CN117003922A - Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same - Google Patents
Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same Download PDFInfo
- Publication number
- CN117003922A CN117003922A CN202210463213.2A CN202210463213A CN117003922A CN 117003922 A CN117003922 A CN 117003922A CN 202210463213 A CN202210463213 A CN 202210463213A CN 117003922 A CN117003922 A CN 117003922A
- Authority
- CN
- China
- Prior art keywords
- random copolymer
- aromatic vinyl
- vinyl monomer
- conjugated diene
- hollow
- 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.)
- Pending
Links
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 86
- 239000000178 monomer Substances 0.000 title claims abstract description 73
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 69
- 150000001993 dienes Chemical class 0.000 title claims abstract description 67
- 238000001035 drying Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 17
- 208000005156 Dehydration Diseases 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 25
- 239000002245 particle Substances 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011115 styrene butadiene Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 alkyl lithium Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B17/00—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement
- F26B17/18—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotating helical blades or other rotary conveyors which may be heated moving materials in stationary chambers, e.g. troughs
- F26B17/20—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotating helical blades or other rotary conveyors which may be heated moving materials in stationary chambers, e.g. troughs the axis of rotation being horizontal or slightly inclined
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B23/00—Heating arrangements
- F26B23/10—Heating arrangements using tubes or passages containing heated fluids, e.g. acting as radiative elements; Closed-loop systems
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/14—Drying solid materials or objects by processes not involving the application of heat by applying pressure, e.g. wringing; by brushing; by wiping
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Sustainable Development (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polymer post-treatment, and discloses an aromatic vinyl monomer-conjugated diene random copolymer and a drying method thereof. The drying method comprises the following steps: drying the aromatic vinyl monomer-conjugated diene random copolymer by adopting a hollow blade dryer; the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is below 0.75wt%. The drying method of the aromatic vinyl monomer-conjugated diene random copolymer provided by the invention can obviously reduce the volatile matters, particularly the moisture content, in the random copolymer after drying, obviously reduce the energy consumption and the environmental pollution, and simultaneously ensure that the dried random copolymer maintains excellent tearing strength, elasticity and wear resistance.
Description
Technical Field
The invention relates to the field of polymer post-treatment, in particular to an aromatic vinyl monomer-conjugated diene random copolymer and a drying method thereof.
Background
The aromatic vinyl monomer-conjugated diene random copolymer is an important high molecular polymer obtained by random copolymerization of aromatic vinyl monomer and conjugated diene monomer, the physical structural performance, the processing performance and the service performance of products are close to those of natural rubber, and some performances such as wear resistance, heat resistance, ageing resistance and vulcanization speed are better than those of natural rubber, so that the aromatic vinyl monomer-conjugated diene random copolymer can be used together with natural rubber and various synthetic rubbers, and can be widely applied to the fields of tires, adhesive tapes, rubber tubes, wires, cables, medical appliances, various rubber products and the like. As the aromatic vinyl monomer-conjugated diene random copolymer used in the prior art, there are styrene-1, 3-butadiene random copolymer, styrene-isoprene random copolymer and the like.
The preparation method of the aromatic vinyl monomer-conjugated diene random copolymer includes bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., wherein the kind of random copolymer obtained by the solution polymerization method is the largest. When the solution polymerization method is adopted to prepare the aromatic vinyl monomer-conjugated diene random copolymer, a wet condensation process is adopted to remove the solvent added in the polymerization process after the polymerization reaction is completed, and the water content of the random copolymer colloidal particles obtained after condensation is usually about 50%. In the prior art, the drying technique of a combination of an extrusion dehydrator and an expansion dryer is generally used to remove moisture and residual solvent from the coagulated aqueous colloidal particles. Firstly, feeding random copolymer colloidal particles containing water and a small amount of organic matters into an extrusion dehydrator, and removing the water content in the random copolymer colloidal particles to about 10% through extrusion; the extruded and dehydrated colloidal particles enter an expansion dryer, the operation temperature of the expansion dryer is more than or equal to 100 ℃, and the drying temperature of the expansion dryer is more than or equal to 150 ℃ at the outlet. Even if the drying is carried out at such a relatively high temperature, the volatile content of the obtained aromatic vinyl monomer-conjugated diene random copolymer colloidal particles can be reduced only to about 1.5%; and because the operation temperature of the expansion dryer is higher, the colloidal particles are easy to plasticize, and even the firing accident of the drying box can be caused. In order to meet the product index requirement that the volatile content in the aromatic vinyl monomer-conjugated diene random copolymer is lower than 0.75%, a large amount of hot air is required to fluidize and dry after the expansion drying operation, and a large amount of VOC-containing tail gas is generated in the operation, and if the tail gas is not treated timely and effectively, serious atmospheric pollution is caused, so that the environment is not protected.
Disclosure of Invention
The invention aims to solve the problems of reduced quality of random copolymer in the drying process of aromatic vinyl monomer-conjugated diene random copolymer and energy consumption and tail gas emission in the drying process in the prior art, and provides an aromatic vinyl monomer-conjugated diene random copolymer and a drying method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for drying an aromatic vinyl monomer-conjugated diene random copolymer, comprising:
drying the aromatic vinyl monomer-conjugated diene random copolymer by adopting a hollow blade dryer;
the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is below 0.75wt%.
The second aspect of the present invention provides an aromatic vinyl monomer-conjugated diene random copolymer produced by the above-mentioned drying method.
Through the technical scheme, the aromatic vinyl monomer-conjugated diene random copolymer and the drying method thereof provided by the invention have the following beneficial effects:
according to the drying method of the aromatic vinyl monomer-conjugated diene random copolymer, the hollow blade dryer is used for replacing the existing expansion dryer to dry the aromatic vinyl monomer-conjugated diene random copolymer colloidal particles obtained by solution polymerization, so that the volatile matters, particularly the moisture content, in the dried random copolymer can be remarkably reduced, the energy consumption and the environmental pollution are remarkably reduced, and the performance of the dried random copolymer is ensured.
Furthermore, the hollow blade dryer with the specific structure provided by the invention can realize the simultaneous heating of the outer jacket and the inner hollow stirring blade of the dryer, has large heat transfer area and high heat efficiency, improves the uniformity of heating materials and improves the heat and mass transfer effect. Compared with the traditional drying mode, the drying method provided by the invention has the advantages of uniform drying, product quality improvement, energy consumption reduction, clean production, easiness in realizing automatic control and the like.
Further, the drying method provided by the invention can remarkably reduce the volatile matters, particularly the moisture content, in the dried random copolymer, remarkably reduce the energy consumption and the pollution to the environment, and simultaneously ensure that the dried random copolymer keeps excellent tearing strength, elasticity and wear resistance.
Drawings
FIG. 1 is a flow chart showing a method for drying an aromatic vinyl monomer-conjugated diene random copolymer according to the present invention.
Description of the reference numerals
1 aqueous colloidal particles; 2 coarse dewatering screen; 3, extruding a dehydrator; 4, a hollow blade dryer; 5 aromatic vinyl monomer-conjugated diene random copolymer.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for drying an aromatic vinyl monomer-conjugated diene random copolymer, comprising:
drying the aromatic vinyl monomer-conjugated diene random copolymer by adopting a hollow blade dryer;
the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is below 0.75wt%.
According to the invention, a hollow blade dryer is adopted to replace a traditional expansion dryer, and the aromatic vinyl monomer-conjugated diene random copolymer colloidal particles obtained by solution polymerization reaction are subjected to drying treatment, so that the volatile content, particularly the moisture content, in the dried random copolymer can be remarkably reduced, and the dried random copolymer can maintain excellent performance.
Compared with the traditional expansion drying technology, the drying method provided by the invention can improve the uniformity of heated materials and improve the product quality; and the energy consumption for drying is reduced, the drying time is shortened, the emission of the VOC-containing tail gas is obviously reduced, the tail gas treatment cost is greatly reduced, and the advantages of energy conservation, consumption reduction, clean production, easiness in realizing automatic control and the like are realized.
According to the present invention, the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is 0.5wt% or less.
According to the invention, the hollow blade dryer comprises a jacket and at least 2 hollow stirring shafts and at least 8 hollow blades;
the hollow stirring pump is arranged in the dryer in parallel along the horizontal direction;
at least 8 hollow paddles are uniformly arranged on each hollow stirring pump, and the hollow paddles arranged on the adjacent 2 hollow stirring pumps are in an intermeshing state when rotating.
According to the hollow blade dryer with the specific structure, the external jacket and the internal hollow stirring blade of the dryer can be heated simultaneously, the heat transfer area is large, the heat efficiency is high, the uniformity of heating materials is improved, and the heat and mass transfer effect is improved. Compared with the traditional drying mode, the drying method provided by the invention has the advantages of uniform drying, product quality improvement, energy consumption reduction, clean production, easiness in realizing automatic control and the like.
According to the invention, the hollow blade dryer comprises 4 hollow stirring pumps.
According to the invention, 8-16 hollow paddles are uniformly arranged on each hollow stirring pump;
further, the hollow blade is a wedge-shaped hollow blade.
According to the invention, a heating medium is introduced into the jacket, the hollow stirring shaft and the hollow blades.
In the present invention, the heating medium is at least one selected from the group consisting of steam, hot water and heat transfer oil.
According to the invention, the operating temperature of the hollow blade dryer is 80-140 ℃, the operating time is 0.5-1.3h, and the power consumption is 1.2-2.6kW/kg of pure polymer.
In the present invention, the aromatic vinyl monomer-conjugated diene random copolymer is dried at the above temperature and time, so that the drying efficiency of the aromatic vinyl monomer-conjugated diene random copolymer can be improved, and a random copolymer product having a satisfactory volatile content (water content) can be obtained.
In order to further improve the drying effect on the aromatic vinyl monomer-conjugated diene random copolymer, it is preferable that the hollow blade dryer is operated at a temperature of 90 to 130℃for a time of 0.7 to 1.1 hours and a power consumption of 1.5 to 2.3kW/kg of pure polymer.
According to the invention, the operating pressure of the hollow blade dryer is negative, normal or micro-positive pressure, preferably normal.
In the present invention, the micro positive pressure means a pressure whose absolute pressure value is 0.02 to 0.15atm higher than the normal pressure.
According to the present invention, the content of the structural unit provided by the aromatic vinyl monomer is 20 to 40wt% based on the total weight of the aromatic vinyl monomer-conjugated diene random copolymer.
In the present invention, the weight average molecular weight and the like of the aromatic vinyl monomer-conjugated diene random copolymer are not particularly limited, and various aromatic vinyl monomer-conjugated diene random copolymers having different weight average molecular weights in the prior art may be used.
In the present invention, the types of the aromatic vinyl monomer and the conjugated diene are not particularly limited, and may be aromatic vinyl monomers or conjugated dienes which are conventional in the art, for example, styrene, and butadiene and/or isoprene.
Further, in the present invention, the aromatic vinyl monomer-conjugated diene random copolymer includes styrene-butadiene random copolymer (SBR), styrene-isoprene random copolymer (SIR), styrene-isoprene-butadiene random copolymer (SIBR).
According to the present invention, the aromatic vinyl monomer-conjugated diene random copolymer is derived from solution polymerization.
In the present invention, the polymerization method of the aromatic vinyl monomer-conjugated diene random copolymer is not particularly limited, and a solution polymerization method conventional in the art, for example, may be employed: styrene and butadiene are used as comonomers, or styrene and isoprene are used as comonomers, or styrene, isoprene and butadiene are used as comonomers, and all the monomers are fed simultaneously; and (3) taking saturated straight-chain alkane or cycloalkane as a solvent, and taking alkyl lithium as an initiator to carry out random copolymerization on two monomers or three monomers, thus obtaining the aromatic vinyl monomer-conjugated diene random copolymer.
In the present invention, the polymerization system of the aromatic vinyl monomer-conjugated diene random copolymer is not particularly limited, and a continuous solution polymerization system or a batch solution polymerization system may be employed.
In the present invention, the conditions for the solution polymerization and the amounts of the aromatic vinyl monomer, conjugated diene, initiator and the like are not particularly limited, and the polymerization may be carried out in conventional amounts under the conditions of the solution polymer which are conventional in the art.
According to the invention, the drying method comprises the following steps:
s1, carrying out wet condensation on an aromatic vinyl monomer-conjugated diene random copolymer from solution polymerization to obtain an aqueous sizing material;
s2, sequentially carrying out coarse dehydration treatment and extrusion dehydration treatment on the water-containing colloidal particles to obtain a preform;
s3, drying the preform by adopting a hollow blade dryer to obtain the aromatic vinyl monomer-conjugated diene random copolymer.
In the present invention, a large amount of solvent carried by the aromatic vinyl monomer-conjugated diene random copolymer from solution polymerization can be removed by wet coagulation.
In the present invention, the coarse dewatering treatment is not particularly limited, and the coarse dewatering treatment may be carried out on the aqueous colloidal particles by using a vibrating screen apparatus commonly used in the art, such as a linear vibrating screen, a reciprocating vibrating screen, a rotary vibrating screen, and the like.
In the present invention, the extrusion dehydration treatment is not particularly limited, and extrusion dehydration treatment of aqueous colloidal particles can be performed by using extruder equipment commonly used in the art, such as a single screw extruder, a twin screw extruder, a multi-screw extruder, etc.
In the invention, the volatile content in the preform obtained by rough dehydration treatment and extrusion dehydration treatment is about 10 wt%.
Referring to fig. 1, in one embodiment of the present invention, the method for drying the aromatic vinyl monomer-conjugated diene random copolymer comprises the steps of:
the aromatic vinyl monomer-conjugated diene random copolymer from solution polymerization is subjected to wet coagulation to obtain water-containing colloidal particles 1;
the water-containing colloidal particles 1 sequentially undergo coarse dehydration treatment by a vibrating screen 2, and then undergo extrusion dehydration treatment by a single screw extruder 3 to obtain a preform;
and drying the preform by adopting a hollow blade dryer 3 to obtain the aromatic vinyl monomer-conjugated diene random copolymer 5.
The second aspect of the present invention provides an aromatic vinyl monomer-conjugated diene random copolymer produced by the above-mentioned drying method.
In the present invention, the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer is 0.75wt% or less, preferably 0.5wt% or less.
The present invention will be described in detail by examples.
The random copolymerization of the aromatic vinyl monomer-conjugated diene used in the following examples and comparative examples was prepared as follows:
styrene-butadiene random copolymer obtained by solution polymerization of styrene, 1, 3-butadiene as a comonomer and hexane as a solvent in a kettle polymerization reactor using n-butyllithium as an initiator is used as an aromatic vinyl monomer-conjugated diene random copolymer, wherein the content of structural units provided by styrene is 27wt% based on the total weight of the styrene-butadiene random copolymer.
The tear strength of the vulcanizate was measured according to the method described in GB/T529 standard;
the rebound value of the vulcanized rubber is measured according to the method described in GB/T1681 standard;
DIN abrasion of the vulcanizate is determined according to the method described in GB/T9867 standard.
In the following examples and comparative examples, other various raw materials were used from commercial sources unless otherwise specified.
In the following examples and comparative examples, the method for measuring the volatile content was an oven method unless otherwise specified.
Example 1
S1, carrying out wet condensation on a styrene-butadiene random copolymer from solution polymerization, and removing a solvent to obtain water-containing colloidal particles;
s2, sequentially carrying out coarse dehydration treatment of a vibrating screen and extrusion dehydration treatment of a single screw extruder on the water-containing colloidal particles to obtain a preform; wherein the volatile content in the preform is 10wt%;
s3, drying the preform by adopting a hollow blade dryer to obtain the styrene-butadiene random copolymer.
The hollow blade dryer comprises a jacket and 2 hollow stirring shafts which are parallel in the horizontal direction, and 12 wedge-shaped hollow blades are uniformly arranged on each hollow stirring shaft along the horizontal direction; saturated steam of 1MPa is introduced into the jacket, the hollow stirring shaft and the hollow blade to serve as a heating medium.
Wherein the operating pressure of the hollow blade dryer is normal pressure (absolute pressure is 1 atm), the operating temperature is 90 ℃, the operating time is 0.7h, and the power consumption is 1.8kW/kg of pure polymer.
The volatile content and appearance quality of the dried styrene-butadiene random copolymer product are shown in Table 1, respectively.
Example 2
Example 1 was essentially repeated except that the hollow blade dryer was operated for a period of 0.9h.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 3
Example 1 was essentially repeated except that the hollow blade dryer was operated for 1.1 hours.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 4
Example 1 was essentially repeated except that the operating temperature of the hollow blade dryer was 110 ℃.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 5
Example 1 was essentially repeated except that the hollow blade dryer was operated at a temperature of 110℃for a period of 0.9h.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 6
Example 1 was essentially repeated except that the hollow blade dryer was operated at a temperature of 110℃for a period of 1.1h.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 7
Example 1 was essentially repeated except that the operating temperature of the hollow blade dryer was 130 ℃.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 8
Example 1 was essentially repeated except that the hollow blade dryer was operated at 130℃for 0.9 hours.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 9
Example 1 was essentially repeated except that the hollow blade dryer was operated at 130℃for a period of 1.1h.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 10
Example 1 was essentially repeated except that the hollow blade dryer was operated at 80℃for a period of 1.3 hours.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 11
Example 1 was essentially repeated except that the hollow blade dryer was operated at a temperature of 140℃for a period of 0.5h.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 12
Example 1 was essentially repeated except that the hollow blade dryer was operated for 1.4 hours.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 13
Example 1 was essentially repeated except that the operating temperature of the hollow blade dryer was 150 ℃.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Example 14
Example 1 was essentially repeated except that 6 wedge-shaped hollow paddles were uniformly mounted on each hollow stirring shaft of the hollow paddle dryer.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
Comparative example 1
Example 1 was essentially repeated except that the hollow blade dryer of example 1 was replaced with an expansion dryer having a power consumption of 1.8kW/kg of pure polymer, wherein the first stage temperature was controlled to 90℃and the second stage temperature was controlled to 110℃and the third stage temperature was controlled to 130 ℃.
The volatile content and appearance quality of the styrene-butadiene rubber product after expansion drying are shown in Table 1, respectively.
Comparative example 2
Example 1 was essentially repeated except that the hollow blade dryer of example 1 was replaced with an expansion dryer having a power consumption of 2.7kW/kg of pure polymer, wherein the first stage temperature was controlled to 110℃and the second stage temperature was controlled to 130℃and the third stage temperature was controlled to 150 ℃.
The volatile content and appearance quality of the styrene-butadiene rubber product after expansion drying are shown in Table 1, respectively.
Comparative example 3
Example 1 was essentially repeated except that a solid paddle dryer was used instead of a hollow paddle dryer.
The volatile content and appearance quality of the dried styrene-butadiene rubber products are shown in Table 1, respectively.
TABLE 1
As can be seen from the data shown in table 1, according to the present invention, when the extruded styrene-butadiene rubber crumb is dried using a hollow blade dryer, the volatile content in the crumb can be removed as much as possible under milder temperature conditions; and the product is white and transparent from the appearance, and the phenomenon of clamping generation is not easy to occur in the drying process.
Test case
The physical and mechanical properties of the aromatic vinyl monomer-conjugated diene random copolymer obtained by drying according to the drying methods of examples and comparative examples were measured, and the results are shown in Table 2.
The formula used for the test is as follows: 100 parts of dried aromatic vinyl monomer-conjugated diene random copolymer, 50 parts of carbon black, 3 parts of zinc oxide, 1 part of stearic acid, 2 parts of sulfur and 1 part of accelerator.
The vulcanization conditions include: the vulcanization temperature is 145 ℃, the vulcanization time is 35min, and the vulcanization pressure is 15MPa.
TABLE 2
As can be seen from the data shown in Table 2, according to the present invention, the aromatic vinyl monomer-conjugated diene random copolymer (styrene-butadiene rubber) product with acceptable volatile content obtained by using the hollow blade dryer has higher tearing strength, lower rebound value and DIN abrasion loss, thus having better mechanical properties.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for drying an aromatic vinyl monomer-conjugated diene random copolymer, characterized by comprising:
drying the aromatic vinyl monomer-conjugated diene random copolymer by adopting a hollow blade dryer;
the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is below 0.75wt%.
2. The drying method according to claim 1, wherein the volatile content of the aromatic vinyl monomer-conjugated diene random copolymer after the drying treatment is 0.5% by weight or less.
3. The drying method according to claim 1 or 2, wherein the hollow blade dryer comprises a jacket and at least 2 hollow stirring shafts and at least 8 hollow blades;
the hollow stirring pump is arranged in the dryer in parallel along the horizontal direction;
at least 8 hollow paddles are uniformly arranged on each hollow stirring pump, and the hollow paddles arranged on the adjacent 2 hollow stirring pumps are in an intermeshing state when rotating.
4. A drying method according to claim 3, wherein the hollow paddle dryer comprises 4 hollow stirring pumps;
preferably, 8-16 hollow paddles are uniformly arranged on each hollow stirring pump;
preferably, the hollow blade is a wedge-shaped hollow blade.
5. The drying method according to claim 3 or 4, wherein a heating medium is introduced into the jacket, the hollow stirring shaft and the hollow blade;
preferably, the heating medium is selected from at least one of steam, hot water and heat transfer oil.
6. Drying process according to any one of claims 1-5, wherein the hollow blade dryer is operated at a temperature of 80-140 ℃, preferably 90-130 ℃;
preferably, the hollow blade dryer is operated for a time period of 0.5 to 1.3 hours, preferably 0.7 to 1.1 hours;
preferably, the hollow blade dryer has a power consumption of 1.2-2.6kW/kg of pure polymer, preferably 1.5-2.3kW/kg of pure polymer;
preferably, the operating pressure of the hollow blade dryer is negative, normal or micro-positive pressure, preferably normal.
7. The drying method according to any one of claims 1 to 6, wherein the content of the structural unit provided by the aromatic vinyl monomer is 20 to 40% by weight based on the total weight of the aromatic vinyl monomer-conjugated diene random copolymer.
8. The drying method according to any one of claims 1 to 7, wherein the aromatic vinyl monomer-conjugated diene random copolymer is derived from solution polymerization.
9. The drying method according to any one of claims 1 to 8, wherein the drying method comprises the steps of:
s1, carrying out wet condensation on an aromatic vinyl monomer-conjugated diene random copolymer from solution polymerization to obtain an aqueous sizing material;
s2, sequentially carrying out coarse dehydration treatment and extrusion dehydration treatment on the water-containing sizing material to obtain a preform;
and S3, drying the preform by adopting a hollow blade dryer to obtain the aromatic vinyl monomer-conjugated diene random copolymer.
10. An aromatic vinyl monomer-conjugated diene random copolymer produced by the drying method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463213.2A CN117003922A (en) | 2022-04-28 | 2022-04-28 | Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463213.2A CN117003922A (en) | 2022-04-28 | 2022-04-28 | Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117003922A true CN117003922A (en) | 2023-11-07 |
Family
ID=88562272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210463213.2A Pending CN117003922A (en) | 2022-04-28 | 2022-04-28 | Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117003922A (en) |
-
2022
- 2022-04-28 CN CN202210463213.2A patent/CN117003922A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3683511A (en) | Method of removing volatiles from an elastomer | |
| EP3031590B1 (en) | Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom | |
| RU2638960C2 (en) | Butadiene rubber with drawfully increased viscosity by mooney received with use of inodimic catalyst | |
| JP2018536719A (en) | Itaconate / butadiene copolymer type bioengineering rubber and method for preparing the same | |
| AU729556B2 (en) | Process for the production of elastomer-modified thermoplastics | |
| CN102731723A (en) | Diene polymer and production method thereof | |
| CN114127137A (en) | Acrylic rubber bale with excellent strength characteristic and processability | |
| CN114072431A (en) | Acrylic rubber bale with excellent storage stability and processability | |
| CN117003922A (en) | Aromatic vinyl monomer-conjugated diene random copolymer and method for drying same | |
| TW202030215A (en) | Method of preparing vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound graft copolymer, and thermoplastic resin composition including graft copolymer | |
| CN110982013B (en) | Preparation method of polybutadiene latex with low gel content and prepared polybutadiene latex | |
| CN114051506A (en) | Acrylic rubber bag with excellent storage stability and water resistance | |
| CN106832490B (en) | A kind of rubber production technology | |
| CN114907590A (en) | Synthetic rubber wet masterbatch and preparation method and application thereof | |
| US2854426A (en) | Process of milling synthetic rubber latex coagulum containing water | |
| CN112707994B (en) | Preparation method of end-epoxy-terminated functionalized solution-polymerized styrene-butadiene rubber | |
| CN114316090B (en) | Polymer with low solvent residue and preparation method thereof | |
| CN110016151B (en) | Modified butadiene rubber and preparation method and application thereof | |
| CN117003912A (en) | Aromatic vinyl monomer-conjugated diene block copolymer and method for drying same | |
| CN117003913A (en) | Hydrogenated nitrile rubber and drying method and drying process thereof | |
| US3645940A (en) | Polysaccharide-reinforced rubber | |
| CN110483900A (en) | A kind of rotational moulding polypropylene and preparation method thereof | |
| CN108841017B (en) | Heat treatment method for improving cross-linking activity of tetrafluoroethylene-propylene rubber | |
| USRE24904E (en) | Process of milling synthetic rubber | |
| CN115286822B (en) | Polar natural rubber masterbatch and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |