CN115417938A - Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin - Google Patents
Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin Download PDFInfo
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 143
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 143
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 title claims abstract description 81
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000005086 pumping Methods 0.000 claims abstract description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 19
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 19
- 239000011976 maleic acid Substances 0.000 claims abstract description 19
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 64
- 239000002002 slurry Substances 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 28
- 230000035484 reaction time Effects 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
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- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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Abstract
The invention belongs to the technical field of high molecular materials, and relates to a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin, which comprises the following steps: respectively preparing mixed liquor from rosin, maleic acid and a catalyst, and respectively pumping the mixed liquor into a coil reactor to react to obtain maleated rosin; respectively preparing mixed liquid of maleated rosin, hydroxyethyl methacrylate and a catalyst and pumping the mixed liquid into a coil reactor; the maleic rosin hydroxyethyl methacrylate and the mixed solution with the initiator are pumped into a coil type microwave reactor to prepare the maleic rosin hydroxyethyl methacrylate polymer. The method adopts continuous coil pipe reaction, has mild reaction conditions, high reaction rate and high conversion rate, does not need to add polymerization inhibitor during esterification, and has simple and convenient separation method and easy operation; good subsequent homopolymerization effect and good thermal stability of the polymer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin.
Background
Rosin is a renewable resource which is rich and cheap, and how to replace non-renewable petroleum with rosin is an increasingly important research topic, but the use of rosin is limited by the characteristics of sensitivity to light, heat and sample, easy oxidation, high acid value, poor thermal stability and the like; in the prior art, rosin is commonly used to prepare a rosin polymer for use.
The Chinese patent application 201911037148.1 discloses a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin, wherein in the synthesis of the maleic rosin, the synthesis of the maleic rosin hydroxyethyl methacrylate and the synthesis of the maleic rosin hydroxyethyl methacrylate polymer, a pure substance reaction is adopted, the reaction is an intermittent reaction, the system concentration is high, the local reaction is violent, the overall required reaction time is long, the reaction temperature is high, and byproducts can be easily generated in the reaction system due to overlong time, overhigh temperature and high concentration; when a polymer is formed, the homopolymerization effect is poor, and the thermal stability of the obtained polymer is affected.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects, the invention provides a method for preparing a maleic rosin hydroxyethyl methacrylate polymer from rosin, which is a continuous coil reaction, has mild reaction conditions, high reaction rate and high conversion rate, does not need to add a polymerization inhibitor during esterification, and has simple and easy separation method; good subsequent homopolymerization effect and good thermal stability of the polymer.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, comprising the steps of:
step 1, continuous preparation of maleated rosin: dissolving rosin in an organic solvent A to form a mixed solution A, and dissolving maleic acid and a catalyst in the organic solvent A to form a mixed solution B; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, wherein the reaction temperature is 125-150 ℃, the reaction time is 2-10 min, the pressure in the coil reactor is 0.1-0.4 MPa, adding the collected reaction liquor A into a water bath after the reaction, collecting and quenching the reaction liquor, and concentrating and purifying the quenched reaction liquor to obtain maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in an organic solvent B to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst into the organic solvent B to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, wherein the reaction temperature is 60-80 ℃, the reaction time is 1-5 min, the pressure in the coil reactor is 0.1-0.2 MPa, the reaction solution B after the reaction is added into ice water for quenching, and the maleic rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving the purified maleic rosin hydroxyethyl methacrylate in an organic solvent C to form a mixed solution E, dissolving an initiator in the organic solvent C to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, reacting at the temperature of 50-80 ℃, the microwave frequency of 1500 MHz-2500 MHz for 5-10 min, concentrating the collected reaction solution C after reaction, adding the concentrated reaction solution C into petroleum ether to precipitate, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.
Further, the organic solvent A is dichloromethane or toluene; the organic solvent B is toluene; the organic solvent C is toluene or butyl acetate.
Further, the catalyst in the step 1 is one or more of aluminum trichloride, boron trifluoride and lead iodide.
Furthermore, the molar ratio of the rosin in the mixed solution A to the maleic acid in the mixed solution B is 1:1; the adding amount of the catalyst in the step 1 is 0.1-0.2% of the molar amount of the maleic acid.
Further, the catalyst in the step 2 is one of zinc oxide and aluminum trichloride.
Furthermore, the molar ratio of the maleated rosin in the mixed liquid C to the hydroxyethyl methacrylate in the slurry D is 1:2; the dosage of the catalyst in the step 2 is 1.5-5% of the molar weight of the maleated rosin.
Further, the initiator of the step 3 is a mixture of azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1.
Furthermore, the amount of the initiator in the mixed solution F is 5 to 10 percent of the molar weight of the maleated rosin hydroxyethyl methacrylate in the mixed solution E.
Further, the pipe diameters of the coil pipe reactor and the coil pipe type microwave reactor are 0.2cm-5cm.
Further, the organic solvent A, the organic solvent B and the organic solvent C are all recycled.
The beneficial effects of the invention are:
1. by adopting the technical scheme, the intermediate maleated rosin, maleated rosin hydroxyethyl methacrylate and the target maleated rosin hydroxyethyl methacrylate polymer are all carried out in a coil reactor or a coil microwave reactor, continuous reaction is adopted, the collision area between raw material molecules is large, the chemical activation energy requirement can be quickly met under the condition of less raw materials, the reaction rate is high, the conversion rate is high, the whole reaction condition is mild, the reaction efficiency is high, and the reaction time is short.
2. Compared with an intermittent reaction kettle, the raw material has short retention time in a reaction system, the probability of side reaction is reduced, a polymerization inhibitor is not required to be added into the system during the preparation of the maleic rosin hydroxyethyl methacrylate, the introduction of impurities is reduced, and the separation method is simple and easy to operate.
3. The target product maleated rosin hydroxyethyl methacrylate polymer is prepared by adopting an initiator, the polymerization process is controllable, the homopolymerization effect is good, and the thermal stability of the polymer is good.
4. The organic solvent in the process is recycled, and the production cost is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, comprising the steps of:
step 1, continuous preparation of maleated rosin: dissolving rosin in dichloromethane to form a mixed solution A, and dissolving maleic acid and a catalyst aluminum trichloride in dichloromethane to form a mixed solution B; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, calculating the volume flow rate of the mixed liquor A and the mixed liquor B according to the pipe diameter of the coil reactor and the volumes of the mixed liquor A and the mixed liquor B, ensuring that the molar ratio of rosin in the mixed liquor A to maleic acid in the mixed liquor B is 1:1, and the adding amount of the catalyst in the step 1 is 0.1 percent of the molar amount of the maleic acid; the reaction temperature is 125 ℃, the reaction time is 10min, the pressure in the coil reactor is 0.1MPa, the collected reaction liquid A is added into a water bath after the reaction to be collected and quenched, and the solvent is dried, concentrated and purified to obtain the maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in toluene to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst aluminum trichloride into the toluene to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, and calculating the volume flow rate of the mixed solution C and the slurry D according to the pipe diameter of the coil reactor and the volume of the mixed solution C and the slurry D to ensure that the molar ratio of the maleated rosin in the mixed solution C to the hydroxyethyl methacrylate in the slurry D is 1:2; in the step 2, the using amount of the catalyst is 1.5 percent of the molar weight of the maleated rosin, the reaction temperature is 80 ℃, the pressure in the coil reactor is 0.1MPa, the reaction time is 5min, the reaction liquid B after the reaction is added into ice water for quenching, and the maleated rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving purified maleic rosin hydroxyethyl methacrylate in toluene to form a mixed solution E, dissolving an initiator prepared by mixing azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1 in the toluene to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, calculating the volume flow rates of the mixed solution E and the slurry F according to the pipe diameter of the coil type microwave reactor and the volumes of the mixed solution E and the slurry F, ensuring that the using amount of the initiator in the mixed solution F is 5% of the molar amount of the maleic rosin hydroxyethyl methacrylate in the mixed solution E, the reaction temperature is 50 ℃, the microwave frequency is 1500 MHz, the reaction time is 10min, concentrating the collected reaction solution C after reaction, adding petroleum ether to precipitate, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.
Example 2
A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin comprises the following steps:
step 1, continuous preparation of maleated rosin: dissolving rosin in toluene to form a mixed solution A, and dissolving maleic acid and a catalyst boron trifluoride in toluene to form a mixed solution B; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, calculating the volume flow rate of the mixed liquor A and the mixed liquor B according to the pipe diameter of the coil reactor and the volumes of the mixed liquor A and the mixed liquor B, ensuring that the molar ratio of rosin in the mixed liquor A to maleic acid in the mixed liquor B is 1:1, and the adding amount of the catalyst in the step 1 is 0.2% of the molar amount of the maleic acid; the reaction temperature is 150 ℃, the pressure in the coil reactor is 0.4 MPa, the reaction time is 3min, the collected reaction liquid A is added into a water bath after the reaction, the quenching is collected, and the reaction liquid after the quenching is concentrated and purified to obtain the maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in toluene to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst zinc oxide into the toluene to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, and calculating the volume flow rate of the mixed solution C and the slurry D according to the pipe diameter of the coil reactor and the volume of the mixed solution C and the slurry D to ensure that the molar ratio of the maleated rosin in the mixed solution C to the hydroxyethyl methacrylate in the slurry D is 1:2; in the step 2, the dosage of the catalyst is 5% of the molar weight of the maleated rosin, the reaction temperature is 80 ℃, the pressure in the coil reactor is 0.2 MPa, the reaction time is 1min, the reaction solution B after the reaction is added into ice water for quenching, and the maleated rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving purified maleated rosin hydroxyethyl methacrylate in toluene to form a mixed solution E, dissolving an initiator prepared by mixing azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1 in toluene to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, calculating the volume flow rates of the mixed solution E and the slurry F according to the pipe diameter of the coil type microwave reactor and the volumes of the mixed solution E and the slurry F, ensuring that the using amount of the initiator in the mixed solution F is 5% of the molar amount of the maleated rosin hydroxyethyl methacrylate in the mixed solution E, the reaction temperature is 80 ℃, the microwave frequency is 2000MHz, the reaction time is 8min, concentrating the collected reaction solution C after reaction, adding petroleum ether for precipitation, and drying to obtain the maleated rosin hydroxyethyl methacrylate polymer.
Example 3
A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin comprises the following steps:
step 1, continuous preparation of maleated rosin: dissolving rosin in dichloromethane to form a mixed solution A, and dissolving maleic acid and a catalyst lead iodide in dichloromethane to form a mixed solution B; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, calculating the volume flow rate of the mixed liquor A and the mixed liquor B according to the pipe diameter of the coil reactor and the volumes of the mixed liquor A and the mixed liquor B, ensuring that the molar ratio of rosin in the mixed liquor A to maleic acid in the mixed liquor B is 1:1, and the adding amount of the catalyst in the step 1 is 0.15 percent of the molar amount of the maleic acid; the reaction temperature is 145 ℃, the pressure in the coil reactor is 0.2 MPa, the reaction time is 4min, the collected reaction liquid A is added into a water bath after the reaction, the quenching is collected, and the reaction liquid after the quenching is concentrated and purified to obtain the maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in toluene to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst zinc oxide into the toluene to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, and calculating the volume flow rate of the mixed solution C and the slurry D according to the pipe diameter of the coil reactor and the volume of the mixed solution C and the slurry D to ensure that the molar ratio of the maleated rosin in the mixed solution C to the hydroxyethyl methacrylate in the slurry D is 1:2; in the step 2, the dosage of the catalyst is 2.5 percent of the molar weight of the maleated rosin, the reaction temperature is 70 ℃, the reaction time is 3min, the pressure in the coil reactor is 0.15 MPa, the reaction liquid B after the reaction is added into ice water for quenching, and the maleated rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving purified maleic rosin hydroxyethyl methacrylate in butyl acetate to form a mixed solution E, dissolving an initiator prepared by mixing azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1 in butyl acetate to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, calculating the volume flow rates of the mixed solution E and the slurry F according to the pipe diameter of the coil type microwave reactor and the volumes of the mixed solution E and the slurry F, ensuring that the dosage of the initiator in the mixed solution F is 10% of the molar quantity of the maleic rosin hydroxyethyl methacrylate in the mixed solution E, the reaction temperature is 80 ℃, the microwave frequency is 2500MHz, the reaction time is 5min, concentrating the collected reaction solution C after reaction, adding the concentrated reaction solution C into petroleum ether for precipitation, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.
Example 4
A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin comprises the following steps:
step 1, continuous preparation of maleated rosin: dissolving rosin in toluene to form a mixed solution A, and dissolving maleic acid, aluminum trichloride, boron trifluoride and lead iodide in toluene according to a molar ratio of 1; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, calculating the volume flow rate of the mixed liquor A and the mixed liquor B according to the pipe diameter of the coil reactor and the volumes of the mixed liquor A and the mixed liquor B, ensuring that the molar ratio of rosin in the mixed liquor A to maleic acid in the mixed liquor B is 1:1, and the adding amount of the catalyst in the step 1 is 0.2% of the molar amount of the maleic acid; the reaction temperature is-150 ℃, the reaction time is 2min, the pressure in the coil reactor is 0.1MPa-0.4 MPa, the collected reaction liquid A is added into a water bath after the reaction, the mixture is collected and quenched, and the quenched reaction liquid is concentrated and purified to obtain the maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in toluene to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst aluminum trichloride into the toluene to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, and calculating the volume flow rate of the mixed solution C and the slurry D according to the pipe diameter of the coil reactor and the volume of the mixed solution C and the slurry D to ensure that the molar ratio of the maleated rosin in the mixed solution C to the hydroxyethyl methacrylate in the slurry D is 1:2; in the step 2, the dosage of the catalyst is 4% of the molar weight of the maleated rosin, the reaction temperature is 80 ℃, the pressure in the coil reactor is 0.2 MPa, the reaction time is 2min, the reaction solution B after the reaction is added into ice water for quenching, and the maleated rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving purified maleic rosin hydroxyethyl methacrylate in butyl acetate to form a mixed solution E, dissolving an initiator prepared by mixing azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1 in butyl acetate to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, calculating the volume flow rates of the mixed solution E and the slurry F according to the pipe diameter of the coil type microwave reactor and the volumes of the mixed solution E and the slurry F, ensuring that the dosage of the initiator in the mixed solution F is 8% of the molar quantity of the maleic rosin hydroxyethyl methacrylate in the mixed solution E, the reaction temperature is 65 ℃, the microwave frequency is 2400MHz, the reaction time is 6min, concentrating the collected reaction solution C after reaction, adding the concentrated reaction solution C into petroleum ether for precipitation, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.
The pipe diameters of the coil reactor and the coil microwave reactor in the above embodiments are 0.2cm-5cm, and are determined according to the physical properties of the prepared mixed solution A, mixed solution B, mixed solution C, slurry D, mixed solution E and mixed solution F.
In order to save resources and meet the requirement of green chemistry, the organic solvent A, the organic solvent B and the organic solvent C are all recycled.
By adopting the technical scheme, the intermediate maleated rosin, maleated rosin hydroxyethyl methacrylate and the target maleated rosin hydroxyethyl methacrylate polymer are all carried out in a coil reactor or a coil microwave reactor, continuous reaction is adopted, the collision area between molecules of raw materials is large, the requirement of chemical activation energy can be quickly met under the condition of less raw materials, the reaction rate is high, the conversion rate is high, the whole reaction condition is mild, the reaction efficiency is high, and the reaction time is short; because the raw materials have short retention time in the reaction system, the probability of side reaction is reduced, a polymerization inhibitor is not required to be added into the system during the preparation of the maleic rosin hydroxyethyl methacrylate, the introduction of impurities is reduced, and the separation method is simple and convenient and is easy to operate; the target product maleated rosin hydroxyethyl methacrylate polymer is prepared by adopting an initiator, the polymerization process is controllable, the homopolymerization effect is good, and the thermal stability of the polymer is good.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined by the scope of the claims.
Claims (10)
1. A method for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin is characterized by comprising the following steps:
step 1, continuous preparation of maleated rosin: dissolving rosin in an organic solvent A to form a mixed solution A, and dissolving maleic acid and a catalyst in the organic solvent A to form a mixed solution B; respectively pumping the mixed liquor A and the mixed liquor B into a coil reactor through a pump A and a pump B, respectively, wherein the reaction temperature is 125-150 ℃, the reaction time is 2-10 min, the pressure in the coil reactor is 0.1-0.4 MPa, adding the collected reaction liquor A into a water bath after the reaction, collecting and quenching the reaction liquor, and concentrating and purifying the quenched reaction liquor to obtain maleated rosin;
step 2, continuously preparing maleated rosin hydroxyethyl methacrylate: dissolving purified maleated rosin in an organic solvent B to form a mixed solution C, and adding hydroxyethyl methacrylate and a catalyst into the organic solvent B to form a slurry D; respectively pumping the mixed solution C and the slurry D into a coil reactor through a pump C and a pump D, wherein the reaction temperature is 60-80 ℃, the reaction time is 1-5 min, the pressure in the coil reactor is 0.1-0.2 MPa, the reaction solution B after the reaction is added into ice water for quenching, and the maleic rosin hydroxyethyl methacrylate is obtained after liquid separation, concentration and drying;
step 3, continuously homopolymerizing the maleic rosin hydroxyethyl methacrylate polymer: dissolving the purified maleic rosin hydroxyethyl methacrylate in an organic solvent C to form a mixed solution E, dissolving an initiator in the organic solvent C to form a mixed solution F, respectively pumping the mixed solution E and the mixed solution F into a coil type microwave reactor through a pump E and a pump F, respectively, reacting at the temperature of 50-80 ℃, the microwave frequency of 1500 MHz-2500 MHz for 5-10 min, concentrating the collected reaction solution C after reaction, adding the concentrated reaction solution C into petroleum ether to precipitate, and drying to obtain the maleic rosin hydroxyethyl methacrylate polymer.
2. A process according to claim 1 for the preparation of maleated rosin methacrylic acid from rosin: a process for preparing hydroxyethyl acetate polymers, characterized by: the organic solvent A is dichloromethane or toluene; the organic solvent B is toluene; the organic solvent C is toluene or butyl acetate.
3. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the catalyst in the step 1 is one or more of aluminum trichloride, boron trifluoride and lead iodide.
4. The process of claim 3 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the molar ratio of the rosin in the mixed solution A to the maleic acid in the mixed solution B is 1:1; the adding amount of the catalyst in the step 1 is 0.1-0.2% of the molar amount of the maleic acid.
5. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the catalyst in the step 2 is one of zinc oxide and aluminum trichloride.
6. The process of claim 5 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the molar ratio of the maleated rosin in the mixed liquid C to the hydroxyethyl methacrylate in the slurry D is 1:2; the dosage of the catalyst in the step 2 is 1.5-5% of the molar weight of the maleated rosin.
7. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the initiator in the step 3 is a mixture of azodiisobutyronitrile and benzoyl peroxide in a molar ratio of 1:1.
8. The process of claim 7 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the dosage of the initiator in the mixed solution F is 5-10% of the molar weight of the maleic rosin hydroxyethyl methacrylate in the mixed solution E.
9. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: the pipe diameters of the coil pipe reactor and the coil pipe type microwave reactor are 0.2cm-5cm.
10. The process of claim 1 for preparing a maleated rosin hydroxyethyl methacrylate polymer from rosin, wherein: and the organic solvent A, the organic solvent B and the organic solvent C are all recycled.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286243A (en) * | 1999-08-16 | 2001-03-07 | 株式会社日本触媒 | Process for producing hydroxyalkyl ester |
| JP2002356457A (en) * | 2001-03-28 | 2002-12-13 | Mitsubishi Rayon Co Ltd | Method for producing adduct of cyclopentadiene-vinyl compound |
| CN110746528A (en) * | 2019-10-29 | 2020-02-04 | 四会市邦得利化工有限公司 | Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin |
| CN114133484A (en) * | 2021-12-09 | 2022-03-04 | 江西联合化工有限公司 | Method for preparing acrylic resin by adopting tubular reactor |
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2022
- 2022-09-06 CN CN202211083971.8A patent/CN115417938A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286243A (en) * | 1999-08-16 | 2001-03-07 | 株式会社日本触媒 | Process for producing hydroxyalkyl ester |
| JP2002356457A (en) * | 2001-03-28 | 2002-12-13 | Mitsubishi Rayon Co Ltd | Method for producing adduct of cyclopentadiene-vinyl compound |
| CN110746528A (en) * | 2019-10-29 | 2020-02-04 | 四会市邦得利化工有限公司 | Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin |
| CN114133484A (en) * | 2021-12-09 | 2022-03-04 | 江西联合化工有限公司 | Method for preparing acrylic resin by adopting tubular reactor |
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