Cardanol methyl ether for synthesizing alkenyl succinic anhydride as well as preparation method and application of cardanol methyl ether

Abstract

The invention belongs to the technical field of papermaking chemical synthesis, particularly discloses anacardol methyl ether for synthesizing alkenyl succinic anhydride as well as a preparation method and application thereof, and aims to solve the technical problems that the existing alkenyl succinic anhydride synthesis depends on imported internal olefin, and the cost is high. The preparation method comprises the following steps: under the protection of nitrogen, adding cardanol and absolute methanol into a reaction kettle, adding a catalyst and an antioxidant, and reacting at 150-200 DEG C for 4-8 hours; and after the reaction is finished, removing generated water and excessive methanol through reduced pressure distillation to obtain the target product anacardol methyl ether. Renewable and cheap cardanol is used as a core raw material, the technical monopoly of alkenyl succinic anhydride synthesis is effectively broken through, and the production cost of alkenyl succinic anhydride is remarkably reduced. In addition, the preparation process is simple, reaction conditions are mild, the sizing performance of alkenyl succinic anhydride synthesized by using the cardanol methyl ether is equivalent to that of commercially available products, and the cardanol methyl ether has a good industrial popularization prospect.

Description

Technical Field

[0001] This invention relates to the field of papermaking chemical synthesis technology, specifically to a cashew phenol methyl ether for synthesizing alkenyl succinic anhydride, its preparation method, and its application. Background Technology

[0002] Neutral sizing agent alkenyl succinic anhydride (ASA) is a highly efficient in-sizing agent with advantages such as a wide sizing pH range, good compatibility with alkaline fillers, high paper strength, and strong resistance to permeation. It is widely used in the papermaking industry.

[0003] Currently, the synthesis of alkenyl succinic anhydride (ASA) typically involves the addition reaction of an inner olefin with maleic anhydride. However, the production technology of the inner olefin has long been monopolized by foreign companies, resulting in high prices. Although domestic research is underway to develop inner olefin production technology, the catalysts used largely rely on imports, leading to problems such as short catalyst life and poor economic efficiency. This severely restricts the domestic production and widespread application of alkenyl succinic anhydride (ASA).

[0004] Therefore, developing a new type of raw material that is widely available, inexpensive, and can replace traditional internal olefins is of great significance for breaking through technological monopolies and reducing the production cost of alkenyl succinic anhydride (ASA). Summary of the Invention

[0005] The purpose of this invention is to provide a raw material and its preparation method for synthesizing alkenyl succinic anhydride (ASA) as an alternative to olefins. By modifying cashew phenol, a product with a structure similar to an inner olefin is obtained for subsequent ASA synthesis, thus solving the problems of reliance on imports and high costs in the prior art for inner olefins.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride includes the following steps:

[0008] Under nitrogen protection, cashew phenol and anhydrous methanol are added to a reaction vessel, along with a catalyst and antioxidant, and reacted at 150–200°C for 4–8 hours. After the reaction is completed, vacuum distillation is performed to remove the generated water and excess methanol, thus obtaining the cashew phenol methyl ether.

[0009] As a further embodiment of the present invention, the catalyst is one or more of concentrated sulfuric acid, thionyl chloride, phosphoric acid, and formic acid.

[0010] As a further embodiment of the present invention, the antioxidant is at least one of hydroquinone, phenothiazine, triphosphite, and 2,6-di-tert-butylcresol.

[0011] As a further aspect of the present invention: in step (1), the molar ratio of cashew phenol to anhydrous methanol is 1:1 to 1.5.

[0012] As a further aspect of the present invention: in step (1), the amount of catalyst added is 0.5 to 5% of the mass of cashew phenol.

[0013] As a further aspect of the present invention: in step (1), the amount of antioxidant added is 0.5 to 2% of the mass of cashew phenol.

[0014] In a second aspect, the present invention provides a cashew phenol methyl ether prepared by the above-described preparation method.

[0015] In a third aspect, the present invention provides the application of the above-mentioned cashew methyl ether in the synthesis of alkenyl succinic anhydride.

[0016] The beneficial effects of this invention are as follows:

[0017] 1. This invention uses renewable and inexpensive cashew phenol as the main raw material. Through a catalytic reaction with methanol under specific conditions, the reactivity of the phenolic hydroxyl group is completely lost, while the activity of the side chain double bond is retained. Cashew phenol methyl ether, which can be used to synthesize ASA, can undergo a side chain double bond addition reaction with maleic anhydride without being interfered with by the phenolic hydroxyl group. This effectively breaks through the foreign technology monopoly on domestic olefins and significantly reduces production costs.

[0018] 2. The preparation process of this invention is simple, the reaction conditions are mild, no complex equipment or expensive catalysts are required, and it is easy to store and transport, thus having good prospects for industrial application.

[0019] 3. The ASA sizing agent synthesized using the raw materials of this invention exhibits excellent water resistance in paper sizing applications, and can meet the production requirements of high-quality paper. Detailed Implementation

[0020] The present invention is further illustrated below by way of examples, but these examples do not limit the invention to the scope of the embodiments described. Experimental methods in the following examples, unless otherwise specified, were performed according to conventional methods and conditions, or as selected in the product instructions. Furthermore, all reagents and raw materials used in this invention are commercially available.

[0021] Example 1

[0022] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0023] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1 mol of anhydrous methanol to the reactor;

[0024] (2) Add 1% by weight of concentrated sulfuric acid to cashew phenol and 1% by weight of hydroquinone to cashew phenol as an antioxidant.

[0025] (3) Heat to 180℃ and react for 6 hours;

[0026] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether A.

[0027] Example 2

[0028] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0029] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1.5 mol of anhydrous methanol into the reactor;

[0030] (2) Add 2% by weight of phosphate as a catalyst and 1.5% by weight of 2,6-di-tert-butylcresol as an antioxidant.

[0031] (3) Heat to 200℃ and react for 4 hours with stirring;

[0032] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether B.

[0033] Example 3

[0034] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0035] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1.2 mol of anhydrous methanol into the reactor;

[0036] (2) Add 0.5% thionyl chloride of cashew phenol by weight as a catalyst, and add 1% phosphite of cashew phenol by weight as an antioxidant.

[0037] (3) Heat to 150℃ and react for 8 hours with stirring;

[0038] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether C.

[0039] Example 4

[0040] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0041] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1.1 mol of anhydrous methanol into the reactor;

[0042] (2) Add 5% formic acid by weight of cashew phenol as a catalyst and 2% triphosphite by weight of cashew phenol as an antioxidant.

[0043] (3) Heat to 190℃ and react for 5 hours with stirring;

[0044] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether D.

[0045] Example 5

[0046] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0047] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1.3 mol of anhydrous methanol into the reactor;

[0048] (2) Add 2% by weight of thionyl chloride of cashew phenol as a catalyst and 1.5% by weight of phenothiazine of cashew phenol as an antioxidant.

[0049] (3) Heat to 200℃ and react for 4 hours with stirring;

[0050] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether E.

[0051] Example 6

[0052] A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride specifically includes the following steps:

[0053] (1) Purge and replace the air in the reactor with nitrogen, and add 1 mol of cashew phenol and 1.4 mol of anhydrous methanol into the reactor;

[0054] (2) Add 4% by weight of thionyl chloride of cashew phenol as a catalyst and 0.8% by weight of 2,6-di-tert-butylcresol of cashew phenol as an antioxidant.

[0055] (3) Heat to 170℃ and react for 7 hours with stirring;

[0056] (4) After the reaction is complete, perform vacuum distillation to remove the generated water and excess methanol to obtain cashew phenol methyl ether F.

[0057] Comparative Example 1

[0058] The difference from Example 1 is that no antioxidant is added. The remaining steps and parameters are exactly the same as in Example 1.

[0059] Comparative Example 2

[0060] The difference from Example 1 is that the amount of catalyst added is 0.1% of the mass of cashew phenol. The remaining steps and parameters are exactly the same as in Example 1.

[0061] Effect Example

[0062] The cashew phenol methyl ether obtained in Examples 1-6 and Comparative Examples 1 and 2 of this invention, and commercially available imported olefins were respectively subjected to addition reactions with maleic anhydride to synthesize ASA sizing agents.

[0063] The synthesized ASA was applied to the internal sizing of paper pulp, and its sizing performance was tested. The specific testing process is as follows.

[0064] The experimental instruments included: Hamilton Beach HMD200 mixer (with three speed settings: 13000 r / min, 16000 r / min, and 18000 r / min), LABTECH 73-62 semi-automatic paper forming machine, electronic balance, Cobb surface absorption gravimetric analyzer, and paper drum dryer.

[0065] Step 1: ASA emulsification:

[0066] Cationic starch was diluted to a solid content of 4%, and the pH was adjusted to about 4.0 with citric acid. The mixture was kept in a water bath at 60°C. Then, ASA and the treated starch were mixed at a ratio of 3:10. The mixture was dispersed and stirred at speed 3 for 5 minutes. The temperature during high-speed dispersion and emulsification was 45-50°C to obtain mixture A.

[0067] Mixture A was mixed with the treated cationic starch (i.e., diluted to a solid content of 4%, and the pH value was adjusted to about 4.0 with citric acid) at a ratio of 1:25. The mixture was dispersed and stirred for 5 minutes at speed 3 to obtain an ASA emulsion mixture. The particle size was then measured. For samples with a particle size of ≥90% of 2.0 μm in the mixture, the solid content, viscosity, pH and other indicators were measured. A comparative application experiment was also conducted by adding the mixture to hand-made sheets.

[0068] Step 2: Papermaking quantity 100g / m 2 :

[0069] Slurry formulation: Slurry (65%) + ASA emulsion + filler (mixed with calcium 35%) + CPAM (100ppm) + microparticles 200ppm;

[0070] ASA addition rate: 1.2 kg / t paper (converted to ASA stock solution addition);

[0071] According to the above process, weigh the pulp, add ASA emulsion, calcium mixture, CPAM and microparticles in sequence, and stir for 1 minute each to mix evenly. Take out the prepared pulp, form sheets using a 73-62 semi-automatic paper sheet former, press with a 73-50 standard paper sheet press, dry in a drum dryer, and test the Cobb value of the paper sample for 1 minute.

[0072] Step 3, edge penetration testing:

[0073] ① Cut a paper pattern of 85mm×40mm and mark the sample number in the center;

[0074] ② Detect the thickness (μm) of each paper sample and calculate the average thickness D;

[0075] ③ Use an edge sealer to symmetrically and completely glue the paper pattern to both sides, making sure it is flat and avoiding air bubbles;

[0076] ④ Trim the transparent tape around the glued paper pattern neatly to avoid pressing it flat and sticking it to the roller (just make sure it doesn't stick to the roller; if it's too small, it won't be good for the next cutting step);

[0077] ⑤ Use a calender to cold press the trimmed paper pattern twice at 0.2 kPa to remove internal air bubbles and make the paper pattern flat;

[0078] ⑥ Cut a sample to 75mm × 25mm, weigh it G1 (g), and perform a permeation test:

[0079] Take an appropriate amount of distilled water (enough to completely immerse the sample) and put it into a water bath. Heat the water to (90±1)℃. Immerse the sample in the distilled water at (90±1)℃ for 10 minutes. Remove the sample and wipe the surface dry with absorbent paper. Weigh the sample and calculate its wet weight G2 (g). Calculate the edge penetration. The specific calculation method is as follows:

[0080] Permeability (kg / m²) = (G2 - G1) / (S × D) × 10 -6

[0081] In the formula, G1 is the mass of the sample in grams (g); G2 is the wet weight of the sample after wiping the surface dry with filter paper in grams (g); S is the perimeter of the sample in millimeters (mm); and D is the average thickness of the sample in micrometers (μm).

[0082] The 1-minute Cobb value and edge penetration test results of the above paper samples are shown in Table 1.

[0083] Table 1

[0084]

[0085]

[0086] As can be seen from Table 1, the ASA synthesized from the raw materials prepared by the method of the present invention has sizing performance comparable to commercially available products and superior to the comparative example, indicating that the process parameters of the present invention are optimized and necessary.

[0087] Based on current market prices and actual raw material consumption data in production, the price of commercially available imported olefins is approximately 25,000 yuan / ton, and the price of cashew phenol is 7,000 yuan / ton. When producing one ton of ASA, the traditional process consumes 0.98 tons of imported domestic olefins, while the cashew phenol methyl ether produced by this invention consumes 1.2 tons. Calculations show that compared to the traditional preparation process that relies on imported domestic olefins, the process of this invention can achieve a cost saving of approximately 16,100 yuan per ton of ASA, demonstrating a significant economic advantage.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing cashew phenol methyl ether for the synthesis of alkenyl succinic anhydride, characterized in that, Includes the following steps: Under nitrogen protection, cashew phenol and anhydrous methanol are added to a reaction vessel, along with a catalyst and antioxidant, and the reaction is carried out at 150–200°C for 4–8 hours. After the reaction is completed, vacuum distillation is performed to remove the generated water and excess methanol, thereby obtaining the cashew phenol methyl ether.

2. The method for preparing cashew phenol methyl ether for synthesizing alkenyl succinic anhydride according to claim 1, characterized in that, The catalyst is one or more of concentrated sulfuric acid, thionyl chloride, phosphoric acid, and formic acid.

3. The method for preparing cashew phenol methyl ether for synthesizing alkenyl succinic anhydride according to claim 1, characterized in that, The antioxidant is at least one of hydroquinone, phenothiazine, triphosphite, and 2,6-di-tert-butylcresol.

4. The method for preparing cashew phenol methyl ether for synthesizing alkenyl succinic anhydride according to claim 1, characterized in that, The molar ratio of cashew phenol to anhydrous methanol is 1:1 to 1.

5.

5. The method for preparing cashew phenol methyl ether for synthesizing alkenyl succinic anhydride according to claim 1, characterized in that, The amount of catalyst added is 0.5 to 5% of the mass of cashew phenol.

6. The method for preparing cashew phenol methyl ether for synthesizing alkenyl succinic anhydride according to claim 1, characterized in that, The amount of antioxidant added is 0.5% to 2% of the mass of cashew nutmeg.

7. A cashew phenol methyl ether prepared by any one of the preparation methods according to claims 1-6.

8. The use of cashew phenol methyl ether prepared by any one of the preparation methods according to claims 1-6 in the synthesis of alkenyl succinic anhydride.

Images