Machine Translated by Google

Material Sciences , 2022, 12(10), 965-971 Published Online October

2022 in Hans. http://www.hanspub.org/journal/ms https://doi.org/10.12677/ms.2022.1210108

Research and Application of Modified Phenolic Resin Composite Material

Zhang Boyu 1 , Li Yakun 1* , Wang Yanming 1 , Zhang Zhixiao 1 , Li Ping 1 , Zhang Xiaoliang 1 , Wang Guangshuo 1,2,3*

1
School of Materials Science and Engineering, Hebei Engineering University, Handan,
2
Hebei Hebei Engineering University, Hebei Province Modified Plastics Technology Innovation Center,
3
Handan Hebei Engineering University, Handan Key Laboratory of New Inorganic Non-metallic Composite Materials, Handan, Hebei

Date of receipt: September 20, 2022; date of acceptance: October 16, 2022; date of publication: October 25, 2022

Summary

Phenolic resin materials are widely used in daily life and engineering because of their low production cost, readily available raw materials, and simple production process. However, with the

advancement of science and technology and the improvement of use requirements, traditional phenolic resin materials are severely limited in the field of high-performance engineering materials.

Therefore, it has become an inevitable trend to compound and modify phenolic resins to prepare composite materials with excellent properties and various forms. This paper mainly systematically

expounds the research status and application of phenolic resin-based composite materials.

Key words

Phenolic resin, composite material, research progress, application

Study and Application of Modified Phenolic

Resin Composites
Boyu Zhang1, Yakun Li1*, Yanming Wang1, Zhixiao Zhang1, Ping Li1, Xiaoliang Zhang1,
Guangshuo Wang1,2,3*
1
School of Materials Science and Engineering, Hebei University of Engineering, Handan Hebei
2
Technology Innovation Center of Modified Plastics of Hebei Province, Hebei University of Engineering,
Handan Hebei
3
Key Laboratory of New Inorganic Nonmetallic Composite of Handan, Hebei University of Engineering,
Handan Hebei

Received: Sep. 20th, 2022; accepted: Oct. 16th, 2022; published: Oct. 25th, 2022

Abstract

Phenolic resin materials are widely used in daily life and engineering fields due to their low pro-
*
Corresponding Author.

Citation: Zhang Boyu, Li Yakun, Wang Yanming, Zhang Zhixiao, Li Ping, Zhang Xiaoliang, Wang Guangshuo. Research and Application of Modified Phenolic Resin
Composites[J]. Materials Science, 2022, 12(10): 965-971. DOI: 10.12677 /ms.2022.1210108
Machine Translated by Google

Zhang Boyu and others

duction cost, easy availability of raw materials and simple production process. However, with the progress of science
and technology and the improvement of application requirements, traditional phenolic resin materials can no longer
meet the requirements of high-performance engineering materials. Therefore, it is an inevitable trend to composite
modify phenolic resin to prepare com posite materials in various forms. In this paper, the research status and
application of phenolic re sin matrix composites are systematically described.

Keywords

Phenolic Resin, Composite Materials, Research Progress, Application

Copyright © 2022 by author(s) and Hans Publishers Inc.

This work is licensed under the Creative Commons Attribution International License (CC BY 4.0). http://creativecommons.org/
licenses/by/4.0/
Open Access

1. Research status of phenolic resin-based composite materials

1.1. Brief Introduction of Phenolic Resin

Phenolic resin is mainly formed by polycondensation of phenol and formaldehyde, and its molecular structure is shown in Figure 1 . Phenolic resin was first

accidentally prepared by German scientist Bayer in the 1880s. He mixed phenol and formaldehyde to obtain a fluid product, but Bayer did not conduct research and

discussion on this product until the 19th century. Bloomer began to use tartaric acid as a catalyst on the basis of the German chemist Bayer, and successfully produced

phenolic resin, but due to factors such as complicated operation and high cost, it did not realize industrialization. Until the 1920s, the American scientist Buckland

opened the first year of phenolic resin, because he noticed the chemical product of phenolic resin, and through systematic discussion and research on phenolic resin,

he finally proposed that phenolic resin "pressurization, heating "The curing method, and with its successful patent application, laid the foundation for the development of

phenolic resin in the future, and the development of this type of resin has entered the fast lane since then.

Figure 1. Molecular structure formula of phenolic resin

1.2. Research on modified phenolic resin

However, with the development of science and technology, scientists have found that traditional phenolic resin materials are increasingly unable to meet the needs of new industries.

Therefore, the concept of modified phenolic resin was proposed, that is, using phenolic resin as a matrix, adding a reinforcing phase, through the enhanced phase. performance to enhance the

performance of phenolic resin. Traditional phenolic resin has remarkable heat resistance and oxidation resistance due to the introduction of rigid groups such as benzene rings in the matrix, but it

also has many shortcomings. During the preparation, because the phenolic hydroxyl group is easily oxidized, it does not participate in the reaction during the process, so there will be many phenolic

hydroxyl groups in the finished product, resulting in impure product. Moreover, the polarity of the phenolic hydroxyl group is also very strong, and it is easy to attract each other with water. Under the

action of water, it is easy to make the strength of the phenolic resin product very low, and the electrical conductivity is also very poor. Especially when exposed to the sun for a long time, it is very

easy to change the phenolic resin, resulting in discoloration and increased brittleness of the material. These shortcomings limit the application of phenolic resin to a large extent, so the phenolic resin is modified to

DOI: 10.12677/ms.2022.1210108 966 material science

Machine Translated by Google

Zhang Boyu and others

It is very necessary to improve these shortcomings. The shortcomings of high brittleness and poor conductivity of phenolic formaldehyde can be changed by adding materials with high hardness or high conductivity

as reinforcing phases. It is also possible to increase the viscosity of the reinforcing phase material to improve the bonding performance of the phenolic resin. Engineering often uses blocking phenolic hydroxyl to

prevent it from being oxidized in contact with air, or introducing other components, or introducing other heteroatoms such as oxygen, nitrogen, and sulfur into the polymer chain [1] [2]. At present, the modification of

phenolic resin mainly includes polyvinyl acetal resin, epoxy modified phenolic resin, silicone modified phenolic resin, boron phenolic resin, aralkyl ether formaldehyde resin and the like.

1.3. Polyvinyl acetal resin

Polyvinyl acetal resin is currently improved by introducing other components. The principle is mainly to produce polyvinyl acetal by condensation of polyvinyl alcohol and aldehyde under acidic conditions.

The main purpose is that polyvinyl alcohol is water-soluble. After the condensation of sex and aldehyde, it can be prevented from being dissolved by water. Afterwards, it is mixed and reacted with phenolic resin under

certain conditions, so that the hydroxyl groups in the phenolic resin and the polyvinyl acetal are combined to carry out polycondensation to remove a molecule of water to form a graft copolymer. Due to the introduction

of flexible groups, the added polyvinyl acetal can enhance the toughness of the phenolic resin and reduce the solidification speed of the phenolic resin, so it can reduce the molding pressure of polyvinyl acetal resin

products, but the only The disadvantage is that the heat resistance of polyvinyl acetal resin products will be reduced. Therefore, the modified phenolic resin is often used in injection plastics and other fields

[3] [4]ÿ

1.4. Epoxy modified phenolic resin

The epoxy-modified phenolic resin is usually prepared by using a diphenolic propane type (referred to as bisphenol A) epoxy resin as a reinforcing phase and a phenolic resin as a matrix. It is mainly the

etherification reaction between the phenolic hydroxyl group in the phenolic resin and the hydroxyl group in the bisphenol A epoxy resin, so that the hydroxyl group in the phenolic resin and the hydroxyl group in the

bisphenol A epoxy resin are combined with each other, and a molecule of water is removed. , forming an ether bond. After that, the methylol group in the phenolic resin and the epoxy group at the end of the bisphenol

A epoxy resin undergo a ring-opening reaction to form a body structure. It can also be said that the curing effect of the bisphenol A epoxy resin is stimulated by the phenolic resin. Further structural changes occurred.

Due to its complex structure, the modified resin will have good adhesion and toughness. Moreover, the modified product also has the heat resistance of bisphenol A epoxy resin, so it can be seen that the two

materials complement each other and improve each other. Therefore, the material is mainly used in the fields of molding, adhesives, coatings, etc. [5].

1.5. Silicone modified phenolic resin

Silicone-modified phenolic resin uses silicone as a reinforcing phase, because of the presence of silicon-oxygen bonds in silicone, silicone has good heat resistance, and the heat resistance is much higher

than that of general polymer materials, but Silicone has poor adhesion. Therefore, silicone can be introduced to enhance the heat resistance of phenolic resin. The principle is mainly that the organic silicon monomer

reacts with the phenolic hydroxyl group in the phenolic resin to form a cross-linked structure. Due to this special cross-linking structure, the new composite material has good heat resistance and toughness after

modification. And after testing, the material can work for a long time at high temperature, so it is generally used in rockets or missiles that require high temperature resistant materials [6] [7].

1.6. Boron phenolic resin

Boron phenolic resin was first proposed by the United States and began to be studied. Its only feature is the introduction of the flexible bond -BO- in the phenolic resin molecule.

The reaction between boric acid and phenol under certain conditions generates boric acid phenol ester with a certain molecular weight, and then boric acid aldehyde resin is formed under the action of formaldehyde

aqueous solution solidification. Since the flexible bond -BO- is introduced into the resin molecule, the toughness of the traditional phenolic resin material can be enhanced after modification, and its brittleness factor

can be improved. Moreover, the hydrogen atoms in the phenolic hydroxyl group are replaced by boron, the polarity decreases, and the compatibility with water, a polar molecule, becomes poor, resulting in improved

water resistance of the new material. At the same time, the three-way cross-linked structure of the material leads to an improvement in the toughness and high temperature resistance of the material compared with

the phenolic resin material [8].

1.7. Aralkyl ether formaldehyde resin

The aralkyl ether formaldehyde resin adopts the introduction of a rigid group-aryl group on the phenolic ring. Due to its steric hindrance effect, it has a shielding effect on the bond, resulting in

DOI: 10.12677/ms.2022.1210108 967 material science

Machine Translated by Google

Zhang Boyu and others

The resin has the characteristics of alkali resistance and high mechanical strength. The principle is to treat the two alkyl groups of aromatic hydrocarbons with chlorine gas, so that each of the two

methyl groups has a chlorine atom, then put them into methanol to etherify them, and finally perform ether exchange under the condition of phenol as a catalyst to generate The aralkyl ether

compound with two phenolic rings can be solidified with methane under certain conditions and cross-linked to form a macromolecule aralkyl ether formaldehyde resin. The resin is characterized by

a fast curing speed, and the products made of it are heat-resistant and moisture-resistant. Therefore, it can be used in high temperature resistant parts such as rocket casings and engines.

Phenolic resin is mainly modified by the above several ways. Like epoxy modified phenolic resin, silicone modified phenolic resin, polyvinyl alcohol

Modified resins such as acetal resins can be modified on the basis of phenolic resins. Aldehydes or phenols can also be used to synthesize other substances first, and then react with phenols

or aldehydes to indirectly generate modified resins, such as boron phenolic resins and xylene modified phenolic resins. Or without the participation of phenol, it can first generate a first-order

phenolic resin, and then undergo a reaction to generate a second-order phenolic resin, such as diphenyl ether formaldehyde resin [9].

2. Application of phenolic resin and its composite materials

Modified phenolic resin improves the shortcomings of phenolic resin such as poor heat resistance and low mechanical strength, and has good mechanical properties, strong heat resistance, and strong adhesion

It is widely used in compression molding powder, coating, solid glue, fiber, anti-corrosion, heat preservation and other fields[10].

2.1. Application of modified phenolic resin in compression molding powder

Compression molding powder is an indispensable thing for the production of molded products. It is mainly made of modified phenolic resin. In industry, the rolling method and the double-

screw extrusion method are often used to infiltrate the resin with wood as a filler. Then add other reagents, mix evenly, and obtain compression molding powder after crushing. In order to prepare

compression molding powder with strong insulation performance and heat resistance, materials such as quartz can be added. Compression molding powder is one of the raw materials for preparing

various plastic products. Various plastic products can be prepared industrially by injection molding or compression molding. Figure 2. The application of modified phenolic resin in compression

powder. The compression molding powder made of thermoplastic modified phenolic resin is mainly used for electrical parts such as electric switches and daily necessities plugs. Thermosetting

modified phenolic resin compression molding powder can be used to manufacture products that require high insulation properties [11].

Figure 2. Application of modified phenolic resin in compression molding powder

2.2. Application of modified phenolic resin in coating field

Phenolic resins have been used in the field of coatings for 70 years. In the field of phenolic coatings, phenolic resins modified with rosin or p-tert-butylphenolic resins are mainly formulated.

Because rosin-modified phenolic resin and tert-butylphenolic resin have good miscibility to tung oil, they can be miscible to formulate high-performance paint. Phenolic resin can improve the acid

resistance and heat resistance of coatings, and is widely used in various engineering fields, but its unique yellow color makes it unsuitable for making light-colored coatings. In addition to mixing

with tung oil, it can also be mixed with other resins

DOI: 10.12677/ms.2022.1210108 968 material science

Machine Translated by Google

Zhang Boyu and others

use. If you want to increase the alkali resistance and air-dried hardness of the coating, you can add alkyd resin to improve the alkali resistance and hardness of the coating, or if you need a

coating that is resistant to acid and alkali and has good adhesion, you can mix epoxy resin into the coating to improve the coating. performance. Therefore, the important raw materials of

coatings in the factory are all phenolic coatings made of modified phenolic resins. Figure 3 shows the application of modified phenolic resins in coatings.

Figure 3. Application of modified phenolic resin in coatings

2.3. Application of modified phenolic resin in the field of phenolic adhesive

Phenolic adhesive is a kind of adhesive. Its raw material is mainly modified thermosetting phenolic resin, among which phenolic-butyronitrile and phenolic-acetal are the main ones.

These two types of adhesives play a pivotal role in the adhesive field. If you want to use phenolic resin as a raw material to prepare an adhesive, it will greatly limit the use of the phenolic

adhesive made because of the poor viscosity of the phenolic resin, so it can only be used for bonding plywood. However, the phenolic adhesive modified with high polymer has significantly

improved heat resistance and adhesion, and even the phenolic-nitrile adhesive has strong mechanical strength and toughness, mainly in terms of impact resistance[ 12].

2.4. Application of modified phenolic resin in fiber

Phenolic resin is also widely used in the field of fibers. Using phenolic resin as a raw material, it is melted and drawn, and put into polyoxymethylene for treatment. After a period

of time, the filamentous phenolic resin will solidify, and then obtain a fiber with a body structure. If you want to further enhance the strength and modulus of the fiber, you can mix it with

molten low-concentration polyamide and then draw it to prepare a modified phenolic resin spinning, as shown in Figure 4 . Usually, the spun fiber is yellow in color and has high strength,

and the phenolic fiber will not melt and burn even if it is placed at a temperature of 8000 degrees. And it will extinguish itself in this harsh environment, preventing the occurrence of fire at

the root. At room temperature, the phenolic resin fiber modified by polyamide has strong resistance to concentrated hydrochloric acid and hydrofluoric acid, but poor resistance to strong

acids and alkalis such as sulfuric acid and nitric acid. This type of product is mainly used for factory protective clothing or interior decoration of factory buildings to minimize the probability of

employee injury and death in the event of a fire. It is also often used as insulation and heat insulation materials in engineering [13].

2.5. Application of modified phenolic resin in anticorrosion materials

Anti-corrosion materials are also the application of phenolic resins in engineering, but the most common anti-corrosion materials are modified phenolic resins, because they have

better moisture resistance and acid and alkali resistance than single phenolic resins. Mainly based on phenolic resin cement, phenolic-epoxy resin composite glass fiber reinforced plastics,

and phenolic-epoxy coatings. Taking phenolic-epoxy coatings as an example, this type of anti-corrosion coating has both the good acid resistance of phenolic resin and the alkali resistance

and adhesion of epoxy resin, so it is widely used in the anti-corrosion of pipeline surfaces and vehicle surfaces [14].

DOI: 10.12677/ms.2022.1210108 969 material science

Machine Translated by Google

Zhang Boyu and others

Figure 4. Application of modified phenolic re sin in fibers

2.6. Application of modified phenolic resin in the field of thermal insulation materials

Since the heat resistance of modified phenolic resin is stronger than that of pure phenolic resin, the foaming material of modified phenolic resin is used in heat insulation materials.

Domains dominate, as shown in Figure 5 . At the same time, the modified phenolic resin foam material also has the characteristics of heat preservation, heat insulation, light weight, and low spontaneous combustion, and

when it encounters a flame, the material does not drip, which can effectively prevent the fire from spreading. Therefore, this material is widely used in thermal insulation color steel plate, room insulation layer, central air

conditioner and pipelines that need to keep low temperature. At present, polystyrene foam is the most widely used insulation material on the market, but its performance is far inferior to that of modified phenolic resin foam.

Modified phenolic foam has the characteristics of poor thermal conductivity and good thermal insulation effect, and has been dubbed the title of "king of thermal insulation" in the thermal insulation industry. In addition, phenolic

foam also has the advantages of stable chemical properties, strong acid and alkali resistance, high mechanical strength, and not easily damaged. Moreover, phenolic foam has rich raw materials, simple production process,

and is very cheap, so it is widely used [15].

Figure 5. Application of modified phenolic resin in thermal insulation materials

3. Conclusion

Since the advent of phenolic resin, it has been favored by various fields, but with the advancement of science and technology, the performance of traditional phenolic resin has become more and more unsatisfactory.

DOI: 10.12677/ms.2022.1210108 970 material science

Machine Translated by Google

Zhang Boyu and others

meet the requirements of modern technology. Therefore, the modified phenolic resin is used to prepare modified phenolic resin-based composite materials with different properties.

Especially in the aspects of reinforcement, flame retardancy, low smoke and molding applicability, it can be used in thermal insulation, anti-corrosion, electronics, aerospace and other fields.

The domain shows its talents.

references
[1] He Dong, Qi Shuhua, Cheng Bo, Malina. Research Progress of Nanomaterials Modified Phenolic Resin [J]. China Adhesives, 2011, 20(4): 58-62. [2] Cai Xueguang,

Liu Xiaohui, Zhang Dayong , Rong Liping, Zhao Ying, Wang Gang, Zhu Jinhua, Li Xin, Mi Changhong. Effect of cardanol-modified phenolic resin on resin preparation process

Research on the Effect of Bonding Properties[J]. Chemistry and Adhesion, 2019, 41(6): 412-416.

[3] Xiong, J.M., Li, Y.C., Wang, W.Q. and Xia, C. (2009) Preparation of Montmorillonite Modified Phenolic Resin for
Shell Process. China Foundry, 2, 119-123.

[4] Zhu Baohua. Influence of polyvinyl butyral resin forming process on product quality [J]. Anhui Science and Technology, 2017(3): 52-53. [5] Xia Tao,

Wang Zhuang, Huang Ying, Yuwen Hongjuan, Shi Xiaomin. Preparation and Properties of Epoxy Modified Phenolic Resin Nanocomposites[J]. New Chemical Materials,

2019, 47(12): 66-70.

[6] Li, C., Ma, Z.Z., Zhang, X.W., Fan, H. and Wan, J.T. (2016) Silicone-Modified Phenolic Resin: Relationships between Molecular Structure and Curing Behavior. Thermochimica Acta, 639,
53-65. https://doi.org/10.1016/j.tca.2016.07.011

[7] Liu Chenglin, Zhou Chuanjian, Zhao Xinxin, Zhang Chen, Chen Guowen. Research Progress of Silicone Modified Phenolic Resin[J]. Silicone Materials, 2014, 28(5): 395-402.

[8] Yun, J., Chen, L.X., Zhao, H., Zhang, X.F., Ye, W.L. and Zhu, D.F. (2019) Boric Acid as a Coupling Agent for Prepa ration of Phenolic Resin Containing Boron and Silicon with Enhanced
Char Yield. Macromolecular Rapid Communi cations, 40, Article ID: 1800702. https://doi.org/10.1002/marc.201800702

[9] Wang Yanan, Li Zhao, Cao Jing, Wu Kunyao. Research progress on pyrolysis and carbonization of phenolic resin and boron-containing phenolic resin [J]. Modern Chemical Industry, 2021, 50(9):
2235-2241.

[10] Sun Xin, Wang Gang, Ling Fang. Research progress and development trend of phenolic resin [J]. Shanghai Chemical Industry, 2022, 47(1): 59-63.

[11] Wang, B., Shi, M.X., Ding, J. and Huang, Z.X. (2021) Polyhedral Oligomeric Silsesquioxane (POSS)-Modified Phe
nolic Resin: Synthesis and Anti-Oxidation Properties. e-Polymers, 21, 316-326.

https://doi.org/10.1515/epoly-2021-0031
[12] Gao Hongna, Shen Pengfei, Li Shen, Sui Chengxiang, Shen Dejun. Research on the production of outdoor plywood with modified phenolic glue[J]. Science and Technology Innovation and Application, 2016(18):
74.

[13] Liu Can, Ren Yu, Li Xin, Liu Jianxiang, Shi Zhengjun, Zheng Zhifeng. Preparation of high-ortho phenolic resin fibers from eucalyptus biomass[J]. Forest Products Chemistry and Industry,

2020, 40(6): 70-76.

[14] Lu Gang. Performance characteristics and application prospects of epoxy resin anticorrosion materials [J]. Chemical Industry, 2015, 33(9):

23-26+40. [15] Wang Zhenfei, Zhao Ren, Shang Pan. Building exterior Modification of phenolic resin foam for wall insulation [J]. Contemporary Chemical Research, 2019(12): 104-105.

DOI: 10.12677/ms.2022.1210108 971 material science