CN112390931A - Preparation method of dihydroxydicyclohexyl propane - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
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- C08K2003/329—Phosphorus containing acids
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Abstract
The invention discloses a preparation method of dihydroxydicyclohexylpropane, which comprises the following specific steps: preparing raw materials and preparing a catalyst, namely putting 10-100% of raw material solution of bisphenol A into a metering pump for metering and pressurizing, mixing the pressurized raw material solution with high-pressure hydrogen metered by a flow controller in a pipeline, adding 10-100% of bisphenol A, 10-100% of dihydric alcohol and 1-100% of epoxy chloropropane into a closed pipe after the pressurizing is finished, preheating to about 80 ℃, then adding 1-100% of catalyst and 1-100% of curing agent, heating and pressurizing under stirring, keeping the temperature of a reaction system at 100 ℃ and 200 ℃, keeping the hydrogen pressure at 3-5MPa, and obtaining a product, namely dihydroxydicyclohexyl propane. And the ultraviolet-resistant coating is not easily influenced by ultraviolet rays, so that the ultraviolet-resistant coating has excellent ultraviolet resistance, the cost is reduced, and the yield is high.
Description
Technical Field
The invention relates to the technical field of dihydroxydicyclohexyl propane, in particular to a preparation method of dihydroxydicyclohexyl propane.
Background
Enamel, also known as enamel, is a composite material in which an inorganic vitreous material is fused to a base metal and is firmly bonded to the metal.
Dihydroxydicyclohexylpropane, also known as hydrogenated bisphenol a (HBPA, CAS: 1980-4-6, C15H28O2, M ═ 240.38), is an alicyclic diol obtained by hydrogenating and saturating two benzene rings in the bisphenol a molecule. The dihydroxydicyclohexyl propane has three isomers, the common product is generally a mixture of the three isomers, the boiling point is 253-257 ℃ (2.67KPa), the product is white solid, insoluble in water, soluble in organic solvents such as benzene and acetone, and hygroscopic.
Dihydroxydicyclohexyl propane is one of the most commonly used substances in the preparation of polymers such as epoxy resin, polycarbonate, polyacrylic resin, unsaturated resin and the like, has the advantages of thermal stability, chemical stability, weather resistance and the like, and is particularly suitable for outdoor use. Such as dihydroxy dicyclohexyl propane, dibasic acid phthalic acid, maleic acid and the like to obtain high-temperature-resistant and moisture-resistant polyester resin; the epoxy resin obtained by reacting dihydroxydicyclohexylpropane with epichlorohydrin exhibits excellent electrical characteristics and weather resistance. This is mainly because dihydroxydicyclohexylpropane does not contain an aromatic structure, has high stability and yellowing resistance, and has excellent processability even at low viscosity, and the like. Therefore, the dihydroxydicyclohexyl propane is an important chemical raw material and has extremely wide application and development prospects in various aspects such as special epoxy resin and the like.
Dihydroxydicyclohexylpropane is usually prepared from bisphenol a in solution by catalytic hydrogenation. The reaction is a hydrogenation reaction of aromatic compounds, and theoretically, substances having hydrogenation catalytic activity to aromatic compounds such as benzene rings can be used for hydrogenation reduction of bisphenol a. In the past decades, researchers have proposed various methods for preparing dihydroxydicyclohexylpropane, wherein optimization and improvement of the hydrogenation catalyst are the key research content in various preparation methods. At present, there are three main types of catalysts for bisphenol a hydrogenation reduction: metal framework type catalysts, noble metal supported catalysts and modified alkaline earth metal catalysts. Among them, the method of hydrogenating and reducing the aromatic ring of bisphenol A by using a noble metal-supported catalyst (metal-impregnated catalyst) is most widely used. Although the noble metal supported catalyst is expensive, the noble metal supported catalyst has higher activity and better selectivity, and makes up for the defect of high price, so the noble metal supported catalyst is widely seen. The research results reported so far mostly adopt a modified noble metal supported catalyst or a method of selecting a certain reaction solvent to improve the reaction yield or/and the reaction rate, the reaction conditions are generally 50-250 ℃, the hydrogen pressure is 1-30MPa, a batch or continuous hydrogenation process flow can be adopted, and the reaction products can be separated and purified by using a vacuum rectification or recrystallization process.
Dihydroxydicyclohexyl propane is one of the most commonly used substances in the preparation of polymers such as epoxy resin, polycarbonate, polyacrylic resin, unsaturated resin and the like, and hydrogenated bisphenol A type epoxy resin formed by dihydroxydicyclohexyl propane prepared in the prior art has low weather resistance, low tracking resistance, low dielectric strength, chemical resistance, susceptibility to the influence of ultraviolet rays, high cost and high energy consumption.
Therefore, it is necessary to develop a method for preparing dihydroxydicyclohexylpropane to solve the above problems.
Disclosure of Invention
In order to overcome the above defects in the prior art, embodiments of the present invention provide a method for preparing dihydroxydicyclohexylpropane, which comprises the following specific steps:
the method comprises the following steps: preparation of raw materials: 10-100% of bisphenol A, 30-80% of pseudo-boehmite, 10-40% of aluminum hydroxide, 1-5% of alkali metal element, 1-5% of phosphoric acid, 1-3% of noble metal, 0.5-1.5% of graphene, 1-100% of curing agent, 10-100% of dihydric alcohol and 1-100% of epoxy chloropropane;
step two: preparation of the catalyst: preparing 1-100% of catalyst by using 30-80% of pseudo-boehmite, 10-40% of aluminium hydroxide, 1-5% of alkali metal element, 1-5% of phosphoric acid, 1-3% of noble metal and 0.5-1.5% of graphene;
step three: putting the raw material solution of bisphenol A10% -100% into a metering pump for metering and pressurizing, and mixing the pressurized raw material solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 10-100% of bisphenol A, 10-100% of dihydric alcohol and 1-100% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: adding 1-100% of catalyst and 1-100% of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Preferably, 1% -3% of the active components of the noble metal in the catalyst are pd, Ru and Rh,
preferably, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Preferably, the phosphoric acid can also be replaced by phosphorous acid.
Preferably, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Preferably, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
The invention has the technical effects and advantages that:
through the experimental process flow, the dihydroxydicyclohexyl propane is one of the most commonly used substances in the preparation of polymers such as epoxy resin, polycarbonate, polyacrylic resin, unsaturated resin and the like, and the hydrogenated bisphenol A epoxy resin formed by the dihydroxydicyclohexyl propane designed by the technology has good weather resistance, corona resistance, tracking resistance, high dielectric strength and chemical resistance, is not easily influenced by ultraviolet rays, has excellent ultraviolet resistance, reduces the cost and simultaneously ensures that the output is higher.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a preparation method of dihydroxydicyclohexyl propane, which comprises the following steps:
the method comprises the following steps: preparation of raw materials: 10% of bisphenol A, 30% of pseudo-boehmite, 10% of aluminum hydroxide, 1% of alkali metal element, 1% of phosphoric acid, 1% of noble metal, 0.5% of graphene, 1% of curing agent, 10% of dihydric alcohol and 1% of epichlorohydrin;
step two: preparation of the catalyst: preparing a catalyst 1% by using 30% of pseudo-boehmite, 10% of aluminum hydroxide, 1% of alkali metal element, 1% of phosphoric acid, 1% of noble metal and 0.5% of graphene;
step three: adding 10% bisphenol A raw material solution into a metering pump for metering and pressurizing, and mixing the pressurized solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 10% of bisphenol A, 10% of dihydric alcohol and 1% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: adding 1-100% of catalyst and 1% of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Further, in the scheme, 1-3% of active components of the noble metal in the catalyst are pd, Ru and Rh,
further, in the above scheme, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Further, in the above scheme, the phosphoric acid may be used instead of phosphorous acid.
Further, in the above scheme, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Further, in the scheme, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
The hydrogenated bisphenol A epoxy resin formed by the dihydroxydicyclohexyl propane prepared in the embodiment has low weather resistance, low corona resistance, low tracking resistance, low dielectric strength, no chemical resistance, and excellent ultraviolet resistance due to the influence of ultraviolet rays, and the output is low although the cost is reduced.
Example 2:
the invention provides a preparation method of dihydroxydicyclohexyl propane, which comprises the following steps:
the method comprises the following steps: preparation of raw materials: 20% of bisphenol A, 30% of pseudo-boehmite, 10% of aluminum hydroxide, 1.5% of alkali metal element, 2% of phosphoric acid, 1% of noble metal, 0.5% of graphene, 20% of curing agent, 20% of dihydric alcohol and 20% of epoxy chloropropane;
step two: preparation of the catalyst: preparing a catalyst 20% by using 30% of pseudo-boehmite, 10% of aluminum hydroxide, 1.5% of alkali metal element, 2% of phosphoric acid, 1% of noble metal and 0.5% of graphene;
step three: adding 20% bisphenol A raw material solution into a metering pump for metering and pressurizing, and mixing the pressurized solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 20% of bisphenol, 20% of dihydric alcohol and 20% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: then adding 20 percent of catalyst and 20 percent of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Further, in the scheme, 1-3% of active components of the noble metal in the catalyst are pd, Ru and Rh,
further, in the above scheme, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Further, in the above scheme, the phosphoric acid may be used instead of phosphorous acid.
Further, in the above scheme, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Further, in the scheme, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
The hydrogenated bisphenol A epoxy resin formed by the dihydroxydicyclohexyl propane prepared in the embodiment has low weather resistance, low corona resistance, low tracking resistance, low dielectric strength, no chemical resistance, and excellent ultraviolet resistance due to the influence of ultraviolet rays, and the output is low although the cost is reduced.
Example 3:
the invention provides a preparation method of dihydroxydicyclohexyl propane, which comprises the following steps:
the method comprises the following steps: preparation of raw materials: 50% of bisphenol A, 40% of pseudo-boehmite, 20% of aluminum hydroxide, 3% of alkali metal element, 2.5% of phosphoric acid, 2% of noble metal, 1% of graphene, 50% of curing agent, 50% of dihydric alcohol and 50% of epoxy chloropropane;
step two: preparation of the catalyst: preparing 50% of catalyst by using 40% of pseudo-boehmite, 20% of aluminum hydroxide, 3% of alkali metal element, 2.5% of phosphoric acid, 2% of noble metal and 1% of graphene;
step three: adding 50% bisphenol A raw material solution into a metering pump for metering and pressurizing, and mixing the pressurized solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 50% of bisphenol A, 50% of dihydric alcohol and 50% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: then adding 50 percent of catalyst and 50 percent of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Further, in the scheme, 1-3% of active components of the noble metal in the catalyst are pd, Ru and Rh,
further, in the above scheme, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Further, in the above scheme, the phosphoric acid may be used instead of phosphorous acid.
Further, in the above scheme, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Further, in the scheme, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
As is apparent from the comparison of example 2, the hydrogenated bisphenol a epoxy resin formed from dihydroxydicyclohexylpropane prepared in this example has good weather resistance, corona resistance, tracking resistance, high dielectric strength, chemical resistance, and is not easily affected by ultraviolet rays, so that the epoxy resin has excellent ultraviolet resistance, the cost is reduced, and the yield is high.
Example 4:
the invention provides a preparation method of dihydroxydicyclohexyl propane, which comprises the following steps:
the method comprises the following steps: preparation of raw materials: 80% of bisphenol A, 60% of pseudo-boehmite, 30% of aluminum hydroxide, 3% of alkali metal element, 4% of phosphoric acid, 3% of noble metal, 1.2% of graphene, 80% of curing agent, 80% of dihydric alcohol and 80% of epoxy chloropropane;
step two: preparation of the catalyst: preparing 80% of catalyst by using 60% of pseudo-boehmite, 30% of aluminium hydroxide, 3% of alkali metal element, 4% of phosphoric acid, 3% of noble metal and 1.2% of graphene;
step three: adding 80% bisphenol A raw material solution into a metering pump for metering and pressurizing, and mixing the pressurized solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 80% of bisphenol A, 80% of dihydric alcohol and 80% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: adding 80% of catalyst and 80% of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Further, in the scheme, 1-3% of active components of the noble metal in the catalyst are pd, Ru and Rh,
further, in the above scheme, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Further, in the above scheme, the phosphoric acid may be used instead of phosphorous acid.
Further, in the above scheme, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Further, in the scheme, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
As is apparent from the comparison of example 3, the hydrogenated bisphenol a epoxy resin formed from dihydroxydicyclohexylpropane prepared in this example has better weather resistance, better corona resistance, better tracking resistance, higher dielectric strength, better chemical resistance, and is not affected by ultraviolet rays so that the epoxy resin has excellent ultraviolet resistance, and although the cost is reduced, the output is moderate.
Experimental example 5:
the invention provides a preparation method of dihydroxydicyclohexyl propane, which comprises the following steps:
the method comprises the following steps: preparation of raw materials: 100% of bisphenol A, 80% of pseudo-boehmite, 40% of aluminum hydroxide, 5% of alkali metal element, 5% of phosphoric acid, 3% of noble metal, 1.5% of graphene, 100% of curing agent, 100% of dihydric alcohol and 100% of epoxy chloropropane;
step two: preparation of the catalyst: preparing 100% of catalyst by using 80% of pseudo-boehmite, 40% of aluminum hydroxide, 5% of alkali metal element, 5% of phosphoric acid, 3% of noble metal and 1.5% of graphene;
step three: putting 100% bisphenol A raw material solution into a metering pump for metering and pressurizing, and mixing the pressurized raw material solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, 100 percent of bisphenol A, 100 percent of dihydric alcohol and 100 percent of epoxy chloropropane are added into a closed pipe and preheated to about 80 ℃;
step five: adding 1-100% of catalyst and 100% of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
Further, in the scheme, 1-3% of active components of the noble metal in the catalyst are pd, Ru and Rh,
further, in the above scheme, the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
Further, in the above scheme, the phosphoric acid may be used instead of phosphorous acid.
Further, in the above scheme, the component in 1% -5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
Further, in the scheme, 1% -100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
As is apparent from the comparison of example 4, the hydrogenated bisphenol a epoxy resin formed from dihydroxydicyclohexylpropane prepared in this example has good weather resistance, good corona resistance, good tracking resistance, high dielectric strength, good chemical resistance, and is not affected by ultraviolet rays, so that the resin has excellent ultraviolet resistance, and although the cost is reduced, the output is moderate.
The following table is obtained according to examples 1 to 3:
as can be seen from the above table, the raw material ratio for the production in example 3 is moderate, and the hydrogenated bisphenol a epoxy resin formed from the dihydroxy dicyclohexyl propane prepared by the method has good weather resistance, corona resistance, tracking resistance, high dielectric strength, chemical resistance, and is not easily affected by ultraviolet rays, so that the epoxy resin has excellent ultraviolet resistance, the cost is reduced, and the yield is high.
Finally, it should be noted that: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of dihydroxydicyclohexyl propane is characterized in that: the preparation steps are as follows:
the method comprises the following steps: preparation of raw materials: 10-100% of bisphenol A, 30-80% of pseudo-boehmite, 10-40% of aluminum hydroxide, 1-5% of alkali metal element, 1-5% of phosphoric acid, 1-3% of noble metal, 0.5-1.5% of graphene, 1-100% of curing agent, 10-100% of dihydric alcohol and 1-100% of epoxy chloropropane;
step two: preparation of the catalyst: preparing 1-100% of catalyst by using 30-80% of pseudo-boehmite, 10-40% of aluminium hydroxide, 1-5% of alkali metal element, 1-5% of phosphoric acid, 1-3% of noble metal and 0.5-1.5% of graphene;
step three: putting the raw material solution of bisphenol A10% -100% into a metering pump for metering and pressurizing, and mixing the pressurized raw material solution with high-pressure hydrogen metered by a flow controller in a pipeline;
step four: after mixing, adding 10-100% of bisphenol A, 10-100% of dihydric alcohol and 1-100% of epichlorohydrin into a closed pipe, and preheating to about 80 ℃;
step five: adding 1-100% of catalyst and 1-100% of curing agent, heating and boosting under stirring, keeping the temperature of the reaction system at 100 ℃ and 200 ℃ and the hydrogen pressure at 3-5MPa, and obtaining the product, namely the dihydroxydicyclohexyl propane.
2. The method according to claim 1, wherein the dihydroxy dicyclohexyl propane is prepared by: the catalyst contains 1-3% of noble metal Pd, Ru and Rh as active components.
3. The method according to claim 2, wherein the dihydroxy dicyclohexyl propane is prepared by: the pd content ranges from 0.5 to 2.0 wt%, the Ru content ranges from 0.5 to 2.0 wt%, and the Rh content ranges from 0.1 to 1.0 wt%.
4. The method according to claim 1, wherein the dihydroxy dicyclohexyl propane is prepared by: instead of using phosphorous acid, the phosphoric acid may be used.
5. The method according to claim 1, wherein the dihydroxy dicyclohexyl propane is prepared by: the component in 1-5% of the alkali metal elements is one of nitrates of Na, k, mg and Ca.
6. The method according to claim 1, wherein the dihydroxy dicyclohexyl propane is prepared by: 1-100% of the curing agent is prepared from 60-65g of methyl hexahydrophthalic anhydride.
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