CN113024724B - Method for continuous polymerization of cracked fractions - Google Patents
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- CN113024724B CN113024724B CN201911353754.4A CN201911353754A CN113024724B CN 113024724 B CN113024724 B CN 113024724B CN 201911353754 A CN201911353754 A CN 201911353754A CN 113024724 B CN113024724 B CN 113024724B
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- 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
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Abstract
The invention discloses a method for continuously polymerizing cracking fractions. The method comprises the following steps: (1) Mixing the cracked fraction, olefinic compound and optional solvent A to form mixture A; mixing a free radical initiator and a solvent B to form a mixture B; (2) Continuously flowing the mixture A and the mixture B into a reactor for polymerization reaction to obtain a reaction product; continuously discharging the obtained reaction product from the reactor; (3) The solid and liquid substances in the reaction product flowing out of the reactor were separated, and the solid substances were washed and dried to obtain a polymer. The method has mild reaction conditions and simple reaction steps, and can realize continuous production.
Description
Technical Field
The invention relates to a method for continuously polymerizing a cracking fraction, in particular to a method for continuously polymerizing a petroleum and/or coal cracking fraction.
Background
Cracking petroleum to obtain low molecular weight olefins is currently an important process for the industrial production of ethylene. Petroleum cracking produces a large amount of cracked fractions in addition to low molecular weight olefins. How to change the cracking fractions into valuable substances and apply the cracking fractions to industrial production becomes the key point of current research. In addition, coal chemicals also produce large amounts of cracked fractions.
CN107163186A discloses a method for preparing petroleum resin by a diolefin thermal polymerization method, which comprises the following steps: cyclopentadiene as initiator is added into one or several kinds of diene of piperylene, isoprene, styrene derivative and indene derivative, and the cyclopentadiene, piperylene, isoprene, styrene derivative and indene derivative are thermally polymerized at 205-280 deg.c and 2.2-3.0 MPa in the presence of solvent oil to obtain petroleum resin polymer in different molecular weights. The reaction needs to be carried out at high temperature and high pressure, and is not beneficial to industrial production.
CN110183577A discloses a preparation process of a C9 cold polymerization petroleum resin product: (1) rectification treatment: rectifying the C9 raw material to remove heavy components and part of light components in the C9 raw oil; (2) prepolymerization: pre-polymerizing the rectified raw oil to remove components with higher reaction activity in the reaction raw materials; (3) catalytic polymerization: dissolving the reaction raw materials in a solvent, and adding the reaction raw materials into a reaction kettle in a dropwise manner. The method has low efficiency and is not suitable for industrial production.
CN109180880A discloses a preparation method of a maleic anhydride high-grafting-rate C5 petroleum resin: c5 fraction obtained by cracking ethylene is taken as a main raw material, the content range of active diolefin components in the C5 fraction is controlled to be 20-80%, and the C5 matrix petroleum resin is prepared through cationic catalytic polymerization; and adding maleic anhydride and an initiator into the prepared C5 matrix petroleum resin in a molten state, and carrying out grafting reaction to obtain the C5 petroleum resin. The petroleum resin is maleic anhydride C5 petroleum resin with a graft structure.
CN1036999C discloses a method for producing C9 petroleum resin: pre-polymerizing the residual fraction (C8-C11) of heavy byproduct pyrolysis oil at 80-120 ℃, then carrying out cationic catalytic polymerization, adding an alkaline polymerization inhibitor into the product after the polymerization reaction is complete to inhibit polymerization, and carrying out catalyst removal, washing and reduced pressure distillation on the product to obtain C9 petroleum resin; wherein the residual fraction is treated by activated clay, then the molecular sieve is used for removing moisture, the raw materials are added with maleic anhydride, prepolymerization is carried out under the protection of inert gas, and the prepolymerization product is subjected to reduced pressure distillation and then the fraction is subjected to polymerization reaction under the protection of inert gas at the temperature of-5 to 25 ℃. The method adopts cation polymerization, the reaction condition is harsh, other reactants such as polymerization inhibitor and the like need to be added, and the product purification difficulty is high.
CN1257924C discloses a preparation method of a C9-maleic anhydride copolymer: (1) distillation: carrying out vacuum distillation on the crude C9, and intercepting a fraction at 38-120 ℃; (2) heating and refluxing: heating the fraction and maleic anhydride in water bath, stirring, adding an initiator which accounts for 0.6-5% of the total mass of the reaction monomers when the temperature is 70-80 ℃, and refluxing for 6-10 hours at constant temperature, wherein the initiator is a peroxide, an azo compound or a redox system; (3) precipitation: adding butanone to the reaction product and the residual reactant solvent, and adding methanol to precipitate; (4) filtering and drying: washing, filtering and precipitating, and then drying under the vacuum condition to obtain the C9-maleic anhydride bipolymer. The method can precipitate the reactant only by adding butanone-methanol, has complex reaction steps and is not suitable for continuous production.
Disclosure of Invention
In view of the above, the invention provides a method for continuously polymerizing a cracked fraction, which has mild reaction conditions and simple reaction steps and can realize continuous production.
The technical scheme is adopted to achieve the purpose.
The invention provides a method for continuously polymerizing cracking fractions, which comprises the following steps:
(1) Mixing the cracked fraction, olefinic compound and optional solvent A to form mixture A; mixing a free radical initiator and a solvent B to form a mixture B;
wherein the ethylenic bond-containing compound is selected from a maleic anhydride compound shown in formula (1), a maleimide compound shown in formula (2) or an itaconic anhydride compound shown in formula (3):
in the formula (1), R 1 And R 2 Each independently selected from a hydrogen atom or a C1-C5 alkyl group;
in the formula (2), R 3 And R 4 Each independently selected from a hydrogen atom or a C1-C3 alkyl group; r 5 One selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, or an aralkyl group substituted with a group containing a heteroatom selected from N, O or S;
in the formula (3), R 6 、R 7 、R 8 Each independently selected from a hydrogen atom or a C1-C5 alkyl group;
(2) Continuously flowing the mixture A and the mixture B into a reactor for polymerization reaction to obtain a reaction product; continuously discharging the obtained reaction product from the reactor;
(3) Solid and liquid substances in the reaction product flowing out of the reactor were separated, and the solid substances were washed and dried to obtain a polymer.
According to the method of the present invention, preferably, in the step (1), the cracking fraction is selected from one or more of C4 cracking fraction, C5 cracking fraction, C8 cracking fraction, ethylene tar and coal tar.
According to the process of the present invention, preferably, in formula (1), R 1 And R 2 Each independently selected from hydrogen atomsA methyl or ethyl group; in the formula (2), R 3 And R 4 Each independently selected from a hydrogen atom or a methyl group; r 5 One selected from hydrogen atom, C1-C4 alkyl, cyclohexyl, phenyl or benzyl; in the formula (3), R 6 、R 7 、R 8 Each independently selected from a hydrogen atom or a C1-C3 alkyl group.
According to the process of the present invention, preferably, in step (1), the radical initiator is an azo initiator or an organic peroxide initiator.
According to the method of the present invention, preferably, in the step (1), the radical initiator is one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.
According to the method of the present invention, preferably, in the step (1), the mass ratio of the cleavage fraction to the ethylenic compound is 1.
According to the method of the present invention, preferably, in the step (2), the flow rate of the mixture A flowing into the reactor is 10 to 1000cm 3 Min, the flow rate of the mixture B flowing into the reactor is 10-1000 cm 3 Min, the flow rate of the reaction product flowing out of the reactor is 20-80 cm 3 /min。
According to the method of the present invention, preferably, in the step (2), the reaction temperature is 30 to 120 ℃ and the reaction time is 2.5 to 15 hours.
According to the method of the present invention, preferably, in the step (3), the solid substance in the reaction product is separated from the body fluid substance by centrifugation, the rotation speed of the centrifuge is 3000-8000 rpm, and the centrifugation time is 2-10 min.
According to the method of the present invention, preferably, the method further comprises the step of collecting the liquid substance separated in step (3) in a storage tank.
The invention utilizes the free radical polymerization method to polymerize the ethylenic bond-containing compound and the unsaturated organic matters in the cracking fraction, has mild reaction conditions and simple reaction steps, and can realize continuous production.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
The method for continuously polymerizing the pyrolysis fraction comprises the following steps: (1) preparing a solution; (2) a step of polymerization; and (3) post-treating the reaction product. As described in detail below.
< step of preparing solution >
Mixing the cracked fraction, olefinic bond-containing compound and optional solvent A to form mixture A; a free radical initiator and a solvent B to form a mixture B. According to one embodiment of the invention, the pyrolysis fraction and the olefinic compound are formed into a mixture A; a free radical initiator and a solvent B to form a mixture B. Thus, the solubility of the components in the cracking fraction can be fully utilized, the solvent A is omitted, and the cost is reduced.
The ethylenic bond-containing compound in the invention is a maleic anhydride compound, a maleimide compound or an itaconic anhydride compound, and the specific structure is as follows.
Maleic anhydride compound
The maleic anhydride compound of the invention has a chemical structure shown in formula (1):
in the formula (1), R 1 And R 2 Each independently selected from a hydrogen atom or a C1-C5 alkyl group. Examples of C1-C5 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and the like. Preferably, R 1 And R 2 Each independently selected from a hydrogen atom, a methyl group or an ethyl group. The substituent groups have proper volume and small steric hindrance, and can ensure the smooth proceeding of free radical polymerization reaction.
Examples of the maleic anhydride-based compound of the present invention include, but are not limited to, maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride, diethyl maleic anhydride, di-n-propyl maleic anhydride, diisopropyl maleic anhydride, 1-methyl-2-ethyl maleic anhydride, 1-methyl-2-n-propyl maleic anhydride, 1-methyl-2-isopropyl maleic anhydride, 1-methyl-2-n-butyl maleic anhydride, 1-methyl-2-isobutyl maleic anhydride, 1-methyl-2-tert-butyl maleic anhydride, 1-methyl-2-n-pentyl maleic anhydride, 1-methyl-2-isopentyl maleic anhydride, 1-methyl-2-neopentyl maleic anhydride, 1-ethyl-2-n-propyl maleic anhydride, 1-ethyl-2-isopropyl maleic anhydride, and the like. Preferably, the maleic anhydride compound of the present invention is selected from one or more of maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride and diethyl maleic anhydride. This facilitates the polymerization reaction.
Maleimide compound
The maleimide compound of the invention is shown as a formula (2):
in the formula (2), R 3 And R 4 Each independently selected from a hydrogen atom or a C1-C3 alkyl group; r is 5 One selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, or an aralkyl group substituted with a group containing a heteroatom selected from N, O or S.
In the formula (2), R 3 And R 4 Each independently selected from a hydrogen atom or a C1-C3 alkyl group. Examples of C1-C3 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl. According to one embodiment of the invention, R 3 And R 4 Each independently selected from a hydrogen atom and a methyl group.
In the formula (2), R 5 One selected from a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C6-C20 aralkyl group, a C7-C20 alkaryl group, an aryl group substituted with a group containing a heteroatom selected from N, O or S, or an aralkyl group substituted with a group containing a heteroatom selected from N, O or S. Preferably, R 5 One member selected from the group consisting of a hydrogen atom, a C1-C4 alkyl group, a C5-C6 cycloalkyl group, a C7-C15 aralkyl group and a C7-C15 alkaryl groupAnd (4) seed selection. More preferably, R 5 One selected from a hydrogen atom, a C1-C4 alkyl group, a cyclohexyl group, a phenyl group and a benzyl group.
Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and the like. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of C6 to C20 aralkyl groups include, but are not limited to, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, and the like. Examples of C7-C20 alkaryl include, but are not limited to, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 3-dimethylbenzyl, 2, 4-dimethylbenzyl, and the like. Examples of aryl substituted with a group containing a heteroatom selected from N, O or S include, but are not limited to, O-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, O-nitrophenyl, m-nitrophenyl, p-nitrophenyl, and the like, O-cyanophenyl, m-cyanophenyl, p-cyanophenyl, and the like. Examples of the aralkyl group substituted with a group containing a hetero atom selected from N, O or S include, but are not limited to, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 3-dimethylbenzyl, 2, 4-dimethylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2, 3-dimethoxybenzyl, 2, 4-dimethoxybenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-cyanobenzyl, 3-cyanobenzyl, 4-cyanobenzyl, and the like. The substituent groups have proper volume and small steric hindrance, and are favorable for the polymerization reaction. In addition, the maleimide compounds of these substituents can be directly dissolved in the cleavage fraction without adding an additional solvent.
<xnotran> , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- , N- (2- ) , N- (3- ) , N- (4- ) , N- (2- ) , N- (3- ) , N- (4- ) , N- (2- ) , N- (3- ) , </xnotran> N- (4-nitrobenzyl) maleimide, N- (3-cyanobenzyl) maleimide, and N- (4-cyanobenzyl) maleimide. Preferably, the maleimide-based compound of the present invention is selected from one or more of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide, N-isopropylmaleimide, N-N-butylmaleimide, N-isobutylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide.
According to a further preferred embodiment of the invention, R 3 And R 4 Are each a hydrogen atom; r 5 One selected from a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
According to a further preferred embodiment of the present invention, the maleimide-based compound of the present invention is selected from one or more of maleimide, N-methylmaleimide, N-ethylmaleimide, N-N-propylmaleimide or N-isopropylmaleimide.
Itaconic anhydride compound
The itaconic anhydride compound of the invention has a structure shown in a formula (3):
in the formula (3), R 6 、R 7 、R 8 Each independently selected from a hydrogen atom or a C1-C5 alkyl group. The C1-C5 alkyl group can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl. According to a particular embodiment of the invention, R 6 、R 7 、R 8 Each independently selected from a hydrogen atom or a C1-C3 alkyl group. The C1-C3 alkyl group can be selected from methyl, ethyl, n-propyl and isopropyl. According to another particular embodiment of the invention, formula (3) is itaconic anhydride. Thus, the polymerization reaction can be smoothly carried out; the reaction raw material can be directly dissolved in the cracking fraction without adding extra solvent.
Examples of the itaconic anhydride-based compound of the present invention include, but are not limited to, itaconic anhydride, 2-ethylene-succinic anhydride, 2-propylene-succinic anhydride, 3- (propyl-2-alkylene) oxolane-2, 5-dione, 3- (butyl-2-alkylene) oxolane-2, 5-dione, 3- (pentyl-3-alkylene) oxolane-2, 5-dione, 2-methylene-3-methyl-succinic anhydride, 2-methylene-3-ethyl-succinic anhydride, 2-methylene-3-propyl-succinic anhydride, 2-methylene-3-isopropyl-succinic anhydride, 2-methylene-3-butyl-succinic anhydride, 2-methylene-3-isobutyl-succinic anhydride, 2-methylene-3-tert-butyl-succinic anhydride, 2-ethylene-3-methyl-succinic anhydride, 2-ethylene-3-ethyl-succinic anhydride, 2-ethylene-3-propyl-succinic anhydride, 2-ethylene-3-isopropyl-succinic anhydride, 2-ethylene-3-butyl-succinic anhydride, 2-ethylene-3-isobutyl-succinic anhydride, 2-ethylene-3-tert-butyl-succinic anhydride, 2-propylene-3-methyl-succinic anhydride, 2-propylene-3-ethyl-succinic anhydride, 2-propylene-3-propyl-succinic anhydride, 2-propylene-3-isopropyl-succinic anhydride, 2-propylene-3-butyl-succinic anhydride, 2-propylene-3-isobutyl-succinic anhydride, 2-propylene-3-tert-butyl-succinic anhydride, 3-methyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-propyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 2-propylene-3-isopropyl-succinic anhydride, 2-propylene-3-isopropyl-3-tert-butyl-succinic anhydride, 2-methyl-4-oxolane-2, 5-dione, 3-methyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 2, and mixtures thereof 3-isopropyl-4- (propyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-ethyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, and mixtures thereof 3-propyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (butyl-2-alkylene) oxolane-2, 5-dione, 3-methyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, and mixtures thereof, 3-ethyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-propyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione, 3-isopropyl-4- (pentyl-3-alkylene) oxolane-2, 5-dione.
The cracking fraction of the present invention may be a petroleum cracking fraction or a coal cracking fraction. The cracking fraction is preferably one or more of C4 cracking fraction, C5 cracking fraction, C8 cracking fraction, ethylene tar and coal tar. The cracking fractions contain a large amount of unsaturated organic matters, which is beneficial to the polymerization reaction.
In the invention, the mass ratio of the cracking fraction to the ethylenic bond-containing compound is 1; preferably 1.2 to 6; more preferably 1.5 to 3. This allows the unsaturated organic compounds in the cracked fractions to react more fully and saves the amount of olefinic compounds.
In certain embodiments of the present invention, mixture a comprises solvent a, examples of which include, but are not limited to, xylene. In other embodiments of the present invention, mixture a does not contain a solvent. In still other embodiments of the present invention, mixture A contains only the cracked fraction and the olefinic bond-containing compound.
The initiator of the present invention may be a free radical initiator. The free radical initiator may be an azo initiator or an organic peroxide initiator. Preferably, the initiator may be selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide. More preferably, the initiator may be selected from one or two of azobisisobutyronitrile, dibenzoyl peroxide. According to a particular embodiment of the invention, the initiator is azobisisobutyronitrile. Solvent B of the present invention may be xylene.
< step of polymerization reaction >
Continuously flowing the mixture A and the mixture B into a reactor for polymerization reaction to obtain a reaction product; the resulting reaction product was continuously discharged from the reactor.
The mixture a and the mixture B may be placed in raw material tanks provided with mass flow meters, respectively, to control the flow rates of the mixture a and the mixture B. The mixture A and the mixture B flow into the reactor in a cocurrent mode. The reactor is provided with a single loop control system to control the output of the product, so that the product leaves the reactor at a certain flow rate.
The flow rate of the mixture A flowing into the reactor is 15-1000 cm 3 Min; preferably, 30 to 500cm 3 Min; more preferably, 40 to 100cm 3 And/min. Thus, the reaction rate can be ensured, and the free radical polymerization reaction can be fully carried out.
The flow rate of the mixture B flowing into the reactor is 15-1000 cm 3 Min; preferably, 30 to 500cm 3 Min; more preferably, it is 40 to 100cm 3 And/min. Thus, the reaction rate can be ensured, and the free radical polymerization reaction can be fully carried out.
The polymerization reaction may be carried out under stirring in an inert atmosphere. The inert atmosphere can be nitrogen, helium, argon or other inert gases.
The temperature of the polymerization reaction may be 30 to 120 ℃. Preferably, the polymerization temperature is 40 to 100 ℃. More preferably, the polymerization temperature is from 50 to 80 ℃. The time for the polymerization reaction may be 2.5 to 15 hours. Preferably, the polymerization time is 4 to 12 hours. More preferably, the time of the polymerization reaction is 6 to 10 hours.
The flow rate of the polymer flowing out of the reactor is 20-80 cm 3 And/min. Preferably, the flow rate of the polymer out of the reactor is from 25 to 55cm 3 And/min. More preferably, the flow rate of the polymer out of the reactor is from 30 to 45cm 3 And/min. Thus, the reaction rate can be ensured, and the free radical polymerization reaction can be fully carried out.
< step of post-treatment of reaction product >
The solid and liquid substances in the reaction product flowing out of the reactor were separated, and the solid substances were washed and dried to obtain a polymer. Optionally, a step of collecting the separated liquid material in a storage tank may be further included. The liquid material is mainly unreacted reaction raw material. In the present invention, the solid matter in the reaction product can be separated from the liquid matter by a method conventional in the art, and is not particularly limited. Preferably, the solid reaction product is separated by centrifugation.
According to one embodiment of the invention, the solid material is separated from the mixed liquor by centrifugation. The rotating speed of the centrifugal machine is 2000-6000 rpm; preferably 3000-6000 rpm; more preferably 3000 to 5000rpm. The centrifugation time is 3-15 min; preferably 3-10 min; more preferably 5 to 8min. This allows for better separation of the solid reaction product.
Examples 1 to 2
And uniformly mixing the cracking fraction, maleic anhydride and a solvent A to form a mixture A. And uniformly mixing the free radical initiator and the solvent B to form a mixture B. The mixture A and the mixture B were placed in a raw material tank equipped with a mass flow meter, respectively, and the mixture A and the mixture B were allowed to flow into the reactor at a constant flow rate. And carrying out polymerization reaction on the mixture A and the mixture B in a reactor to obtain a reaction product. The reactor is provided with a single-loop control system, so that reaction products can continuously flow out of the reactor at a certain flow rate. The solid and liquid substances of the reaction product flowing out of the reactor are separated by centrifugation, the solid substance is washed and dried to obtain a polymer, and the liquid substance is collected in a storage tank. The process parameters of examples 1-2 are shown in Table 1.
TABLE 1
Examples 3 to 5
The cracked fraction and maleic anhydride were mixed well to form mixture a. And uniformly mixing the free radical initiator and the solvent B to form a mixture B. The mixture A and the mixture B were placed in a raw material tank equipped with a mass flow meter, respectively, and the mixture A and the mixture B were allowed to flow into the reactor at a constant flow rate. And carrying out polymerization reaction on the mixture A and the mixture B in a reactor to obtain a reaction product. The reactor is provided with a single-loop control system, so that reaction products can continuously flow out of the reactor at a certain flow rate. The solid and liquid substances of the reaction product flowing out of the reactor are separated by centrifugation, the solid substance is washed and dried to obtain a polymer, and the liquid substance is collected in a storage tank. The process parameters for examples 3 to 5 are shown in Table 2.
TABLE 2
The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may occur to those skilled in the art may fall within the scope of the present invention without departing from the spirit of the present invention.
Claims (2)
1. A method for continuously polymerizing a cracked fraction, comprising the steps of:
(1) Uniformly mixing the C8 cracking fraction and maleic anhydride to form a mixture A; uniformly mixing azodiisobutyronitrile and xylene to form a mixture B; the mass ratio of the C8 cracking fraction to the maleic anhydride is 1.2-1.5;
(2) Continuously flowing the mixture A and the mixture B into a reactor for free radical polymerization reaction to obtain a reaction product; continuously discharging the obtained reaction product from the reactor; the flow rate of the mixture A is 30-100 cm 3 Min, the flow rate of the mixture B is 30-100 cm 3 Min, the flow rate of the reaction product flowing out of the reactor is 25-55 cm 3 Min; the reaction temperature is 50-80 ℃, and the reaction time is 6-10 hours;
(3) Separating solid substances and liquid substances in reaction products flowing out of the reactor in a centrifugal mode, and washing and drying the solid substances to obtain a polymer; wherein, the rotating speed of the centrifuge is 3000-5000 rpm, and the centrifugation time is 3-5 min.
2. The method of claim 1, further comprising the step of collecting the liquid material separated in step (3) in a storage tank.
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