Preparation process and application of rosin glyceride

Abstract

The present application relates to a preparation process and application of rosin glyceride, and belongs to the technical field of rosin deep processing. The preparation process of the rosin glyceride discloses the modified ZSM-5 molecular sieve as a catalyst, utilizes silver ion to replace the proton site to form Si-O-Ag-Al structure, forms Lewis acid site, simultaneously Ce 3+ The valence electron configuration of Ce is 4f 1 It is a good electron acceptor, is easy to form a coordination bond with O atom, cooperates with Ag + Modification can produce more Lewis acid sites, thereby effectively reducing the combination of B acid sites and water in the esterification reaction process, preventing catalyst deactivation; in addition, the use of trifluoropropyl trimethoxysilane modified molecular sieve makes it have strong hydrophobicity, and overcomes the problem of long-chain plugging pores, and the catalyst has strong hydrophobicity, which can accelerate the diffusion of water from the catalytic site, promote the forward movement of the reaction, and improve the reaction rate.

Description

Technical Field

[0001] This invention belongs to the field of rosin deep processing technology, and relates to a preparation process and application of rosin glycerol ester. Background Technology

[0002] Rosin possesses excellent properties such as thickening, emulsification, softening, moisture resistance, corrosion resistance, and insulation, making it widely used in industry. However, it also has drawbacks, including high sensitivity to heat and light, poor aging resistance, easy oxidation, high acid value, and low softening point, which limit its industrial applications. To improve the application value of rosin, it is necessary to modify it to produce rosin esters with excellent properties such as low acid value, high softening point, strong thermal stability, and resistance to acids and alkalis. The main component of rosin is abietic acid, which can undergo esterification reactions with alcohols. Because the carboxyl group of rosin is located on a tertiary carbon atom, it results in large steric hindrance and high activation energy, making the esterification reaction conditions quite harsh. Therefore, selecting a highly active catalyst is crucial in the rosin esterification process. Summary of the Invention

[0003] This invention relates to a preparation process and application of rosin glycerol esters, belonging to the field of rosin deep processing technology. The preparation process of rosin glycerol esters disclosed in this invention uses modified ZSM-5 molecular sieve as a catalyst, utilizing silver ions to replace proton sites to form a Si-O-Ag-Al structure, forming Lewis acidic sites, while Ce... 3+ The valence electron configuration is 4f 1 It is a good electron acceptor, readily forming coordinate bonds with O atoms, and cooperating with Ag. + The modification process generates more Lewis acid sites, thereby effectively reducing the binding of Brønsted acid sites with water during the esterification process and preventing catalyst deactivation. In addition, the molecular sieve is modified with trifluoropropyltrimethoxysilane to make it highly hydrophobic and overcome the problem of long chain clogging of pores. The catalyst's strong hydrophobicity can accelerate the diffusion of water from the catalytic sites, promote the forward movement of the reaction, and increase the reaction rate.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A process for preparing rosin glycerol ester, wherein the specific steps of the process are as follows: rosin, glycerol and catalyst are placed together in a reaction vessel, vacuum is drawn under nitrogen protection, then heated and kept at a certain temperature, and after cooling, nitrogen flow and vacuum are stopped, and rosin glycerol ester is obtained by discharging.

[0006] Furthermore, the mass ratio of rosin, glycerol and catalyst is 15-20:3-5:0.1-0.3, the vacuum pressure is -0.01~0.03MPa, the heat preservation temperature and time are 130-230℃ and 4-10h respectively, and the cooling refers to cooling down to 50-60℃.

[0007] Furthermore, the method for preparing the catalyst includes the following steps:

[0008] (1) Tetrapropylammonium hydroxide is dissolved in deionized water by stirring. Tetraethyl orthosilicate, sodium aluminate and sodium hydroxide are added and stirred. The mixture is heated and kept warm. After crystal formation, it is filtered and washed with distilled water. After drying, it is placed in a Marfät furnace for calcination. After cooling, ZSM-5 molecular sieve is obtained.

[0009] (2) ZSM-5 molecular sieve, silver nitrate solution and cerium nitrate solution are mixed and heated, and then potassium hydroxide solution is added under stirring. After solid-liquid separation, the solid is dried and calcined, and then cooled to room temperature to obtain Ce-Ag-ZSM-5 molecular sieve.

[0010] (3) Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene are mixed, then refluxed, the solid is collected by rotary evaporation, washed with anhydrous ethanol and dried to obtain the catalyst.

[0011] Further, in step (1), the mass ratio of tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium aluminate, sodium hydroxide and deionized water is 4-5:3-3.5:0.8-1:2-3:30-35, and the mixing time is 2-3 hours.

[0012] Furthermore, the temperature and time for heat preservation in step (1) are 200-220℃ and 20-24h, respectively, and the temperature and time for roasting are 560-600℃ and 3-4h, respectively.

[0013] Further, in step (2), the mass ratio of ZSM-5 molecular sieve, silver nitrate solution, cerium nitrate solution and potassium hydroxide solution is 1-3:20-30:20-25:40-43, wherein the mass fractions of silver nitrate solution, cerium nitrate solution and potassium hydroxide solution are 8-10%, 5-6%, and 20-30%, respectively; the heating temperature and time are 90-120℃ and 60-90min, respectively; the drying temperature is 90-100℃; and the calcination temperature and time are 500-600℃ and 3-4h, respectively.

[0014] Further, in step (3), the mass ratio of Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene is 3-5:1-1.2:50-60, the reflux temperature and time are 60-70℃ and 10-12h respectively, and the drying temperature and time are 90-110℃ and 1-2h respectively.

[0015] Furthermore, the rosin glycerol ester is used in coatings and pressure-sensitive adhesives.

[0016] The beneficial effects of this invention are:

[0017] 1. This invention uses modified ZSM-5 molecular sieve as a catalyst, utilizing silver ions to replace proton sites to form a Si-O-Ag-Al structure, creating Lewis acid sites, while Ce... 3+ The valence electron configuration is 4f 1 It is a good electron acceptor, readily forming coordinate bonds with O atoms, and cooperating with Ag. + The modification process generates more Lewis acid sites, thereby effectively reducing the binding of Brønsted acid sites with water during the esterification process and preventing catalyst deactivation. In addition, the molecular sieve is modified with trifluoropropyltrimethoxysilane to make it highly hydrophobic and overcome the problem of long chain clogging of pores. The catalyst's strong hydrophobicity can accelerate the diffusion of water from the catalytic sites, promote the forward movement of the reaction, and increase the reaction rate. Detailed Implementation

[0018] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with embodiments, is provided below.

[0019] The rosin involved in this invention was purchased from Fujian Xingli New Materials Co., Ltd.

[0020] Example 1

[0021] A process for preparing rosin glycerol ester, wherein the specific steps of the process are as follows: rosin, glycerol and catalyst are placed together in a reaction vessel, vacuum is drawn under nitrogen protection, then heated and kept at a certain temperature, and after cooling, nitrogen flow and vacuum are stopped, and rosin glycerol ester is obtained by discharging.

[0022] The mass ratio of rosin, glycerol and catalyst is 15:3:0.1, the vacuum pressure is -0.01MPa, the heat preservation temperature and time are 130℃ and 4h respectively, and the cooling refers to cooling down to 50℃.

[0023] The method for preparing the catalyst includes the following steps:

[0024] (1) Tetrapropylammonium hydroxide is dissolved in deionized water by stirring. Tetraethyl orthosilicate, sodium aluminate and sodium hydroxide are added and stirred. The mixture is heated and kept warm. After crystal formation, it is filtered and washed with distilled water. After drying, it is placed in a Marfät furnace for calcination. After cooling, ZSM-5 molecular sieve is obtained.

[0025] (2) ZSM-5 molecular sieve, silver nitrate solution and cerium nitrate solution are mixed and heated, and then potassium hydroxide solution is added under stirring. After solid-liquid separation, the solid is dried and calcined, and then cooled to room temperature to obtain Ce-Ag-ZSM-5 molecular sieve.

[0026] (3) Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene are mixed, then refluxed, the solid is collected by rotary evaporation, washed with anhydrous ethanol and dried to obtain the catalyst.

[0027] In step (1), the mass ratio of tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium aluminate, sodium hydroxide and deionized water is 4:3:0.8:2:30, and the mixing and stirring time is 2 hours.

[0028] The temperature and time for heat preservation in step (1) are 200℃ and 20h, respectively, and the temperature and time for roasting are 560℃ and 3h, respectively.

[0029] In step (2), the mass ratio of ZSM-5 molecular sieve, silver nitrate solution, cerium nitrate solution and potassium hydroxide solution is 1:20:20:40, wherein the mass fractions of silver nitrate solution, cerium nitrate solution and potassium hydroxide solution are 8%, 5% and 20% respectively, the heating temperature and time are 90℃ and 60min respectively, the drying temperature is 90℃, and the calcination temperature and time are 500℃ and 3h respectively.

[0030] In step (3), the mass ratio of Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene is 3:1:50, the reflux temperature and time are 60℃ and 10h respectively, and the drying temperature and time are 90℃ and 1h respectively.

[0031] The rosin glycerol ester is used in coatings and pressure-sensitive adhesives.

[0032] Example 2

[0033] A process for preparing rosin glycerol ester, wherein the specific steps of the process are as follows: rosin, glycerol and catalyst are placed together in a reaction vessel, vacuum is drawn under nitrogen protection, then heated and kept at a certain temperature, and after cooling, nitrogen flow and vacuum are stopped, and rosin glycerol ester is obtained by discharging.

[0034] The mass ratio of rosin, glycerol and catalyst is 18:4:0.2, the vacuum pressure is -0.02MPa, the heat preservation temperature and time are 160℃ and 6h respectively, and the cooling refers to cooling down to 55℃.

[0035] The method for preparing the catalyst includes the following steps:

[0036] (1) Tetrapropylammonium hydroxide is dissolved in deionized water by stirring. Tetraethyl orthosilicate, sodium aluminate and sodium hydroxide are added and stirred. The mixture is heated and kept warm. After crystal formation, it is filtered and washed with distilled water. After drying, it is placed in a Marfät furnace for calcination. After cooling, ZSM-5 molecular sieve is obtained.

[0037] (2) ZSM-5 molecular sieve, silver nitrate solution and cerium nitrate solution are mixed and heated, and then potassium hydroxide solution is added under stirring. After solid-liquid separation, the solid is dried and calcined, and then cooled to room temperature to obtain Ce-Ag-ZSM-5 molecular sieve.

[0038] (3) Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene are mixed, then refluxed, the solid is collected by rotary evaporation, washed with anhydrous ethanol and dried to obtain the catalyst.

[0039] In step (1), the mass ratio of tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium aluminate, sodium hydroxide and deionized water is 4.5:3.3:0.9:2.5:33, and the mixing time is 2.5 hours.

[0040] The temperature and time for heat preservation in step (1) are 210℃ and 22h, respectively, and the temperature and time for roasting are 580℃ and 3.5h, respectively.

[0041] In step (2), the mass ratio of ZSM-5 molecular sieve, silver nitrate solution, cerium nitrate solution and potassium hydroxide solution is 2:25:23:42, wherein the mass fractions of silver nitrate solution, cerium nitrate solution and potassium hydroxide solution are 9%, 5.5% and 25%, respectively; the heating temperature and time are 100℃ and 75min, respectively; the drying temperature is 95℃; and the calcination temperature and time are 550℃ and 3.5h, respectively.

[0042] In step (3), the mass ratio of Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene is 4:1.1:55. The reflux temperature and time are 65℃ and 11h, respectively, and the drying temperature and time are 100℃ and 1.5h, respectively.

[0043] The rosin glycerol ester is used in coatings and pressure-sensitive adhesives.

[0044] Example 3

[0045] A process for preparing rosin glycerol ester, wherein the specific steps of the process are as follows: rosin, glycerol and catalyst are placed together in a reaction vessel, vacuum is drawn under nitrogen protection, then heated and kept at a certain temperature, and after cooling, nitrogen flow and vacuum are stopped, and rosin glycerol ester is obtained by discharging.

[0046] The mass ratio of rosin, glycerol and catalyst is 20:5:0.3, the vacuum pressure is 0.03 MPa, the heat preservation temperature and time are 230℃ and 10h respectively, and the cooling refers to cooling down to 60℃.

[0047] The method for preparing the catalyst includes the following steps:

[0048] (1) Tetrapropylammonium hydroxide is dissolved in deionized water by stirring. Tetraethyl orthosilicate, sodium aluminate and sodium hydroxide are added and stirred. The mixture is heated and kept warm. After crystal formation, it is filtered and washed with distilled water. After drying, it is placed in a Marfät furnace for calcination. After cooling, ZSM-5 molecular sieve is obtained.

[0049] (2) ZSM-5 molecular sieve, silver nitrate solution and cerium nitrate solution are mixed and heated, and then potassium hydroxide solution is added under stirring. After solid-liquid separation, the solid is dried and calcined, and then cooled to room temperature to obtain Ce-Ag-ZSM-5 molecular sieve.

[0050] (3) Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene are mixed, then refluxed, and the solid is collected by rotary evaporation. The solid is washed with anhydrous ethanol and dried to obtain the catalyst.

[0051] In step (1), the mass ratio of tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium aluminate, sodium hydroxide and deionized water is 5:3.5:1:3:35, and the mixing and stirring time is 3 hours.

[0052] The temperature and time for heat preservation in step (1) are 220℃ and 24h, respectively, and the temperature and time for roasting are 600℃ and 4h, respectively.

[0053] In step (2), the mass ratio of ZSM-5 molecular sieve, silver nitrate solution, cerium nitrate solution and potassium hydroxide solution is 3:30:25:43, wherein the mass fractions of silver nitrate solution, cerium nitrate solution and potassium hydroxide solution are 10%, 6% and 30% respectively, the heating temperature and time are 120℃ and 90min respectively, the drying temperature is 100℃, and the calcination temperature and time are 600℃ and 4h respectively.

[0054] In step (3), the mass ratio of Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene is 5:1.2:60. The reflux temperature and time are 70℃ and 12h, respectively, and the drying temperature and time are 110℃ and 2h, respectively.

[0055] The rosin glycerol ester is used in coatings and pressure-sensitive adhesives.

[0056] Comparative Example 1

[0057] Based on Example 2, the silver nitrate solution in step (2) of catalyst preparation was replaced with an equal mass of cerium nitrate solution, while other conditions remained the same as in Example 2.

[0058] Comparative Example 2

[0059] Based on Example 2, the cerium nitrate solution in step (2) of catalyst preparation was replaced with an equal mass of silver nitrate solution, while other conditions remained the same as in Example 2.

[0060] Comparative Example 3

[0061] Based on Example 2, the trifluoropropyltrimethoxysilane in the catalyst preparation step (3) was removed and replaced with an equal mass of dimethyldimethoxysilane, while other conditions remained the same as in Example 2.

[0062] Comparative Example 4

[0063] Based on Example 2, the trifluoropropyltrimethoxysilane in the catalyst preparation step (3) was removed and replaced with an equal mass of phenyltrimethoxysilane, while other conditions remained the same as in Example 2.

[0064] Comparative Example 5

[0065] Based on Example 2, the trifluoropropyltrimethoxysilane in the catalyst preparation step (3) was removed and replaced with an equal mass of n-dodecyltrimethoxysilane, while other conditions remained the same as in Example 2.

[0066] Performance testing

[0067] Esterification rate test: The rosin glycerides prepared in Examples 1-3 and Comparative Examples 1-5 were used as samples. The determination method was as follows: Weigh approximately 2g (accurate to 0.001g) of the pulverized sample (after removing the outer surface) into a 250mL Erlenmeyer flask, add 50mL of neutral benzene-ethanol solution to dissolve it (if necessary, gently heat until the sample is completely dissolved and then cool), add 4-5 drops of phenolphthalein indicator, and then titrate with 0.05mol / L potassium hydroxide ethanol standard solution until a faint red color persists for 30 seconds. Neutral benzene-ethanol solution: Mix benzene and anhydrous ethanol (analytical grade) at a volume ratio of 2:1, use phenolphthalein as an indicator (add two drops per 100mL), and titrate with 0.05mol / L potassium hydroxide ethanol standard solution until a faint red color persists for 30 seconds. 1% phenolphthalein indicator: Weigh 1.0g of phenolphthalein, dissolve it in anhydrous ethanol (analytical grade), and dilute with anhydrous ethanol (analytical grade) to 100mL. 0.05 mol / L potassium hydroxide ethanol standard solution: Weigh 2.8 g of analytical grade potassium hydroxide, dissolve it in a small amount of CO2-free water, add anhydrous ethanol to 1000 mL, and shake well;

[0068] The formula for calculating the acid value X1 (mg KOH) is: X1 = V × M × 56.11 / W, where: V - the volume of potassium hydroxide ethanol standard solution consumed during titration, mL; M - the concentration of potassium hydroxide ethanol standard solution, mol / L; W - the mass of the sample, g; 56.11 - the equivalent amount of 1 mL of 1 mol / L potassium hydroxide, mg. Esterification rate % = [(initial acid value - product acid value) / initial acid value] × 100%. Additionally, the catalysts used in Examples 1-3 and Comparative Examples 1-5 five times were tested according to the above method to determine the esterification rate % of the synthesized rosin glycerol esters, and labeled as A. The results of the esterification rate % are shown in Table 1.

[0069] Table 1 Test Results

[0070]

[0071] Analysis of the results in Table 1 shows that the esterification rates of Examples 1-3 are higher than those of Comparative Examples 1-5, indicating that the catalysts of Examples 1-3 have excellent activity and durability. Comparative Examples 1-2 used only silver nitrate or cerium nitrate solutions to load a single metal atom onto the molecular sieve, reducing the proportion of L-acid. The increase in Brønsted acid led to catalyst deactivation due to water binding, resulting in a significant decrease in esterification rate and a substantial reduction in activity after repeated use. Comparative Example 3 used short-chain methylsiloxanes to modify the hydrophobicity of the molecular sieve. Its poor hydrophobicity slowed the forward propagation of the reaction equilibrium, leading to a decrease in esterification rate. Comparative Examples 4-5 used long-chain methylsiloxanes and phenylsiloxanes, both of which have good hydrophobicity, but their larger molecular structures created significant steric hindrance in the molecular sieve, reducing its porosity and affecting activity. This invention increases the proportion of L-acid by loading with dual metal atoms, while simultaneously introducing a highly hydrophobic and sterically unhindered trifluoropropyltrimethoxysilane, thereby improving the conversion rate of rosin glycerol esters and enhancing the activity of the catalyst after repeated use.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A preparation process for rosin glycerol esters, characterized in that, The specific steps of the preparation process of the rosin glycerol ester are as follows: rosin, glycerol and catalyst are put into a reaction vessel together, vacuum is drawn under nitrogen protection, then heated and kept at a certain temperature, and after cooling, nitrogen gas supply and vacuum are stopped, and rosin glycerol ester is obtained by discharging the material. The method for preparing the catalyst includes the following steps: (1) Tetrapropylammonium hydroxide is dissolved in deionized water by stirring. Tetraethyl orthosilicate, sodium aluminate and sodium hydroxide are added and stirred. The mixture is heated and kept warm. After crystal formation, it is filtered and washed with distilled water. After drying, it is placed in a Marfät furnace for calcination. After cooling, ZSM-5 molecular sieve is obtained. (2) ZSM-5 molecular sieve, silver nitrate solution and cerium nitrate solution are mixed and heated, and then potassium hydroxide solution is added under stirring. After solid-liquid separation, the solid is dried and calcined, and then cooled to room temperature to obtain Ce-Ag-ZSM-5 molecular sieve. (3) Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene are mixed, then reacted and refluxed. The solid is collected by rotary evaporation, washed with anhydrous ethanol and dried to obtain the catalyst. In step (1), the mass ratio of tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium aluminate, sodium hydroxide and deionized water is 4-5:3-3.5:0.8-1:2-3:30-35, and the mixing and stirring time is 2-3 hours. In step (2), the mass ratio of ZSM-5 molecular sieve, silver nitrate solution, cerium nitrate solution, and potassium hydroxide solution is 1-3:20-30:20-25:40-43, wherein the mass fractions of silver nitrate solution, cerium nitrate solution, and potassium hydroxide solution are 8-10%, 5-6%, and 20-30%, respectively; the heating temperature and time are 90-120℃ and 60-90min, respectively; the drying temperature is 90-100℃; and the calcination temperature and time are 500-600℃ and 3-4h, respectively. In step (3), the mass ratio of Ce-Ag-ZSM-5 molecular sieve, trifluoropropyltrimethoxysilane and toluene is 3-5:1-1.2:50-60, the reaction temperature and time are 60-70℃ and 10-12h respectively, and the drying temperature and time are 90-110℃ and 1-2h respectively. The mass ratio of rosin, glycerol and catalyst is 15-20:3-5:0.1-0.3, the vacuum pressure is -0.01~0.03MPa, the heat preservation temperature and time are 130-230℃ and 4-10h respectively, and the cooling refers to cooling down to 50-60℃.

2. The preparation process of rosin glycerol ester according to claim 1, characterized in that, The temperature and time for heat preservation in step (1) are 200-220℃ and 20-24h, respectively, and the temperature and time for roasting are 560-600℃ and 3-4h, respectively.

3. The preparation process of rosin glycerol ester according to claim 1, characterized in that, The rosin glycerol ester is used in coatings and pressure-sensitive adhesives.

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