of natural rubber is one of the most promising and practical methods. Through epoxidation modification, partial double bonds on a molecular chain of the natural rubber are randomly replaced by polar epoxy bonds, so that on one hand, the excellent performance of the natural rubber is maintained, on the other hand, the polarity of the natural rubber is increased, and the glass transition temperature of the natural rubber is increased, so that the performances of solvent resistance, air tightness, wet skid resistance and the like of the natural rubber are greatly improved, and the natural rubber can be used as an automobile cover tire, a high-performance load-carrying tire, a damping vibration-absorbing material, a bicycle inner tube and the like, and can be compounded with materials such as PVC, NBR and the like.
Many research institutions at home and abroad have conducted extensive researches on preparation, structure, performance, application and the like of epoxidized natural rubber. Today, both thailand and malaysia have commercial grades of epoxidized natural rubber applied to high performance tire tread stock and further exported worldwide. However, one of the impediments to further expanding the use of epoxidized natural rubber is the problem of production cost. Firstly, because the requirements on temperature control are higher in the production process, the thermal conductivity of the reaction kettle is good, the peroxyformic acid is used as an oxidant, and the requirements on corrosion resistance of equipment are higher, the common stainless steel reaction kettle has strong thermal conductivity but is not corrosion-resistant, and the cost of the corrosion-resistant reaction kettle made of noble metal materials is extremely high; secondly, in the rubber production process, the latex needs to be flocculated into blocks for the next processing, but because a large amount of surfactant is added into the epoxidized natural latex, the flocculation is difficult to be carried out by a common mode (acid addition, high-valence metal salt addition and the like), and if solvents such as methanol, ethanol and the like are used for flocculation, the cost is extremely high; thirdly, the latex needs to be dehydrated and dried after the post-treatment, but the traditional hot air drying method has long time, low production efficiency and high cost, so that the problem of how to reduce the production cost of the epoxidized natural rubber is a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the problems of high requirements on temperature control and corrosion resistance, high cost and the like of a preparation device of epoxidized natural rubber in the prior art, the invention provides the preparation device of epoxidized natural rubber, which has the advantages of good corrosion resistance and temperature control effect, and functions of steam flocculation, water washing, drying and the like, the reaction temperature can be controlled within a range of +/-3 ℃ of a set temperature by using the device, and rapid solidification and drying can be realized after the reaction is finished, and a final dry rubber product is obtained.
The invention aims at providing a drying integrated device for preparing epoxidized natural rubber, which comprises a reaction tank body 1 and a multi-module double-screw extruder; the multi-module double-screw extruder is connected with a discharge port of the reaction tank body.
In the technical scheme, the multi-module double-screw extruder sequentially comprises a steam solidification section 2, a water washing section 3 and a drying section 4 according to the feeding sequence.
In the technical scheme, the steam solidification section comprises a feed inlet 8, a steam inlet 9 and a flocculation screw module, wherein the flocculation screw module is specifically designed in such a way that the clearance between a screw and a feed cylinder is 0.3-0.4 mm and the clearance between the screw and the feed cylinder is 1.5-2 mm; the length of the screw is 1-1.5 m.
In the technical scheme, the water washing section comprises a water inlet 10 and a water washing screw rod module, wherein the water washing screw rod module is specifically designed in such a way that the gap between a screw rod and a charging barrel is 0.3-0.4 mm, the gap between the screw rod and the charging barrel is 1-1.2 mm, and the length of the screw rod is 1-1.5 m.
In the above technical scheme, the drying section comprises a vacuum pump 11 and a drying screw module, the specific design of the drying screw module is that the gap between the screw and the charging barrel is 0.3-0.4 mm, the gap between the screw is 1-1.2 mm, and the length of the screw is 2-3 m.
In the technical scheme, the length ratio of the steam solidification section to the water washing section to the drying section is 1 (1-1.2) (2-2.2), and is preferably 1:1:2; wherein the length of the steam solidification section is less than or equal to 1.5m.
The steam coagulation section is used for directly contacting high-temperature steam with latex to demulsify and coagulate the latex, and the rubber obtained by steam flocculation is transported forwards; the water washing section washes out residual reagent in the rubber block by utilizing water flow under the shearing and mixing of the screw rod; and the drying section extrudes the water of the rubber block through high-temperature shearing extrusion, and pumps the residual water by utilizing a vacuum pump to finally obtain the dried rubber.
In the above technical scheme, be equipped with feed inlet 5 on the cover at the top of the retort body 1, pass the cover and set up (mixing) shaft 6, the upper end of (mixing) shaft 6 links to each other with the outer motor of cover, and the lower extreme stretches into in the jar body, is connected with stirring vane.
In the technical scheme, a discharge port 7 of the reaction tank body 1 is connected with a feed port 8 of a steam solidification section 2 of the double-screw extruder, and a steam inlet 9 is arranged at the upper part of the steam solidification section; the upper part of the water washing section 3 is provided with a water inlet 10; the upper part of the drying section 4 is provided with a vacuum air pump extraction opening 11, and the tail part is provided with a discharge opening 12.
In the above technical scheme, the reaction tank body 1 is provided with a hollow outer interlayer, the outer interlayer is provided with an outer interlayer water outlet pipe and an outer interlayer water inlet pipe, and the outer layer, the water outlet pipe and the water inlet pipe form an independent water circulation pipeline. The temperature of the water in the circulating pipeline is 30-50 ℃.
In the above technical scheme, be equipped with condensation circulating water inlet 13 on the outer intermediate layer and go into water piping connection with outer intermediate layer, be equipped with condensation circulating water outlet 14 on the outer intermediate layer and go out water piping connection with outer intermediate layer, condensation circulating water outlet 14 position is higher than condensation circulating water inlet 13 position.
In the technical scheme, the inner layer of the reaction tank body 1 is made of enamel material, and the thickness of the enamel material is more preferably 0.8-2 cm; the outer layer of the tank body is made of a metal material, and preferably stainless steel material.
In the technical scheme, the coating inside the charging barrel of the multi-module double-screw extruder is subjected to corrosion prevention treatment, and the coating is preferably a polytetrafluoroethylene coating.
In the technical scheme, the surfaces of the screw rod and the screw block in the multi-module double-screw extruder are subjected to corrosion prevention treatment, and a stainless steel screw rod or a polytetrafluoroethylene screw rod is preferable. The screw block is further preferably a Cr12MoV material meshing block, and the surface of the screw block is subjected to corrosion prevention treatment to prevent the screw block from being corroded by latex with stronger acidity.
In the technical scheme, the stirring blade is a double-folded blade paddle stirring blade; the rotation speed is 100r/min and above, preferably 100-120r/min.
In the technical scheme, the motor is a turbine speed reducer.
It is a further object of the present invention to provide a process for preparing epoxidized natural rubber.
In the technical scheme, the reaction temperature of the reaction tank body is 35-45 ℃, preferably 38-42 ℃.
In the technical scheme, the reaction time of the reaction tank body is 4-15 h, preferably 6-12 h.
In the technical scheme, the steam pressure in the steam solidification section is 0.5-0.7MPa, the steam inlet amount is 50-60Kg/h, and the steam temperature is 140-170 ℃.
In the above technical scheme, the temperature of the water washing section is 20-30 ℃, preferably room temperature.
In the technical scheme, the heating temperature of the twin screw in the drying section is 110-120 ℃, preferably 115-120 ℃.
In the technical scheme, the screw rotating speed of the multi-module double-screw extruder is 10-25 r/min, preferably 10-15 r/min.
Compared with the prior art, the invention has the following beneficial effects: the inner layer of the reaction tank is an enamel coating, so that the cost is low, the heat conduction performance is good, and the corrosion of peroxyformic acid can be effectively resisted. The multi-module double-screw extruder connected in series with the reaction tank has the functions of steam flocculation, water washing and drying, so that the flocculation cost is reduced, and the influence of the addition of a flocculating agent on the rubber performance is avoided; and the double screws and the vacuum pump are combined to dehydrate and dry the rubber, so that the drying effect is good, the efficiency is high, and finally, the epoxidized natural rubber product is prepared in a continuous and full-production chain mode.
The integrated whole process from reaction to solidification to final water washing and drying is realized, the problems of strong corrosiveness to equipment, difficult flocculation and high flocculation cost of the epoxidized natural latex are solved, and the rubber block can be rapidly dehydrated and dried to carry out continuous production, so that the production flow is simplified, the production cost is reduced, and the production efficiency is greatly improved.
300kg of the device is fed once, and the epoxidation degree of the epoxidized natural rubber with the epoxidation degree less than 25mol percent can be controlled to be +/-2% of the theoretical value; the degree of epoxidation of epoxidized natural rubber having a degree of epoxidation of 25 to 60mol% can be controlled to + -3% of theoretical. The precision is slightly higher than the prior art by 1-2 percentage points. The accuracy of the epoxy degree is also higher as the temperature control is finer.
Drawings
Fig. 1 is a schematic structural view of the device of the present invention.
1-a reaction tank body; 2-a steam flocculation section; 3-washing section; 4-a drying section; 5-a feed inlet; 6, a stirring shaft; 7, a discharge hole of the tank body; 8-a steam flocculation section feed inlet; 9-steam inlet; 10-a water inlet; 11-a vacuum air pump extraction opening; 12-a discharge hole; 13-condensing the circulating water inlet; 14 condensing the recycled water outlet.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The integrated device for preparing the epoxidized natural rubber used in the embodiment of the invention is shown in fig. 1. The invention relates to a drying integrated device for preparing epoxidized natural rubber, which comprises a reaction tank body 1 and a multi-module double-screw extruder; the multi-module double-screw extruder is connected with a discharge port of the reaction tank body.
The multi-module double-screw extruder sequentially comprises a steam solidification section 2, a water washing section 3 and a drying section 4 according to the feeding sequence.
The steam solidification section comprises a feed inlet 8, a steam inlet 9 and a flocculation screw module, wherein the flocculation screw module is specifically designed in such a way that the clearance between a screw and a feed cylinder is 0.35mm and the clearance between the screw is 1.5mm; the length of the screw is 1.5m; the washing section comprises a water inlet 10 and a washing screw rod module, wherein the specific design of the washing screw rod module is that the gap between a screw rod and a charging barrel is 0.35mm, the gap between the screw rod and the charging barrel is 1mm, and the length of the screw rod is 1.5m; the drying section comprises a vacuum pump 11 and a drying screw module, wherein the specific design of the drying screw module is that the clearance between a screw and a charging barrel is 0.35mm, the clearance between the screw and the charging barrel is 1mm, and the length of the screw is 3m.
A tank cover at the top of the reaction tank body 1 is provided with a feed inlet 5, a stirring shaft 6 penetrates through the tank cover, the upper end of the stirring shaft 6 is connected with a turbine speed reduction motor outside the tank cover, and the lower end of the stirring shaft extends into the tank body and is connected with a double-folded blade paddle stirring blade; the rotation speed is 120r/min.
The discharge port 7 of the reaction tank body 1 is connected with the feed port 8 of the steam solidification section 2 of the double-screw extruder, and the upper part of the steam solidification section is provided with a steam inlet 9; the upper part of the water washing section 3 is provided with a water inlet 10; the upper part of the drying section 4 is provided with a vacuum air pump extraction opening 11, and the tail part is provided with a discharge opening 12.
The reaction tank body 1 is provided with a hollow outer interlayer, the outer interlayer is provided with an outer interlayer water outlet pipe and an outer interlayer water inlet pipe, and the outer layer, the water outlet pipe and the water inlet pipe form an independent water circulation pipeline. The water temperature in the circulation pipeline is 40 ℃. The outer interlayer is provided with a condensation circulating water inlet 13 which is connected with an outer interlayer water inlet pipe, the outer interlayer is provided with a condensation circulating water outlet 14 which is connected with an outer interlayer water outlet pipe, and the position of the condensation circulating water outlet 14 is higher than the position of the condensation circulating water inlet 13.
The inner layer of the reaction tank body 1 is made of enamel material with the thickness of 1 cm; the outer layer of the tank body is made of stainless steel. The coating inside the charging barrel of the multi-module double-screw extruder is subjected to corrosion prevention treatment, and the coating is a polytetrafluoroethylene coating. The surface of a stainless steel screw rod in the multi-module double-screw extruder is subjected to corrosion prevention treatment; the screw block is a Cr12MoV material meshing block, and the surface of the screw block is subjected to corrosion prevention treatment.
Example 1
When the device is used, 300kg of materials are firstly added into the reaction tank body 1 of the device, circulating water at 40 ℃ is introduced into an interlayer of the reaction tank body to heat the materials, a motor is started to drive a stirring shaft 6 to rotate, and under the condition of continuous stirring and rotation, the circulating water in the interlayer exchanges heat with the materials, so that the temperature of the materials is gradually increased to 40 ℃ required by the reaction, and the temperature is maintained at +/-3 ℃. The reaction time was set to 6 hours to prepare an epoxidized natural rubber having an epoxy degree of 25%. After the set reaction time is reached, a neutralizing agent is added to terminate the reaction, the materials are discharged into a steam solidification section 2, the steam pressure in the steam solidification section is 0.5MPa, the steam inlet amount is 30Kg/h, the steam temperature is 120 ℃, and the high-temperature steam entering from a steam inlet 9 is directly contacted with latex to carry out demulsification solidification. The solidified rubber block enters the water washing section 3 at room temperature, and residual reagent in the rubber block is washed out by utilizing water flow entering through the water inlet 10 under the shearing and mixing of the screw. The washed rubber block enters a drying section 4, the temperature of the drying section is 110 ℃, the water content of the rubber block is extruded through high-temperature shearing extrusion, residual water content is pumped out through a pumping hole 11 by utilizing a vacuum pump, and then the residual water content is discharged from a discharging hole 12, wherein the screw rotating speed of a multi-module double-screw extruder is 20r/min, and the solidified and dried epoxidized natural rubber ENR25B is obtained. The epoxy degree obtained after nuclear magnetic testing of the prepared epoxidized natural rubber is 23.6%, which accords with the theoretical value within + -2%.
Example 2
When the device is used, 300kg of materials are firstly added into the reaction tank body 1 of the device, circulating water at 40 ℃ is introduced into an interlayer of the reaction tank body to heat the materials, a motor is started to drive a stirring shaft 6 to rotate, and under the condition of continuous stirring and rotation, the circulating water in the interlayer exchanges heat with the materials, so that the temperature of the materials is gradually increased to 40 ℃ required by the reaction, and the temperature is maintained at +/-3 ℃. The reaction time was set to 12 hours to prepare an epoxidized natural rubber having an epoxy degree of 50%. After the set reaction time is reached, a neutralizing agent is added to terminate the reaction, the materials are discharged into a second steam flocculation section 2, the steam pressure in the steam coagulation section is 0.5MPa, the steam inlet amount is 30Kg/h, the steam temperature is 120 ℃, and the high-temperature steam entering from a steam inlet 9 is directly contacted with latex to carry out demulsification and coagulation. The solidified rubber block enters the water washing section 3 at room temperature, and residual reagent in the rubber block is washed out by utilizing water flow entering through the water inlet 10 under the shearing and mixing of the screw. The washed rubber block enters a drying section 4, the temperature of the drying section is 110 ℃, the water content of the rubber block is extruded through high-temperature shearing extrusion, residual water content is pumped out through a pumping hole 11 by utilizing a vacuum pump, and then the residual water content is discharged from a discharging hole 12, wherein the screw rotating speed of a multi-module double-screw extruder is 20r/min, and the solidified and dried epoxidized natural rubber ENR50B is obtained. The epoxy degree obtained after nuclear magnetic testing of the prepared epoxidized natural rubber is 51.9%, which accords with the theoretical value within the range of +/-3%.
Comparative test example
ENR25C and ENR50C were prepared using conventional preparation techniques. The traditional process comprises the following steps: and after the epoxidation reaction is finished in the reaction kettle, directly heating and flocculating, extruding and washing the flocculated rubber blocks by using a crepe machine, and transferring the washed rubber blocks into an oven for drying to obtain the product.
The performance of the preparation of ENR25B and ENR50B using the apparatus of the present invention is shown in table 1 as compared to the performance of ENR25C and ENR50C obtained by conventional preparation processes. Wherein the epoxy degree and the ring-opened matter ratio are characterized by adopting nuclear magnetic resonance hydrogen spectrum, and the aging performance is characterized by 100 ℃/48 h. The traditional process has complicated production flow and poor continuity, and the direct heating flocculation can aggravate side reaction, is unfavorable for product stability, and has inferior washing effect of a creper compared with a double screw. Compared with the traditional process, the epoxy degree of the invention is more stable and the ring opening ratio (side reaction ratio) is smaller, because the faster flocculation flow reduces the ring opening reaction in the flocculation process, the control of the epoxy degree and the inhibition of the side reaction are obviously superior to the traditional process; the aging performance test is carried out on the rubber at 150 ℃ for 48 hours, and the rubber is obviously superior to the traditional process because the acid remained in the rubber is better removed by adopting double screws for water washing.
TABLE 1
| Epoxy degree | Ring-opened matter ratio | Rate of aging Performance loss | ||
| Example 1 | ENR25B | 23.6 | 0.3％ | 31.6％ |
| Traditional process | ENR25C | 26.8 | 0.62％ | 35.3％ |
| Example 2 | ENR50B | 51.9 | 1.5％ | 42.9％ |
| Traditional process | ENR50C | 53.6 | 2.6％ | 47.2％ |
The above-described embodiment is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (11)
1. An integrated device for preparing epoxidized natural rubber comprises a reaction tank body and a multi-module double-screw extruder; the multi-module double-screw extruder sequentially comprises a steam solidification section, a water washing section and a drying section according to the feeding sequence; the steam solidification section comprises a feed inlet, a steam inlet and a flocculation screw module, and the steam inlet is positioned behind the feed inlet; the water washing section comprises a water inlet and a water washing screw module; the drying section comprises a vacuum pump pumping pump and a drying screw module; the multi-module double-screw extruder is connected with a discharge port of the reaction tank body; the inner layer of the reaction tank body is made of enamel material; the outer layer of the tank body is made of metal materials; the inside of the charging barrel of the multi-module double-screw extruder is subjected to corrosion prevention treatment; and the surfaces of the screws and the screw blocks in the multi-module double-screw extruder are subjected to corrosion prevention treatment.
2. The apparatus of claim 1, wherein the device comprises a plurality of sensors,
the clearance between the screw and the charging barrel in the flocculation screw module is 0.3-0.4 mm, the clearance between the screw and the charging barrel is 1.5-2 mm, and the length of the screw is 1-1.5 m;
the clearance between the screw and the charging barrel in the water-washing screw module is 0.3-0.4 mm, the clearance between the screw and the charging barrel is 1-1.2 mm, and the length of the screw is 1-1.5 m;
the gap between the screw and the charging barrel in the drying screw module is 0.3-0.4 mm, the gap between the screw and the charging barrel is 1-1.2 mm, and the length of the screw is 2-3 m;
the length ratio of the steam solidification section, the water washing section and the drying section is 1 (1-1.2) (2-2.2); wherein the length of the steam solidification section is less than or equal to 1.5m.
3. The apparatus of claim 1, wherein the device comprises a plurality of sensors,
a feed inlet is formed in a tank cover at the top of the reaction tank body, a stirring shaft penetrates through the tank cover, the upper end of the stirring shaft is connected with an external motor of the tank cover, and the lower end of the stirring shaft extends into the tank body and is connected with stirring blades; and/or the number of the groups of groups,
the discharge port of the reaction tank body is connected with the feed port of the steam solidification section of the double-screw extruder, and the upper part of the steam solidification section is provided with a steam inlet; the upper part of the water washing section is provided with a water inlet; the upper part of the drying section is provided with a vacuum air pump extraction opening, and the tail part is provided with a discharge opening; and/or the number of the groups of groups,
the reaction tank body is provided with a hollow outer interlayer, the outer interlayer is provided with an outer interlayer water outlet pipe and an outer interlayer water inlet pipe, and the outer interlayer, the water outlet pipe and the water inlet pipe form an independent water circulation pipeline.
4. The device according to claim 3, wherein the outer interlayer is provided with a condensation circulating water inlet connected with the outer interlayer water inlet pipe, the outer interlayer is provided with a condensation circulating water outlet connected with the outer interlayer water outlet pipe, and the position of the condensation circulating water outlet is higher than that of the condensation circulating water inlet.
5. The apparatus of claim 1, wherein the device comprises a plurality of sensors,
the inner layer of the reaction tank body is made of enamel material with the thickness of 0.8-2 cm; the outer layer of the tank body is made of stainless steel material; and/or the number of the groups of groups,
the coating inside the charging barrel of the multi-module double-screw extruder is a polytetrafluoroethylene coating; and/or the number of the groups of groups,
the screws in the multi-module double-screw extruder are stainless steel screws or polytetrafluoroethylene screws.
6. A device according to claim 3, wherein the stirring blade is a double-folded blade paddle stirring blade; and/or the motor is a turbine speed reducer.
7. An integrated apparatus for producing an epoxidized natural rubber according to any one of claims 1 to 6, a method for producing an epoxidized natural rubber.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
the reaction temperature of the reaction tank body is 35-45 ℃; and/or the number of the groups of groups,
the reaction time of the reaction tank body is 4-15 h.
9. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
the reaction temperature of the reaction tank body is 38-42 ℃; and/or the number of the groups of groups,
the reaction time of the reaction tank body is 6-12 h.
10. The method of claim 7, wherein the step of determining the position of the probe is performed,
the steam pressure in the steam solidification section is 0.5-0.7MPa, the steam inlet amount is 50-60Kg/h, and the steam temperature is 140-170 ℃; and/or
The temperature of the water washing section is 20-30 ℃;
the heating temperature of the twin screws in the drying section is 110-120 ℃;
the screw rotating speed of the multi-module double-screw extruder is 10-25 r/min.
11. The method of claim 10, wherein the step of determining the position of the first electrode is performed,
the temperature of the water washing section is room temperature;
the heating temperature of the twin screws in the drying section is 115-120 ℃;
the screw rotating speed of the multi-module double-screw extruder is 10-15 r/min.
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| CN201736367U (en) * | 2010-06-13 | 2011-02-09 | 中国热带农业科学院农产品加工研究所 | Wet natural rubber single-screw dehydration machine |
| CN205953900U (en) * | 2016-06-30 | 2017-02-15 | 株洲安宝麟锋新材料有限公司 | Natural latex high efficiency coagulation device |
| CN108905945A (en) * | 2018-07-11 | 2018-11-30 | 南通通江橡胶制品有限公司 | A kind of epoxy natural rubber prepares reaction unit |
| CN209438562U (en) * | 2018-09-11 | 2019-09-27 | 中山市鸿盛新材料有限公司 | Multi-module combined double screw rod applied to extrusion granulation of spraying-free material |
| CN109569477A (en) * | 2018-11-09 | 2019-04-05 | 杨建强 | A kind of Screw Extrusion-autoclave stirring combination type reactor and its application |
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