A preparation method and application of rosin-modified phenolic resin
By simplifying the preparation process of rosin-modified phenolic resin, the reaction of rosin with alcohol and catalyst is used to generate derivatives, and the condensation reaction with formaldehyde and alkyl phenol is solved, and the problem of catalyst reaction to generate rosin salt is achieved, achieving high viscosity and high dissolution The production of the elastic resin reduces costs and improves the stability of the reaction.
Patent Information
- Application Number
- CN202211688367.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-27
- Publication Date
- 2025-01-03
- Estimated Expiration
- 2042-12-27
AI Technical Summary
In the existing preparation method for rosin-modified phenolic resin, the catalyst reacts with rosin to form rosin salt, which affects the water resistance and emulsification of the ink, and the production process is complex and costly, making it difficult to meet the rapidly developing high viscosity and high solubility requirements.
Rosin derivatives are formed by reacting rosin with alcohol and catalyst, followed by condensation reaction with formaldehyde and alkyl phenol under the action of the catalyst to form a rosin-modified phenolic resin, which simplifies the process steps and reduces production costs.
The preparation of rosin-modified phenolic resin with high viscosity and high solubility is achieved, which improves reaction stability and production efficiency, reduces the emission of harmful substances, reduces production costs, and maintains the excellent performance of the ink.
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Figure BDA0004020288910000101
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of resin preparation, and in particular to a preparation method of a rosin-modified phenolic resin and application thereof. Background Art
[0002] Rosin-modified phenolic resin has good pigment wetting properties due to its unique honeycomb structure. At the same time, it can react with appropriate gelling agents to obtain a binder with certain viscoelasticity, so it is widely used in offset lithographic inks. Offset lithographic inks have many advantages, such as fast printing speed, fine graphics, rich layers, relatively stable printing quality, and short printing cycle. Books, newspapers, and a considerable part of commercial printing are all using offset printing, and they occupy a dominant position in the entire printing market. Due to the characteristics of the printing process of traditional offset lithographic inks, the binder requires a low acid value, high viscosity, structure, high elasticity and high mineral oil tolerance. The processing technology of rosin-modified phenolic resin used in offset lithographic inks is to react alkylphenol, formaldehyde, rosin, polyols with rosin to finally generate a polymer product. The main technical indicators are drying, viscosity, viscosity, fluidity, color development, water resistance, etc.
[0003] At present, there are usually two processes for preparing rosin-modified phenolic resin:
[0004] (1) After the rosin is heated and dissolved, the required raw materials are added in sequence, firstly at 100-140°C for phenol-formaldehyde condensation reaction, and then the temperature is raised to 240-280°C for esterification reaction to produce rosin-modified phenolic resin, which is called the one-step process.
[0005] (2) Phenol and formaldehyde are first subjected to condensation reaction in the presence of a catalyst, then rosin is added for modification, and then polyols are added for esterification reaction to produce rosin-modified phenolic resin, which is called the two-step method. Regardless of the method used, the catalysts generally used in the phenol-formaldehyde condensation reaction are as follows: (1) alkali metal oxides or hydroxides, such as NaOH, KOH, CaO, Ca(OH)2, MgO, Mg(OH)2; (2) organic volatile alkaline compounds: ethanolamine, triethylamine, fatty amines, etc.
[0006] When using alkali metal oxides or hydroxides as catalysts, if the condensation reaction is not neutralized and washed with water, the catalyst will react with rosin to form rosin salt. If rosin salt is soluble in water, it will have a serious impact on the water resistance and emulsification of the ink; those that are insoluble in water (such as calcium abietic acid) are very difficult to dissolve in many solvents, and are also difficult to dissolve in vegetable oils and mineral oils, which is very unfavorable for synthesizing highly soluble products. If neutralization and washing are to be performed, the condensation reaction must be carried out in the presence of a solvent, which increases production costs and brings safety hazards, and also generates a large amount of wastewater, bringing environmental problems. At the same time, washing with water will cause a decrease in product yield and increase production costs.
[0007] With the development of social economy, printing speed is getting faster and faster, and the requirements for offset ink are getting higher and higher, which requires the development of a light-colored, high-viscosity, and high-solubility rosin-modified resin.
[0008] Chinese patent CN114989377A discloses a rosin-modified phenolic resin and its preparation method and application. The preparation method comprises the following steps: mixing resol phenolic resin, rosin and / or rosin derivatives with vegetable oil and / or its derivatives containing conjugated double bonds, and performing an addition reaction to obtain an addition product; mixing the addition product, polyol and esterification catalyst, and performing an esterification reaction to obtain a rosin-modified phenolic resin precursor; mixing the rosin-modified phenolic resin precursor with a chain extender, and performing a chain extension reaction to obtain a rosin-modified phenolic resin; the chain extender is a diisocyanate and / or polyisocyanate with more than two functional groups, or a glycidyl ether resin with more than two functional groups. This invention increases the molecular weight of the resin and reduces the solubility of the resin in vegetable oil. However, its preparation method includes addition reaction, esterification reaction and chain extension reaction, the operation process is relatively complicated, and the production cost is relatively high.
[0009] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a new method for preparing high-performance rosin-modified phenolic resin with simple operation. Summary of the invention
[0010] The purpose of the invention is to provide a method for preparing a rosin-modified phenolic resin with high viscosity and high solubility, which has simple production process, low production cost and ensures that the color of the resin is relatively light.
[0011] To achieve the above purpose, the technical solution adopted by the present invention is as follows:
[0012] In one aspect, the present invention provides a method for preparing a rosin-modified phenolic resin, the preparation method comprising the following steps:
[0013] (1) reacting rosin with alcohol and a catalyst to obtain a rosin derivative;
[0014] (2) reacting formaldehyde and alkylphenol under the action of a catalyst to obtain a resol phenolic resin;
[0015] (3) adding the resol phenolic resin obtained in step (2) to the rosin derivative obtained in step (1) to obtain a rosin-modified phenolic resin.
[0016] Preferably, in step (1), the rosin is selected from at least one of horsetail rosin, wetland rosin, Indonesian rosin, Vietnamese rosin and tall oil rosin.
[0017] Further preferably, in step (1), the rosin is selected from at least one of wetland rosin, Indonesian rosin and tall oil rosin.
[0018] Further preferably, the rosin in step (1) is a combination of wetland rosin, Indonesian rosin and tall oil rosin.
[0019] Still more preferably, the mass ratio of the wetland rosin, Indonesian rosin and tall oil rosin is 1:(0.2-0.8):(1-3).
[0020] Most preferably, the mass ratio of the wetland rosin, Indonesian rosin and tall oil rosin is 1:0.5:1.
[0021] Preferably, the alcohol in step (1) is selected from at least one of a monohydric saturated alcohol, a dihydric saturated alcohol, and a polyhydric saturated alcohol;
[0022] More preferably, in step (1), the alcohol is at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerol, pentaerythritol and neopentyl glycol.
[0023] Still more preferably, in step (1), the alcohol is selected from at least one of glycerol and pentaerythritol.
[0024] Most preferably, the alcohol in step (1) is a combination of glycerol and pentaerythritol.
[0025] Preferably, the mass ratio of pentaerythritol to glycerol is (5.5-8):1.
[0026] Further preferably, the mass ratio of pentaerythritol to glycerol is 5.5:1.
[0027] Optionally, in step (1), rosin is modified with alcohol and acid to obtain a rosin derivative.
[0028] Preferably, the acid in step (1) is selected from at least one of a saturated acid and an unsaturated acid.
[0029] More preferably, the acid in step (1) is an unsaturated acid.
[0030] Preferably, the unsaturated acid in step (1) is at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, malonic acid and itaconic acid.
[0031] More preferably, the unsaturated acid in step (1) is at least one selected from acrylic acid and maleic anhydride.
[0032] More preferably, the unsaturated acid in step (1) is a combination of acrylic acid and maleic anhydride.
[0033] Preferably, the mass ratio of maleic anhydride to acrylic acid is (1-5):1;
[0034] More preferably, the mass ratio of maleic anhydride to acrylic acid is (1.8):1.
[0035] In some specific embodiments, the step (1) comprises melting the rosin, and the melting is performed by heating the rosin to 200-250° C. under nitrogen protection.
[0036] Preferably, in step (1), the rosin is heated to 200° C. to melt.
[0037] In some specific embodiments, the step (1) is reacted after adding the catalyst, and the reaction is carried out at 220° C. and 250° C. for 1-3 hours respectively, and then the temperature is raised to 270-290° C. and kept for 6-8 hours.
[0038] Preferably, in step (1), the catalyst is added before the reaction is carried out at 220° C. and 250° C. for 1 h, respectively, and then the temperature is raised to 275° C. and kept at this temperature for 6 h.
[0039] Preferably, the formaldehyde in step (2) includes but is not limited to liquid formaldehyde and solid formaldehyde.
[0040] More preferably, the formaldehyde in step (2) is solid formaldehyde.
[0041] Preferably, the purity of formaldehyde in step (2) is 80-98%;
[0042] Further preferably, the purity of formaldehyde in step (2) is 90-95%;
[0043] More preferably, the purity of formaldehyde in step (2) is 92-94%;
[0044] Most preferably, the purity of formaldehyde in step (2) is 92%.
[0045] Preferably, in step (2), the alkylphenol is selected from at least one of bisphenol A, p-tert-butylphenol, p-octylphenol, p-nonylphenol, cardanol and p-dodecylphenol.
[0046] More preferably, the alkylphenol in step (2) is p-octylphenol.
[0047] Preferably, the catalyst in step (2) is selected from at least one of a basic catalyst and an acidic catalyst.
[0048] More preferably, the catalyst in step (2) is an alkaline catalyst.
[0049] Further preferably, the alkaline catalyst in step (2) is selected from at least one of sodium hydroxide, calcium hydroxide, sodium formate, sodium acetate, sodium oxalate, aqueous ammonia, diethylamine, triethylamine, and hexamethylenetetramine.
[0050] Still more preferably, the alkaline catalyst in step (2) is triethylamine.
[0051] Further preferably, the weakly acidic catalyst is selected from at least one of zinc acetate, oxalic acid, acetic anhydride, phosphoric acid, sulfonate, acetic acid, and carboxylic acid.
[0052] Still further preferably, the weakly acidic catalyst is zinc acetate.
[0053] Preferably, the reaction in step (2) is a polycondensation reaction.
[0054] Further preferably, the temperature of the polycondensation reaction in step (2) is 50-100°C;
[0055] Further preferably, the temperature of the polycondensation reaction in step (2) is 60-95°C;
[0056] Still more preferably, the temperature of the polycondensation reaction in step (2) is 80-95°C;
[0057] Most preferably, the temperature of the polycondensation reaction in step (2) is 90°C.
[0058] Preferably, the polycondensation reaction time in step (2) is 1-5h;
[0059] Further preferably, the polycondensation reaction time in step (2) is 2-3.5h;
[0060] Most preferably, the polycondensation reaction time in step (2) is 2 hours.
[0061] Preferably, the polycondensation reaction in step (2) is carried out in an inorganic solvent.
[0062] In some specific embodiments, in step (2), the alkylphenol is heated to melt at a temperature of 70-100°C.
[0063] Preferably, in step (2), the alkylphenol is heated to a melting temperature of 80°C.
[0064] Preferably, the method for obtaining the rosin-modified phenolic resin in step (3) is through a Diels-Alder reaction.
[0065] Specifically, the Diels-Alder reaction is an organic reaction, specifically a cycloaddition reaction, in which a conjugated diene reacts with an olefin or an alkyne to generate a six-membered ring.
[0066] On the other hand, the present invention provides the use of the rosin-modified phenolic resin prepared by the above preparation method in ink.
[0067] Compared with the prior art, the present invention has at least the following advantages:
[0068] (1) The preparation method of the present invention divides the reaction steps into three steps, thereby improving the reaction stability, increasing the reaction rate, and reducing the emission of VOCs, which is beneficial to the environment. The obtained rosin-modified phenolic resin reduces the production cost and is more economical.
[0069] (2) The rosin-modified phenolic resin obtained by the preparation method of the present invention has light color, high viscosity, high solubility, and good drying property, fluidity, color development, and water resistance in ink applications. DETAILED DESCRIPTION
[0070] The specific implementation modes of the present invention are further described in detail below with reference to examples.
[0071] Raw materials purchased from:
[0072] Wetland rosin: purchased from Lingshan HSBC Forest Chemical Co., Ltd.; item number: 2211250001;
[0073] Tall oil rosin: purchased from Guangdong Kemao Forest Products Chemical Co., Ltd.; item number: 20220921655;
[0074] Indonesian rosin: purchased from Guangdong Kemao Forest Products and Chemical Industry Co., Ltd.; item number: 20220418309;
[0075] Maleic anhydride: purchased from Foshan Nanhai Lishui German Chemical Co., Ltd.; product number: 2211230221;
[0076] Acrylic acid: purchased from Jiangsu Runhan Chemical Co., Ltd.; product number: 20221004101;
[0077] Fumaric acid: purchased from Foshan Nanhai Lishui Zhongde Chemical Co., Ltd.; item number: 2210270001;
[0078] Pentaerythritol: purchased from Jiangsu Runhan Chemical Co., Ltd.; product number: 2209270002;
[0079] Glycerol: purchased from Qingyuan Futai Glycerol Refining Co., Ltd.; product number: 2209150001;
[0080] Zinc oxide: purchased from Guangzhou Aohai Trading Co., Ltd.; item number: 202000201;
[0081] Octylphenol: purchased from Tengzhou Aoxing Chemical Co., Ltd.; item number: 101312;
[0082] Solid formaldehyde: purchased from Guangzhou Yuehua Trading Co., Ltd.; item number: 22110113;
[0083] Triethylamine: purchased from Jiangsu Runhan Chemical Co., Ltd.; product number: 20221103001;
[0084] Example 1 Preparation method of rosin-modified phenolic resin
[0085] (1) 825 g of wetland rosin and 350 g of floating oil rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, heated to 200° C. under nitrogen protection to melt, 220 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the mixture was kept at 220° C. and 250° C. for 1 h each, then the temperature was raised to 275° C. and kept at this temperature for 6 h to obtain 1320 g of rosin derivative.
[0086] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 500 g of
[0087] phenol, heated to 80 ° C to fully melt; slowly add 159 grams of 92% solid formaldehyde, stir and disperse for 10 minutes, pay attention to the heating phenomenon, slowly add 11g triethylamine; heat to 90 ° C, maintain this temperature for 2 hours, cool to room temperature, and obtain 652 grams of resol phenolic resin.
[0088] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 1000g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 600g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours. After the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by reduced pressure distillation to obtain a rosin-modified phenolic resin.
[0089] Example 2 Preparation method of rosin-modified phenolic resin
[0090] (1) 400 g of wetland rosin, 200 g of floating oil rosin, and 400 g of Indonesian rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, and heated to 200° C. under nitrogen protection to melt. 220 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the mixture was kept at 220° C. and 250° C. for 1 h each, and then the temperature was raised to 275° C. and kept at this temperature for 6 h to obtain 1190 g of rosin derivative.
[0091] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 600 g of octylphenol was added and heated to 80°C to fully dissolve it; 170 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 13 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 755 g of resol phenolic resin was obtained.
[0092] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 800 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 670 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by vacuum distillation to obtain a rosin-modified phenolic resin.
[0093] Example 3 Preparation method of rosin-modified phenolic resin
[0094] (1) 800 g of wetland rosin and 300 g of floating oil rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, heated to 180° C. under nitrogen protection to melt, 55 g of maleic anhydride and 30 g of acrylic acid were added, and the temperature was kept at 180° C. for 2 h; 220 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the temperature was kept at 220° C. and 250° C. for 1 h respectively, and the temperature was raised to 275° C. and kept for 6 h to obtain 1362 g of rosin derivative.
[0095] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 500 g of octylphenol was added and heated to 80°C to fully dissolve it; 159 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 11 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 652 g of resol phenolic resin was obtained.
[0096] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 1000 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 600 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by reduced pressure distillation to obtain a rosin-modified phenolic resin.
[0097] Example 4
[0098] (1) 400 g of wetland rosin, 200 g of floating oil rosin, and 400 g of Indonesian rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, and heated to 200° C. under nitrogen protection to melt. 200 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the reaction was carried out at 220° C. and 250° C. for 1 h each. The temperature was raised to 275° C. and kept for 6 h to obtain 1202 g of rosin derivative.
[0099] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 600 g of octylphenol was added and heated to 80°C to fully dissolve it; 170 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 13 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 752 g of resol phenolic resin was obtained.
[0100] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 800 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 670 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by vacuum distillation to obtain a rosin-modified phenolic resin.
[0101] Comparative Example 1
[0102] A method for preparing a rosin-modified phenolic resin comprises the following steps:
[0103] (1) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 500 g of octylphenol was added and heated to 80°C to fully dissolve it; 159 g of solid formaldehyde with a content of 92% was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 11 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 652 g of resol phenolic resin was obtained.
[0104] (2) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 800 g of wetland rosin and 200 g of floating oil rosin were added to fully melt the mixture, and stirring was started; the temperature was raised to 200°C, and the temperature was maintained, and 600 g of the resol phenolic resin prepared in step (1) was added dropwise within 4 hours; after the addition was completed, 180 g of pentaerythritol and 40 g of glycerol were added, the temperature was raised to 275°C, and the reaction was carried out for 6 hours, and low-boiling components were removed by reduced pressure distillation to obtain a rosin-modified phenolic resin.
[0105] Comparative Example 2
[0106] A method for preparing a rosin-modified phenolic resin comprises the following steps:
[0107] (1) 200 g of wetland rosin, 200 g of floating oil rosin, and 800 g of Indonesian rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, heated to 200° C. under nitrogen protection to melt, 180 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the mixture was kept at 220° C. and 250° C. for 1 h each, then heated to 275° C. and kept at this temperature for 6 h to obtain 1200 g of rosin derivative.
[0108] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 600 g of octylphenol was added and heated to 80°C to fully dissolve it; 170 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 13 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 755 g of resol phenolic resin was obtained.
[0109] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 800 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 670 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by vacuum distillation to obtain a rosin-modified phenolic resin.
[0110] Comparative Example 3
[0111] A method for preparing a rosin-modified phenolic resin comprises the following steps:
[0112] (1) 800 g of wetland rosin and 300 g of floating oil rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, heated to 180° C. under nitrogen protection to melt, 115 g of maleic anhydride and 20 g of acrylic acid were added, and the mixture was kept at 180° C. for 2 h; 220 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the mixture was kept at 220° C. and 250° C. for 1 h each, and the temperature was raised to 275° C. and kept at this temperature for 6 h to obtain 1380 g of rosin derivative.
[0113] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 500 g of octylphenol was added and heated to 80°C to fully dissolve it; 159 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes, paying attention to the heating phenomenon, and 11 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 650 g of resol phenolic resin was obtained.
[0114] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 1000 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 600 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by reduced pressure distillation to obtain a rosin-modified phenolic resin.
[0115] Comparative Example 4
[0116] The difference from Example 4 is that the mass ratio of pentaerythritol to glycerol is 9:1, and the rest are the same.
[0117] (1) 400 g of wetland rosin, 200 g of floating oil rosin, and 400 g of Indonesian rosin were placed in a reaction bottle equipped with a thermometer and a stirrer, and heated to 200° C. under nitrogen protection to melt. 360 g of pentaerythritol, 40 g of propylene glycol, and 1.2 g of zinc oxide were added, and the mixture was kept at 220° C. and 250° C. for 1 h each, then the temperature was raised to 275° C. and kept at this temperature for 6 h to obtain 1315 g of rosin derivative.
[0118] (2) In a 1L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 600 g of octylphenol was added and heated to 80°C to fully dissolve it; 170 g of 92% solid formaldehyde was slowly added, and the mixture was stirred and dispersed for 10 minutes while paying attention to the heating phenomenon; 13 g of triethylamine was slowly added; the temperature was raised to 90°C, and the reaction was maintained at this temperature for 2 hours. After cooling to room temperature, 750 g of resol phenolic resin was obtained.
[0119] (3) In a 3L four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, add 800 g of the rosin derivative obtained in step (1), heat to 160°C to fully melt it, and stir; raise the temperature to 200°C, maintain this temperature, and dropwise add 670 g of the resol phenolic resin obtained in step (2), and complete the dropwise addition within 4 hours; after the dropwise addition is completed, stir for another hour, and remove the low-boiling point components by vacuum distillation to obtain a rosin-modified phenolic resin.
[0120] Comparative Example 5: The resin was prepared using the preparation method of Example 1 in patent CN105330800A.
[0121] Example 5 Detection of rosin-modified phenolic resin
[0122] The detection of the acid value of rosin-modified phenolic resin includes the following steps:
[0123] Accurately put 1 gram of resin in a 250ml flask, add 100ml of toluene / ethanol (2 / 1) mixed solution to dissolve, use phenolphthalein as an indicator, drop 0.1mol / L sodium hydroxide solution until the solution turns slightly red, and the titration endpoint is when it does not fade after 30 seconds of shaking. The amount of sodium hydroxide consumed is converted into milligrams of potassium hydroxide, which is the acid value of the resin.
[0124] The softening point of rosin modified phenolic resin is tested using the ring and ball method.
[0125] The detection of the rotational viscosity of rosin-modified phenolic resin includes the following steps:
[0126] The resin and linseed oil were mixed in a mass ratio of 1:2, and then heated and dissolved at 200°C for 20 minutes. The viscosity was then measured using a NDJ-79 viscometer at a temperature of 25°C.
[0127] The test of n-heptane solubility of rosin-modified phenolic resin includes the following steps:
[0128] Place 2 grams of a 1:2 mixture of resin and linseed oil fired at 200°C in a 100ml beaker, control the temperature at 25°C, then add n-heptane dropwise while stirring until the No. 5 font on the newspaper underneath can no longer be read, and measure the amount of n-heptane added.
[0129] The detection of iron-cobalt color of rosin-modified phenolic resin includes the following steps:
[0130] Pour the resin liquid into the sample tube and arrange it horizontally with the iron-cobalt colorimeter, compare through the side and take the closest color number.
[0131] The test results of the rosin-modified phenolic resins obtained in Examples 1-4 and Comparative Examples 1-4 are shown in Table 1 below:
[0132] Table 1.
[0133]
[0134] It can be seen from the data in Table 1 that the rosin-modified phenolic resin prepared in Example 1 has the same rotational viscosity as that of Comparative Example 1, but the n-heptane solubility of the rosin-modified phenolic resin of Example 1 is higher; the difference between Example 2 and Comparative Example 2 is that the mass ratio of pentaerythritol to glycerol is different and the rosin type is different. When the mass ratio of pentaerythritol to glycerol exceeds the protection scope of this application (Comparative Example 2), its rotational viscosity is lower than that of Example 2, and the solubility of n-heptane is lower; compared with Comparative Example 3, when the mass ratio of the unsaturated acid in Comparative Example 3 is outside the protection scope of this application, the rotational viscosity of the rosin-modified phenolic resin prepared is lower, and the solubility of n-heptane is lower; when the mass ratio of pentaerythritol to glycerol in Comparative Example 4 is 9:1, its rotational viscosity is slightly higher than that of Example 4, but the solubility of n-heptane is lower. The rotational viscosity and n-heptane solubility of the resin prepared by the preparation method of Example 1 in Patent CN105330800A are lower than those of Examples 1-4 of this application.
[0135] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a rosin-modified phenolic resin, characterized in that: The preparation method comprises the following steps: (1) reacting rosin with alcohol and a catalyst to obtain a rosin derivative; (2) reacting formaldehyde with alkylphenol in the presence of a catalyst to obtain a resol phenolic resin; (3) adding the resol phenolic resin obtained in step (2) to the rosin derivative obtained in step (1) to obtain a rosin-modified phenolic resin; The mass ratio of the alcohol to the catalyst is (200-230): 1; In step (1), the alcohol is a combination of pentaerythritol and glycerol, and the mass ratio of pentaerythritol to glycerol is (5.5-8) 1; In the step (2), the alkylphenol is p-octylphenol; The catalyst in step (2) is triethylamine.
2. The preparation method according to claim 1, characterized in that: In the step (1), the rosin is selected from at least one of horsetail rosin, wetland rosin, Indonesian rosin, Vietnamese rosin and tall oil rosin.
3. The preparation method according to claim 1, characterized in that: The mass ratio of pentaerythritol to glycerol is 5.5:
1.
4. Application of the rosin-modified phenolic resin obtained by the preparation method according to any one of claims 1 to 3 in ink.