CN110540637A - method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method - Google Patents
method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method Download PDFInfo
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Abstract
The invention relates to a method for preparing crosslinked polypropylene carbonate by a one-pot method of maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization, belonging to the field of carbon dioxide copolymer materials; during the polymerization of carbon dioxide (CO 2)/Propylene Oxide (PO), maleic anhydride copolymer is introduced to prepare the cross-linked PPC in one pot. The third monomer molecule for crosslinking contains the cyclic carboxylic anhydride functional group which can participate in CO2/PO copolymerization, and the crosslinking degree and physical properties of the obtained crosslinked PPC can be adjusted. The introduction of the maleic anhydride copolymer can not only increase the catalytic efficiency and reduce the CO2 pressure, but also shorten the polymerization time, obviously enhance the thermal stability, the mechanical strength and the dimensional stability of the PPC, overcome the problems that the PPC material is easy to decompose in thermal processing and the product is easy to deform, and ensure that the polymer is still thermoplastic due to proper crosslinking degree, thereby having good application prospect in the fields of plastics and rubber; the method for preparing the cross-linked PPC by the one-pot method has the advantages of few synthesis steps, simple preparation process and suitability for industrial production.
Description
Technical Field
The invention relates to a method for preparing crosslinked polypropylene carbonate by a one-pot method, in particular to a method for preparing crosslinked polypropylene carbonate by a one-pot method of maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization, belonging to the field of carbon dioxide copolymer materials.
background
The polypropylene carbonate (PPC) material is prepared by catalytic copolymerization of CO2 and Propylene Oxide (PO), so that CO2 is changed into valuable, the PPC belongs to a biodegradable environment-friendly high polymer material, has excellent gas barrier property, and can be used for low-temperature preservative films, adhesives, printing and heat sealing. However, the PPC has a low glass transition temperature and poor dimensional stability, and thus the product is easily deformed at room temperature, and also easily decomposed during hot working, and has weak mechanical strength, thereby limiting the range of application.
PPC materials can be modified by physical blending and chemical methods. The physical blending method is to add inorganic or another organic polymer into the PPC for modification, and although the method is simple to operate, the inherent compatibility problem of the method often causes the damage phenomenon of the blended material at the phase interface during the use process. The chemical modification can radically modify the carbon dioxide copolymer, and multiple copolymerization and crosslinking measures are commonly used. Although the copolymerization of plural components can work, the use of a large amount of other monomers results in a reduction in the utilization of carbon dioxide as a resource, and the use of a large amount of other monomers sometimes results in a reduction in the polymerization degradability. The crosslinking measure can achieve the comprehensive modification purpose under the premise of using less second component. For example, chinese patent CN1775828 discloses a method for preparing cross-linked PPC, which introduces 5% of double bonds in the molecular chain of PPC by propylene oxide/allyl glycidyl ether/carbon dioxide (PO/AGE/CO2) ternary polymerization, and then adds an initiator to crosslink the double bonds to prepare cross-linked PPC, thereby improving the dimensional stability of PPC. Song et al (j.polym.res.2009,16,91) prepared crosslinked PPC using a two-step process, by first introducing double bonds into the molecular chain of the PPC by propylene oxide/maleic anhydride/carbon dioxide (PO/MA/CO2) copolymerization, and then adding dicumyl peroxide as the initiator to crosslink the PPC. Higher amounts of MA increase the thermal stability of PPC, but both polymer yield and molecular weight decrease. Chinese patents CN102746503, CN102775594 and CN103601879 respectively disclose a method for preparing a cross-linked carbon dioxide copolymer by copolymerizing CO2 and other monomers under the catalysis of zinc glutarate, the thermal stability and the mechanical strength of the copolymer are improved, the patents do not mention the size stability of the polymer, and compared with the preparation of PPC by binary copolymerization of PO/CO2, the introduction of other monomers reduces the catalytic efficiency, and the catalytic efficiency is basically unchanged and cannot be obviously increased. Although the literature reports that the crosslinked PPC can be obtained in one step by adding a third monomer, the third monomer used is a small molecular compound, the number of functional groups capable of participating in copolymerization is limited, and the crosslinking effect and the physical property adjustment window are limited.
Disclosure of Invention
The invention aims to provide a method for preparing crosslinked polypropylene carbonate by a one-pot copolymerization method of maleic anhydride copolymer/propylene oxide/carbon dioxide, overcomes the defects of the prior art, and improves the thermal stability, dimensional stability and mechanical strength of PPC by a simple method.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
propylene Oxide (PO) and carbon dioxide (CO2) are respectively used as a first monomer and a second monomer, a maleic anhydride copolymer is used as a third monomer, and zinc glutarate is used as a catalyst to carry out copolymerization reaction;
The specific method comprises the following steps:
Putting zinc glutarate and MA/THPA copolymer into a high-pressure reaction kettle, vacuum-drying for 24 hours at 80 ℃, cooling while filling nitrogen to replace air for three times, vacuumizing, then filling propylene oxide, and filling carbon dioxide; maintaining the polymerization reaction temperature and the pressure of carbon dioxide, stirring for reaction, dissolving a polymer in dichloromethane after the reaction is finished, wherein partial gel is not dissolved, then adding 5% hydrochloric acid to dissolve a zinc glutarate catalyst, washing the solution with distilled water until the pH value is neutral, separating out the polymer from a polymer dichloromethane solution by using ethanol, and drying the solution in vacuum at the temperature of 80 ℃ for 24 hours to obtain the polymer;
Wherein the mass ratio of the zinc glutarate to the propylene oxide is 1: 100-500; the mass ratio of the third monomer to the propylene oxide is 1-5: 100; the polymerization temperature is 60-80 ℃, and the initial pressure of carbon dioxide is 4.5 MPa; the reaction time is 15-25 hours;
The third monomer is maleic anhydride/styrene copolymer, maleic anhydride/vinyl acetate copolymer, maleic anhydride/methyl acrylate copolymer, maleic anhydride/methyl methacrylate copolymer, maleic anhydride/acrylamide copolymer, maleic anhydride/vinyl methyl ether copolymer, maleic anhydride/1, 2,3, 6-tetrahydrophthalic anhydride copolymer.
The number average molecular weight of the maleic anhydride copolymer is 600-2000.
Compared with the prior art, the invention has the beneficial effects that:
The third monomer maleic anhydride copolymer contains more than three cyclic carboxylic anhydride groups which can participate in the copolymerization reaction of PO/CO2 catalyzed by zinc glutarate, so that when PO, CO2 and the third monomer are copolymerized under the catalysis of zinc glutarate, two PPC molecular chains can extend out by the ring-opening participation of one cyclic carboxylic anhydride group in the copolymerization reaction, and the maleic anhydride copolymer contains more than three cyclic carboxylic anhydride groups, so that the PPC molecular chains can be connected by adding the maleic anhydride copolymer, and the preparation of the crosslinked PPC in one pot is realized. The third monomer contains more cyclic carboxylic anhydride, so that the crosslinking effect is good, the obtained polymer has better thermal stability, dimensional stability and mechanical strength compared with PPC, the 5 percent thermal decomposition temperature and the maximum thermal decomposition temperature are respectively higher than 285 ℃ and 300 ℃, the temperature is higher than 70 ℃ and higher than 60 ℃ respectively than the PPC, the permanent deformation rate can reach 0, the PPC has 179 percent, the tensile strength reaches 37MPa, and the PPC has only 13 MPa. The crosslinking degree can be adjusted by controlling the dosage of the third monomer, so that the polymer is still thermoplastic, the hot processing molding is convenient, and the application range of the polymer can be widened. The preparation method has simple process, low CO2 pressure and short polymerization time, and the catalytic efficiency can reach 2 times of that of the PPC after the third monomer is introduced, thereby being beneficial to controlling the production cost of the polymer.
The copolymerization conditions and the polymer properties are related to the data shown in Table 1:
TABLE 1 copolymerization conditions and Polymer Properties
Note: the third monomer used in examples 1-4 was a Maleic Anhydride (MA)/1,2,3, 6-tetrahydrophthalic anhydride (THPA) copolymer having a number average molecular weight of 894; the third monomers used in examples 5 to 10 were a MA/vinyl acetate (VAc) copolymer having a number average molecular weight of 725, a MA/Methyl Acrylate (MAC) copolymer having a number average molecular weight of 1147, a MA/Methyl Methacrylate (MMA) copolymer having a number average molecular weight of 1420, a MA/acrylamide (ACA) copolymer having a number average molecular weight of 860, a MA/Methyl Vinyl Ether (MVE) copolymer having a number average molecular weight of 626, and a MA/styrene (St) copolymer having a number average molecular weight of 1970, respectively; example 11 is a comparative example and is a propylene oxide and carbon dioxide bipolymer.
Drawings
FIG. 1 is a schematic structural diagram of a cross-linked PPC prepared according to the present invention, wherein the letter A represents a structural unit formed from a monomer of propylene oxide and B represents a structural unit formed from a monomer of carbon dioxide;
FIG. 2 is an infrared spectrum of a polymer prepared in example 3 of the present invention;
FIG. 3 is an infrared spectrum of a PO/CO2 copolymer PPC;
FIG. 4 is a 1H NMR chart of polymer (lower) and PPC (upper) prepared in example 3 of the present invention;
FIG. 5 is a thermogravimetric analysis of the polymer produced in accordance with the invention and of PPC (corresponding respectively to examples 1,2,3, 4, 11);
FIG. 6 is a graph of the tensile test stress-strain curves of the polymer prepared according to the invention and of PPC (corresponding to examples 1,2,3, 4, 11, respectively);
the infrared spectrum of the polymer prepared in example 3 shows absorption peaks at wave numbers of 2985, 1740, 1580, 1454, 1400, 1381, 1226, 1165, 1125, 1065, 973, 916, 856, 818 and 787cm-1 substantially identical to that of the PO/CO2 binary copolymer PPC, which are absorption peaks of CH3, CH2, CH stretching and bending vibration, C ═ O stretching vibration, C ═ O) — O and C — O — C stretching vibration, derived from polyether structural units formed when carbonate structures, maleate esters and PO are continuously inserted into the polymer chain extension, and there is a peak overlap phenomenon between carbonate esters and maleate esters. In addition, the CO2/PO/P (MA-CO-THPA) copolymer has new absorption peaks at wavenumbers of 1621 and 717cm-1, which are respectively the stretching vibration of the aromatic ring skeleton in the structural unit end group benzoyloxy formed by the third monomer P (MA-CO-THPA) and the bending vibration of the C-H out-of-plane. The possibility that these newly appeared absorption peaks come from P (MA-co-THPA) which does not participate in the terpolymerization can be excluded by 1H NMR, because no signal peak of a mono-substituted benzene ring is found in the 1H NMR of the polymer, which indicates that P (MA-co-THPA) monomer which does not participate in the terpolymerization does not exist in the polymer. The gel generation in the combined polymer is confirmed, and the third monomer P (MA-co-THPA) participates in copolymerization reaction and reacts with each other to form a cross-linked structure. The 1H NMR of the polymer and the CO2/PO copolymers are substantially identical (. delta.ppm). the symbols 5.00(s, CH), 4.19 to 4.27(m, CH2) and 1.34(s, CH3) are alternating CO2 and PO copolymers, and the signal peaks at 3.82, 3.72, 3.56 and 1.17ppm are derived from the CH, CH2 and CH3 groups of polyether building blocks formed when PO is continuously inserted into the polymer chain extender, respectively. Since P (MA-co-THPA) plays a role in forming a cross-linked structure, the structural units formed by them are confined in the gel, which is insoluble in the deuterated chloroform solvent used in the 1H NMR test, and thus their signal peaks do not appear.
Detailed Description
The present invention is further illustrated in detail by the following examples, which are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
0.25 g of zinc glutarate and 0.25 g of MA/THPA copolymer with the number average molecular weight of 894 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 30mL of propylene oxide is injected, and carbon dioxide is filled. Maintaining the polymerization temperature at 70 ℃ and the carbon dioxide pressure at 4.5MPa, and stirring for reaction for 15 hours. After the reaction, the polymer was dissolved in 200mL of methylene chloride, and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, and the solution was washed with distilled water until the pH was neutral, and the polymer was precipitated from the methylene chloride solution of the polymer with ethanol, and vacuum-dried at 80 ℃ for 24 hours to obtain 60 g of the polymer. The gel content was found to be 15%. The 5% thermal decomposition temperature was 281 ℃ and the maximum thermal decomposition temperature was 294 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was 53.9%. The tensile strength is 25MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
example 2
0.25 g of zinc glutarate and 2 g of MA/THPA copolymer with the number average molecular weight of 894 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 60mL of propylene oxide is injected, and carbon dioxide is filled. The polymerization temperature is maintained at 70 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 18 hours. After the reaction, the polymer was dissolved in 200mL of methylene chloride, and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, and the solution was washed with distilled water until the pH was neutral, and the polymer was precipitated from the methylene chloride solution of the polymer with ethanol, and vacuum-dried at 80 ℃ for 24 hours to obtain 62 g of the polymer. The gel content was found to be 18%. The 5% thermal decomposition temperature was 285 ℃ and the maximum thermal decomposition temperature was 305 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was measured to be 15.2%. The tensile strength is 29MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 3
0.25 g of zinc glutarate and 3.5 g of MA/THPA copolymer with the number average molecular weight of 894 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 60mL of propylene oxide is injected, and carbon dioxide is filled. The polymerization temperature is maintained at 70 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 20 hours. After the reaction, the polymer was dissolved in 250mL of dichloromethane and some gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the mixture was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the mixture was dried under vacuum at 80 ℃ for 24 hours to obtain 70 g of the polymer. The gel content was found to be 22%. The 5% thermal decomposition temperature was 288 ℃ and the maximum thermal decomposition temperature was 304 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was 2.8%. The tensile strength is 35MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 4
0.25 g of zinc glutarate and 7.5 g of MA/THPA copolymer with the number average molecular weight of 894 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 90mL of propylene oxide is injected, and carbon dioxide is filled. The polymerization temperature is maintained at 70 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 18 hours. After the reaction, the polymer was dissolved in 250mL of dichloromethane and some gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the mixture was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the mixture was vacuum-dried at 80 ℃ for 24 hours to obtain 73 g of the polymer. The gel content was found to be 26%. The 5% thermal decomposition temperature was 290 ℃ and the maximum thermal decomposition temperature was 306 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation ratio was 0%. The tensile strength is 42MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 5
0.25 g of zinc glutarate and 3.75 g of MA/VAc copolymer with the number average molecular weight of 725 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 90mL of propylene oxide is injected, and carbon dioxide is filled. The polymerization temperature is maintained at 60 ℃ and the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 25 hours. After the reaction, the polymer was dissolved in 200mL of methylene chloride, and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, and the solution was washed with distilled water until the pH was neutral, and the polymer was precipitated from the methylene chloride solution, and vacuum-dried at 80 ℃ for 24 hours to obtain 68 g of the polymer. The gel content was found to be 37%. The 5% thermal decomposition temperature was 293 ℃ and the maximum thermal decomposition temperature was 310 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation ratio was 0%. The tensile strength is 39MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 6
0.25 g of zinc glutarate and 3 g of MA/MAC copolymer with the number average molecular weight of 1147 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 120mL of propylene oxide is injected, and carbon dioxide is filled. The polymerization temperature is maintained at 60 ℃ and the carbon dioxide pressure is maintained at 4.5MPa, and the stirring reaction is carried out for 23 hours. After the reaction, the polymer was dissolved in 200mL of dichloromethane and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the solution was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the solution was dried under vacuum at 80 ℃ for 24 hours to obtain 64 g of a polymer. The gel content was found to be 30%. The 5% thermal decomposition temperature was 291 ℃ and the maximum thermal decomposition temperature was 306 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was measured to be 0.2%. The tensile strength is 40MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 7
0.25 g of zinc glutarate and 5 g of MA/MMA copolymer having a number average molecular weight of 1420 were placed in a high-pressure reactor, vacuum-dried at 80 ℃ for 24 hours, then the temperature was lowered while replacing the air with nitrogen gas three times, and then the reactor was evacuated, and then 150mL of propylene oxide was injected and charged with carbon dioxide. The polymerization temperature is maintained at 60 ℃ and the carbon dioxide pressure is maintained at 4.5MPa, and the stirring reaction is carried out for 23 hours. After the reaction, the polymer was dissolved in 200mL of methylene chloride, and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, and the solution was washed with distilled water until the pH was neutral, and the polymer was precipitated from the methylene chloride solution of the polymer with ethanol, and vacuum-dried at 80 ℃ for 24 hours to obtain 55 g of the polymer. The gel content was found to be 32%. The 5% thermal decomposition temperature was 292 ℃ and the maximum thermal decomposition temperature was 309 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was measured to be 0.1%. The tensile strength is 38MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 8
0.25 g of zinc glutarate and 2.25 g of MA/ACA copolymer with the number average molecular weight of 860 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 90mL of propylene oxide is filled, and carbon dioxide is filled. The polymerization temperature is maintained at 80 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 25 hours. After the reaction, the polymer was dissolved in 200mL of dichloromethane and some gel was not dissolved, 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the mixture was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the mixture was vacuum-dried at 80 ℃ for 24 hours to give 58 g of a polymer. The gel content was found to be 35%. The 5% thermal decomposition temperature was 293 ℃ and the maximum thermal decomposition temperature was 310 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was measured to be 0.1%. The tensile strength is 37MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 9
0.25 g of zinc glutarate and 2.25 g of MA/MVE copolymer with the number average molecular weight of 626 are placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 90mL of propylene oxide is filled, and carbon dioxide is filled. The polymerization temperature is maintained at 80 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 25 hours. After the reaction, the polymer was dissolved in 100mL of methylene chloride, and a part of the gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, and the solution was washed with distilled water until the pH was neutral, and the polymer was precipitated from the methylene chloride solution of the polymer with ethanol, and vacuum-dried at 80 ℃ for 24 hours to obtain 62 g of the polymer. The gel content was found to be 38%. The 5% thermal decomposition temperature was 293 ℃ and the maximum thermal decomposition temperature was 311 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation ratio was 0%. The tensile strength is 40MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 10
0.25 g of zinc glutarate and 2.25 g of MA/St copolymer having a number average molecular weight of 1970 are placed in a high-pressure reaction vessel, vacuum-dried at 80 ℃ for 24 hours, then the temperature is reduced while nitrogen gas is introduced to replace air three times, vacuum-pumping is performed, then 90mL of propylene oxide is injected, and carbon dioxide is introduced. The polymerization temperature is maintained at 80 ℃, the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 25 hours. After the reaction, the polymer was dissolved in 200mL of dichloromethane and some gel was not dissolved, 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the mixture was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the mixture was vacuum-dried at 80 ℃ for 24 hours to obtain 65 g of a polymer. The gel content was found to be 40%. The 5% thermal decomposition temperature was 294 ℃ and the maximum thermal decomposition temperature was 310 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation ratio was 0%. The tensile strength is 41MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Example 11
0.25 g of zinc glutarate is placed in a high-pressure reaction kettle, vacuum drying is carried out for 24 hours at the temperature of 80 ℃, nitrogen is filled for replacing air for three times while the temperature is reduced, vacuum pumping is carried out, then 90mL of propylene oxide is filled, and carbon dioxide is filled. The polymerization temperature is maintained at 60 ℃ and the pressure of carbon dioxide is maintained at 4.5MPa, and the stirring reaction is carried out for 25 hours. After the reaction, the polymer was dissolved in 100mL of dichloromethane and some gel was not dissolved, then 10mL of 5% hydrochloric acid was added to dissolve the zinc glutarate catalyst, the mixture was washed with distilled water until the pH was neutral, the polymer was precipitated from the polymer dichloromethane solution with ethanol, and the mixture was vacuum-dried at 80 ℃ for 24 hours to obtain 26 g of a polymer. The gel content was found to be 0%. The 5% thermal decomposition temperature was 226 ℃ and the maximum thermal decomposition temperature was 240 ℃. The dimensional stability was measured by a heat elongation test under the conditions of 60 ℃ and a load of 0.14MPa, and the permanent deformation rate was found to be 166%. The tensile strength is 13MPa, and the test conditions are as follows: the temperature is 23 ℃, the humidity is 50 percent, and the stretching speed is 50 mm/min.
Claims (10)
1. The method for preparing the crosslinked polypropylene carbonate by using the maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method is characterized by comprising the following steps of: the method comprises the following steps:
Propylene oxide and carbon dioxide are respectively used as a first monomer and a second monomer, a maleic anhydride copolymer is used as a third monomer, zinc glutarate is used as a catalyst to carry out polymerization reaction, and the crosslinked polypropylene carbonate is prepared in one pot.
2. The method for preparing crosslinked polypropylene carbonate by the one-pot method of maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1, wherein: the method comprises the following specific steps:
Putting zinc glutarate and MA/THPA copolymer in a high-pressure reaction kettle, vacuum drying for 24 hours at 80 ℃, cooling while filling nitrogen to replace air for three times, vacuumizing, then filling propylene oxide, filling carbon dioxide, maintaining the polymerization temperature and the carbon dioxide pressure, stirring for reaction, dissolving the polymer in dichloromethane after the reaction is finished, then adding 5% hydrochloric acid to dissolve the zinc glutarate catalyst, washing with distilled water until the pH value is neutral, separating out the polymer from the polymer dichloromethane solution by using ethanol, and vacuum drying for 24 hours at 80 ℃ to obtain the polymer.
3. the one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the mass ratio of the zinc glutarate to the propylene oxide is 1: 100-500.
4. The one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the mass ratio of the maleic anhydride copolymer to the propylene oxide is 1-10: 100.
5. The one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the polymerization reaction temperature is 60-80 ℃.
6. The one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the pressure of the carbon dioxide is 4.5 MPa.
7. The one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the reaction time of the polymerization reaction is 15-25 hours.
8. The method for preparing crosslinked polypropylene carbonate by the one-pot method of maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1, wherein: the third monomer is maleic anhydride copolymer.
9. The one-pot method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization according to claim 1 or 2, characterized in that: the maleic anhydride copolymer is maleic anhydride/styrene copolymer, maleic anhydride/vinyl acetate copolymer, maleic anhydride/methyl acrylate copolymer, maleic anhydride/methyl methacrylate copolymer, maleic anhydride/acrylamide copolymer, maleic anhydride/vinyl methyl ether copolymer or maleic anhydride/1, 2,3, 6-tetrahydrophthalic anhydride copolymer.
10. The method for preparing the crosslinked polypropylene carbonate by the maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method according to claim 1 or 2, wherein the number average molecular weight of the maleic anhydride copolymer is 600-2000.
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| CN115521448A (en) * | 2022-10-21 | 2022-12-27 | 北京旭阳科技有限公司 | Copolymerization modified polypropylene carbonate copolymer and preparation method and application thereof |
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