CN116332951A

CN116332951A - Preparation method and application of isosorbide diacid

Info

Publication number: CN116332951A
Application number: CN202310295406.6A
Authority: CN
Inventors: 刘艳林; 叶子贤; 汤兆宾
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2023-03-22
Filing date: 2023-03-22
Publication date: 2023-06-27

Abstract

The invention discloses isosorbide diacid and a preparation method and application thereof. The isosorbide diacid has the structural formula:

the preparation method comprises the following steps: reacting isosorbide and chloroacetic acid in an alkaline solution, and acidifying to obtain an isosorbide-containing diacid solution; and purifying the isosorbide diacid solution to obtain an isosorbide diacid solid. The isosorbide diacid can react with certain diamine to prepare novel bio-based high-performance polyamide nylon, and epoxy ether bonds in the structure can improve the performance of polyamide. The invention adopts the renewable isosorbide with wide sources as the raw material, is environment-friendly, overcomes the problem of raw material shortage existing in the traditional petroleum coke products, can reduce the dependence of the plastic industry on petrochemical products and can also reduce the production processThe pollution to the environment; the preparation method has the advantages of simple process, mild condition, less side reaction, higher yield and simple post treatment.

Description

Preparation method and application of isosorbide diacid

Technical Field

The invention belongs to the technical field of synthesis of bio-based monomers, and particularly relates to a preparation method and application of isosorbide diacid.

Background

The polyamide compound has excellent mechanical property, heat resistance, self-wetting property, electrical insulation property and chemical corrosion resistance, is widely used in industries such as automobiles, electric appliances, communication, electronics, machinery and the like, and is the variety with the largest yield, the largest variety and the largest application in five general engineering plastics. With the development of society, the demand for polyamide compounds is enormous and is growing rapidly. The existing polyamide such as nylon 6 and nylon 66 monomer is mainly obtained from fossil resources, has huge consumption and has the problem of non-renewable. And biomass resources are widely available and green and renewable, so the development of biomass-based polyamide materials is of great significance.

The bio-based polyamide is prepared from biomass material, and the raw materials of the bio-based polyamide mainly comprise bio-based amino acid, bio-based lactam, bio-based dibasic acid, bio-based diamine and the like. Polyamides are generally classified into two types according to the source of raw materials, one type is a polyamide obtained by polycondensation of amino acids or ring-opening polymerization of lactams, also called AB type polyamide; one type is polyamides obtained by polycondensation of dibasic acids and diamines, also known as AABB type polyamides. The raw materials of the bio-based polyamide are mainly derived from renewable raw materials such as starch, cellulose, lignin, animal and vegetable oils, etc.

For AABB type polyamide, the preparation of dibasic acid is very important, and the preparation methods of dibasic acid are various at present, for example, chinese patent No. 101328165A discloses a macrolide perfume dodeca dibasic acid propylene glycol ester and a production method thereof, which take natural vegetable oil and fat as raw materials, and obtain lauric acid lower alcohol ester and glycerin through transesterification with lower alcohol. And then respectively preparing the dodecadiacid and the 1, 3-propanediol by using lauric acid low-carbon alcohol ester and glycerol as substrates through a biological fermentation method, wherein the method realizes biomass of raw materials, but has a complicated flow. The Chinese patent CN113061629A adopts candida tropicalis or candida vista as fermentation microorganisms to produce long-chain diacid through biological fermentation, but the method relies on the fermentation microorganisms, is not easy to obtain and difficult to culture, and is difficult to realize the mass production of the diacid.

Isosorbide, (IS) IS a bio-based material derived from biological sources, a glycol hydrogenated hexanol, a renewable bifunctional glycol with an uncoiled structure consisting of two tetrahydrofuran rings. It is this bicyclic structure that results in an increase in the glass transition temperature (Tg) of the isosorbide-intercalated polymer. Isosorbide also has the property of increasing light transmittance and reducing smoke, and therefore, is also considered as a polymer having excellent optical properties. Because of such characteristics, isosorbide esters can be used in the industrial production of polyesters and polycarbonates. Legrand et al synthesized poly (tricyclodecanediol) dimethyl ester-co-isosorbide terephthalate starting from Purified Terephthalic Acid (PTA), isosorbide and tricyclodecanediol dimethanol.

Now, in the face of the current situation that petroleum resources are increasingly exhausted, the use of bio-based materials such as isosorbide instead of non-renewable materials such as petroleum oils has become a serious issue for human research. The preparation method of the bio-based dibasic acid is highly urgent for the development of bio-based polyamide.

Disclosure of Invention

The invention discloses isosorbide diacid which can react with certain diamine to prepare novel bio-based high-performance polyamide nylon, wherein epoxy ether bond in the structure can improve the excellent characteristics of a high polymer material. The invention also provides a preparation method of the isosorbide diacid, which uses isosorbide and chloroacetic acid as raw materials, has simple process, less side reaction and high yield, and overcomes the problem of raw material shortage of the traditional petroleum coke products.

In order to achieve the technical effects, the technical scheme adopted by the invention is as follows:

the invention discloses isosorbide diacid, which has the structural formula:

the invention also provides a preparation method of the isosorbide diacid, which comprises the following steps of;

s1, reacting isosorbide and chloroacetic acid in an alkaline solution to obtain an isosorbide-containing diacid solution;

s2, extracting and purifying the isosorbide diacid solution to obtain an isosorbide diacid solid.

Further, the molar ratio of the isosorbide to the chloroacetic acid is 1:1-5.

Further, the alkaline solution solute comprises sodium hydroxide;

further, the alkaline solution solvent includes water.

Further, when the reaction is performed in S1, nitrogen or inert gas is continuously introduced into the alkaline solution.

Further, when the reaction is performed in the step S1, the pH value of the alkaline solution is measured, and the alkaline solution solute is added to maintain an alkaline environment.

Further, under the condition that nitrogen or inert gas is continuously introduced into the alkaline solution, firstly adding the isosorbide, heating and finally adding the chloroacetic acid.

Further, heating the alkaline solution to 80-90 ℃ in the reaction in the step S1;

further, the reaction time of S1 is 6-8 hours.

Further, after the reaction in S1 is completed, an excess amount of acid is added to the alkaline solution so that the pH value of the alkaline solution is less than 3.

Further, the acid includes any one of hydrochloric acid and sulfuric acid.

The isosorbide diacid or the isosorbide diacid prepared by the preparation method provided by the invention is applied to the preparation of polyamide.

Compared with the prior art, the invention has the following beneficial effects:

the isosorbide diacid synthesized by the preparation method provided by the invention can react with certain diamine to prepare novel bio-based high-performance polyamide nylon, and the epoxy ether bond in the structure can improve the performance of polyamide. The invention is green and environment-friendly, overcomes the problem of raw material shortage of the traditional petroleum coke products, can reduce the dependence of the plastic industry on petrochemical products, and can also reduce the pollution to the environment in the production process; the preparation method has the advantages of simple process, mild condition, less side reaction, higher yield and simple post treatment.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a mass spectrum of isosorbide diacid prepared in example 1 of the present invention.

Detailed Description

The invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.

Example 1

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (0.8 g,20 mmol); isosorbide (1.4614 g,10 mmol); chloroacetic acid (1.8899 g,20 mmol).

(2) Preparation of isosorbide-containing diacid solution

a. 100mL of deionized water was added to a 200mL beaker, and the weighed sodium hydroxide (0.8 g,20 mmol) was added to the deionized water all, and stirred with a glass rod until the sodium hydroxide was dissolved all together.

b. The sodium hydroxide solution in the beaker was transferred to a 250mL three-necked flask equipped with a reflux condenser, and isosorbide (1.4614 g,10 mmol) was added to the three-necked flask with stirring, and the mixture was stirred continuously and heated to 70℃with an oil bath.

c. Chloroacetic acid (1.8899 g,20 mmol) was added gradually and batchwise to the three-necked flask, the temperature was kept at 80℃or higher by continuing the heating, and the initial pH of the solution was recorded to be 13.

d. Maintaining the temperature, continuously reacting, measuring the pH value when the reaction is carried out for 1h, adding a proper amount of sodium hydroxide to ensure that the pH value is more than 13, and keeping the solution to be strongly alkaline.

e. After the reaction is carried out for about 6 hours, the pH value does not change obviously, the heating is stopped, the reaction is stopped, the solution is cooled to room temperature, 30mL of sulfuric acid with the concentration of 1mol/L is added, and the pH value of the solution is measured to be less than 3, so that the isosorbide-containing diacid solution is obtained.

(3) Purifying to obtain isosorbide diacid solid

And (3) adding 100mL of acetone with the concentration of 13.5mol/L into the solution obtained in the step (2), extracting, precipitating a white precipitate, separating the solution by using a separating funnel, carrying out suction filtration, washing by using ethanol, and drying the white solid in a vacuum oven at 70 ℃ for 5 hours. 2.45g of isosorbide diacid solid was finally obtained in 73% yield.

(4) Characterization of the product

And (3) obtaining a mass spectrum of the isosorbide diacid solid obtained in the step (3) by a mass spectrometer, wherein 283m/z is a molecular ion peak of a product, and referring to figure 1.

(5) Preparation of polyamide nylon by isosorbide diacid and diamine reaction

And (3) reacting the isosorbide diacid solid obtained in the step (3) with ethylenediamine to obtain the novel bio-based high-performance polyamide nylon. The epoxy ether bond in the structure improves the performance of nylon.

Example 2

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (0.8 g,20 mmol); isosorbide (1.4614 g,10 mmol); chloroacetic acid (2.8348 g,30 mmol)

(2) Preparation of isosorbide-containing diacid solution

c. Chloroacetic acid (2.8348 g,30 mmol) was added gradually and batchwise to the three-necked flask, the temperature was kept at 80℃or higher continuously, and the initial pH of the solution was recorded to be 13.

e. After the reaction is carried out for about 8 hours, the pH value does not change obviously, the heating is stopped, the reaction is stopped, the solution is cooled to room temperature, 30mL of sulfuric acid with the concentration of 1mol/L is added, and the pH value of the solution is measured to be less than 3, so that the isosorbide-containing diacid solution is obtained.

(3) Extracting and purifying to obtain isosorbide diacid solid

And (3) adding 100mL of acetone with the concentration of 13.5mol/L into the solution obtained in the step (2), extracting, precipitating a white precipitate, separating the solution by using a separating funnel, carrying out suction filtration, washing by using ethanol, and drying the white solid in a vacuum oven at 70 ℃ for 5 hours. Finally, 2.51g of isosorbide diacid solid was obtained in 58.1% yield.

Example 3

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (1.2 g,30 mmol); isosorbide (2.9228 g,20 mmol); chloroacetic acid (2.8348 g,30 mmol)

(2) Preparation of isosorbide-containing diacid solution

a. 150mL of deionized water was added to a 200mL beaker, and the weighed sodium hydroxide (1.2 g,30 mmol) was added to the deionized water in its entirety and stirred with a glass rod until the sodium hydroxide was dissolved in its entirety.

b. The sodium hydroxide solution in the beaker was transferred to a 250mL three-necked flask equipped with a reflux condenser, and isosorbide (2.9228 g,20 mmol) was added to the three-necked flask with stirring, and the mixture was stirred continuously and heated to 70℃with an oil bath.

(3) Extracting and purifying to obtain isosorbide diacid solid

And (3) adding 100mL of acetone with the concentration of 13.5mol/L into the solution obtained in the step (2), extracting, precipitating a white precipitate, separating the solution by using a separating funnel, carrying out suction filtration, washing by using ethanol, and drying the white solid in a vacuum oven at 70 ℃ for 5 hours. 3.53g of isosorbide diacid solid was finally obtained in a yield of 61.3%.

Example 4

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (1.6 g,40 mmol); isosorbide (2.9228 g,20 mmol); chloroacetic acid (3.7798 g,40 mmol)

(2) Preparation of isosorbide-containing diacid solution

a. 200mL of deionized water was added to a 400mL beaker, and the weighed sodium hydroxide (1.6 g,40 mmol) was added to the deionized water all, and stirred with a glass rod until the sodium hydroxide was dissolved all together.

c. Chloroacetic acid (3.7798 g,40 mmol) was added gradually and batchwise to the three-necked flask, the temperature was kept at 80℃or higher continuously, and the initial pH of the solution was recorded to be 13.

d. Maintaining the temperature, continuously reacting, measuring the pH value when the reaction is carried out for 2 hours, adding a proper amount of sodium hydroxide to ensure that the pH value is more than 13, and keeping the solution to be strongly alkaline.

(3) Extracting and purifying to obtain isosorbide diacid solid

And (3) adding 100mL of acetone with the concentration of 13.5mol/L into the solution obtained in the step (2), extracting, precipitating a white precipitate, separating the solution by using a separating funnel, carrying out suction filtration, washing by using ethanol, and drying the white solid in a vacuum oven at 70 ℃ for 5 hours. The isosorbide diacid solid was finally obtained in a yield of 66.54% in 4.46 g.

Example 5

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (0.8 g,20 mmol); isosorbide (1.4614 g,10 mmol); chloroacetic acid (1.8899 g,20 mmol)

(2) Preparation of isosorbide-containing diacid solution

(3) Purifying to obtain isosorbide diacid solid

Transferring the isosorbide-containing diacid solution obtained in the step (2) into a 150ml single-neck flask, performing rotary evaporation on the solution by using a rotary evaporator, setting the rotary evaporation temperature to be 70 ℃, and evaporating the solution for about 25 minutes to obtain a white solid after all the moisture is evaporated. And (3) putting the obtained white solid into a 70 ℃ oven for drying, taking out 100mL of acetone with the concentration of 13.5mol/L after 3 hours, dissolving part of the solid, filtering, taking filtrate in a suction filter flask, and performing rotary evaporation on the filtrate again. Setting the spin-steaming temperature to be 30 ℃, steaming for about 15min, evaporating all acetone to obtain white solid, and drying the white solid in a vacuum oven at 60 ℃ for 5h. Finally, 2.26g of isosorbide diacid solid was obtained in 67% yield.

Example 6

(1) Raw material preparation

Weighing by an electronic balance: sodium hydroxide (0.8 g,20 mmol); isosorbide (1.4614 g,10 mmol); chloroacetic acid (4.72475 g,50 mmol).

(2) Preparation of isosorbide-containing diacid solution

c. Chloroacetic acid (4.72475 g,50 mmol) was added stepwise in portions to the three-necked flask, the temperature was kept at 90℃with continued heating, and the initial pH of the solution was recorded to be 13.

e. After the reaction is carried out for about 7 hours, the pH value does not change obviously, the heating is stopped, the reaction is stopped, the solution is cooled to room temperature, 30mL of hydrochloric acid with the concentration of 1mol/L is added, and the pH value of the solution is measured to be less than 3, so that the isosorbide-containing diacid solution is obtained.

(3) Purifying to obtain isosorbide diacid solid

And (3) adding 100mL of acetone with the concentration of 13.5mol/L into the solution obtained in the step (2), extracting, precipitating a white precipitate, separating the solution by using a separating funnel, carrying out suction filtration, washing by using ethanol, and drying the white solid in a vacuum oven at 70 ℃ for 5 hours. 2.23g of isosorbide diacid solid was finally obtained in 67% yield.

The invention adopts isosorbide with wide sources as a raw material, belongs to a bio-based renewable raw material, and makes isosorbide and chloroacetic acid react in alkaline solution, and acidify to obtain a diacid solution containing isosorbide groups; and purifying the isosorbide diacid solution to obtain an isosorbide diacid solid. The isosorbide bio-based diacid synthesized by the preparation method provided by the invention can be used for preparing novel bio-based high-performance polyamide nylon by reacting with certain diamine, and the epoxy ether bond in the structure can improve the performance of polyamide. The invention is green and environment-friendly, overcomes the problem of raw material shortage of the traditional petroleum coke products, can reduce the dependence of the plastic industry on petrochemical products, and can also reduce the pollution to the environment in the production process; the preparation method has the advantages of simple process, mild condition, less side reaction, higher yield and simple post treatment.

Claims

1. An isosorbide-based diacid characterized in that: the chemical formula is C ₁₀ H ₁₄ O ₈ Is obtained by the reaction of isosorbide and chloroacetic acid, and has the following structural formula:

2. the method for producing isosorbide diacid according to claim 1, comprising the steps of:

s1, reacting isosorbide and chloroacetic acid in an alkaline solution, and acidifying to obtain a diacid solution containing isosorbide groups;

s2, purifying the isosorbide diacid solution to obtain an isosorbide diacid solid.

3. The method for producing isosorbide diacid according to claim 2, characterized in that: the molar ratio of the isosorbide to the chloroacetic acid is 1:1-5.

4. A process for the preparation of isosorbide diacid according to claim 3, characterized in that: the alkaline solution solute comprises sodium hydroxide;

and/or the alkaline solution solvent comprises water.

5. The method for producing isosorbide diacid according to claim 4, characterized in that: in the reaction in S1, nitrogen or inert gas is continuously introduced into the alkaline solution.

6. The method for producing isosorbide diacid according to claim 4, characterized in that: and (2) measuring the pH value of the alkaline solution when the reaction is carried out in the step (S1), and adding the solute of the alkaline solution to maintain an alkaline environment.

7. The method for producing isosorbide diacid according to claim 2, characterized in that: and under the condition that nitrogen or inert gas is continuously introduced into the alkaline solution, firstly adding the isosorbide, heating and finally adding the chloroacetic acid.

8. The method for producing isosorbide diacid according to claim 2, characterized in that: heating the alkaline solution to 80-90 ℃ during the reaction in S1;

and/or the reaction time of the S1 is 6-8 hours.

9. The method for producing isosorbide diacid according to claim 8, characterized in that: adding acid into the alkaline solution after the reaction in the step S1 is finished so that the pH value of the alkaline solution is less than 3;

and/or the added acid comprises any one of hydrochloric acid and sulfuric acid;

and/or, the purification mode in S2 includes: extracting, rotary steaming, suction filtering, washing and drying.

10. Use of isosorbide diacid according to claim 1 or prepared by the preparation method according to any one of claims 2 to 9 for the preparation of polyamides.