CN111087492B - Reaction device and method for preparing light hydrocarbon alternating copolymerization microspheres - Google Patents
Reaction device and method for preparing light hydrocarbon alternating copolymerization microspheres Download PDFInfo
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- CN111087492B CN111087492B CN201811241717.XA CN201811241717A CN111087492B CN 111087492 B CN111087492 B CN 111087492B CN 201811241717 A CN201811241717 A CN 201811241717A CN 111087492 B CN111087492 B CN 111087492B
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
Abstract
The invention relates to the field of polymerization reaction, and discloses a reaction device for preparing light hydrocarbon alternating copolymerization microspheres and a method for preparing the light hydrocarbon alternating copolymerization microspheres. The reaction device comprises a reactor (1) and a gas-liquid separator (2); the reactor (1) comprises a reactor shell (101), two diversion baffles (110), a plurality of hollow diversion pipes (105), a diversion baffle (109), a first material introduction port (102), a second material introduction port (104), a material discharge port (103) and a material channel (108), wherein the second material introduction port (104) is positioned at 40-60% of the total length of the material channel (108). The reaction device and the method can improve the conversion rate of the reaction and control the form of the light hydrocarbon alternate copolymerization microspheres.
Description
Technical Field
The invention relates to the field of polymerization reaction, in particular to a reaction device for preparing light hydrocarbon alternating copolymerization microspheres and a method for preparing the light hydrocarbon alternating copolymerization microspheres.
Background
The production of polymers generally comprises units of raw material treatment, catalyst unit, polymerization, separation and recycling, among which the polymerization unit is the more central and important unit, and the polymerization unit directly determines the operation of the polymerization reaction and the quality of the obtained polymerization product.
Unlike small molecule reactions, polymerization reactions have their own specificities such as increased viscosity during the reaction, a more intense exotherm associated with the reaction, and the like. In general, the polymerization reactor should meet the following general process requirements: the polymerization heat of the reaction can be effectively removed, and the polymerization reaction temperature can be better controlled; providing the necessary residence time of the reaction mass; providing necessary material mixing conditions to ensure that the concentration distribution in the reactor is relatively uniform; the operation cost is low, etc.
In general, polymerization reactors are classified into a suspension polymerization reactor, a slurry polymerization reactor, an emulsion polymerization reactor, a solution polymerization reactor and a bulk polymerization reactor according to the reaction method, and classified into a stirred tank reactor, a tubular reactor, a tower reactor, a fluidized bed reactor, etc. according to the structural form of the reactors. With the advancement of polymerization techniques, the structure and form of polymerization reactors have become more and more complicated (synthetic rubber industry, 1994,17(1): 47-51). Generally, reactors for producing different polymers have their specificity. The reactors for producing polymer particles are usually batch stirred reactors, helical ribbon stirred reactors, loop reactors, etc. (synthetic rubber industry, 1994,17(5): 299-. Developing new polymer production processes often requires new reactor designs to meet the control requirements of a particular polymerization reaction. For the reaction of maleic anhydride and C2-4The self-stabilization precipitation polymerization of unsaturated hydrocarbons to obtain reaction products with specific properties, and the related reaction apparatus and reaction method are not disclosed in the prior art.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a reaction device for preparing light hydrocarbon alternating copolymerization microspheres and a method for preparing the light hydrocarbon alternating copolymerization microspheres.
In order to achieve the above objects, the present invention provides, in one aspect, a reaction apparatus for preparing light hydrocarbon alternating copolymerization microspheres, the reaction apparatus comprising a reactor and a gas-liquid separator;
the reactor comprises: the shell of the reactor is provided with a reactor shell,
two flow guide baffles which are arranged inside the reactor shell and divide the inside of the reactor shell into a heat exchange cavity between the two and a first reaction cavity and a second reaction cavity at two sides,
a plurality of hollow draft tubes which are arranged between the two draft baffles in parallel and have openings at two ends respectively in the first reaction cavity and the second reaction cavity,
a baffle plate disposed inside the first reaction chamber to divide the first reaction chamber into an upper reaction chamber and a lower reaction chamber;
a first material introducing port arranged on the lower reaction chamber of the first reaction chamber,
a second material introducing port arranged on the second reaction chamber,
a material outlet port provided on the upper reaction chamber of the first reaction chamber, an
The material channel is a material passage which is sequentially connected with a first material introducing port, a lower reaction cavity of the first reaction cavity, the second reaction cavity, an upper reaction cavity of the first reaction cavity and a material leading-out port;
wherein the second material introducing port is positioned at 40-60% of the total length of the material channel; the reactor is connected with the gas-liquid separator through a material outlet.
Preferably, the heat exchange cavity is further provided with a temperature control medium inlet, a temperature control medium outlet and a temperature control medium cavity which is arranged inside the heat exchange cavity and outside the flow guide pipe.
Preferably, the gas-liquid separator comprises a housing divided by a perforated baffle into an upper gas-liquid zone and a lower gas-liquid separation zone,
the gas area is connected with a gas outlet,
the upper part of the gas-liquid separation area is connected with the material outlet, the lower part of the gas-liquid separation area is provided with a liquid outlet, and the inside of the gas-liquid separation area is provided with a stirring component.
Preferably, a cooling component is arranged outside the gas area, and a heating component is arranged outside the gas-liquid separation area.
The second aspect of the present invention provides a method for preparing light hydrocarbon alternating copolymerization microspheres by using the reaction device of the present invention, which comprises the following steps:
(1) the first material introducing port will contain C2-4Introducing a mixture of an unsaturated hydrocarbon, maleic anhydride and an initiator into the reactor so that the material undergoes a first polymerization reaction in the material passage, introducing divinylbenzene into the reactor at a material second introduction port so that the material undergoes a second polymerization reaction in the material passage, and discharging a reaction product from a material discharge port;
(2) and introducing the reaction product into a gas-liquid separator for gas-liquid separation.
Preferably, said C2-4The unsaturated hydrocarbon includes one or more of 1-butene, isobutylene, 1, 3-butadiene, 1, 2-butadiene, vinyl acetylene, cis-2-butene, and trans-2-butene.
Preferably, the mixture also comprises C2-4An alkane.
Preferably, said C2-4Alkanes include n-butane and/or isobutane.
Preferably, said C2-4Unsaturated hydrocarbons and C2-4The alkane includes 1-99 wt% of 1-butene, 1-99 wt% of isobutene, 0-99 wt% of 1, 3-butadiene, 0-50 wt% of 1, 2-butadiene, 0-99 wt% of n-butane, 1-99 wt% of isobutane, 5-20 wt% of vinyl acetylene, 0-99 wt% of cis-2-butene and 1-99 wt% of trans-2-butene.
Preferably, said C2-4Unsaturated hydrocarbons and C2-4The alkane comprises 0.1-2 wt% of 1-butene and 10-30 wt% of isobuteneThe amount%, 1, 3-butadiene 0.01-0.1 wt%, n-butane 0.5-5 wt%, isobutane 30-40 wt%, cis-2-butene 20-40 wt%, trans-2-butene 5-20 wt%.
Preferably, said C2-4Unsaturated hydrocarbons and C2-4The alkane comprises 5-15 wt% of 1-butene, 0.5-3 wt% of isobutene, 20-30 wt% of n-butane, 15-30 wt% of cis-2-butene and 35-45 wt% of trans-2-butene.
Preferably, the initiator is one or more of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
Preferably, the maleic anhydride is present in the mixture in an amount of 5 to 25% by weight, preferably 10 to 20% by weight.
Preferably, said C2-4The molar ratio of terminal olefin, maleic anhydride and divinylbenzene in the unsaturated hydrocarbon is 1: 0.8-7: 0.008-0.07.
Preferably, the mixture comprises an organic solvent.
Preferably, the organic solvent is one or more of organic acid alkyl ester, alkane, aromatic hydrocarbon and halogenated aromatic hydrocarbon.
Preferably, the organic acid alkyl ester is one or more of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate. More preferably, the organic acid alkyl ester is isoamyl acetate.
Preferably, the alkane is one or more of propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane and isooctane.
Preferably, the aromatic hydrocarbon is one or more of benzene, toluene and xylene.
Preferably, the halogenated aromatic hydrocarbon is chlorobenzene and/or bromobenzene.
Preferably, the reaction conditions in the reactor include: the first copolymerization reaction time is 0.5-3h, and the second copolymerization reaction time is 0.5-3 h.
Preferably, the first copolymerization time is 1 to 2 hours and the second copolymerization time is 1 to 2 hours.
Preferably, the reaction temperature is 50-100 ℃ and the reaction pressure is 0.2-2 MPa.
Preferably, the reaction temperature is 70-90 ℃ and the reaction pressure is 0.5-1 MPa.
Preferably, the rotation speed of the stirring part is 5-100 rpm.
Preferably, the method further comprises subjecting the liquid phase product to solid-liquid separation;
preferably, the solid-liquid separation mode is centrifugation.
Through the technical scheme, the reaction device for preparing the light hydrocarbon alternating copolymerization microspheres and the method for preparing the light hydrocarbon alternating copolymerization microspheres can realize maleic anhydride and C2-4The self-stabilization precipitation polymerization of unsaturated hydrocarbon realizes the effective removal of reaction heat, accurately controls reaction temperature, realizes the effective requirement on residence time, controls the concentration distribution of reactants, finally produces uniform superfine polymer powder, and can effectively improve the conversion rate of reaction.
Drawings
FIG. 1 is a schematic structural diagram of a reaction apparatus for preparing light hydrocarbon alternating copolymerization microspheres according to the present invention.
Description of the reference numerals
1. Reactor 2, gas-liquid separator
101. Reactor shell 102, first introducing port of material
103. Material outlet 104 and second material inlet
105. Flow guide pipe 106 and temperature control medium inlet
107. Temperature control medium outlet 108 and material channel
109. Deflection baffle 110, diversion baffle
111. First reaction chamber 112, heat exchange chamber
113. Second reaction chamber
201. Gas-liquid separation region 202, gas region
203. Perforated baffle 204 and motor
205. Stirring member 206 and gas outlet port
207. Liquid outlet 208 and heating medium inlet
209. Heating medium outlet 210 and cooling medium inlet
211. Coolant outlet
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the use of directional terms such as "upper, lower, left, right" generally means upper, lower, left, right in the drawings, unless otherwise specified. For example, "upper" and "lower" in the upper reaction chamber and the lower reaction chamber only indicate upper and lower in the drawing. The pressures are gage pressures.
The invention provides a reaction device for preparing light hydrocarbon alternating copolymerization microspheres, as shown in figure 1, the reaction device comprises a reactor 1 and a gas-liquid separator 2; the reactor 1 comprises:
the reactor shell (101) is provided with a plurality of reaction chambers,
two flow guide baffles 110 arranged inside the reactor shell 101, dividing the inside of the reactor shell 101 into a heat exchange cavity 112 and a first reaction cavity 111 and a second reaction cavity 113 at two sides,
a plurality of hollow draft tubes 105 arranged in parallel between the two draft baffles 110 and having openings at both ends thereof in the first reaction chamber 111 and the second reaction chamber 113,
a baffle plate 109 disposed inside the first reaction chamber 111 to divide the first reaction chamber 111 into an upper reaction chamber and a lower reaction chamber;
a first material introducing port 102 provided in a lower reaction chamber of the first reaction chamber 111,
a second material introducing port 104 provided in the second reaction chamber 113,
a material outlet port 103 provided on an upper reaction chamber of the first reaction chamber 111, an
A material channel 108 which is a material passage for sequentially connecting the first material inlet 102, the lower reaction chamber of the first reaction chamber 111, the second reaction chamber 113, the upper reaction chamber of the first reaction chamber 111, and the material outlet 103;
wherein the second material introducing port 104 is positioned at 40-60% of the total length of the material channel 108; the reactor 1 is connected with the gas-liquid separator 2 through a material outlet 103.
In the present invention, by appropriately setting the position of the second introduction port 104 for the raw material, the reaction product can be added at an appropriate reaction stage to control the progress of the alternating copolymerization reaction; the reaction temperature in the reactor of the present invention can be conveniently adjusted by introducing a temperature control medium into the heat exchange cavity 112, so as to control the reaction. Thus, maleic anhydride and C can be conveniently carried out by using the reactor of the present invention2-4The copolymerization reaction of unsaturated hydrocarbon can obtain light hydrocarbon alternate copolymerization microspheres with the particle size of 200-2000nm (preferably 600-1500nm) and uniform particle shape.
According to the present invention, the position of the second material introducing port 104 can be adjusted appropriately according to the reaction conditions used in the reactor, and is preferably located at 42 to 58%, more preferably 45 to 55% of the entire length of the material passage 108. The material passage 108 in fig. 1 is only one of the possible flow ways of the material, and the material can flow in all the draft tubes 105.
In the present invention, the arrangement and position of the baffle 110 and the baffle 109 are not particularly limited as long as the purpose of separating the liquid streams is achieved. As shown in fig. 1, the reactor shell 101 is horizontally disposed, and the guide baffle 110 and the baffle 109 are vertically disposed.
In the present invention, the flow guide 105 is used to control the reaction to be carried out at an appropriate temperature, and the length, number and diameter thereof may be appropriately set according to the reaction. Preferably, the length of the draft tube 105 is 60 to 90%, preferably 65 to 75% of the length of the reactor shell 101. Preferably, the number of the draft tubes 105 is more than 4, preferably more than 10, and the diameter is 20-90cm, preferably 30-60 cm.
By providing the flow baffle 110, the baffle 109 and the flow guide 105 as above, the reaction time of the reaction materials in the reactor is prolonged, and the reaction is carried out at a proper temperature in the flow guide 105, while it is possible to ensure uniform mixing of the materials with the materials added through the material second introduction port 104, so that the reaction materials are stably reacted in the reactor 1.
In the present invention, the reactor shell 101 may be any reactor shell capable of providing the desired alternate copolymerization reaction conditions, and for example, an existing reactor shell for polymerization may be used. Preferably, the reactor shell 101 is a jacket structure, and the temperature control medium can be introduced into the reactor shell, so as to further facilitate temperature control of the reaction materials.
According to a preferred embodiment of the present invention, a temperature-controlled medium inlet 106 and a temperature-controlled medium outlet 107 are further disposed on the heat exchange chamber 112, and a temperature-controlled medium chamber is disposed inside the heat exchange chamber 112 and outside the flow guide tube 105.
According to the invention, a temperature-control medium can be introduced into the heat exchange chamber 112 in order to regulate the reaction temperature in the reactor 1. The introduction manner of the temperature control medium is not particularly limited, and from the viewpoint of facilitating the control of the reaction temperature, as shown in fig. 1, for example, one side of the heat exchange cavity 112 may be connected to the temperature control medium introduction port 106, and the other side thereof may be connected to the temperature control medium introduction port 107, and the temperature control medium may be introduced through the temperature control medium introduction port 106, so that the temperature control medium cavity is filled with the temperature control medium, and the temperature of the reaction material inside the reactor is adjusted by sufficient heat exchange with the material inside the heat conduction pipe 105. Preferably, the flow direction of the temperature control medium is the same as the flow direction of the material.
As the temperature control medium in the present invention, any medium that is conventionally used for adjusting the temperature of the reactant, such as warm water having an appropriate temperature, can be used.
In the present invention, the gas-liquid separator 2 is not particularly limited as long as it can complete gas-liquid separation of the reaction product in the reactor 1. For example, the reaction product may be depressurized and cooled to separate gas from liquid.
According to a preferred embodiment of the present invention, the gas-liquid separator 2 comprises a housing, the housing is divided into a gas area 202 located at the upper part and a gas-liquid separation area 201 located at the lower part by a baffle plate 203, the gas area 202 is connected with a gas outlet 206, the upper part of the gas-liquid separation area 201 is connected with a material outlet 103, the lower part is provided with a liquid outlet 207, and the inside is provided with a stirring component 205.
The perforated baffle 203 is used to block splashing of liquid caused by agitation, thereby ensuring that liquid does not enter the gas zone 202, and the perforated baffle 203 may be, for example, a stainless steel perforated baffle.
According to the present invention, the stirring component 205 can be, for example, a stirring paddle, and as shown in fig. 1, the stirring component 205 is driven by a motor 204, and the motor can be, for example, disposed on the top of the gas-liquid separator 2.
According to the above-mentioned gas-liquid separator 2 of the present invention, the gas-liquid separation zone 201 is used for separating a gas phase and a liquid phase, and the gas zone 202 is used for cooling a gas. The gas and the liquid in the reaction product are separated by adjusting the pressure in the gas-liquid separation zone 201 and by the stirring action of the stirring member 205, and the gas further rises into the gas zone 202, is cooled, and is then discharged through the gas outlet 206, and the liquid is discharged through the liquid outlet 207. In order to further improve the gas-liquid separation efficiency, it is preferable that a temperature decreasing member is provided outside the gas region 202, and a temperature increasing member is provided outside the gas-liquid separation region 201.
As the temperature lowering means and the temperature raising means, a jacket structure may be used, and a cooling medium or a temperature raising medium may be introduced into the jacket structure. For example, as shown in fig. 1, the gas-liquid separation region 201 of the shell is provided with a jacket structure, the bottom of the gas-liquid separation region is provided with a heating medium inlet 208, and the top of the gas-liquid separation region is provided with a heating medium outlet 209; the gas area 202 of the housing is provided as a jacket structure and is provided with a cooling medium introduction port 210 and a cooling medium discharge port 211. As the cooling medium or temperature raising medium, cooling water or warm water of an appropriate temperature can be used.
According to the present invention, the liquid outlet may be further connected to a solid-liquid separation device (not shown) for separating light hydrocarbon alternating copolymerization microspheres. The prepared light hydrocarbon alternate copolymerization microspheres can be separated from the solvent and the like through a solid-liquid separation device. The solid-liquid separator can use the existing solid-liquid separator which can be used for separating the C2-4Unsaturated hydrocarbon, maleic anhydride and the like and light hydrocarbon are copolymerized alternately in any device, such as a centrifuge and the like. The conditions of the centrifugation may include: the rotating speed is more than 4000rpm, and the time is more than 20 min; preferably, the rotation speed is 4000-.
The second aspect of the present invention provides a method for preparing light hydrocarbon alternating copolymerization microspheres by using the reaction device of the present invention, which comprises the following steps:
(1) c is introduced into the first material introduction port 1022-4Introducing a mixture of an unsaturated hydrocarbon, maleic anhydride and an initiator into the reactor 1 so that the material undergoes a first polymerization reaction in the material passage 108, introducing divinylbenzene into the reactor 1 at a material second introduction port 104 so that the material undergoes a second polymerization reaction in the material passage 108, and discharging a reaction product from a material discharge port 103;
(2) the reaction product is introduced into a gas-liquid separator 2 for gas-liquid separation.
Preferably, in the gas-liquid separator 2, the gas and the liquid in the reaction product are separated by the rotation of the stirring member 205, and the liquid-phase product is obtained from the liquid outlet 207.
The reaction device for preparing the light hydrocarbon alternating copolymerization microspheres is adopted for C2-4The copolymerization reaction of unsaturated hydrocarbon and maleic anhydride, and the timely addition of divinylbenzene, thereby efficiently preparing the light hydrocarbon alternating copolymerization microspheres with the particle size of 200-2000nm (preferably 600-1500nm) and uniform particle shape.
In the present invention, said C2-4The unsaturated hydrocarbon is not particularly limited as long as it is a hydrocarbon having a carbon-carbon double bond having 2 to 4 carbon atoms, and is preferably a C4 olefin, and may include, for example, one or more of 1-butene, isobutylene, 1, 3-butadiene, 1, 2-butadiene, vinylacetylene, cis-2-butene and trans-2-butene.
According to the invention, preferably, the mixture also comprises C2-4Alkanes, preferably C4 alkanes. As said C2-4The alkane, for example, can be n-butane and/or isobutane. That is, the mixture may be a mixture containing mixed carbon four, maleic anhydride, and an initiator. The mixed C4 is liquefied fuel (C four fraction) produced in the petroleum refining process, pyrolysis gas produced by naphtha cracking, gas produced by methanol-to-olefin and the like, the main components of the mixed C four are normal butane, isobutane, isobutene, butadiene, 1-butene, 2-butene and the like, and the content of each component in the mixed C four from different sources is also different.
According to the present invention, the first polymerization reaction and the second polymerization reaction can selectively copolymerize the C2-4 terminal olefin in the material with maleic anhydride, and thus the apparatus and method of the present invention can be used to separate the C2-4 terminal olefin (i.e., α -olefin) from the C2-4 internal olefin. In the material of the invention, the C2-4 internal olefin is 2-butene, including cis-2-butene and trans-2-butene.
According to a more preferred embodiment of the present invention,said C is2-4Unsaturated hydrocarbons and C2-4The alkane includes 1-99 wt% of 1-butene, 1-99 wt% of isobutene, 0-99 wt% of 1, 3-butadiene, 0-50 wt% of 1, 2-butadiene, 0-99 wt% of n-butane, 1-99 wt% of isobutane, 5-20 wt% of vinyl acetylene, 0-99 wt% of cis-2-butene and 1-99 wt% of trans-2-butene.
According to a more preferred embodiment of the present invention, said C2-4Unsaturated hydrocarbons and C2-4The alkane comprises 0.1-2 wt% of 1-butene, 10-30 wt% of isobutene, 0.01-0.1 wt% of 1, 3-butadiene, 0.5-5 wt% of n-butane, 30-40 wt% of isobutane, 20-40 wt% of cis-2-butene and 5-20 wt% of trans-2-butene.
According to a more preferred embodiment of the present invention, said C2-4Unsaturated hydrocarbons and C2-4The alkane comprises 5-15 wt% of 1-butene, 0.5-3 wt% of isobutene, 20-30 wt% of n-butane, 15-30 wt% of cis-2-butene and 35-45 wt% of trans-2-butene.
According to the present invention, the initiator may be one or more selected from dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile. Preferably, the initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
According to the invention, the mixture contains maleic anhydride in an amount of 5 to 25% by weight, preferably 10 to 20% by weight.
According to the invention, the mixture also comprises an organic solvent. Preferably, the organic solvent is one or more of organic acid alkyl ester, alkane, aromatic hydrocarbon and halogenated aromatic hydrocarbon. The organic acid alkyl ester may be, for example, one or more of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate, with isoamyl acetate being preferred; as the alkane, for example, one or more of propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane, and isooctane; as the aromatic hydrocarbon, for example, one or more of benzene, toluene, and xylene; the halogenated aromatic hydrocarbon may be, for example, chlorobenzene and/or bromobenzene.
In the present invention, C is2-4The mixture obtained by uniformly mixing unsaturated hydrocarbon, maleic anhydride, initiator and the like is introduced into the reactor 1, reacts in the material channel, and then reacts with divinylbenzene added through the material second introduction port 104, so that the required light hydrocarbon alternating copolymerization microspheres are obtained.
According to the present invention, in order to improve the size uniformity of the obtained light hydrocarbon alternating copolymerization microspheres, it is preferable that C is2-4The molar ratio of terminal olefin, maleic anhydride and divinylbenzene in the unsaturated hydrocarbon is 1: 0.8-7: 0.008-0.07, more preferably 1: 1-4: 0.01-0.04.
According to the present invention, the reaction conditions of the reactor 1 may be appropriately adjusted according to the setting of the reactor, for example, the reaction conditions in the reactor 1 may include: the first copolymerization reaction time is 0.5-3h, and the second copolymerization reaction time is 0.5-3 h; preferably, the first copolymerization time is 1 to 2 hours and the second copolymerization time is 1 to 2 hours. By respectively controlling the first copolymerization reaction time and the second copolymerization reaction time within the above ranges, the obtained light hydrocarbon alternating copolymerization microspheres can be more uniformly distributed in size, and the conversion rate of the reaction is improved. Preferably, the reaction conditions in the reactor 1 may include: the reaction temperature is 50-100 ℃, and the reaction pressure is 0.2-2 MPa; preferably, the reaction temperature is 70-90 ℃ and the reaction pressure is 0.5-1 MPa. The above reaction is preferably carried out in an inert gas atmosphere, for example, nitrogen, argon, etc. By controlling the polymerization reaction under the above conditions, the size uniformity of the obtained light hydrocarbon alternating copolymerization microspheres can be improved.
In order to control the reaction conditions, the temperature of the temperature control medium (e.g., warm water) introduced through the temperature control medium introduction port 106 may be 55 to 100 ℃ and preferably 75 to 95 ℃.
After the reaction in the reactor 1, the obtained reaction product is introduced into the gas-liquid separator 2 through the material outlet 103. The pressure of the reaction product in the gas-liquid separator 2 is reduced to, for example, normal pressure, and the separation of the gas from the liquid is accelerated by the rotation of the stirring member 205, preferably, the rotation speed of the stirring member 205 is 5 to 100rpm, more preferably, 10 to 50 rpm.
According to the invention, the method also comprises the step of carrying out solid-liquid separation on the liquid-phase product obtained by gas-liquid separation. The solid-liquid separation can be carried out by using a conventional method which can be used for separating the C2-4The alternating copolymerization of the unsaturated hydrocarbon, maleic anhydride, etc. with the light hydrocarbon can be carried out by any method, for example, centrifugation, etc. The centrifugation condition can be that the rotating speed is more than 4000rpm, and the time is more than 20 min; preferably, the rotation speed is 4000-. Separating the liquid phase product into a supernatant and a lower solid by centrifugation; the clear liquid is an organic solvent and can be reused for the copolymerization reaction.
The present invention will be described in detail below by way of examples. In the following examples, the composition of mixed C.sub.D was analyzed by Agilent's 7890A gas chromatograph.
Example 1
The method is carried out by using a reaction device for preparing light hydrocarbon alternating copolymerization microspheres as shown in figure 1. The reaction apparatus comprises a reactor 1, a gas-liquid separator 2 and a centrifuge (not shown) connected in this order.
The reactor 1 comprises: a horizontally disposed reactor shell 101 having a circular cross-section,
two flow guide baffles 110 vertically arranged inside the reactor shell 101, dividing the inside of the reactor shell 101 into a heat exchange cavity 112 and a first reaction cavity 111 and a second reaction cavity 113 at two sides,
8 hollow draft tubes 105, the length of which is 70% of the length of the reactor shell 101, the diameter of which is 50cm, are evenly arranged between the two guide baffles 110 in parallel, and the openings at the two ends are respectively opened in the first reaction chamber 111 and the second reaction chamber 113,
a baffle plate 109 vertically disposed inside the first reaction chamber 111, and dividing the first reaction chamber 111 into an upper reaction chamber and a lower reaction chamber having equal volumes;
a first material introducing port 102 provided in a lower reaction chamber of the first reaction chamber 111,
a second material introducing port 104 provided in the second reaction chamber 113,
a material outlet port 103 provided on an upper reaction chamber of the first reaction chamber 111, an
A material passage 108 which is a material passage for sequentially connecting the first material inlet 102, the lower reaction chamber of the first reaction chamber 111, the draft tube 105, the second reaction chamber 113, the draft tube 105, the upper reaction chamber of the first reaction chamber 111, and the material outlet 103; the second material inlet 104 is located at 50% of the total length of the material passage 108.
One side of the heat exchange chamber 112 is connected to the temperature control medium inlet port 106, and the other side is connected to the temperature control medium outlet port 107, and the temperature control medium (warm water) is introduced through the temperature control medium inlet port 106.
The reactor shell 101 is a jacket structure, and the temperature control medium (warm water) is introduced into the reactor shell.
The gas-liquid separator 2 comprises a housing, the housing is divided into a gas area 202 located at the upper part and a gas-liquid separation area 201 located at the lower part by a stainless steel hole baffle 203, the gas area 202 is connected with a gas outlet 206, the upper part of the gas-liquid separation area 201 is connected with a material outlet 103, a liquid outlet 207 is arranged at the lower part, a stirring part 205 (stirring paddle) is arranged inside the gas-liquid separation area, and the stirring part 205 can be driven by a motor 204 arranged at the top of the gas-liquid separator 2 to rotate.
The gas-liquid separation area 201 of the shell is of a jacket structure, the bottom of the gas-liquid separation area is provided with a heating medium inlet 208, and the top of the gas-liquid separation area is provided with a heating medium outlet 209; the gas area 202 of the housing is provided as a jacket structure and is provided with a cooling medium introduction port 210 and a cooling medium discharge port 211.
The mixed C-C alloy comprises the following components (in percentage by weight): 8.92 percent of 1, 2-butadiene; 14.14% of 1, 3-butadiene; 8.38 percent of 1-butene; 5.84 percent of trans-2-butene; 31.7 percent of cis-2-butene; 10.99 percent of vinyl acetylene; 1.3 percent of isobutane; 12.78% of isobutene; n-butane 2.58%, others 3.37%. The preparation method comprises the following steps:
(1) mixing 14kg of mixed C-IV A, 20kg of maleic anhydride, 2.4kg of azobisisobutyronitrile and 100L of isoamyl acetate to obtain an organic reaction liquid, introducing the organic reaction liquid into the reactor 1 at a material first introduction port 102, wherein the flow rate of liquid material flow is 0.1m/min, so that the material is subjected to a first polymerization reaction in the material channel 108; at the second introduction port 104, 0.26kg (flow rate of 0.01kg/min) of divinylbenzene was introduced into the reactor 1 so that the second polymerization of the materials was carried out in the material passage 108. Warm water is introduced into the temperature control medium inlet and the jacket structure of the reactor shell 101, and the reaction temperature is controlled so that the copolymerization reaction pressure is 0.9MPa, the copolymerization reaction temperature is 70 ℃, the first copolymerization reaction time is 2 hours, and the second copolymerization reaction time is 2 hours.
(2) The reaction product is introduced into the gas-liquid separator 2 through the material outlet port 103, gas and liquid in the reaction product are separated by rotation (rotation speed of 20rpm) of the stirring member 205, and a liquid-phase product is obtained from the liquid outlet port 207. The temperature of the gas-liquid separation zone 201 was controlled to 80 ℃ by introducing warm water into the warm medium inlet 208, and the temperature of the gas-liquid separation zone 202 was controlled to 0 ℃ by introducing cooling water into the cooling medium inlet 210.
(3) The liquid-phase product was subjected to centrifugation at 4000rpm for 20min to obtain solid copolymer particles powder A.
Example 2
The procedure is as in example 1, except that:
mixed carbon four B is used for replacing mixed carbon four A, and the mixed carbon four B comprises the following components in percentage by weight: 0.06% of 1, 3-butadiene, 12.67% of trans-2-butene, 37.09% of isobutane, 19.48% of isobutene, 27.79% of cis-2-butene, 1.02% of 1-butene and the rest 1.89%;
the organic reaction solution consists of 13.5kg of mixed C-C, 20kg of maleic anhydride, 4kg of dibenzoyl peroxide and 100L of isoamyl acetate;
the copolymerization reaction pressure is 1MPa, the copolymerization reaction temperature is 80 ℃, the first copolymerization reaction time is 2.5h, and the second copolymerization reaction time is 2.5 h;
centrifuging at 4000rpm for 20 min;
thus, a solid copolymer particle powder B was obtained.
Example 3
The procedure is as in example 1, except that:
mixed carbon tetra C is used to replace mixed carbon tetra a, and the mixed carbon tetra C comprises the following components in percentage by weight: trans-2-butene 20.83%, cis-2-butene 18.18%, n-butane 24.29%, 1-butene 9.52%, isobutene 22.78%, and other 4.4%.
The organic reaction solution consists of 15kg of mixed C, 20kg of maleic anhydride, 4.5kg of dibenzoyl peroxide, 0.26kg of divinylbenzene and 100L of isoamyl acetate;
the copolymerization reaction pressure is 1.5MPa, the copolymerization reaction temperature is 80 ℃, the first copolymerization reaction time is 1.5h, and the second copolymerization reaction time is 3 h;
thus, a solid copolymer particle powder C was obtained.
Examples 4 to 7
The procedure of example 1 was followed, except that: the second material introduction ports 104 are respectively located at 40%, 45%, 55% and 60% of the total length of the material passage 108. Thus, solid copolymer particle powders D, E, F and G were obtained.
Examples 8 to 9
The procedure of example 1 was followed, except that: the amounts of divinylbenzene introduced were 0.13kg and 0.52kg, respectively. Thus, solid copolymer particle powders H and I were obtained.
Example 10
The procedure of example 1 was followed, except that the flow rate of the reaction mass was 0.5 m/min. Thus, solid copolymer particle powder J was obtained.
Comparative example 1
The process of example 1 was carried out, except that the reaction apparatus for preparing light hydrocarbon alternating copolymerization microspheres of the present invention was not used, but a general reaction vessel was used, and divinylbenzene was directly mixed with the organic reaction solution and reacted. Thus, solid copolymer particle powder DA1 was obtained.
Comparative example 2
The process of example 1 was carried out, except that the reaction apparatus for preparing light hydrocarbon alternating copolymerization microspheres of the present invention was not used, but a general reaction vessel was used, and the organic reaction solution was reacted for 2 hours (i.e., the first polymerization time), then divinylbenzene was added, and the reaction was further carried out for 2 hours (i.e., the second polymerization time). Thus, solid copolymer particle powder DA2 was obtained.
Comparative examples 3 to 4
The procedure of example 1 was followed, except that: the second material introduction port 104 is located at 30% and 70% of the total length of the material passage 108, respectively. Thus, solid copolymer particle powders DA3 and DA4 were obtained.
Test example 1
The solid copolymer particle powders obtained in the above examples and comparative examples were subjected to the following tests:
testing of morphology of polymer particles: and spraying polymer powder on a sample table paved with conductive adhesive, spraying gold, and analyzing the morphology of the polymer by using a scanning electron microscope Hitachi S4800.
Measurement of particle size of polymer particles: the particle size of the polymer particles was analyzed by the own software of a scanning electron microscope Hitachi S4800.
Measurement of polymerization conversion:
the test results are shown in table 1 below.
TABLE 1
| Detailed description of the preferred embodiments | Morphology of | Particle size (micron) | Dispersibility | Conversion rate |
| Example 1 | Ball shape | 1.3 | Good effect | 85％ |
| Example 2 | Ball shape | 1.8 | Good effect | 80％ |
| Example 3 | Ball shape | 1.5 | Good effect | 72％ |
| Example 4 | Ball shape | 1.3 | Good effect | 75％ |
| Example 5 | Ball shape | 1.3 | Good effect | 76％ |
| Example 6 | Ball shape | 1.3 | Good effect | 76％ |
| Example 7 | Ball shape | 1.3 | Good effect | 75％ |
| Example 8 | Ball shape | 1.2 | Good effect | 70％ |
| Example 9 | Ball shape | 1.5 | Good effect | 77％ |
| Example 10 | Ball shape | 1.2 | Good effect | 72％ |
| Comparative example 1 | Irregular particle | 0.8 | Difference (D) | 35％ |
| Comparative example 2 | Irregular particle | 0.6 | Difference (D) | 32％ |
| Comparative example 3 | Irregular particle | 1.3 | Difference (D) | 41％ |
| Comparative example 4 | Irregular particle | 1.4 | Difference (D) | 43％ |
It can be seen from the above results that the examples 1 to 10 of the present invention have a high reaction conversion rate, and the obtained polymer has a good spherical morphology and a good material dispersion state, and has significantly better effects than the comparative examples of the conventional reactor and reaction method.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (28)
1. A reaction device for preparing light hydrocarbon alternating copolymerization microspheres is characterized by comprising a reactor (1) and a gas-liquid separator (2);
the reactor (1) comprises:
a reactor shell (101) is provided,
two flow guide baffles (110) which are arranged inside the reactor shell (101) and divide the inside of the reactor shell (101) into a heat exchange cavity (112) between the two and a first reaction cavity (111) and a second reaction cavity (113) at two sides,
a plurality of hollow draft tubes (105) which are arranged between the two draft baffles (110) in parallel and have openings at two ends respectively in the first reaction chamber (111) and the second reaction chamber (113),
a baffle plate (109) which is provided inside the first reaction chamber (111) and divides the first reaction chamber (111) into an upper reaction chamber and a lower reaction chamber;
a first material introducing port (102) provided in a lower reaction chamber of the first reaction chamber (111),
a second material introducing port (104) provided in the second reaction chamber (113),
a material outlet (103) provided on an upper reaction chamber of the first reaction chamber (111), an
The material channel (108) is a material passage which is sequentially connected with a first material introducing port (102), a lower reaction cavity of the first reaction cavity (111), the guide pipe (105), the second reaction cavity (113), the guide pipe (105), an upper reaction cavity of the first reaction cavity (111) and the material outlet (103);
wherein the material second introducing port (104) is positioned at 40-60% of the total length of the material channel (108); the reactor (1) is connected with the gas-liquid separator (2) through a material outlet (103);
and a temperature control medium inlet (106) and a temperature control medium outlet (107) are also arranged on the heat exchange cavity (112), and the temperature control medium cavity is arranged in the heat exchange cavity (112) and is positioned outside the flow guide pipe (105).
2. The reactor apparatus according to claim 1, wherein the gas-liquid separator (2) comprises a housing divided by a perforated baffle plate (203) into an upper gas zone (202) and a lower gas-liquid separation zone (201),
the gas area (202) is connected with a gas outlet (206),
the upper part of the gas-liquid separation area (201) is connected with the material outlet (103), the lower part is provided with a liquid outlet (207), and the inside is provided with a stirring component (205).
3. The reactor according to claim 2, wherein a temperature lowering means is provided outside the gas zone (202), and a temperature raising means is provided outside the gas-liquid separation zone (201).
4. The reactor according to claim 2, wherein the stirring member (205) rotates at a speed of 5-100 rpm.
5. A method for preparing light hydrocarbon alternating copolymerization microspheres by using the reaction device of any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) c is introduced into the first material inlet (102)2-4Introducing a mixture of an unsaturated hydrocarbon, maleic anhydride and an initiator into the reactor (1) so that the material undergoes a first polymerization reaction in the material passage (108), introducing divinylbenzene into the reactor (1) at a material second introduction port (104) so that the material undergoes a second polymerization reaction in the material passage (108), and discharging a reaction product from a material discharge port (103);
(2) the reaction product is led into a gas-liquid separator (2) for gas-liquid separation.
6. The method of claim 5, wherein C2-4The unsaturated hydrocarbon includes one or more of 1-butene, isobutylene, 1, 3-butadiene, 1, 2-butadiene, vinyl acetylene, cis-2-butene, and trans-2-butene.
7. The method of claim 6, wherein the mixture isAnd also comprises C2-4An alkane.
8. The method of claim 7, wherein C2-4Alkanes include n-butane and/or isobutane.
9. The method of claim 8, wherein C is2-4Unsaturated hydrocarbons and C2-4The alkane includes 1-99 wt% of 1-butene, 1-99 wt% of isobutene, 0-99 wt% of 1, 3-butadiene, 0-50 wt% of 1, 2-butadiene, 0-99 wt% of n-butane, 1-99 wt% of isobutane, 5-20 wt% of vinyl acetylene, 0-99 wt% of cis-2-butene and 1-99 wt% of trans-2-butene.
10. The method of claim 9, wherein C is2-4Unsaturated hydrocarbons and C2-4The alkane comprises 0.1-2 wt% of 1-butene, 10-30 wt% of isobutene, 0.01-0.1 wt% of 1, 3-butadiene, 0.5-5 wt% of n-butane, 30-40 wt% of isobutane, 20-40 wt% of cis-2-butene and 5-20 wt% of trans-2-butene.
11. The method of claim 9, wherein C is2-4Unsaturated hydrocarbons and C2-4The alkane comprises 5-15 wt% of 1-butene, 0.5-3 wt% of isobutene, 20-30 wt% of n-butane, 15-30 wt% of cis-2-butene and 35-45 wt% of trans-2-butene.
12. The method of claim 5, wherein the initiator is one or more of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.
13. The method of claim 12, wherein the initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
14. A process according to claim 5, wherein the mixture has a maleic anhydride content of 5-25% by weight.
15. The method of claim 14, wherein the mixture has a maleic anhydride content of 10-20 wt%.
16. The method of claim 14, wherein C is2-4The molar ratio of terminal olefin, maleic anhydride and divinylbenzene in the unsaturated hydrocarbon is 1: 0.8-7: 0.008-0.07.
17. The method of claim 5, wherein the mixture comprises an organic solvent.
18. The method of claim 17, wherein the organic solvent is one or more of an organic acid alkyl ester, an alkane, an aromatic hydrocarbon, and a halogenated aromatic hydrocarbon.
19. The method of claim 18, wherein the alkyl organic acid ester is one or more of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
20. The method of claim 18, wherein the alkane is one or more of propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane, cyclohexane, n-heptane, n-octane, and isooctane.
21. The method of claim 18, wherein the aromatic hydrocarbon is one or more of benzene, toluene, and xylene.
22. The process according to claim 18, wherein the halogenated aromatic hydrocarbon is chlorobenzene and/or bromobenzene.
23. The method according to claim 5, wherein the reaction conditions in the reactor (1) comprise: the first polymerization time is 0.5-3h, and the second polymerization time is 0.5-3 h.
24. The method according to claim 23, wherein the reaction conditions in the reactor (1) comprise: the first polymerization reaction time is 1-2h, and the second polymerization reaction time is 1-2 h.
25. The method according to claim 23, wherein the reaction conditions in the reactor (1) comprise: the reaction temperature is 50-100 ℃, and the reaction pressure is 0.2-2 MPa.
26. The method according to claim 25, wherein the reaction conditions in the reactor (1) comprise: the reaction temperature is 70-90 ℃, and the reaction pressure is 0.5-1 MPa.
27. The process as claimed in any one of claims 5 to 25, further comprising subjecting the liquid-phase product obtained by the gas-liquid separation to solid-liquid separation.
28. The method of claim 27, wherein the solid-liquid separation is by centrifugation.
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