Zinc-free polymerized rosin and preparation method thereof

Abstract

The present application relates to the field of polymerized rosin, more specifically, it relates to a zinc-free polymerized rosin and a preparation method thereof. A zinc-free polymerized rosin comprises the following raw materials: masson rosin, inorganic acid, zinc chloride, solvent, oxaloacetic acid, and phosphotungstic acid; the inorganic acid is 0.6-1% of the mass of masson rosin, the zinc chloride is 2.5-4.5% of the mass of masson rosin, the solvent is 75-85% of the mass of masson rosin, the oxaloacetic acid is 0.04-0.08% of the mass of masson rosin, and the phosphotungstic acid is 0.04-0.08% of the mass of masson rosin. The zinc-free polymerized rosin provided in this application can not only maintain a high yield of the product, but also thoroughly remove zinc residues, which helps to break the foreign technology monopoly, enhance the overall competitiveness of the domestic ink industry, and contribute to the healthy development of the national economy.

Description

Technical Field

[0001] The present application relates to the field of polymerized rosin, and more specifically, to a zinc-free polymerized rosin and a preparation method thereof. Background Art

[0002] Polymerized rosin is an important chemical raw material, primarily composed of dimers. It is a mixture of rosin and other substances, including rosin hydrocarbons. This mixture does not crystallize, has a higher softening point than ordinary rosin, and exhibits more stable physical properties. The dimer content is approximately 20%-50%, making it highly stable and less susceptible to oxidation. Due to its unique chemical properties, polymerized rosin is widely used in the preparation of products such as adhesives and inks.

[0003] Currently, there are two main methods for producing polymerized rosin on the market: the sulfuric acid method and the zinc chloride / sulfuric acid method. While the sulfuric acid method avoids zinc residue during production, its polymerization yield is relatively low, typically ranging from 80% to 83%. This not only leads to low production efficiency but also increases production costs. Furthermore, the pure sulfuric acid method presents significant safety risks. In contrast, the zinc chloride / sulfuric acid method offers a higher polymerization yield, reaching 90%, significantly improving production efficiency. However, this method suffers from an inability to completely remove zinc, limiting the zinc content to 35-50 mg / g. This poses a significant limitation for applications with stringent zinc content requirements, such as ink manufacturing.

[0004] Domestic industry standards require polymerized rosin products used in inks to meet softening point requirements of 115-140°C, an acid value of approximately 150 mgKOH / g, and a zinc content not exceeding 32 mg / kg. However, due to zinc residue, polymerized rosin produced using existing technologies often suffers from insufficient antioxidant (aging) properties when used in high-end inks due to excessive zinc content. Over time, the acidic components and residual zinc in the ink are easily oxidized by moisture, causing printed text or colors to become blurred. This makes it impossible to meet the requirements of high-end printed products such as murals, which require long-term color retention and clarity.

[0005] Therefore, how to maintain a high product yield while completely removing zinc residues has become a technical problem that needs to be solved urgently. Summary of the Invention

[0006] In order to maintain a high product yield and completely remove zinc residues, the present application provides a zinc-free polymerized rosin and a preparation method thereof.

[0007] In a first aspect, the present application provides a zinc-free polymerized rosin, which adopts the following technical solution:

[0008] A zinc-free polymerized rosin, comprising the following raw materials: horsetail rosin, inorganic acid, zinc chloride, solvent, oxaloacetic acid, and phosphotungstic acid;

[0009] The inorganic acid accounts for 0.6-1% of the mass ...

[0010] Preferably, the inorganic acid is 0.8-1% of the mass of mass rosin, the zinc chloride is 3-3.5% of the mass of mass rosin, the solvent is 75-80% of the mass of mass rosin, the oxaloacetic acid is 0.06-0.08% of the mass of mass rosin, and the phosphotungstic acid is 0.04-0.06% of the mass of mass rosin.

[0011] The zinc in zinc chloride is a heavy metal and will form a complex in the reaction system. However, it is difficult to completely remove the trace amount of zinc during the water washing process. This is precisely the technical problem that the current zinc chloride sulfuric acid method cannot solve.

[0012] The entire preparation process of this application includes three steps: polymerization, water washing (washing the reaction liquid), and distillation. The purpose of the water washing step is to remove the acidity of the polymerization reaction liquid, that is, to maintain the pH under neutral conditions. After washing the reaction liquid, a clean polymerized rosin ester solution is obtained, and finally distillation is performed to obtain the product. However, paradoxically, under neutral water washing conditions, trace amounts of zinc will dissolve in the water, making it difficult to remove.

[0013] The present application effectively addresses the aforementioned technical challenges by combining oxaloacetic acid and phosphotungstic acid. After water washing, oxaloacetic acid and phosphotungstic acid are added to react with trace amounts of zinc to form a complex (a white precipitate that can be removed by filtration), thereby removing trace amounts of zinc. Finally, water washing is performed to remove unreacted oxaloacetic acid and phosphotungstic acid. The use of oxaloacetic acid and phosphotungstic acid removes zinc without affecting the quality and yield of polymerized rosin.

[0014] Furthermore, the zinc-free polymerized rosin provided herein is specifically designed for use in inks. Even if the oxaloacetic acid and phosphotungstic acid are not completely removed, the ink quality will not be affected. The small amount of oxaloacetic acid and phosphotungstic acid in the zinc-free polymerized rosin can improve the dispersibility of the ink system, allowing pigments and fillers to be more evenly dispersed, thereby effectively enhancing the printing quality and color saturation of the ink.

[0015] Preferably, the mass ratio of oxaloacetic acid to phosphotungstic acid is (0.8-1.2): (0.8-1.2).

[0016] By adopting this technical solution, the mass ratio of oxaloacetic acid to phosphotungstic acid is further limited, allowing oxaloacetic acid and phosphotungstic acid to more fully coordinate with zinc ions, forming a stable complex. Furthermore, oxaloacetic acid and phosphotungstic acid compete with zinc ions, forming a more complex acid-base equilibrium system, thereby accelerating the removal of zinc ions.

[0017] Preferably, the inorganic acid is concentrated sulfuric acid.

[0018] Preferably, the solvent is at least a mixture of one or more of toluene, xylene, gasoline, and naphtha.

[0019] Preferably, the zinc chloride is anhydrous zinc chloride.

[0020] In a second aspect, the present application provides a method for preparing zinc-free polymerized rosin, which adopts the following technical solution:

[0021] A method for preparing zinc-free polymerized rosin comprises the following steps:

[0022] Step 1: Mix the solvent and horsetail rosin and heat at 50-60℃ until completely dissolved;

[0023] Step 2: Add inorganic acid dropwise to the material of step 1 for isomerization, and the isomerization time is 1-2 hours;

[0024] Step 3: Add zinc chloride to the material in step 2 and polymerize at 105-115°C for 4-6 hours;

[0025] Step 4: Wash the supernatant from step 3 with water;

[0026] Step 5: Add oxaloacetic acid and phosphotungstic acid to the material washed in step 4, mix well, and continue washing;

[0027] Step 6: Distill the organic phase obtained from the water washing in step 5 to remove the solvent at 235-245° C., maintain a vacuum degree of -0.085 to -0.099 MPa, and steam with active gas for 20-40 minutes to obtain zinc-free polymerized rosin.

[0028] By adopting the above technical solution, during the water washing process, an appropriate amount of oxaloacetic acid and phosphotungstic acid are introduced, which chemically react with the trace zinc remaining in the system to form an easily separable zinc complex, thereby achieving efficient removal of trace zinc.

[0029] The synergistic use of oxaloacetic acid and phosphotungstic acid not only effectively removes zinc, but also has a good promoting effect on the quality and yield of polymerized rosin, and also provides new ideas and methods for technological progress in ink manufacturing and related fields.

[0030] Preferably, before mixing the solvent and the masson rosin in step 1, the masson rosin is crushed into pieces of 1-3 cm in size.

[0031] By adopting the above technical solution, the horsetail rosin is broken into small sizes, so that it can be quickly and fully dissolved in the solvent, which is convenient for subsequent reactions.

[0032] In summary, this application has the following beneficial effects:

[0033] 1. Traditional inks may contain trace amounts of zinc. These zinc ions can trigger chemical reactions under certain conditions, causing ink color changes or blurring of printed surfaces. The zinc-free polymerized rosin provided in this application achieves zero zinc residue, a breakthrough that effectively resolves the discoloration and blurring issues that commonly occur when inks are applied to products.

[0034] 2. This application not only solves the problem of a product without zinc residue, but also maintains a high yield, which brings significant economic value to manufacturers. Conventional zinc chloride sulfuric acid method products have a zinc content of up to 32 mg / g, while the product of the present invention is completely zinc-free. This means that while maintaining product quality, manufacturers can significantly reduce the waste and cost increase caused by zinc residue.

[0035] 3. This application can not only maintain a high product yield but also completely remove zinc residues. The solution to this technical problem is not only a major breakthrough in the industry, but also in line with one of the key directions supported by the state. At present, the demand for high-quality polymerized rosin in domestic applications such as high-end inks is growing, and traditional production methods often find it difficult to meet these requirements. The technical solution of this application effectively fills the gap in this field in China and provides strong support for the realization of domestic substitution. This will help break the foreign technology monopoly, enhance the overall competitiveness of the domestic ink industry, and contribute to the healthy development of the national economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a sample diagram for detecting the zinc content of the zinc-free polymerized rosin in Example 1 of the present application.

[0037] Figure 2 This is a graph showing the zinc content test results of the zinc-free polymerized rosin of Example 1 of the present application.

[0038] Figure 3 This is a sample diagram of the zinc content detection of the polymerized rosin in Comparative Example 1 of the present application.

[0039] Figure 4 This is a graph showing the zinc content test results of the polymerized rosin of Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0040] The present application is further described in detail below with reference to the accompanying drawings and examples.

[0041] The raw materials used in the following examples and comparative examples are all commercially available products.

[0042] Example

[0043] Example 1

[0044] A zinc-free polymerized rosin comprises the following raw materials: horsetail rosin, inorganic acid, zinc chloride, solvent, oxaloacetic acid and phosphotungstic acid.

[0045] The inorganic acid is 98% concentrated sulfuric acid, the zinc chloride is anhydrous zinc chloride, and the solvent is 200# gasoline.

[0046] The specific amount of each raw material is shown in Table 1.

[0047] The present application also provides a method for preparing zinc-free polymerized rosin, comprising the following steps:

[0048] Step 1: Crush the horsetail rosin into 1-3cm pieces (for easier dissolution).

[0049] Step 2: Pour the crushed horsetail rosin prepared in step 1 into the solvent quickly, stir and dissolve, and heat to 55°C for 1 hour to observe whether it is completely dissolved.

[0050] Step 3: Slowly drip concentrated sulfuric acid into the completely dissolved material in step 2 to carry out isomerization for 1.5 hours.

[0051] Step 4: Add anhydrous zinc chloride to the isomerized material from step 3 and heat to 110°C for polymerization for 5 hours. After 5 hours, observe whether the acid residue in the reaction flask is evenly distributed in the reaction flask.

[0052] Step 5: Pour the supernatant from step 4 into a water washing kettle for water washing. Add 80% of the total amount of hot water to the material, stir and wash for 15 minutes, let it stand for 20 minutes, and drain the lower aqueous phase. Repeat the water washing.

[0053] When washing for the third time, add oxaloacetic acid and phosphotungstic acid, mix well, and continue washing according to the above method.

[0054] Wash eight times in total.

[0055] Step 6: The organic phase washed in step 5 was distilled at 240° C. to remove the solvent, maintained at a vacuum degree of -0.096 MPa and steamed for 30 minutes, and then discharged.

[0056] The softening point of the product was determined to be 140°C, the acid value was 142 mgKOH / g, the product yield was 96.8%, and the residual zinc content was 0 mg / kg.

[0057] Specific test report reference Figure 1 、 2 .

[0058] Example 2

[0059] A zinc-free polymerized rosin, which is different from Example 1 in that the solvent is xylene.

[0060] The specific amount of each raw material is different, see Table 1 for details.

[0061] A method for preparing zinc-free polymerized rosin is different from Example 1 in that some parameters are different.

[0062] The specific steps include:

[0063] Step 1: Crush the horsetail rosin into 1-3cm pieces (for easier dissolution).

[0064] Step 2: Pour the crushed horsetail rosin prepared in step 1 into the solvent quickly, stir and dissolve it, and heat it to 50°C for 1.5 hours to observe whether it is completely dissolved.

[0065] Step 3: Slowly drip concentrated sulfuric acid into the completely dissolved material in step 2 to carry out isomerization for 1 hour.

[0066] Step 4: Add anhydrous zinc chloride to the isomerized material from step 3 and heat to 105°C for polymerization for 6 hours. After 6 hours, observe whether the acid residue in the reaction flask is evenly distributed in the reaction flask.

[0067] Step 5: Pour the supernatant from step 4 into a water washing kettle for water washing. Add 80% of the total amount of hot water to the material, stir and wash for 15 minutes, let it stand for 20 minutes, and drain the lower aqueous phase. Repeat the water washing.

[0068] When washing for the third time, add oxaloacetic acid and phosphotungstic acid, mix well, and continue washing according to the above method.

[0069] Wash eight times in total.

[0070] Step 6: The organic phase washed in step 5 was distilled at 235° C. to remove the solvent, maintaining a vacuum degree of -0.085 MPa and steam distillation for 40 minutes, and then the material was discharged.

[0071] The softening point of the product was determined to be 130°C, the acid value was 146 mgKOH / g, the product yield was 93.5%, and the residual zinc content was 0 mg / kg.

[0072] Example 3

[0073] A zinc-free polymerized rosin, which differs from Example 1 in that:

[0074] The solvent is toluene.

[0075] The specific amount of each raw material is different, see Table 1 for details.

[0076] A method for preparing zinc-free polymerized rosin is different from Example 1 in that some parameters are different.

[0077] The specific steps include:

[0078] Step 1: Crush the horsetail rosin into 1-3cm pieces (for easier dissolution).

[0079] Step 2: Pour the crushed horsetail rosin prepared in step 1 into the solvent quickly, stir and dissolve it, and heat it to 60°C for 1 hour to observe whether it is completely dissolved.

[0080] Step 3: Slowly drip concentrated sulfuric acid into the completely dissolved material in step 2 to carry out isomerization for 2 hours.

[0081] Step 4: Add anhydrous zinc chloride to the isomerized material from step 3 and heat to 115°C for polymerization for 4 hours. After 4 hours, observe whether the acid residue in the reaction flask is evenly distributed in the reaction flask.

[0082] Step 5: Pour the supernatant from step 4 into a water washing kettle for water washing. Add 80% of the total amount of hot water to the material, stir and wash for 15 minutes, let it stand for 20 minutes, and drain the lower aqueous phase. Repeat the water washing.

[0083] When washing for the third time, add oxaloacetic acid and phosphotungstic acid, mix well, and continue washing according to the above method.

[0084] Wash eight times in total.

[0085] Step 6: The organic phase washed in step 5 was distilled at 245° C. to remove the solvent, maintaining a vacuum degree of -0.099 MPa and steam distillation for 20 minutes, and then the material was discharged.

[0086] The softening point of the product was determined to be 132°C, the acid value was 145 mgKOH / g, the product yield was 93.8%, and the residual zinc content was 0 mg / kg.

[0087] Example 4

[0088] A zinc-free polymerized rosin is different from Example 1 in that the specific amounts of the raw materials are different, as shown in Table 1.

[0089] The softening point of the product was determined to be 138°C, the acid value was 141 mgKOH / g, the product yield was 96.4%, and the residual zinc content was 0 mg / kg.

[0090] Table 1

[0091] raw material Example 1 Example 2 Example 3 Example 4 Horsetail rosin (g) 300 300 300 300 Inorganic acid (g) 1.8 2.4 3 1.8 Zinc chloride (g) 10.5 7.5 13.5 9 Solvent (g) 240 225 255 240 Oxaloacetic acid (g) 0.18 0.24 0.18 0.12 Phosphotungstic acid (g) 0.18 0.15 0.12 0.24

[0092] Comparative Example

[0093] Comparative Example 1

[0094] A polymerized rosin, which is different from Example 1 in that oxaloacetic acid and phosphotungstic acid are omitted.

[0095] The product yield was determined to be 90.4% and the residual zinc content was 28 mg / kg.

[0096] Specific test report reference Figure 3 、 4 .

[0097] Comparative Example 2

[0098] A polymerized rosin, which is different from Example 1 in that oxaloacetic acid and phosphotungstic acid are replaced by oxalic acid.

[0099] The product yield was determined to be 91.1% and the residual zinc content was 10 mg / kg.

[0100] Comparative Example 3

[0101] A polymerized rosin, which is different from Example 1 in that oxaloacetic acid is replaced by phosphotungstic acid, that is, the amount of oxaloacetic acid is 0 g and the amount of phosphotungstic acid is 0.36 g.

[0102] The product yield was determined to be 92.6% and the residual zinc content was 5 mg / kg.

[0103] Comparative Example 4

[0104] A polymerized rosin, which is different from Example 1 in that oxaloacetic acid is replaced by phosphotungstic acid, that is, the amount of oxaloacetic acid is 0.36 g and the amount of phosphotungstic acid is 0.

[0105] The product yield was determined to be 92.3% and the residual zinc content was 6 mg / kg.

[0106] Performance testing

[0107] Sample preparation:

[0108] 30 parts of the polymerized rosin of Examples 1-4 and Comparative Examples 1-4, 100 parts of acrylate resin, 5 parts of aqueous wax emulsion (D-816), 1 part of propylene glycol butyl ether, 200 parts of water, 0.5 parts of aqueous dispersant, 5 parts of ethanol, and 0.5 parts of pigment red were placed in a disperser and stirred at 400 r / min to obtain a sample to be tested.

[0109] The above test samples were tested with reference to GB / T 13217.2-2024 "Test method for ink gloss" and the initial gloss was recorded in Table 2.

[0110] The tested printed sample was placed in an environment with a humidity of 95% and a temperature of 50°C for 7 days. During the placement period, it was also required to be exposed to ultraviolet light with an intensity of 42mW / cm 2 After irradiation for 2 hours under the conditions of 40°C and 80°C, the glossiness of the treated prints was tested again. The glossiness after treatment was recorded in Table 2.

[0111] Table 2

[0112]

[0113] Combining the performance measurements of the polymerized rosins of Examples 1-4 and Comparative Examples 1-4, it can be seen that the polymerized rosins of Examples 1-4 can all be zinc-free, while those of Comparative Examples 1-4 cannot be zinc-free and exhibit varying degrees of zinc residue.

[0114] According to the test data in Table 2, the initial glossiness of the zinc-free polymerized rosin of Examples 1-4 is higher than that of Comparative Examples 1-4, indicating that the inks prepared from the zinc-free polymerized rosin of Examples 1-4 have better gloss and quality.

[0115] After treatment, the glossiness of the zinc-free polymerized rosins of Examples 1-4 did not decrease or only decreased slightly compared to the initial glossiness. This indicates that since the polymerized rosin does not contain residual zinc, the problem of zinc affecting ink quality is avoided, thereby effectively enhancing the antioxidant properties of the ink.

[0116] In contrast, the polymerized rosins of Comparative Examples 1-4, while having initial gloss comparable to, and only slightly lower than, that of Examples 1-4, showed a significant decrease in gloss after treatment. This suggests that the polymerized rosins of Comparative Examples 1-4, when used in high-quality inks, are unable to impart good antioxidant properties. Over time, the printing quality of the inks deteriorates significantly, failing to meet the requirements of high-end printed products.

[0117] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A method for preparing zinc-free polymerized rosin, characterized in that: The following steps are involved: Step 1: Mix the solvent and horsetail rosin and heat at 50-60℃ until completely dissolved; Step 2: Add inorganic acid dropwise to the material of step 1 for isomerization, and the isomerization time is 1-2 hours; Step 3: Add zinc chloride to the material in step 2 and polymerize at 105-115°C for 4-6 hours; Step 4: Wash the supernatant from step 3 with water; Step 5: Add oxaloacetic acid and phosphotungstic acid to the material washed in step 4, mix well, and continue washing; Step 6: Distill the organic phase washed in step 5 at 235-245°C to remove the solvent, maintain a vacuum of -0.085~-0.099MPa, and steam with active gas for 20-40min to obtain zinc-free polymerized rosin. The inorganic acid accounts for 0.6-1% of the mass ...

2. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: The mass ratio of the oxaloacetic acid to the phosphotungstic acid is (0.8-1.2): (0.8-1.2).

3. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: The inorganic acid accounts for 0.8-1% of the mass of mass rosin, the zinc chloride accounts for 3-3.5% of the mass of mass rosin, the solvent accounts for 75-80% of the mass of mass rosin, the oxaloacetic acid accounts for 0.06-0.08% of the mass of mass rosin, and the phosphotungstic acid accounts for 0.04-0.06% of the mass of mass rosin.

4. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: The inorganic acid is concentrated sulfuric acid.

5. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: The solvent is at least a mixture of one or more of toluene, xylene, gasoline and naphtha.

6. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: The zinc chloride is anhydrous zinc chloride.

7. The method for preparing zinc-free polymerized rosin according to claim 1, wherein: In the step 1, before mixing the solvent and the masson rosin, the masson rosin is crushed into pieces of 1-3 cm.

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