CN110357998B - Conjugated diene and monovinylarene random copolymer and preparation method thereof - Google Patents

Conjugated diene and monovinylarene random copolymer and preparation method thereof Download PDF

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CN110357998B
CN110357998B CN201810319556.5A CN201810319556A CN110357998B CN 110357998 B CN110357998 B CN 110357998B CN 201810319556 A CN201810319556 A CN 201810319556A CN 110357998 B CN110357998 B CN 110357998B
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conjugated diene
reaction
polymerization
butadiene
copolymer
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CN110357998A (en
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吕万树
王雪
徐林
康新贺
王妮妮
王世朝
胡保利
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium

Abstract

The invention relates to the field of random copolymers of conjugated diene and monovinyl aromatic hydrocarbon, and discloses a random copolymer of conjugated diene and monovinyl aromatic hydrocarbon and a preparation method thereof. The method is to carry out continuous copolymerization reaction in a single reaction kettle, and comprises the following steps: under the condition of anionic polymerization, continuously introducing a reaction material containing a first part of conjugated diene, monovinylarene, a solvent, a gel inhibitor and a mono-organolithium initiator from the bottom of the reaction kettle, continuously introducing a second part of conjugated diene into the middle of the reaction kettle, continuously introducing a third part of conjugated diene into the upper part of the reaction kettle, and controlling the polymerization temperature to be 90-140 ℃. By the method, the conjugated diene and monovinyl arene random copolymer with controllable basic molecular weight and low vinyl content can be prepared under the conditions of higher reaction temperature and reasonable residence time without adding any structure regulator or randomizer.

Description

Conjugated diene and monovinylarene random copolymer and preparation method thereof
Technical Field
The invention relates to the field of conjugated diene and monovinyl aromatic hydrocarbon random copolymers, in particular to a preparation method of a conjugated diene and monovinyl aromatic hydrocarbon random copolymer and the random copolymer prepared by the method.
Background
As a styrene-butadiene copolymer which is a general-purpose rubber, styrene structural units in the molecular chain of a solution-polymerized styrene-butadiene rubber are required to be distributed randomly as much as possible. The existence of the styrene block can change the dynamic mechanical property of the rubber, and when the molecular chain of the solution polymerized butadiene styrene rubber contains a small amount of the styrene block, van der Waals force can be generated between the tail end of the flexible butadiene molecular chain and the styrene block, so that the tensile strength is improved. The presence of a large amount of styrene blocks seriously impairs the elasticity, strength and abrasion resistance of the rubber, and increases heat generation and rolling resistance. Therefore, the styrene block content of the solution-polymerized styrene-butadiene rubber is generally controlled to 2 wt% or less in the industry.
In the styrene-butadiene copolymer, there is a difference in the number of styrene structural units contained in the styrene block, and it is impossible to industrially produce the styrene structural units randomly embedded in the polybutadiene chain composed of the poly-cis-1, 4-butadiene, the poly-trans-1, 4-butadiene and the vinyl structure. For solution-polymerized styrene-butadiene rubber, if the number of styrene structural units in the styrene block is less than 6, the styrene-butadiene rubber is considered to be random.
In order to obtain a random solution-polymerized styrene-butadiene copolymer, a method of adding a structure regulator or a randomizer to a polymerization system is generally adopted. When structural regulators or randomizers such as ethers, amines, potassium alkoxide, organic barium compounds and the like exist, the relative reaction activity of the styrene monomer is improved, the system reactivity ratio of the styrene monomer is changed, and the styrene monomer can be subjected to copolymerization reaction with butadiene at the initial reaction stage, so that the generation of a styrene block is inhibited.
US3294768 relates to a method of using an alkali metal alkoxide compound such as lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, rubidium tert-butoxide, cesium tert-butoxide or the like as a randomizer. The randomizer can adjust the microstructure of the copolymerization of the butylbenzene, so that the randomness of the styrene in the product is greatly improved. Among them, potassium t-butoxide (t-BuOK) is the most effective, but t-BuOK is not soluble in aliphatic hydrocarbon solvent at all, and must be added to the reaction system in solid form, which is not suitable for large-scale industrial production.
EP0238784A2 relates to a process using sodium magnesium trihydroxy as randomizer in the preparation of random solution-polymerized butylbenzene. The randomizer can make the vinyl content of the polymer between 10 and 20 weight percent, but the synthesis process of the regulator is complex and the production cost is high.
Although the use of the above-mentioned structure regulator or randomizer can effectively suppress the formation of styrene block in the styrene-butadiene copolymer, it also has a certain limitation: firstly, the production cost is increased; secondly, some randomizers can be applied after being dissolved in polar solvents such as toluene, and the toluene has high toxicity and great environmental pollution; thirdly, the amine structure regulator and the like can have residues in the product and can not meet the environmental protection requirement; fourthly, the solubility of some structure regulators in a reaction system is poor, the repeatability is poor and the raw material source is not smooth; and fourthly, the addition of the structure regulator can cause the improvement of the vinyl structure content of the solution polymerized styrene butadiene rubber, and the preparation of the low-vinyl solution polymerized styrene butadiene rubber copolymer cannot be realized.
The reactivity ratio of styrene can also be changed by increasing the polymerization temperature, and GB1203063A discloses a method for preparing a styrene-butadiene copolymer without block polystyrene. The randomization of the random copolymer is realized by increasing the polymerization temperature, which requires a peak temperature of over 154 ℃, but too high temperature, which not only consumes high energy, but also makes the system gel not easy to control.
US6372863 relates to a method for synthesizing an all-random low-vinyl solution-polymerized styrene-butadiene rubber in a nonpolar environment in two reactors connected in series by supplementing 1, 3-butadiene at a reaction temperature of 70-100 ℃. Wherein, when the butadiene is supplemented in the second kettle, the total conversion rate of the styrene and the 1, 3-butadiene in the first kettle needs to be controlled between 60 and 90 percent, and the addition amount of the 1, 3-butadiene monomer in the second kettle is 20 to 40 percent of the total addition amount of the 1, 3-butadiene. Under the condition of not adding a structure regulator and a randomizer and under the reaction temperature condition of 70-100 ℃, the conversion of butadiene and styrene monomers at the outlet of the second kettle is not complete, so that the industrial application of the butadiene and styrene monomers is limited.
Disclosure of Invention
The invention aims to overcome the defects caused by adding various reaction auxiliary agents and supplementing butadiene monomers for synthesizing a conjugated diene and monovinyl aromatic hydrocarbon random copolymer in the prior art, and provides a conjugated diene and monovinyl aromatic hydrocarbon random copolymer which is controllable in basic molecular weight and low in vinyl content and a preparation method thereof, wherein the conjugated diene and monovinyl aromatic hydrocarbon random copolymer is prepared without adding any structure regulator or randomizer under the conditions of higher reaction temperature and reasonable residence time.
The inventors of the present invention have unexpectedly found in the course of their research that, in the course of preparing a random copolymer of conjugated diene and monovinyl aromatic hydrocarbon without using a structure regulator or randomizer, a random copolymer of conjugated diene and monovinyl aromatic hydrocarbon having a monovinyl aromatic hydrocarbon block content of less than 2 wt% can be obtained by controlling the addition mode of the conjugated diene monomer and the polymerization reaction temperature using stable mono-organolithium as an anionic polymerization initiator, thereby completing the present invention.
That is, the first aspect of the present invention provides a process for preparing a random copolymer of a conjugated diene and a monovinyl aromatic hydrocarbon by carrying out a continuous copolymerization reaction in a single reaction vessel, the process comprising: under the condition of anionic polymerization, continuously introducing a reaction material containing a first part of conjugated diene, monovinylarene, a solvent, a gel inhibitor and a mono-organolithium initiator from the bottom of the reaction kettle, continuously introducing a second part of conjugated diene into the middle of the reaction kettle, continuously introducing a third part of conjugated diene into the upper part of the reaction kettle, and controlling the polymerization temperature to be 90-140 ℃.
In a second aspect, the present invention provides a random copolymer of conjugated diene and monovinylarene prepared by the above process.
By adopting the technical scheme, the random copolymer of the conjugated diene and the monovinyl aromatic hydrocarbon with controllable basic molecular weight and low vinyl content can be prepared without adding any structural regulator or randomizer under the conditions of higher reaction temperature and reasonable residence time.
In addition, the preparation method of the conjugated diene and monovinylarene random copolymer provided by the invention is simple in preparation process, low in temperature in the early stage of reaction, good in system activity maintenance, and capable of effectively increasing the polymerization temperature of the system through material reaction heat in the later stage, so that the Mw/Mn of the polymer is increased. The method has the advantages of short polymerization time, high monomer conversion rate and complete conversion, and has great industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
The invention provides a preparation method of a conjugated diene and monovinyl aromatic hydrocarbon random copolymer, which is to carry out continuous copolymerization reaction in a single reaction kettle, and comprises the following steps: under the condition of anionic polymerization, continuously introducing a reaction material containing a first part of conjugated diene, monovinylarene, a solvent, a gel inhibitor and a mono-organolithium initiator from the bottom of a reaction kettle, continuously introducing a second part of conjugated diene into the middle of the reaction kettle, continuously introducing a third part of conjugated diene into the upper part of the reaction kettle, and controlling the polymerization temperature to be 90-140 ℃.
In the present invention, when the vertical distance between the upper and lower vertexes of the reaction vessel is taken as a reference, the length ratio of the vertical distance from the upper feed port of the reaction vessel to the upper vertex to the vertical distance between the upper and lower vertexes of the reaction vessel is 1:2.7-3.5; the length ratio of the vertical distance from the middle feed inlet of the reaction kettle to the upper vertex to the vertical distance between the upper vertex and the lower vertex of the reaction kettle is 1:1.2-2.
In addition, in the invention, the length-diameter ratio of the reaction kettle is 6-2:1, preferably 5 to 3:1.
in the invention, conjugated diene introduced into a reaction kettle is divided into three parts, wherein the first part of conjugated diene is continuously introduced from the bottom of the reaction kettle together with monovinylarene, a solvent, a gel inhibitor and a mono-organolithium initiator, the second part of conjugated diene is continuously introduced in the middle of the reaction kettle, and the third part of conjugated diene is continuously introduced at the upper part of the reaction kettle for copolymerization reaction. In this way, the copolymerization reaction can be carried out in stages, specifically, after a first portion of the conjugated diene is continuously introduced together with the monovinylarene, the solvent, the gel inhibitor and the mono-organolithium initiator from the bottom of the reaction vessel, a first stage copolymerization reaction is carried out before the middle portion of the reaction vessel, after a second portion of the conjugated diene is continuously introduced into the middle portion, a second stage copolymerization reaction is carried out, and after a third portion of the conjugated diene is continuously introduced into the upper portion, a third stage copolymerization reaction is carried out.
According to the invention, the amount of the second portion of conjugated diene introduced in the middle of the reaction vessel is from 15 to 45% by weight, preferably from 20 to 40% by weight, based on the total amount of the first portion of conjugated diene, the second portion and the third portion of conjugated diene (i.e. based on the amount of all conjugated dienes used). The third portion of conjugated diene is introduced in the upper portion of the reaction vessel in an amount of 15 to 45% by weight, preferably 15 to 40% by weight.
Specific examples of the amount of the second and third conjugated diene introduced into the middle and upper parts of the reaction vessel include: 15, 17.6, 18, 20, 21, 23, 23.5, 25, 27, 30, 32, 33, 35, 36, 38, 40, 42, 45, etc.
In a preferred embodiment of the present invention, the amount of conjugated diene introduced from the bottom of the reaction vessel is 30 to 70% by weight based on the total amount of the first portion of conjugated diene, the second portion of conjugated diene and the third portion of conjugated diene (i.e., based on the amount of all conjugated dienes used).
In a preferred embodiment of the present invention, the amount of conjugated diene introduced from the middle portion of the reaction vessel is 15 to 45% by weight based on the total amount of the first portion of conjugated diene, the second portion of conjugated diene and the third portion of conjugated diene (i.e., based on the amount of all conjugated dienes used).
In a preferred embodiment of the present invention, the amount of conjugated diene introduced from the upper portion of the reaction vessel is 15 to 30% by weight based on the total amount of the first portion of conjugated diene, the second portion of conjugated diene and the third portion of conjugated diene (i.e., based on the amount of all conjugated dienes used).
The conditions for the anionic polymerization are not particularly limited in the present invention, and generally include polymerization temperature, polymerization pressure and polymerization time. As described above, the polymerization temperature in the plurality of reaction tanks is controlled to 90 to 140 ℃ and preferably 95 to 135 ℃. Further, in order to more favorably carry out the polymerization reaction, the polymerization pressure of the polymerization vessel may be controlled to 0.6 to 1MPa, preferably 0.7 to 0.8MPa; the total residence time of the reactants in the continuous polymerization apparatus is preferably 45 to 90 minutes, more preferably 50 to 70 minutes. In the present invention, the pressures are gauge pressures.
According to the present invention, the polymerization reaction is an exothermic reaction, and thus, the polymerization temperature spontaneously rises as the polymerization reaction proceeds. Preferably, the reaction temperature when the reaction materials are continuously introduced from the bottom of the reaction kettle for the first time is controlled to be 90-115 ℃ (namely the reaction temperature is controlled to be 90-115 ℃ at the bottom of the reaction kettle), and is preferably 95-105 ℃; the reaction temperature is controlled between 98 ℃ and 130 ℃ when the conjugated diene monomer is added for the second time (when the second part of the conjugated diene is continuously introduced into the middle part of the reaction kettle) (namely the reaction temperature is controlled between 98 ℃ and 130 ℃ in the middle part of the reaction kettle), and is preferably between 100 ℃ and 120 ℃; the reaction temperature during the three times of feeding the conjugated diene monomer (during the continuous introduction of the third portion of the conjugated diene in the upper portion of the reaction vessel) is controlled to be 105 to 140 deg.c (i.e., the reaction temperature is controlled to be 105 to 140 deg.c in the upper portion of the reaction vessel), preferably 120 to 135 deg.c. Under non-adiabatic conditions, it is necessary to bring the temperature of each reactor or each zone to the desired level by appropriate heating, provided that the heat of polymerization is insufficient to control the polymerization temperature within the above-mentioned range.
Specific examples of the polymerization temperature include: 90 deg.C, 93 deg.C, 95 deg.C, 98 deg.C, 100 deg.C, 101 deg.C, 102 deg.C, 103 deg.C, 104 deg.C, 105 deg.C, 108 deg.C, 110 deg.C, 112 deg.C, 114 deg.C, 117 deg.C, 120 deg.C, 122 deg.C, 125 deg.C, 128 deg.C, 130 deg.C, 133 deg.C, 135 deg.C, 138 deg.C or 140 deg.C.
According to the invention, the mono-organolithium initiator may be represented by the general formula RLi, wherein R is a linear or branched alkyl, cycloalkyl or aryl group. Specifically, the mono-organolithium initiator may be selected from one or more of ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, phenyllithium, methylphenyllithium, and naphthyllithium, preferably n-butyllithium and/or sec-butyllithium.
The amount of the mono-organolithium initiator used in the present invention is not particularly limited, and may be appropriately selected according to the designed molecular weight. It will be readily understood by those skilled in the art that when it is desired to prepare a conjugated diene monovinylarene copolymer having a relatively large molecular weight, the amount of the mono-organolithium initiator may be reduced, but the rate of polymerization will be correspondingly reduced; when it is desired to prepare a conjugated diene monovinylarene copolymer having a relatively small molecular weight, the amount of the mono-organolithium initiator may be increased, but the polymerization rate will also be increased accordingly. Therefore, in consideration of the polymerization rate and the molecular weight of the resulting conjugated diene polymer, the amount of the mono-organolithium initiator is preferably 0.125 to 3.33mmol, more preferably 0.2 to 2.5mmol, based on 100g of the conjugated diene.
According to the present invention, the conjugated diolefins refer to various unsaturated chain hydrocarbons having a conjugated double bond (i.e., -C = C-) in the molecular structure. The type of the conjugated diene can be reasonably selected according to the application of the finally obtained conjugated diene and monovinylarene copolymer, and can be C in general 4 -C 12 Preferably C 4 -C 8 A conjugated diene. Specifically, the conjugated diene may be one or more of 1, 3-butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, and substituted 1, 3-butadienes (e.g., 2-chloro-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 1-phenyl-1, 3-butadiene, etc.). From the viewpoint of the wide applicability of the copolymer of a conjugated diene and a monovinylaromatic hydrocarbon, the conjugated diene is particularly preferably butadiene and/or isoprene.
According to the present invention, the monovinylarene monomer refers to an arene monomer having one vinyl substituent on its aromatic ring, such as a C8-C20 monovinylarene, preferably a C8-C12 monovinylarene, specific examples of which include styrene, C1-C6 alkyl-substituted styrene such as m-methylstyrene, p-methylstyrene or p-tert-butylstyrene, or a styrene derivative having a substituent on the vinyl group such as alpha-methylstyrene. The monovinylarene monomers can be used alone or in admixture. From the viewpoint of ease of availability, styrene and p-methylstyrene are preferably used, and styrene is most preferably used.
In the present invention, the conjugated diene monomer and the monovinylarene monomer may be used in amounts generally used in the art for preparing random copolymers of conjugated diene and monovinylarene, for example, the conjugated diene monomer may be used in an amount of 55 to 85% by weight, preferably 60 to 80% by weight, based on 100% by weight of the total amount of the monomers; accordingly, the monovinylarene monomer may be used in an amount of 15 to 45 wt%, preferably 20 to 40 wt%.
According to the present invention, the solvent may be any of various substances capable of acting as a reaction medium in the preparation of the random copolymer of conjugated diene and monovinyl aromatic hydrocarbon, for example, a hydrocarbon solvent and/or an ether solvent. The hydrocarbon solvent may be C 5 -C 7 And (3) one or more of cycloalkanes, aromatics and isoparaffins. Specific examples of the hydrocarbon solvent may include, but are not limited to: benzene, toluene, xylene, ethylbenzene, propane, butane, n-pentane, cyclopentane, methylOne or more of cyclopentane, n-heptane, cycloheptane, n-hexane, cyclohexane, n-octane, decane, and cyclooctane. The ether solvent may be C 4 -C 15 Monoethers and/or polyethers. Specific examples of the ether solvent may include, but are not limited to: t-butoxyethoxyethane and/or tetrahydrofuran. These solvents may be used alone or in combination. In addition, the amount of the solvent may be selected depending on the amounts of the conjugated diene and the monovinyl aromatic hydrocarbon, and for example, the amount of the solvent may be such that the total concentration of the conjugated diene and the monovinyl aromatic hydrocarbon is 10 to 30% by weight, preferably 20 to 25% by weight.
According to the present invention, the gel inhibitor may be any of various gel inhibitors commonly used in the art during the preparation of the conjugated diene and monovinylarene random copolymer, and is not particularly limited. Preferably, the gel inhibitor may be selected from at least one of 1, 2-butadiene, potassium tert-pentoxy, silicon tetrachloride, tetramethylethylenediamine and tetrahydrofuran, preferably 1, 2-butadiene.
The content of the gel inhibitor in the present invention is not particularly limited, and may be conventionally selected in the art. Preferably, the gel inhibitor is used in an amount of 0.45 to 0.75g, preferably 0.55 to 0.65g, based on 1000g of the conjugated diene.
According to the present invention, the water vapor in the air can terminate the anionic polymerization reaction, and therefore, in order to further facilitate the polymerization reaction, the polymerization reaction is preferably carried out in an inert atmosphere. The inert atmosphere refers to any gas or gas mixture that does not chemically react with the reactants and the product, such as one or more of nitrogen and a gas from group zero of the periodic table of elements. The inert atmosphere may be maintained by introducing any one or a mixture of the above gases which do not chemically react with the reactants and the products into the reaction system.
According to the present invention, it is generally necessary to subject the resulting random copolymer of conjugated diene and monovinyl aromatic hydrocarbon to a termination treatment after the polymerization reaction is completed. The terminator may be any one of various substances capable of inactivating the anionic active site, for example, one or more of water, methanol, ethanol and isopropanol, preferably water. The amount of the terminator used may be, for example, such that the molar ratio of terminator to mono-organolithium initiator is from 0.5 to 1:1.
in addition, in order to obtain a random copolymer of a conjugated diene and a monovinyl aromatic hydrocarbon having more excellent aging resistance, it is generally necessary to contact the polymerization product with an antioxidant after contacting the polymerization product with a terminator. The antioxidant can be various existing substances capable of preventing rubber from aging, for example, phenolic antioxidant and/or amine antioxidant, and specifically can be one or more selected from 2, 6-di-tert-butyl-p-cresol (Irganox 264 for short), tert-butyl catechol, 2' -methylene-bis (4-methyl-6-tert-butylphenol) (Irganox 2246 for short) and 2, 4-bis (n-octylthiomethylene) -6-methylphenol (Irganox 1520 for short). The antioxidant may be used in an amount of usually 0.1 to 1 part by weight, relative to 100 parts by weight of the conjugated diene and monovinylarene random copolymer.
According to the present invention, after the polymerization reaction is completed, it is necessary to remove the solvent from the conjugated diene and monovinyl aromatic hydrocarbon random copolymer finally obtained. The method for removing the solvent is well known to those skilled in the art, and for example, the conjugated diolefin and monovinyl aromatic hydrocarbon random copolymer can be precipitated out of the solvent by means of alcoholization precipitation, centrifugal separation, filtration, decantation, steam condensation, etc., or the volatile solvent in the conjugated diolefin and monovinyl aromatic hydrocarbon random copolymer can be separated out by means of steam stripping. As will be appreciated by those skilled in the art, further description will not be provided.
The invention also provides the conjugated diene and monovinylarene random copolymer prepared by the method.
According to the present invention, the amount of the structural unit formed in a 1, 2-polymerization manner by the conjugated diene and monovinylarene random copolymer prepared by the method of the present invention is 5-15 wt%; the polymer has a number average molecular weight of 30000-800000, a Mooney viscosity ML1+4 at 100 ℃ of 30-170, and a molecular weight distribution index of 2.0-3.0.
Preferably, the amount of structural units formed by 1, 2-polymerization of the conjugated diene is from 8 to 13% by weight, based on the total amount of the conjugated diene and monovinylarene random copolymer; the number average molecular weight of the polymer is 50000-500000; a Mooney viscosity ML1+4 at 100 ℃ of from 40 to 150; the molecular weight distribution index is 2.4-2.8.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) The number average molecular weight and molecular weight distribution of the polymer were measured by means of a Nippon Shimadzu LC-10A gel permeation chromatograph, at a test temperature of 25 ℃ with a mobile phase solvent of THF.
(2) The microstructure of the polymer is measured by AVANCE DRX 400MHz nuclear magnetic vibration spectrometer of Bruker company of Switzerland, wherein the measuring temperature is 25 ℃, the liquid pool method is adopted, and the solvent is CS 2 。
(3) Mooney viscosity (ML) was measured by the method specified in GB/T1232-92 using a Shimadzu SMV-300 Mooney viscometer in Japan.
(4) The monomer conversion is calculated as follows:
Figure BDA0001624886940000101
in the following examples and comparative examples:
the polymerization reaction is carried out in a 16-liter tower polymerization kettle, materials enter from the bottom, the middle part and the upper part of the kettle and overflow from the top of the kettle. The residence time is controlled by the material flow. The reaction temperature of each part of the tower type polymerization kettle is comprehensively controlled by the hot medium in the jacket and the reaction heat release, the raw materials are fed at normal temperature, and the reaction materials are subjected to adiabatic reaction in the kettle.
Wherein, when the vertical distance between the upper and lower vertexes of the reaction vessel is taken as a reference, the length ratio of the vertical distance from the upper feed port of the reaction vessel to the upper vertex to the vertical distance between the upper and lower vertexes of the reaction vessel in examples 1-3 is 1:2.7,1:3.1 and 1:3.5; the length ratio of the vertical distance from the middle feed inlet of the reaction kettle to the upper vertex to the vertical distance between the upper vertex and the lower vertex of the reaction kettle is respectively 1:1.2,1:1.6 and 1:2.0. in addition, the length-diameter ratio of the reaction kettle is 4:1.
example 1
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 50 minutes, and the polymerization reaction pressure is controlled to be 0.7 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: 9792g/h of hexane fraction, 1305.6g/h of styrene, 1175g/h of 1, 3-butadiene, 21.76mmol/h of n-butyllithium and 6.36g/h of 1, 2-butadiene were polymerized;
(2) 392g/h of 1, 3-butadiene is added into the middle part of the reaction kettle;
(3) 392g/h of 1, 3-butadiene is added into the upper part of the reaction kettle;
(4) Adding terminator water at 0.39g/h at the kettle top outlet of the reaction kettle (the discharge temperature of reactants is 130 ℃) to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. Then, the copolymer gum solution is subjected to steam coagulation and solvent removal treatment to obtain a copolymer J1.
The reaction temperature at each part of the pot, the pot outlet monomer conversion, the content of the structural unit formed in a 1,2-polymerization manner in the copolymer J1, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer J1, and the Mooney viscosity are shown in Table 1.
Comparative example 1
This comparative example illustrates the preparation of a reference copolymer.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 50 minutes, and the polymerization reaction pressure is controlled to be 0.7 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: a continuous polymerization was conducted using 9792g/h of hexane fraction, 1306g/h of styrene, 1958g/h of 1, 3-butadiene, 21.76mmol/h of n-butyllithium and 6.36g/h of 1, 2-butadiene;
(2) Adding a terminating agent water at the outlet of the top of the reaction kettle at a ratio of 0.39g/h to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain a copolymer glue solution. And then carrying out steam condensation and solvent removal treatment on the copolymer glue solution to obtain the copolymer DJ1.
The reaction temperature of each part of the pot, the pot outlet monomer conversion rate, the content of the structural unit formed in a 1, 2-polymerization manner in the copolymer DJ1, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer DJ1, and the Mooney viscosity are shown in Table 1.
Example 2
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total retention time of reaction materials in a kettle is 60 minutes, and the polymerization reaction pressure is controlled to be 0.8 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: 8486g/h of cyclohexane, 479g/h of styrene, 575g/h of 1, 3-butadiene, 10.88mmol/h of n-butyl lithium and 4.67g/h of 1, 2-butadiene for carrying out first kettle continuous polymerization reaction;
(2) 766g/h of 1, 3-butadiene is added into the middle part of the reaction kettle;
(3) Adding 574g/h of 1, 3-butadiene at the upper part of the reaction kettle;
(4) Adding terminator water at 0.16mg/h at the kettle top outlet of the reaction kettle (the discharge temperature of reactants is 129 ℃) to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. And then carrying out steam condensation and solvent removal treatment on the copolymer glue solution to obtain the copolymer DJ2.
The reaction temperature of each part of the pot, the conversion of the monomers at the top of the pot, the content of the structural units formed in a 1, 2-polymerization manner in the copolymer DJ2, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer DJ2, and the Mooney viscosity are shown in Table 1.
Comparative example 2
This comparative example illustrates the preparation of a reference copolymer.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 60 minutes, and the polymerization reaction pressure is controlled to be 0.8 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: hexane fraction 8486g/h, styrene 479g/h, 1, 3-butadiene 1915g/h, n-butyllithium 10.88mmol/h and 1, 2-butadiene 4.67g/h, to carry out first-pot continuous polymerization;
(2) Adding a terminating agent water at the outlet of the top of the reaction kettle at a rate of 0.16mg/h to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain a copolymer glue solution. And then carrying out steam condensation and desolventization treatment on the copolymer glue solution to obtain the copolymer DJ2.
The reaction temperature at each part of the pot, the conversion of the monomer at the outlet of the pot, the content of the structural unit formed in a 1, 2-polymerization manner in the copolymer DJ2, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer DJ2, and the Mooney viscosity are shown in Table 1.
Example 3
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 70 minutes, and the polymerization reaction pressure is controlled to be 0.75 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: 7461g/h of mixed solvent (a mixture of cyclohexane and n-hexane in a weight ratio of 88: 12), 466g/h of styrene, 560g/h of 1, 3-butadiene, 6.22mmol/h of n-butyllithium and 4.48g/h of 1, 2-butadiene) for first-kettle continuous polymerization;
(2) 560g/h of 1, 3-butadiene is added into the middle part of the reaction kettle;
(3) 263g/h of 1, 3-butadiene is added into the upper part of the reaction kettle;
(4) Adding terminator water at 0.07g/h at the kettle top outlet of the reaction kettle (the discharge temperature of reactants is 120 ℃) to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. Then, the copolymer gum solution is subjected to steam coagulation and solvent removal treatment to obtain a copolymer J3.
The reaction temperature at each part of the pot, the conversion of the monomer at the top of the pot, the content of the structural unit formed in a 1, 2-polymerization manner in the copolymer J3, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer J3, and the Mooney viscosity are shown in Table 1.
Comparative example 3
This comparative example illustrates the preparation of a reference copolymer.
A16-liter tower polymerization reactor is used as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total retention time of reaction materials in a kettle is 70 minutes, and the polymerization reaction pressure is controlled to be 0.75 +/-0.05 Mpa:
(1) Adding reaction materials from the bottom of the reaction kettle: 7461g/h, 466g/h of styrene, 1399g/h of 1, 3-butadiene, 6.22mmol/h of n-butyllithium and 4.48g/h of 1, 2-butadiene by using a mixed solvent (a mixture of cyclohexane and n-hexane in a weight ratio of 88;
(2) Adding a terminating agent water at the outlet of the top of the reaction kettle at a ratio of 0.07g/h to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain a copolymer glue solution. And then carrying out steam condensation and solvent removal treatment on the copolymer glue solution to obtain the copolymer DJ3.
The respective pot polymerization temperatures, the three pot outlet monomer conversion rates, the contents of the structural units formed in a 1, 2-polymerization manner in the copolymer DJ3, the styrene block contents, the number average molecular weights and molecular weight distributions of the copolymer DJ3, and the Mooney viscosities are shown in Table 1.
TABLE 1
Figure BDA0001624886940000151
As can be seen from Table 1, the styrene block content of the copolymer can be adjusted well by adding 1, 3-butadiene in stages. By adjusting the monomer ratio of butadiene to styrene in the early stage of the reaction, the styrene monomer can participate in the reaction in the early stage of the reaction, and the styrene block content of the copolymer in Table 1 is controlled within 1 wt%. It can also be seen that the copolymer Mw/Mn is influenced more significantly by the reaction temperature.
Example 4
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower polymerization reactor is used as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 45 minutes, and the polymerization reaction pressure is controlled to be 0.9 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: hexane 10155g/h, styrene 1958g/h, 1, 3-butadiene 1676g/h, n-butyl lithium 87.04mmol/h and 1, 2-butadiene 7.62 g/h;
(2) 359g/h of 1, 3-butadiene is added into the middle part of the reaction kettle;
(3) 359g/h of 1, 3-butadiene is added into the upper part of the reaction kettle;
(4) Adding terminating agent water at the outlet of the top of the reaction kettle (the discharge temperature of reactants is 140 ℃) at 1.57g/h to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. Then, the copolymer glue solution is subjected to steam coagulation and solvent removal treatment to obtain a copolymer J4.
The reaction temperature at each part of the pot, the conversion of the monomer at the top of the pot, the content of the structural unit formed in a 1, 2-polymerization manner in the copolymer J4, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer J4, and the Mooney viscosity are shown in Table 2.
Example 5
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower polymerization reactor is used as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 75 minutes, and the polymerization reaction pressure is controlled to be 0.65 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: hexane 7137g/h, styrene 282g/h, 1, 3-butadiene 642g/h, n-butyllithium 4.48mmol/h and 1, 2-butadiene 3.57 g/h;
(2) 385g/h of 1, 3-butadiene is added into the middle part of the reaction kettle;
(3) Adding 257g/h of 1, 3-butadiene into the upper part of the reaction kettle;
(4) Adding terminator water at 0.65g/h at the kettle top outlet of the reaction kettle (the discharge temperature of reactants is 110 ℃) to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. Then, the copolymer gum solution is subjected to steam coagulation and solvent removal treatment to obtain a copolymer J5.
The reaction temperature at each part of the pot, the conversion of the monomer at the top of the pot, the content of the structural unit formed in a 1,2-polymerization manner in the copolymer J5, the styrene block content, the number average molecular weight and the molecular weight distribution of the copolymer J5, and the Mooney viscosity are shown in Table 2.
Example 6
This example illustrates the preparation of a random copolymer of conjugated diene and monovinylarene according to the present invention.
A16-liter tower type polymerization reaction kettle is taken as a continuous polymerization reaction device.
In a continuous polymerization reaction device, under the atmosphere of high-purity nitrogen, the total residence time of reaction materials in a kettle is 90 minutes, and the polymerization reaction pressure is controlled to be 0.6 +/-0.05 MPa:
(1) Adding reaction materials from the bottom of the reaction kettle: hexane 6165g/h, styrene 163g/h, 1, 3-butadiene 370g/h, n-butyllithium 2.72mmol/h and 1, 2-butadiene 3.98g/h for polymerization;
(2) Adding 416g/h of 1, 3-butadiene into the middle part of the reaction kettle;
(3) 139g/h of 1, 3-butadiene is added into the upper part of the reaction kettle;
(4) Adding terminator water at 0.05g/h at the kettle top outlet of the reaction kettle (the discharge temperature of reactants is 105 ℃) to terminate the reaction, and adding an anti-aging agent Irganox 1520 accounting for 0.2 percent of the weight of the monomers to obtain copolymer glue solution. Then, the copolymer gum solution is subjected to steam coagulation and solvent removal treatment to obtain a copolymer J6.
The respective pot polymerization temperatures, the three pot outlet monomer conversion rates, the contents of the structural units formed in a 1, 2-polymerization manner in the copolymer J6, the styrene block contents, the number average molecular weights and the molecular weight distributions of the copolymer J6, and the Mooney viscosities are shown in Table 2.
TABLE 2
Figure BDA0001624886940000181
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 (10)

1. A process for the preparation of random copolymers of conjugated diolefins and monovinylarenes by continuous copolymerization in a single reactor, comprising: continuously introducing a reaction mass comprising a first portion of conjugated diene, monovinyl aromatic hydrocarbon, solvent, gel inhibitor and mono-organolithium initiator from the bottom of said reaction vessel, a second portion of conjugated diene in the middle of said reaction vessel, and a third portion of conjugated diene in the upper portion of said reaction vessel under anionic polymerization conditions comprising: the polymerization temperature is 101-140 ℃, the polymerization pressure is 0.6-1MPa, the total residence time is 45-90 minutes, the gel inhibitor is 1, 2-butadiene, the dosage of the gel inhibitor is 0.55-0.65g based on 1000g of the conjugated diene, the dosage of the second part of the conjugated diene introduced into the middle part of the reaction kettle is 15-45 wt% based on the total amount of the first part of the conjugated diene, the second part of the conjugated diene and the third part of the conjugated diene, and the dosage of the third part of the conjugated diene introduced into the upper part of the reaction kettle is 15-45 wt%.
2. The process according to claim 1, wherein the amount of the second part of the conjugated diene introduced into the middle portion of the reaction tank is 20 to 40% by weight and the amount of the third part of the conjugated diene introduced into the upper portion of the reaction tank is 15 to 40% by weight, based on the total amount of the first part of the conjugated diene, the second part of the conjugated diene and the third part of the conjugated diene.
3. The production process according to claim 1 or 2, wherein the mono-organolithium initiator is used in an amount of 0.125 to 3.33mmol based on 100g of the conjugated diene.
4. The preparation method according to claim 1 or 2, wherein the mono-organolithium initiator is selected from one or more of ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, phenyllithium, methylphenyllithium, and naphthyllithium.
5. The process according to claim 1 or 2, wherein said conjugated diene is C 4 -C 12 A conjugated diene.
6. The method according to claim 5, wherein the conjugated diene is selected from one or more of 1, 3-butadiene, isoprene, 1, 3-pentadiene and 1, 3-hexadiene.
7. The production method according to claim 1 or 2, wherein the monovinyl aromatic hydrocarbon is a C8-C20 monovinyl aromatic hydrocarbon.
8. The method of claim 7, wherein the monovinyl aromatic hydrocarbon is styrene.
9. The production method according to claim 1 or 2, further comprising contacting the polymerization reaction product with a terminating agent and an anti-aging agent in this order.
10. A random copolymer of a conjugated diene and a monovinylarene, prepared by the process of any one of claims 1 to 9.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US6372863B1 (en) * 1999-08-12 2002-04-16 The Goodyear Tire & Rubber Company Synthesis of styrene-butadiene rubber
CN107286292A (en) * 2016-03-30 2017-10-24 中国石油化工股份有限公司 A kind of preparation method of random distribution high-phenylethylene medium vinyl content solution polymerized butadiene styrene rubber
CN107337754A (en) * 2016-05-03 2017-11-10 中国石油化工股份有限公司 Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372863B1 (en) * 1999-08-12 2002-04-16 The Goodyear Tire & Rubber Company Synthesis of styrene-butadiene rubber
CN107286292A (en) * 2016-03-30 2017-10-24 中国石油化工股份有限公司 A kind of preparation method of random distribution high-phenylethylene medium vinyl content solution polymerized butadiene styrene rubber
CN107337754A (en) * 2016-05-03 2017-11-10 中国石油化工股份有限公司 Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene

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