Method for comprehensive utilization of phenol ketone tar and bisphenol a tar

Abstract

The application provides a method for comprehensive utilization of phenolic ketone tar and bisphenol A tar, which comprises the following steps: reacting the phenolic ketone tar and the bisphenol A tar in the presence of a catalyst to obtain an intermediate product containing polyphenol; mixing the intermediate product with formaldehyde to synthesize phenolic aldehyde resin; and reacting the phenolic aldehyde resin with epichlorohydrin to synthesize phenolic aldehyde epoxy resin; wherein the weight ratio of the phenolic ketone tar and the bisphenol A tar is 20:1 to 1:20, preferably 10:1 to 1:10.

Description

Technical Field

[0001] This invention relates to the fields of industrial waste resource utilization and polymer synthesis technology, specifically to a method for producing low-density phenolic epoxy resin by synergistically utilizing phenolic ketone tar and bisphenol A tar. Background Technology

[0002] Phenolic tar and bisphenol A tar are large quantities of byproducts generated during related chemical production processes. Phenolic tar mainly contains phenolic compounds such as phenol, acetophenone, and 4-cumylphenol, as well as small amounts of hydrocarbon impurities such as 2-phenyl-1-propene and its dimers. Bisphenol A tar is mainly composed of bisphenol A and its isomers, polyphenols, and phenolic oligomers, while also containing unreacted phenol. Both types of tar have complex compositions and are difficult to process. Current treatment methods primarily involve incineration, which leads to resource waste and environmental pollution. Although some research has attempted to utilize them as resources, such as for resin production, significant bottlenecks exist: 1) The components contained in a single tar are limited, resulting in a single molecular structure of the synthesized resin, leading to performance defects such as low crosslinking density or slow curing; 2) More importantly, resins synthesized from single tars, especially bisphenol A tar, often have a high density (typically greater than 1.20 g / cm³) due to the dense molecular packing caused by their polycyclic and polyphenolic structures. 3 This limits its application in fields requiring lightweight materials, such as high-end composite materials and electronic packaging materials.

[0003] Therefore, developing a novel comprehensive utilization method that can synergistically utilize both phenolic tar and bisphenol A tar, overcome the aforementioned performance defects, and especially effectively reduce resin density, has significant technological value and market prospects. Summary of the Invention

[0004] The purpose of this application is to provide a method for the combined production of resin from phenolic ketone tar and bisphenol A tar, achieving high-value utilization of waste. The key to this invention lies in the specific combination of the two tars, utilizing the ketones and olefins in the phenolic ketone tar to react with the phenolic substances in the bisphenol A tar under the action of a catalyst, generating an intermediate product containing polyphenols. This intermediate product is then used to synthesize resin, overcoming the performance deficiencies of resin produced from single tars, significantly reducing the density of the synthesized phenolic epoxy resin, thereby obtaining a novel resin material with excellent mechanical properties, curing characteristics, and lightweight properties. The resin density obtained by this invention can be stably maintained at 1.10-1.18 g / cm³. 3 Within this range, it is far lower than that of resins made from single bisphenol A tar (typically >1.20 g / cm³). 3 This achieves the lightweighting of materials.

[0005] Therefore, this application provides a method for the comprehensive utilization of phenolic tar and bisphenol A tar, the method comprising: In the presence of a catalyst, phenolic tar and bisphenol A tar react to yield an intermediate product containing polyphenols. The intermediate product was mixed with formaldehyde to synthesize phenolic resin. Phenolic epoxy resin is synthesized by reacting phenolic resin with epichlorohydrin. The weight ratio of phenolic tar to bisphenol A tar is 20:1 to 1:20, preferably 10:1 to 1:10.

[0006] In some embodiments, the phenol-ketone tar comprises: phenol, acetophenone, 4-cumylphenol, 2-cumylphenol, α,α-dimethylbenzyl alcohol, β-methylphenylethanol, and α-methylstyrene dimer.

[0007] In some embodiments, the bisphenol A tar comprises: phenol, bisphenol A, bisphenol A isomers, diphenols, and isopropylphenol.

[0008] In some embodiments, the catalyst is an acidic catalyst, preferably selected from one or more of oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid.

[0009] In some embodiments, the process for preparing the intermediate product further includes a co-catalyst selected from one or more of the following: mercaptoacetic acid, 3-mercapto-1-propanesulfonic acid, 1-dodecylthiol, 2-mercaptoethanol, and 2-mercaptopyridine.

[0010] In a specific embodiment, a method for co-producing resin from phenolic tar and bisphenol A tar is provided, the method comprising the following steps: (1) Add phenol ketone tar and bisphenol A tar to a reaction flask, add solvent and co-catalyst, add acid catalyst, collect the oil layer after reaction, and synthesize intermediate products containing polyphenols. (2) The oil layer from step (1) is mixed with formaldehyde, and a catalyst is added to synthesize phenolic resin; (3) Phenolic resin is reacted with epichlorohydrin, alkali and phase transfer catalyst to synthesize phenolic epoxy resin.

[0011] In some embodiments, the reaction temperature range in step (1) is 40-150°C.

[0012] In some embodiments, in step (1), the acid catalyst is added over a time of 0.5-6 hours.

[0013] In some embodiments, the reaction time in step (1) is 1-8 hours, preferably 2-4 hours.

[0014] In some embodiments, in step (1), the solvent is selected from one or more of benzene, phenol, toluene, xylene, n-hexane, methanol, ethanol, and isopropanol.

[0015] In some embodiments, in step (1), the weight ratio of the solvent amount to the sum of the weights of the two tars is 2:1 to 5:1.

[0016] In some embodiments, in step (1), the catalyst is an organic acid or an inorganic acid, preferably one or more of oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid.

[0017] In some embodiments, in step (1), the amount of catalyst used is 0.7-15% of the weight of phenol tar.

[0018] In some embodiments, in step (1), the co-catalyst is selected from one or more of the following: mercaptoacetic acid, 3-mercapto-1-propanesulfonic acid, 1-dodecylthiol, 2-mercaptoethanol, and 2-mercaptopyridine.

[0019] In some embodiments, in step (1), the amount of co-catalyst used is 0.5-6% of the weight of phenol tar.

[0020] In some embodiments, in step (2), formaldehyde may be 10-40% by weight of an aqueous solution of formaldehyde or solid formaldehyde.

[0021] In some embodiments, in step (2), the amount of formaldehyde used is 0.4-6% of the weight of the product obtained in step (1).

[0022] In some embodiments, in step (2), the catalyst is a protic acid or Lewis acid, preferably oxalic acid.

[0023] In some embodiments, in step (2), the amount of catalyst used is 0.5-10% of the weight of the oil layer in step (1).

[0024] In some embodiments, the reaction temperature range in step (2) is 40°C to 160°C.

[0025] In some embodiments, the reaction time in step (2) is 1-8 hours, preferably 2-4 hours.

[0026] In some embodiments, in step (3), the amount of epichlorohydrin consumed is 0.7-1.5 times the molar amount of the phenolic hydroxyl groups in the system.

[0027] In some embodiments, in step (3), the phase transfer catalyst is one or more of quaternary ammonium salt, quaternary phosphine salt, imidazole salt, pyridine salt, and piperidine salt, preferably tetrabutylammonium bromide.

[0028] In some embodiments, in step (3), the amount of phase transfer catalyst used is 0.5-5% by weight of the obtained phenolic resin.

[0029] In some embodiments, the reaction temperature in step (3) is 40-150°C.

[0030] In some embodiments, in step (3), the base is a 10-50 wt.% aqueous solution of sodium hydroxide.

[0031] In some embodiments, in step (3), the amount of alkali used is 5-25% of the weight of the phenolic resin.

[0032] In some embodiments, in step (3), the alkali is added over a time of 0.5-6 hours.

[0033] In some implementations, the reaction time in step (3) is 1-8 hours. Detailed Implementation

[0034] The "range" disclosed herein is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0035] Unless otherwise specified in this application, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0036] Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0037] In this application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, if the method may also include step (c), it means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0038] In this application, unless otherwise specified, the terms "comprising" and "including" as used herein are open-ended or closed-ended. For example, "comprising" and "including" may mean that other components not listed may also be included, or that only the listed components may be included.

[0039] In the description of this article, it should be noted that, unless otherwise stated, "above" and "below" include the number itself, and "several" in "one or more" means two or more.

[0040] In this description, unless otherwise stated, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0041] Unless otherwise specified, percentages (%) or parts refer to weight percentages or parts by weight of the composition.

[0042] Unless otherwise stated herein, the sum of the contents of the components in the composition is 100%.

[0043] Unless otherwise stated herein, the sum of the parts of each component in the composition may be 100 parts by weight.

[0044] In this document, unless otherwise stated, “combination of” means a multi-component mixture of the elements, such as two, three, four, and up to the maximum possible multi-component mixture.

[0045] Unless otherwise specified, the term "a" as used in this specification means "at least one".

[0046] In this paper, unless otherwise stated, all reactions were carried out at room temperature and pressure.

[0047] The main objective of this invention is to provide a method for the combined production of resin from phenolic tar and bisphenol A tar, achieving high-value utilization of waste materials. The key to this invention lies in the specific combination of phenolic tar and bisphenol A tar. The ketones and olefins in the phenolic tar react with the phenolic substances in the bisphenol A tar under the action of a catalyst to generate an intermediate product containing polyphenols. This intermediate product is then used to synthesize resin, overcoming the performance limitations of resin produced from single tar. This significantly reduces the density of the synthesized phenolic epoxy resin (for example, the density of the obtained resin can be stably maintained at 1.10-1.18 g / cm³). 3 Within the specified range, a new type of resin material with excellent mechanical properties, curing characteristics, and lightweight features can be obtained.

[0048] Phenolic tar

[0049] In this article, "phenol tar," also known as phenol tar, refers to the heavy component tar produced as a byproduct of the cumene process for producing phenol and acetone. During the cumene process, benzene and propylene react under a catalyst to produce cumene. Cumene then undergoes oxidation with oxygen to produce cumene hydroperoxide. Cubic hydroperoxide decomposes under the action of an acid (such as sulfuric acid) to produce phenol and acetone. Phenol and acetone are separated, leaving phenol tar as the remaining byproduct. Phenol tar has a complex composition, and due to differences in process routes and catalyst types used by different manufacturers, the proportions of each component in the phenol tar produced by different manufacturers will vary. The main components of phenol tar may include phenol, acetophenone, 4-cumylphenol, and other phenolic compounds, as well as small amounts of hydrocarbon impurities such as 2-phenyl-1-propylene and its dimers.

[0050] In a specific embodiment, the present invention uses phenol-ketone tar from Ruiheng New Materials Technology Co., Ltd. In a specific embodiment, the phenol-ketone tar comprises phenol, acetophenone, methylstyrene, and other components including methylstyrene dimer, 4-cumylphenol, 2-cumylphenol, and dimethylbenzyl alcohol.

[0051] Bisphenol A tar

[0052] The main components of bisphenol A tar include unreacted raw materials, bisphenol A isomers, polyhydroxy compounds, condensation products, impurities, and catalyst residues. In the synthesis of bisphenol A, phenol and acetone may not have fully reacted, thus unreacted raw materials may remain in the tar. Besides producing the main product 4,4'-bisphenol A, the reaction also generates a certain amount of isomers, such as 2,4'-bisphenol A. Side reactions produce compounds containing multiple hydroxyl groups, such as triphenols and polyphenols. Further condensation of phenol, acetone, or bisphenol A forms condensation products, which are substances with higher molecular weights. The tar may also contain catalyst residues from the reaction, such as hydrochloric acid, as well as other impurities. Phenolic ketone tar is mainly composed of bisphenol A and its isomers, polyphenols, and phenolic oligomers, and also contains unreacted phenol.

[0053] In a specific embodiment, the present invention uses bisphenol A tar from Ruiheng New Materials Technology Co., Ltd. In a specific embodiment, the bisphenol A tar comprises phenol, bisphenol A, isopropylphenol, and other components such as bisphenol A isomers, cyclic dimers, hydroxy trimers, triphenols, tetraphenols, colorants, and heavy components.

[0054] Comprehensive utilization

[0055] One aspect of this application provides a method for the comprehensive utilization of phenolic tar and bisphenol A tar, the method comprising: In the presence of a catalyst, phenolic tar and bisphenol A tar react to yield an intermediate product containing polyphenols. The intermediate product was mixed with formaldehyde to synthesize phenolic resin. Phenolic epoxy resin is synthesized by reacting phenolic resin with epichlorohydrin. The weight ratio of phenolic tar to bisphenol A tar is 20:1 to 1:20, preferably 10:1 to 1:10.

[0056] In a specific embodiment, the present invention provides a method for producing low-density phenolic epoxy resin by comprehensively utilizing phenolic tar and bisphenol A tar, the method comprising: (1) Synthesis of bisphenol AP (4,4'-(1-phenylethyl)bisphenol) and 4-cumylphenol Phenolic ketone tar and bisphenol A tar were added to a reaction flask in a certain mass ratio, along with a solvent and a catalyst. An acidic catalyst was added at a certain temperature, and the oil layer was collected after the reaction. (2) Synthesis of phenolic resin Add the oil layer, formaldehyde and catalyst from step (1) to the reaction flask, heat the reaction for a certain time, and remove the excess solvent after the reaction is completed; (3) Synthesis of phenolic epoxy resin Phenolic resin reacts with epichlorohydrin, alkali, and phase transfer catalyst at a certain temperature. After the reaction, desalting and removal of excess ECH are performed.

[0057] In step (1), the mass ratio of phenolic tar to bisphenol A tar is in the range of 20:1 to 1:20, preferably 10:1 to 1:10.

[0058] In step (1), the reaction temperature range is 40-150℃.

[0059] In step (1), the catalyst is added over a period of 0.5-6 hours.

[0060] In step (1), the reaction time is 1-8 hours, preferably 2-4 hours.

[0061] In step (1), the solvent is one or more of benzene, phenol, toluene, xylene, n-hexane, methanol, ethanol, and isopropanol.

[0062] In step (1), the catalyst may be one or more organic or inorganic acids, preferably oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, or p-toluenesulfonic acid.

[0063] In step (1), the co-catalyst may be one or more of mercaptoacetic acid, 3-mercapto-1-propanesulfonic acid, 1-dodecylthiol, 2-mercaptoethanol, and 2-mercaptopyridine.

[0064] In step (2), formaldehyde can be an aqueous solution of formaldehyde or solid formaldehyde.

[0065] In step (2), the amount of formaldehyde used is 0.4-6% of the weight of the product obtained in step (1).

[0066] In step (2), the catalyst used may be one or more of protic acids or Lewis acids, preferably oxalic acid.

[0067] In step (2), the amount of catalyst used is 0.5-10% of the weight of the oil layer in step (1).

[0068] In step (2), the reaction temperature range is 40℃-160℃.

[0069] In step (2), the reaction time is 1-8 hours, preferably 1-4 hours.

[0070] In step (3), the amount of epichlorohydrin (ECH) consumed is 0.7-1.5 times the molar amount of the phenolic hydroxyl groups in the system.

[0071] In step (3), the phase transfer catalyst is one or more of quaternary ammonium salts, quaternary phosphine salts, imidazole salts, pyridinium salts, and piperidine salts. In a specific embodiment, the phase transfer catalyst is tetrabutylammonium bromide.

[0072] In step (3), the amount of phase transfer catalyst used is 0.5-5% by weight of the obtained phenolic resin.

[0073] In step (3), the reaction temperature range is 40-150℃.

[0074] In step (3), an aqueous solution of sodium hydroxide with a concentration of 10-50% by weight is added dropwise.

[0075] In step (3), the amount of alkali used is 5-25% of the weight of the phenolic resin.

[0076] In step (3), the alkali is added over a period of 0.5-6 hours.

[0077] In step (3), the reaction time is 1-8 hours.

[0078] Compared with the prior art, the present invention has the following outstanding advantages: (1) Resource utilization and low cost: Waste treatment reduces raw material costs by more than 50%; (2) Significantly reduced product density: This is the most unexpected effect of this invention. Through synergistic reaction, the dense molecular structure formed by single tar is broken, and the density of the resulting resin can be stabilized at 1.10-1.18 g / cm³. 3 This is significantly lower than that of resins made from single bisphenol A tar (typically >1.20 g / cm³). 3 This achieves the lightweighting of materials; (3) Excellent and adjustable performance: The epoxy equivalent, softening point and other parameters of the resin can be adjusted within a wide range, and the overall performance is excellent.

[0079] Unless otherwise specified, all raw materials used in this application are commercially available or prepared according to conventional methods in the art. Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this disclosure. Other aspects of this disclosure will be apparent to those skilled in the art from the content of this disclosure. Experimental methods in the following examples, unless otherwise specified, are performed according to conventional methods and conditions or as selected in the product instructions. In the examples, unless otherwise specified, percentages (%) or parts refer to weight percentages or parts by weight.

[0080] Example

[0081] To make the technical solution and effects of the present invention clearer, the technical solution of the present invention will be further described below in conjunction with some specific embodiments. The described embodiments are for further illustrating the present invention and should not be construed as limiting the scope of protection of the present invention.

[0082] Source of raw materials

[0083] Phenolic acetone tar: Ruiheng New Materials Technology Co., Ltd., comprising 4-9 wt% phenol, 18-25 wt% acetophenone, 22.5-26.5 wt% 4-cumylphenol and 2-cumylphenol, 2-4 wt% α,α-dimethylbenzyl alcohol, 1-2 wt% β-methylphenylethanol, 8-9 wt% α-methylstyrene dimer, and 26-40 wt% other unavoidable components; Bisphenol A tar: Ruiheng New Materials Technology Co., Ltd., containing 3-15% phenol, approximately 30-70% bisphenol A, 20-40% bisphenol A isomers and diphenols (such as bisphenol A isomers, cyclic dimers, hydroxy trimers, triphenols, tetraphenols, colorants and heavy components), and 0.1-1.5% isopropylphenol.

[0084] Toluene: National Pharmaceutical Reagent; Paraformaldehyde: Sinopharm Reagent; Oxalic acid: National Pharmaceutical Reagent; Epichlorohydrin: Ruiheng New Materials Technology Co., Ltd.; Phenol: National Pharmaceutical Reagent; Tetrabutylammonium bromide: Shanghai Aladdin Biochemical Technology Co., Ltd.; Thioglycolic acid: Sinopharm Reagent; 3-Mercapto-1-propanesulfonic acid: National Pharmaceutical Reagent; 1-Dodecanethiol: National Pharmaceutical Reagent; 2-Mercaptoethanol: National Pharmaceutical Reagent; 2-Mercaptopyridine: National Pharmaceutical Reagent; p-Toluenesulfonic acid: Sinopharm Reagent; Hydrochloric acid: National Pharmaceutical Reagent; Sulfuric acid: National Pharmaceutical Reagent.

[0085] Calculation formula: Epoxy Equivalent: EEQ = cV M / m X100 c: Concentration of perchloric acid solution, mol / L V: Volume of perchloric acid solution consumed, mL m: Sample mass, g

[0086] Example 1: Add 200g of phenol-ketone tar, 10g of bisphenol A tar (mass ratio 20:1), 400g of toluene, and 0.6g of mercaptoacetic acid to a four-necked flask, and heat to 40℃. Set up a water separator, and add 5g of 30wt% p-toluenesulfonic acid solution dropwise (addition time 0.5h). After the addition is complete, maintain the temperature for 1h. After the reaction is complete, wash with water until neutral, and separate the layers to obtain the oil layer.

[0087] The oil layer was mixed with 1g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 40℃ for 1 hour. The solvent was removed under negative pressure to obtain phenolic resin.

[0088] Add 550g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 40℃. Add 55g of 50wt% NaOH solution dropwise (0.5h addition time) and maintain the temperature for 1h. Remove excess ECH after the reaction.

[0089] Product performance: Epoxy equivalent 248 g / eq, density 1.10 g / cm³ 3 , softening point 86 ℃.

[0090] Example 2: Add 10g of phenol-acetone tar, 200g of bisphenol A tar (mass ratio 1:20), 400g of ethanol, and 0.6g of 2-mercaptoethanol to a four-necked flask, and heat to 150°C. Add 5g of 30wt% hydrochloric acid solution dropwise (dropwise over 6 hours), and maintain the temperature for 8 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0091] The oil layer was mixed with 5g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 160℃ for 6 hours to obtain phenolic resin.

[0092] Add excess 250g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 150℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 6h), keep warm for 8h, and remove excess ECH after the reaction.

[0093] Product performance: Epoxy equivalent 182 g / eq, density 1.18 g / cm³ 3 , softening point 45 ℃.

[0094] Example 3: Add 100g of phenol-acetone tar, 10g of bisphenol A tar (mass ratio 10:1), 400g of phenol, and 0.6g of mercaptoacetic acid to a four-necked flask, and heat to 70°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise (dropwise over 2 hours), and maintain the temperature for 4 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0095] The oil layer was mixed with 2g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 80℃ for 3 hours to obtain phenolic resin.

[0096] Add 150g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 80℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 2 hours), keep warm for 4 hours, and remove excess ECH after the reaction.

[0097] Product performance: Epoxy equivalent 222 g / eq, density 1.11 g / cm³3 , softening point 45 ℃.

[0098] Example 4: Add 10g of phenol-acetone tar, 100g of bisphenol A tar (mass ratio 1:10), 400g of toluene, and 0.6g of dodecanethiol to a four-necked flask, and heat to 100°C. Add 5g of 30wt% sulfuric acid solution dropwise (over 3 hours), and maintain the temperature for 5 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0099] The oil layer was mixed with 3g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 100℃ for 4 hours to obtain phenolic resin.

[0100] Add 150g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 100℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 3 hours), keep warm for 5 hours, and remove excess ECH after the reaction.

[0101] Product performance: Epoxy equivalent 203 g / eq, density 1.15 g / cm³ 3 Softening point 79℃.

[0102] Example 5: Add 50g of phenol-acetone tar, 10g of bisphenol A tar (mass ratio 5:1), 200g of toluene, and 0.2g of mercaptoacetic acid to a four-necked flask, and heat to 90°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise (dropwise over 2 hours), and keep warm for 3 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0103] The oil layer was mixed with 1.5g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 90℃ for 2 hours to obtain phenolic resin.

[0104] Add 120g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 70℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 2 hours), keep warm for 3 hours, and remove excess ECH after the reaction.

[0105] Product performance: Epoxy equivalent 218 g / eq, density 1.12 g / cm³ 3 , softening point 74℃.

[0106] Example 6: Add 10g of phenol-ketone tar, 50g of bisphenol A tar (mass ratio 1:5), 200g of ethanol, and 0.2g of 2-mercaptoethanol to a four-necked flask, and heat to 110°C. Add 5g of 30wt% phosphoric acid solution dropwise (over 2 hours), and maintain the temperature for 3 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0107] The oil layer was mixed with 2.5g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 110℃ for 2 hours to obtain phenolic resin.

[0108] Add 100g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 90℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 2 hours), keep warm for 3 hours, and then remove excess ECH after the reaction.

[0109] Product performance: epoxy equivalent 195 g / eq, density 1.16 g / cm³, softening point 55℃.

[0110] Example 7: Add 50g of phenol-acetone tar, 50g of bisphenol A tar (mass ratio 1:1), 400g of n-hexane, and 0.6g of 3-mercapto-1-propanesulfonic acid to a four-necked flask, and heat to 50°C. Add 5g of 30wt% oxalic acid solution dropwise (over 1 hour), and maintain the temperature for 8 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0111] The oil layer was mixed with 1g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 50℃ for 8 hours to obtain phenolic resin.

[0112] Add 150g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 50℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 1 hour) and maintain the temperature for 8 hours.

[0113] Product quality: epoxy equivalent 238 g / eq, density 1.13 g / cm³, softening point 92℃.

[0114] Example 8: Add 50g of phenol-acetone tar, 50g of bisphenol A tar (mass ratio 1:1), 400g of isopropanol, and 0.6g of 2-mercaptopyridine to a four-necked flask, and heat to 140°C. Add 5g of 30wt% hydrochloric acid solution dropwise (over 5 hours), and maintain the temperature for 1 hour after the addition is complete. Post-treatment is the same as in Example 1.

[0115] The oil layer was mixed with 5g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 140℃ for 1 hour to obtain phenolic resin.

[0116] Add 150g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 140℃. Add 55g of 50wt% NaOH solution dropwise (over 5 hours), and remove excess ECH after the reaction.

[0117] Product specifications: epoxy equivalent 188 g / eq, density 1.17 g / cm³, softening point 48 ℃.

[0118] Example 9: Add 40g of phenol-acetone tar, 20g of bisphenol A tar (mass ratio 2:1), 300g of toluene, and 0.4g of mercaptoacetic acid to a four-necked flask, and heat to 80°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise (dropping time 2.5h), and keep warm for 4.5h after the addition is complete. Post-treatment is the same as in Example 1.

[0119] The oil layer was mixed with 2g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 100℃ for 3.5h to obtain phenolic resin.

[0120] Add 90g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 80℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 2.5h), keep warm for 4.5h, and remove excess ECH after the reaction.

[0121] Product specifications: epoxy equivalent 212 g / eq, density 1.12 g / cm³, softening point 72℃.

[0122] Example 10: Add 20g of phenol-acetone tar, 40g of bisphenol A tar (mass ratio 1:2), 300g of ethanol, and 0.4g of dodecanethiol to a four-necked flask, and heat to 90°C. Add 5g of 30wt% sulfuric acid solution dropwise (dropwise over 3.5h), and maintain the temperature for 5.5h after the addition is complete. Post-treatment is the same as in Example 1.

[0123] The oil layer was mixed with 3g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 110℃ for 4.5h to obtain phenolic resin.

[0124] Add 120g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 100℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 3.5h), keep warm for 5.5h, and remove excess ECH after the reaction.

[0125] Product specifications: epoxy equivalent 198 g / eq, density 1.15 g / cm³, softening point 63℃.

[0126] Example 11: Add 150g of phenol-acetone tar, 10g of bisphenol A tar (mass ratio 15:1), 500g of toluene, and 0.7g of mercaptoacetic acid to a four-necked flask, and heat to 60°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise (dropwise over 4 hours), and maintain the temperature for 6 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0127] The oil layer was mixed with 1g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 60℃ for 6 hours to obtain phenolic resin.

[0128] Add 120g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 60℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 4h), keep warm for 6h, and remove excess ECH after the reaction.

[0129] Product specifications: Epoxy equivalent 235 g / eq, density 1.11 g / cm³ 3 , softening point 88℃.

[0130] Example 12: Add 10g of phenol-acetone tar, 150g of bisphenol A tar (mass ratio 1:15), 500g of ethanol, and 0.7g of 2-mercaptoethanol to a four-necked flask, and heat to 120°C. Add 5g of 30wt% phosphoric acid solution dropwise (over 4 hours), and maintain the temperature for 6 hours after the addition is complete. Post-treatment is the same as in Example 1.

[0131] The oil layer was mixed with 4g of paraformaldehyde, and 0.5g of oxalic acid was added. The mixture was reacted at 120℃ for 6 hours to obtain phenolic resin.

[0132] Add 420g ECH and 10g tetrabutylammonium bromide to phenolic resin and react at 120℃. Add 55g of 50wt% NaOH solution dropwise (dropwise over 4h), keep warm for 6h, and remove excess ECH after the reaction.

[0133] Product specifications: Epoxy equivalent 190 g / eq, density 1.17 g / cm³ 3 , softening point 53 ℃.

[0134] Comparative Example 1: Add 50g of phenol-acetone tar, 0g of bisphenol A tar, 200g of phenol, and 0.2g of mercaptoacetic acid to a four-necked flask, and heat to 100°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise for 30 minutes, and maintain the temperature for 4 hours. Post-treatment is the same as in Example 1. Mix the oil layer with 1g of paraformaldehyde, add 0.5g of oxalic acid, and react at 95°C for 3 hours. Phenolic resin is obtained. Subsequent steps are the same as in Example 1.

[0135] Product specifications: Epoxy equivalent 350 g / eq, density 1.18 g / cm³ 3 , softening point 38℃.

[0136] Comparative Example 2: Add 0g of phenol-acetone tar, 50g of bisphenol A tar, 200g of phenol, and 0.2g of mercaptoacetic acid to a four-necked flask, and heat to 100°C. Add 5g of 30wt% p-toluenesulfonic acid solution dropwise for 30 minutes, and maintain the temperature for 4 hours. Post-treatment is the same as in Example 1. Mix the oil layer with 1g of paraformaldehyde, add 0.5g of oxalic acid, and react at 95°C for 3 hours. Phenolic resin is obtained. Subsequent steps are the same as in Example 1.

[0137] Product specifications: Epoxy equivalent 250 g / eq, density 1.28 g / cm³ 3 The softening point cannot be measured.

[0138] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for the comprehensive utilization of phenolic tar and bisphenol A tar, the method comprising: In the presence of a catalyst, phenolic tar and bisphenol A tar react to yield an intermediate product containing polyphenols. The intermediate product was mixed with formaldehyde to synthesize phenolic resin. Phenolic epoxy resin is synthesized by reacting phenolic resin with epichlorohydrin. The weight ratio of phenolic tar to bisphenol A tar is 20:1 to 1:

20. The phenol-ketone tar contains: phenol, acetophenone, 4-cumylphenol, 2-cumylphenol, α,α-dimethylbenzyl alcohol, β-methylphenylethanol, and α-methylstyrene dimer. The bisphenol A tar contains: phenol, bisphenol A, bisphenol A isomers, diphenols, and isopropylphenol.

2. The method as described in claim 1, characterized in that, The weight ratio of phenolic tar to bisphenol A tar is 10:1 to 1:

10.

3. The method as described in claim 1, characterized in that, The catalyst is an acidic catalyst.

4. The method as described in claim 3, characterized in that, The catalyst is selected from one or more of the following: oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid.

5. The method as described in claim 1, characterized in that, The process for preparing the intermediate product also includes a co-catalyst selected from one or more of the following: mercaptoacetic acid, 3-mercapto-1-propanesulfonic acid, 1-dodecylthiol, 2-mercaptoethanol, and 2-mercaptopyridine.

6. The method of claim 1, wherein the method comprises the following steps: (1) Add phenol ketone tar and bisphenol A tar to a reaction flask, add solvent and co-catalyst, add acid catalyst, collect the oil layer after reaction, and synthesize intermediate products containing polyphenols. (2) The oil layer from step (1) is mixed with formaldehyde, and a catalyst is added to synthesize phenolic resin; (3) Phenolic resin is reacted with epichlorohydrin, alkali and phase transfer catalyst to synthesize phenolic epoxy resin.

7. The method as described in claim 6, characterized in that, In step (1): The reaction temperature range is 40-150℃; The acidic catalyst is added over a period of 0.5-6 hours. The reaction time is 1-8 hours; The solvent is selected from one or more of the following: benzene, phenol, toluene, xylene, n-hexane, methanol, ethanol, and isopropanol; The weight ratio of solvent usage to the sum of the weights of the two types of tar is 2:1 to 5:

1. The acidic catalyst is an organic acid or an inorganic acid; The amount of acidic catalyst used is 0.7-15% of the weight of phenol-acetone tar; The co-catalyst is selected from one or more of the following: mercaptoacetic acid, 3-mercapto-1-propanesulfonic acid, 1-dodecylthiol, 2-mercaptoethanol, and 2-mercaptopyridine; The amount of co-catalyst used is 0.5-6% of the weight of phenol tar.

8. The method as described in claim 7, characterized in that, In step (1): The acidic catalyst is selected from one or more of the following: oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid.

9. The method as described in claim 7, characterized in that, In step (1): The reaction time is 2-4 hours.

10. The method as described in claim 6, characterized in that, In step (2): Formaldehyde is a 10-40% by weight aqueous solution or solid formaldehyde; The amount of formaldehyde used is 0.4-6% of the weight of the product obtained in step (1); The catalyst is a protic acid or Lewis acid; The amount of catalyst used is 0.5-10% by weight of the oil layer in step (1). The reaction temperature range is 40℃-160℃; The reaction time is 1-8 hours.

11. The method as described in claim 10, characterized in that, In step (2): The reaction time is 2-4 hours.

12. The method as described in claim 10, characterized in that, In step (2): The catalyst is oxalic acid.

13. The method as described in claim 6, characterized in that, In step (3): The consumption of epichlorohydrin is 0.7-1.5 times the molar amount of the phenolic hydroxyl groups in the system; The phase transfer catalyst is one or more of the following: quaternary ammonium salt, quaternary phosphine salt, imidazole salt, pyridinium salt, and piperidine salt; The amount of phase transfer catalyst used is 0.5-5% by weight of the obtained phenolic resin. The reaction temperature is 40-150℃; The alkali is a 10-50 wt.% sodium hydroxide aqueous solution; The amount of alkali used is 5-25% by weight of the phenolic resin. The alkali is added over a period of 0.5-6 hours. The reaction time is 1-8 hours.

14. The method as described in claim 13, characterized in that, In step (3): The phase transfer catalyst is tetrabutylammonium bromide.