CN113620968A - Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof - Google Patents
Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113620968A CN113620968A CN202111035872.8A CN202111035872A CN113620968A CN 113620968 A CN113620968 A CN 113620968A CN 202111035872 A CN202111035872 A CN 202111035872A CN 113620968 A CN113620968 A CN 113620968A
- Authority
- CN
- China
- Prior art keywords
- reaction
- och
- cyclic acetal
- bio
- acetal structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002009 diols Chemical class 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 239000004386 Erythritol Substances 0.000 claims abstract description 28
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims abstract description 28
- 229940009714 erythritol Drugs 0.000 claims abstract description 28
- 235000019414 erythritol Nutrition 0.000 claims abstract description 28
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical group CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 229940073505 ethyl vanillin Drugs 0.000 claims description 6
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 claims description 6
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- RMSOEGBYNWXXBG-UHFFFAOYSA-N 1-chloronaphthalen-2-ol Chemical compound C1=CC=CC2=C(Cl)C(O)=CC=C21 RMSOEGBYNWXXBG-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- 239000012265 solid product Substances 0.000 description 58
- 239000008367 deionised water Substances 0.000 description 54
- 229910021641 deionized water Inorganic materials 0.000 description 54
- 239000011541 reaction mixture Substances 0.000 description 31
- 230000001376 precipitating effect Effects 0.000 description 29
- 238000005406 washing Methods 0.000 description 29
- 238000000967 suction filtration Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 5
- 235000012141 vanillin Nutrition 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 diol compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a rigid bio-based diol monomer with a cyclic acetal structure, and a preparation method and application thereof. The rigid bio-based diol monomer has the formula:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3. The preparation method comprises the following steps: carrying out a first reaction on a first mixed reaction system containing benzaldehyde substances, erythritol, a first organic solvent and a first catalyst to obtain an intermediate with a cyclic acetal structure; reacting a second mixture comprising the intermediate, ethylene carbonate, a third organic solvent, and a second catalystThe system is subjected to a second reaction to obtain a rigid bio-based diol monomer having a cyclic acetal structure. The invention prepares a brand new rigid bio-based diol with a cyclic acetal structure in high yield through two-step reaction, and the rigid bio-based diol is used as a polymerization monomer to synthesize bio-based polyester and polyurethane materials, so that the mechanical property and the heat resistance of the bio-based polyester and polyurethane materials are improved to a certain extent.
Description
Technical Field
The invention relates to the technical field of chemistry and materials, in particular to a preparation method and application of a rigid bio-based diol monomer with a cyclic acetal structure.
Background
Polymer materials such as polyester and polyurethane are widely and importantly applied in various fields such as agriculture, food, kitchen electricity, medical appliances and the like. In recent years, due to the large consumption of petrochemical resources, bio-based raw materials are receiving more and more attention, bio-based polymer materials are being researched and applied, and diol compounds are one of the most important raw materials for synthesizing polymer materials such as polyester and polyurethane. At present, most of bio-based diol monomers are flexible aliphatic chain structures and lack rigid cyclic structures, and the problems of poor mechanical property, poor heat resistance and the like of polyesters and polyurethanes synthesized by using the flexible bio-based diols as raw materials often occur. Therefore, the synthesis of bio-based diol monomers with rigid structures is an important part of the development of bio-based polymer materials.
Disclosure of Invention
The invention mainly aims to provide a rigid bio-based diol monomer with a cyclic acetal structure, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
some embodiments of the present invention provide a rigid bio-based diol monomer having a cyclic acetal structure, the bio-based diol monomer having a structural formula as shown in formula I:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
Some embodiments of the present invention provide a method of preparing a rigid bio-based diol monomer having a cyclic acetal structure, comprising:
carrying out a first reaction on a first mixed reaction system containing benzaldehyde substances, erythritol, a first organic solvent, a second organic solvent and a first catalyst to obtain an intermediate with a cyclic acetal structure;
subjecting a second mixed reaction system comprising the intermediate, ethylene carbonate, a third organic solvent and a second catalyst to a second reaction to obtain a rigid bio-based diol monomer having a cyclic acetal structure;
wherein the structure of the benzaldehyde substance is shown as a formula II:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
In some embodiments, the benzaldehyde substance includes any one or a combination of two or more of p-hydroxybenzaldehyde, vanillin, ethyl vanillin, syringaldehyde and the like.
In some embodiments, the intermediate having a cyclic acetal structure has the structure shown in formula III:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
In some embodiments, the temperature of the first reaction is 20 ℃ to 150 ℃ and the reaction time is 0.5h to 72 h.
In some embodiments, the temperature of the second reaction is 60 ℃ to 250 ℃ and the reaction time is 0.5h to 72 h.
The embodiment of the invention also provides the rigid bio-based diol monomer with the cyclic acetal structure, which is synthesized by the preparation method.
The embodiment of the invention also provides application of the rigid bio-based diol monomer with the cyclic acetal structure in synthesizing bio-based polyester or polyurethane materials.
After the technical scheme is adopted, compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts benzaldehyde substances and erythritol which are sourced from biology as raw materials, and prepares a brand new rigid biology-based diol monomer with a cyclic acetal structure in high yield through two-step reaction;
2) because the alcoholic hydroxyl groups of the diol molecules provided by the invention are primary alcohols, the polymer has good reactivity when being polymerized, and a polymer with high molecular weight is easily obtained. The acetal ring and benzene ring structures in the molecular structure endow the diol molecules with very high rigidity, and when the diol molecules are used as a polymerization monomer to synthesize bio-based polyester and polyurethane materials, the mechanical property and the heat resistance of the materials are improved to a certain extent. Meanwhile, as the acetal structure can be broken under acidic conditions, the rigid diol with the cyclic acetal structure is introduced into the polyester or polyurethane material, and the polymer has better degradability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a drawing of an embodiment of the present inventionPreparation of intermediate B having a Cyclic Acetal Structure prepared in example 11An H-NMR spectrum;
FIG. 2 is a diagram of the preparation of rigid bio-based diol monomers having cyclic acetal structure according to example 1 of the present invention1H-NMR spectrum.
Detailed Description
As described above, in view of the defects of the prior art, after a great deal of research and creative work, the present inventors have proposed a technical solution of the present invention to improve the comprehensive performance of novel bio-based polyesters and polyurethanes, and successfully synthesized a rigid bio-based diol monomer having a cyclic acetal structure by using a benzaldehyde substance a derived from a bio-based source and erythritol as raw materials. The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a rigid bio-based diol monomer having a cyclic acetal structure, which has a structural formula shown in formula I:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
In particular, in the formula R1And R2Combinations in table 1 can be taken, respectively:
TABLE 1
| Substituent group | Combination 1 | Combination 2 | |
Combination 4 |
| R1 | -H | -H | -H | -OCH3 |
| R2 | -H | -OCH3 | -OCH2CH3 | -OCH3 |
In some embodiments, the structural formula of the rigid bio-based diol monomer having a cyclic acetal structure includes at least any one of formulas IV to VII:
specifically, since the alcoholic hydroxyl groups of the diol molecules are primary alcohols, the polymerization reaction has good reactivity, and a polymer with high molecular weight is easily obtained. The acetal ring and benzene ring structures in the molecular structure endow the diol molecules with very high rigidity, and when the diol molecules are used as a polymerization monomer to synthesize bio-based polyester and polyurethane materials, the mechanical property and the heat resistance of the materials are improved to a certain extent. Meanwhile, as the acetal structure can be broken under acidic conditions, the rigid diol with the cyclic acetal structure is introduced into the polyester or polyurethane material, and the polymer has better degradability.
Another aspect of the embodiments of the present invention provides a method for preparing a rigid bio-based diol monomer having a cyclic acetal structure, comprising:
carrying out a first reaction on a first mixed reaction system containing benzaldehyde substances, erythritol, a first organic solvent, a second organic solvent and a first catalyst to obtain an intermediate with a cyclic acetal structure;
and (3) carrying out a second reaction on a second mixed reaction system containing the intermediate, the ethylene carbonate, a third organic solvent and a second catalyst to obtain the rigid bio-based diol monomer with the cyclic acetal structure.
In some embodiments, the process for preparing the rigid bio-based diol monomer having a cyclic acetal structure specifically comprises the following steps:
s1, adding the benzaldehyde substance A, erythritol, a first organic solvent, a second organic solvent and a first catalyst into a reactor, and heating for reaction.
S2, after the reaction, separating and purifying the reaction mixture to obtain intermediate B having a cyclic acetal structure.
S3, adding the intermediate B, the ethylene carbonate, the third organic solvent and the second catalyst into the reactor, and heating for reaction.
And S4, stopping stirring after the reaction is finished, and separating and purifying the reaction mixture to obtain the rigid bio-based diol monomer with the cyclic acetal structure.
In some more specific embodiments, the preparation process of the rigid bio-based diol monomer with a cyclic acetal structure specifically comprises the following steps:
s1, adding the benzaldehyde substance A, erythritol, the first organic solvent and the second organic solvent into a reaction container with a stirring device, and adding the first catalyst for reaction.
S2, precipitating and separating the reaction mixture in water to obtain a solid product, washing the solid product with water for three times, and fully drying the solid product to obtain the intermediate B with a cyclic acetal structure.
S3, adding the intermediate B, the ethylene carbonate and the third organic solvent into a reaction vessel with a stirring device, and adding the second catalyst for reaction.
S4, precipitating and separating the reaction mixture in water to obtain a solid product, washing the solid product with water for three times, and fully drying to obtain the rigid bio-based diol monomer with the cyclic acetal structure.
In the present invention, as a preferred technical solution, in step S1, the structural formula of the benzaldehyde substance a is shown as formula II:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
In particular, in the formula R1And R2Combinations in table 1 can be taken, respectively:
TABLE 1
| | Combination | 1 | |
|
Combination 4 |
| R1 | -H | -H | -H | -OCH3 | |
| R2 | -H | -OCH3 | -OCH2CH3 | -OCH3 |
Specifically, the four combinations of substituents listed in table 1 respectively represent four different benzaldehyde substances, such as any one or a combination of two or more of p-hydroxybenzaldehyde, vanillin, ethyl vanillin, syringaldehyde, and the like, and the four benzaldehyde substances can be obtained from a bio-based source.
Specifically, the reaction equation of step S1 is shown in formula VIII:
in the formula R1And R2Combinations in table 1 can be taken, respectively:
TABLE 1
| | Combination | 1 | |
|
Combination 4 |
| R1 | -H | -H | -H | -OCH3 | |
| R2 | -H | -OCH3 | -OCH2CH3 | -OCH3 |
In the present invention, as a preferable embodiment, in step S1, the molar ratio of the benzaldehyde substance a to erythritol is 2: (0.9-1.1).
In the present invention, as a preferred embodiment, in step S1, the first organic solvent includes an organic solvent for dissolving the benzaldehyde substance a, erythritol and the catalyst, and in consideration of the solubility of erythritol and the catalyst, the first organic solvent is preferably any one or a combination of two or more of tetrahydrofuran, dioxane, diethyl ether, acetone, butanone, N' -dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like, but is not limited thereto.
Furthermore, in consideration of the requirement of proper solid content for organic reaction, the mass ratio of the first organic solvent to the benzaldehyde substance A is (1-20) to 1.
More specifically, as a preferred technical solution, in step S1, in addition to the first organic solvent, a second organic solvent for carrying out water generated by the reaction through a water separator should be included. The second organic solvent is preferably any one or a combination of two or more of dichloromethane, chloroform, petroleum ether, cyclohexane, methanol, ethanol, ethyl acetate, etc., in consideration of the condition of carrying water, but is not limited thereto.
Furthermore, the mass ratio of the second organic solvent to the benzaldehyde substance A is (1-20) to 1 in consideration of the amount of the solvent required for carrying water.
In the present invention, as a preferable embodiment, the first catalyst in step S1 includes any one or a combination of two or more of ferric chloride, indium fluoride, p-toluenesulfonic acid, and the like, and the first catalyst is preferably p-toluenesulfonic acid in consideration of acidity of the first catalyst.
Further, in the present invention, as a preferable technical solution, in consideration of the catalytic efficiency of the catalyst, in step S1, the amount of the first catalyst is 0.5% to 5% of the molar amount of the benzaldehyde substance a, that is, the molar ratio of the first catalyst to the benzaldehyde substance is 0.5 to 5: 100.
In the present invention, as a preferred embodiment, in step S1, the reaction temperature of the reaction (i.e., the first reaction) is 20 to 150 ℃, and the reaction time is 0.5 to 72 hours.
Further, the temperature of the first reaction is 80-120 ℃, and the reaction time is 8-72 h.
In the present invention, as a preferred embodiment, in step S2, the structure of the intermediate B having a cyclic acetal structure is represented by formula III:
in the formula R1And R2Combinations in table 1 can be taken, respectively:
TABLE 1
| | Combination | 1 | |
|
Combination 4 |
| R1 | -H | -H | -H | -OCH3 | |
| R2 | -H | -OCH3 | -OCH2CH3 | -OCH3 |
Specifically, the reaction equation of step S3 is shown in formula IX:
in the present invention, as a preferable embodiment, in step S3, the molar ratio of the intermediate B to ethylene carbonate is preferably 1: (4 to 8) in view of ensuring completion of the hydroxyethylation reaction.
In the present invention, as a preferred embodiment, in step S3, the third organic solvent includes any one or a combination of two or more of tetrahydrofuran, dioxane, diethyl ether, acetone, butanone, N' -dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like, in consideration of the solubility of the intermediate B, ethylene carbonate, and the catalyst, but is not limited thereto.
In the present invention, as a preferable embodiment, in step S3, the second catalyst may include any one or a combination of two or more of potassium carbonate, sodium hydrogen carbonate, and the like, but is not limited thereto.
Further, in step S3, in consideration of the catalytic efficiency of the catalyst, the amount of the second catalyst is preferably 0.1% to 1% of the molar amount of the intermediate B, that is, in other words, the molar ratio of the second catalyst to the intermediate is 0.1 to 1: 100.
In the present invention, as a preferred embodiment, in step S3, the reaction temperature of the reaction (i.e., the second reaction) is 60 to 250 ℃, and the reaction time is 0.5 to 72 hours.
In another aspect of the embodiments of the present invention, there is also provided a use of the rigid bio-based diol monomer having a cyclic acetal structure in the synthesis of a bio-based polyester or polyurethane material.
Furthermore, since the alcoholic hydroxyl groups of the diol molecules are all primary alcohols, the polymerization reaction has good reactivity, and a polymer with high molecular weight is easily obtained. The acetal ring and benzene ring structures in the molecular structure endow the diol molecules with very high rigidity, and when the diol molecules are used as a polymerization monomer to synthesize bio-based polyester and polyurethane materials, the mechanical property and the heat resistance of the materials are improved to a certain extent. Meanwhile, as the acetal structure can be broken under acidic conditions, the rigid diol with the cyclic acetal structure is introduced into the polyester or polyurethane material, and the polymer has better degradability.
According to the technical scheme, in the preparation method, the benzaldehyde substance A and the erythritol are used as raw materials, and the rigid bio-based diol with the cyclic acetal structure is prepared in a high yield through two-step simple chemical reaction. The preparation process has simple process, simple and convenient operation, good controllability and easy implementation, and is suitable for large-scale industrial production. Moreover, the rigid diol has very high bio-based content, the benzaldehyde substance A and the erythritol which are used as raw materials can be prepared from bio-based sources, the ethylene carbonate used for the hydroxyethylation reaction can also be prepared from the bio-based sources, and the synthetic process is very green and environment-friendly and has important significance on resources and environment.
The rigid bio-based diol monomer containing a cyclic acetal structure and the method for preparing the same will be described in further detail with reference to several preferred embodiments and the accompanying drawings, and it is apparent that the embodiments described are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
In the following examples, NMR spectra1H-NMR was measured using a 400AVANCEIII Spectrometer (Spectrometer) from Bruker, 400MHz, deuterated dimethyl sulfoxide (DMSO).
Example 1
S1, adding 0.4mol of vanillin, 0.2mol of erythritol, 60g N, N' -dimethylformamide, 90g of petroleum ether and 2mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting for 48h at 90 ℃ under stirring.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing with the deionized water for three times, and drying to obtain an intermediate B, wherein the reaction yield in the first step is 95%. The nuclear magnetic resonance hydrogen spectrum of intermediate B having a cyclic acetal structure is shown in fig. 1.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of anhydrous potassium carbonate and 90g of dimethyl sulfoxide are added to a reaction vessel and reacted at 180 ℃ for 8 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times, and drying to obtain the rigid diol monomer with the structural formula shown in the formula V, wherein the reaction yield in the second step is 96%. The hydrogen nuclear magnetic resonance spectrum of the rigid diol monomer having a cyclic acetal structure obtained in this example is shown in FIG. 2.
Example 2
S1, 0.4mol of ethyl vanillin, 0.19mol of erythritol, 40g of dimethyl sulfoxide, 90g of ethyl acetate and 3mmol of p-toluenesulfonic acid are added into a 1L reaction vessel and reacted for 24 hours at 100 ℃ under stirring.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing with the deionized water for three times, and drying to obtain an intermediate B, wherein the reaction yield in the first step is 92%.
S3, 0.1mol of intermediate B, 0.5mol of ethylene carbonate, 0.1mmol of anhydrous potassium carbonate and 90g of dioxane are added to a reaction vessel and reacted at 200 ℃ for 24 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times, and drying to obtain the rigid diol monomer with the structural formula shown in the formula VI, wherein the reaction yield of the second step is 95%.
Example 3
S1, 0.4mol of syringaldehyde, 0.18mol of erythritol, 60g N, N' -dimethylformamide, 90g of petroleum ether and 2mmol of p-toluenesulfonic acid are added into a 1L reaction vessel, and the mixture is reacted for 72 hours at 90 ℃ under stirring.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 90%.
S3, 0.1mol of intermediate B, 0.8mol of ethylene carbonate, 1mmol of sodium carbonate and 70g N-methyl pyrrolidone are added into a reaction vessel and reacted at 250 ℃ for 0.5 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times, and drying to obtain the rigid diol monomer with the structural formula shown in the formula VII, wherein the reaction yield of the second step is 86%.
Example 4
S1, 0.4mol of p-hydroxybenzaldehyde, 0.22mol of erythritol, 50g N, N' -dimethylformamide, 100g of petroleum ether and 3mmol of p-toluenesulfonic acid were added to a 1L reaction vessel, and the mixture was reacted at 95 ℃ for 30 hours with stirring.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 90%.
S3, 0.1mol of intermediate B, 0.8mol of ethylene carbonate, 1mmol of sodium carbonate and 120g of diethyl ether are added to the reaction vessel and reacted at 60 ℃ for 72 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula IV, wherein the reaction yield in the second step is 96%.
Example 5
S1, adding 0.4mol of vanillin, 0.2mol of erythritol, 60g of dioxane, 100g of dichloromethane and 2mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting at 150 ℃ for 5 h.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times, and fully drying the solid product in a vacuum oven at 80 ℃ to obtain an intermediate B, wherein the reaction yield of the first step is 94%.
S3, 0.1mol of intermediate B, 0.5mol of ethylene carbonate, 0.5mmol of sodium carbonate and 90g of acetone are added to the reaction vessel and reacted at 80 ℃ for 72 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula V, wherein the reaction yield of the second step is 94%.
Example 6
S1, adding 0.4mol of vanillin, 0.2mol of erythritol, 30g N-methyl pyrrolidone, 100g of petroleum ether and 2mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting at 130 ℃ for 8 h.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 93%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of sodium bicarbonate and 90g of N-methylpyrrolidone are added to the reaction vessel and reacted at 170 ℃ for 12 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula V, wherein the reaction yield in the second step is 95%.
Example 7
S1, 0.4mol of ethyl vanillin, 0.22mol of erythritol, 60g N, N' -dimethylformamide, 100g of petroleum ether and 20mmol of p-toluenesulfonic acid are added into a 1L reaction vessel and reacted at 150 ℃ for 0.5 h.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 94%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 0.5mmol of anhydrous potassium carbonate and 90g N-methyl pyrrolidone are added into a reaction vessel and reacted at 190 ℃ for 8 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula VI, wherein the reaction yield in the second step is 94%.
Example 8
S1, adding 0.4mol of syringaldehyde, 0.2mol of erythritol, 60g of tetrahydrofuran, 90g of trichloromethane and 2mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting at 90 ℃ for 48 hours.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 90%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of anhydrous potassium carbonate and 90g of dimethyl sulfoxide are added to a reaction vessel and reacted at 180 ℃ for 8 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula VII, wherein the reaction yield in the second step is 92%.
Example 9
S1, 0.4mol of p-hydroxybenzaldehyde, 0.2mol of erythritol, 60g of diethyl ether, 90g of cyclohexane and 2mmol of p-toluenesulfonic acid are added into a 1L reaction vessel and reacted at 90 ℃ for 48 hours.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 91%.
S3, 0.1mol of intermediate B, 0.6mol of ethylene carbonate, 0.1mmol of sodium bicarbonate and 90g of butanone are added to the reaction vessel and reacted at 250 ℃ for 4 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula IV, wherein the reaction yield in the second step is 85%.
Example 10
S1, 0.4mol of p-hydroxybenzaldehyde, 0.18mol of erythritol, 50g of acetone, 100g of methanol and 20mmol of p-toluenesulfonic acid were added to a 1L reaction vessel, and reacted at 20 ℃ for 72 hours.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 95%.
S3, 0.1mol of intermediate B, 0.7mol of ethylene carbonate, 0.5mmol of anhydrous potassium carbonate and 90g of dimethyl sulfoxide are added to a reaction vessel, and the mixture is reacted at 220 ℃ for 18 hours.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula IV, wherein the reaction yield in the second step is 93%.
Example 11
S1, 0.4mol of ethyl vanillin, 0.2mol of erythritol, 60g of dioxane, 100g of ethanol and 10mmol of ferric chloride are added into a 1L reaction vessel and reacted for 72 hours at 70 ℃.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 89%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of anhydrous potassium carbonate and 90g of N, N' -dimethylformamide are added to the reaction vessel and reacted at 230 ℃ for 0.5 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula VI, wherein the reaction yield in the second step is 92%.
Example 12
S1, 0.4mol of syringaldehyde, 0.2mol of erythritol, 40g of butanone, 90g of petroleum ether and 3mmol of indium fluoride are added into a 1L reaction vessel and reacted at 90 ℃ for 48 hours.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 92%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of sodium carbonate and 90g of tetrahydrofuran are added to the reaction vessel and reacted at 180 ℃ for 8 h.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula VII, wherein the reaction yield in the second step is 91%.
Comparative example 1
S1, adding 0.4mol of vanillin, 0.2mol of erythritol, 60g N, N' -dimethylformamide, 90g of petroleum ether and 2mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting at 15 ℃ for 72 h.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 32%.
S3, 0.1mol of intermediate B, 0.4mol of ethylene carbonate, 1mmol of anhydrous potassium carbonate and 90g of dimethyl sulfoxide are added to a reaction vessel and reacted at 140 ℃ for 12 hours.
S4, precipitating and separating the reaction mixture in deionized water to obtain a solid product, washing the solid product with the deionized water for three times to obtain the rigid diol monomer with the structural formula shown in the formula V, wherein the yield of the second step is 75%, and the total yield of the two steps is only 24%.
As can be seen from the comparative analysis of comparative example 1 and examples 1 to 12, the reaction temperature used in comparative example 1 is relatively low, and the target product can be obtained even if the reaction time is prolonged, but the reaction yield is very low, and the practical value is not high. Therefore, it is necessary to obtain a more desirable yield, and the reaction temperature is set within a suitable range.
Comparative example 2
S1, adding 0.4mol of vanillin, 0.2mol of erythritol, 40g of dimethyl sulfoxide and 3mmol of p-toluenesulfonic acid into a 1L reaction vessel, and reacting at 90 ℃ for 48 hours.
S2, precipitating and separating the reaction mixture in deionized water, performing suction filtration to obtain a solid product, washing the solid product with the deionized water for three times to obtain an intermediate B, wherein the reaction yield in the first step is 13%.
As is clear from the comparative analysis between comparative example 2 and examples 1 to 12, in comparative example 2, no organic solvent for carrying water was added in step S1, so that the reaction equilibrium was hardly shifted toward the formation of intermediate B, and the yield in the first step was low, and thus it was not practical. Therefore, it is necessary to obtain a desired reaction yield, and a suitable organic solvent must be added in step S1.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A rigid bio-based diol monomer having a cyclic acetal structure, wherein the bio-based diol monomer has a structural formula as shown in formula I:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
2. A rigid bio-based diol monomer having a cyclic acetal structure according to claim 1, wherein: the structural formula of the rigid bio-based diol monomer with the cyclic acetal structure comprises at least any one of formulas IV to VII:
3. the method for producing a rigid bio-based diol monomer having a cyclic acetal structure according to claim 1 or 2, comprising:
carrying out a first reaction on a first mixed reaction system containing benzaldehyde substances, erythritol, a first organic solvent, a second organic solvent and a first catalyst to obtain an intermediate with a cyclic acetal structure;
subjecting a second mixed reaction system comprising the intermediate, ethylene carbonate, a third organic solvent and a second catalyst to a second reaction to obtain a rigid bio-based diol monomer having a cyclic acetal structure;
wherein the structure of the benzaldehyde substance is shown as a formula II:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
4. The production method according to claim 3, characterized in that: the benzaldehyde substance comprises one or more of p-hydroxybenzaldehyde, vanillin, ethyl vanillin and syringaldehyde;
and/or the first organic solvent comprises one or the combination of more than two of tetrahydrofuran, dioxane, diethyl ether, acetone, butanone, N' -dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; preferably, the second organic solvent comprises any one or a combination of more than two of dichloromethane, trichloromethane, petroleum ether, cyclohexane, methanol, ethanol and ethyl acetate;
and/or the first catalyst comprises at least any one of ferric chloride, indium fluoride and p-toluenesulfonic acid, and is preferably p-toluenesulfonic acid.
5. The production method according to claim 3, characterized in that: the molar ratio of the benzaldehyde substance to the erythritol is 2: 0.9-1.1; and/or the molar ratio of the first catalyst to the benzaldehyde substances is 0.5-5: 100; and/or the mass ratio of the first organic solvent to the benzaldehyde substance is (1-20) to 1; and/or the mass ratio of the second organic solvent to the benzaldehyde substance is (1-20) to 1.
6. The production method according to claim 3, characterized in that: the temperature of the first reaction is 20-150 ℃, preferably 80-120 ℃, and the reaction time is 0.5-72 h, preferably 8-72 h;
and/or the intermediate with the cyclic acetal structure has a structure shown in a formula III:
wherein R is1including-H or-OCH3，R2including-H, -OCH3or-OCH2CH3。
7. The production method according to claim 3, characterized in that: the third organic solvent comprises one or the combination of more than two of tetrahydrofuran, dioxane, diethyl ether, acetone, butanone, N' -dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; and/or the catalyst comprises any one or the combination of more than two of potassium carbonate, sodium carbonate and sodium bicarbonate.
8. The production method according to claim 3, characterized in that: the molar ratio of the intermediate to the ethylene carbonate is 1: 4-8; and/or the molar ratio of the second catalyst to the intermediate is (0.1-1) to 100.
9. The production method according to claim 3, characterized in that: the temperature of the second reaction is 60-250 ℃, and the reaction time is 0.5-72 h.
10. Use of the rigid bio-based diol monomer having a cyclic acetal structure according to claim 1 or 2 for the synthesis of a bio-based polyester or polyurethane material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111035872.8A CN113620968A (en) | 2021-09-03 | 2021-09-03 | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111035872.8A CN113620968A (en) | 2021-09-03 | 2021-09-03 | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113620968A true CN113620968A (en) | 2021-11-09 |
Family
ID=78389194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111035872.8A Pending CN113620968A (en) | 2021-09-03 | 2021-09-03 | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113620968A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603430A (en) * | 2024-01-22 | 2024-02-27 | 西南石油大学 | Light response three-section shape memory polyurethane material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262355A (en) * | 2014-08-29 | 2015-01-07 | 北京化工大学常州先进材料研究院 | Preparation method of biodegradable allyl monomer containing double-dioxane cyclic acetal structure |
| CN109320521A (en) * | 2018-09-28 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | Epoxy monomer and preparation method thereof, epoxy resin |
| CN109456298A (en) * | 2018-12-11 | 2019-03-12 | 常州南京大学高新技术研究院 | A kind of loop coil class diol compound and loop coil class polycarbonate and preparation method thereof |
| CN109516933A (en) * | 2018-10-29 | 2019-03-26 | 安徽省庆云医药股份有限公司 | A kind of preparation method of Silodosin intermediate |
| CN110483259A (en) * | 2019-09-12 | 2019-11-22 | 江苏永星化工股份有限公司 | - two-(2- hydroxyl-oxethyl) -1,1 '-dinaphthalene crystal of a kind of (±) -2,2 ' and preparation method thereof |
-
2021
- 2021-09-03 CN CN202111035872.8A patent/CN113620968A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262355A (en) * | 2014-08-29 | 2015-01-07 | 北京化工大学常州先进材料研究院 | Preparation method of biodegradable allyl monomer containing double-dioxane cyclic acetal structure |
| CN109320521A (en) * | 2018-09-28 | 2019-02-12 | 中国科学院宁波材料技术与工程研究所 | Epoxy monomer and preparation method thereof, epoxy resin |
| CN109516933A (en) * | 2018-10-29 | 2019-03-26 | 安徽省庆云医药股份有限公司 | A kind of preparation method of Silodosin intermediate |
| CN109456298A (en) * | 2018-12-11 | 2019-03-12 | 常州南京大学高新技术研究院 | A kind of loop coil class diol compound and loop coil class polycarbonate and preparation method thereof |
| CN110483259A (en) * | 2019-09-12 | 2019-11-22 | 江苏永星化工股份有限公司 | - two-(2- hydroxyl-oxethyl) -1,1 '-dinaphthalene crystal of a kind of (±) -2,2 ' and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MITSUKAZU OCHI, 等: "Mechanical and Dielectric Relaxations of Epoxide Resins Containing the Spiro-ring Structure. 11. Effect of the Introduction of Methoxy Branches on Low-temperature Relaxations of Epoxide Resins", 《JOURNAL OF POLYMER SCIENCE, PART B, POLYMER PHYSICS》 * |
| SMITA V. MANKAR，等: "Synthesis, Life Cycle Assessment, and Polymerization of a Vanillin-Based Spirocyclic Diol toward Polyesters with Increased Glass-Transition Temperature", 《ACS SUSTAINABLE CHEM. ENG.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603430A (en) * | 2024-01-22 | 2024-02-27 | 西南石油大学 | Light response three-section shape memory polyurethane material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109988290B (en) | Preparation method of oligomeric metalloporphyrin complex and polycarbonate | |
| CN109734684B (en) | Bio-based flame-retardant epoxy resin precursor based on natural phenolic monomers, and preparation method and application thereof | |
| CN111423580B (en) | Shape memory resin based on biomass benzoxazine and preparation method and application thereof | |
| CN110922394B (en) | Bio-based intrinsic flame-retardant epoxy resin precursor based on natural flavonoid compound and preparation method and application thereof | |
| CN114478635B (en) | Chromium compound, preparation method thereof and preparation method of multi-block polyester material | |
| CN113620968A (en) | Rigid bio-based diol monomer with cyclic acetal structure, and preparation method and application thereof | |
| CN110835402B (en) | Low-viscosity bio-based epoxy resin based on vanillin and preparation method thereof | |
| CN114011459B (en) | Titanium double-acid ionic liquid catalyst and preparation method and application thereof | |
| CN114591188A (en) | Full-bio-based aryl diamine chain extender and preparation method and application thereof | |
| CN104031256B (en) | A kind of method preparing polycarbonate | |
| CN111138285A (en) | Method for synthesizing organic carbonate from carbon dioxide, alcohol and brominated alkanes under mild condition | |
| CN108570143B (en) | Method for catalyzing polymerization of glycolide by using aluminum compound containing chiral cyclohexanediamine | |
| CN113234394B (en) | Polyester-based hydrogenated rosin, preparation method and application thereof | |
| CN102531970B (en) | Carbohydrazide and fast synthesis method thereof | |
| CN112920300B (en) | Large steric hindrance alpha-diimine ligand, nickel catalyst, preparation method and application thereof | |
| CN108623795A (en) | A kind of polyester, Preparation method and use based on full biomass monomer | |
| CN107641197A (en) | A kind of copolyreaction catalyst using carbon dioxide with 7-oxa-bicyclo[4.1.0 as monomer | |
| TW202000636A (en) | Process for preparing bis(2-hydroxyethyl) terephthalate | |
| CN108003183B (en) | Method for catalyzing caprolactone polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound | |
| CN111574513A (en) | Monomer for biomass benzoxazine shape memory resin and preparation method and application thereof | |
| CN114933622B (en) | Preparation method of glucoside ruthenium compound | |
| CN115028834B (en) | Polyaryltriazole and preparation method and application thereof | |
| CN115093565B (en) | Polyphenyl sulfone ether triazole and preparation method and application thereof | |
| CN111499524B (en) | Method for preparing amino alcohol compound by using halogenated intermediate | |
| KR101921484B1 (en) | Norbornene-based compound and method of preparing the norbornene-based compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211109 |