Preparation method of environment-friendly phenolic reinforced resin

Abstract

Relates to the technical field of high polymer materials, in particular to a preparation method of environment-friendly reinforced phenolic resin, and aims to overcome the defects and provide the preparation method of the environment-friendly reinforced phenolic resin. Part of cardanol is used for replacing phenol and reacts with aldehydes to synthesize a matrix, then tall oil is added to improve the softening point, and the problem that the production curing speed is high due to the high biomass content is solved from the technical perspective.

Description

Technical Field

[0001] The invention relates to a method for preparing an environmentally friendly reinforced phenolic resin. Background Art

[0002] The rubber of some parts of the tire has certain requirements for hardness. In order to obtain higher hardness while meeting processing requirements, 10 to 20 parts of organic resin are usually used to replace part of the carbon black. The rubber can not only obtain better mechanical properties, but also because the resin has the functions of softener and plasticizer. The commonly used reinforcing agents are pure phenolic reinforcing resin, cashew oil modified phenolic resin and tall oil modified phenolic resin. In the production process of phenolic resin, oil modifiers such as tall oil, cashew oil, tung oil, etc. are often added to improve the solubility of the resin in rubber, thereby increasing the compatibility between the resin and rubber.

[0003] As the chemical industry is now tending towards green development, environmentally friendly products have become the industry's trend. How to strike a balance between chemical production and environmental protection has become a research topic for many companies. Commonly used modifiers for phenolic resins are derived from organisms themselves and are renewable resources, so they can increase the biomass content in the resin. The biomass content in existing oil-modified phenolic resins is less than 50%. In the modification of a single biomass oil, excessive addition will result in poor product plasticity, easy cross-linking and other unstable product quality, which brings difficulties to process production. Summary of the invention

[0004] The first object of the present invention is to overcome the above disadvantages and provide a method for preparing an environmentally friendly reinforced phenolic resin. By replacing phenol with a portion of cardanol to react with aldehydes to synthesize a matrix, and then adding tall oil to increase the softening point, the problem of high production curing speed caused by high biomass content is solved from a technical perspective.

[0005] The second purpose of the present invention is to increase the organic biomass content to more than 60%, reduce the use of inorganic substances from petrochemical resources, and save energy and reduce consumption through technological innovation.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted: The present invention provides a method for preparing biomass-modified phenolic resin powder, comprising the following steps: (A) phenol, cashew nut shell phenol, an acidic catalyst and formaldehyde are subjected to a reflux reaction to obtain a reaction liquid, and the reaction liquid is subjected to reduced pressure distillation to obtain a resin matrix; (B) the above resin matrix, tall oil, and an acid catalyst are reacted and dehydrated to obtain; Furthermore, in step (A), the mass ratio of the phenol to the cardanol is 1:1.0-1.5.

[0007] Furthermore, in step (A), the molar ratio of the phenol to the formaldehyde is 1:0.5-0.8.

[0008] Preferably, the mass ratio of the phenol to the acidic catalyst is 1:0.01 to 0.03.

[0009] Furthermore, in step (A), the reduced pressure distillation includes reduced pressure distillation to a softening point of 65-75° C. in the reaction solution.

[0010] Furthermore, in step (A), the reflux reaction time is 3 to 5 hours.

[0011] Furthermore, in step (B), the mass ratio of the resin matrix to the tall oil is 1:0.2-0.4.

[0012] Preferably, the mass ratio of the resin matrix to the acid catalyst is 1:0.005-0.03.

[0013] Furthermore, in step (B), the reaction temperature is 140-170° C.; and the reaction time is 2-3 h.

[0014] Furthermore, the acidic catalyst includes one or more of oxalic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and glacial acetic acid.

[0015] Compared with the prior art, the present invention has the following beneficial effects: In the preparation method of high biomass modified phenolic resin provided by the present invention, phenol, cashew nut shell phenol, acid catalyst and formaldehyde are refluxed for 3 to 5 hours, and a resin matrix is ​​obtained after reduced pressure distillation; the resin matrix, tall oil and acid catalyst are reacted at 140 to 170°C, and dehydrated to obtain high biomass modified phenolic resin. Cardanol is used to replace part of phenol, which reduces the use of petrochemical energy, improves environmental pollution problems and saves costs; the side chain of cardanol contains an unsaturated fatty chain, and the long olefin chain can enhance the toughness of the phenolic resin; tall oil is then added, which has more active points, fast curing and improved production rate. DETAILED DESCRIPTION

[0016] The technical solution of the present invention will be clearly and completely described below in conjunction with specific implementation methods. The embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments, and are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Example 1

[0017] The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100° C., 259 g of a 42 wt % formaldehyde aqueous solution was added dropwise for 1 h. After the addition was completed, the mixture was refluxed at 100° C. for 3 h to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 67° C.

[0018] (B) 180 g of tall oil and 6 g of p-toluenesulfonic acid were added to the matrix, reacted at 140° C. for 3 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin. Example 2

[0019] The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100° C., 259 g of a 42 wt % formaldehyde aqueous solution was added dropwise for 1 h. After the addition was completed, the mixture was refluxed at 100° C. for 3 h to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 67° C.

[0020] (B) 180 g of tall oil and 6 g of p-toluenesulfonic acid were added to the matrix, reacted at 155° C. for 2.5 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin. Example 3

[0021] The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100° C., 259 g of a 42 wt % formaldehyde aqueous solution was added dropwise for 1 h. After the addition was completed, the mixture was refluxed at 100° C. for 3 h to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 67° C.

[0022] (B) 180 g of tall oil and 6 g of p-toluenesulfonic acid were added to the matrix, reacted at 170° C. for 2 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin. Example 4

[0023] The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100° C., 259 g of a 42 wt % formaldehyde aqueous solution was added dropwise for 1 h. After the addition was completed, the mixture was refluxed at 100° C. for 3 h to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 67° C.

[0024] (B) 180 g of tall oil and 6 g of dodecylbenzene sulfonic acid were added to the matrix, reacted at 155° C. for 2.5 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin. Example 5

[0025] The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100° C., 259 g of a 42 wt % formaldehyde aqueous solution was added dropwise for 1 h. After the addition was completed, the mixture was refluxed at 100° C. for 3 h to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 67° C.

[0026] (B) 180 g of tall oil and 6 g of oxalic acid were added to the matrix, reacted at 170° C. for 2 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin.

[0027] Comparative Example 1 The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: 300 g of phenol, 300 g of cardanol and 9 g of oxalic acid were placed in a reaction container, heated to 100°C, and 259 g of a 42 wt% formaldehyde aqueous solution was added dropwise for 1 hour. After the addition was completed, the mixture was refluxed at 100°C for 3 hours to obtain a reaction solution, which was then distilled under reduced pressure until the softening point of the reaction matrix was 90-100°C.

[0028] Comparative Example 2 The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol and 9 g of oxalic acid are placed in a reaction container, heated to 100°C, and 259 g of a 42 wt% formaldehyde aqueous solution is added dropwise for 1 hour. After the addition is completed, the reaction is refluxed at 100°C for 3 hours to obtain a reaction liquid, and the reaction liquid is distilled under reduced pressure until the softening point of the reaction matrix is ​​65-75°C.

[0029] (B) 180 g of tall oil and 6 g of oxalic acid were added to the matrix, reacted at 170° C. for 2 hours, and solidified after dehydration under reduced pressure.

[0030] Comparative Example 3 The method for preparing the environmentally friendly reinforced phenolic resin powder provided in this embodiment comprises the following steps: (A) 300 g of phenol and 9 g of oxalic acid are placed in a reaction container, heated to 100°C, and 259 g of a 42 wt% formaldehyde aqueous solution is added dropwise for 1 hour. After the addition is completed, the reaction is refluxed at 100°C for 3 hours to obtain a reaction liquid, and the reaction liquid is distilled under reduced pressure until the softening point of the reaction matrix is ​​65-75°C.

[0031] (B) 180 g of tall oil and 10 g of oxalic acid were added to the matrix, reacted at 170° C. for 2 hours, and dehydrated under reduced pressure to a softening point of 90-100° C. to obtain a high biomass modified phenolic resin.

[0032]

[0033] It can be seen from the above table that the softening point and appearance of the environmentally friendly reinforced phenolic resin prepared by the present invention meet the design requirements; the biomass content is increased while solving the problem of unstable product production quality.

Claims

1. A method for preparing an environmentally friendly phenolic reinforced resin, characterized by comprising the following components, in weight parts. The amount of phenol is 50-100 parts; the amount of cardanol is 50-100 parts; the amount of the catalyst is 0.1-5 parts; the amount of 37% formaldehyde water solution is 30-90 parts; the amount of the compounded tall oil is 1-100 parts; the amount of the terminator is 0.1-5 parts; The preparation method is as follows: (1) heating 70-100 parts of phenol, 70-100 parts of cardanol, and 0.2-2 parts of a catalyst to 80-100° C., adding 40-80 parts of a 37% formaldehyde aqueous solution dropwise over 10-120 minutes, continuing to reflux for 10-120 minutes, then heating to 120-150° C., and dehydrating for 10-120 minutes to obtain a resin matrix; (2) adding 20-60 parts of compounded tall oil to the resin matrix, heating to 160-200° C. and vacuuming for 10-120 minutes, adding 0.2-2 parts of a terminator and stirring for 5-15 minutes, and then vacuum dehydrating for 5-60 minutes to obtain a high biomass modified phenolic resin; (3) Among them, In step 2), compounded tall oil is added to the resin matrix. Rosin and fatty acid may be added to the resin matrix separately, or the rosin and fatty acid may be mixed before adding to the resin matrix.

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