CN114989187A - Spiro-carbon ortho ester and preparation method thereof - Google Patents
Spiro-carbon ortho ester and preparation method thereof Download PDFInfo
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- CN114989187A CN114989187A CN202111295808.3A CN202111295808A CN114989187A CN 114989187 A CN114989187 A CN 114989187A CN 202111295808 A CN202111295808 A CN 202111295808A CN 114989187 A CN114989187 A CN 114989187A
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- 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
- C07D493/10—Spiro-condensed systems
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the technical field of C07D expansion monomers, and particularly provides a spiro-carbon orthoester and a preparation method thereof. The invention provides a spiro-carbon orthoester, which is prepared from a polyol compound, a catalyst and an organic solvent. Compared with the prior art, the prepared spiro-carbon orthoester has an aromatic ring structure and polar groups with certain density, and a rigid structure with certain density is introduced into the composite material while the volume shrinkage of the composite material is eliminated, so that the mechanical property of the composite material is improved, the service life of the composite material is prolonged, and the application range of the composite material is widened.
Description
Technical Field
The invention relates to the technical field of C07D expansion monomers, and particularly provides a spiro-carbon orthoester and a preparation method thereof.
Background
In the industrial field, various resins are inevitably used in the preparation and processing processes of the composite material, and the resins are easy to generate volume shrinkage in the actual use process, so that the performance of the prepared composite material is correspondingly reduced. The appearance of the expansion monomer provides a new idea for solving the problems, and the spiro-carbon orthoester compound is used as an important expansion monomer and is widely applied to various fields of medicines, industries, materials and the like due to excellent physical and chemical properties.
The method for preparing spiro cyclic orthoesters in the prior art comprises the following steps: firstly, ketone and ethylene oxide are catalyzed by Lewis acid to prepare spiro-orthocarbonate and derivatives thereof; secondly, obtaining a spiro-ring carbon orthoester compound containing an unsaturated bond by using lactone and olefin oxide containing halogen under the condition of Lewis acid catalysis; and thirdly, carrying out addition reaction on unsaturated acetal and olefin with an electron-withdrawing group to prepare spiro cyclic orthoester and derivatives thereof.
Chinese patent with patent publication No. CN111039952A discloses a synthesis method and application of an epoxy resin low-curing-shrinkage expansion monomer, wherein tetrahydrobenzaldehyde and formaldehyde solution are used as raw materials to obtain corresponding epoxy group-containing spiro-carbonate through a series of chemical reactions. However, the tetrahydrobenzaldehyde adopted in the scheme has serious stimulation effect on the skin, respiratory tract, eyes, lungs and the like of an operator, and is not beneficial to the long-term popularization and application of the scheme.
Chinese patent publication No. CN112812124A discloses a method for preparing a novel spiro-swelling monomer matrix containing unsaturated bonds and ester groups, which uses trimethylolpropane as a raw material to synthesize corresponding unsaturated spiro-ring orthoester and its derivatives in the presence of a catalyst, but the synthesis process steps are numerous, and are not suitable for industrial-scale mass production.
Therefore, the development of the spiro-carbon orthoester expansion monomer which has the advantages of simple and easily obtained raw materials, simple synthesis process and good expansion efficiency has potential market value.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a spiro-orthocarbonate, which is prepared from the following raw materials: polyol compound, catalyst and organic solvent.
The structural formula of the polyalcohol compound is as follows:
wherein R is any one of hydrogen, methyl and chlorine.
In a preferred embodiment of the present invention, the catalyst is an organometallic tin catalyst.
In a more preferred embodiment of the present invention, the organometallic tin catalyst is di-n-butyltin oxide.
In a preferred embodiment of the present invention, the organic solvent is at least one of toluene and xylene.
In a more preferred embodiment of the present invention, the organic solvent is toluene.
The second aspect of the present invention provides a method for preparing a spiro-orthocarbonate, comprising the steps of:
(1) adding a polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 10-15 hours at the reaction temperature of 110-150 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 20-30 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 95-105 ℃, and reacting for 10-15 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) washing the crude product A in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester;
the structural formula of the spiro cyclic orthoester is as follows:
wherein R is any one of hydrogen, methyl and chlorine.
As a preferred technical scheme of the invention, the reaction temperature in the step (1) is 130 ℃.
In a preferred embodiment of the present invention, the molar ratio of the polyol compound, the catalyst, and the carbon disulfide is (0.5 to 1.5): (1-2): (1.5-2.5).
In a more preferred embodiment of the present invention, the molar ratio of the polyol compound, the catalyst, and carbon disulfide is (0.8 to 1.2): (1-1.5): (1.7-2.4).
In a most preferred embodiment of the present invention, the molar ratio of the polyol compound, the catalyst, and the carbon disulfide is 1: 1.2: 1.6.
compared with the prior art, the invention has the following beneficial effects:
1. when the reaction substrate is trihydric alcohol with various substituent groups connected on the aromatic ring, the spiro carbonate prepared by the invention is found to have no obvious influence on the yield of spiro carbonate no matter whether the spiro carbonate is connected with an electron-donating group such as 4-methyl or an electron-withdrawing group such as 4-nitro, and the corresponding target product is obtained with the yield of 70-85%; when the aromatic ring of the trihydric alcohol is connected with electron-donating groups such as 2-methyl, 3-methyl and 4-methyl, the corresponding spiro-carbonate can be obtained at a yield of 75-90%, which shows that the electronic property and steric hindrance of the reaction substrate trihydric alcohol have no obvious influence on the reaction, and the scheme has excellent functional group tolerance;
2. the spiro-carbon orthoester is prepared by the method, and when the molar ratio of the polyol compound to the di-n-butyltin oxide to the carbon disulfide is 1: 1.2: 1.6, the metal complexing effect of di-n-butyltin oxide and the polyalcohol compounds is the best, the atom utilization rate of the polyalcohol compounds is effectively improved, and the yield of the spiro-orthocarbonate is improved;
3. the spiro-carbonate prepared by the invention adopts the trihydric alcohol and the derivative thereof which are harmless and pollution-free to the environment and human body, the raw materials of the whole synthesis process are simple and easy to obtain, safe and harmless, the operation is simple and convenient, the post-treatment is simple, and meanwhile, when the reaction temperature is 145 ℃, the volatilization rate of toluene can be effectively reduced, the effective components of the reaction system are controlled within a certain concentration range, the conversion rate of the reaction substrate polyalcohol compounds is improved, and the yield of the spiro-carbonate is improved;
4. the spiro-carbon orthoester prepared by the invention has an aromatic ring structure with a certain density, and in the industrial practical application process, a rigid structure with a certain density is introduced into the composite material while the volume shrinkage of the composite material is eliminated, so that the mechanical property of the composite material is improved; meanwhile, an electron-donating group or an electron-withdrawing group with a certain concentration is connected in the aromatic ring structure, so that the collision frequency among components in a composite material system can be improved through the electronic effect among all groups, and the overall performance of the composite material is improved;
5. the spiro-carbon orthoester prepared by the invention contains an aromatic ring structure with electronic property and polar groups with certain density, and in the application process of the industrial field, the spiro-structure can effectively solve the phenomenon of composite material shrinkage while carrying out ring-opening volume expansion, and simultaneously the polar groups in the molecular structure can also interact with other active groups in a composite material system, so that the compatibility of the system is enhanced, the interaction among active components is promoted, the stability of the composite material is improved, the service life of the composite material is prolonged, and the application range of the composite material is enlarged.
Detailed Description
Examples
Example 1
Embodiment 1 provides a spiro-carboorthoester, which is prepared from the following components: polyol compound, catalyst and organic solvent.
The structural formula of the polyalcohol compound is as follows:
the catalyst is di-n-butyl tin oxide;
the organic solvent is toluene.
The preparation method of the spiro cyclic orthoester comprises the following steps:
(1) adding 1g of polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 12 hours at the reaction temperature of 130 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 25 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 100 ℃, and reacting for 10 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) and (4) washing the crude product A obtained in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester.
The volume of the organic solvent in the step (1) is 10 mL;
the reaction temperature in the step (1) is 130 ℃;
the molar ratio of the polyol compound to the di-n-butyl tin oxide to the carbon disulfide is 1: 1.2: 1.6;
the structural formula of the spiro cyclic orthoester is as follows:
the yield of the spirocyclic orthoester was 85%.
Example 2
Embodiment 2 provides a spiro-orthocarbonate, which is prepared from the following components: polyol compound, catalyst and organic solvent.
The structural formula of the polyalcohol compound is as follows:
the catalyst is di-n-butyl tin oxide;
the organic solvent is toluene.
The preparation method of the spiro cyclic orthoester comprises the following steps:
(1) adding 1g of polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 12 hours at the reaction temperature of 130 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 25 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 100 ℃, and reacting for 10 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) and (4) washing the crude product A obtained in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester.
The volume of the organic solvent in the step (1) is 10 mL;
the reaction temperature in the step (1) is 130 ℃;
the molar ratio of the polyol compound to the di-n-butyl tin oxide to the carbon disulfide is 1: 1.2: 1.6;
the structural formula of the spiro cyclic orthoester is as follows:
the yield of the spiro cyclic orthoester was 70%.
Example 3
Embodiment 3 provides a spiro-carboorthoester, which is prepared from the following components: polyol compounds, catalysts and organic solvents.
The structural formula of the polyalcohol compound is as follows:
the catalyst is di-n-butyl tin oxide;
the organic solvent is toluene.
The preparation method of the spiro cyclic orthoester comprises the following steps:
(1) adding 1g of polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 12 hours at the reaction temperature of 130 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 25 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 100 ℃, and reacting for 10 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) and (4) washing the crude product A obtained in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester.
The volume of the organic solvent in the step (1) is 10 mL;
the reaction temperature in the step (1) is 130 ℃;
the molar ratio of the polyalcohol compound to the di-n-butyltin oxide to the carbon disulfide is 1: 1.2: 1.6;
the structural formula of the spiro cyclic orthoester is as follows:
the yield of the spiro cyclic orthoester was 82%.
Example 4
Embodiment 4 provides a spiro-carboorthoester, which is prepared from the following components: polyol compound, catalyst and organic solvent.
The structural formula of the polyalcohol compound is as follows:
the catalyst is di-n-butyl tin oxide;
the organic solvent is toluene.
The preparation method of the spiro cyclic orthoester comprises the following steps:
(1) adding 1g of polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 12 hours at the reaction temperature of 130 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 25 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 100 ℃, and reacting for 10 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) and (4) washing the crude product A obtained in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester.
The volume of the organic solvent in the step (1) is 10 mL;
the reaction temperature in the step (1) is 130 ℃;
the molar ratio of the polyalcohol compound to the di-n-butyltin oxide to the carbon disulfide is 1: 1.2: 1.6;
the structural formula of the spiro cyclic orthoester is as follows:
the yield of the spiro cyclic orthoester was 83%.
Evaluation of Properties
1. Yield:
yield ═ 100% of (m2/m1), m2 for the actual mass of the spirocyclic orthocarbonate and m1 for the theoretical mass of the spirocyclic orthocarbonate, and the measured data are shown in table 1;
2. and (3) testing the expansibility of the system:
the spirocyclic orthocarbonates prepared in examples 1-4 were tested for volume expansion rate.
(1) The volume V1 of PA6, model TF100S, available from Xuzhou Tengfei engineering plastics, Inc,
(2) the PA6 and the spiro-orthocarbonate prepared in examples 1 to 4 were melt-blended at 230 ℃ for 10min, cooled to room temperature and measured for volume V2;
the volume shrinkage of PA6 is (V2-V1)/V1X 100%, and the smaller the volume shrinkage of PA6 is, the better the volume expansion of spiro cyclic orthoester is shown, and the measured data are shown in Table 1.
TABLE 1
| Yield of | Volume shrinkage/% of PA6 | |
| Example 1 | 85 | 0.47 |
| Example 2 | 70 | 0.45 |
| Example 3 | 82 | 0.56 |
| Example 4 | 83 | 0.48 |
Claims (10)
1. The spiro-carbon orthoester is characterized in that the preparation raw materials comprise the following components: polyol compounds, catalysts, organic solvents;
the structural formula of the polyalcohol compound is shown as a formula (1):
wherein R is any one of hydrogen, methyl and chlorine.
2. A spiro cyclic orthoester according to claim 1, wherein said catalyst is an organometallic tin catalyst.
3. A spirocyclic orthoester in accordance with claim 2, wherein said organo-metallic tin catalyst is di-n-butyltin oxide.
4. A spiro cyclic orthoester according to claim 1, wherein said organic solvent is at least one of toluene and xylene.
5. A spiro cyclic orthoester according to claim 1 or 3, characterized in that said organic solvent is toluene.
6. A process for the preparation of a spirocyclic orthoester as claimed in any of claims 1 to 5, comprising the steps of:
(1) adding a polyol compound, a catalyst and an organic solvent into a round-bottom flask, and reacting for 10-15 hours at the reaction temperature of 110-150 ℃ to obtain a mixture A;
(2) cooling the mixture A in the step (1) to 20-30 ℃, slowly dropwise adding carbon disulfide into a round-bottom flask, heating the reaction temperature to 95-105 ℃, and reacting for 10-15 hours to obtain a mixture B;
(3) cooling the mixture B in the step (2) to room temperature, and evaporating the organic solvent on a rotary evaporator to obtain a crude product A;
(4) washing the crude product A in the step (3) by using normal hexane, and then carrying out suction filtration, toluene recrystallization and drying to obtain the spiro-carbon orthoester;
the structural formula of the spiro-carbon orthoester is shown as a formula (2):
wherein R is any one of hydrogen, methyl and chlorine.
7. A process according to claim 6, wherein the molar ratio of said polyol compound to said catalyst to said carbon disulfide is (0.5 to 1.5): (1-2): (1.5-2.5).
8. A process for the preparation of a spirocyclic orthoester according to claim 6 or 7, wherein the molar ratio of said polyol compound, catalyst, carbon disulfide is (0.8-1.2): (1-1.5): (1.7-2.4).
9. A process according to claim 6, wherein the molar ratio of said polyol compound to said catalyst to said carbon disulfide is 1: 1.2: 1.6.
10. a process for the preparation of a spirocyclic orthoester according to claim 6, wherein said reaction temperature in step (1) is 130 ℃.
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Citations (5)
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| CN102153563A (en) * | 2011-03-10 | 2011-08-17 | 沈阳化工大学 | Method for synthesizing spiro-orthocarbonate expansive monomer |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
| CN102321097A (en) * | 2011-07-18 | 2012-01-18 | 沈阳化工大学 | Synthesis method of screw ring orthocarbonicester monomer |
| CN103601734A (en) * | 2013-11-19 | 2014-02-26 | 沈阳化工大学 | Method for synthesizing chlorinated spiro-orthocarbonate from hydrolyzate of epoxy chloropropane |
| CN112830934A (en) * | 2021-02-26 | 2021-05-25 | 汕头市骏码凯撒有限公司 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
-
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- 2021-11-03 CN CN202111295808.3A patent/CN114989187A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153563A (en) * | 2011-03-10 | 2011-08-17 | 沈阳化工大学 | Method for synthesizing spiro-orthocarbonate expansive monomer |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
| CN102321097A (en) * | 2011-07-18 | 2012-01-18 | 沈阳化工大学 | Synthesis method of screw ring orthocarbonicester monomer |
| CN103601734A (en) * | 2013-11-19 | 2014-02-26 | 沈阳化工大学 | Method for synthesizing chlorinated spiro-orthocarbonate from hydrolyzate of epoxy chloropropane |
| CN112830934A (en) * | 2021-02-26 | 2021-05-25 | 汕头市骏码凯撒有限公司 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
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