A rosin emulsion based on boron-modified rosin and its preparation method and application

Abstract

The present invention relates to the technical field of papermaking, and discloses a rosin emulsion based on boron-modified rosin, a preparation method thereof, and an application thereof; specifically, the present invention relates to modifying rosin using boric acid, diethanolamine, stearic acid, etc., and then emulsifying it using a compounding technology of anionic emulsifiers and nonionic emulsifiers, thereby preparing the rosin emulsion. By carefully optimizing the reaction conditions and formula combination, the prepared boron-modified rosin emulsion significantly surpasses the existing technology in multiple aspects such as emulsification effect, stability, and water resistance, and is very suitable for being widely used in many fields such as coatings and adhesives.

Description

Technical Field

[0001] The invention relates to the technical field of papermaking, and in particular to a rosin emulsion based on boron-modified rosin, and a preparation method and application thereof. Background Art

[0002] In the papermaking industry, rosin emulsion is widely used as a papermaking sizing agent, which can improve the water resistance and strength of paper. However, there are some problems with traditional rosin emulsion during use, such as poor stability, easy stratification, uneven sizing effect, etc. These problems limit its application in high-speed papermaking machines and also affect the quality of paper. In order to solve these problems, people have tried a variety of modification methods, among which boron-modified rosin emulsion has attracted attention due to its excellent performance. Boron-modified rosin emulsion improves the chemical stability and physical stability of rosin emulsion by introducing boron element, and improves the sizing effect at the same time. However, the existing preparation method of boron-modified rosin emulsion is complicated, costly, and difficult to achieve large-scale production.

[0003] Therefore, it is of great practical significance to develop a simple, efficient and low-cost boron-modified rosin emulsion and its preparation method. Summary of the invention

[0004] In view of this, the present invention proposes a rosin emulsion based on boron-modified rosin and a preparation method and application thereof, aiming to overcome the shortcomings of the prior art and provide a boron-modified rosin emulsion and a preparation method thereof which has good stability, low cost and is easy for large-scale production.

[0005] The present invention provides a method for preparing boron-modified rosin, comprising:

[0006] Diethanolamine and stearic acid are mixed, heated to react under the action of NaOH as a catalyst, and then the reaction product is further reacted with boric acid, isopropanol and a water-carrying agent to obtain product I;

[0007] The reinforced rosin, isopropyl alcohol and water-carrying agent are mixed, and KOH is added as a catalyst to react; after the reaction is completed, product II is obtained;

[0008] The product I and the product II are mixed and heated at a molar ratio of 1:1.0-1.5 to carry out an ester exchange reaction to obtain the boron-modified rosin.

[0009] Preferably, the molar ratio of diethanolamine to stearic acid is 2.0-2.5:1;

[0010] The molar ratio of the reaction product to boric acid and isopropanol is 1:3-5:0.5-1.2;

[0011] The molar ratio of the fortified rosin to isopropyl alcohol is 1.5-2:1.

[0012] The present invention also provides a boron-modified rosin, which is prepared by the above-mentioned preparation method.

[0013] The present invention also proposes an application of the above-mentioned boron-modified rosin, and the application includes at least one of the following:

[0014] A1) Application of the boron modified rosin in the preparation of rosin emulsion;

[0015] A2) Application of the boron modified rosin in the preparation of papermaking additives;

[0016] A3) Application of the boron modified rosin in papermaking.

[0017] The present invention also proposes a method for preparing a rosin emulsion based on boron-modified rosin, comprising:

[0018] After the boron modified rosin is melted, an emulsifier and water are added to perform shear emulsification, and after cooling, the rosin emulsion based on the boron modified rosin is obtained.

[0019] Preferably, the emulsifier includes a nonionic emulsifier and an anionic emulsifier;

[0020] The ratio of the nonionic emulsifier to the anionic emulsifier is 1:0.5-1.5.

[0021] Preferably, the anionic emulsifier is sodium dioctyl sulfosuccinate and / or sodium lauryl polyoxyethylene (3) ether succinic acid monoester sulfonate.

[0022] The present invention also provides a rosin emulsion based on boron-modified rosin, and the rosin emulsion is prepared by the above-mentioned preparation method.

[0023] The present invention also proposes an application of the above-mentioned rosin emulsion based on boron-modified rosin, and the application includes at least one of the following:

[0024] A1) Application of the rosin emulsion in the preparation of papermaking additives;

[0025] A2) Application of the rosin emulsion in papermaking.

[0026] The present invention also provides a papermaking additive, which comprises the above-mentioned rosin emulsion based on boron-modified rosin.

[0027] Preferably, the papermaking additive is a papermaking sizing agent.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. Excellent emulsification effect: The present invention prepares a boron-modified rosin emulsion by precisely adjusting the ratio and reaction conditions of diethanolamine, stearic acid, boric acid and fortified rosin.

[0030] 2. Uniform particle size distribution: The particle size of the emulsion of the present invention is small and uniformly distributed, which helps to improve the physical stability and application performance of the emulsion.

[0031] 3. Good stability: By optimizing the selection and ratio of emulsifiers, the prepared emulsion showed no stratification phenomenon when placed under different temperature conditions (40°C and 4°C) for 7 days, indicating that the emulsion has good storage stability and is suitable for long-term storage and use.

[0032] 4. Low surface tension: The surface tension of the emulsion of the present invention is low, indicating that it has better wettability and spreadability, so that the emulsion can better cover and adhere to the surface of various substrates in practical applications, thereby improving its application effect.

[0033] 5. Excellent water resistance: The boron-modified rosin emulsion of the present invention exhibits significant water resistance, can maintain the integrity of the coating film after long-term water immersion, avoids bubbling, shedding and the like, and exhibits excellent hydrolysis resistance and weather resistance.

[0034] 6. Adjustable formula and process flexibility: By adjusting the raw material ratio, reaction temperature, reaction time, and the type and amount of emulsifier, the present invention can produce an emulsion with controllable performance to meet the needs of different fields and has wide applicability.

[0035] In summary, the boron-modified rosin emulsion prepared by the present invention by optimizing the reaction conditions and formula combination shows significantly better performance than the prior art in terms of emulsification effect, stability, water resistance and other aspects, and is suitable for being widely used in the fields of coatings, adhesives and the like. DETAILED DESCRIPTION

[0036] The exemplary embodiments of the present disclosure will be described in more detail below. Although the exemplary embodiments of the present disclosure are shown below, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present disclosure and to be able to fully convey the scope of the present disclosure to those skilled in the art. It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0037] Example 1

[0038] (1) Mix 2 mol of diethanolamine with 1 mol of stearic acid, heat to 160°C in the presence of 3% NaOH as a catalyst, and react for 6 hours. Subsequently, add 1 mol of the reaction product, 3 mol of boric acid, and 0.5 mol of isopropanol into a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water carrier, and continue the reaction for 5 hours. The reaction is terminated when the water separator no longer separates the by-product water. Remove the water carrier and unreacted products by vacuum distillation.

[0039] The reaction path is:

[0040] .

[0041] (2) Add 1.5 mol of fortified rosin and 1 mol of isopropanol to a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water-carrying agent, add a small amount of 0.3% KOH as a catalyst, and react for 3 hours. When the water separator no longer separates the by-product water, the reaction is over. Remove the water-carrying agent and unreacted products by vacuum distillation.

[0042] The reaction path is:

[0043] .

[0044] (3) The above two substances were mixed in a molar ratio of 1:1, heated to 100°C, and reacted for 2 hours to perform an ester exchange reaction. The generated product was removed by vacuum distillation to obtain the final boron-modified rosin product.

[0045] The reaction path is:

[0046] .

[0047] (4) Melt the boron modified rosin at 130°C; use nonionic emulsifier OP-10 and sodium lauryl polyoxyethylene (3) ether succinic acid monoester sulfonate to compound in a ratio of 1:1 to obtain nonionic and anionic emulsifiers. The amount of nonionic and anionic emulsifiers is 3% of the boron modified rosin, and the emulsified solid content of rosin is 50%. Turn on the agitator of the emulsification kettle and slowly add the compounded nonionic and anionic emulsifiers. After the emulsifier is added, slowly add 90°C hot water, high shear for 15 minutes, and discharge after cooling.

[0048] Example 2

[0049] (1) Mix 2.3 mol of diethanolamine with 1 mol of stearic acid, heat to 160°C in the presence of 3% NaOH as a catalyst, and react for 6 hours. Then add 1 mol of the reaction product, 4 mol of boric acid, and 1 mol of isopropanol into a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water carrier, and continue the reaction for 8 hours. The reaction is terminated when the water separator no longer separates the by-product water. Remove the water carrier and unreacted product by vacuum distillation.

[0050] The reaction path is:

[0051] .

[0052] (2) Add 1.8 mol of fortified rosin and 1 mol of isopropanol to a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water-carrying agent, add a small amount of 0.3% KOH as a catalyst, and react for 4 hours. When the water separator no longer separates the by-product water, the reaction is over. Remove the water-carrying agent and unreacted products by vacuum distillation.

[0053] The reaction path is:

[0054] .

[0055] (3) The above two substances were mixed at a molar ratio of 1:1.2, heated to 110°C, and reacted for 3 hours to perform an ester exchange reaction. The generated product was removed by vacuum distillation to obtain the final boron-modified rosin product.

[0056] The reaction path is:

[0057] .

[0058] (4) Melt the boron modified rosin at 150°C; compound the nonionic emulsifier OP-10 and sodium diisooctyl sulfosuccinate in a ratio of 1:0.5 to obtain nonionic and anionic emulsifiers. The amount of nonionic and anionic emulsifiers is 5% of the boron modified rosin, and the emulsified solid content of rosin is 50%. Turn on the agitator of the emulsifier and slowly drip the compounded nonionic and anionic emulsifiers. After dripping the emulsifier, slowly drip 90°C hot water, high shear for 30 minutes, and discharge after cooling.

[0059] Example 3

[0060] (1) Mix 2.5 mol of diethanolamine with 1 mol of stearic acid, heat to 160°C in the presence of 3% NaOH as a catalyst, and react for 6 hours. Then add 1 mol of the reaction product, 5 mol of boric acid, and 1.2 mol of isopropanol into a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water carrier, and continue the reaction for 12 hours. The reaction is terminated when the water separator no longer separates the by-product water. Remove the water carrier and unreacted products by vacuum distillation.

[0061] The reaction path is:

[0062] .

[0063] (2) Add 2 mol of fortified rosin and 1 mol of isopropanol to a three-necked flask with a water separator equipped with a stirrer and a condenser, add 50 mL of toluene as a water-carrying agent, add a small amount of 0.3% KOH as a catalyst, and react for 5 hours. When the water separator no longer separates the by-product water, the reaction is over. Remove the water-carrying agent and unreacted products by vacuum distillation.

[0064] The reaction path is:

[0065] .

[0066] (3) The above two substances were mixed at a molar ratio of 1:1.5, heated to 120°C, and reacted for 4 hours to perform an ester exchange reaction. The generated product was removed by vacuum distillation to obtain the final boron-modified rosin product.

[0067] The reaction path is:

[0068] .

[0069] (4) Melt the boron modified rosin at 150°C; use nonionic emulsifier OP-10, sodium dioctyl sulfosuccinate and sodium lauryl polyoxyethylene (3) ether succinate monoester sulfonate to compound in a ratio of 1:0.5:1 to obtain nonionic and anionic emulsifiers. The amount of nonionic and anionic emulsifiers is 10% of the boron modified rosin, and the emulsified solid content of rosin is 50%. Turn on the agitator of the emulsifier kettle and slowly add the compounded nonionic and anionic emulsifiers. After the emulsifier is added, slowly add 90°C hot water, high shear for 20 minutes, and discharge after cooling.

[0070] Comparative Example 1

[0071] After 100g of fortified rosin is melted, start the high shear head, set the speed to 10,000 rpm, and then slowly drip 5g of emulsifier. After 10 minutes, gradually increase the dripping speed, and the viscosity begins to gradually increase. After the emulsifier is added, keep warm for 5 minutes, and then slowly drip 105g of hot water preheated to 90℃. Continue stirring under high shear conditions for 15 minutes, and then cool and discharge.

[0072] Test Example 1

[0073] The rosin emulsions prepared in Examples 1-3 and Comparative Example 1 were subjected to performance characterization tests, specifically including:

[0074] 1. Emulsification efficiency test: Use a spectrophotometer to measure the transmittance of the emulsion. Low transmittance indicates good emulsification effect.

[0075] 2. Particle size distribution measurement: Use a laser particle size analyzer to measure the particle size distribution of the emulsion to ensure that the particle size distribution of the emulsion is uniform.

[0076] 3. Stability test: Place the emulsion at 40℃ and 4℃ for 7 days respectively to observe whether stratification occurs. Samples with high stability will not show obvious stratification.

[0077] 4. Surface tension test: Use a surface tension meter to measure the surface tension of the emulsion to evaluate the wetting properties of the emulsion.

[0078] The rosin emulsions prepared in Examples 1-3 and Comparative Example 1 were subjected to a water resistance test, and the test steps were as follows:

[0079] 1. Coating preparation: Each emulsion was evenly coated on a standard glass sheet with a thickness of about 100 microns. After natural drying for 48 hours, a water resistance test was performed.

[0080] 2. Water resistance test: Soak the coated glass in deionized water, take it out after 1 hour, 3 hours and 24 hours, and observe whether the coating has bubbling, falling off or color change.

[0081] 3. Water resistance evaluation: The coating integrity and appearance changes after immersion are scored, with 0 points indicating complete detachment and 5 points indicating no change. The higher the score, the better the water resistance.

[0082] The experimental data are shown in Table 1.

[0083] Table 1

[0084] Example 1 Example 2 Example 3 Comparative Example 1 Emulsification efficiency (transmittance%) 12 10 8 25 Average particle size (nm) 150 140 130 220 Particle size distribution range (nm) 120-200 100-180 90-160 180-280 Stability (40℃ / 4℃, 7 days) No stratification No stratification No stratification Obvious stratification Surface tension (mN / m) 28.5 26.8 25.5 32.4 Water resistance (1h / 3h / 24h rating, full score 5 points) 4 / 4 / 3 4 / 4 / 4 5 / 5 / 5 2 / 1 / 0

[0085] According to the experimental data in Table 1, the following conclusions can be drawn:

[0086] Emulsification efficiency: The emulsification efficiency of Examples 1, 2, and 3 is significantly better than that of Comparative Example 1, among which Example 3 has the highest emulsification efficiency, and the transmittance reaches 8%, indicating that its emulsification effect is the best. The emulsification efficiency of Comparative Example 1 is the lowest, and the transmittance is 25%, indicating that its emulsification effect is poor.

[0087] Particle size distribution: The average particle size of Examples 1, 2, and 3 is smaller than that of Comparative Example 1, and the particle size distribution range is narrower, indicating that the particle size distribution of the emulsion in the examples is more uniform. Among them, the average particle size of Example 3 is the smallest, which is 130 nm, and the particle size distribution range is 90-160 nm, showing better particle size control.

[0088] Stability: The emulsions of Examples 1, 2, and 3 showed no stratification after being placed at 40°C and 4°C for 7 days, showing good stability. However, the emulsion of Comparative Example 1 showed obvious stratification under the same conditions, indicating that its stability was poor.

[0089] Surface tension: The surface tensions of Examples 1, 2, and 3 are all lower than those of Comparative Example 1, among which Example 3 has the lowest surface tension of 25.5 mN / m, indicating that it has the best wetting performance. Comparative Example 1 has the highest surface tension of 32.4 mN / m, and its wetting performance is relatively poor.

[0090] Water resistance: The boron modified rosin emulsions prepared in Examples 1-3 performed well in terms of water resistance, especially Example 3, which was able to maintain the integrity of the coating film during long-term immersion, showing excellent water resistance. However, Comparative Example 1 performed poorly in terms of water resistance, and the coating film was significantly damaged in a short period of time, further proving that its emulsification effect and stability were insufficient.

[0091] In summary, the beneficial effects of the present invention are mainly reflected in the following aspects:

[0092] 1. Excellent emulsification effect: The present invention prepares a boron-modified rosin emulsion by precisely adjusting the ratio and reaction conditions of diethanolamine, stearic acid, boric acid and fortified rosin. Compared with comparative example 1, examples 1-3 of the present invention show lower transmittance, indicating that the emulsification effect is better and the generated emulsion is more stable and uniform.

[0093] 2. Uniform particle size distribution: The particle size of the emulsion of the present invention is small and uniformly distributed, especially Example 3 has the smallest average particle size and a narrow particle size distribution range, which helps to improve the physical stability and application performance of the emulsion.

[0094] 3. Good stability: By optimizing the selection and ratio of emulsifiers, the prepared emulsion showed no stratification phenomenon when placed under different temperature conditions (40°C and 4°C) for 7 days, indicating that the emulsion has good storage stability and is suitable for long-term storage and use.

[0095] 4. Low surface tension: The surface tension of the emulsion of the present invention is low, especially in Example 3, indicating that it has better wettability and spreadability, so that the emulsion can better cover and adhere to various substrate surfaces in practical applications, thereby improving its application effect.

[0096] 5. Excellent water resistance: The boron-modified rosin emulsion of the present invention exhibits significant water resistance, especially Example 3 can still maintain the integrity of the coating after long-term water immersion, avoiding bubbling, shedding and other phenomena, showing excellent hydrolysis resistance and weather resistance.

[0097] 6. Adjustable formula and process flexibility: By adjusting the raw material ratio, reaction temperature, reaction time, and the type and amount of emulsifier, the present invention can produce an emulsion with controllable performance to meet the needs of different fields and has wide applicability.

[0098] In summary, the boron-modified rosin emulsion prepared by the present invention by optimizing the reaction conditions and formula combination shows significantly better performance than the prior art in terms of emulsification effect, stability, water resistance and other aspects, and is suitable for being widely used in the fields of coatings, adhesives and the like.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing boron-modified rosin, characterized in that: include: Diethanolamine and stearic acid are mixed, heated to react under the action of NaOH as a catalyst, and then the reaction product is further reacted with boric acid, isopropanol and a water-carrying agent to obtain product I; The reinforced rosin, isopropyl alcohol and water-carrying agent are mixed, and KOH is added as a catalyst to react; after the reaction is completed, product II is obtained; Mixing product I and product II at a molar ratio of 1:1.0-1.5, heating and performing an ester exchange reaction to obtain the boron-modified rosin; The molar ratio of diethanolamine to stearic acid is 2.0-2.5:1; The molar ratio of the reaction product to boric acid and isopropanol is 1:3-5:0.5-1.2; The molar ratio of the fortified rosin to isopropyl alcohol is 1.5-2:

1.

2. A boron-modified rosin, characterized in that: The boron-modified rosin is prepared by the preparation method described in claim 1.

3. An application of the boron-modified rosin according to claim 2, characterized in that: The application includes at least one of the following: A1) Application of the boron modified rosin in the preparation of rosin emulsion; A2) Application of the boron modified rosin in the preparation of papermaking additives; A3) Application of the boron modified rosin in papermaking.

4. A method for preparing a rosin emulsion based on boron-modified rosin, characterized in that: include: After the boron modified rosin according to claim 2 is melted, an emulsifier and water are added to perform shear emulsification, and after cooling, the rosin emulsion based on the boron modified rosin is obtained.

5. The method for preparing a rosin emulsion based on boron-modified rosin according to claim 4, characterized in that: The emulsifier includes nonionic emulsifier and anionic emulsifier; The ratio of the nonionic emulsifier to the anionic emulsifier is 1:0.5-1.

5.

6. The method for preparing a rosin emulsion based on boron-modified rosin according to claim 5, characterized in that: The anionic emulsifier is sodium dioctyl sulfosuccinate and / or sodium lauryl polyoxyethylene (3) ether succinic acid monoester sulfonate.

7. A rosin emulsion based on boron-modified rosin, characterized in that: The rosin emulsion is prepared by the preparation method according to any one of claims 4 to 6.

8. An application of the rosin emulsion based on boron-modified rosin according to claim 7, characterized in that: The application includes at least one of the following: A1) Application of the rosin emulsion in the preparation of papermaking additives; A2) Application of the rosin emulsion in papermaking.

9. A papermaking additive, characterized in that: The papermaking additive comprises the rosin emulsion based on boron-modified rosin according to claim 7.