CN115926032A - Polar polyolefin copolymer containing biomass group and preparation method thereof - Google Patents
Polar polyolefin copolymer containing biomass group and preparation method thereof Download PDFInfo
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- CN115926032A CN115926032A CN202211553447.2A CN202211553447A CN115926032A CN 115926032 A CN115926032 A CN 115926032A CN 202211553447 A CN202211553447 A CN 202211553447A CN 115926032 A CN115926032 A CN 115926032A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 61
- 239000002028 Biomass Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 51
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 17
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 15
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 15
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 15
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 14
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims abstract description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 14
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- RHBGITBPARBDPH-UHFFFAOYSA-N (2E,4E)-5-(3,4-methylenedioxyphenyl)-2,4-pentadienoic acid Natural products OC(=O)C=CC=CC1=CC=C2OCOC2=C1 RHBGITBPARBDPH-UHFFFAOYSA-N 0.000 claims abstract description 7
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims abstract description 7
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims abstract description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 claims abstract description 7
- RHBGITBPARBDPH-ZPUQHVIOSA-N (E,E)-piperic acid Chemical compound OC(=O)\C=C\C=C\C1=CC=C2OCOC2=C1 RHBGITBPARBDPH-ZPUQHVIOSA-N 0.000 claims abstract description 7
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims abstract description 7
- 239000005642 Oleic acid Substances 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000021319 Palmitoleic acid Nutrition 0.000 claims abstract description 7
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims abstract description 7
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims abstract description 7
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims abstract description 7
- 235000013985 cinnamic acid Nutrition 0.000 claims abstract description 7
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 7
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims abstract description 7
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 claims abstract description 7
- 235000001785 ferulic acid Nutrition 0.000 claims abstract description 7
- 229940114124 ferulic acid Drugs 0.000 claims abstract description 7
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940074391 gallic acid Drugs 0.000 claims abstract description 7
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960004488 linolenic acid Drugs 0.000 claims abstract description 7
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims abstract description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 7
- 229960002969 oleic acid Drugs 0.000 claims abstract description 7
- 235000021313 oleic acid Nutrition 0.000 claims abstract description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 7
- WVWHRXVVAYXKDE-UHFFFAOYSA-N piperine Natural products O=C(C=CC=Cc1ccc2OCOc2c1)C3CCCCN3 WVWHRXVVAYXKDE-UHFFFAOYSA-N 0.000 claims abstract description 7
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims abstract description 7
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 7
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 7
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 claims abstract description 7
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 claims abstract description 7
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000007334 copolymerization reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- KNDQHSIWLOJIGP-RNGGSSJXSA-N (3ar,4r,7s,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound C1[C@@H]2[C@@H]3C(=O)OC(=O)[C@@H]3[C@H]1C=C2 KNDQHSIWLOJIGP-RNGGSSJXSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 150000002848 norbornenes Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical group CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a polar polyolefin copolymer containing biomass groups and a preparation method thereof, wherein comonomers adopted by the polar polyolefin copolymer containing the biomass groups comprise: ethylene and the first comonomer are of the formula
Description
Technical Field
The invention relates to the field of functional high-molecular polyolefin materials, in particular to a polar polyolefin copolymer containing a biomass group and a preparation method thereof.
Background
Polyolefins, one of the most common polymeric materials, have polymerized monomers that are typically extracted from petroleum-based chemicals. However, the increasing consumption of fossil fuels has stimulated an urgent need for renewable biomass resources. Also, conventional polyolefin materials, such as polyethylene and polypropylene, are non-polar, which limits the applications of polyolefin materials. Therefore, copolymerizing biomass-based monomers with conventional olefins to replace a portion of the petroleum-based components in polyolefins with biomass components is a two-purpose process. The demand of petroleum-based olefin monomers is reduced, and the obtained polyolefin material has polarity so as to expand the application of the polyolefin material.
Disclosure of Invention
In view of the above, the present invention provides a polar polyolefin copolymer containing biomass groups and a preparation method thereof, so as to at least partially solve the above technical problems.
In order to achieve the above objects, in one aspect, the present invention provides a biomass group-containing polar polyolefin copolymer using comonomers including: ethylene and the first comonomer are of the formula
The norbornene polar monomer is represented by the general formula (I), wherein X-OH and Y-OH are respectively corresponding alcohol compounds obtained by reduction of biological hyaluronic acid, and the biological hyaluronic acid comprises at least one of the following components: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid or salicylic acid.
According to an embodiment of the present invention, wherein
The norbornene polar monomer includes one of the following isomers: />
(endo ) isomer and/or sugar>
(inner, outer) isomer or->
(exo ) isomers.
According to an embodiment of the present invention, wherein the (endo ) isomer is obtained by alcoholysis of endo nadic anhydride with the corresponding alcohol compound; the (exo ) isomer is obtained by alcoholysis reaction of exo nadic anhydride and corresponding alcohol compound; the (endo, exo) isomer is obtained from the (endo, exo) isomer by isomerization.
According to the embodiment of the invention, the polymerization degree of the polar polyolefin copolymer containing biomass groups is 50 to 5000.
According to an embodiment of the present invention, wherein the biomass group containing polar polyolefin copolymer has a number average molecular weight of greater than or equal to 60000.
In another aspect, the present invention further provides a preparation method of the above polar polyolefin copolymer containing biomass groups, comprising: carrying out copolymerization reaction on a comonomer under the preset condition in the presence of an organic solvent and a catalyst to obtain a polar polyolefin copolymer containing a biomass group;
wherein the comonomer comprises ethylene monomer and first comonomer, the first comonomer is represented by formula
The norbornene polar monomer is represented by the general formula (I), wherein X-OH and Y-OH are respectively corresponding alcohol compounds obtained by reduction of biological hyaluronic acid, and the biological hyaluronic acid comprises at least one of the following components: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid, or salicylic acid; the catalyst comprises at least one of the following: />
According to the embodiment of the invention, the concentration of the catalyst is 0.1-10 mmol/L; the concentration of the first comonomer is 0.01-2 mol/L.
According to an embodiment of the present invention, wherein the organic solvent comprises at least one of: toluene, xylene, chlorobenzene, n-hexane, n-heptane, methylcyclohexane.
According to an embodiment of the present invention, wherein the preset conditions include: the reaction temperature of the copolymerization reaction is 40-120 ℃, the reaction time is 0.1-12 h, and the reaction pressure is 1-30 atmospheric pressures.
According to an embodiment of the present invention, wherein the reaction temperature of the copolymerization reaction is provided by a water bath heating or oil bath heating system.
Based on the technical scheme, compared with the prior art, the polar polyolefin copolymer containing the biomass group and the preparation method thereof provided by the invention have at least one of the following technical effects:
(1) Compared with the prior copolymer with low polymer molecular weight, the polar polyolefin copolymer containing biomass groups provided by the invention has high polymer molecular weight and number average molecular weight (M) n ) Up to 188000.
(2) The first copolymerization monomer used in the copolymerization reaction of the invention has bifunctional groups, thereby improving the content of biomass groups in polar polyolefin, and the mass insertion ratio of the first copolymerization monomer can reach more than 80 percent, so that the content of the biomass groups can be regulated and controlled in a large range.
(3) The first comonomer used in the copolymerization reaction of the invention contains polar functional groups, and the nonpolar characteristic of the polyolefin can be greatly improved by a large amount of monomer insertions.
(4) Compared with the common metal catalyst which catalyzes the copolymerization reaction of ethylene and polar monomer and has the characteristics of low activity and low molecular weight, the copolymerization reaction for preparing the polar polyolefin copolymer containing the biomass group has high activity, and the activity can reach 10 6 g·mol -1 ·h -1 The obtained polar polyolefin copolymer containing biomass groups has high molecular weight which can reach 188,000 g.mol -1 。
(5) The polar polyolefin copolymer containing biomass groups provided by the invention can be simply and effectively prepared in the presence of a specific PO-Pd catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
In the related art, conventional polyolefins are generally prepared from olefin monomers extracted from petroleum-based chemicals, and the polyolefins are non-polar. Based on this, the technicians in the field can carry out copolymerization reaction on the biomass-based monomer and the traditional olefin, thereby not only reducing the demand on petroleum-based olefin monomer, but also enabling the obtained polyolefin material to have polarity so as to expand the application of the polyolefin material.
In one aspect, the present invention provides a biomass group-containing polar polyolefin copolymer, wherein comonomers used in the biomass group-containing polar polyolefin copolymer may include an ethylene monomer and a first comonomer.
According to embodiments of the present invention, the first comonomer may be of the formula
The norbornene-type polar monomer is represented.
According to an embodiment of the present invention, the formula
X-OH and Y-OH in the norbornene polar monomer are respectively corresponding alcohol compounds obtained by reduction of biological hyaluronic acid.
According to embodiments of the invention, the biological acid may comprise at least one of: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid, or salicylic acid.
According to an embodiment of the invention, X-OH and Y-OH may represent alcohol compounds corresponding to the formation of ester bonds COOX and COOY, -OH represents a hydroxyl function. X-OH and Y-OH are used for respectively representing groups of X and Y, so that the expression is clearer, simpler and unambiguous.
According to an embodiment of the present invention, the formula
The norbornene-type polar monomer represented may include one of the following isomers: />
(the inner type of the mold, endo) isomers device for selecting or keeping>
(endo, exo) isomer or
(exo ) isomers.
According to an embodiment of the invention, the groups COOX and COOY are of the formula
The designation of norbornene-attached chemical bond "/" or "\" is not intended to refer to either a dashed wedge line or a solid wedge line, but rather to indicate that the attached COOX or COOY group may be positioned either endo or exo, e.g., a solid wedge line @>
Indicates an inner type, wedge-shaped broken line->
Showing the outer shape.
According to the embodiment of the invention, the (endo ) isomer is obtained by alcoholysis reaction of endo nadic anhydride and corresponding alcohol compound; the (exo ) isomer is obtained by alcoholysis reaction of an alcohol slow compound corresponding to exo nadic anhydride; the (endo, exo) isomer is obtained from the (endo, exo) isomer by isomerization.
According to an embodiment of the present invention, the polymerization degree of the polar polyolefin copolymer containing a biomass group may be 50 to 5000.
According to embodiments of the present invention, the biomass group-containing polar polyolefin copolymer may have a number average molecular weight of greater than or equal to 60000, and may be up to 188000.
In another aspect, the present invention also provides a method for preparing the above polar polyolefin copolymer containing biomass groups, which may include: and in the presence of an organic solvent and a catalyst, reducing the comonomer under a preset condition to carry out copolymerization reaction to obtain the polar polyolefin copolymer containing the biomass group.
According to embodiments of the present invention, the comonomer may include ethylene monomerAnd a first comonomer. The first comonomer may be a copolymer of
The norbornene-type polar monomer is shown.
According to an embodiment of the invention, the method comprises
In the norbornene polar monomer, X-OH and Y-OH are corresponding alcohol compounds obtained by reduction of biological hyaluronic acid, and the biological hyaluronic acid comprises at least one of the following: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid, or salicylic acid.
According to embodiments of the invention, the catalyst may comprise at least one of:
according to the embodiment of the invention, the concentration of the catalyst can be 0.1-10 mmol/L; the concentration of the first comonomer may be 0.01 to 2mol/L.
According to the embodiment of the present invention, the concentration of the catalyst may be 0.1mmol/L, 1.0mmol/L, 2.0mmol/L, 3.0mmol/L, 4.0mmol/L, 5.0mmol/L, 6.0mmol/L, 7.0mmol/L, 8.0mmol/L, 9.0mmol/L, 10mmol/L.
According to an embodiment of the present invention, the amount of the catalyst used may be 20. Mu. Mol, and in the case of the amount of the catalyst, the amount of the first comonomer may be about 10 to 20mmol.
According to the embodiment of the present invention, the concentration of the first comonomer may be 0.01mol/L, 0.3mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, and preferably may be 0.3 to 1mol/L.
According to an embodiment of the present invention, the organic solvent may include at least one of: toluene, xylene, chlorobenzene, n-hexane, n-heptane, methylcyclohexane. In the present invention, the amount of the organic solvent used is not particularly limited, and may be appropriately adjusted as needed.
According to an embodiment of the present invention, the comonomer is copolymerized under predetermined conditions, and the predetermined conditions may include: the reaction temperature of the copolymerization reaction is 40-120 ℃, the reaction time is 0.1-12 h, and the reaction pressure is 1-30 atmospheric pressures.
According to an embodiment of the present invention, the reaction temperature may be 40 ℃, 60 ℃, 80 ℃,100 ℃, 120 ℃, preferably 80 ℃; the reaction time may preferably be 0.1 to 0.5h; the reaction pressure may be preferably 1 to 15 atmospheres, more preferably 3 to 9 atmospheres.
According to an embodiment of the present invention, the reaction temperature for the copolymerization reaction may be provided by a water bath heating or oil bath heating system.
According to embodiments of the present invention, the polar polyolefin copolymers containing biomass groups of the present invention may be represented by the formula CH 2 ＝CH 2 An ethylene monomer represented by the formula
The random copolymer formed by random copolymerization of the norbornene polar monomer is the biomass group-containing polar polyolefin copolymer provided by the invention. Preferably, the random copolymer may be represented by the following formula (I):
in the above formula (I), the random copolymer of the present invention is represented by two kinds of repeating units obtained by copolymerizing a vinyl monomer and a different first comonomer (separated by the symbol "/" in (I)), but the random copolymer of the present invention is not represented by the fact that the two kinds of monomers in each formula are polymerized in an equimolar ratio, for example, a molar ratio of 1: 1.
According to an embodiment of the present invention, in the formula (I), n is a polymerization degree, and n may be 50 to 5000.
According to the embodiment of the invention, specifically, a first comonomer, an organic solvent and a catalyst which are needed by the comonomer are added into a polymerization reaction kettle, a small amount of ethylene is introduced, the temperature is rapidly raised to a specified temperature, the reaction pressure is adjusted to a specified pressure, after a certain time of copolymerization reaction, a large amount of methanol is added for quenching, and the polymer is obtained by filtering. Further extraction was performed using a soxhlet extractor to remove residual monomers, to obtain a polar polyolefin copolymer containing biomass groups.
According to the embodiments of the present invention, the present invention provides a novel method for directly copolymerizing ethylene monomer and first comonomer under mild conditions using specific palladium phosphine sulfonate catalysts PO-Pd-1 and PO-Pd-2, and obtains a desired polyolefin material.
According to an embodiment of the invention, the catalysts used have palladium phosphine sulfonate catalysts PO-Pd-1 and PO-Pd-2 of the structures shown below, namely:
in the structural formulae of PO-Pd-1 and PO-Pd-2, me represents a methyl group, O represents an oxygen atom, meO represents a methoxy group, P represents a phosphorus atom, pd represents a metallic palladium atom, S represents a sulfur atom, and DMSO represents dimethyl sulfoxide. The PO-Pd-1 and PO-Pd-2 catalysts used can be synthesized according to the procedures in the prior art and are not described in detail here.
In order to further illustrate the present invention, the following examples are provided to describe the polar polyolefin material and the preparation method thereof in detail. It should be understood that these examples are for illustrative purposes only to aid understanding of the concept of the present invention, and are not intended to limit the scope of the claims, nor are the scope of the present invention limited to the following examples.
It should be noted that the data given in the examples include the specific processes and parameters for the copolymerization of ethylene monomer and the first comonomer, all carried out in an anhydrous and oxygen-free inert atmosphere or environment, all sensitive substances stored in a glove box or refrigerator at-30 ℃, all solvents strictly dried to remove water; all other raw materials are purchased and used without specific mention.
Example 1: preparation of norbornene polar monomer containing biomass group
Taking the bi-substituted norbornene monomer containing oleyl alcohol group as an example, the preparation methods of the rest biomass groups are the same.
Endo-nadic anhydride (16.4 g, 100mmol), p-toluenesulfonic acid (0.95g, 5 mmol) and oleyl alcohol (80.5 g, 300mmol) were dissolved in 100mL of a toluene solvent under a nitrogen atmosphere, and refluxed at 130 ℃ for 24 hours. After the solvent was spin-dried, a (endo ) dioleyl-substituted norbornene monomer was obtained after purification by column chromatography (yield: 56g, 82%).
When the endo-nadic anhydride is replaced by exo-nadic anhydride in the above process, the (exo ) dioleyl-substituted norbornene monomer is obtained with similar yield.
(endo ) dioleyl-substituted norbornene monomer (41.4 g, 100mmol) and 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (0.7 g, 5mmol) were dissolved in 200mL tetrahydrofuran solvent under nitrogen atmosphere, and refluxed at 100 ℃ for 12 hours. The solvent was spun dry and dissolved in 200mL of dichloromethane solvent, and washed three times with 100mL of hydrochloric acid (1 mol/L) to remove 1,5, 7-triazabicyclo (4.4.0) dec-5-ene. Finally, the solvent was spin-dried and dried to obtain a (endo, exo) dioleyl-substituted norbornene monomer (yield: 40.1g, 97%).
Examples 2 to 11: preparation and characterization of polar polyolefin material containing biomass group content
In a glove box, norbornene-type polar monomers were added to 100mL autoclaves under nitrogen atmosphere in toluene solvents at the concentrations shown in table 1 below, and the molar concentrations of the monomers are indicated in parentheses after the respective comonomers.
For example, in the case where the total reaction volume was 20mL, the number of moles of the (endo ) dioleyl-substituted norbornene monomer was 20mmol with respect to the random copolymer obtained by random copolymerization of the polar monomer of ethylene- (endo ) dioleyl-substituted norbornene obtained in example 1 (example 2), and 2mL of methylene chloride dissolved in 2mL of methylene chloride was added to the reaction vessel0. Mu. Mol of catalyst PO-Pd-1. Then, an ethylene gas source pipe was connected to introduce ethylene (monomer E) gas into the reaction kettle, and after adjusting the ethylene pressure to 8atm, the reaction kettle was heated to 80 ℃ by water bath heating under magnetic stirring, and reacted for 10min under magnetic stirring. After the reaction is finished, cooling the reaction kettle to room temperature, then opening the reaction kettle, adding 50mL of ethanol into the obtained reaction solution for quenching, finally filtering under reduced pressure, and drying the obtained solid product in a vacuum drying oven at 50 ℃ for 24 hours to obtain the needed multifunctional polar polyolefin copolymer containing the biomass groups, wherein the obtained product is light yellow green solid, and the product yield (namely the mass g of the obtained copolymer in the polymerization time) and the reaction activity (the unit is g.mol.mol.) are calculated -1 .h -1 I.e., the mass of copolymer produced per mole of catalyst per hour of polymerization).
The reaction conditions of the random copolymers obtained by random copolymerization of ethylene and the polar norbornene-type monomers corresponding to examples 3 to 13 were the same as those of example 2, and thus the details thereof are not repeated.
Specifically, the reaction scheme may be:
in the above reaction scheme, the compound represented by formula (II) is
Expressed as ethylene monomer, in the formula->
Polar norbornene-based polar monomers are shown. N in the polymer molecule is a polymerization degree, and may be, for example, in the range of 50 to 5000.
The monomer insertion ratio (the mole percentage of the polar norbornene-type monomer in the resulting copolymer polymer chain, and the higher the insertion ratio, the higher the proportion of the polar comonomer in the copolymer polymer chain) is 1 H NMR or 13 C NMR spectra on deuterated tetrachloroethane (C) 2 D 2 Cl 4 ) Measured at 120 ℃.
The number average molecular weight (M) of the biomass group-containing polar copolymer product obtained was measured by high-temperature gel permeation chromatography GPC (trichlorobenzene as a solvent, test temperature 150 ℃ C.) n ) And a polydispersity index (PDI), while measuring the melting point T of the product by differential scanning calorimetry (DSC, scanning temperature range-50-150 ℃, ramp rate of 10 ℃/min) m And glass transition temperature T g
The characterization results of the biomass group-containing polar polyolefin copolymers obtained in examples 2 to 13 are shown in the following Table 1.
In the following table 1, wherein:
a the polymerization conditions were: PO-Pd-1=20 μmol, vtol =20ml, t =80 ℃, ethylene pressure =8atm, polymerization time =10min;
b the unit is g.mol < -1 > h < -1 >;
c the mass insertion ratio of the monomers, i.e. the mass of the comonomers in the polymer as a percentage of the total polymer mass;
d the number average molecular weight Mn and the polydispersity index PDI are determined by GPC;
e melting points Tm, tg were determined by DSC, where "-" represents no significant melting point found;
f the catalyst is changed from PO-Pd-1 to PO-Pd-2;
g the polymer was an oily viscous liquid.
TABLE 1 catalytic copolymerization of PO-Pd-1 or PO-Pd-2 a Data of
As can be seen from the above Table 1, the novel polar polyolefin material containing biomass groups obtained by the present invention has a high polymer molecular weight, the number average molecular weight (M) n ) Are all over 60,000 and can be as high as over 188,000, and the mass insertion ratio of the polar monomers of the material can beUp to more than 80%.
Example 14 Water contact Angle testing of Biomass group-containing polar polyolefin copolymer
The non-polar nature of conventional polyolefin copolymers (e.g., polyethylene, polypropylene, etc.) limits their utility and thus it is often desirable to incorporate polar functional groups into the material. The polyolefin copolymers prepared according to the present invention have polar functional groups (ester groups), such as the biomass group-containing polar polyolefin copolymers prepared in examples 2 to 9, and thus the surface properties thereof can be improved. For example, table 2 compares the results of water contact angle tests of polyethylene versus the polar polyolefin copolymers containing biomass groups provided herein.
TABLE 2
As can be seen from table 2, the water contact angle of the polar polyolefin copolymer containing biomass groups provided by the present invention is greatly reduced compared to the conventional polyethylene copolymer.
According to an embodiment of the present invention, the biomass group-containing polar polyolefin copolymer provided by the present invention may have various applications, for example, may be used as a packaging material, an automobile manufacturing material, an electric appliance manufacturing material, a medical instrument manufacturing material, or an agricultural implement manufacturing material, and the like.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A biomass group-containing polar polyolefin copolymer, wherein the biomass group-containing polar polyolefin copolymer adopts comonomers comprising: a vinyl monomer and a first comonomer, said first comonomer being of the formula
The norbornene polar monomer is represented by the general formula (I), wherein X-OH and Y-OH are respectively corresponding alcohol compounds obtained by reduction of biological hyaluronic acid, and the biological hyaluronic acid comprises at least one of the following: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid or salicylic acid.
2. The polar biomass group-containing polyolefin copolymer of claim 1, wherein the copolymer is of formula (la)
The norbornene polar monomer includes one of the following isomers: />
(endo ) isomer and/or sugar>
(endo, exo) isomer or->
(exo ) isomers.
3. The biomass group-containing polar polyolefin copolymer according to claim 2, wherein,
the (endo ) isomer is obtained by alcoholysis reaction of endo nadic anhydride and alcohol compounds obtained by reduction of the biological hyaluronic acid;
the (exo ) isomer is obtained by alcoholysis reaction of exo nadic anhydride and alcohol compounds obtained by reduction of the biological hyaluronic acid;
the (endo, exo) isomer is obtained from the (endo, exo) isomer by isomerization.
4. The biomass group-containing polar polyolefin copolymer according to claim 1, wherein,
the polymerization degree of the polar polyolefin copolymer containing the biomass group is 50-5000.
5. The biomass group-containing polar polyolefin copolymer according to claim 1, wherein,
the biomass group-containing polar polyolefin copolymer has a number average molecular weight of greater than or equal to 60000.
6. A method for preparing the biomass group-containing polar polyolefin copolymer according to any one of claims 1 to 5, comprising:
carrying out copolymerization reaction on a comonomer under the conditions of an organic solvent and a catalyst and under a preset condition to obtain a polar polyolefin copolymer containing a biomass group;
wherein the comonomer comprises ethylene monomer and a first comonomer, and the first comonomer is represented by the formula
The norbornene polar monomer is represented by the general formula (I), wherein X-OH and Y-OH are respectively corresponding alcohol compounds obtained by reduction of biological hyaluronic acid, and the biological hyaluronic acid comprises at least one of the following: eleostearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, cinnamic acid, piperic acid, ferulic acid, vanillic acid, gallic acid, protocatechuic acid, or salicylic acid;
the catalyst comprises at least one of:
7. the method of claim 6, wherein,
the concentration of the catalyst is 0.1-10 mmol/L;
the concentration of the first comonomer is 0.01-2 mol/L.
8. The method of claim 6, wherein,
the organic solvent includes at least one of: toluene, xylene, chlorobenzene, n-hexane, n-heptane, methylcyclohexane.
9. The method of claim 6, wherein,
the preset conditions include: the reaction temperature of the copolymerization reaction is 40-120 ℃, the reaction time is 0.1-12 h, and the reaction pressure is 1-30 atmospheric pressures.
10. The process of claim 9, wherein the reaction temperature for the copolymerization reaction is provided by a water bath heating or oil bath heating system.
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| CN110938164A (en) * | 2019-11-12 | 2020-03-31 | 中国科学技术大学 | One-pot method for tandem catalytic copolymerization of ethylene and 1, 2-disubstituted polar internal olefin and product thereof |
| CN111171204A (en) * | 2020-01-20 | 2020-05-19 | 中国科学技术大学 | Polar polyolefin material, preparation method and application thereof |
| CN112898464A (en) * | 2021-01-20 | 2021-06-04 | 中国科学技术大学 | Polar polyolefin material and preparation method and application thereof |
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| CN110938164A (en) * | 2019-11-12 | 2020-03-31 | 中国科学技术大学 | One-pot method for tandem catalytic copolymerization of ethylene and 1, 2-disubstituted polar internal olefin and product thereof |
| CN111171204A (en) * | 2020-01-20 | 2020-05-19 | 中国科学技术大学 | Polar polyolefin material, preparation method and application thereof |
| CN112898464A (en) * | 2021-01-20 | 2021-06-04 | 中国科学技术大学 | Polar polyolefin material and preparation method and application thereof |
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