CN115872967A - Preparation method of dicyclic carbonate containing benzene ring structure - Google Patents
Preparation method of dicyclic carbonate containing benzene ring structure Download PDFInfo
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 56
- 125000002619 bicyclic group Chemical group 0.000 title claims abstract description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 21
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims abstract description 14
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- -1 methoxy, ethoxy, propoxy, butoxy, tert-butoxy, nitro, amino, hydroxyl Chemical group 0.000 claims description 53
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011981 lindlar catalyst Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- QKSQWQOAUQFORH-UHFFFAOYSA-N tert-butyl n-[(2-methylpropan-2-yl)oxycarbonylimino]carbamate Chemical compound CC(C)(C)OC(=O)N=NC(=O)OC(C)(C)C QKSQWQOAUQFORH-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 3
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 239000012948 isocyanate Substances 0.000 abstract description 10
- 150000002513 isocyanates Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 2
- 238000006751 Mitsunobu reaction Methods 0.000 abstract 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 29
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 20
- 238000001914 filtration Methods 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 14
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GXIAMNASXHEUSZ-UHFFFAOYSA-N 4-[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1CC1OC(=O)OC1 GXIAMNASXHEUSZ-UHFFFAOYSA-N 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010009 beating Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- QKMNFFSBZRGHDJ-UHFFFAOYSA-N 1,4-dichloro-2-methoxybenzene Chemical compound COC1=CC(Cl)=CC=C1Cl QKMNFFSBZRGHDJ-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical group CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 description 1
- IYOYOEKCRDEIPQ-UHFFFAOYSA-N 1-bromo-4-[(4-bromophenyl)methyl]benzene Chemical compound C1=CC(Br)=CC=C1CC1=CC=C(Br)C=C1 IYOYOEKCRDEIPQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Abstract
The invention relates to a preparation method of dicyclic carbonate containing a benzene ring structure, which comprises the following steps: the method comprises the following steps of firstly carrying out Mitsunobu reaction on 4- (hydroxymethyl) -1, 3-dioxolan-2-one and propargyl alcohol to generate triple-bond monocyclic carbonate, then carrying out Sonogashira reaction on the triple-bond monocyclic carbonate and a para-position double-halogen benzene ring compound to generate triple-bond bicyclic carbonate, carrying out triple bond hydrogenation on the bicyclic carbonate to generate double-bond bicyclic carbonate under the action of a catalyst A, and further carrying out hydrogenation on the double-bond bicyclic carbonate to generate single-bond bicyclic carbonate under the action of a catalyst B. The method has the advantages of mild reaction conditions in each step, low and easily obtained raw materials, simple operation, convenient separation and high yield, has an expandable industrial prospect, and can provide raw materials for preparing high-performance non-isocyanate polyurethane (NIPU).
Description
Technical Field
The invention relates to a method for preparing thermoplastic non-isocyanate polyurethane raw material bicyclocarbonate, in particular to a method for preparing bicyclocarbonate containing a benzene ring structure.
Background
The traditional polyurethane is a high polymer material with excellent performance and extremely wide application, but the preparation process of the traditional polyurethane uses isocyanate which is harmful to the environment and human health, so that the traditional polyurethane does not meet the requirements of social development trends of safety, environmental protection and the like. Efforts have been made in the United states to develop non-isocyanate polyurethanes (NIPUs) in the nineties of the last century, with some positive results (W C Crawford, E T Marquis, H P Klein. USP:5340889, 1994L Rappoport, RD Brown. USP 5175891, 1992B Tamami, S Sohn, wilkes. J.Appl. Polym. Sci.,2004,92 (2): 883-891). The hydroxyl group and carbonyl oxygen atom in the non-isocyanate polyurethane can form intramolecular hydrogen bond, so that the chemical resistance, hydrolysis resistance and permeability resistance of the traditional polyurethane are greatly improved.
The dicyclic carbonate and polyamine are used in preparing non-isocyanate polyurethane, and the structure of the dicyclic carbonate and the polyamine may play the important role in the mechanical performance, molecular weight and use of the final product NIPU. The NIPU bicyclic carbonates reported in the literature have a double ring structure in which two ends are connected by a chain hydrocarbon, carbon oxygen or carbon thioether (poly.chem.2011, 2,2661-2667, eur.poly.j.2015, 70, 125-135.), and the final product NIPU has a slightly smaller molecular weight and a weaker mechanical property. In order to effectively improve the conditions of small molecular weight and weak mechanical property of an NIPU final product, the molecular weight and the mechanical property can be effectively improved by introducing a benzene ring into the structure of the bicyclic carbonate.
Disclosure of Invention
The invention provides a preparation method of dicyclic carbonate containing a benzene ring structure, and the preparation method has the advantages of simple reaction process operation, high product yield and process scalability.
A preparation method of dicyclic carbonate containing a benzene ring structure comprises the following steps: 4- (hydroxymethyl) -1, 3-dioxolan-2-one and propargyl alcohol react through Mitsunobu to generate triple-bond monocyclic carbonate with a structural formula shown in (i), then the triple-bond monocyclic carbonate and a para-double-halogen benzene ring compound generate Sonogashira to generate triple-bond bicyclic carbonate with a structural formula shown in (ii), the bicyclic carbonate (ii) is hydrogenated into double-bond bicyclic carbonate with a structural formula shown in (iii) under the action of a catalyst A, and the double-bond bicyclic carbonate (iii) is further hydrogenated to generate single-bond bicyclic carbonate (iv) under the action of a catalyst B;
wherein R is 1 、R 2 Represents a substituent group on a benzene ring, R 1 、R 2 Is hydrogen, methyl, ethyl, propyl, butyl, tertiary butyl, methoxy, ethoxy, propylOne of oxy, butoxy, tert-butoxy, nitro, amino, hydroxyl, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate and butyl acetate, R 1 、R 2 The groups may be the same or different; x in para-bis-halogeno-benzene ring compound 1 ，X 2 Represents halogen, is one of chlorine, bromine and iodine, X 1 ，X 2 The groups may be the same or different;
n represents the number of carbons of the same unit, n =0 to 15, m represents the number of repeating units, and m =0 to 15.
The preparation routes of the bicyclic carbonates (ii), (iii) and (iv) containing a benzene ring structure are shown as formula 1:
preferably, the triple bond monocyclic carbonate (i) is prepared by: adding 4- (hydroxymethyl) -1, 3-dioxolane-2-one, alkynol, a phosphorus reagent, an azo reagent and an anhydrous solvent into a reaction vessel, wherein the reaction temperature is-20-80 ℃, and the reaction time is 1-24 h.
Preferably, the phosphorus reagent is: one or more of triphenylphosphine, tributylphosphine and trimethylphos; the azo reagent is one or more of diethyl azodicarboxylate, diisopropyl azodicarboxylate and di-tert-butyl azodicarboxylate; the anhydrous solvent is one or any combination of more than two of tetrahydrofuran, methyl tert-butyl ether, ethyl acetate, acetonitrile and dichloromethane; the mass ratio of the 4- (hydroxymethyl) -1, 3-dioxolan-2-one to the alkynol to the phosphorus reagent to the azo reagent is 1:1 to 1.2:1 to 2:1 to 2.
Preferably, the triple bond bicyclic carbonate (ii) is prepared by the following method: the triple-bond single-ring carbonic ester (i), the para-position double-halogenated benzene ring compound, a catalyst and alkali are reacted at the temperature of 100-160 ℃ for 1-15 h.
As a preferenceThe catalyst is CuI 2 、CuBr 2 、CuCl 2 、Cu(OAc) 2 One or more than two of them are combined randomly; the alkali is one or any combination of more than two of triethylamine, dimethylethylamine and diisopropylethylamine; the amount ratio of the triple-bond monocyclic carbonate (i), the para-double halogen benzene ring compound, the catalyst and the alkali is 1: 0.45-0.55: 0.1 to 0.5:3 to 10.
Preferably, the double-bond bicyclic carbonate (iii) is prepared by the following method: the triple bond bicyclic carbonate (ii) reacts with hydrogen, a catalyst A and a solvent at the temperature of 0-50 ℃ for 1-24 h.
Preferably, the catalyst A is Lindlar catalyst/quinoline or Lindlar catalyst/pyridine; the solvent is one or any combination of more than two of ethyl acetate, tetrahydrofuran, methyl tert-butyl ether and dichloromethane; the mass ratio of the triple-bond bicyclic carbonate (ii) to the catalyst A is 1:0.001 to 0.2; the reaction pressure is 0.1-1 MPa.
Preferably, the single-bond bicyclic carbonate (iv) is prepared by the following method: reacting the double-bond bicyclic carbonate (iii) with hydrogen, a catalyst B and a solvent at the temperature of 0-70 ℃ for 1-15 h.
Preferably, the catalyst B is Pd/C or Rany-Ni; the solvent is one or more of tetrahydrofuran, methyl tert-butyl ether, ethyl acetate and water; the mass ratio of the double-bond bicyclic carbonate (iii) to the catalyst B is 1:0.001 to 0.1; the reaction pressure is 0.1-1 MPa.
Preferably, X in the para-bis-halogenophenyl ring compound 1 ，X 2 Bromine or iodine is selected, n represents the number of carbons of the same unit, preferably n = 0-5, m represents the number of repeat units, preferably m = 0-5.
The method for preparing the dicyclic carbonate containing the benzene ring has the advantages of mild reaction conditions in each step, low and easily obtained raw materials, simple operation, convenient separation and high yield, has an expandable industrial prospect, and can provide raw materials for preparing high-performance non-isocyanate polyurethane (NIPU).
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the protection scope of the present invention.
Example 1
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (28.03g, 0.5 mol), triphenylphosphine (144.3g, 0.55mol), and anhydrous tetrahydrofuran (200 g) were sequentially added to a flask under a nitrogen atmosphere at room temperature, and stirred for 10min. 50g of anhydrous tetrahydrofuran solution of diethyl azodicarboxylate (95.8g, 0.55mol) was slowly added dropwise to the system, and the reaction was continued for 4 hours after completion of the dropwise addition. After the reaction, the mixture was desolventized, and then cyclohexane was added to the mixture to conduct beating and filtration to obtain 69.5g of 4- ((propyl-2-alkynyl-1-yloxy) methyl) -1, 3-dioxolane-2-one, the yield was 89.0%, and the purity was 98.1%. [ MS + H ]] + :157.2。
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxopentacyclo-2-one (50.0g, 0.32mol), 4 '-diiodo-1, 1' -bibenzoyl (58.5g, 0.144mol), triethylamine (162.0g, 1.6mol), cuI 2 (20.3 g, 0.064mol) under nitrogen atmosphere, controlling the temperature at 130 ℃ to react for 10h, extracting, washing, and recrystallizing methylene dichloride to obtain the product
4,4'- ((([ 1,1' -biphenyl)]55.3g of (E) -4,4' -diylbis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained in 83% yield and 95% purity. [ MS + H ]] + :463.5.
4,4'- ((([ 1,1' -biphenyl)]4,4' -diylbis (propyl-2-alkyne-3, 1-diyl)) bis (oxy)) bis (methylene) (50.0 g, 0.108mol), lindlar catalyst 0.05g, quinoline 0.05g and ethyl acetate 50g, wherein after vacuumizing, the hydrogen pressure of the reaction vessel is kept consistent with the normal pressure, the reaction vessel is stirred for 4 hours at room temperature, the catalyst is removed after the reaction is finished, water washing is added, and extraction recrystallization is carried out to obtain a product 4,4' - (([ 1,1' -biphenyl ] 2-carbonyl) compound]47.9g of (E) -4,4' -diylbis (propyl-2-en-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained in a yield of 95% and a purity of 98.1%. [ MS + H ]] + :467.5
Adding 4,4'- ((([ 1,1' -biphenyl)]-4,4' -diylbis (propyl-2-en-3, 1-diyl)) bis (oxy)) bis (methylene) bis (1, 3-dioxolan-2-one) (30.0 g, 0.061mol), pd/C0.03 g, and tetrahydrofuran 30g were charged into a reaction flask, and after evacuation, the container was stirred at room temperature for 5 hours under a hydrogen pressure equal to atmospheric pressure, and after completion of the reaction, the catalyst was removed by filtration, and recrystallization was carried out to obtain 4,4' - ((((([ 1,1' -biphenyl ])]29.05g of (E) -4,4' -diylbis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained in a yield of 96% and a purity of 98.5%. [ MS + H ]] + :471.5.
Example 2
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (28.03g, 0.5 mol), tributylphosphorus (26.1g, 0.466 mol), and 200g of anhydrous methyl t-butyl ether were sequentially added to a flask under a nitrogen atmosphere at 30 ℃ and stirred for 10min. 50g of a solution of diisopropyl azodicarboxylate (171.2g, 0.847mol) in 50g of anhydrous methyl t-butyl ether was slowly added dropwise to the system, and the reaction was continued for 4 hours after completion of the dropwise addition. After the reaction, the mixture was desolventized, and then cyclohexane was added to the mixture to conduct beating and filtration to obtain 55.5g of 4- ((propyl-2-alkynyl-1-yloxy) methyl) -1, 3-dioxolane-2-one, the yield was 84.0%, and the purity was 98.0%. [ MS + H ]] + :157.2
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxo-pentacyclo-2-one (50.0g, 0.32mol), bis (4-bromophenyl) methane (52.2g, 0.144mol), dimethylethylamine (187.4g, 2.56mol), cuBr 2 (21.5g, 0.096 mol) was reacted at 110 ℃ for 12 hours under nitrogen atmosphere, after the reaction was completed, the product 4,4' - (((((methylenebis (4, 1-phenylene)) bis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained by extraction, washing with water, and recrystallization with methylene chloride, and the yield was 76% and the purity was 96.1%. [ MS + H ]] + :477.5
4,4' - ((((methylenebis (4, 1-phenylene)) bis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (50.0 g, 0.105mol), lindlar catalyst 0.01g, quinoline 0.01g, tetrahydrofuran 50g, after evacuation, the reaction vessel was kept under a hydrogen pressure at atmospheric pressure, stirred at room temperature for 6 hours, after completion of the reaction, the catalyst was removed, and water was added to wash the reaction vessel with waterThe product, 4' - (((((methylenebis (4, 1-phenylene)) bis (propyl-2-en-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained by extractive recrystallization in 46.9g at a yield of 93.0% and a purity of 97.8%. [ MS + H ]] + :481.5.
4,4'- ((((((methylenebis (4, 1-phenylene)) bis (propyl-2-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (30.0 g, 0.062mol), 0.03g of Pd/C, and 30g of methyl tert-butyl ether were charged into a reaction flask, and after evacuation, the vessel was stirred at room temperature for 8 hours under atmospheric pressure, and after completion of the reaction, the catalyst was removed by filtration and recrystallized to obtain 29.4g of product 4,4' - (((((((methylenebis (4, 1-phenylene)) bis (propylalkane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one), yield was 97.1%, and purity was 98.2%. [ MS + H ]] + :485.5.
Example 3
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (28.03g, 0.5 mol), trimethylphosphorus (45.6 g, 0.60mol), and 200g of anhydrous ethyl acetate were sequentially added to a flask under a nitrogen atmosphere at-20 ℃ and stirred for 10min. 50g of anhydrous ethyl acetate solution of di-tert-butyl azodicarboxylate (138.2g, 0.60mol) is slowly added dropwise into the system, and the reaction is continued for 8 hours after the dropwise addition. After the reaction is finished, adding cyclohexane for pulping, and filtering to obtain 62.5g of 4- ((propyl-2-alkyne-1-oxyl) methyl) -1, 3-dioxygen pentacyclic-2-ketone, wherein the yield is 80.1 percent, and the purity is 98.2 percent. [ MS + H ]] + :157.2.
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxan-2-one (50.0g, 0.32mol), 4 '-dibromo-1, 1':4', 1' -terphenyl (55.9g, 0.144mol), diisopropylethylamine (248.3g, 1.92mol), cuCl 2 (21.5g, 0.11umol) is reacted for 10 hours at the temperature of 130 ℃ under nitrogen atmosphere, after the reaction is finished, the product 4,4'- (((([ 1,1':4', 1' -terphenyl) is obtained by extraction, water washing and recrystallization of dichloromethane]58.2g of (E) -4,4 "-diylbis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained in a yield of 75.0% and a purity of 96.8%. [ MS + H ]] + :539.5。
4,4'- ((([ 1,1':4', 1' -terphenyl)]-4,4 "-diylbis (propyl-2-yn-3, 1-diyl)) bis (oxy)) bis (methylene) Bis (1, 3-dioxolan-2-one) (50.0 g,0.093 mol), lindlar catalyst 0.03g, pyridine 0.03g, tetramethyl tert-butyl ether 50g, vacuum pumping, maintaining hydrogen 0.13MPa in the reaction container, stirring at room temperature for 3h, removing catalyst, washing with water, extracting and recrystallizing to obtain product 4,4'- ((((([ 1,1':4', 1' -terphenyl)]47.4g of (E) -4,4 "-diylbis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) was obtained in 94.2% yield and 98.0% purity. [ MS + H ]] + :543.6。
4,4'- ((([ 1,1':4', 1' -terphenyl)]-4,4 "-diylbis (propyl-2-alkyne-3, 1-diyl)) bis (oxy)) bis (methylene) (30.0 g, 0.055mol), rany-Ni 3.0g (net content), water 30g, ethyl acetate 50g were put into a reaction flask, after evacuation, the vessel hydrogen pressure was 0.5MPa, stirring was carried out at 50 ℃ for 2 hours, after completion of the reaction, the catalyst was removed by filtration, and recrystallization was carried out to obtain 4,4' - (((((([ 1,1':4',1" -terphenyl)]-4,4 "-diylbis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxopentacyclo-2-one) 29.1g, yield 96.4%, purity 98.5%, [ MS + H ]] + :547.6.
Example 4
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (32.2g, 0.575 mol), triphenylphosphine (262.3g, 1.0 mol) and 300g of anhydrous ethyl acetate were sequentially added to a flask under a nitrogen atmosphere at 25 ℃ and stirred for 10min. A solution of di-tert-butyl azodicarboxylate (230.3 g,1.0 mol) in 100g of anhydrous ethyl acetate was slowly added dropwise to the system, and the reaction was continued for 7 hours after completion of the addition. After the reaction is finished, adding cyclohexane for pulping, and filtering to obtain 64.65g of 4- ((propyl-2-alkyne-1-oxyl) methyl) -1, 3-dioxygen pentacyclic-2-ketone, wherein the yield is 82.8 percent, the purity is 98.4 percent, and the [ MS + H ] content] + :157.2。
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxopentacyclo-2-one (50.0g, 0.32mol), 1, 4-bis (4-bromobenzyl) benzene (60.0g, 0.144mol), diisopropylethylamine (248.3g, 1.92mol), cu (OAc) 2 (8.72g, 0.048mol) is reacted for 15h at the temperature of 120 ℃ under the nitrogen atmosphere, after the reaction is finished, the product 4,4' - ((((((1, 4-phenylenebis (methylene)) bis (4, 1-phenylene)) bis (propyl-2-alkyne-3) is obtained by extraction, water washing and recrystallization of dichloromethane1-diyl)) bis (oxy)) bis (methylene) bis (1, 3-dioxolan-2-one) 62.8g, yield 77.0%, purity 95.6%. [ MS + H ]] + :567.6.
4,4'- ((((((1, 4-phenylenebis (methylene)) bis (4, 1-phenylene)) bis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (30.0 g,0.053 mol), lindlar catalyst 0.3g, pyridine 0.3g, dichloromethane 50g, after evacuation the reaction vessel was kept under hydrogen 0.2MPa, stirred at room temperature for 2H, after completion of the reaction, the catalyst was removed, washed with water and extracted to recrystallize to give the product 4,4' - (((((((((1, 4-phenylenebis (methylene)) bis (4, 1-phenylene)) bis (propyl-2-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) 48.7g, yield 92.0%, MS + H97.6% purity] + :571.6。
4,4'- ((((((1, 4-phenylenebis (methylene)) bis (4, 1-phenylene)) bis (4, 1-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (30.0 g, 0.053mol), rany-Ni 3.0g (net content), water 30g, tetrahydrofuran 50g were charged into a reaction flask, and after evacuation, the vessel was stirred at 0.3MPa, at 40 ℃ for 3 hours, the catalyst was removed by filtration after completion of the reaction, and recrystallization was carried out to obtain 28.8g of product 4,4' - (((((((((((1, 4-phenylenebis (methylene)) bis (4, 1-phenylene)) bis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) in a yield of 95.3%, purity of 98.7%, [ MS + H ] H + H ], [] + :575.6。
Example 5
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (30.8g, 0.55mol), tributylphosphorus (151.7g, 0.75mol), and anhydrous acetonitrile 200g were sequentially added to a flask under a nitrogen atmosphere at 35 ℃ and stirred for 10min. 100g of anhydrous acetonitrile solution of di-tert-ethyl azodicarboxylate (130.6g, 0.75mol) was slowly added dropwise to the system, and the reaction was continued for 9 hours after the addition. After the reaction is finished, adding cyclohexane for pulping, and filtering to obtain 62.5g of 4- ((propyl-2-alkyne-1-oxyl) methyl) -1, 3-dioxygen pentacyclic-2-ketone, wherein the yield is 80.0 percent, the purity is 98.6 percent, and the [ MS + H ] content] + :157.2。
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxo-pentacyclo-2-one (50.0g, 0.32mol), 1, 4-dichloro-2-methoxybenzene (25.5 g)0.144 mol), diisopropylethylamine (331.1g, 2.56mol), cuI 2 (20.3g, 0.064 mol) is reacted for 15H at the temperature of 150 ℃ under nitrogen atmosphere, after the reaction is finished, the product 4,4' - ((((((2-methoxy-1, 4-phenylene) bis (prop-2-alkyne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolane-2-one) 31.8g is obtained by extraction, water washing and dichloromethane recrystallization, the yield is 53.0 percent, the purity is 95.1 percent, and [ MS + H ] is] + :417.4。
4,4'- (((((2-methoxy-1, 4-phenylene) bis (prop-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (50.0 g, 0.12mol), lindlar catalyst 0.5g, pyridine 0.5g, dichloromethane 50g, after evacuation, the reaction vessel was kept under hydrogen of 0.1MPa, and stirred at room temperature for 3 hours, after completion of the reaction, the catalyst was removed, washed with water and extracted to recrystallize to obtain the product 4,4' - (((((((2-methoxy-1, 4-phenylene) bis (prop-2-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) 47.6g, yield 94.2%, purity 97.1%, [ MS + H ] -bis (oxy)) bis (methylene) ], and the product was obtained by filtration, precipitation and recrystallization] + :421.4。
4,4'- ((((((2-methoxy-1, 4-phenylene) bis (propyl-2-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (30.0 g, 0.071mol), pd/C0.5 g (net content), ethyl acetate 50g were charged in a reaction flask, and after evacuation, the vessel was stirred under a hydrogen pressure of 0.1MPa at 40 ℃ for 4 hours, after completion of the reaction, the catalyst was removed by filtration, and recrystallization was conducted to obtain 28.3g of product 4,4' - (((((((2-methoxy-1, 4-phenylene) bis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) in a yield of 93.8% and a purity of 98.2%, [ MS + H ], ((((((2-methoxy-1, 4-phenylene) bis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one)) bis (1, 3-dioxy)) bis (2-one)] + :425.4。
Example 6
Propiolic alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (32.2g, 0.575 mol), trimethylphosphorus (49.5 g, 0.65mol) and anhydrous dichloromethane (200 g) were sequentially added to a flask under a nitrogen atmosphere at 30 ℃ and stirred for 10min. 100g of anhydrous dichloromethane solution of di-tert-isopropyl azodicarboxylate (131.5g, 0.65mol) is slowly dripped into the system, and the reaction is continued for 10 hours after the dripping is finished. After the reaction is finished, adding cyclohexane for pulping after desolventizing, filtering to obtain 63.4g of 4- ((propyl-2-alkyne-1-oxyl) methyl) -1, 3-dioxygen pentacyclic-2-ketone, wherein the yield is 81.2 percent, the purity is 97.8 percent, and the [ M ] isS+H] + :157.2。
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxopentacyclo-2-one (50.0g, 0.32mol), 1, 3-bis (4-iodophenyl) propane (64.6 g, 0.144mol), diisopropylethylamine (194.4g, 1.92mol), cuBr 2 (7.15g, 0.032mol) is reacted for 8 hours at the temperature of 120 ℃ under nitrogen atmosphere, after the reaction is finished, the product 4,4' - (((((propane-1, 3-diylbis (4, 1-phenylene)) bis (propyl-2-alkyne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolane-2-one) is obtained by extraction, water washing and recrystallization of dichloromethane, the yield is 85.4 percent, the purity is 96.2 percent, and [ MS + H ] pentacyclo-2-one)] + :505.5。
4,4'- ((((propane-1, 3-diylbis (4, 1-phenylene)) bis (propyl-2-yne-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (50.0 g, 0.099mol), lindlar catalyst 0.8g, quinoline 0.8g, ethyl acetate 50g, after evacuation, the reaction vessel was kept under hydrogen pressure of 0.15MPa, and stirred at room temperature for 2 hours, after completion of the reaction, the catalyst was removed, washed with water and recrystallized by extraction to obtain 4,4' - ((((((propane-1, 3-diylbis (4, 1-phenylene)) bis (propyl-2-ene-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) 47.5g, yield 94.3%, purity 97.0%, [ MS + H ] was obtained by mixing] + :509.6。
4,4'- ((((propane-1, 3-diylbis (4, 1-phenylene)) bis (propyl-2-en-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) (30.0 g, 0.059mol), pd/C0.2 g (net content), methyl tert-butyl ether 50g were charged into a reaction flask, and after evacuation, the vessel was stirred at a hydrogen pressure of 0.13MPa at 35 ℃ for 4 hours, after completion of the reaction, the catalyst was removed by filtration, and recrystallization was conducted to obtain the product 4,4' - ((((((((propane-1, 3-diylbis (4, 1-phenylene)) bis (propane-3, 1-diyl)) bis (oxy)) bis (methylene)) bis (1, 3-dioxolan-2-one) 29.6g, yield 95.3%, purity 98.4%, [ MS + H ], [] + :513.6。
Example 7
Propargyl alcohol (59.05g, 0.5 mol), 4- (hydroxymethyl) -1, 3-dioxolan-2-one (32.2g, 0.575 mol), triphenylphosphine (157.4g, 0.60mol) and anhydrous acetonitrile (200 g) were sequentially added to a nitrogen atmosphere flask at-10 ℃ and stirred for 10min. Di-tert-butyl azodicarboxylate (138.2 g, 0.60mol) in 100g of anhydrous acetonitrileThe solution is slowly dripped into the system, and the reaction is continued for 15 hours after the dripping is finished. After the reaction is finished, adding cyclohexane for pulping after desolventizing, and filtering to obtain 62.0g of 4- ((propyl-2-alkyne-1-oxyl) methyl) -1, 3-dioxygen pentacyclic-2-ketone, wherein the yield is 79.4 percent, the purity is 97.1 percent, and the [ MS + H ]] + :157.2。
4- ((propyl-2-yn-1-yloxy) methyl) -1, 3-dioxolan-2-one (50.0g, 0.32mol), dimethyl 5,5' - (pentane-1, 3-diyl) bis (2-iodobenzoate) (81.3g, 0.144mol), diisopropylethylamine (194.4g, 1.92mol), cuI 2 (10.16g, 0.032mol) is reacted for 7H at the temperature of 100 ℃ under nitrogen atmosphere, after the reaction is finished, the product 5,5' - (pentane-1, 3-diyl) bis (2- (3- ((2-oxo-1, 3-dioxolane-4-yl) methoxy) propyl-1-alkyne-1-yl) dimethyl benzoate) is obtained by extraction, water washing and dichloromethane recrystallization, the yield is 81.6 percent, the purity is 95.8 percent, and [ MS + H ] +] + :621.6。
5,5'- (pentane-1, 3-diyl) bis (2- (3- ((2-oxo-1, 3-dioxolan-4-yl) methoxy) propyl-1-yn-1-yl) dimethyl benzoate) (50.0 g, 0.082mol), lindlar catalyst 0.6g, quinoline 0.6g and tetrahydrofuran 50g, after vacuumizing, keeping the hydrogen pressure in the reaction vessel at 0.14MPa, stirring for 3H at room temperature, removing the catalyst, adding water for washing, extracting and recrystallizing to obtain 5,5' - (pentane-1, 3-diyl) bis (2- (3- ((2-oxo-1, 3-dioxolan-4-yl) methoxy) propyl-1-en-1-yl) dimethyl benzoate) 47.3g, the yield is 93.9%, the purity is 97.3%, [ MS + H ] bis (2- (3- ((2-oxo-1, 3-dioxolan-4-yl) methoxy) propyl-1-en-1-yl) dimethyl benzoate)] + :625.6。
Putting 5,5'- (pentane-1, 3-diyl) bis (2- (3- ((2-oxo-1, 3-dioxolan-4-yl) methoxy) propyl-1-en-1-yl) dimethyl benzoate) (30.0 g,0.049 mol), pd/C (net content), and 50g of methyl tert-butyl ether into a reaction flask, vacuumizing, stirring at 0.13Mpa and 35 ℃ for 4H, filtering to remove the catalyst, recrystallizing to obtain 28.5g of a product, namely 5,5' - (pentane-1, 3-diyl) bis (2- (3- ((2-oxo-1, 3-dioxolan-4-yl) methoxy) propyl) dimethyl benzoate), wherein the yield is 94.4%, the purity is 98.6%, and the product is (MS + H)] + :629.7。
Example 8
NIPU synthetic experiment and physical properties
100g of five-membered cyclic carbonate synthesized in example 1, 23.5g of hexamethylenediamine and 0.2g of potassium iodide are fully stirred and mixed for 3 hours at normal temperature, then the temperature is increased to 100 ℃ for reaction for 12 hours, after defoaming, the mixture is cast on a mould and tabletted at 150 ℃, after the sheeting time is 8 hours, the mixture is placed for 1 day at room temperature to obtain non-isocyanate polyurethane, the conversion rate is 98%, the GPC (gel permeation chromatography) test number average molecular weight is 28200, the molecular weight distribution is 2.1, and the physical and mechanical properties are tested.
The physical properties of the test piece are as follows: hardness (Shore a), 73; permanent tensile set, 24%; elongation at break, 500%; tensile strength, 7.6MPa;100% tensile set modulus, 120MPa; tear Strength, 32.6KN/m.
100g of five-membered cyclic carbonate prepared in example 2, 34.56g of IPDA diamine and 0.2g of potassium bromide are fully stirred and mixed for 3h at normal temperature, then the temperature is raised to 100 ℃ to react for 12h, after defoaming, a piece is poured on a mould, the temperature for forming the piece is 150 ℃, after the time for forming the piece is 8h, the non-isocyanate polyurethane is obtained after being placed for 1 day at room temperature, the conversion rate is 98%, the GPC tests show that the number average molecular weight is 33600, the molecular weight distribution is 2.7, and the physical and mechanical properties are tested.
The physical properties of the test piece are as follows: hardness (Shore a), 79; permanent tensile set, 15%; elongation at break, 200%; tensile strength, 18.0MPa;100% tensile set modulus, 360MPa; tear strength, 51.6KN/m.
100g of five-membered cyclic carbonate prepared in example 3, 36.9g of decamethylene diamine and 0.2g of potassium bromide are fully stirred and mixed for 3 hours at normal temperature, then the temperature is increased to 100 ℃ for reaction for 12 hours, after defoaming, the mixture is cast on a die and is sliced at 150 ℃, after the slicing time is 8 hours, the mixture is placed at room temperature for 1 day to obtain non-isocyanate polyurethane, the conversion rate is 98%, the GPC (gel permeation chromatography) test shows that the number average molecular weight is 34100, the molecular weight distribution is 3.3, and the physical and mechanical properties of the polyurethane are tested.
The physical properties of the test piece are as follows: hardness (Shore a), 68; permanent tensile set, 25%; elongation at break, 680%; tensile strength, 2.3MPa;100% tensile set modulus, 40MPa; tear strength, 51.6KN/m.
The invention successfully prepares the NIPU resin with adjustable and controllable mechanical properties. By regulating the molecular structures of the soft and hard segments of the resin, the tensile strength, the elongation at break and the tensile modulus of the NIPU resin can be greatly adjusted. As the molecular chain of the NIPU contains rich hydroxyl groups, the wet adhesion and the self-repairability of the material are obviously improved compared with the conventional thermoplastic polyurethane. Is expected to be applied in the fields of adhesives, coatings, special coating materials and the like.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and it is intended to cover in the claims the invention any modifications and equivalents.
Claims (10)
1. A preparation method of dicyclic carbonate containing a benzene ring structure is characterized by comprising the following steps: 4- (hydroxymethyl) -1, 3-dioxolan-2-one and propargyl alcohol react through Mitsunobu to generate triple-bond monocyclic carbonate with a structural formula shown in (i), then the triple-bond monocyclic carbonate and a para-double-halogen benzene ring compound generate Sonogashira to generate triple-bond bicyclic carbonate with a structural formula shown in (ii), the bicyclic carbonate (ii) is hydrogenated into double-bond bicyclic carbonate with a structural formula shown in (iii) under the action of a catalyst A, and the double-bond bicyclic carbonate (iii) is further hydrogenated to generate single-bond bicyclic carbonate (iv) under the action of a catalyst B;
wherein R is 1 、R 2 Represents a substituent group on a benzene ring, R 1 、R 2 Respectively is one of hydrogen, methyl, ethyl, propyl, butyl, tert-butyl, methoxy, ethoxy, propoxy, butoxy, tert-butoxy, nitro, amino, hydroxyl, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate and butyl acetate; x in para-bis-halogeno-benzene ring compound 1 ，X 2 Represents halogen and is one of chlorine, bromine and iodine; n represents the number of carbons of the same unit, n =0 to 15, m represents the number of repeating units, and m =0 to 15.
2. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 1, wherein said triple-bond monocyclic carbonate (i) is prepared by the following method: adding 4- (hydroxymethyl) -1, 3-dioxolane-2-one, alkynol, phosphorus reagent, azo reagent and anhydrous solvent into a reaction vessel, wherein the reaction temperature is-20-80 ℃, and the reaction time is 1-24 h.
3. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 2, wherein: the phosphorus reagent is one or any combination of more than two of triphenylphosphine, tributylphosphorus and trimethylphosphorus; the azo reagent is one or more of diethyl azodicarboxylate, diisopropyl azodicarboxylate and di-tert-butyl azodicarboxylate; the anhydrous solvent is one or any combination of more than two of tetrahydrofuran, methyl tert-butyl ether, ethyl acetate, acetonitrile and dichloromethane; the mass ratio of the 4- (hydroxymethyl) -1, 3-dioxolan-2-one to the alkynol to the phosphorus reagent to the azo reagent is 1: 1-1.2: 1 to 2:1 to 2.
4. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 1, wherein said triple-bond bicyclocararbonate (ii) is prepared by the following steps: the triple-bond single-ring carbonic ester (i), the para-position double-halogenated benzene ring compound, a catalyst and alkali are reacted at the temperature of 100-160 ℃ for 1-15 h.
5. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 4, wherein: the catalyst is CuI 2 、CuBr 2 、CuCl 2 、Cu(OAc) 2 One or more than two of them are combined randomly; the alkali is one or two of triethylamine, dimethylethylamine and diisopropylethylamineAny combination of the above; the weight ratio of the triple-bond single-ring carbonate (i), the para-double halogen benzene ring compound, the catalyst and the alkali is 1: 0.45-0.55: 0.1 to 0.5:3 to 10.
6. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 1, wherein said bicyclocararbonate (iii) having a double bond is prepared by the following method: the triple bond bicyclic carbonate (ii) reacts with hydrogen, a catalyst A and a solvent at the temperature of 0-50 ℃ for 1-24 h.
7. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 6, wherein: the catalyst A is Lindlar catalyst/quinoline or Lindlar catalyst/pyridine; the solvent is one or any combination of more than two of ethyl acetate, tetrahydrofuran, methyl tert-butyl ether and dichloromethane; the mass ratio of the triple-bond bicyclic carbonate (ii) to the catalyst A is 1:0.001 to 0.2; the reaction pressure is 0.1-1 MPa.
8. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 1, wherein the single-bond bicyclocararbonate (iv) is prepared by the following method: reacting the double-bond bicyclic carbonate (iii) with hydrogen, a catalyst B and a solvent at the temperature of 0-70 ℃ for 1-15 h.
9. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 8, wherein: the catalyst B is Pd/C or Rany-Ni; the solvent is one or more of tetrahydrofuran, methyl tert-butyl ether, ethyl acetate and water; the mass ratio of the double-bond bicyclic carbonate (iii) to the catalyst B is 1:0.001 to 0.1; the reaction pressure is 0.1-1 MPa.
10. The method for preparing bicyclocararbonate having a benzene ring structure according to claim 1, wherein: x in para-bis-halogeno-benzene ring compound 1 ，X 2 SelectingBromine or iodine, n =0 to 5, m =0 to 5.
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