CN110950738A - Preparation method of tricyclodecanediol and product thereof - Google Patents

Preparation method of tricyclodecanediol and product thereof Download PDF

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Publication number
CN110950738A
CN110950738A CN201910757785.XA CN201910757785A CN110950738A CN 110950738 A CN110950738 A CN 110950738A CN 201910757785 A CN201910757785 A CN 201910757785A CN 110950738 A CN110950738 A CN 110950738A
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catalyst
cation exchange
reaction
tricyclodecanediol
resin
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Inventor
李燕平
徐飞飞
左洪亮
刘阳
张晓超
李红仙
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Guangdong Cpd New Material Technology Co ltd
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Guangdong Xinhuayue Petrochemical Inc Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a preparation method of tricyclodecanediol, which comprises the following steps: step a: under the action of a resin catalyst, dicyclopentadiene of a substance in a formula (1) undergoes hydration reaction to obtain hydroxyl dihydrodicyclopentadiene of a substance in a formula (II); step b: hydrogenating the substance of the formula (II) under the action of a catalyst to obtain tricyclodecane diol of the following substance of the formula (III). The novel synthetic method of tricyclodecanediol provided by the invention takes dicyclopentadiene which is cheap and easy to obtain in the chemical industry as a raw material, and a common rhodium catalyst is not used in the catalyst, so that the reaction has the cost advantage and has good industrial prospect.

Description

Preparation method of tricyclodecanediol and product thereof
Technical Field
The invention relates to a preparation method of tricyclodecane diol, in particular to a method for preparing novel tricyclodecane diol from dicyclopentadiene.
Background
Dicyclopentadiene (DCPD) can be used for synthesizing high value-added fine chemicals namely tricyclodecane unsaturated monoaldehyde or tricyclodecane dicarbaldehyde through hydroformylation, and the product is hydrogenated to prepare tricyclodecane dimethanol, which is an important chemical raw material. Unsaturated amorphous polyester resin composite materials developed by tricyclodecane dimethanol and containing no benzene and formaldehyde have the characteristics of yellowing resistance, low viscosity and the like, and are widely applied to the aspects of water-based dispersants, coating compositions, lubricating oil and the like. Dicidol is useful as an intermediate in the synthesis of solvent-free paints, heat and corrosion resistant polyesters and epoxy resin hardeners of excellent strength, such as tricyclodecanedimethanol diacrylate, which is characterized by high reactivity, high electrical resistance, good heat and chemical resistance, toughness and high hardness, low shrinkage, and is used for UV coating of CD/DVD discs, UV products, metal substrates.
U.S. Pat. No. 4,7015362 reports hydroformylation in two steps, the first step is carried out in a heterogeneous reaction system, water-soluble organic phosphorus is used as a ligand, metal rhodium is used as a catalyst to obtain tricyclodecane mono-formaldehyde, then in the second hydroformylation step, the reaction is carried out in a homogeneous system, rhodium octanoate is used as a catalyst, triphenylphosphine is used as a ligand, the yield of dialdehyde obtained by two-step distillation is more than 90%, and the tricyclodecane dimethanol is obtained after aldehyde is hydrogenated. Basff patent CN1890203A reports that rhodium salt without added phosphine ligand is used as a catalyst, methylbenzene is used as a reaction solvent, hydroformylation is carried out in a two-stage reaction zone, the pressure is 20-35 MPa, the temperature of the first reaction zone is 80-120 ℃, the temperature of the second reaction zone is 120-150 ℃, and the selectivity of tricyclodecane dimethyl aldehyde is 93%, and then hydrogenation reaction is carried out. Chinese patents (CN201310380400.5 and CN201410710821.4) respectively report a cobaltosic oxide supported nano gold catalyst and a silica supported cobalt rhodium copper trimetal catalyst, and the two solid phase catalysts can be used for hydroformylation of dicyclopentadiene and then hydrogenation is carried out to prepare tricyclodecanedimethanol.
The tricyclodecane dimethanol is mainly prepared into tricyclodecane dicarbaldehyde through a rhodium catalyst, and then the product is obtained through an aldehyde hydrogenation process. However, the hydroformylation reaction of high carbon chain olefin by rhodium has the problems of high boiling point of products, difficult separation of rhodium catalyst and products, easy rhodium loss and inactivation in the separation process, difficult recycling of the catalyst and high cost of the catalyst, thereby limiting the industrial use of the catalyst.
The invention provides a method for preparing novel tricyclodecanediol without using a rhodium catalyst, which has the advantages of simple operation, low catalyst price and easy industrial realization.
Disclosure of Invention
The first aspect of the present invention provides a method for producing tricyclodecane diol, which comprises the steps of:
step a: under the action of a resin catalyst, dicyclopentadiene of a substance in a formula (1) undergoes hydration reaction to obtain hydroxyl dihydrodicyclopentadiene of a substance in a formula (II);
step b: under the action of a catalyst, hydrogenating a substance in a formula (II) to obtain tricyclodecane diol in a formula (III);
、、。
as an embodiment of the present invention, the resin catalyst is a cation exchange resin.
As an embodiment of the present invention, the cation exchange resin is one or more selected from 732 cation exchange resins, DH cation exchange resins, 061 cation exchange resins, D072 cation exchange resins, 734 cation exchange resins, D001 cation exchange resins, and JK008 cation exchange resins.
In one embodiment of the present invention, the cation exchange resin is 732 cation exchange resin or 061 cation exchange resin.
As an embodiment of the present invention, the specific steps of step a are as follows:
(1) dispersing a resin catalyst into distilled water, and then dropwise adding dicyclopentadiene into the distilled water containing the resin catalyst;
(2) and after the dropwise addition is finished, continuing the heat preservation reaction for 1-6 hours, filtering the catalyst after the reaction is finished, standing and separating the liquid, and distilling the upper organic phase to obtain the hydroxyl dihydrodicyclopentadiene.
In one embodiment of the present invention, in the step (1), the temperature of dicyclopentadiene is 50 to 120 ℃ during the dropping; the dropping time is 1-5 hours.
As an embodiment of the present invention, the specific steps of step b are as follows:
(a) sequentially adding the hydroxyl dihydrodicyclopentadiene as a substance in the formula (II), a catalyst and an organic solvent into a high-pressure reaction kettle, and sealing;
(b) purging with nitrogen and synthesis gas, filling the synthesis gas until the pressure is 2-6 MPa, the reaction temperature is 100-180 ℃, the reaction pressure is 3-10 MPa, the reaction time is 1-5 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain the tricyclodecanediol.
In one embodiment of the present invention, in the step (a), the catalyst contains a cobalt compound, a ruthenium compound and manganese powder.
The second aspect of the present invention provides a tricyclodecane diol produced by the above-mentioned method for producing a tricyclodecane diol.
The invention provides the tricyclodecane diol which is applied to the field of polyester high-performance materials.
Has the advantages that:
1. in the synthesis method, the target product is prepared by catalyzing the hydroformylation and hydrogenation of the hydroxyl dihydrodicyclopentadiene with the combined catalyst of cobalt, ruthenium and manganese, so that the coupling of the hydroformylation and hydrogenation reaction is realized, the reaction can be completed in one step, the reaction can be realized by a one-pot method, and the process flow is simplified.
2. The novel synthetic method of tricyclodecanediol provided by the invention takes dicyclopentadiene which is cheap and easy to obtain in the chemical industry as a raw material, and a common rhodium catalyst is not used in the catalyst, so that the reaction has the cost advantage and has good industrial prospect.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The first aspect of the present invention provides a method for producing tricyclodecane diol, which comprises the steps of:
step a: under the action of a resin catalyst, dicyclopentadiene of a substance in a formula (1) undergoes hydration reaction to obtain hydroxyl dihydrodicyclopentadiene of a substance in a formula (II);
step b: under the action of a catalyst, hydrogenating a substance in a formula (II) to obtain tricyclodecane diol in a formula (III);
、、。
wherein the resin catalyst is cation exchange resin, and the cation exchange resin is one or more selected from 732 cation exchange resin, DH cation exchange resin, 061 cation exchange resin, D072 cation exchange resin, 734 cation exchange resin, D001 cation exchange resin and JK008 cation exchange resin.
In one embodiment of the present invention, the cation exchange resin is 732 cation exchange resin or 061 cation exchange resin.
In a preferred embodiment of the present invention, the cation exchange resin is 732 cation exchange resin.
The specific steps of the step a are as follows:
(1) dispersing a resin catalyst into distilled water, and then dropwise adding dicyclopentadiene into the distilled water containing the resin catalyst;
(2) and after the dropwise addition is finished, continuing the heat preservation reaction for 1-6 hours, filtering the catalyst after the reaction is finished, standing and separating the liquid, and distilling the upper organic phase to obtain the hydroxyl dihydrodicyclopentadiene.
Wherein the dosage of the resin catalyst is 1 to 10 percent of the mass of the dicyclopentadiene; more preferably 2% to 6%.
The amount of the distilled water is 0.5-1.5 times of the mass of the dicyclopentadiene; more preferably 0.8 to 1.2 times.
The dropping temperature is 50-120 ℃, the dropping time is 1-5 hours, the reaction is continued for 1-6 hours after the dropping is finished, the catalyst is filtered after the reaction is finished, the liquid is separated by standing, and the upper organic phase is distilled to obtain the hydroxyl dihydrodicyclopentadiene; the yield is more than 90%.
The specific steps of the step b are as follows:
(a) sequentially adding the hydroxyl dihydrodicyclopentadiene as a substance in the formula (II), a catalyst and an organic solvent into a high-pressure reaction kettle, and sealing;
(b) purging with nitrogen and synthesis gas, filling the synthesis gas until the pressure is 2-6 MPa, the reaction temperature is 100-180 ℃, the reaction pressure is 3-10 MPa, the reaction time is 1-5 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain the tricyclodecanediol.
The more specific steps of the step b are as follows:
(a) sequentially adding the hydroxyl dihydrodicyclopentadiene as a substance in the formula (II), a catalyst and an organic solvent into a high-pressure reaction kettle, and sealing;
(b) purging with nitrogen for three times, purging with synthesis gas for two times, charging the synthesis gas until the pressure is 2-6 MPa, the reaction temperature is 100-180 ℃, the reaction pressure is 3-10 MPa, the reaction time is 1-5 hours, and performing reduced pressure distillation after the reaction to obtain the tricyclodecanediol with the yield of more than 80%.
Wherein, in the step (a), the catalyst contains cobalt compound, ruthenium compound and manganese powder; and the mass ratio of the cobalt compound to the manganese powder to the ruthenium compound is 10: 5: 1-100: 100: 1; and the dosage of the catalyst is 0.1-1% of the mass of the hydroxyl dihydrodicyclopentadiene.
In one embodiment of the present invention, the cobalt compound is one of cobalt chloride, cobalt sulfate, cobalt acetate, and cobalt acetylacetonate; the ruthenium compound is one of ruthenium trichloride, ruthenium acetate, ruthenium iodide and ruthenium acetylacetonate.
As an embodiment of the present invention, the organic solvent is one of tetrahydrofuran, toluene, xylene, n-hexane, cyclohexane, n-heptane, and isooctane; more preferably tetrahydrofuran or toluene.
In the invention, the synthesis gas is a mixed gas of carbon monoxide and hydrogen, and the ratio of the carbon monoxide to the hydrogen is 1: 1-1: 5.
the second aspect of the present invention provides a tricyclodecane diol produced by the above-mentioned method for producing a tricyclodecane diol.
The tricyclodecane diol provided by the third aspect of the invention is applied to the field of polyester high-performance materials.
The present invention will be described in detail with reference to specific examples.
Example 1:
adding 1g of domestic 732 resin into a 500mL four-neck flask filled with 100mL of deionized water, heating to 80 ℃, then beginning to dropwise add 100g of dicyclopentadiene, controlling the temperature to be about 100 ℃, keeping the dropwise adding time for about 1.5 hours, and after the dropwise adding is finished, keeping the temperature to be about 100 ℃ and reacting for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the phases of the reaction liquid, and distilling the upper organic phase under reduced pressure to obtain about 107.3g of a product with the yield of about 95%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 10mg of ruthenium acetylacetonate and 80mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2: 1), supplementing the synthesis gas to 3MPa, heating to 130 ℃, keeping the reaction pressure at 3-5 MPa, reacting for about 2 hours, taking out the kettle after the reaction, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 19.4g of tricyclodecanediol, wherein the yield is about 80%.
Example 2:
adding 0.2g of perfluorosulfonic acid resin into a 500mL four-neck flask containing 60mL of deionized water, heating to 80 ℃, then beginning to dropwise add 100g of dicyclopentadiene, controlling the temperature to be about 80 ℃, keeping the temperature to be about 80 ℃ for about 1.5 hours, and after the dropwise addition is finished, keeping the temperature to be about 80 ℃ for reaction for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the phases of the reaction liquid, and distilling the upper organic phase under reduced pressure to obtain about 110.2g of a product with the yield of about 97%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 30mg of ruthenium acetylacetonate and 100mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2.5: 1), supplementing the synthesis gas to 3MPa, heating to 150 ℃, keeping the reaction pressure at 5-6 MPa, reacting for about 2 hours, taking out the reaction kettle, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 20.4g of tricyclodecanediol, wherein the yield is about 84%.
Example 3:
0.8g of domestic 732 resin is added into a 500mL four-neck flask filled with 200mL of deionized water, the mixture is heated to 80 ℃, then 100g of dicyclopentadiene is added dropwise, the temperature is controlled to be about 100 ℃, the dropwise adding time is about 1.5 hours, and after the dropwise adding is finished, the temperature is kept at about 100 ℃ for reaction for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the reaction liquid into phases, and distilling the upper organic phase under reduced pressure to obtain about 107.3g of a product with the yield of about 75%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 10mg of ruthenium acetylacetonate and 80mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2: 1), supplementing the synthesis gas to 3MPa, heating to 130 ℃, keeping the reaction pressure at 3-5 MPa, reacting for about 2 hours, taking out the kettle after the reaction, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 19.4g of tricyclodecanediol, wherein the yield is about 61%.
Example 4:
adding 1g of domestic 732 resin into a 500mL four-neck flask filled with 100mL of deionized water, heating to 80 ℃, then beginning to dropwise add 100g of dicyclopentadiene, controlling the temperature to be about 100 ℃, keeping the dropwise adding time for about 1.5 hours, and after the dropwise adding is finished, keeping the temperature to be about 100 ℃ and reacting for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the phases of the reaction liquid, and distilling the upper organic phase under reduced pressure to obtain about 107.3g of a product with the yield of about 95%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 10mg of ruthenium acetylacetonate and 10mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2: 1), supplementing the synthesis gas to 3MPa, heating to 130 ℃, keeping the reaction pressure at 3-5 MPa, reacting for about 2 hours, taking out the kettle after the reaction, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 19.4g of tricyclodecanediol with the yield of about 60%.
Example 5:
adding 0.01g of perfluorosulfonic acid resin into a 500mL four-neck flask containing 60mL of deionized water, heating to 80 ℃, then beginning to dropwise add 100g of dicyclopentadiene, controlling the temperature to be about 80 ℃, keeping the temperature to be about 80 ℃ for about 1.5 hours, and after the dropwise addition is finished, keeping the temperature to be about 80 ℃ for reaction for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the reaction liquid into phases, and distilling the upper organic phase under reduced pressure to obtain about 110.2g of a product with the yield of about 85%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 30mg of ruthenium acetylacetonate and 100mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2.5: 1), supplementing the synthesis gas to 3MPa, heating to 150 ℃, keeping the reaction pressure at 5-6 MPa, reacting for about 2 hours, taking out the reaction kettle, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 20.4g of tricyclodecanediol, wherein the yield is about 63%.
Example 5:
adding 0.2g of perfluorosulfonic acid resin into a 500mL four-neck flask containing 60mL of deionized water, heating to 80 ℃, then beginning to dropwise add 100g of dicyclopentadiene, controlling the temperature to be about 80 ℃, keeping the temperature to be about 80 ℃ for about 1.5 hours, and after the dropwise addition is finished, keeping the temperature to be about 80 ℃ for reaction for 2 hours. Then cooling to room temperature, filtering the resin catalyst, repeatedly regenerating the resin catalyst for use, separating the phases of the reaction liquid, and distilling the upper organic phase under reduced pressure to obtain about 110.2g of a product with the yield of about 97%.
Sequentially adding 20g of hydroxy dicyclopentadiene and 100mL of toluene into a 250mL high-pressure reaction kettle, then adding 100mg of catalyst cobalt acetylacetonate, 30mg of ruthenium acetylacetonate and 10mg of manganese powder, sealing, performing nitrogen replacement for three times, then performing replacement for two times by using synthesis gas (hydrogen: carbon monoxide is 2.5: 1), supplementing the synthesis gas to 3MPa, heating to 150 ℃, keeping the reaction pressure at 5-6 MPa, reacting for about 2 hours, taking out the reaction kettle, filtering, evaporating the toluene from the filtrate, and performing reduced pressure distillation to obtain 20.4g of tricyclodecanediol, wherein the yield is about 52%.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of tricyclodecane diol is characterized by comprising the following steps:
step a: under the action of a resin catalyst, dicyclopentadiene of a substance in a formula (1) undergoes hydration reaction to obtain hydroxyl dihydrodicyclopentadiene of a substance in a formula (II);
step b: under the action of a catalyst, hydrogenating a substance in a formula (II) to obtain tricyclodecane diol in a formula (III);
、、。
2. the method for producing tricyclodecanediol as claimed in claim 1, wherein the resin catalyst is a cation exchange resin.
3. The method of producing tricyclodecanediol as claimed in claim 2, wherein the cation exchange resin is one or more selected from 732 cation exchange resins, DH cation exchange resins, 061 cation exchange resins, D072 cation exchange resins, 734 cation exchange resins, D001 cation exchange resins, and JK008 cation exchange resins.
4. The method for producing tricyclodecanediol as claimed in claim 3, wherein the cation exchange resin is 732 cation exchange resin or 061 cation exchange resin.
5. The method for preparing tricyclodecanediol as claimed in claim 1, wherein the specific steps of step a are as follows:
(1) dispersing a resin catalyst into distilled water, and then dropwise adding dicyclopentadiene into the distilled water containing the resin catalyst;
(2) and after the dropwise addition is finished, continuing the heat preservation reaction for 1-6 hours, filtering the catalyst after the reaction is finished, standing and separating the liquid, and distilling the upper organic phase to obtain the hydroxyl dihydrodicyclopentadiene.
6. The method for preparing tricyclodecanediol as claimed in claim 5, wherein in the step (1), the temperature of dicyclopentadiene is 50 to 120 ℃ when dropwise adding; the dropping time is 1-5 hours.
7. The method for preparing tricyclodecanediol as claimed in any one of claims 1 to 5, wherein the specific steps of step b are as follows:
(a) sequentially adding the hydroxyl dihydrodicyclopentadiene as a substance in the formula (II), a catalyst and an organic solvent into a high-pressure reaction kettle, and sealing;
(b) purging with nitrogen and synthesis gas, filling the synthesis gas until the pressure is 2-6 MPa, the reaction temperature is 100-180 ℃, the reaction pressure is 3-10 MPa, the reaction time is 1-5 hours, and carrying out reduced pressure distillation after the reaction is finished to obtain the tricyclodecanediol.
8. The method for producing tricyclodecanediol as claimed in claim 7, wherein in the step (a), the catalyst comprises a cobalt compound, a ruthenium compound and manganese powder.
9. A tricyclodecane diol produced by the method for producing a tricyclodecane diol as claimed in any one of claims 1 to 8.
10. The tricyclodecane diol as claimed in claim 9, which is used in the field of polyester high-performance materials.
CN201910757785.XA 2019-08-16 2019-08-16 Preparation method of tricyclodecanediol and product thereof Pending CN110950738A (en)

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