CN110105559A - The method of one step preparation crosslinking carbon dioxide copolymer - Google Patents
The method of one step preparation crosslinking carbon dioxide copolymer Download PDFInfo
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- CN110105559A CN110105559A CN201910410278.9A CN201910410278A CN110105559A CN 110105559 A CN110105559 A CN 110105559A CN 201910410278 A CN201910410278 A CN 201910410278A CN 110105559 A CN110105559 A CN 110105559A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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Abstract
The invention belongs to carbon dioxide copolymer Material Fields, are related to a kind of preparation method of step preparation crosslinking carbon dioxide copolymer.In carbon dioxide (CO2When)/propylene oxide (EP) polymerize, furancarboxylic acid ethylene oxidic ester Third monomer and the 4th monomer of cyclic dicarboxylic acid anhydride containing alkene, step preparation crosslinking carbon dioxide copolymer are introduced.The introducing of other monomers not only can increase catalytic efficiency, reduce CO2Pressure, polymerization time is short, and and CO2/ EP bipolymer compares, and other monomers polymer obtained less than 3% mole that EP is added is thermoplasticity, has good thermal stability, dimensional stability and elasticity, overcomes CO2/ EP bipolymer materials hot working easily decomposes and the easily-deformable problem of product, has applications well prospect in plastics, rubber materials.One-step preparation method step provided by the invention is few, and preparation process is simple, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of methods of step preparation crosslinking carbon dioxide copolymer, belong to carbon dioxide copolymer material
Field.
Background technique
From CO2Carbon dioxide copolymer material is prepared with propylene oxide (EP) catalyzed copolymerization, carbon dioxide is not only made to become useless
For treasured, its utilization of resources is realized, mitigate the degree of dependence to petroleum resources, and the copolymer belongs to biodegradable environment
Friendly high molecular material has excellent barrier properties for gases, can be used for preservation by low temperature film, adhesive, printing and heat-sealing.But this is total
Polymer glass transition temperature is low, and is armorphous state, poor dimensional stability, cause at room temperature its product be easily deformed, and
It is also easy to decompose when hot-working, limits its application range.In addition, CO2Although/EP is copolymerized glutaric acid zinc catalyst synthesis letter used
It is single, but catalytic efficiency is relatively not prominent enough, leads to carbon dioxide copolymer high production cost.
Physical blending is usually taken in people and chemical method carrys out modified carbon dioxide copolymer material.The method of physical blending
It is inorganic or another organic polymer to be added in carbon dioxide copolymer material to be modified, this method is although easy to operate,
But its intrinsic consistency problem often makes intermingling material that breakoff phenomenon occur at phase interface in use.Chemistry changes
Property can fundamentally modified carbon dioxide copolymer, Li et al. people (Polym.J.2011,43,121) be urged with Salen-Co (III)
Agent makes propylene oxide/cyclohexene oxide/carbon dioxide (PO/CHO/CO2) copolymerization, it obtains the vitrifying of terpolymer maximum and turns
Temperature (Tg) is 88.5 DEG C, and PO/CO2The Tg of bipolymer is about 40 DEG C.It can be seen that the introducing of CHO can significantly improve glass
Change transition temperature, but will lead to polymeric degradation decline.The inventors of the present invention (J.Appl.Polym.Sci.2008,108,
1037；J.Appl.Polym.Sci.2008,108,3626 one kind) is reported by PO/CO2Third monomer is added when copolymerization
Ternary polymerization occurs for the alkylene oxide containing rigid radical (such as carbazyl and naphthalene), and reaching improves PO/CO2Binary copolymerization physical performance
Purpose, but can all be reduced with the introducing of Third monomer, polymer yield and molecular weight.Chinese patent CN1775828 discloses one
Kind propylene oxide/allyl glycidyl ether/carbon dioxide (PO/AGE/CO2) terpolymer and preparation method thereof, in PPC
5% mole of double bond is introduced in strand, initiator, which is then added, to be crosslinked double bond to prepare cross-linking type carbon dioxide copolymer,
The dimensional stability of PPC can be improved, but this method needs two step synthesis processes, complex process.Song et al.
(J.Polym.Res.2009,16,91) pass through propylene oxide/maleic anhydride/carbon dioxide (PO/MA/CO2) copolymerization make titanium dioxide
Double bond is introduced in carbon copolymer molecule chain, initiator cumyl peroxide (DCP), which is then added, sends out carbon dioxide copolymer
Raw crosslinking.MA additional amount (molar fraction) increases with additional amount from 3% to 20%, improves Tg and thermostabilization to some extent
Property, but polymer yield and molecular weight can all reduce.Chinese patent CN102746503, CN102775594 and
CN103601879 individually discloses a kind of glutaric acid zinc catalysis carbon dioxide and other monomer copolymerization prepare cross-linking type carbon dioxide
The method of copolymer, copolymer thermal stability and mechanical strength are all improved, these patents all do not refer to the ruler of polymer
Very little stability, and opposite PO/CO2Binary copolymerization prepares carbon dioxide copolymer, some reductions of the introducing of other monomers are urged
Change efficiency, some catalytic efficiencies are basically unchanged, and can not dramatically increase catalytic efficiency.Chinese patent CN104440157 is disclosed
The bipolymer and preparation method of a kind of furan glycidyl ether or ester and carbon dioxide, used catalyst are rare-earth ternary catalysis
Agent, glutaric acid zinc catalyst can realize furancarboxylic acid ethylene oxidic ester and carbon dioxide, propylene oxide and cyclic dicarboxylic acid anhydride containing alkene into
The quarternary copolymerized step preparation crosslinking carbon dioxide copolymer of row still belongs to unknown project, and has no document report.
Summary of the invention
The object of the present invention is to provide a kind of methods of step preparation crosslinking carbon dioxide copolymer.The prior art is overcome to deposit
Deficiency, with simple method improve carbon dioxide copolymer thermal stability and dimensional stability.
To solve the above problems, the technical scheme adopted by the invention is that:
With propylene oxide (EP) and carbon dioxide (CO2) be respectively the first and second monomers, with furancarboxylic acid ethylene oxidic ester and
Cyclic dicarboxylic acid anhydride containing alkene is respectively the third and fourth monomer, carries out copolyreaction by catalyst of glutaric acid zinc, wherein glutaric acid zinc
Molar ratio with propylene oxide is 1:600~1200；The molar ratio of third, the 4th monomer and propylene oxide be 0.5~3:0.5~
3:100；55~70 DEG C of polymeric reaction temperature, carbon dioxide initial pressure is 4.2MPa；Reaction time 12~24 hours.
The Third monomer is furancarboxylic acid ethylene oxidic ester, and the 4th monomer is citraconic anhydride, 1,2,3,6- tetrahydro O-phthalics
Acid anhydrides.The beneficial effect of the present invention compared with the existing technology is:
Third and fourth monomer, which all contains, can participate in glutaric acid zinc catalysis EP/CO2Copolyreaction, while respectively containing poly-
The functional group that can be reacted to each other when closing reaction temperature, therefore, glutaric acid zinc are catalyzed PO, CO2It is copolymerized with third, the 4th monomer
When, the functional group that can be reacted to each other is introduced into EP/CO2In bipolymer side group, it is able to achieve step preparation crosslinking titanium dioxide
Carbon copolymer.Preparation method simple process of the invention, CO2Pressure is low, and polymerization time is short, urges after introducing the third and fourth monomer
Changing efficiency can achieve preparation EP/CO23 times of bipolymer catalytic efficiency are conducive to the production cost for controlling polymer.Institute
Polymer phase is obtained to EP/CO2Bipolymer has good thermal stability, dimensional stability and elasticity, and 5% and maximum heat are divided
Solution temperature is respectively greater than 250 DEG C and 280 DEG C, EP/CO2Bipolymer only has 209 DEG C and 236 DEG C respectively, and permanent set can
To reach 0, and PPC has 165%.By controlling the 3rd the 4th adjustable crosslinking degree of monomer dosage, remain as polymer
Thermoplasticity facilitates thermo forming, is conducive to widen its application range.
Related data is shown in Table 1.
1 copolymerization conditions of table and polymer performance
Note: Examples 1 to 4 provides EP/CO2/ furancarboxylic acid ethylene oxidic ester/citraconic anhydride copolymerization conditions and polymer performance, it is real
It applies example 5~8 and provides EP/CO2/ furancarboxylic acid ethylene oxidic ester/1,2,3,6- tetrabydrophthalic anhydride copolymerization conditions and polymer
Can, it is propylene oxide and carbon dioxide binary copolymerization situation that embodiment 9, which is comparative example,.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy of polymer prepared by the present invention；
Fig. 2 is CO2The infrared spectrogram of/EP bipolymer；
Fig. 3 be polymer prepared by the present invention chloroform soluble fraction (on) and CO2/ EP (under) bipolymer1H
NMR spectra.
With CO2/ EP bipolymer compares, the infrared spectroscopy of polymer prepared by embodiment 3 1633.3,
754.0cm-1There is new absorption peak, they are from introducing CO respectively2The citraconic anhydride and furancarboxylic acid of/EP bipolymer side group contract
Cis- the two of generation is reacted between water glyceride structure unit replaces C=C stretching vibration and the vibration of C-H out-of-plane bending in carbon-carbon double bond
It is dynamic, other wave numbers 2985.2,1739.9,1582.8,1529.3,1456.8,1381.1,1228.7,1163.7,1066.0,
974.6,854.8and 788.7cm-1Absorption peak and CO2/ EP bipolymer is almost the same, they be structural carbonate and
The absorption peak of EP open loop structure.Emerging absorption peak can pass through1It is sweet from citraconic anhydride and furancarboxylic acid shrink that H NMR excludes them
The possibility of carbon-carbon double bond in grease, because of polymer1It shrinks in H NMR without discovery citraconic anhydride monomer 6.68ppm and furancarboxylic acid
The signal peak of glyceride monomers 6.26ppm.There is gel generation in conjugated polymer, illustrates that the third and fourth monomer takes part in copolymerization
Reaction, and interreaction forms cross-linked structure.Polymer1H NMR and CO2/ EP bipolymer it is almost the same (δ,
Ppm): 5.00 (s, CH), 4.19~4.27 (m, CH2) and 1.32 (s, CH3), they are that carbon dioxide and propylene oxide are alternately total
Poly structure, since third, the 4th monomer are the nodes to form cross-linked structure, the structural unit that they are formed is limited to gel
In, gel cannot be dissolved in1Deuterated chloroform solvent H NMR used when testing, therefore do not occur their signal peak.
Specific embodiment
The present invention is described in further details below by embodiment, these embodiments are only used to illustrate the present invention, and
It does not limit the scope of the invention.
Embodiment 1
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 2.45
Gram furancarboxylic acid ethylene oxidic ester and 1.76 grams of citraconic anhydrides are placed in autoclave, and inflated with nitrogen displaced air three times, then vacuumizes, and then infuses
Enter 220mL propylene oxide, is filled with carbon dioxide.55 DEG C of polymeric reaction temperature are maintained, pressure carbon dioxide 4.2MPa is stirred to react
24 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble, 10mL 5% is then added
Dissolving with hydrochloric acid glutaric acid zinc catalyst, and be washed with distilled water pH value and be in neutrality, polymer dichloromethane solution is analysed with ethyl alcohol
Polymer out, 80 DEG C are dried in vacuo 24 hours, obtain 69 grams of polymer.Measuring gel content is 13%.5% thermal decomposition temperature is
253 DEG C, maximum thermal decomposition temperature is 281 DEG C.With hot elongation test test size stability, condition is 60 DEG C, bears a heavy burden
0.14MPa, measuring hot elongation percentage is 365%, permanent set 51.3%.
Embodiment 2
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 6.7 grams
Furancarboxylic acid ethylene oxidic ester and 4.8 grams of citraconic anhydrides are placed in autoclave, and inflated with nitrogen displaced air three times, then vacuumizes, and is then injected into
300mL propylene oxide, is filled with carbon dioxide.60 DEG C of polymeric reaction temperature are maintained, pressure carbon dioxide 4.2MPa is stirred to react 24
Hour.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble, 5% salt of 10mL is then added
Acid dissolution glutaric acid zinc catalyst, and be washed with distilled water pH value and be in neutrality, polymer dichloromethane solution is precipitated with ethyl alcohol
Polymer, 80 DEG C are dried in vacuo 24 hours, obtain 72 grams of polymer.Measuring gel content is 20%.5% thermal decomposition temperature is
260 DEG C, maximum thermal decomposition temperature is 286 DEG C.With hot elongation test test size stability, condition is 60 DEG C, bears a heavy burden
0.14MPa, measuring hot elongation percentage is 212%, permanent set 14.2%.
Embodiment 3
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 19.2
Gram furancarboxylic acid ethylene oxidic ester and 13.8 grams of citraconic anhydrides are placed in autoclave, and inflated with nitrogen displaced air three times, then vacuumizes, and then infuses
Enter 430mL propylene oxide, is filled with carbon dioxide.70 DEG C of polymeric reaction temperature are maintained, pressure carbon dioxide 4.2MPa is stirred to react
20 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble, 10mL 5% is then added
Dissolving with hydrochloric acid glutaric acid zinc catalyst, and be washed with distilled water pH value and be in neutrality, polymer dichloromethane solution is analysed with ethyl alcohol
Polymer out, 80 DEG C are dried in vacuo 24 hours, obtain 76 grams of polymer.Measuring gel content is 28%.5% thermal decomposition temperature is
262 DEG C, maximum thermal decomposition temperature is 288 DEG C.With hot elongation test test size stability, condition is 60 DEG C, bears a heavy burden
0.14MPa, measuring hot elongation percentage is 83%, permanent set 3.5%.
Embodiment 4
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 23.4
Gram furancarboxylic acid ethylene oxidic ester and 16.8 grams of citraconic anhydrides are placed in autoclave, and inflated with nitrogen displaced air three times, then vacuumizes, and then infuses
Enter 350mL propylene oxide, is filled with carbon dioxide.70 DEG C of polymeric reaction temperature are maintained, pressure carbon dioxide 4.2MPa is stirred to react
15 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble, 10mL 5% is then added
Dissolving with hydrochloric acid glutaric acid zinc catalyst, and be washed with distilled water pH value and be in neutrality, polymer dichloromethane solution is analysed with ethyl alcohol
Polymer out, 80 DEG C are dried in vacuo 24 hours, obtain 83 grams of polymer.Measuring gel content is 35%.5% thermal decomposition temperature is
273 DEG C, maximum thermal decomposition temperature is 292 DEG C.With hot elongation test test size stability, condition is 60 DEG C, bears a heavy burden
0.14MPa, measuring hot elongation percentage is 58%, permanent set 0.2%.
Embodiment 5
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 2.68
Gram furancarboxylic acid ethylene oxidic ester and 2.61 gram 1,2,3,6- tetrabydrophthalic anhydrides are placed in autoclave, inflated with nitrogen displaced air three
It is secondary, then vacuumize, it is then injected into 240mL propylene oxide, is filled with carbon dioxide.65 DEG C of polymeric reaction temperature are maintained, carbon dioxide
Pressure 4.2MPa is stirred to react 15 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble
Then solution is added 5% dissolving with hydrochloric acid glutaric acid zinc catalyst of 10mL, and is washed with distilled water pH value and is in neutrality, polymer two
Polymer is precipitated in chloromethanes solution ethyl alcohol, and 80 DEG C are dried in vacuo 24 hours, obtains 72 grams of polymer.Measuring gel content is
16%.5% thermal decomposition temperature is 257 DEG C, and maximum thermal decomposition temperature is 290 DEG C.With hot elongation test test size stability, item
Part is 60 DEG C, bear a heavy burden 0.14MPa, and measuring hot elongation percentage is 298%, permanent set 33.4%.
Embodiment 6
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 6.3 grams
Furancarboxylic acid shrinks sweet ester and 6.1 gram 1, and 2,3,6- tetrabydrophthalic anhydrides are placed in autoclave, inflated with nitrogen displaced air three times, then
It vacuumizes, is then injected into 280mL propylene oxide, is filled with carbon dioxide.60 DEG C of polymeric reaction temperature are maintained, pressure carbon dioxide
4.2MPa is stirred to react 12 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel not dissolve,
Then 5% dissolving with hydrochloric acid glutaric acid zinc catalyst of 10mL is added, and is washed with distilled water pH value and is in neutrality, polymer dichloro
Polymer is precipitated in dichloromethane ethyl alcohol, and 80 DEG C are dried in vacuo 24 hours, obtains 77 grams of polymer.Measuring gel content is
25%.5% thermal decomposition temperature is 278 DEG C, and maximum thermal decomposition temperature is 295 DEG C.With hot elongation test test size stability, item
Part is 60 DEG C, bear a heavy burden 0.14MPa, and measuring hot elongation percentage is 156%, permanent set 11.3%.
Embodiment 7
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 15.6
Gram furancarboxylic acid shrinks sweet ester and 15.2 gram 1, and 2,3,6- tetrabydrophthalic anhydrides are placed in autoclave, inflated with nitrogen displaced air three
It is secondary, then vacuumize, it is then injected into 350mL propylene oxide, is filled with carbon dioxide.60 DEG C of polymeric reaction temperature are maintained, carbon dioxide
Pressure 4.2MPa is stirred to react 24 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble
Then solution is added 5% dissolving with hydrochloric acid glutaric acid zinc catalyst of 10mL, and is washed with distilled water pH value and is in neutrality, polymer two
Polymer is precipitated in chloromethanes solution ethyl alcohol, and 80 DEG C are dried in vacuo 24 hours, obtains 80 grams of polymer.Measuring gel content is
30%.5% thermal decomposition temperature is 283 DEG C, and maximum thermal decomposition temperature is 303 DEG C.With hot elongation test test size stability, item
Part is 60 DEG C, bear a heavy burden 0.14MPa, and measuring hot elongation percentage is 62%, permanent set 1.1%.
Embodiment 8
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, then 26.8
Gram furancarboxylic acid shrinks sweet ester and 26.1 gram 1, and 2,3,6- tetrabydrophthalic anhydrides are placed in autoclave, inflated with nitrogen displaced air three
It is secondary, then vacuumize, it is then injected into 400mL propylene oxide, is filled with carbon dioxide.65 DEG C of polymeric reaction temperature are maintained, carbon dioxide
Pressure 4.2MPa is stirred to react 20 hours.After reaction, polymer is dissolved in 200ml methylene chloride, has partial gel insoluble
Then solution is added 5% dissolving with hydrochloric acid glutaric acid zinc catalyst of 10mL, and is washed with distilled water pH value and is in neutrality, polymer two
Polymer is precipitated in chloromethanes solution ethyl alcohol, and 80 DEG C are dried in vacuo 24 hours, obtains 85 grams of polymer.Measuring gel content is
41%.5% thermal decomposition temperature is 292 DEG C, and maximum thermal decomposition temperature is 305 DEG C.With hot elongation test test size stability, item
Part is 60 DEG C, bear a heavy burden 0.14MPa, and measuring hot elongation percentage is 32%, permanent set 0.
Embodiment 9
1 gram of glutaric acid zinc is placed in autoclave, after 120 DEG C are dried in vacuo 8 hours, drops to room temperature, inflated with nitrogen is set
It ventilates three times, then vacuumizes, be then injected into 350mL propylene oxide, be filled with carbon dioxide.60 DEG C of polymeric reaction temperature are maintained,
Pressure carbon dioxide 4.2MPa is stirred to react 24 hours.After reaction, polymer is dissolved in 200ml methylene chloride, there is part
Gel is insoluble, 5% dissolving with hydrochloric acid glutaric acid zinc catalyst of 10mL is then added, and be washed with distilled water pH value and be in neutrality,
Polymer is precipitated in polymer dichloromethane solution ethyl alcohol, and 80 DEG C are dried in vacuo 24 hours, obtains 23 grams of polymer.Measure gel
Content is 0%.5% thermal decomposition temperature is 209 DEG C, and maximum thermal decomposition temperature is 236 DEG C.Stablized with hot elongation test test size
Property, condition is 60 DEG C, bear a heavy burden 0.14MPa, and measuring hot elongation percentage is 321%, permanent set 165%.
Claims (8)
1. the method for step preparation crosslinking carbon dioxide copolymer, it is characterised in that: this method comprises the following steps:
With propylene oxide EP and carbon dioxide CO2Respectively the first and second monomers, using furancarboxylic acid ethylene oxidic ester as Third monomer,
Cyclic dicarboxylic acid anhydride containing alkene is the 4th monomer, carries out polymerization reaction by catalyst of glutaric acid zinc, it is total that crosslinking carbon dioxide is made in a step
Polymers.
2. the method for step preparation crosslinking carbon dioxide copolymer according to claim 1, it is characterised in that: described penta
The molar ratio of diacid zinc and propylene oxide is 1:600~1200.
3. the method for a step according to claim 1 preparation crosslinking carbon dioxide copolymer, it is characterised in that: described the
Three, the molar ratio of the 4th monomer and propylene oxide is 0.5~3:0.5~3:100.
4. the method for step preparation crosslinking carbon dioxide copolymer according to claim 1, it is characterised in that: described is poly-
Closing reaction temperature is 55~70 DEG C.
5. the method for step preparation crosslinking carbon dioxide copolymer according to claim 1, it is characterised in that: described two
Carbonoxide initial pressure is 4.2MPa.
6. the method for step preparation crosslinking carbon dioxide copolymer according to claim 1, it is characterised in that: described is poly-
The reaction time for closing reaction is 12~24 hours.
7. the method for a step according to claim 1 preparation crosslinking carbon dioxide copolymer, it is characterised in that: described the
Three monomers are furancarboxylic acid ethylene oxidic ester.
8. the method for a step according to claim 1 preparation crosslinking carbon dioxide copolymer, it is characterised in that: described the
Four monomers are citraconic anhydride or 1,2,3,6- tetrabydrophthalic anhydride.
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Cited By (1)
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| CN110540637A (en) * | 2019-09-06 | 2019-12-06 | 岭南师范学院 | method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method |
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| CN105473637A (en) * | 2013-09-05 | 2016-04-06 | 科思创德国股份公司 | Radical crosslinking of polyether carbonate polyols that have electron-poor and electron-rich double bonds |
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| CN101440158A (en) * | 2008-12-25 | 2009-05-27 | 中国科学院长春应用化学研究所 | Furan glycidyl ether or ester-epoxypropane-CO2 copolymer and preparation thereof |
| CN105473637A (en) * | 2013-09-05 | 2016-04-06 | 科思创德国股份公司 | Radical crosslinking of polyether carbonate polyols that have electron-poor and electron-rich double bonds |
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| CN110540637A (en) * | 2019-09-06 | 2019-12-06 | 岭南师范学院 | method for preparing crosslinked polypropylene carbonate by maleic anhydride copolymer/propylene oxide/carbon dioxide copolymerization one-pot method |
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