CN111234081B - Low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and preparation method thereof - Google Patents
Low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and preparation method thereof Download PDFInfo
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- CN111234081B CN111234081B CN202010151001.1A CN202010151001A CN111234081B CN 111234081 B CN111234081 B CN 111234081B CN 202010151001 A CN202010151001 A CN 202010151001A CN 111234081 B CN111234081 B CN 111234081B
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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
- 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
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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
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/02—Low molecular weight, e.g. <100,000 Da.
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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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
Abstract
The invention provides a low molecular weight narrow distribution styrene-maleic anhydride copolymer and a preparation method thereof, belonging to the technical field of high polymer material preparation. The invention adopts the high-temperature continuous free radical polymerization method to prepare the styrene-maleic anhydride copolymer, has simple process, less solvent and initiator consumption, low cost, continuous production, short reaction time, high reaction rate and high conversion rate; the low molecular weight narrow distribution styrene-maleic anhydride copolymer prepared by the method has a small molecular weight distribution range, the product molecular weight distribution is more uniform, the product performance is more stable, and the method has a good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a preparation method thereof.
Background
The styrene-maleic anhydride copolymer is an important functional polymer material, has the advantages of good heat resistance, low melt viscosity, excellent processability, good chemical stability, high hardness, high transparency, good compatibility with other polymer materials and the like, and is widely applied to the industries of buildings, electric appliances, automobile manufacturing, office supplies, coatings, chemical engineering, pharmacy, well drilling and the like. They can be classified into alternating copolymers and random copolymers according to their molecular structures; the molecular weight fractions are classified into high molecular weight and low molecular weight styrene-maleic anhydride copolymers. The high molecular weight styrene-maleic acid copolymer is mainly used as engineering plastics, composite materials, compatilizers, chain extenders or natural heat-resistant modifiers. Compared with the high molecular weight copolymer, the low molecular weight styrene-maleic anhydride copolymer has wider application, and can be used as a water-soluble high molecular material, a tackifier, a sizing agent, a dyeing assistant, a protective colloid, a pigment dispersant, cleaning power and an emulsifier. In addition, the molecular chain of the styrene-maleic acid copolymer contains anhydride groups with high reaction activity, the low molecular weight styrene-maleic acid copolymer can be subjected to saponification, esterification and amidation reactions to prepare various styrene-maleic anhydride copolymer derivatives, and the functional derivatives can be widely applied to the industries of textile printing and dyeing, coatings, electronics, daily chemicals, chemical engineering and the like. Therefore, the low molecular weight styrene-maleic acid copolymer is a functional polymer material with wide application.
The styrene-maleic anhydride copolymer is generally synthesized by a polymerization method such as solution polymerization, precipitation polymerization, bulk polymerization, and bulk-suspension polymerization. These polymerization methods can synthesize both high molecular weight styrene-maleic anhydride copolymers and low molecular weight styrene-maleic anhydride copolymers. At present, the styrene maleic acid copolymer synthesized by the above polymerization method is all carried out by a batch polymerization method. Since styrene and maleic anhydride are apt to form an electron complex and the polymerization process is carried out intermittently, the maleic anhydride content of the copolymer formed at the early stage of the polymerization is high and the maleic anhydride content of the copolymer formed at the later stage is low. Therefore, the styrene-maleic anhydride copolymer obtained by polymerization such as batch solution polymerization, precipitation polymerization, bulk-suspension polymerization, etc. is usually a mixture of copolymers with different compositions, the copolymer has a wide copolymerization composition, segment and molecular weight distribution, and when the polymerization reaction is performed at a temperature lower than 100 ℃, even the obtained polymer is usually a mixture of polystyrene and styrene-maleic anhydride alternating copolymer due to strong alternating polymerization tendency, which seriously affects the use effect and application range of the styrene-maleic anhydride copolymer. In addition, the quality of the styrene-maleic anhydride copolymer synthesized by batch polymerization varies from batch to batch, so that the stability of the quality of the product is poor, and the application range and the application effect of the copolymer are also severely limited.
At present, when synthesizing low molecular weight styrene-maleic anhydride copolymer, there are two methods for reducing molecular weight, one method is to reduce molecular weight of copolymer by increasing the amount of initiator used in the polymerization process to obtain low molecular weight styrene-maleic anhydride copolymer; the initiator is usually used in an amount of about 3.5 to 7% of the monomer to achieve the desired effect. However, although the molecular weight of the polymer can be reduced by increasing the amount of the initiator, the increase in the amount of the initiator causes the exothermic reaction of the polymerization to be severe, and the reaction is difficult to withdraw and control; in addition, when the amount of the initiator is relatively high, side reactions such as grafting and crosslinking occur in the polymerization process, and a large amount of undecomposed initiator remains in the product, thereby affecting the use performance of the final product. More importantly, the initiator is expensive, and the use of a large amount thereof can seriously increase the production cost of the product. Another approach is to reduce the molecular weight of the styrene-maleic anhydride copolymer by using a molecular weight regulator in large amounts during the polymerization. Although molecular weight regulators are very effective in reducing the molecular weight of the polymer, the desire to synthesize low molecular weight styrene-maleic anhydride copolymers having molecular weights in the range of 2000 to 10000 still requires the addition of relatively large amounts of molecular weight regulators (typically 5 to 20% by weight of the monomer used). Generally, most of the used molecular weight regulators are thiol substances which have strong odor and are difficult to eliminate residual molecular weight regulators in the post-treatment process of products, so that the styrene-maleic acid copolymer synthesized by the method also has strong odor, and the method can pollute the environment and influence the body health of operators.
Disclosure of Invention
The invention aims to provide a low molecular weight narrow distribution styrene-maleic anhydride copolymer and a preparation method thereof, wherein the method can be used for continuous production, and the prepared low molecular weight styrene-maleic anhydride copolymer has the advantages of high conversion rate, pure product, uniform copolymer composition and narrow molecular weight distribution.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer, which comprises the following steps:
mixing styrene, maleic anhydride and an initiator, carrying out polymerization reaction on the obtained mixed material, and devolatilizing the obtained reaction material to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; post-treating the removed material;
the temperature of the polymerization reaction is 130-300 ℃; the polymerization is carried out in a tubular reactor with a static mixer;
the initiator is a thermal decomposition type initiator, and the thermal decomposition type initiator comprises an organic peroxide initiator and an azo initiator;
the organic peroxide initiator comprises benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate or diisopropyl peroxydicarbonate;
the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
Preferably, the molar ratio of the maleic anhydride to the styrene is 1.
Preferably, the mass of the initiator accounts for 0.1 to 1 percent of the sum of the mass of the styrene and the mass of the maleic anhydride.
Preferably, the mixed material further comprises a molecular weight regulator, and the mass of the molecular weight regulator accounts for 0-1% of the sum of the masses of the styrene and the maleic anhydride.
Preferably, the molecular weight regulator comprises a vinyl monomer or a chain transfer agent, the vinyl monomer comprises vinyl acetate, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate or alpha-methyl styrene; the chain transfer agent includes aliphatic mercaptans, dodecyl mercaptan, carbon tetrachloride, dithioesters, iodoform, or 1-chloro-1-iodoalkane.
Preferably, the mixed material further comprises a reaction solvent, and the mass of the reaction solvent accounts for 0-50% of the total mass of all materials in the polymerization reaction system.
Preferably, the reaction solvent comprises one or more of acetone, butanone or cyclohexanone.
Preferably, the average residence time of the mixture in the tubular reactor is from 1 to 30min.
Preferably, the post-treatment process comprises: condensing and recovering the removed material to obtain a recovered material; rectifying the recovered material, and reusing the rectified material in the polymerization reaction.
The invention provides the low molecular weight narrow distribution styrene-maleic anhydride copolymer prepared by the preparation method of the technical scheme, wherein the number average molecular weight of the low molecular weight narrow distribution styrene-maleic anhydride copolymer is 1500-10000 g/mol, and the molecular weight distribution index is 1.1-1.5.
The invention provides a preparation method of a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer, which comprises the following steps of: mixing styrene, maleic anhydride and an initiator, carrying out polymerization reaction on the obtained mixed material, and devolatilizing the obtained reaction material to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; post-treating the removed material; the temperature of the polymerization reaction is 130-300 ℃; the polymerization is carried out in a tubular reactor with a static mixer; the initiator is a thermal decomposition type initiator, and the thermal decomposition type initiator comprises an organic peroxide initiator and an azo initiator; the organic peroxide initiator comprises benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate or diisopropyl peroxydicarbonate; the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate. The invention adopts the high-temperature continuous free radical polymerization method to prepare the styrene-maleic anhydride copolymer, has simple process, small using amount of solvent and initiator, low cost, continuous production, short reaction time, high reaction rate and high conversion rate; the low molecular weight narrow distribution styrene-maleic anhydride copolymer prepared by the method has a small molecular weight distribution range, the product has more uniform molecular weight distribution, the product performance is more stable, and the method has a good industrialization prospect;
in the prior art, a reaction kettle is adopted for polymerization, the monomer amount in the polymerization reaction kettle is large, implosion is easy to occur, reaction heat is difficult to withdraw, the reaction is difficult to control, and when the existing kettle type reactor is adopted for polymerization, the reaction is a full back-mixing type continuous reaction, the kinetic chain lengths of radicals generated by decomposition in the polymerization process are difficult to ensure to be the same or close, high molecular weight products can be generated in the obtained polymer, and the molecular weight distribution is too wide. The tubular reactor with the static mixer is adopted for polymerization reaction, the tubular reactor is rapid in heating, good in heat transfer effect, easy in temperature control and stable in temperature, the initiator can be guaranteed to enter the tubular reactor and be immediately decomposed in all parts to generate free radicals and initiate polymerization, and the problem that the initiator is not decomposed simultaneously due to temperature gradient can be avoided; the tubular reactor is convenient for realizing the high-speed flow of the monomer and the polymer in the reactor, and can avoid the problems that the polymer adhesion is caused to influence the heat conduction and cause the polymerization degradation in a reaction kettle because the temperature of the kettle wall is overhigh; the mixture of the monomer and the polymer flows in a plug flow mode in the tubular reactor, so that the back mixing problem generated when a kettle type reactor is adopted for continuous polymerization can be avoided, the kinetic chain length is the same or basically similar from the initiation of a free radical chain to the termination of real kinetics, and the styrene-maleic anhydride copolymer with low molecular weight and narrow distribution can be obtained.
Drawings
FIG. 1 is a flow diagram of a polymerization reaction of the present invention, wherein, 1-monomer mixing reactor; 2-a feed pump; 3-a tubular reactor; 4-devolatilization device; 5-a melt pump; 6-a condensation system; 7-recycling the monomer storage tank; 8-vacuum system.
Detailed Description
The invention provides a preparation method of a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer, which comprises the following steps of:
mixing styrene, maleic anhydride and an initiator, carrying out polymerization reaction on the obtained mixed material, and devolatilizing the obtained reaction material to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; post-treating the removed material;
the temperature of the polymerization reaction is 130-300 ℃; the polymerization is carried out in a tubular reactor with a static mixer;
the initiator is a thermal decomposition type initiator, and the thermal decomposition type initiator comprises an organic peroxide initiator and an azo initiator;
the organic peroxide initiator comprises benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate or diisopropyl peroxydicarbonate;
the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate.
In the present invention, the starting materials or reagents required are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes styrene, maleic anhydride and an initiator, carries out polymerization reaction on the obtained mixed material, and carries out devolatilization on the obtained reaction material to obtain the low molecular weight narrow distribution styrene-maleic anhydride copolymer and the devolatilized material. In the present invention, the molar ratio of maleic anhydride to styrene is preferably 1.
In the present invention, the initiator is a thermal decomposition type initiator including an organic peroxide type initiator and an azo type initiator; the organic peroxide initiator comprises Benzoyl Peroxide (BPO), lauroyl peroxide, di-tert-butyl peroxide (DTBP), dicumyl peroxide, tert-butyl peroxybenzoate or diisopropyl peroxydicarbonate; the azo initiator comprises Azobisisobutyronitrile (AIBN), azobisisoheptonitrile or dimethyl azobisisobutyrate. In the present invention, the mass of the initiator is preferably 0.1 to 1%, more preferably 0.3 to 0.8%, and still more preferably 0.5 to 0.6% of the sum of the masses of styrene and maleic anhydride.
In the present invention, the mixed material preferably further comprises a molecular weight regulator; the mass of the molecular weight modifier is preferably 0 to 1%, more preferably 0.1 to 0.8%, even more preferably 0.3 to 0.6%, and even more preferably 0.5% of the sum of the masses of styrene and maleic anhydride. In the present invention, the molecular weight regulator preferably includes a vinyl monomer preferably including vinyl acetate, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate or α -methylstyrene or a chain transfer agent; the chain transfer agent preferably comprises an aliphatic mercaptan, dodecyl mercaptan, carbon tetrachloride, dithioester, iodoform or 1-chloro-1-iodoalkane.
In the present invention, the mixture preferably further comprises a reaction solvent; the mass of the reaction solvent is preferably 0 to 50%, more preferably 5 to 40%, and still more preferably 15 to 30% of the total mass of all materials in the polymerization reaction system. In the invention, the reaction solvent preferably comprises one or more of acetone, butanone or cyclohexanone; when the reaction solvent is preferably one or more of the above, the ratio of different solvents in the present invention is not particularly limited, and any ratio may be used.
In the invention, the process of mixing the styrene, the maleic anhydride and the initiator is preferably to add the reagents into a monomer mixing reaction kettle respectively, discharge air by using nitrogen, stir and mix until the maleic anhydride is dissolved, so as to obtain a mixed material. When the mixed material also comprises a molecular weight regulator and/or a reaction solvent, the molecular weight regulator and/or the reaction solvent are added into the monomer mixing reaction kettle together. The stirring process is not particularly limited in the present invention, and a process known in the art may be selected. In the invention, the monomer mixing reaction kettle only mixes materials and does not carry out polymerization reaction.
After the mixed material is obtained, the mixed material is uniformly and quickly fed into the tubular reactor by using a feeding pump to carry out the polymerization reaction. In the present invention, the temperature of the polymerization reaction is 130 to 300 ℃, preferably 150 to 260 ℃, more preferably 200 to 250 ℃, and the average residence time of the mixed material in the tubular reactor is preferably 1 to 30min, more preferably 10 to 20min; the polymerization is carried out in a tubular reactor with a static mixer. The tubular reactor with the static mixer is not particularly limited in the present invention, and any equipment known in the art may be used. In the invention, the mixed material is conveyed into the tubular reactor for polymerization reaction, and the process of removing the product obtained by polymerization reaction from the tubular reactor is a continuous process.
In the polymerization reaction process, under the condition of higher polymerization reaction temperature, the thermal decomposition half-life period of the initiator selected by the invention is extremely short and is about 0.1-100 s, the mixture of the initiator and the monomer (styrene and maleic anhydride) is instantly decomposed to generate free radicals immediately after entering the reactor, and although the addition amount of the initiator is small, the concentration of the free radicals in the system is very high (similar to that in low-temperature polymerization, the concentration of the instant free radicals in the system is improved by increasing the amount of the initiator so as to reduce the molecular weight) because the initiator is instantly decomposed to generate the free radicals, and the chain transfer rate constant to the monomer and the solvent is extremely high under the high-temperature condition, the termination rate of the free radicals is extremely high (caused by the higher concentration of the free radicals and the lower viscosity of the system under the high-temperature condition), and the molecular weight of the product is extremely low. In addition, because the polymerization reaction of the invention is carried out in a tubular reactor, the mixture of the monomer and the generated polymer flows in the reactor in a plug flow manner, the monomer is instantly and totally reacted to form the polymer after entering the reactor (namely, the monomer is instantly and totally converted into the polymer or almost completely polymerized into the polymer under the conditions of high free radical concentration and strong chain transfer), and the melt of the mixture formed by the monomer and the generated polymer flows in the reactor in a plug flow manner without back mixing, and the residual free radicals do not further undergo chain propagation because of no monomer supply, so that the high molecular weight polymer is not formed, therefore, the molecular weight distribution of the prepared styrene-maleic anhydride copolymer is narrow.
After the polymerization reaction is finished, the invention carries out devolatilization on the obtained reaction material to obtain the styrene-maleic anhydride copolymer with low molecular weight and narrow distribution and the devolatilized material. In the present invention, the reaction material is preferably fed to a devolatilizer for devolatilization to remove unreacted monomers and/or reaction solvent (stripping material). The devolatilization process is not particularly limited in the present invention, and may be performed by a process known in the art. In the present invention, the low molecular weight narrow distribution styrene-maleic anhydride copolymer obtained in the devolatilizer is preferably discharged by a melt pump, and then granulated and packaged to obtain a finished product.
After the stripped material is obtained, the invention preferably carries out post-treatment on the stripped material, and the post-treatment process preferably comprises the following steps: condensing and recovering the removed material to obtain a recovered material; the present invention preferably stores the reclaimed materials in a reclaimed monomer storage tank. The process of condensing and recovering is not limited in particular, and a condensing system well known in the art can be selected for the process. After the recovered material is obtained, the recovered material is rectified, and the rectified material is reused for polymerization reaction. The rectification process is not particularly limited in the present invention, and a process well known in the art may be selected. The invention preferably reuses the material after rectification as monomer and/or solvent for the synthesis of copolymers. The present invention is not particularly limited to the process of reusing the rectified material in the polymerization reaction, and a process well known in the art may be selected.
In the devolatilization process, the present invention preferably decompresses the devolatilizer using the vacuum system 8, preferably < -0.0985MPa, to remove unreacted monomers and/or reaction solvents.
The flow schematic diagram of the preparation method of the invention is shown in figure 1, styrene, maleic anhydride and an initiator (which may also comprise a molecular weight regulator and/or a reaction solvent) are added into a monomer mixing reaction kettle 1, the obtained mixed material is uniformly and quickly sent into a tubular reactor 3 by a feed pump 2 for polymerization reaction, the obtained reaction material is sent into a devolatilization device 4 for devolatilization, and simultaneously, a vacuum system 8 is used for reducing the pressure of the devolatilization device; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump 5, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized materials in a condensing system 6, storing the obtained recovered materials in a recovered monomer storage tank 7, rectifying, and reusing the obtained materials in the polymerization reaction.
The invention provides the low molecular weight narrow distribution styrene-maleic anhydride copolymer prepared by the preparation method of the technical scheme, wherein the number average molecular weight of the low molecular weight narrow distribution styrene-maleic anhydride copolymer is 1500-10000 g/mol, and the molecular weight distribution index is 1.1-1.5.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Material proportioning: 30kg of cyclohexanone serving as a reaction solvent accounts for 30 percent of the total mass of all materials; the molar ratio of maleic anhydride to styrene is 1; 0.21kg of azodiisobutyronitrile serving as an initiator, wherein the mass of the initiator accounts for 0.3 percent of the total mass of maleic anhydride and styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 200 ℃ by using a feeding pump, keeping the mixed material for 10min, conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 2
The only difference from example 1 is: the residence time of the mixture in the tubular reactor at 220 ℃ was 10min.
Example 3
The only difference from example 1 is: the residence time of the mixture in the tube reactor at 240 ℃ was 10min.
Example 4
The only difference from example 1 is: the residence time of the mixture in the tube reactor at 240 ℃ was 15min.
Example 5
The only difference from example 1 is: the residence time of the mixture in the tube reactor at 240 ℃ was 20min.
Example 6
Material proportioning: 30kg of cyclohexanone serving as a reaction solvent accounts for 30 percent of the total mass of all materials; the molar ratio of maleic anhydride to styrene is 1; 0.31kg of initiator benzoyl peroxide, wherein the mass of the initiator accounts for 0.44 percent of the total mass of maleic anhydride and styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, keeping the mixed material for 20min, conveying the obtained reaction material into a devolatilization device for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized materials in a condensing system, storing the recovered materials in a recovered monomer storage tank, rectifying, and reusing the materials in the polymerization reaction.
Example 7
Proportioning materials: 30kg of cyclohexanone serving as a reaction solvent accounts for 30 percent of the total mass of all materials; the molar ratio of maleic anhydride to styrene is 1; 0.187kg of di-tert-butyl peroxide as an initiator, wherein the mass of the initiator accounts for 0.27 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, using nitrogen to exhaust air, stirring and mixing until the maleic anhydride is dissolved, then using a charging pump to uniformly and quickly send the obtained mixed material into a tubular reactor at 240 ℃, wherein the retention time of the mixed material is 20min, and conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 8
Material proportioning: 40kg of cyclohexanone serving as a reaction solvent accounts for 40 percent of the total mass of all materials; the molar ratio of monomer maleic anhydride to styrene is 1; 0.18kg of azodiisobutyronitrile as an initiator accounts for 0.3 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, keeping the mixed material for 10min, conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized materials in a condensing system, storing the recovered materials in a recovered monomer storage tank, rectifying, and reusing the materials in the polymerization reaction.
Example 9
Proportioning materials: 50kg of cyclohexanone serving as a reaction solvent accounts for 50 percent of the total mass of all the materials; the molar ratio of monomer maleic anhydride to styrene is 1; 0.15kg of azodiisobutyronitrile as an initiator accounts for 0.3 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, keeping the mixed material for 10min, conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 10
Proportioning materials: 30kg of solvent cyclohexanone accounting for 30 percent of the total mass of all materials; the molar ratio of monomer maleic anhydride to styrene is 1; 0.21kg of azodiisobutyronitrile as an initiator, which accounts for 0.3 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, keeping the mixed material for 10min, conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized materials in a condensing system, storing the recovered materials in a recovered monomer storage tank, rectifying, and reusing the materials in the polymerization reaction.
Example 11
Material proportioning: 30kg of solvent cyclohexanone accounting for 30 percent of the total mass of all materials; the molar ratio of monomer maleic anhydride to styrene is 1; 0.7kg of azodiisobutyronitrile serving as an initiator accounts for 1 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, using nitrogen to exhaust air, stirring and mixing until the maleic anhydride is dissolved, then using a charging pump to uniformly and quickly send the obtained mixed material into a tubular reactor at 240 ℃, wherein the retention time of the mixed material is 10min, and conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 12
Proportioning materials: 30kg of cyclohexanone serving as a reaction solvent, which accounts for 30 percent of the total mass of all the materials; the molar ratio of the monomer maleic anhydride to the styrene is 1; 0.7kg of azodiisobutyronitrile serving as an initiator accounts for 1 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator and a reaction solvent into a monomer mixing reaction kettle, using nitrogen to exhaust air, stirring and mixing until the maleic anhydride is dissolved, then using a charging pump to uniformly and quickly send the obtained mixed material into a tubular reactor at 240 ℃, wherein the retention time of the mixed material is 10min, and conveying the obtained reaction material into a devolatilizer for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 13
Material proportioning: the molar ratio of the monomer maleic anhydride to the styrene is 1, 9.5kg of maleic anhydride and 90.5kg of styrene; 1kg of azodiisobutyronitrile serving as an initiator accounts for 1 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride and an initiator into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly and quickly feeding the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, allowing the mixed material to stay for 10min, conveying the obtained reaction material into a devolatilization device for devolatilization to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, and then granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Example 14
Proportioning materials: 30kg of solvent cyclohexanone accounting for 30 percent of the total mass of all materials; the molar ratio of the monomer maleic anhydride to the styrene is 1, 6.6kg of maleic anhydride and 63.4kg of styrene; 0.7kg of azodiisobutyronitrile serving as an initiator, which accounts for 1 percent of the total mass of maleic anhydride and styrene; 0.7kg of molecular weight regulator alpha-methyl styrene accounts for 1 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator, a reaction solvent and a molecular weight regulator into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly conveying the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, allowing the mixed material to stay for 10min, conveying the obtained reaction material into a devolatilization device for devolatilization, and obtaining a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized materials in a condensing system, storing the recovered materials in a recovered monomer storage tank, rectifying, and reusing the materials in the polymerization reaction.
Example 15
Material proportioning: 30kg of solvent cyclohexanone accounting for 30 percent of the total mass of all materials; the molar ratio of the monomer maleic anhydride to the styrene is 1, 6.6kg of maleic anhydride and 63.4kg of styrene; 0.7kg of azodiisobutyronitrile serving as an initiator accounts for 1 percent of the total mass of the maleic anhydride and the styrene; 0.7kg of dodecyl mercaptan serving as a molecular weight regulator accounts for 1 percent of the total mass of the maleic anhydride and the styrene.
Preparation of the copolymer: adding styrene, maleic anhydride, an initiator, a reaction solvent and a molecular weight regulator into a monomer mixing reaction kettle, discharging air by using nitrogen, stirring and mixing until the maleic anhydride is dissolved, uniformly conveying the obtained mixed material into a tubular reactor at 240 ℃ by using a feeding pump, allowing the mixed material to stay for 10min, conveying the obtained reaction material into a devolatilization device for devolatilization, and obtaining a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; discharging the low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer obtained by devolatilization through a melt pump, granulating and packaging to obtain a finished product; and condensing and recovering the devolatilized material in a condensing system, storing the recovered material in a recovered monomer storage tank, rectifying, and reusing the material for polymerization reaction.
Comparative example 1
A copolymer synthesized by the prior art (synthesis of styrene-maleic anhydride copolymer (SMA) with low molecular weight, heilongjiang petrochemical, 2000 (01): 15-18.) is taken as a comparative example 1, wherein 3-thiopropionic acid is taken as a chain transfer agent, azobisisobutyronitrile is taken as an initiator, 1, 2-dichloroethane is taken as a solvent, the low molecular weight SMA is synthesized by adopting a free radical solution polymerization method, the optimal process conditions are that the reaction temperature is 80 ℃, the reaction time is 4 hours, the solvent consumption is 78%, the initiator consumption is 5.0%, the chain transfer agent is 4.0%, the yield of the prepared copolymer is 96.04%, and the intrinsic viscosity is 0.077.
Comparative example 2
The copolymer synthesized by the prior art (Liuyan, synthesis of low-relative molecular mass styrene-maleic anhydride alternating copolymer, molecular science, 2017 (2): 138-145.) is taken as a comparative example 2, wherein the low-molecular mass SMA is synthesized by a precipitation polymerization method, and the optimal reaction conditions are as follows: the reaction temperature is 86 ℃, the reaction time is 2 hours, the solvent concentration is 80%, the initiator dosage is 0.6%, the yield is 86.86%, the number average molecular weight is 17700, and the relative molecular weight distribution index is 1.64.
The low molecular weight narrow distribution styrene-maleic anhydride copolymers prepared in examples 1 to 11 were subjected to number average molecular weight measurement and molecular weight distribution index measurement, and the results are shown in Table 1.
TABLE 1 polymerization yield, number average molecular weight and distribution of low molecular weight narrow distribution styrene-maleic anhydride copolymers prepared in examples 1 to 11
As can be seen from Table 1, the styrene-maleic anhydride copolymer prepared by the present invention has not only a low molecular weight but also a narrow molecular weight distribution, but also a high polymerization yield, indicating that the conversion rate of the process is high. In the method of the present invention, the amount of the solvent and the initiator is small and the reaction time is short, compared to the copolymers prepared in comparative examples 1 to 2.
According to the embodiments, the invention provides the low molecular weight narrow distribution styrene-maleic anhydride copolymer and the preparation method thereof, the styrene-maleic anhydride copolymer is prepared by adopting the high-temperature continuous free radical polymerization method, the process is simple, the using amount of the solvent and the initiator is small, the cost is low, the continuous production can be realized, the reaction time is short, the reaction rate is high, and the conversion rate is high; the low molecular weight narrow distribution styrene-maleic anhydride copolymer prepared by the method has the advantages of small molecular weight distribution range, more uniform molecular weight distribution of products, more stable product performance and good industrial prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of a low molecular weight narrow distribution styrene-maleic anhydride copolymer comprises the following steps:
mixing styrene, maleic anhydride and an initiator, carrying out polymerization reaction on the obtained mixed material, and devolatilizing the obtained reaction material to obtain a low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and a devolatilized material; post-treating the removed material;
the temperature of the polymerization reaction is 130 to 300 ℃; the polymerization is carried out in a tubular reactor with a static mixer;
the initiator is a thermal decomposition type initiator, and the thermal decomposition type initiator comprises an organic peroxide initiator and an azo initiator;
the organic peroxide initiator comprises benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate or diisopropyl peroxydicarbonate;
the azo initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate;
the mass of the initiator accounts for 0.1 to 1 percent of the sum of the masses of the styrene and the maleic anhydride.
2. The method according to claim 1, wherein the molar ratio of the maleic anhydride to the styrene is 1 to 9.
3. The preparation method according to claim 1, wherein the mixed material further comprises a molecular weight regulator, and the mass of the molecular weight regulator accounts for 0 to 1 percent of the sum of the masses of the styrene and the maleic anhydride.
4. The method of claim 3, wherein the molecular weight regulator comprises a vinyl monomer or a chain transfer agent, the vinyl monomer comprising vinyl acetate, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate or alpha-methyl styrene; the chain transfer agent includes dodecyl mercaptan, carbon tetrachloride, dithioester, iodoform, or 1-chloro-1-iodoalkane.
5. The preparation method according to claim 1, wherein the mixed materials further comprise a reaction solvent, and the mass of the reaction solvent accounts for 0 to 50% of the total mass of all the materials in the polymerization reaction system.
6. The method according to claim 5, wherein the reaction solvent comprises one or more of acetone, butanone, or cyclohexanone.
7. The method of claim 1, wherein the average residence time of the mixture in the tubular reactor is 1 to 30min.
8. The method of claim 1, wherein the post-treating comprises: condensing and recovering the removed material to obtain a recovered material; rectifying the recovered material, and reusing the rectified material in the polymerization reaction.
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| CN112694554A (en) * | 2021-01-11 | 2021-04-23 | 浙江阿尔法化工科技有限公司 | Synthesis method and production equipment of SMA resin |
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| CN115181200B (en) * | 2022-07-06 | 2023-11-07 | 中国石油天然气股份有限公司 | Preparation method of C4-C8 alpha-mono-olefin-maleic anhydride copolymer |
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