Preparation method and application of bio-based modified rosin resin

Abstract

The invention discloses a bio-based modified rosin resin preparation method, which comprises: placing rosin in a container, introducing carbon dioxide, heating and stirring until the rosin is molten, cooling, sequentially adding phenol and solvent oil, stirring, adding a catalyst, and heating to obtain a mixed material liquid; adding water into the mixed material liquid, stirring and washing, introducing carbon dioxide after washing, heating to evaporate out the solvent oil, heating the mixed material liquid to 200 DEG C, adding an antioxidant, pentaerythritol and octanol, stirring and mixing, heating to 260-280 DEG C, carrying out constant-temperature treatment, cooling to 200-220 DEG C, adding the antioxidant and nano-hydroxyapatite, stirring, cooling to 200-220 DEG C, adding the antioxidant and nano-hydroxyapatite, and carrying out uniform mixing, so as to obtain a finished product. And discharging, cooling, filtering and granulating to obtain the bio-based modified rosin resin. The rosin is used for replacing turpentine to produce the rosin modified phenolic resin, formaldehyde is not added in the production process, volatile organic compounds are not generated after the product is applied, and the rosin modified phenolic resin is environment-friendly and safe and can be applied to the field of automobile adhesives.

Description

Technical Field

[0001] The invention belongs to the technical field of modified rosin resins, and particularly relates to a preparation method and application of a bio-based modified rosin resin. Background Art

[0002] Automotive adhesives are an important auxiliary material required for automobile production. They play a special role in enhancing the structure, sealing and rust prevention, vibration reduction and noise reduction, heat insulation and noise reduction, and interior and exterior decoration of automobile products. For example, the explosion-proof film for automobiles is composed of multiple layers of materials, and the layers are bonded by adhesives. It can not only effectively block ultraviolet rays, but also has a good heat insulation rate, which can effectively reduce the use of automobile air conditioners. In accidental traffic accidents, the explosion-proof film pasted on the car body glass can absorb the impact force generated during the collision, minimize the possibility of the car glass breaking and splashing, and minimize the harm to the occupants caused by accidents. In recent years, my country's automobile industry, especially various types of passenger cars represented by sedans, has developed rapidly. High-quality automobiles have put forward higher requirements for adhesive product indicators. Green environmental protection, high performance and multi-function are the development direction of such products.

[0003] Terpene phenol resin is a phenol-modified product of terpene resin synthesized from turpentine oil. It is widely used in adhesives and other fields. Since turpentine oil is expensive, far exceeding the price of rosin, rosin-modified phenolic resin that replaces turpentine oil has appeared on the market to reduce production costs. However, formaldehyde needs to be added in the production process. The use of formaldehyde is not environmentally friendly and also brings safety risks to production. Summary of the invention

[0004] In view of the above shortcomings, the present invention discloses a method for preparing a bio-based modified rosin resin, in which rosin is used instead of turpentine to produce rosin-modified phenolic resin, no formaldehyde is added during the production process, and no volatile organic matter is generated after the product is used. The product is environmentally friendly and safe, and can be applied to the field of automotive adhesives.

[0005] The present invention is achieved by adopting the following technical solutions: A method for preparing a bio-based modified rosin resin comprises the following steps: (1) Weigh the raw material components according to the following weight proportions: 80-100 parts of rosin, 15-20 parts of phenol, 0.3-0.5 parts of antioxidant, 1-5 parts of octanol, 0.2-0.5 parts of catalyst, 5-10 parts of pentaerythritol, and 10-20 parts of nano-hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 180-220°C and stir until the rosin is completely melted, then cool to 120-150°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 140-145°C and keep the temperature constant for 5-6 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring, wherein the temperature of the mixed liquid is controlled within the range of 75 to 85° C., stirring for 20 min, stopping stirring and stopping the introduction of carbon dioxide, and draining the mixture after standing for 15 to 60 min. When yellow resin liquid begins to be discharged, stopping draining; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. and maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 10 to 15 minutes, and then heated to 260 to 280° C. for constant temperature treatment. When the acid value of the mixed liquid is less than 30, vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the temperature is lowered to 200 to 220° C., and then an antioxidant and nano-hydroxyapatite are added and stirred for 30 to 45 minutes. Then, the material is discharged, cooled, filtered, and granulated to obtain a bio-based modified rosin resin.

[0006] Furthermore, the catalyst is obtained by mixing zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of zinc oxide, cobalt acetate and sodium thiosulfate is 1: (0.3-0.5): (0.5-2); the antioxidant is any one or more combinations of aromatic amine antioxidants, hindered phenol antioxidants and auxiliary antioxidants.

[0007] Furthermore, the preparation method of the nano hydroxyapatite is to weigh the raw material components according to the following weight proportions: 30-40 parts of hydroxyapatite, 5-10 parts of acrylic acid, 10-15 parts of starch, 1-3 parts of p-toluenesulfonic acid, 0.1-0.5 parts of hydroquinone, and 0.5-1 parts of sodium stearate; acrylic acid, p-toluenesulfonic acid and hydroquinone are sequentially added to deionized water and mixed evenly under stirring conditions to obtain a mixed solution A, and then starch and hydroxyapatite are added to the mixed solution A, and then the mixed solution is treated under ultrasonic conditions for 15-20 minutes, and then sodium stearate is added and heated to 60-70°C and then reacted at a constant temperature for 2-4 hours, and then filtered to obtain a precipitate, and then the precipitate is dried to obtain nano hydroxyapatite.

[0008] Furthermore, in step (2), the stirring speed is 100 to 300 r / min.

[0009] Furthermore, in step (3), water is repeatedly added to the mixed liquid for washing, and the number of washing times is 2 to 3 times.

[0010] Furthermore, in step (4), the temperature is raised to 245° C. at a rate of 3 to 5° C. / min.

[0011] Furthermore, in step (5), the temperature is raised to 260-280° C. at a rate of 0.5-1° C. / min. The heating rate is controlled to avoid heating too fast so that the mixed material can react fully and smoothly, which is conducive to obtaining high-quality bio-based modified rosin resin products.

[0012] Compared with the prior art, this technical solution has the following beneficial effects: 1. In the current production process, most of the phenol and formaldehyde react, and the obtained phenolic resin is then condensed with rosin to obtain rosin terpene phenol resin. A large amount of formaldehyde is added during the reaction process, making it difficult to meet the subsequent environmental protection standards. The present invention adds an effective catalyst and strictly controls the temperature of the reaction to make rosin and phenol react directly, thereby avoiding the addition of formaldehyde. At the same time, the present invention adds modified nano-hydroxyapatite to the formula of bio-based modified rosin resin, improves the bonding performance, thermal stability and chemical stability of the bio-based modified rosin resin, so that the obtained bio-based modified rosin resin can be used to produce adhesives used in automotive explosion-proof films, so that automotive explosion-proof films can effectively prevent ultraviolet radiation and improve the safety performance of automotive glass.

[0013] 2. In the present invention, under the action of initiators p-toluenesulfonic acid and hydroquinone, starch is cross-linked and grafted onto the surface of hydroxyapatite through acrylic acid to modify the ultrafine hydroxyapatite. The modified ultrafine hydroxyapatite has better compatibility with polymer materials, can be evenly mixed with polymer resin materials, and has high dispersibility, thereby improving the bonding performance and thermal stability of the bio-based modified rosin resin. DETAILED DESCRIPTION

[0014] The present invention is further described by the following examples, but is not intended to be limiting of the present invention. Specific experimental conditions and methods not specified in the following examples are conventional methods known to those skilled in the art.

[0015] Embodiment 1: A method for preparing a bio-based modified rosin resin, comprising the following steps: (1) Weigh the following raw material components in parts by weight: 100 parts of rosin, 17 parts of phenol, 0.3 parts of antioxidant, 2 parts of octanol, 0.4 parts of catalyst, 9 parts of pentaerythritol, and 15 parts of nano-hydroxyapatite; the catalyst is a mixture of zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of zinc oxide, cobalt acetate and sodium thiosulfate is 1:0.4:1; the antioxidant is a hindered phenol antioxidant; the preparation method of the nano-hydroxyapatite is to weigh the following raw material components in parts by weight: hydroxyapatite 35 parts of limestone, 8 parts of acrylic acid, 12 parts of starch, 2 parts of p-toluenesulfonic acid, 0.3 parts of hydroquinone, and 0.6 parts of sodium stearate; acrylic acid, p-toluenesulfonic acid and hydroquinone are sequentially added to deionized water and mixed evenly under stirring to obtain a mixed solution A, and then starch and hydroxyapatite are added to the mixed solution A, and then the mixed solution is treated under ultrasonic conditions for 16 minutes, and then sodium stearate is added and heated to 65°C and then reacted at a constant temperature for 3 hours, and then filtered to obtain a precipitate, and then the precipitate is dried to obtain nano hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 200°C and stir at a speed of 200 r / min until the rosin is completely melted, then cool to 130°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 142°C and keep the temperature constant for 5.5 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring the mixture. During the stirring process, the temperature of the mixed liquid is controlled within 80° C. After stirring for 20 minutes, the stirring is stopped and the introduction of carbon dioxide is stopped. After standing for 30 minutes, the mixture is drained. When yellow resin liquid begins to be discharged, the drainage is stopped. Repeatedly adding water to the mixed liquid for washing, and the number of washing times is 3 times; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. at a rate of 3.5° C. / min and then maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 12 minutes, and then the mixture is heated to 270° C. at a rate of 0.6° C. / min and kept at a constant temperature. When the acid value of the mixed liquid is less than 30, a vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the mixture is cooled to 210° C., and an antioxidant and nano-hydroxyapatite are added and stirred for 40 minutes. Then, the mixture is cooled, filtered and granulated to obtain a bio-based modified rosin resin.

[0016] Embodiment 2: A method for preparing a bio-based modified rosin resin, comprising the following steps: (1) Weigh the following raw material components in parts by weight: 80 parts of rosin, 15 parts of phenol, 0.3 parts of antioxidant, 1 part of octanol, 0.2 parts of catalyst, 8 parts of pentaerythritol, and 10 parts of nano-hydroxyapatite; the catalyst is a mixture of zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of zinc oxide, cobalt acetate and sodium thiosulfate is 1:0.3:0.5; the antioxidant is an aromatic amine antioxidant; the preparation method of the nano-hydroxyapatite is to weigh the following raw material components in parts by weight: hydroxyapatite 30 parts of limestone, 5 parts of acrylic acid, 10 parts of starch, 1 part of p-toluenesulfonic acid, 0.1 part of hydroquinone, and 0.5 parts of sodium stearate; acrylic acid, p-toluenesulfonic acid and hydroquinone are sequentially added to deionized water and mixed evenly under stirring to obtain a mixed solution A, and then starch and hydroxyapatite are added to the mixed solution A, and then the mixed solution is treated under ultrasonic conditions for 15 minutes, and then sodium stearate is added and heated to 70°C and then reacted at a constant temperature for 2 hours, and then filtered to obtain a precipitate, and then the precipitate is dried to obtain nano hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 180°C and stir at a speed of 100 r / min until the rosin is completely melted, then cool to 120°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 140°C and keep the temperature constant for 6 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring, wherein the temperature of the mixed liquid is controlled within 75° C. during the stirring process, stirring is stopped after 20 minutes and the introduction of carbon dioxide is stopped, and the mixture is allowed to stand for 15 minutes and then drained. When yellow resin liquid begins to be discharged, the drainage is stopped; repeatedly adding water to the mixed liquid for washing, and the number of washing times is 2 times; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. at a rate of 3° C. / min and then maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 10 minutes, and then the mixture is heated to 260° C. at a rate of 0.5° C. / min and kept at a constant temperature. When the acid value of the mixed liquid is less than 30, a vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the mixture is cooled to 200° C., and then an antioxidant and nano-hydroxyapatite are added and stirred for 30 minutes. Then, the mixture is cooled, filtered, and granulated to obtain a bio-based modified rosin resin.

[0017] Embodiment 3: A method for preparing a bio-based modified rosin resin, comprising the following steps: (1) Weigh the following raw material components in parts by weight: 90 parts of rosin, 18 parts of phenol, 0.4 parts of antioxidant, 2 parts of octanol, 0.4 parts of catalyst, 9 parts of pentaerythritol, and 15 parts of nano-hydroxyapatite; the catalyst is a mixture of zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of zinc oxide, cobalt acetate and sodium thiosulfate is 1:0.4:1.2; the antioxidant is an auxiliary antioxidant; the preparation method of the nano-hydroxyapatite is to weigh the following raw material components in parts by weight: hydroxyapatite 35 parts of limestone, 8 parts of acrylic acid, 14 parts of starch, 2 parts of p-toluenesulfonic acid, 0.4 parts of hydroquinone, and 0.8 parts of sodium stearate; acrylic acid, p-toluenesulfonic acid and hydroquinone are sequentially added to deionized water and mixed evenly under stirring to obtain a mixed solution A, and then starch and hydroxyapatite are added to the mixed solution A, and then the mixed solution is treated under ultrasonic conditions for 18 minutes, and then sodium stearate is added and heated to 68°C and then reacted at a constant temperature for 3 hours, and then filtered to obtain a precipitate, and then the precipitate is dried to obtain nano hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 210°C and stir at a speed of 200 r / min until the rosin is completely melted, then cool to 140°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 144°C and keep the temperature constant for 5.5 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring the mixture. During the stirring process, the temperature of the mixed liquid is controlled within 82° C. After stirring for 20 minutes, the stirring is stopped and the introduction of carbon dioxide is stopped. After standing for 45 minutes, the mixture is drained. When yellow resin liquid begins to be discharged, the drainage is stopped. Repeatedly adding water to the mixed liquid for washing, and the number of washing times is 3 times; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. at a rate of 4° C. / min and then maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 12 minutes, and then the mixture is heated to 270° C. at a rate of 0.8° C. / min and kept at a constant temperature. When the acid value of the mixed liquid is less than 30, a vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the mixture is cooled to 210° C., and an antioxidant and nano-hydroxyapatite are added and stirred for 40 minutes. Then, the mixture is cooled, filtered and granulated to obtain a bio-based modified rosin resin.

[0018] Embodiment 4: A method for preparing a bio-based modified rosin resin, comprising the following steps: (1) Weigh the raw material components according to the following weight parts: 100 parts of rosin, 20 parts of phenol, 0.5 parts of antioxidant, 4 parts of octanol, 0.5 parts of catalyst, 10 parts of pentaerythritol, and 20 parts of nano-hydroxyapatite; the catalyst is a mixture of zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of zinc oxide, cobalt acetate and sodium thiosulfate is 1:0.5:2; the antioxidant is an aromatic amine antioxidant; the preparation method of the nano-hydroxyapatite is to weigh the raw material components according to the following weight parts: hydroxy 40 parts of apatite, 10 parts of acrylic acid, 15 parts of starch, 3 parts of p-toluenesulfonic acid, 0.5 parts of hydroquinone, and 1 part of sodium stearate; acrylic acid, p-toluenesulfonic acid and hydroquinone are sequentially added to deionized water and mixed evenly under stirring to obtain a mixed solution A, and then starch and hydroxyapatite are added to the mixed solution A, and then the mixed solution is treated under ultrasonic conditions for 18 minutes, and then sodium stearate is added and heated to 70°C and then reacted at a constant temperature for 3 hours, and then filtered to obtain a precipitate, and then the precipitate is dried to obtain nano hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 220°C and stir at 300 r / min until the rosin is completely melted, then cool to 150°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 145°C and keep the temperature constant for 5 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring the mixture. During the stirring process, the temperature of the mixed liquid is controlled within 85° C. After stirring for 20 minutes, the stirring is stopped and the introduction of carbon dioxide is stopped. After standing for 60 minutes, the mixture is drained. When yellow resin liquid begins to be discharged, the drainage is stopped. Repeatedly adding water to the mixed liquid for washing, and the number of washing times is 2 times; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. at a rate of 5° C. / min and then maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 15 minutes, and then the mixture is heated to 280° C. at a rate of 1° C. / min and kept at a constant temperature. When the acid value of the mixed liquid is less than 30, a vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the mixture is cooled to 220° C., and an antioxidant and nano-hydroxyapatite are added and stirred for 45 minutes. The mixture is then discharged, cooled, filtered, and granulated to obtain a bio-based modified rosin resin.

[0019] Comparative Example 1: The preparation method of the bio-based modified rosin resin described in this comparative example is different from the method described in Example 1 only in that nano-hydroxyapatite is not added.

[0020] Comparative Example 2: The preparation method of the bio-based modified rosin resin described in this comparative example is different from the method described in Example 1 only in that, instead of using acrylic acid, starch, p-toluenesulfonic acid, hydroquinone, sodium stearate and hydroxyapatite to mix for modification, hydroxyapatite is directly added to the formula of the bio-based modified rosin resin.

[0021] Comparative Example 3: The preparation method of the bio-based modified rosin resin described in this comparative example is different from the method described in Example 1 only in that the raw material components are weighed according to the following weight portions: 100 parts of rosin, 10 parts of phenol, 0.3 parts of antioxidant, 2 parts of octanol, 0.4 parts of catalyst, 9 parts of pentaerythritol, and 15 parts of nano-hydroxyapatite.

[0022] Comparative Example 4: The preparation method of the bio-based modified rosin resin described in this comparative example is different from the method described in Example 1 only in that the raw material components are weighed according to the following weight portions: 100 parts of rosin, 25 parts of phenol, 0.3 parts of antioxidant, 2 parts of octanol, 0.4 parts of catalyst, 9 parts of pentaerythritol, and 15 parts of nano-hydroxyapatite.

[0023] Experimental Example 1: Bio-based modified rosin resins were prepared according to the methods described in Examples 1 to 4 and Comparative Examples 1 to 4, and then their performance tests were performed, including color test (iron-cobalt method), softening point test (ring and ball method), acid value test, and viscosity test. The specific results are shown in Table 1.

[0024] Table 1 Performance test results of bio-based modified rosin resin prepared by different methods

[0025] It can be seen from the data in Table 1 that the bio-based modified rosin resin prepared according to the method of the present invention has good performance.

[0026] Experimental Example 2: Bio-based modified rosin resin was prepared according to the method described in Example 1, wherein the amount of antioxidant added was 0, 0.1, 0.2, 0.3, and 0.4 parts. Color detection was performed according to the method described in Experimental Example 1. The specific results are shown in Table 2.

[0027] Table 2 Test results of bio-based modified rosin resin obtained with different antioxidant addition amounts

[0028] It can be seen from the data in Table 2 that the bio-based modified rosin resin prepared by adding an antioxidant according to the method of the present invention has better color.

[0029] Experimental Example 3: Bio-based modified rosin resin was prepared according to the method described in Example 1, wherein different ratios of octanol and pentaerythritol were used. The acid value was tested according to the method described in Experimental Example 1. The specific results are shown in Table 3.

[0030] Table 3 Test results of bio-based modified rosin resin obtained by using different ratios of octanol and pentaerythritol

[0031] It can be seen from the data in Table 3 that the acid value of the bio-based modified rosin resin prepared according to the method of the present invention is smaller.

[0032] Experimental Example 4: A bio-based modified rosin resin was prepared according to the method described in Example 1. In step (4), an antioxidant, pentaerythritol and octanol were added and stirred for 12 minutes. The mixture was then heated to 250°C, 260°C, 270°C, 280°C and 290°C at a rate of 0.6°C / min and treated at a constant temperature. The color and acid value were tested according to the method described in Experimental Example 1. The specific results are shown in Table 4.

[0033] Table 4 Test results of bio-based modified rosin resin obtained by different temperature treatment steps

[0034] It can be seen from the data in Table 4 that the bio-based modified rosin resin prepared according to the method of the present invention has a smaller acid value and better color.

[0035] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing a bio-based modified rosin resin, characterized in that: The following steps are involved: (1) Weigh the raw material components according to the following weight proportions: 80-100 parts of rosin, 15-20 parts of phenol, 0.3-0.5 parts of antioxidant, 1-5 parts of octanol, 0.2-0.5 parts of catalyst, 5-10 parts of pentaerythritol, and 10-20 parts of nano-hydroxyapatite; (2) Place rosin in a container, then introduce carbon dioxide and heat to 180-220°C and stir until the rosin is completely melted, then cool to 120-150°C and keep the temperature constant, add phenol and solvent oil in sequence and stir for 15 minutes, then add a catalyst and heat to 140-145°C and keep the temperature constant for 5-6 hours, then add solvent oil and sodium hydroxide solution and stir for 20 minutes to obtain a mixed liquid; (3) adding water to the mixed liquid obtained in step (2) and stirring, wherein the temperature of the mixed liquid is controlled within the range of 75 to 85° C., stirring for 20 min, stopping stirring and stopping the introduction of carbon dioxide, and draining the mixture after standing for 15 to 60 min. When yellow resin liquid begins to be discharged, stopping draining; (4) introducing carbon dioxide into the mixed liquid treated in step (3) and heating to evaporate the solvent oil, heating to 245° C. and maintaining the temperature for 10 min to completely evaporate the solvent oil; (5) The mixed liquid treated in step (4) is heated to 200° C., and then an antioxidant, pentaerythritol and octanol are added and stirred for 10 to 15 minutes, and then heated to 260 to 280° C. for constant temperature treatment. When the acid value of the mixed liquid is less than 30, vacuum treatment is performed for 3 hours, and then carbon dioxide is introduced to break the vacuum. Then, the temperature is lowered to 200 to 220° C., and then an antioxidant and nano-hydroxyapatite are added and stirred for 30 to 45 minutes. Then, the material is discharged, cooled, filtered, and granulated to obtain a bio-based modified rosin resin.

2. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: The catalyst is obtained by mixing zinc oxide, cobalt acetate and sodium thiosulfate, and the mass ratio of the zinc oxide, cobalt acetate and sodium thiosulfate is 1: (0.3-0.5): (0.5-2); the antioxidant is any one or more combinations of aromatic amine antioxidants, hindered phenol antioxidants and auxiliary antioxidants.

3. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: The preparation method of the nano hydroxyapatite comprises the following steps: weighing raw material components according to the following weight proportions: 30-40 parts of hydroxyapatite, 5-10 parts of acrylic acid, 10-15 parts of starch, 1-3 parts of p-toluenesulfonic acid, 0.1-0.5 parts of hydroquinone, and 0.5-1 parts of sodium stearate; sequentially adding acrylic acid, p-toluenesulfonic acid and hydroquinone into deionized water and mixing them evenly under stirring conditions to obtain a mixed solution A; then adding starch and hydroxyapatite into the mixed solution A; then treating the mixed solution under ultrasonic conditions for 15-20 minutes; then adding sodium stearate and heating the mixed solution to 60-70°C and reacting the mixed solution at a constant temperature for 2-4 hours; then filtering the mixed solution to obtain a precipitate; and then drying the precipitate to obtain the nano hydroxyapatite.

4. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: In step (2), the stirring speed is 100 to 300 r / min.

5. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: In step (3), water is repeatedly added to the mixed liquid for washing 2 to 3 times.

6. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: In step (4), the temperature is raised to 245°C at a rate of 3-5°C / min.

7. The method for preparing the bio-based modified rosin resin according to claim 1, characterized in that: In step (5), the temperature is raised to 260-280° C. at a rate of 0.5-1° C. / min.

Images