阅读说明：本技术 一种含桥环结构的环状二元醇的制备方法及其应用 (Preparation method and application of cyclic diol containing bridged ring structure ) 是由 李燕平 左洪亮 刘阳 张晓超 李红仙 于 2020-07-22 设计创作，主要内容包括：本发明涉及环状二元醇的制备方法,更具体地,本发明涉及一种含桥环结构的环状二元醇的制备方法及其应用。申请人提供了一种含桥环结构的环状二元醇的制备方法,制备得到的二元醇同时含有桥环和脂环族结构,具有合成新型聚酯或聚氨酯等高性能新材料的良好前景；另外,本发明利用工业上较成熟的技术,设计的制备路线具有工艺简单高效的特点,且通过使用价格低廉的原料,可在较温和的条件下得到具有高的产率和纯度的新型二元醇产品,可以显著降低新材料产品的开发成本,为制备脂环族二元醇产品提供了一种可工业化的实施路线。(The invention relates to a preparation method of cyclic diol, in particular to a preparation method of cyclic diol containing a bridged ring structure and application thereof. The applicant provides a preparation method of cyclic diol containing a bridged ring structure, the prepared diol contains both bridged rings and alicyclic structures, and has a good prospect of synthesizing novel high-performance materials such as novel polyester or polyurethane; in addition, the invention utilizes the mature technology in industry, the designed preparation route has the characteristics of simple and efficient process, and by using the raw materials with low price, the novel dihydric alcohol product with high yield and purity can be obtained under the mild condition, the development cost of the novel material product can be obviously reduced, and an industrialized implementation route is provided for preparing the alicyclic dihydric alcohol product.)

1. A preparation method of cyclic diol containing a bridged ring structure is characterized in that the cyclic diol is represented by formula (1) and/or formula (2):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

2. The method for preparing the cyclic diol containing the bridged ring structure according to claim 1, wherein the cyclic diol is obtained by catalytic hydrogenation of a dialdehyde intermediate, and the dialdehyde intermediate is represented by formula (3) and/or formula (4):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

3. The method for preparing cyclic diol containing a bridged ring structure according to claim 2, wherein in the catalytic hydrogenation, the reaction pressure is 1-10 MPa, and the reaction temperature is 80-150 ℃.

4. The method for preparing cyclic diol containing bridged ring structure according to claim 2, wherein the dialdehyde intermediate is obtained by hydroformylation of monoaldehyde cycloolefins, and the monoaldehyde cycloolefins are represented by formula (5) and/or formula (6):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

5. The method of claim 4, wherein the hydroformylation comprises reacting a monoaldehyde cyclic olefin with syngas in the presence of a hydroformylation catalyst to obtain a dialdehyde intermediate.

6. The method for preparing cyclic diol containing bridged ring structure according to claim 4, wherein the hydroformylation is carried out under a reaction pressure of 1-5 MPa and at a reaction temperature of 90-150 ℃.

7. The method for producing a cyclic diol having a bridged ring structure according to claim 5, wherein the hydroformylation catalyst is a combination of a metal salt and an organic phosphorus.

8. The method for preparing the cyclic diol containing the bridged ring structure according to any one of claims 4 to 7, wherein the monoaldehyde cyclic olefin is obtained by cycloaddition of a cyclic diene and a monoolefin aldehyde, wherein the cyclic diene is cyclopentadiene and/or 1, 3-cyclohexadiene, and the monoolefin aldehyde is represented by the formula (7):

r is hydrogen atom or C1-C6 alkyl.

9. The method according to claim 8, wherein the molar ratio of the cyclic diene to the monoalkene aldehyde is 1: (1-1.5).

10. Use of the cyclic diol having a bridged ring structure according to any one of claims 1 to 9 for the preparation of a polymer.

Technical Field

The invention relates to a preparation method of cyclic diol, in particular to a preparation method of cyclic diol containing a bridged ring structure and application thereof.

Background

Dihydric alcohol is an important and widely applied basic organic chemical raw material, such as ethylene glycol, propylene glycol, 1, 4-butanediol and the like which are widely applied to producing materials such as polyester fiber, polyester plastic, polyurethane and the like. The dihydric alcohol containing aliphatic cyclic structure is a special dihydroxy compound, and the unique cyclic structure can improve the heat resistance, weather resistance, hardness and other properties of the high polymer material, and has no odor and low toxicity. For example, 1, 4-Cyclohexanedimethanol (CHDM) is alicyclic diol containing a six-membered ring, is an important monomer for synthesizing various high-performance polyester materials, such as PCT, PETG, PCTA and the like, and has the characteristics of excellent thermal stability, good balance of hardness and flexibility, higher glass transition temperature and the like. Dicidol (TCD-DM) is another special alicyclic diol, can be used for synthesizing polymers such as polyacrylate, polyester, epoxy resin, polyurethane and the like, and can endow the polymers with good adhesion, high tensile strength, heat resistance, weather resistance and impact resistance.

At present, the preparation process of the cyclic diol is complex, and the yield and the purity cannot be ensured, so a new preparation method is designed to develop the novel diol, which is beneficial to developing new material products with high technical content, high added value and high performance.

Disclosure of Invention

In order to solve the above problems, the first aspect of the present invention provides a method for preparing a cyclic diol having a bridged ring structure, wherein the cyclic diol is represented by formula (1) and/or formula (2):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

As a preferable technical scheme of the invention, the cyclic diol is obtained by catalytic hydrogenation of a dialdehyde intermediate, and the dialdehyde intermediate is shown as a formula (3) and/or a formula (4):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

As a preferred technical scheme, in the catalytic hydrogenation, the reaction pressure is 1-10 MPa, and the reaction temperature is 80-150 ℃.

As a preferred technical solution of the present invention, the dialdehyde intermediate is obtained by hydroformylation of a monoaldehyde cyclic olefin, which is represented by formula (5) and/or formula (6):

R₁、R₂respectively hydrogen atom or C1-C6 alkyl.

In the hydroformylation, the monoaldehyde cycloolefins are reacted with synthesis gas under the action of a hydroformylation catalyst to obtain a dialdehyde intermediate.

As a preferable technical scheme, in the hydroformylation, the reaction pressure is 1-5 MPa, and the reaction temperature is 90-150 ℃.

In a preferred embodiment of the present invention, the hydroformylation catalyst is a combination of a metal salt and organic phosphorus.

As a preferred technical solution of the present invention, the monoaldehyde cyclic olefin is obtained by cycloaddition of a cyclic diene and a monoalkene aldehyde, wherein the cyclic diene is cyclopentadiene and/or 1, 3-cyclohexadiene, and the monoalkene aldehyde is represented by formula (7):

r is hydrogen atom or C1-C6 alkyl.

In a preferred embodiment of the present invention, the molar ratio of the cyclic diene to the monoolefin aldehyde is 1: (1-1.5).

The second aspect of the invention provides an application of the preparation method of the cyclic diol containing the bridged ring structure, which is used for preparing macromolecules.

Compared with the prior art, the invention has the following beneficial effects: the applicant provides a preparation method of cyclic diol containing a bridged ring structure, the prepared diol contains both bridged rings and alicyclic structures, and has a good prospect of synthesizing novel high-performance materials such as novel polyester or polyurethane; in addition, the invention utilizes the mature technology in industry, the designed preparation route has the characteristics of simple and efficient process, and by using the raw materials with low price, the novel dihydric alcohol product with high yield and purity can be obtained under the mild condition, the development cost of the novel material product can be obviously reduced, and an industrialized implementation route is provided for preparing the alicyclic dihydric alcohol product.

Detailed Description

The disclosure may be understood more readily 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 invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

The first aspect of the present invention provides a method for preparing a cyclic diol containing a bridged ring structure, wherein the cyclic diol is represented by formula (1) and/or formula (2):

R₁、R₂are respectively hydrogen atom or C1-C6 alkyl; further, R₁、R₂Respectively hydrogen atom or methyl.

In one embodiment, the cyclic diol of the present invention is obtained by catalytic hydrogenation of a dialdehyde intermediate, which is represented by formula (3) and/or formula (4):

R₁、R₂are respectively hydrogen atom or C1-C6 alkyl; further, R₁、R₂Respectively hydrogen atom or methyl.

Catalytic hydrogenation

In one embodiment, in the catalytic hydrogenation, the reaction pressure is 1-10 MPa, and the reaction temperature is 80-150 ℃; further, in the catalytic hydrogenation, the reaction pressure is 1-4 MPa, and the reaction temperature is 80-130 ℃.

Preferably, in the catalytic hydrogenation of the present invention, the catalytic hydrogenation catalyst is one of a nickel-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a silver-based catalyst, a ruthenium-based catalyst, and a germanium-based catalyst. The catalytic hydrogenation catalyst is not particularly limited, and in one embodiment, the catalytic hydrogenation catalyst is one of a nickel-based catalyst, a palladium-based catalyst and a platinum-based catalyst; examples of catalytic hydrogenation catalysts include, but are not limited to, raney nickel, supported catalytic hydrogenation catalysts. The supported catalytic hydrogenation catalyst comprises a metal and a carrier, wherein the metal is selected from nickel, palladium and platinum; further, in the supported catalytic hydrogenation catalyst, the metal accounts for 3-8 wt% of the supported catalytic hydrogenation catalyst; the carrier of the present invention is not particularly limited, and may be any carrier known in the art, and examples thereof include carbon, alumina, silica gel, diatomaceous earth, zeolite molecular sieves, activated carbon, titania, lithium aluminate, and zirconia.

More preferably, the catalytic hydrogenation catalyst accounts for 4-8% of the weight of the dialdehyde intermediate.

Further preferably, in the catalytic hydrogenation of the present invention, the catalytic hydrogenation solvent is one selected from tetrahydrofuran, dichloromethane, 1, 4-dioxane, methanol, and ethanol.

Further preferably, in the catalytic hydrogenation, the dialdehyde intermediate, the catalytic hydrogenation solvent and the catalytic hydrogenation catalyst are added into a catalytic hydrogenation reaction kettle, the air in the reaction kettle is replaced by hydrogen, the reaction is carried out for 3-7 h at 80-150 ℃ and 1-10 MPa, and the cyclic diol is obtained by filtering and distilling.

In one embodiment, the dialdehyde intermediate is obtained by hydroformylation of a monoaldehyde cycloolefin, wherein the monoaldehyde cycloolefin is represented by the formula (5) and/or the formula (6):

R₁、R₂are respectively hydrogen atom or C1-C6 alkyl; further, R₁、R₂Respectively hydrogen atom or methyl.

Hydroformylation of olefins

In one embodiment, the hydroformylation process of the present invention involves reacting a monoaldehyde cycloolefin with synthesis gas over a hydroformylation catalyst to produce a dialdehyde intermediate.

In one embodiment, the syngas of the present invention comprises CO and H₂Is 1: (0.5 to 2); further, in the synthesis gas of the present invention, CO and H₂Is 1: 1.

preferably, the hydroformylation catalyst of the present invention is a combination of a metal catalyst and an organic phosphorus; further, the molar ratio of the metal salt catalyst to the organic phosphorus is 1: (1-20); further, the molar ratio of the metal salt catalyst to the organic phosphorus is 1: (1-10).

More preferably, the metal catalyst of the present invention is a cobalt-based catalyst or a rhodium-based catalyst; further, the metal catalyst is a rhodium catalyst; further, the rhodium catalyst is selected from one of rhodium chloride, rhodium nitrate, rhodium acetate, rhodium octanoate, rhodium acetylacetonate carbonyl and dicarbonyl acetylacetonate; furthermore, the molar concentration of the rhodium catalyst in the monoaldehyde cycloolefin is 1-100 ppm; furthermore, the molar concentration of the rhodium catalyst in the monoaldehyde cycloolefin is 40-100 ppm.

The molar concentration of the rhodium-based catalyst in the present invention is a concentration expressed in ppm in terms of parts per million of the molar amount of the monoaldehyde cycloolefin.

Further preferably, the organophosphorus disclosed by the invention is selected from one or more of trialkyl phosphine, triaryl phosphine and organic phosphite; further, the organophosphorus is organic phosphite or triaryl phosphorus; further, the organic phosphite ester is selected from one of triphenyl phosphite, trihexyl phosphite, tris (2,2, 2-trifluoroethyl) phosphite and tris (2, 4-di-tert-butyl) phosphite; further, the organic phosphite ester is selected from one of triphenyl phosphite and tris (2,2, 2-trifluoroethyl) phosphite.

Further preferably, in the hydroformylation, the reaction pressure is 1-5 MPa, and the reaction temperature is 90-150 ℃; furthermore, in the hydroformylation of the invention, the reaction pressure is 2MPa, and the reaction temperature is 110 ℃.

In a preferred embodiment, in the hydroformylation of the present invention, the hydroformylation solvent is selected from one or more of hydrocarbon solvents, ether solvents, alcohol solvents, and heterocyclic solvents. The hydroformylation solvent is not particularly limited, and examples thereof include toluene, cyclohexane, n-hexane, octane, tetrahydrofuran, methyl t-butyl ether, n-heptane, benzene, 1, 3-xylene, 1, 4-xylene, 1,3, 5-trimethylbenzene, naphthalene, methyl isopropyl ether, isoprene glycol, and 1, 4-dioxane.

In a more preferable embodiment, in the hydroformylation, the monoaldehyde cycloolefin and the hydroformylation solvent are added into a hydroformylation reaction kettle, a hydroformylation catalyst is added, the air in the reaction kettle is replaced by synthesis gas, the reaction is carried out for 2-5 h at the temperature of 80-150 ℃ under the pressure of 1-10 MPa, and the dialdehyde intermediate is obtained by reduced pressure distillation.

In one embodiment, the monoaldehyde cyclic olefin of the present invention is obtained by cycloaddition of a cyclic diene and a monoalkene aldehyde, wherein the cyclic diene is cyclopentadiene and/or 1, 3-cyclohexadiene, and the monoalkene aldehyde is represented by formula (7):

r is hydrogen atom or C1-C6 alkyl; further, R is a hydrogen atom or a methyl group.

Cycloaddition

In one embodiment, the cyclic diene and monoolefin aldehyde of the present invention are present in a molar ratio of 1: (1-1.5); further, the molar ratio of the cyclic diene to the monoolefin aldehyde according to the present invention is 1: 1.2.

preferably, in the cycloaddition, the reaction temperature is 0-100 ℃.

More preferably, in the cycloaddition, the reaction time is 2-48 h; furthermore, in the cycloaddition, the reaction time is 5-12 h.

Further preferably, in the cycloaddition of the present invention, the cycloaddition catalyst is selected from one of an enzyme catalyst, a metal catalyst and a nonmetal catalyst; further, the cycloaddition catalyst is a non-metal catalyst; further, the cycloaddition catalyst accounts for 0.1-2% of the cyclic diene by mole; further, the cycloaddition catalyst accounts for 1-2% of the cyclic diene by mole; further, the cycloaddition catalyst of the present invention is present in a molar percentage of the cyclic diene of 1.9%.

In one embodiment, the non-metallic catalyst of the present invention is selected from one of a protic acid catalyst, a protic base catalyst, a Lewis acid catalyst, and a Lewis base catalyst. As examples of Lewis acid catalysts, include, but are not limited to, boron trifluoride etherate, trifluoromethanesulfonic acid, tetrafluoroboric acid, trityltetrafluoroborate (TrBF4), tritylhexafluoroborate (TrPF6), trimethylsilanolate trifluoromethanesulfonate (TMSOTf), bis- (trifluoromethanesulfonyl) -iminosilane (TMSNTf 2); examples of Lewis base catalysts include, but are not limited to, N-methylimidazolidone, N-methylimidazole, trimethylphosphine, N-heterocyclic carbenes. In a preferred embodiment, the cycloaddition catalyst of the present invention is a Lewis acid catalyst.

Further preferably, in the cycloaddition of the present invention, the cycloaddition solvent is a solvent well known in the art, and may be, for example, dichloromethane, chloroform, tetrahydrofuran, chlorobenzene, toluene, xylene, ethyl acetate, acetone, or diethylene glycol dimethyl ether.

In a preferred embodiment, in the cycloaddition of the present invention, the polymerization inhibitor is selected from one of p-benzoquinone, p-hydroxyanisole (MEHQ), p-tert-butylcatechol (TBC), tetramethylpiperidine nitroxide radical phosphite triester; further, the polymerization inhibitor accounts for 0.1-0.5 wt% of the monoolefine aldehyde.

In a more preferred embodiment, in the cycloaddition, under the protection of nitrogen, the cyclic diene, the monoolefinic aldehyde, the polymerization inhibitor and the cycloaddition solvent are mixed, the cycloaddition catalyst is added, the mixture reacts at 0-100 ℃ for 2-48 hours, and then the temperature is reduced to room temperature, and the mixture is washed with water, desolventized and rectified under reduced pressure to obtain the monoaldehyde cycloolefin.

The applicant can obtain the cyclic diol with high yield and purity by designing a process route of the cyclic diol and starting from commonly available raw materials of cyclic diene and monoolefin aldehyde and sequentially carrying out mature cycloaddition, hydroformylation and catalytic hydrogenation reaction, and the applicant finds that by adopting a certain proportion of the cyclic diene and the monoolefin aldehyde, because double bonds in the monoolefin aldehyde are connected with acidic aldehyde groups of strong electron-withdrawing groups, the reaction activity of the cycloaddition is increased, the monoaldehyde cycloolefins with high yield and purity can be obtained at lower temperature and in time under the condition of Lewis acid catalysis, the double bonds of the monoaldehyde cycloolefins are subjected to hydroformylation reaction, and one hydrogen and one aldehyde group are respectively added on two sides of the double bonds, wherein the applicant finds that a complex is formed by adding a proper organic phosphorus and a metal catalyst, particularly selects the organic phosphorus and the metal catalyst with larger electronic and steric hindrance substituent to act together, the reaction of the monoaldehyde cycloolefins and the synthesis gas can be promoted under low catalyst concentration and reaction conditions; the applicant finds that when the reaction temperature and time are controlled to carry out catalytic hydrogenation in a hydrogen atmosphere, two aldehyde groups on the dialdehyde intermediate can be completely reduced into alcohol groups, and a diol product containing a bridged ring structure is finally obtained.

In a second aspect, the present invention provides a method for preparing a cyclic diol containing a bridged ring structure, as described above, and an application of the method for preparing a polymer.

In one embodiment, the polymer of the present invention is selected from one or more of polyacrylate, polyester, epoxy, polyurethane, polyurea.