Synthesis method of halogenated olefin-functional monomer copolymer

Abstract

The present invention provides a method for synthesizing a halogenated olefin-functional monomer copolymer. The synthesis method comprises the following steps: step S1, mixing raw materials including functional monomers, initiators, and solvents to obtain a raw material liquid; step S2, in an inert atmosphere, subjecting the raw materials including halogenated olefins and the raw material liquid to a polymerization reaction to obtain a polymerization product system; step S3, post-processing the polymerization product system to obtain a halogenated olefin-functional monomer copolymer. The present application is conducive to achieving efficient copolymerization of halogenated olefins and functional monomers by adopting the above heterogeneous precipitation polymerization method, greatly increasing the concentration of the corresponding molecular segments of the functional monomers in the halogenated olefin-functional monomer copolymer, thereby obtaining a halogenated olefin-functional monomer copolymer with unique properties. The above synthesis method has high production efficiency, mild reaction conditions, simple operating process, easy separation and purification, and low cost.

Description

Technical Field

[0001] The invention relates to the technical field of material science, and in particular to a method for synthesizing a halogenated olefin-functional monomer copolymer. Background Art

[0002] Polyvinyl chloride (PVC) is a commodity thermoplastic, which is mainly produced by emulsion polymerization and suspension polymerization. However, PVC resin has poor processability and thermal stability, mainly due to its inherent properties, such as strong polar interactions between polymer chains and weak C-Cl bonds. In order to find and further broaden the high value-added application areas of PVC, copolymerization of vinyl chloride with monomers containing functional groups such as hydroxyl, carboxyl, and anhydride can give PVC resin a variety of properties. For example, poly[(vinyl chloride)-co-(acrylic acid)] has a high surface modification efficiency for PVC resin. Maleic anhydride (MAH), as a functional monomer, has been widely used in the modification of polyolefins. However, copolymerization of MAH with vinyl chloride monomer (VCM) by suspension or emulsion polymerization remains a challenge. The main reason is that the anhydride group inevitably hydrolyzes in aqueous solution to produce highly acidic maleic acid, which inhibits polymerization in suspended monomer droplets and makes emulsion polymerization unstable. Although some attempts have been made to synthesize binary or ternary PVC copolymers containing MAH, the content of MAH in these copolymers is very low. Summary of the invention

[0003] The main purpose of the present invention is to provide a method for synthesizing a halogenated olefin-functional monomer copolymer to solve the problem of low mass content of maleic anhydride corresponding molecular segments in chlorinated olefin-maleic anhydride copolymers in the prior art.

[0004] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a method for synthesizing a halogenated olefin-functional monomer copolymer is provided, and the method comprises the following steps: step S1, mixing raw materials including functional monomers, initiators, and solvents to obtain a raw material liquid; step S2, subjecting the raw materials including the halogenated olefin and the raw material liquid to a polymerization reaction in an inert atmosphere to obtain a polymerization product system; step S3, post-treating the polymerization product system to obtain a halogenated olefin-functional monomer copolymer; wherein the functional monomer comprises an active functional group and a carbon-carbon double bond; and the halogenated olefin is a C2 to C4 halogenated olefin.

[0005] Furthermore, the above-mentioned active functional group is selected from any one or more of carboxylic acid group, anhydride group and amide group, and the functional monomer is preferably selected from any one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, acrylamide and methacrylamide.

[0006] Furthermore, the halogen in the above-mentioned halogenated olefin is selected from any one or more of chlorine, bromine and iodine, and preferably the halogenated olefin is vinyl chloride.

[0007] Furthermore, the mass ratio of the functional monomer, the initiator and the solvent is 1:0.02-0.04:2-50.

[0008] Furthermore, the above-mentioned step S3 includes: step S31, separating the polymerization product system to obtain halogenated olefins and polymerization products; step S32, filtering and washing the polymerization products in sequence to obtain filter cakes and filtrate; step S33, drying the filter cakes to obtain olefin-functional monomer copolymers; and / or, distilling the filtrate to obtain a recovered solvent, preferably returning the recovered solvent to step S1 or step S32 for use as a solvent; and / or, the distillation pressure is 0.1 to 101 kPa, and the distillation temperature is 40 to 150° C.; and / or the halogenated olefin-functional monomer copolymer is a chloroolefin-maleic anhydride copolymer, and / or the mass content of the molecular chain segment corresponding to maleic anhydride in the chloroolefin-maleic anhydride copolymer is 50 to 65 wt % of the chloroolefin-maleic anhydride copolymer.

[0009] Furthermore, the halogenated olefin in the above step S31 is pressurized and then recycled to step S2. Preferably, the pressure of the halogenated olefin after pressurization is 0.1 to 10 MPa, preferably 3 to 6 MPa.

[0010] Furthermore, in the above step S1, the initiator is an azo initiator and / or a peroxide initiator, and the initiator is preferably selected from any one or more of bis(4-tert-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide and diisopropyl peroxydicarbonate.

[0011] Furthermore, in the above step S1, the solvent is selected from any one or more of an alkyl ester solvent, an alkane solvent, an aromatic compound solvent, and an aromatic compound derivative solvent; wherein the general formula of the alkyl ester solvent is C n H n+ 2COOC m H m+2, wherein n and m are each independently any integer of 1 to 5; preferably, the solvent is selected from any one or more of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, isoamyl phenylacetate, n-hexane, cyclohexane, n-heptane, benzene, ethylbenzene and xylene.

[0012] Furthermore, in the above step S2, the polymerization reaction pressure is 0.1-10 MPa, preferably 0.5-2 MPa, and / or the polymerization reaction temperature is 40-60° C., and / or the polymerization reaction residence time is 0.1-12 h.

[0013] Furthermore, in the above step S2, the reactor used for the polymerization reaction is selected from any one of a polymerization reactor, a tubular reactor, a microchannel reactor, a horizontal reactor, and a tower reactor.

[0014] By applying the technical solution of the present invention, the present application adopts the above heterogeneous precipitation polymerization method, which is conducive to achieving efficient copolymerization of halogenated olefins and functional monomers, greatly increasing the concentration of the corresponding molecular segments of the functional monomers in the halogenated olefin-functional monomer copolymer, thereby obtaining a halogenated olefin-functional monomer copolymer with unique properties. The above synthesis method has high production efficiency, mild reaction conditions, simple operation process, easy separation and purification, and low cost. DETAILED DESCRIPTION

[0015] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0016] As analyzed in the background technology, the prior art has the problem that the mass content of the molecular chain segments corresponding to maleic anhydride in the chlorinated olefin-maleic anhydride copolymer is low. To solve this problem, the present invention provides a method for synthesizing a halogenated olefin-functional monomer copolymer.

[0017] In a typical embodiment of the present application, a method for synthesizing a halogenated olefin-functional monomer copolymer is provided, and the method comprises the following steps: step S1, mixing raw materials including a functional monomer, an initiator, and a solvent to obtain a raw material liquid; step S2, subjecting the raw materials including the halogenated olefin and the raw material liquid to a polymerization reaction in an inert atmosphere to obtain a polymerization product system; step S3, post-treating the polymerization product system to obtain a halogenated olefin-functional monomer copolymer; wherein the functional monomer comprises an active functional group and a carbon-carbon double bond; and the halogenated olefin is a C2 to C4 halogenated olefin.

[0018] The present application adopts the above heterogeneous precipitation polymerization method, which is conducive to the efficient copolymerization of halogenated olefins and functional monomers, greatly increasing the concentration of the corresponding molecular segments of the functional monomers in the halogenated olefin-functional monomer copolymer, thereby obtaining a halogenated olefin-functional monomer copolymer with unique properties. The above synthesis method has high production efficiency, mild reaction conditions, simple operation process, easy separation and purification, and low cost.

[0019] In one embodiment of the present application, the above-mentioned active functional group is selected from any one or more of a carboxylic acid group, an anhydride group and an amide group, and the functional monomer is preferably selected from any one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, acrylamide and methacrylamide.

[0020] By preferably selecting the type of functional monomer within the above range, it is beneficial to effectively copolymerize the functional monomer with the halogenated olefin, so that the chlorinated olefin-maleic anhydride copolymer has more abundant active functional groups that can be modified, thereby forming a chlorinated olefin-maleic anhydride copolymer with specific functions.

[0021] In one embodiment of the present application, the halogen in the above-mentioned halogenated olefin is selected from any one or more of chlorine, bromine and iodine, and preferably the halogenated olefin is vinyl chloride.

[0022] The above-mentioned halogenated olefins preferably have higher reactivity, which is conducive to forming copolymers with functional monomers, and C2-C4 halogenated olefins are widely available in industrial production and have low costs.

[0023] In one embodiment of the present application, the mass ratio of the functional monomer, the initiator and the solvent is 1:0.02-0.04:2-50.

[0024] By controlling the mass ratio of functional monomer, initiator and solvent within the above range, it is beneficial to improve the selectivity and efficiency of the polymerization reaction, reduce the occurrence of side reactions, thereby increasing the yield and purity of the copolymer, while reducing production costs and enhancing economic benefits.

[0025] In one embodiment of the present application, the above-mentioned step S3 includes: step S31, separating the polymerization product system to obtain halogenated olefins and polymerization products; step S32, filtering and washing the polymerization products in sequence to obtain filter cakes and filtrate; step S33, drying the filter cake to obtain olefin-functional monomer copolymers; and / or, distilling the filtrate to obtain a recovered solvent, preferably returning the recovered solvent to step S1 or step S32 for use as a solvent; and / or, the distillation pressure is 0.1 to 101 kPa, and the distillation temperature is 40 to 150° C.; and / or the halogenated olefin-functional monomer copolymer is a chlorinated olefin-maleic anhydride copolymer, and / or the mass content of the maleic anhydride corresponding molecular segment in the chlorinated olefin-maleic anhydride copolymer is 50 to 65 wt % of the chlorinated olefin-maleic anhydride copolymer.

[0026] The present invention is conducive to recovering halogenated olefins and solvents from the polymerization product system through the above post-treatment steps, thereby not only improving the purity of the olefin-functional monomer copolymer, but also reducing the waste of raw materials such as halogenated olefins and solvents, realizing the recycling of solvents, and reducing environmental pollution. At the same time, the above post-treatment conditions are mild, the operation process is simple, and the cost is low. The preferred chlorinated olefin-maleic anhydride copolymer in which the mass content of the above maleic anhydride corresponding molecular chain segment is 50-65wt% of the chlorinated olefin-maleic anhydride copolymer has more stable performance and higher utilization value.

[0027] In one embodiment of the present application, the halogenated olefin in the above step S31 is pressurized and then recycled to step S2. Preferably, the pressure of the halogenated olefin after pressurization is 0.1 to 10 MPa, preferably 3 to 6 MPa.

[0028] By increasing the pressure of halogenated olefins to the above pressure and then reusing them, the effective recycling of halogenated olefin raw materials is achieved, further improving their utilization rate. At the same time, the processing flow of halogenated olefins is simplified, production energy consumption is reduced, and the economy and environmental protection of the entire synthesis process are improved.

[0029] In one embodiment of the present application, in the above step S1, the initiator is selected from an azo initiator and / or a peroxide initiator, and preferably the initiator is selected from any one or more of bis(4-tert-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide and diisopropyl peroxydicarbonate.

[0030] By controlling the initiator type within the above range, it is beneficial to ensure the efficient progress of the polymerization reaction, reduce the occurrence of side reactions, improve the monomer conversion rate, and reduce the molecular weight distribution coefficient of the chloroolefin-maleic anhydride copolymer.

[0031] In one embodiment of the present application, in the above step S1, the solvent is selected from any one or more of an alkyl ester solvent, an alkane solvent, an aromatic compound solvent, and an aromatic compound derivative solvent; wherein the molecular formula of the alkyl ester solvent is C n H n+2 COOC m H m+2 , wherein n and m are each independently any integer of 1 to 5; preferably, the solvent is selected from any one or more of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, isoamyl phenylacetate, n-hexane, cyclohexane, n-heptane, benzene, ethylbenzene and xylene.

[0032] It is preferred to control the type of solvent within the above range, especially alkyl ester solvents can effectively avoid hydrolysis of functional monomers in aqueous solution, maintain their activity, and promote the polymerization reaction, increase the reaction rate and the content of maleic anhydride in the copolymer, thereby improving the performance and application range of the copolymer.

[0033] Furthermore, when the initiator is a peroxide initiator, the preferred solvent is a mixed solvent of butyl acetate and n-hexane, and the preferred volume ratio of butyl acetate to n-hexane is 3:2 to 5:1. When the initiator is an azo initiator, the preferred solvent is a mixed solvent of butyl acetate and ethyl acetate, and the preferred volume ratio of butyl acetate to ethyl acetate is 2:1 to 10:1.

[0034] In one embodiment of the present application, in the above step S2, the polymerization reaction pressure is 0.1-10 MPa, preferably 0.5-2 MPa, and / or the polymerization reaction temperature is 40-60° C., and / or the polymerization reaction residence time is 0.1-12 h.

[0035] Preferably, controlling the polymerization reaction conditions within the above range helps to more accurately control the molecular weight, molecular weight distribution and specific composition of the halogenated olefin-functional monomer copolymer, thereby optimizing the properties of the chlorinated olefin-maleic anhydride copolymer.

[0036] In one embodiment of the present application, in the above step S2, the reactor used for the polymerization reaction is selected from any one of a polymerization reactor, a tubular reactor, a microchannel reactor, a horizontal reactor, and a tower reactor.

[0037] By controlling the type of reactor used in the polymerization reaction within the above range, it is beneficial to optimize the reaction conditions, improve mass transfer efficiency, reduce reaction time, and reduce energy consumption, thereby improving the efficiency and cost-effectiveness of the entire production process and making the product more competitive in the market.

[0038] The beneficial effects of the present application will be described below in conjunction with specific embodiments and comparative examples.

[0039] Example 1

[0040] Functional monomer maleic anhydride, initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and a mixed solvent of butyl acetate and n-hexane are prepared into a raw material solution, wherein the volume ratio of butyl acetate to n-hexane is 3:2, the mass ratio of initiator to maleic anhydride is 0.02:1; and the mass ratio of solvent to maleic anhydride is 20:1. After nitrogen replacement of a tubular reactor (without a static distributor, with an inner diameter of 40 mm and a length of 4000 mm), vinyl chloride is introduced and the temperature is raised to 45°C. The vinyl chloride pressure is controlled to make the reaction pressure 2MPa. The raw material liquid is continuously pumped into a polymerization kettle for reaction. The residence time is controlled to be 8h. After the reaction is completed, the temperature is first lowered and the pressure is released. The olefin released by the pressure release is pressurized in a pressure tank and then reused. The pressure of vinyl chloride after pressurization is 3MPa. The polymer product is pumped into a filter press tank for nitrogen pressure filtration and washed with a solvent. The obtained filter cake is dried to constant weight, and the filtrate is distilled and recycled. The distillation pressure is 50kPa and the distillation temperature is 100°C. The final vinyl chloride-maleic anhydride copolymer product has a maleic anhydride conversion rate of 56.7%, a polymer yield of 55.9%, an anhydride value of 56.9%, and a particle size of 130.7μm.

[0041] Example 2

[0042] The difference from Example 1 is that the functional monomer maleic anhydride, initiator azobisisobutyronitrile (AIBN) and butyl acetate, ethyl acetate mixed solvent are prepared into a raw material liquid, wherein the volume ratio of butyl acetate to ethyl acetate is 2:1, and the molar ratio of initiator to maleic anhydride is 0.03:1; the mass ratio of solvent to maleic anhydride is 5:1, and the polymerization kettle is nitrogen substituted and then vinyl chloride is introduced and the temperature is raised to 65°C. The vinyl chloride pressure is controlled to make the reaction pressure 1.0MPa, and the raw material liquid is continuously pumped into the polymerization kettle for reaction, and the residence time is controlled to be 6h. The maleic anhydride conversion rate of the vinyl chloride-maleic anhydride copolymer product finally obtained is 63.2%, the polymer yield is 61.7%, the anhydride value is 58.7%, and the particle size is 56.7μm.

[0043] Example 3

[0044] The difference from Example 1 is that after nitrogen substitution is performed in the tubular reactor, allyl chloride is introduced and the temperature is raised to 45° C., and finally an allyl chloride-maleic anhydride copolymer product is obtained.

[0045] Example 4

[0046] The difference from Example 1 is that the selected functional monomer is acrylamide, and a vinyl chloride-acrylamide copolymer product is finally obtained.

[0047] Example 5

[0048] The difference from Example 1 is that the functional monomer maleic anhydride, the initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and the mixed solvent of butyl acetate and n-hexane are formulated into a raw material solution, wherein the mass ratio of the initiator to maleic anhydride is 0.02:1, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0049] Example 6

[0050] The difference from Example 1 is that the functional monomer maleic anhydride, the initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and the mixed solvent of butyl acetate and n-hexane are formulated into a raw material solution, wherein the mass ratio of the initiator to maleic anhydride is 0.04:1, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0051] Example 7

[0052] The difference from Example 1 is that the functional monomer maleic anhydride, the initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and the mixed solvent of butyl acetate and n-hexane are formulated into a raw material solution, wherein the mass ratio of the solvent to maleic anhydride is 2:1, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0053] Example 8

[0054] The difference from Example 1 is that the functional monomer maleic anhydride, the initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and the mixed solvent of butyl acetate and n-hexane are formulated into a raw material solution, wherein the mass ratio of the solvent to maleic anhydride is 50:1, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0055] Example 9

[0056] The difference from Example 1 is that after the reaction is completed, the temperature is lowered and the pressure is released, and the olefin released is pressurized in a pressure tank and then reused, wherein the pressure of vinyl chloride after pressurization is 4 MPa, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0057] Example 10

[0058] The difference from Example 1 is that after the reaction is completed, the temperature is lowered and the pressure is released, and the olefin released is pressurized in a pressure tank and then reused, wherein the pressure of vinyl chloride after pressurization is 6 MPa, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0059] Embodiment 11

[0060] The difference from Example 1 is that the polymerization reaction is carried out in a polymerization reactor to finally obtain a vinyl chloride-maleic anhydride copolymer product.

[0061] Example 12

[0062] The difference from Example 1 is that the functional monomer maleic anhydride, the initiator bis(4-tert-butylcyclohexyl) peroxydicarbonate (DTBP) and the solvent butyl acetate are prepared into a raw material liquid to finally obtain a vinyl chloride-maleic anhydride copolymer product.

[0063] Embodiment 13

[0064] The difference from Example 1 is that after nitrogen substitution is performed in the tubular reactor, vinyl chloride is introduced and the temperature is raised to 60° C., and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0065] Embodiment 14

[0066] The difference from Example 1 is that after nitrogen substitution is performed in the tubular reactor, vinyl chloride is introduced and the temperature is raised to 80° C., and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0067] Embodiment 15

[0068] The difference from Example 1 is that the vinyl chloride pressure is controlled so that the reaction pressure is 0.5 MPa, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0069] Example 16

[0070] The difference from Example 1 is that the vinyl chloride pressure is controlled so that the reaction pressure is 1 MPa, and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0071] Comparative Example 1

[0072] The difference from Example 1 is that the polymerization reaction is only carried out in the reactor; and finally a vinyl chloride-maleic anhydride copolymer product is obtained.

[0073] According to the maleic anhydride monomer content before and after the reaction and the maleic anhydride content of the chlorinated olefin-maleic anhydride copolymer product in the above embodiments and comparative examples, the conversion rate of maleic anhydride was calculated, the yield of the chlorinated olefin-maleic anhydride copolymer / vinyl chloride-acrylamide copolymer was calculated, the mass content of the functional groups (wherein the mass content of the functional groups in Example 4 refers to the mass content of the acrylamide groups in the vinyl chloride-acrylamide copolymer product, and the mass content of the functional groups in the remaining embodiments and comparative examples refers to the mass content of the maleic anhydride groups in the chlorinated olefin-maleic anhydride copolymer product), the particle size, the weight average molecular weight and the molecular weight distribution polymer index were tested, and the results are shown in Table 1.

[0074] Test method:

[0075] Titration method GB / T 2895-2008 to test polymer anhydride value;

[0076] The acid-base neutralization reaction is used to determine the amount of acidic substances corresponding to the anhydride group. After the anhydride is hydrolyzed, carboxylic acid is produced. It is titrated with an alkali solution of known concentration, and the acid value is calculated based on the volume of the consumed alkali solution.

[0077] The laser method GB / T 19077-2016 is used to test the polymer particle size;

[0078] Based on the characteristics of laser monochromaticity and strong directionality, laser light scattering technology is used to characterize the particle size distribution of particle samples. When the laser beam passes through the dispersed particle sample, the particle size measurement is completed by measuring the intensity of the scattered light, and the particle size distribution of the scattered light spectrum can be obtained by analysis and calculation.

[0079] Gel permeation chromatography GB / T 21863-2008 tests polymer weight average molecular weight and molecular weight distribution;

[0080] Separation is performed by taking advantage of the different volumes of polymer molecules in the solution. The polymer sample is dissolved in a specific solvent and eluted in a chromatographic column with a porous filler. Small molecules can enter the pores of the filler and stay there for a long time, while large molecules mainly move in the gaps between the filler particles and stay there for a short time. The outflowing polymer solution is detected by a detector to obtain the concentration distribution of molecules of different molecular weights in the solution, thereby calculating the weight average molecular weight and molecular weight distribution.

[0081] Table 1

[0082]

[0083] From the above description, it can be seen that the above embodiments and comparative examples of the present invention achieve the following technical effects:

[0084] By adopting the above heterogeneous precipitation polymerization method, it is beneficial to achieve efficient copolymerization of halogenated olefins and functional monomers, greatly increasing the concentration of the corresponding molecular segments of the functional monomers in the halogenated olefin-functional monomer copolymer, thereby obtaining a halogenated olefin-functional monomer copolymer with unique properties. The above synthesis method has high production efficiency, mild reaction conditions, simple operation process, easy separation and purification, and low cost.

[0085] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a halogenated olefin-functional monomer copolymer, characterized in that: The synthesis method comprises the following steps: Step S1, mixing raw materials including functional monomers, initiators, and solvents to obtain a raw material solution; Step S2, in an inert atmosphere, subjecting the raw materials including the halogenated olefin and the raw material liquid to a polymerization reaction to obtain a polymerization product system; Step S3, post-treating the polymerization product system to obtain a halogenated olefin-functional monomer copolymer; Wherein, the functional monomer comprises an active functional group and a carbon-carbon double bond; and the halogenated olefin is a C2-C4 halogenated olefin.

2. The synthesis method according to claim 1, characterized in that The active functional group is selected from any one or more of a carboxylic acid group, anhydride group and an amide group, and the functional monomer is preferably selected from any one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, acrylamide and methacrylamide.

3. The synthesis method according to claim 1 or 2, characterized in that The halogen in the halogenated olefin is selected from any one or more of chlorine, bromine and iodine, and preferably the halogenated olefin is vinyl chloride.

4. The synthesis method according to any one of claims 1 to 3, characterized in that The mass ratio of the functional monomer, the initiator and the solvent is 1:0.02-0.04:2-50.

5. The synthesis method according to any one of claims 1 to 4, characterized in that The step S3 comprises: Step S31, separating the polymerization product system to obtain halogenated olefins and polymerization products; Step S32, filtering and washing the polymer product in sequence to obtain a filter cake and a filtrate; Step S33, drying the filter cake to obtain the olefin-functional monomer copolymer; and / or, distilling the filtrate to obtain a recovered solvent, preferably returning the recovered solvent to step S1 or step S32 for use as a solvent; And / or, the distillation pressure is 0.1-101 kPa, and the distillation temperature is 40-150° C.; And / or the halogenated olefin-functional monomer copolymer is a chlorinated olefin-maleic anhydride copolymer, and / or the mass content of the molecular chain segment corresponding to maleic anhydride in the chlorinated olefin-maleic anhydride copolymer is 50-65wt% of the chlorinated olefin-maleic anhydride copolymer.

6. The synthesis method according to claim 5, characterized in that The halogenated olefin in the step S31 is pressurized and then recycled to the step S2. The pressure of the halogenated olefin after pressurization is 0.1 to 10 MPa, preferably 3 to 6 MPa.

7. The synthesis method according to any one of claims 1 to 6, characterized in that In the step S1, the initiator is an azo initiator and / or a peroxide initiator, and preferably the initiator is selected from any one or more of bis(4-tert-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, dodecyl peroxide, diisopropyl peroxide and diisopropyl peroxydicarbonate.

8. The synthesis method according to any one of claims 1 to 7, characterized in that In step S1, the solvent is selected from any one or more of an alkyl ester solvent, an alkane solvent, an aromatic compound solvent, and an aromatic compound derivative solvent; wherein the general formula of the alkyl ester solvent is C n H n+2 COOC m H m+2 , wherein n and m are each independently any integer of 1 to 5; preferably, the solvent is selected from any one or more of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, isoamyl phenylacetate, n-hexane, cyclohexane, n-heptane, benzene, ethylbenzene and xylene.

9. The method according to any one of claims 1 to 8, characterized in that In the step S2, the pressure of the polymerization reaction is 0.1 to 10 MPa, preferably 0.5 to 2 MPa, and / or the temperature of the polymerization reaction is 40 to 60° C., and / or the residence time of the polymerization reaction is 0.1 to 12 h.

10. The synthesis method according to any one of claims 1 to 9, characterized in that In the step S2, the reactor used for the polymerization reaction is selected from any one of a polymerization reactor, a tubular reactor, a microchannel reactor, a horizontal reactor, and a tower reactor.

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