CN107216481B - Method for preparing styrene maleic anhydride block copolymer SMA resin - Google Patents
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Abstract
A method for preparing styrene maleic anhydride block copolymer SMA resin is to prepare a degradation solution composed of metal salt and solvent, immerse the crushed unsaturated polyester resin or glass fiber reinforced unsaturated polyester resin composite material into the degradation solution, seal the degradation solution in a reaction kettle for degradation reaction, cool the degradation solution to room temperature, then add a dissolving agent, filter and remove solid residues to obtain a clear solution; and adding a precipitator into the clear solution for precipitation, and filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin. The invention not only solves the environmental problem caused by the waste unsaturated polyester resin material, but also obtains the advantage of high value-added chemicals.
Description
Technical Field
The invention relates to a method for preparing styrene maleic anhydride block copolymer SMA resin, belonging to the field of cyclic utilization and resource utilization of high polymer materials.
Background
Styrene-maleic anhydride block copolymer (SMA) resin is prepared by block copolymerization of styrene monomer and maleic anhydride monomer. In the chemical structure, the maleic anhydride structural unit is hydrolyzed to generate carboxyl, so that the carboxyl on the carbon chain of the SMA resin has hydrophilicity, and the benzene ring has lipophilicity and has the characteristics of high surface activity, low interfacial tension and the like. The low molecular weight SMA resin can be used as a dispersant such as a surfactant. The SMA resin with high molecular weight can be used for engineering plastics, and because carboxyl can be well combined with glass fiber, the SMA resin can be commonly used for preparing glass fiber SMA resin composite materials, manufacturing automobile instrument panels and the like.
The hydrophilic section and the hydrophobic section of the SMA resin have certain orientation on the surface or interface and have good adsorption, so that the surface tension and the interface tension can be reduced. The SMA-based polymer has a hydrophilic maleic anhydride ring and a lipophilic benzene ring, has very high surface activity, and can be even compared with a low-molecular surfactant. The content of maleic anhydride in the SMA resin directly determines the quality of water solubility. When the maleic anhydride content is high, the water solubility is good, whereas the water solubility is not good. The SMA-based polymer belongs to an anionic surfactant, is soluble in water and alkali and has better emulsion stability. The low molecular weight SMA resin is a water-soluble high molecular surfactant and has an anionic surface activity function. The SMA resin has high glass transition temperature and softening point, alkali solubility, high gloss, a block structure, surfactants with different molecular weights, a dispersing agent, compatibility with various emulsions, and excellent compatibility with conventional surfactants. The water solubility is strong to the water resistance is available for a series of choices. The main application markets of the SMA resin comprise heat-resistant varnish or varnish, gold stamping film colored layer coating, heat-resistant emulsion polymer, alkali-resistant and water-resistant cationic emulsion polymer, water-resistant ultrafine particle wax emulsion, rosin emulsion, water-resistant floor polishing wax emulsion and the like, and the adhesive force to a low-surface-energy material can be improved.
The SMA resin has nonpolar aromatic group and polar acid anhydride group in the molecular structure, so the SMA resin can be used with various polar or nonpolar materials, glass fiber, mineral substances and fillers (CaCO)3) The like polar material has good compatibility, so that the like polar material can be widely applied to modification of the material, the mechanical property of the material is greatly improved, and the phenomena of stress cracking, delamination and the like are improved. The high-activity maleic anhydride group in the SMA chain segment can react with the hydroxyl group of the glass fiber, the hydroxyl carboxyl group of the polyester, the amino group of the nylon and other groups to form a firmly combined covalent bond, so that the interface combination of the material is improved, and the thickness and the adhesive force of a phase interface are improved, thereby improving the mechanical properties of the material, such as stretching, bending, toughness and the like. SMA-700 (white and transparent) has high maleic anhydride content (about 18%), and is especially suitable for various fiber reinforced plastics and plastic alloys. The SMA-800 resin is a ternary random copolymer formed by copolymerizing three monomers, namely styrene, acrylonitrile and maleic anhydride. The SMA-800 has better chemical resistance due to the addition of acrylonitrile, and is particularly suitable for reinforcing SAN, ASA, PA and PMMA, filling, alloy and alloy reinforcing. The SMA resin is mainly used as a compatilizer of a high-molecular alloy, a heat-resistant modifier of a polymer and a coupling agent reinforced by glass fibers of the heat-resistant modifier. Rigidity and polarity in its molecular structureThe functional group has the characteristics of higher heat resistance, good dimensional stability, excellent molding processability and better chemical corrosion resistance. The modified polyolefin resin has increasingly expanded application in the fields of building materials, automotive upholsteries, instrument panels, mechanical housings, electronic and electric parts, packaging materials and the like, has excellent comprehensive performance and outstanding molecular polarity and reactivity, is used as a macromolecular compatilizer and a plastic alloy modified component, and has important application in the fine and special macromolecular resin market. In automotive interior structural applications, it is desirable to increase the strength and stiffness of styrene-maleic anhydride by fiberglass reinforcement. Chemical coupling between the surface of the glass fiber treated by the chemical method and the highly polar maleic anhydride component is easy to perform and durable. The adhesiveness can keep the strength, modulus and toughness unchanged for a long time. In order to meet the requirements of many fields of application, the influence of glass fiber reinforcement on the mechanical properties of styrene-maleic anhydride copolymer resins is very important. Currently, most reinforcing glass fibers are present at 20%, which may range from 5 to 40%.
At present, the main methods for preparing SMA resins are: traditional free radical copolymerization, living free radical copolymerization, radiation and photoinitiated copolymerization, etc. In the traditional free radical copolymerization, azo compounds, peroxides and the like are often used as initiators, and the copolymerization can be carried out by a solution method, a bulk method, an emulsion method, a dispersion method and a suspension method. The alternate copolymerization of SMA resins is mostly carried out by solution copolymerization. The solution copolymerization liquid can be divided into homogeneous phase and heterogeneous phase. The field of SMA resin synthesis, the following patents have been granted: a process for copolymerizing styrene with maleic anhydride (ZL 200810101948.0) features that the random copolymerization of styrene and maleic anhydride is carried out by mixing organic acid alkyl ester or ketone with alkane in solution and organic peroxide or azo compound as trigger. In a patent related to the Chinese petrochemical group, in the preparation method (ZL99119956.1) of the styrene-maleic anhydride random copolymer, the content of maleic anhydride in the prepared SMA resin can be more than 16%. A low molecular weight styrene-maleic anhydride copolymer with a molecular weight of 4000-13000 and a molecular weight distribution of 1.5-2.2 can be obtained by a method for synthesizing a low molecular weight styrene-maleic anhydride alternating copolymer (patent No. ZL201210004482.9) from Shanghai Feiki photoelectric materials Co., Ltd. The above methods are all used for preparing the SMA resin by random copolymerization of monomer styrene and maleic anhydride, and related patents and literature reports for preparing the SMA resin by degrading unsaturated polyester resin are not seen.
Disclosure of Invention
The invention aims to provide a method for preparing styrene maleic anhydride block copolymer SMA resin by degrading unsaturated polyester resin.
As known from the chemical structure of general unsaturated polyester resin (PMPS), unsaturated double bonds of copolyester of phthalic anhydride, maleic anhydride and 1, 2-propylene glycol form thermosetting unsaturated polyester resin with three-dimensional structure by using styrene as a crosslinking agent, and the chemical structure of the thermosetting unsaturated polyester resin contains SMA structural units. According to the invention, Lewis acid metal ion coordination catalysis is adopted to selectively activate only functional group ester bonds in SMA resin, so that the carbon skeleton structure of unsaturated polyester resin is kept complete, the PMPS of unsaturated polyester resin is directionally degraded, the degradation product comprises SMA resin and phthalic anhydride, and the SMA resin and the phthalic anhydride are obtained through separation and purification.
The general unsaturated polyester resin (PMPS) comprises phthalic anhydride (phthalic anhydride), maleic anhydride (maleic anhydride) and 1, 2-propylene glycol (1, 2-propylene), and styrene (styrene) as a crosslinking agent. The structural formula is as follows:
the structural formula of the styrene maleic anhydride block copolymer SMA resin is as follows:
wherein x is 1-8, y is 1, and n is 8-12.
The specific technical scheme of the invention is as follows:
a method of preparing a styrene maleic anhydride block copolymer SMA resin comprising the steps of:
(1) preparing degradation liquid consisting of 1-80% of metal salt and solvent by mass percent, and preparing the degradation liquid according to the following formula: the mass ratio of the degradation liquid is 1: 1-100, the crushed unsaturated polyester resin (PMPS) or glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 100 ℃ and 350 ℃, and the reaction time is 10 min-72 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent, wherein the mass ratio of the degradation product mixture to the dissolving agent is 1: 1-10, filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding a precipitating agent into the clear solution, wherein the mass ratio of the adding amount of the precipitating agent to the dissolving agent is 1-5: 1, precipitating and separating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
When the metal salt: when the mass fraction of the solvent is lower than 1%, the degradation effect is obviously reduced, and when the mass fraction of the solvent is higher than 80%, all the metal salt solvent liquid is in a non-solution state and cannot degrade PMPS. When PMPS: the mass ratio of the degradation liquid is less than 1: PMPS could not be completely immersed in degradation liquid at 1, but was higher than 1: at 100 hours, the amount of PMPS degradation products is too small relative to the amount of degradation liquid, which is not beneficial to later separation and purification. When the reaction temperature is lower than 100 ℃, the degradation reaction does not substantially occur, and when it is higher than 350 ℃, the degradation product is dark in color and complicated in composition. When the mass ratio of the degradation product mixture to the dissolving agent is 1: 1-10, the degradation product can be completely dissolved, and the concentration of the product in the solution is not too low. When the mass ratio of the added amount of the precipitating agent to the mass ratio of the dissolving agent is 1-5: 1, the styrene maleic anhydride block copolymer SMA resin can be completely precipitated and separated out, and the excessive precipitant is not generated.
The cation of the metal salt comprises high valence metal ions such as iron ions, cobalt ions, nickel ions, copper ions, zinc ions or aluminum ions, and the anion comprises chloride ions, sulfate ions, nitrate radicals or acetate radicals, and the like, and the soluble metal salt is formed by the two. Specifically, the metal complex comprises ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, aluminum chloride, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, aluminum sulfate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, aluminum nitrate, cobalt acetate, nickel acetate, copper acetate, zinc acetate or aluminum acetate.
The degradation liquid solvent comprises formic acid, acetic acid, propionic acid, butyric acid, methanol, ethanol, propanol, butanol or water and the like. The solvents selected were organic acids, alcohols and water, which were available for acidolysis, alcoholysis and hydrolysis reactions with PMPS.
The unsaturated polyester resin is a general-purpose unsaturated polyester resin (PMPS).
The dissolving agent used for dissolving the degradation products comprises acetone, toluene, tetrahydrofuran, dimethyl sulfoxide or N, N-dimethylformamide and the like. The solvent is selected to achieve separation from the catalyst, fiber and solid residue by dissolving the degradation products.
The precipitant comprises diethyl ether, ethyl acetate, chloroform or acetonitrile, etc. The precipitant is selected to separate out the SMA resin by adjusting the polarity of the dissolvent.
Compared with the prior art, the invention has the following advantages:
(1) the SMA resin is prepared by degrading the waste unsaturated polyester resin, and the chemical structure of the SMA resin is more regular.
(2) Can solve the environmental problem caused by the waste unsaturated polyester resin and obtain high value-added chemicals.
Drawings
FIG. 1 is a solid nuclear magnetic carbon spectrum of the SMA resin obtained by the present invention.
Detailed Description
The unsaturated polyester resins referred to in the following examples are all general-purpose unsaturated polyester resin PMPS.
Example 1
(1) Preparing ZnCl with the mass fraction of 80 percent2And a degradation liquid consisting of water, wherein the degradation liquid is prepared from unsaturated polyester resin (PMPS): the mass ratio of the degradation liquid is 1:100, and the crushed unsaturated polymer is polymerizedEster resin (PMPS) (granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 250 ℃, and the reaction time is 12 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding tetrahydrofuran serving as a dissolving agent, wherein the mass ratio of the degradation product mixture to the added tetrahydrofuran is 1: 2. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding a precipitator ethyl acetate into the clear solution, wherein the mass ratio of the added ethyl acetate to a dissolving agent tetrahydrofuran is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 2
(1) Preparing FeCl with the mass fraction of 10%3And the degradation liquid formed by the degradation liquid and ethanol is prepared by mixing the following components in percentage by weight: the mass ratio of the degradation liquid is 1:50, the glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 160 ℃, and the reaction time is 50 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent acetone, wherein the mass ratio of the degradation product mixture to the added acetone is 1: 3. Filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding a precipitant acetonitrile into the clear solution, wherein the mass ratio of the acetonitrile addition to a dissolving agent acetone is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 3
(1) Preparing 20 mass percent of AlCl3And a degradation liquid consisting of water, wherein the degradation liquid is prepared from unsaturated polyester resin (PMPS): the mass ratio of the degradation solution is 1:75, the crushed unsaturated polyester resin (PMPS) (with the granularity of 1-10 mm) is immersed in the degradation solution and sealed in a reaction kettle, the degradation reaction temperature is 300 ℃, and the reaction is carried outThe reaction time is 6 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent dimethyl sulfoxide, wherein the mass ratio of the degradation product mixture to the dimethyl sulfoxide is 1: 1. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding chloroform as a precipitant into the clear solution, wherein the mass ratio of the added chloroform to the dimethyl sulfoxide is 5: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 4
(1) Preparing FeCl with the mass fraction of 1%3And formic acid, according to the proportion of unsaturated polyester resin (PMPS): the mass ratio of the degradation liquid is 1:1, the crushed unsaturated polyester resin (PMPS) (with the granularity of 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 350 ℃, and the reaction time is 72 hours;
(2) after the degradation reaction is finished, cooling to room temperature, adding a dissolving agent N, N-dimethylformamide, wherein the mass ratio of the degradation product mixture to the added N, N-dimethylformamide is 1: 10. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding a precipitator diethyl ether into the clear solution, wherein the mass ratio of the diethyl ether to the dissolving agent N, N-dimethylformamide is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 5
(1) Preparing 15 percent of Fe by mass fraction2(SO4)3And the degradation liquid is composed of the following components in percentage by weight: the mass ratio of the degradation liquid is 1:20, the crushed glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 200 ℃, and the reaction time is 10 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding tetrahydrofuran serving as a dissolving agent, wherein the mass ratio of the degradation product mixture to the added tetrahydrofuran is 1: 8. Filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding a precipitator ethyl acetate into the clear solution, wherein the mass ratio of the added ethyl acetate to a dissolving agent tetrahydrofuran is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 6
(1) Preparing 20 percent of Al (CH) by mass fraction3COO)3The degradation liquid formed by the degradation liquid and water is prepared by the following steps of: the mass ratio of the degradation liquid is 1:80, the crushed glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 350 ℃, and the reaction time is 72 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding tetrahydrofuran serving as a dissolving agent, wherein the mass ratio of the degradation product mixture to the added tetrahydrofuran is 1: 2. Filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding chloroform as a precipitating agent into the clear solution, wherein the mass ratio of the added chloroform to tetrahydrofuran as a dissolving agent is 2: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 7
(1) Preparing ZnCl with the mass fraction of 70 percent2And a degradation liquid consisting of water, wherein the degradation liquid is prepared from unsaturated polyester resin (PMPS): the mass ratio of the degradation liquid is 1:80, the crushed unsaturated polyester resin (PMPS) (with the granularity of 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 180 ℃, and the reaction time is 15 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent dimethyl sulfoxide, wherein the mass ratio of the degradation product mixture to the dimethyl sulfoxide is 1: 1. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding chloroform as a precipitator into the clear solution, wherein the mass ratio of the chloroform to dimethyl sulfoxide as a dissolving agent is 4: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 8
(1) Preparing 20 percent of Fe (NO) by mass fraction3)3And formic acid, according to the proportion of unsaturated polyester resin (PMPS): soaking pulverized unsaturated polyester resin (PMPS) (with particle size of 1-10 mm) in the degradation solution at a degradation reaction temperature of 350 deg.C for 10min, and sealing in a reaction kettle;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding tetrahydrofuran serving as a dissolving agent, wherein the mass ratio of the degradation product mixture to the added tetrahydrofuran is 1: 2. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding a precipitator diethyl ether into the clear solution, wherein the mass ratio of the diethyl ether to the solvent tetrahydrofuran is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 9
(1) Preparing CoCl with the mass fraction of 15%2And the degradation liquid formed by the degradation liquid and ethanol is prepared by mixing the following components in percentage by weight: the mass ratio of the degradation liquid is 1:80, the crushed glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 180 ℃, and the reaction time is 60 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent acetone, wherein the mass ratio of the degradation product mixture to the added acetone is 1: 1. Filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding a precipitant acetonitrile into the clear solution, wherein the mass ratio of the acetonitrile addition to a dissolving agent acetone is 3: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 10
(1) Preparing 20 mass percent of Ni (NO)3) And propionic acid, according to the ratio of unsaturated polyester resin (PMPS): the mass ratio of the degradation liquid is 1:100, the crushed unsaturated polyester resin (PMPS) (with the granularity of 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 250 ℃, and the reaction time is 24 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding tetrahydrofuran serving as a dissolving agent, wherein the mass ratio of the degradation product mixture to the added tetrahydrofuran is 1: 6. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding chloroform as a precipitating agent into the clear solution, wherein the mass ratio of the added chloroform to tetrahydrofuran as a dissolving agent is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 11
(1) Preparing ZnCl with the mass fraction of 60 percent2And a degradation liquid consisting of water, wherein the degradation liquid is prepared from unsaturated polyester resin (PMPS): the mass ratio of the degradation liquid is 1:50, the crushed unsaturated polyester resin (PMPS) (with the granularity of 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 200 ℃, and the reaction time is 36 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent dimethyl sulfoxide, wherein the mass ratio of the degradation product mixture to the dimethyl sulfoxide is 1: 1. Filtering to remove solid residue (mainly catalyst) to obtain clear solution;
(3) adding a precipitator of ethyl acetate into the clear solution, wherein the mass ratio of the ethyl acetate to a dissolving agent of dimethyl sulfoxide is 5: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Example 12
(1) Preparing CuCl with the mass fraction of 15%2And the degradation liquid formed by the degradation liquid and acetic acid is prepared by the following steps of: the mass ratio of the degradation liquid is 1:80, the crushed glass fiber reinforced unsaturated polyester resin composite material (the granularity is 1-10 mm) is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 200 ℃, and the reaction time is 12 hours;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent acetone, wherein the mass ratio of the degradation product mixture to the added acetone is 1: 5. Filtering to remove solid residues (mainly catalyst and fiber) to obtain a clear solution;
(3) adding a precipitator of ethyl acetate into the clear solution, wherein the mass ratio of the ethyl acetate to a dissolving agent of acetone is 1: 1. Precipitating the styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling the solvent.
Claims (5)
1. A method for preparing styrene maleic anhydride block copolymer SMA resin is characterized by comprising the following steps:
(1) preparing degradation liquid consisting of 1-80% of metal salt and solvent by mass percent, and preparing the unsaturated polyester resin or glass fiber reinforced unsaturated polyester resin composite material according to the following steps: the mass ratio of the degradation liquid is 1: 1-100, the crushed unsaturated polyester resin or glass fiber reinforced unsaturated polyester resin composite material is immersed in the degradation liquid and sealed in a reaction kettle, the degradation reaction temperature is 100 ℃ and 350 ℃, and the reaction time is 10 min-72 h;
(2) after the degradation reaction is finished, cooling to room temperature, and then adding a dissolving agent, wherein the mass ratio of the degradation product mixture to the dissolving agent is 1: 1-10, filtering to remove solid residues to obtain a clear solution;
(3) adding a precipitating agent into the clear solution, wherein the mass ratio of the adding amount of the precipitating agent to the dissolving agent is 1-5: 1, precipitating and separating out styrene maleic anhydride block copolymer SMA resin, filtering, washing and drying to obtain the styrene maleic anhydride block copolymer SMA resin, and distilling, separating and recycling a solvent;
the positive ions of the metal salt are iron ions, cobalt ions, nickel ions, copper ions, zinc ions or aluminum ions, and the negative ions are chloride ions, sulfate ions, nitrate radicals or acetate radicals, and the positive ions and the negative ions are soluble metal salts formed by the chloride ions, the sulfate ions, the nitrate radicals or the acetate radicals; the soluble metal salt is selected from ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, aluminum chloride, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, aluminum sulfate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, aluminum nitrate, cobalt acetate, nickel acetate, copper acetate, zinc acetate or aluminum acetate;
the unsaturated polyester resin is general unsaturated polyester resin; the general unsaturated polyester resin has a structural formula as follows:
2. The method for preparing styrene maleic anhydride block copolymer SMA resin according to claim 1, wherein the degradation liquid solvent is formic acid, acetic acid, propionic acid, butyric acid, methanol, ethanol, propanol, butanol or water.
3. The method for preparing styrene maleic anhydride block copolymer SMA resin according to claim 1, wherein the particle size of the unsaturated polyester resin or glass fiber reinforced unsaturated polyester resin composite is 1-10 mm.
4. The method for preparing styrene maleic anhydride block copolymer SMA resin according to claim 1, wherein the dissolution agent for dissolving the degradation products is acetone, toluene, tetrahydrofuran, dimethylsulfoxide or N, N-dimethylformamide.
5. The method for preparing styrene maleic anhydride block copolymer SMA resin according to claim 1, wherein the precipitating agent is diethyl ether, ethyl acetate, chloroform or acetonitrile.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167539A (en) * | 1975-06-26 | 1979-09-11 | Gulf Oil Corporation | Styrene-grafted polyanhydride copolymer |
| CN102924641A (en) * | 2012-11-07 | 2013-02-13 | 复旦大学 | Nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
| CN106519097A (en) * | 2016-10-28 | 2017-03-22 | 中国科学院新疆理化技术研究所 | Synthesis method for castoryl maleate-styrene copolymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167539A (en) * | 1975-06-26 | 1979-09-11 | Gulf Oil Corporation | Styrene-grafted polyanhydride copolymer |
| CN102924641A (en) * | 2012-11-07 | 2013-02-13 | 复旦大学 | Nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
| CN106519097A (en) * | 2016-10-28 | 2017-03-22 | 中国科学院新疆理化技术研究所 | Synthesis method for castoryl maleate-styrene copolymer |
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