CN115991865A - Semi-aromatic carbon dioxide-based tetrapolymer and preparation and modification methods thereof - Google Patents
Semi-aromatic carbon dioxide-based tetrapolymer and preparation and modification methods thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 51
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 51
- 229920006029 tetra-polymer Polymers 0.000 title claims abstract description 30
- 238000002715 modification method Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 64
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 150000002118 epoxides Chemical class 0.000 claims abstract description 52
- 239000003292 glue Substances 0.000 claims abstract description 20
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 42
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 42
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 20
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 14
- -1 tetra-n-butyl ammonium halide Chemical class 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 8
- 229920006238 degradable plastic Polymers 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 description 36
- 230000009477 glass transition Effects 0.000 description 23
- 238000005979 thermal decomposition reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 4
- YDLFYFXTJGGZLU-UHFFFAOYSA-N 1-fluoro-2,3,4-trimethylbenzene Chemical compound CC1=CC=C(F)C(C)=C1C YDLFYFXTJGGZLU-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920003046 tetrablock copolymer Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FESAXEDIWWXCNG-UHFFFAOYSA-N diethyl(methoxy)borane Chemical compound CCB(CC)OC FESAXEDIWWXCNG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- DWGRAWXTWKMPOT-UHFFFAOYSA-N fluoro-bis(2,3,4-trimethylphenyl)borane Chemical compound CC1=C(C(=C(C=C1)B(C1=C(C(=C(C=C1)C)C)C)F)C)C DWGRAWXTWKMPOT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- YUPAWYWJNZDARM-UHFFFAOYSA-N tri(butan-2-yl)borane Chemical compound CCC(C)B(C(C)CC)C(C)CC YUPAWYWJNZDARM-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
A semi-aromatic carbon dioxide-based tetrapolymer and a preparation and modification method thereof belong to the technical field of carbon dioxide-based degradable plastics. Four temperature-resistant structural formulas are provided, and the preparation steps are as follows: epoxide and phthalic anhydride are copolymerized in solvent by using a catalyst; introducing carbon dioxide to a reaction pressure of 0.13-4.0 MPa, adding a catalyst II for continuous copolymerization, adding epoxide and phthalic anhydride after pressure relief, adding a catalyst III, and copolymerizing to obtain a glue solution; washing and devolatilizing to obtain the product. Solves the problem of poor temperature resistance of the prior PPCEP. And further provides a crosslinking modification method, which further improves the temperature resistance and the dimensional stability.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide-based degradable plastics, and particularly relates to a semi-aromatic carbon dioxide-based tetrapolymer.
Background
The traditional plastic materials such as polyethylene, polypropylene and the like are difficult to degrade, and serious white pollution is caused by entering the environment after being abandoned, so that the plastic materials are limited in the fields of disposable plastics and the like which are difficult to recycle and repeated application, and the requirement of replacing the traditional plastics with the fully-degradable plastic materials in the application fields is urgent.
Propylene oxide and carbon dioxide copolymerizationThe generated polymethyl ethylene carbonate (PPC) is transparent and completely degradable environment-friendly plastic, the tensile strain at break is 600% -1200%, but the glass transition temperature is lower (T) g =30 to 40 ℃). The Chinese patent publication No. CN111378101A discloses a terpolymer of propylene oxide, phthalic anhydride and carbon dioxide, which can raise the glass transition temperature (T) based on PPC g =40 to 50 ℃), but its toughness is poor.
In order to make up for the performance defect of the existing carbon dioxide-based degradable plastic, flexible monomer ethylene oxide is introduced on the basis of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer to prepare the ethylene oxide-propylene oxide-phthalic anhydride-carbon dioxide tetrapolymer, and the water-blocking and oxygen-blocking performances are better and the thermal and mechanical properties can be better compatible on the premise of ensuring biodegradability and transparency. The existing PPCEP is synthesized into a random structure by a one-pot one-step synthesis method: putting propylene oxide, ethylene oxide, phthalic anhydride and a catalyst into a high-pressure reactor with stirring according to a proportion under a dry near-anaerobic condition, charging carbon dioxide to a certain pressure, reacting at a certain temperature, terminating the reaction after the reaction is finished, and washing, devolatilizing and drying to obtain PPCEP. The random structural general formula of PPCEP is:
wherein:
a is more than or equal to 1 and less than or equal to 5000, b is more than or equal to 1 and less than or equal to 5000, c is more than or equal to 1 and less than or equal to 10000, d is more than or equal to 1 and less than or equal to 10000,0, e is more than or equal to 1 and less than or equal to 1000,0, f is more than or equal to 1000,0 and g is more than or equal to 1000, and a, b, c, d, e, f, g are integers.
However, PPCEP has a low thermal decomposition temperature and a low temperature resistance due to the addition of ethylene oxide, so that the use of ethylene oxide-propylene oxide-phthalic anhydride-carbon dioxide tetrapolymer is limited.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a temperature-resistant semi-aromatic carbon dioxide-based quadripolymer with high thermal decomposition temperature and a preparation and modification method thereof.
The technical scheme adopted for solving the technical problems is as follows: the temperature-resistant semi-aromatic carbon dioxide-based quadripolymer is characterized in that the structural formula at least comprises one of the following four types:
formula (1):
in the formula (1), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to 300, d is more than or equal to 1 and less than or equal to 8000, e is more than or equal to 1 and less than or equal to 4000, f is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e, f, g are integers;
formula (2):
in the formula (2), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to 300, d is more than or equal to 1 and less than or equal to 8000, e is more than or equal to 1 and less than or equal to 4000, f is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e, f are integers;
formula (3):
in the formula (3), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to c is more than or equal to 300, d is more than or equal to 1 and less than or equal to 4000, e is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e are integers;
formula (4):
in the formula (4), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to c is more than or equal to 300, d is more than or equal to 1 and less than or equal to 4000, e is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e are integers.
Compared with the prior PPCEP copolymer, the copolymer of the invention has the advantages of maintaining original degradability, transparency, water resistance, oxygen resistance and mechanical property, having higher glass transition temperature and thermal decomposition temperature and obviously improving the temperature resistance of the PPCET copolymer under the condition of better temperature resistance and similar molecular weight.
Preferably, the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer comprises the following steps:
1) Putting epoxide, phthalic anhydride, a catalyst I and a solvent into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is (1.5-5) 1, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is (0.5-5) 1; heating to a reaction temperature of 40-100 ℃ for reaction;
2) After phthalic anhydride is completely reacted, adding a catalyst II, introducing carbon dioxide to a reaction pressure of 0.13-4.0 MPa, keeping the reaction temperature, continuing to react until propylene oxide and ethylene oxide are completely reacted, and cooling and decompressing;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride with the amounts of 20% -35% of the respective amounts in the step 1) again, adding the catalyst III, heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain the glue solution; washing and devolatilizing the glue solution to obtain the product.
The invention provides a PPCEP copolymer with a high-temperature resistant block structure synthesized by a one-pot multi-step method, which comprises the steps of firstly carrying out ternary polymerization of epoxide and phthalic anhydride under the condition of no carbon dioxide to obtain a required molecular chain segment, then introducing carbon dioxide to carry out ternary polymerization of the epoxide and the carbon dioxide, adjusting the molecular structure, finally emptying the carbon dioxide, and continuing carrying out ternary polymerization end capping of the epoxide and the phthalic anhydride.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the solvent in the step 1) is 2-methyltetrahydrofuran, tetrahydrofuran or n-butyl ether. In the preparation method, a proper solvent is selected to provide a polymerization environment, so that the average distribution of the molecular chain length is facilitated, and the PPCEP copolymer with more stable performance is obtained. More preferably, the solvent in step 1) is tetrahydrofuran.
The invention can match with the molecular structure design of the multi-step polymerization awakening copolymer by means of catalyst collocation, material proportioning and the like, and can further improve the proportion of the structural formulas of the formulas (1), (2), (3) and (4) in the obtained copolymer by adjusting the catalyst collocation and the material proportioning, thereby better improving the temperature resistance of the product.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the molar ratio of the epoxide to the phthalic anhydride in the step 1) is (2.0-3.5): 1. The preferable material ratio can better control the molecular structure, reduce the self-polymerization reaction of byproducts and ensure the duty ratio of target products in the product.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the molar ratio of the propylene oxide to the ethylene oxide in the step 1) is (1.2-3.5): 1. The preferable ratio of propylene oxide to ethylene oxide is mainly used for adjusting the transparency, mechanical properties and other basic properties of PPCEP, and the high transparency and mechanical properties of PPCEP are maintained after the molecular structure is adjusted.
Specifically, the first catalyst, the second catalyst and the third catalyst are all nonmetallic catalysts, and the composite catalyst formed by the coordination of Lewis acid/alkali pairs is more. Wherein the Lewis acid comprises one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, and bis (trimethylphenyl) boron fluoride. The lewis base includes one or more of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide, tetra-n-propyl ammonium iodide, bis (triphenylphosphine) ammonium chloride.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the catalyst I in the step 1) is a composite catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:3-7; the catalyst II in the step 2) is triethylboron; the catalyst III in the step 3) is tetra-n-butyl ammonium chloride. The invention provides a preferable scheme of collocating the catalyst in each step, which is more beneficial to the copolymerization reaction in each stage to be carried out to the target product, and the duty ratio of the target product in the obtained copolymer is higher.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the molar ratio of the catalyst I to phthalic anhydride in the step 1) is 1:150-400; the molar ratio of the second catalyst in the step 2) to the epoxide in the step 1) is 1:800-1000; the molar ratio of the catalyst III added in the step 3) to the phthalic anhydride added again is 1:700-1500. The method realizes the adjustment of the reaction rate of copolymerization through the change of the dosage of the catalyst, further adjusts the molecular weight of the obtained copolymer and influences the molecular chain sequencing, and under the copolymerization system of the invention, the molecular weight of the copolymer obtained by the addition of the catalyst can meet the requirement of mechanical properties, and the proportion of the copolymer with the target structural formula is higher.
More preferably, the molar ratio of the catalyst I to phthalic anhydride in the step 1) is 1:200-300; the molar ratio of the second catalyst in the step 2) to the epoxide in the step 1) is 1:900-980; the molar ratio of the catalyst III added in the step 3) to the phthalic anhydride added again is 1:1200-1400. Under the more preferable catalyst dosage and other preferable process conditions, the transparency, mechanical property and temperature resistance of the prepared tetrapolymer reach the optimal state of the invention.
Preferably, in the preparation method of the temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer, the reaction temperature is 70-90 ℃, and the reaction pressure is 1.3-1.8 MPa. The reaction temperature and the reaction pressure also affect the reaction rate of the copolymerization, and the mechanical properties and the temperature resistance of the copolymer obtained at the preferable temperature and pressure are more exhibited.
A modification method of the temperature-resistant semi-aromatic carbon dioxide-based quadripolymer comprises the step 3) of adding a crosslinking agent into the preparation method for copolymerization. After the PPCEP molecular chain is added with the cross-linking agent, the PPCEP molecular chain can be interwoven into a net structure, and the temperature resistance and the dimensional stability of the molecule can be further improved.
Preferably, the method for modifying the heat-resistant semi-aromatic carbon dioxide-based tetrapolymer is characterized in that the cross-linking agent is one or more than two of maleic anhydride, pentaerythritol tripropylester, tetrahydrophthalic anhydride, pyromellitic anhydride, trimethylpropane triacrylate, toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), diisopropyl peroxide, polyethylene glycol dimethyl methacrylate, polyethylene polyphenyl isocyanate, allyl glycidyl ether or furan methyl glycidyl ether. The cross-linking agent can meet the cross-linking requirement of the invention, and the cross-linking agent can cross-link PPCEP molecular chains, thereby improving the temperature resistance and the dimensional stability of the molecules.
Preferably, the cross-linking agent is one or more of maleic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, toluene Diisocyanate (TDI), 4 '-diphenylmethane diisocyanate (MDI) and allyl glycidyl ether, and more preferably, the cross-linking agent is one or more of tetrahydrophthalic anhydride, pyromellitic anhydride, toluene Diisocyanate (TDI) and 4, 4' -diphenylmethane diisocyanate (MDI). When the preferred cross-linking agent is cross-linked in the PPCEP molecular chain, cross-linking nodes are uniformly distributed, and a cross-linked product shows better temperature resistance and dimensional stability. The crosslinker is more preferably pyromellitic anhydride, which after use achieves the best performance of the invention.
Preferably, the crosslinking agent is added in the following amount: the molar ratio of the cross-linking agent to the epoxide in the step 1) is 1:100-600. The cross-linking node density distribution obtained by the preferred cross-linking agent is more proper, and the cross-linking modified PPCEP can maintain better transparency while improving the temperature resistance and mechanical properties.
Preferably, the structural general formula of the pyromellitic anhydride cross-linked modified PPCEP copolymer is shown as formula (5);
formula (5):
wherein:
1-4000 a, 1-4000 b, 1-1200,1 d-1200,1 e-8000,1 f-8000,0 g-1000,0 h-1000,0 i-1000 and a, b, c, d, e, f, g, h, i are integers.
Compared with the prior art, the semi-aromatic carbon dioxide-based tetrapolymer and the preparation and modification methods thereof have the following beneficial effects: the invention provides a high-temperature resistant molecular structure of an ethylene oxide-propylene oxide-phthalic anhydride-carbon dioxide tetrapolymer, provides a preparation method with high yield of target products, and solves the problem of poor temperature resistance of the existing PPCEP. And further provides a crosslinking modification method, which further improves the temperature resistance and the dimensional stability. The invention improves the temperature resistance of the ethylene oxide-propylene oxide-phthalic anhydride-carbon dioxide tetrapolymer by adding a cross-linking agent, synthesizing a temperature resistant sequence structure and the like, and further widens the application range. The temperature-resistant PPCEP has good processing performance after being singly or mixed with other materials, can be used for processing technologies such as film blowing, casting, calendaring, injection molding, blow molding, plastic sucking, biaxial stretching, foaming and the like, and can be widely applied to plastic films, bags, sheets, foaming products, hollow containers and the like.
Drawings
FIG. 1 is a cross-linking structure diagram of PPCEP prepared by cross-linking modification of a temperature-resistant semi-aromatic carbon dioxide-based tetrapolymer.
FIG. 2 is a nuclear magnetic resonance spectrum of example 2 of the present invention.
FIG. 3 is a nuclear magnetic resonance spectrum of example 4 of the present invention.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, a compound catalyst of tetra-n-butyl ammonium chloride and triethylboron according to a molar ratio of 1:5 and tetrahydrofuran into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is 2.5:1, the molar ratio of the compound catalyst to the phthalic anhydride is 1:250, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 2.2:1; heating to a reaction temperature of 80 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding triethylboron, wherein the molar ratio of the triethylboron to the epoxide in the step 1) is 1:940; introducing carbon dioxide to a reaction pressure of 1.5MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 28% of each of the step 1) again, and adding a compound catalyst of tetra-n-butyl ammonium chloride in a molar ratio of 1:8, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the phthalic anhydride added again is 1:1300; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 93.4%.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that pyromellitic anhydride is also added in step 3) for copolymerization, and the molar ratio of pyromellitic anhydride to epoxide in step 1) is 1:350.
Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=1.56×10 5 g/mol/2.09, glass transition temperature (T g ) =44.3 ℃, thermal decomposition temperature (T 5% ）=269℃。
Example 2
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, a compound catalyst of tetra-n-butyl ammonium chloride and triethylboron according to a molar ratio of 1:3 and tetrahydrofuran into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is 3.5:1, the molar ratio of the compound catalyst to the phthalic anhydride is 1:300, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 3.5:1; heating to a reaction temperature of 90 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding triethylboron, wherein the molar ratio of the triethylboron to the epoxide in the step 1) is 1:900; introducing carbon dioxide to a reaction pressure of 1.8MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 30% of each of the step 1) again, and adding tetra-n-butyl ammonium chloride, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the phthalic anhydride added again is 1:1400; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 92.1 percent.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that pyromellitic anhydride is also added in step 3) for copolymerization, and the molar ratio of the added pyromellitic anhydride to the epoxide in step 1) is 1:100.
Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=1.51×10 5 g/mol/2.09, glass transition temperature (T g ) =41.4 ℃, thermal decomposition temperature (T 5% ）=265℃。
Example 3
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, a composite catalyst of tetra-n-butyl ammonium bromide and triethylboron in a molar ratio of 1:7 and tetrahydrofuran into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is 2.0:1, the molar ratio of the composite catalyst to the phthalic anhydride is 1:200, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 1.2:1; heating to 70 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding triethylboron, wherein the mole ratio of the triethylboron to the epoxide in the step 1) is 1:980; introducing carbon dioxide to a reaction pressure of 1.3MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 25% of each of the step 1) again, and adding tetra-n-butyl ammonium chloride, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the phthalic anhydride added again is 1:1200; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 91.7%.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that pyromellitic anhydride is also added in step 3) for copolymerization, and the molar ratio of the added pyromellitic anhydride to the epoxide in step 1) is 1:600.
Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=1.59×10 5 g/mol/2.09, glass transition temperature (T g ) =43.4 ℃, thermal decomposition temperature (T 5% ）=267℃。
Example 4
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, tetra-n-butyl ammonium chloride and tris (pentafluorophenyl) boron into a high-pressure reaction kettle according to a molar ratio of 1:2 of a composite catalyst and tetrahydrofuran, wherein the molar ratio of the epoxide to the phthalic anhydride is 2.5:1, the molar ratio of the composite catalyst to the phthalic anhydride is 1:1000, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 2.2:1; heating to a reaction temperature of 80 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding tris (pentafluorophenyl) boron, wherein the molar ratio of the tris (pentafluorophenyl) boron to the epoxide in the step 1) is 1:300; introducing carbon dioxide to a reaction pressure of 1.5MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 28% of each of the step 1) again, and adding a compound catalyst of tetra-n-butyl ammonium chloride in a molar ratio of 1:8, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the phthalic anhydride added again is 1:600; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 84.2 percent.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that pyromellitic anhydride is also added in step 3) for copolymerization, and the molar ratio of pyromellitic anhydride to epoxide in step 1) is 1:350.
Analyzing the molecular weight by a Gel Permeation Chromatograph (GPC), the glass transition temperature by a Differential Scanning Calorimeter (DSC), and the thermal decomposition temperature by a thermogravimetric analyzer (TG), and analyzing the molecular weight by a Gel Permeation Chromatograph (GPC), the glass transition temperature by a Differential Scanning Calorimeter (DSC), and the thermal decomposition temperature by a thermogravimetric analyzer (TG), thereby obtaining M n /PDI=1.64×10 5 g/mol/3.33, glass transition temperature (T g ) =36.8deg.C, thermal decomposition temperature (T 5% ）=246℃。
Example 5
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, a compound catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:5 and n-butyl ether into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is 1.5:1, the molar ratio of the compound catalyst to the phthalic anhydride is 1:250, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 0.5:1; heating to 40 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding triethylboron, wherein the molar ratio of the triethylboron to the epoxide in the step 1) is 1:950; introducing carbon dioxide to a reaction pressure of 0.13MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 28% of each of the step 1) again, and adding tetra-n-butyl ammonium chloride, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the phthalic anhydride added again is 1:1300; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 87.1 percent.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that a cross-linking agent is also added in step 3) for copolymerization, wherein the cross-linking agent is one or more than two compounds in any proportion in tetrahydrophthalic anhydride. The molar ratio of crosslinker added to epoxide in step 1) was 1:100.
Analyzing the molecular weight by a Gel Permeation Chromatograph (GPC), the glass transition temperature by a Differential Scanning Calorimeter (DSC), and the thermal decomposition temperature by a thermogravimetric analyzer (TG), and analyzing the molecular weight by a Gel Permeation Chromatograph (GPC), the glass transition temperature by a Differential Scanning Calorimeter (DSC), and the thermal decomposition temperature by a thermogravimetric analyzer (TG), thereby obtaining M n /PDI=1.67×10 5 g/mol/3.33, glass transition temperature (T g ) Heat split at 39.4 =Solution temperature (T) 5% ）=251℃。
Example 6
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, tetra-n-propyl ammonium fluoride and boron bis (trimethylphenyl) fluoride into a high-pressure reaction kettle according to a molar ratio of 2:1 of a composite catalyst and n-butyl ether, wherein the molar ratio of the epoxide to the phthalic anhydride is 1.5:1, the molar ratio of the composite catalyst to the phthalic anhydride is 1:150, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 0.5:1; heating to 40 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding boron bis (trimethylphenyl) fluoride, wherein the molar ratio of the boron bis (trimethylphenyl) fluoride to the epoxide in the step 1) is 1:800; introducing carbon dioxide to a reaction pressure of 0.13MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride in the amount of 20% of each of the step 1) again, and adding tetra-n-propyl ammonium fluoride, wherein the molar ratio of the tetra-n-propyl ammonium fluoride to the added phthalic anhydride is 1:700; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 83.3 percent.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same as above except that a cross-linking agent is also added in step 3) for copolymerization, wherein the cross-linking agent is 4, 4' -diphenylmethane diisocyanate. The molar ratio of crosslinker added to epoxide in step 1) was 1:100.
Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=1.12×10 5 g/mol/2.20, glass transition temperature (T g ) =37.6 ℃, thermal decomposition temperature（T 5% ）=248℃。
Example 7
Preparation of the copolymer
1) Putting epoxide, phthalic anhydride, tetra-n-butyl ammonium chloride, tetra-n-propyl ammonium fluoride and triethylboron into a high-pressure reaction kettle according to a molar ratio of 1:1:10 of a composite catalyst and 2-methyltetrahydrofuran, wherein the molar ratio of the epoxide to the phthalic anhydride is 5:1, the molar ratio of the composite catalyst to the phthalic anhydride is 1:400, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is 5:1; heating to 100 ℃ for reaction;
2) After the phthalic anhydride is completely reacted, adding triethylboron, wherein the molar ratio of the triethylboron to the epoxide in the step 1) is 1:1000; introducing carbon dioxide to a reaction pressure of 4.0MPa, keeping the reaction temperature, continuing to react until the epoxypropane and the epoxyethane are completely reacted, and cooling and pressure relief;
3) Adding 35% of the propylene oxide, the ethylene oxide and the phthalic anhydride in the step 1) again, and adding tetra-n-butyl ammonium chloride, wherein the molar ratio of the tetra-n-butyl ammonium chloride to the added phthalic anhydride is 1:1500; heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain glue solution; the glue solution is obtained after washing and devolatilization, and the mass percentage content of the components in the obtained copolymer with the structural formulas of formula (1), formula (2), formula (3) and/or formula (4) is 81.9 percent.
Preparation of crosslinked modified copolymers
Step 1) and step 2) are the same, except that a cross-linking agent is also added in step 3) for copolymerization, wherein the cross-linking agent is one or more than two of toluene diisocyanate in any proportion. The molar ratio of crosslinker added to epoxide in step 1) was 1:600.
Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=9.84×10 4 g/mol/2.17, glass transition temperature (T g ）=29.8 ℃, thermal decomposition temperature (T) 5% ）=218℃。
Comparative example 1
And (3) in a dry kettle, replacing air in the kettle with inert gas (high-purity argon, nitrogen or carbon dioxide), starting feeding, feeding the total amount of the materials in the steps 1) to 3) in the embodiment 1 into a high-pressure reaction kettle, charging carbon dioxide to 1.5MPa, reacting for 4.5 hours at 75 ℃, cooling, decompressing, terminating the reaction, dissolving the generated glue solution with dichloroethane, precipitating with ethanol, separating out, devolatilizing, granulating and drying to obtain the finished product of the epoxypropane-epoxyethane-phthalic anhydride-carbon dioxide tetrapolymer. Analyzing molecular weight by Gel Permeation Chromatograph (GPC), glass transition temperature by Differential Scanning Calorimeter (DSC), thermal decomposition temperature by thermogravimetric analyzer (TG), and obtaining M n /PDI=8.07×10 4 g/mol/2.21, glass transition temperature (T g ) =35.3 ℃, thermal decomposition temperature (T 5% ）=240℃。
Performance test, if no special description exists, the data of the performance test are determined according to relevant national security standards, such as:
1) Molecular weight: the molecular weight of the polymer was analyzed by GPC, see method "GB/T31124-2014 appendix B".
2) Glass transition temperature (T) g ): according to GB/T19466.2.
3) Thermal decomposition temperature (T5%): according to the method of national standard GB/T33047.1.
4) Elongation at break and tensile strength: according to GB/T1040.3.
In addition, the molecular weight, the glass transition temperature, the thermal decomposition temperature, the elongation at break and the tensile strength are the performance parameters of the samples obtained in the preparation of the copolymers in the examples and the comparative examples, and the dimensional stability is the volume shrinkage ratio of the crosslinked and modified material samples at 25-75 ℃.
The properties of the copolymers prepared in examples 1 to 7 according to the invention and comparative example 1 are shown in Table 1:
table 1 sample performance index table
Therefore, the structure formed by the tetrablock copolymer and the cross-linking agent has higher temperature resistance than that of a random chain structure, so that the temperature resistance of the epoxypropane-epoxyethane-phthalic anhydride-carbon dioxide tetrablock copolymer is greatly improved, and the application of the tetrablock copolymer is wider.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A semiaromatic carbon dioxide-based tetrapolymer, characterized by a structural formula comprising at least one of the following four:
formula (1):
in the formula (1), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to 300, d is more than or equal to 1 and less than or equal to 8000, e is more than or equal to 1 and less than or equal to 4000, f is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e, f, g are integers;
formula (2):
in the formula (2), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to 300, d is more than or equal to 1 and less than or equal to 8000, e is more than or equal to 1 and less than or equal to 4000, f is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e, f are integers;
formula (3):
in the formula (3), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to c is more than or equal to 300, d is more than or equal to 1 and less than or equal to 4000, e is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e are integers;
formula (4):
in the formula (4), a is more than or equal to 1 and less than or equal to 4000, b is more than or equal to 1 and less than or equal to 8000,0 and less than or equal to c is more than or equal to 300, d is more than or equal to 1 and less than or equal to 4000, e is more than or equal to 0 and less than or equal to 300, and a, b, c, d, e are integers.
2. A method for preparing a semiaromatic carbon dioxide-based tetrapolymer according to claim 1, comprising the steps of:
1) Putting epoxide, phthalic anhydride, a catalyst I and a solvent into a high-pressure reaction kettle, wherein the molar ratio of the epoxide to the phthalic anhydride is (1.5-5) 1, the epoxide is propylene oxide and ethylene oxide, and the molar ratio of the propylene oxide to the ethylene oxide is (0.5-5) 1; heating to a reaction temperature of 40-100 ℃ for reaction;
2) After phthalic anhydride is completely reacted, adding a catalyst II, introducing carbon dioxide to a reaction pressure of 0.13-4.0 MPa, keeping the reaction temperature, continuing to react until propylene oxide and ethylene oxide are completely reacted, and cooling and decompressing;
3) Adding the propylene oxide, the ethylene oxide and the phthalic anhydride with the amounts of 20% -35% of the respective amounts in the step 1) again, adding the catalyst III, heating to the reaction temperature again for reaction, and stopping the reaction after the monomer reaction is completed to obtain the glue solution; washing and devolatilizing the glue solution to obtain the product.
3. The method for preparing the semi-aromatic carbon dioxide-based tetrapolymer according to claim 2, wherein the method comprises the following steps: the solvent in the step 1) is 2-methyltetrahydrofuran, tetrahydrofuran and n-butyl ether.
4. The method for preparing the semi-aromatic carbon dioxide-based tetrapolymer according to claim 2, wherein the method comprises the following steps: the molar ratio of the epoxide to the phthalic anhydride in the step 1) is (2.0-3.5): 1.
5. The method for preparing the semi-aromatic carbon dioxide-based tetrapolymer according to claim 2, wherein the method comprises the following steps: the molar ratio of the propylene oxide to the ethylene oxide in the step 1) is (1.2-3.5): 1.
6. The method for preparing the semi-aromatic carbon dioxide-based tetrapolymer according to claim 2, wherein the method comprises the following steps: the catalyst I in the step 1) is a composite catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:3-7; the catalyst II in the step 2) is triethylboron; the catalyst III in the step 3) is tetra-n-butyl ammonium chloride.
7. The method for producing a semiaromatic carbon dioxide-based tetrapolymer according to claim 2 or 6, characterized in that: the molar ratio of the catalyst I to phthalic anhydride in the step 1) is 1:150-400; the molar ratio of the second catalyst in the step 2) to the epoxide in the step 1) is 1:800-1000; the molar ratio of the catalyst III added in the step 3) to the phthalic anhydride added again is 1:700-1500.
8. The method for preparing the semi-aromatic carbon dioxide-based tetrapolymer according to claim 2, wherein the method comprises the following steps: the reaction temperature is 70-90 ℃, and the reaction pressure is 1.3-1.8 MPa.
9. A modification method of a semi-aromatic carbon dioxide-based tetrapolymer is characterized by comprising the following steps of: the step 3) of claim 2 wherein a cross-linking agent is added for copolymerization.
10. The method for modifying a semiaromatic carbon dioxide-based tetrapolymer according to claim 9, wherein the crosslinking agent is one or more of maleic anhydride, pentaerythritol tripropylester, tetrahydrophthalic anhydride, pyromellitic anhydride, trimethylpropane triacrylate, toluene diisocyanate, 4' -diphenylmethane diisocyanate, diisopropyl peroxide, polyethylene glycol dimethyl methacrylate, polyethylene polyphenyl isocyanate, allyl glycidyl ether or furan methyl glycidyl ether.
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| CN116333279A (en) * | 2023-05-29 | 2023-06-27 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
| CN116333279B (en) * | 2023-05-29 | 2024-04-12 | 山东联欣环保科技有限公司 | Polycarbonate toughening resin |
| CN117024941A (en) * | 2023-10-08 | 2023-11-10 | 山东联欣环保科技有限公司 | Carbon dioxide-based biodegradable barrier composition |
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