WO2021031343A1

WO2021031343A1 - Phosphorus-containing flame-retardant low-thermal-expansion coefficient epoxy resin, preparation method and use thereof

Info

Publication number: WO2021031343A1
Application number: PCT/CN2019/114286
Authority: WO
Inventors: 朴龙星; 吴涛; 夏宇; 徐伟红
Original assignee: 苏州巨峰电气绝缘系统股份有限公司
Priority date: 2019-08-22
Filing date: 2019-10-30
Publication date: 2021-02-25
Also published as: CN112409572A

Abstract

The present invention relates to a phosphorus-containing flame-retardant low-thermal-expansion coefficient epoxy resin, and a preparation method, an involved intermediate and use thereof, and belongs to the technical field of resin materials. The key points of the technical solution of the present invention are that at least one phosphorus-containing compound and at least one aromatic compound are used as raw materials to prepare the intermediate, which is added with epichlorohydrin and polymerized in the presence of an alkali catalyst to obtain the phosphorus-containing flame-retardant low-thermal-expansion coefficient epoxy resin with a high phosphorus content, a good flame retardancy, a low dielectric constant and a low-thermal-expansion coefficient. The epoxy resin can be used in high-reliability electrical electronic materials, PCB plates and insulating plates requiring excellent low-thermal-expansion coefficients, flame retardancy, heat resistance and low dielectric properties, as well as other fields such as composites, adhesives, coating agents, and coatings that require related properties.

Description

Phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin and preparation method and application thereof

This application claims the priority of the invention patent application with the application number 201910780180.2 filed with the State Intellectual Property Office of China on August 22, 2019. The content of the priority text is expressly incorporated into this application by reference.

Technical field

The invention relates to the technical field of resin materials, and more specifically, it relates to a phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, a preparation method thereof, and related intermediate products and applications.

Background technique

At present, plastics are widely used in various industrial fields such as electrical equipment, transportation equipment, and building materials. However, most plastics are composed of organic materials containing carbon, oxygen, hydrogen and other elements and have flammable characteristics. Considering safety issues in the event of a fire, the demand for flame-retardant plastics continues to increase. Generally, fuel, oxygen, and energy are necessary factors for a fire. As long as one of the conditions is not met, a fire will not occur. In other words, one of the flame-retardant methods of plastics is achieved by eliminating some of the three factors in fire. Flame retardants refer to compounds that have high flame retardancy such as halogen-based, phosphorus-based, nitrogen-based or metal products added by chemical or physical methods to flammable polymer materials to delay fire and prevent expanded combustion substance.

Flame retardants can be divided into various types according to their types and uses, and can be roughly classified into reactive and additive types. Reactive flame retardant refers to a type that has a functional group in the molecule and undergoes a chemical reaction, and is rarely affected by external conditions and maintains the flame retardant effect. Additive flame retardant refers to a type that obtains a flame retardant effect by mixing, adding, and dispersing materials in a plastic or epoxy resin composition, and is mainly used in a thermoplastic resin composition.

At present, various types of additive or reactive flame retardant materials are known. Additive flame retardant materials include tricresyl phosphate, toluene diphenyl phosphate, tributyl phosphate, tris(bromochloropropyl) phosphate, Tris (dichloropropyl) phosphate and the like. Reactive flame retardant materials include bromophenol, bromophenyl allyl ether, vinyl trifluoroacetate, ethylene glycol antimony, tetrabromobisphenol A and so on.

Due to the chemical reaction between the reactive flame retardant and the matrix, it is permanently mixed into the polymer structure. However, the additive flame-retardant resin composition does not chemically react with the flame-retardant material and the polymer matrix. Therefore, the added flame-retardant material is usually simply dispersed or dissolved in the matrix, and is often lost from the matrix. .

On the other hand, epoxy resin has excellent electrical characteristics, stability, high temperature and solvent resistance, low price, adhesiveness, etc., and is most suitable as a material for printed circuit boards and integrated circuits. However, epoxy resins are as easy to burn as plastic materials and are potentially dangerous. Therefore, the flame retardancy of electronic materials is strictly regulated all over the world, especially epoxy resin containing bromine. Although it is suitable as a resin for flame-retardant circuit boards, it releases corrosive harmful substances such as tetrabromodibenzodioxin and tetrabromodibenzofuran during the combustion process.

Although the traditional non-halogen flame-retardant epoxy resin has sufficient flame retardancy, it is not easy to inject a large amount of phosphorus raw materials, and will cause gelation as the molecular weight increases, or even if no gelation occurs, the molecular weight The increase of Zn will lead to a decrease in curing density, resulting in a significant decrease in inherent physical properties such as heat resistance, adhesion, and thermal stability. At the same time, the thermal expansion coefficient will rise sharply. In other words, although a large amount of phosphorus raw materials can be reacted to achieve sufficient flame retardancy, it has a relatively huge chemical molecular structure, and then during the curing reaction due to the three-dimensional obstacles and low curing density and other reasons, the thermal characteristics and Adhesion will decrease, and for the same reason, there is also a big limitation in increasing the phosphorus content. On the contrary, recent RoHS (Restriction of Hazardous Substances, directives on restricting the use of certain hazardous ingredients in electrical and electronic equipment), PoHS (Prohibition on Certain Hazardous Substances in Consumer Products, banning specific hazardous substances in consumer products) are related to the environment. The regulations partially or completely prohibit the use of certain substances (lead, cadmium, hexavalent chromium, etc.) in printed circuit boards, various electrical and electronic component insulating materials, and high-reliability semiconductor packaging materials. Therefore, the desired properties of flame-retardant polymer materials, that is, high cold resistance, thermal stability, adhesion, low water absorption, etc., have been increasing.

In addition, with the continuous upgrading of mobile phones in recent years, the battery capacity has also expanded, and the proportion of the space occupied by the battery has also increased, and then the HDI (High Density Interconnector, high density interconnect) substrate space has become smaller. And with the increase in the number of actual mounted components and high density, SLP (Substrate-like PCB) technology that can reduce the area and thickness of the HDI substrate becomes more and more necessary. SLP substrate is a technology that applies packaging substrate technology to smartphone HDI substrates, thereby reducing the area and width of the plate, increasing the number of layers, and improving volume efficiency. The technology was originally developed to be applied to flexible displays, but in order to improve the utilization of space in mobile phones, it has recently been widely used in smart phone configurations. In order to manufacture and process such a thin substrate, it is necessary to reduce the difference in thermal expansion coefficient between the resin cured product and the substrate. Therefore, the demand for low CTE epoxy resins with flame retardancy is increasing.

Therefore, how to develop a new flame-retardant epoxy resin with strong heat resistance, low dielectric properties and low thermal expansion coefficient while maintaining or improving the original flame retardancy is a problem to be solved in the industry.

Summary of the invention

In view of the shortcomings of the prior art, the present invention provides a phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient, as shown in chemical formula 1.

Chemical formula 1

Wherein, m, n, o, p, q are integers selected from 0 to 5, m, n, o, p, q are not 0 at the same time, and m, q are not 0 at the same time;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , X, Y, and Z are independent of each other and represent each, Wherein R ₁ , R ₂ , R ₁₀ , and R ₁₁ are the same or different, and are respectively selected from C1-C3 alkoxy, or C6-C10 aryl or aralkyl;

R ₃ , R ₄ , R ₁₂ and R ₁₃ are the same or different, and are selected from -H or C1-C3 hydrocarbon groups;

R ₅ , R ₇ , and R ₈ are the same or different, and are respectively selected from -H, a C1-C3 hydrocarbon group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group;

R ₆ , R ₉ and Z are the same or different, and each represents a divalent aryl group;

X and Y are the same or different, and are respectively selected from chemical bonds, or —O—, or

Where R ₀ represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl,

Wherein R ₁₄ and R ₁₅ are the same or different and are respectively selected from -H, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group.

Wherein, the C1-C3 alkoxy represents methoxy, ethoxy, propoxy or isopropoxy;

C1～C3 hydrocarbon group means chain or cyclic alkyl, alkenyl, alkynyl, such as: methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, propenyl, alkene Propyl, isopropenyl, cyclopropenyl, propynyl or propargyl;

The C1-C5 alkyl group means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, etc.;

C5-C6 cycloalkyl means cyclopentyl, cyclohexyl or methyl substituted cyclopentyl, etc.;

The aryl or aralkyl group of C6～C10 means phenyl, hydroxyphenyl, tolyl, Xylyl, Ethylphenyl, α-naphthyl (α -naphthyl, β-naphthyl, indenyl, Benzyl, Phenethyl, etc.;

C6～C18 aryl groups represent phenyl, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, triphenyl, α-naphthyl, β-naphthyl, anthracene Base (anthracyl), phenanthryl (phenanthryl), indenyl (indenyl), fluorenyl (fluorenyl), acenaphthenyl (acenaphthenyl), pyrenyl (pyrenyl),

基 (chrysenyl) etc.;

The divalent aryl group means divalent phenyl, tolyl, xylyl, hydroxyphenyl, biphenyl, terphenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, and the like.

The phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention has a flame-retardant phosphorus element structure located on the side chain of the epoxy resin structure, instead of the existing halogen-containing epoxy resin composition as a flame-retardant component. It has good processability when added to epoxy resin composition. Correspondingly, due to the presence of the side chain structure, the fluidity of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin is reduced, the molecular stability is high at high temperature, it has the characteristics of low thermal expansion coefficient and good heat resistance. The phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention is suitable for the fields of electrical insulation materials, electronic insulation materials, semiconductor packaging materials and the like due to its excellent heat resistance and flame resistance.

Another object of the present invention is to provide a preparation method of the above phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, which specifically includes the following steps:

P1. According to the mass ratio of phosphorus-containing compound and solvent I of 1: (2.0-3.5), weigh the phosphorus-containing compound and solvent I, mix and heat to 50-100 ℃ to completely dissolve the phosphorus-containing compound to obtain a mixed solution ；

P2. Weigh the aromatic compounds according to the molar ratio of phosphorus-containing compounds and aromatic compounds of 1: (0.2-1.1), and put the weighed aromatic compounds into the mixed solution in batches;

P3. After the aromatic compound input is finished, reflux reaction at 50-100℃ and normal pressure for 4-8h to obtain the intermediate product;

P4. Calculated by mole, the intermediate product obtained by the reaction in step P3: epichlorohydrin=1: (2-7), weigh epichlorohydrin; in mass ratio, epichlorohydrin: solvent II =1: Weigh solvent II in a ratio of (0.3-0.6); add the weighed epichlorohydrin and solvent II to the intermediate product obtained by the reaction in step P3, heat up to 40～70℃, keep warm, and stir until epoxy Propane dissolves;

P5. According to the molar ratio of the intermediate product obtained by the reaction in step P3 and the alkali catalyst, the alkali catalyst is weighed at a ratio of 1:(1-2), and the alkali catalyst is added dropwise to the solution obtained in step P4 under stirring. The dripping is completed within ~5h, and the reaction mixture is obtained;

P6. Add water to the reaction mixture, let it stand, recover the upper resin, heat to ≥150°C to remove epichlorohydrin, and obtain phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient.

Wherein, the phosphorus-containing compound in step P1 is selected from one or more of the compounds shown in Chemical Formula 2 and Chemical Formula 3.

Chemical formula 2:

Chemical formula 3:

In Chemical Formula 3, R ₁₆ and R ₁₇ are independent of each other and each represents, R ₁₆ is -H, C1-C5 alkyl, C1-C5 alkoxy, C5-C6 cycloalkyl, or C6-C18 aryl ; R ₁₇ is -H, C1-C5 alkyl, C5-C6 cycloalkyl or C6-C18 aryl; wherein C1-C5 alkyl represents methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, pentyl and other linear or branched alkyl groups; C1-C5 alkoxy represents methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy Straight-chain or branched alkoxy groups such as C5～C6 cycloalkyl group; C5-C6 cycloalkyl group means cyclopentyl, methyl-substituted cyclopentyl and cyclohexyl; C6-C18 aryl group means phenyl, hydroxyphenyl, tolyl , Xylyl, ethylphenyl, biphenyl, terphenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, acenaphthyl, pyrenyl,

Base etc.

The aromatic compound in step P2 is selected from one or more of quinone compounds, chemical formula 4 and chemical formula 5,

Chemical formula 4

In Chemical Formula 4, R ₁₈ and R ₁₉ are independent of each other and represent each,

R ₁₈ and R ₁₉ are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

Chemical formula 5

In chemical formula 5, R ₂₀ and R ₂₁ are independent of each other and represent each,

R ₂₀ and R ₂₁ are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

The quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone;

C1～C3 hydrocarbon group means chain or cyclic alkyl, alkenyl, alkynyl, such as: methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, propenyl, alkene Propyl, isopropenyl, cyclopropenyl, propynyl or propargyl; C5-C6 cycloalkyl means cyclopentyl, methyl-substituted cyclopentyl and cyclohexyl; C6-C18 aryl means benzene Group, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, terphenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, acenaphthyl, Pyrene base,

Base

The quinone compound may specifically be: 1,4-Benzuoquinone, 1,2-Benzuoquinone, 1,4-Naphthoquinone (1,4-Naphthoquinone) , 1,2-Naphthoquinone (1,2-Naphthoquinone), 2,6-Naphthoquinone (2,6-Naphthoquinone), 1,2-anthraquinone (1,2-Anthraquinone), 2,6-anthraquinone ( 2,6-Anthraquinone), 1,4-anthraquinone (1,4-Anthraquinone), 9,10-anthraquinone (9,19-Anthraquinone), 1,4-phenanthrenequinone (1,4-Phenanthrenequinone) or 2 , 3-Phenanthrenequinone (2,3-Phenanthrenequin-one).

Preferably, the raw materials added in step P4 also include as polymerized monomers, compounds represented by chemical formula 6 and chemical formula 7, quinone compounds, and one or more of the compounds represented by chemical formula 2 and chemical formula 3,

Chemical formula 6:

Chemical formula 7:

R ₆ and R ₉ are the same or different, and each represents a divalent aryl group;

Where R ₀ represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl,

Wherein R ₁₄ and R ₁₅ are the same or different and are respectively selected from -H, C1-C3 hydrocarbyl group, C5-C6 cycloalkyl group or C6-C18 aryl group;

Among them, C1-C3 alkyl represents methyl, ethyl, propyl and isopropyl; C5-C6 cycloalkyl represents cyclopentyl, methyl-substituted cyclopentyl and cyclohexyl; C6-C18 aryl Group represents phenyl, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, terphenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, Acenaphthyl, pyrene,

Divalent aryl group means divalent phenyl, tolyl, xylyl, hydroxyphenyl, biphenyl, terphenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, etc.;

The quinone compound may specifically be: 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, 2,6-naphthoquinone, 1,2-anthraquinone , 2,6-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,4-phenanthrenequinone or 2,3-phenanthrenequinone.

Preferably, in order to further improve the purity of the prepared phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, the method further includes a refining step of performing the following treatments on the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared through steps P1-P6:

P7. Add 50-200wt% of solvent III dropwise to the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, heat up to 75-85°C, keep warm and stir to make the phosphorus-containing flame retardant low thermal expansion coefficient epoxy The resin is completely dissolved;

P8. Add alkali catalyst under the condition of keeping warm and stirring at 75～85℃. The addition amount of alkali catalyst is 1-100wt% of the amount of alkali catalyst in step P5, and the addition is completed within 2～5h, and the refining reaction is carried out to obtain epoxy resin mixture;

P9. Add 50-200wt% of water to the epoxy resin mixture, which accounts for the mass of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, stir for 20-40 minutes, and then stand for 20-40 minutes to remove the lower layer of water;

P10. Repeat steps P9 1 to 5 times to recover the upper layer of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin;

P11. Heat the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P10 to ≥150°C, and remove the residual solvent III.

The type and amount of solvent I, solvent II, and solvent III used in the present invention are based on the principle that they can dissolve the reaction product and can be used under the corresponding reaction temperature conditions, and can be adjusted according to the actual amount of reaction raw materials and performance differences. Considering comprehensively, a solvent with a boiling point of 75-150°C is preferred. During the process of preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, the volatilization of the solvent can be minimized to ensure the smooth and efficient reaction. After the reaction, it can be evaporated under reduced pressure. The solvent is removed by other methods to obtain high-purity products. Specifically, solvent I selects any one of organic solvents such as toluene, methyl isobutyl ketone, pyridine, 4-methyl-2-pentanone, butanol, ethylenediamine, acetic acid, etc.; the solvent II is water One or more of, isopropanol, butanol, and ethylene glycol dimethyl ether; the solvent III is toluene, methyl isobutyl ketone, pyridine, 4-methyl-2-pentanone, butanol , Ethylenediamine, acetic acid and other organic solvents.

The alkali catalyst used is sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium methoxide or sodium ethoxide, and the specific type is not limited.

Another object of the present invention is to provide an application of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared by the above method. The phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared by the method of the present invention is a kind of Halogen-free compounds, can be used for high-reliability electrical and electronic insulation materials, semiconductor packaging materials, and can be used for PCB boards and insulation boards that require excellent low thermal expansion coefficient, flame retardancy, heat resistance and low dielectric properties, or other related requirements Performance requirements of resin composite materials, adhesives, coating agents, coatings and other fields.

Another object of the present invention is to provide an intermediate product for preparing the above-mentioned phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, which is prepared through the steps P1-P3 of the above-mentioned preparation method. According to actual needs, solvent I can be removed by means of reduced pressure evaporation, or purification process can be used for purification to obtain high-purity intermediate products; it can also be based on the crude intermediate products prepared through steps P1-P3, Continue to add epichlorohydrin, alkali catalyst, etc. to prepare phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin. This kind of intermediate product has high flame retardancy and can be used for epoxy resin modification to improve the flame retardant and heat resistance properties of epoxy resin, and it can also be used for modification of other polymer materials.

Description of the drawings

Fig. 1 is a process flow diagram of a preparation method of a phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin in an embodiment.

detailed description

The present invention will be further described in detail below in conjunction with the drawings.

Example 1: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

The process flow is shown in Figure 1, and specifically includes the following steps:

P1. Add 442g of toluene (Toluene) and 154g of ethyl phenyl phosphine oxide (EPP) into a reactor equipped with a stirrer, thermometer, and reflux condenser. The temperature is raised to 70°C to completely dissolve the raw materials and keep warm And keep the agitator continuously stirring the raw materials.

P2. When the raw materials are completely dissolved, weigh 31.6g 1,4-naphthoquinone and add it to the reactor in 15 times within 2h.

P3. After the feeding is completed, react at 70°C under reflux (reflux) for 5 hours to obtain an intermediate product.

P4. Continue to add 551.1g of epichlorohydrin, 60.1g of iso-propanol and 54g of water to the intermediate product, purge the nitrogen and heat it up to 50°C to dissolve the added raw materials. Keep warm.

P5. Then, start to add 160 g of sodium hydroxide solution with a concentration of 50 wt% for 3 hours for reaction.

P6. Add 360g of water to the reaction vessel, and after standing for stratification, the upper layer of resin is recovered. The recovered upper layer resin is heated to 150° C. to remove residual epichlorohydrin to obtain phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin.

P7. Add 645g of toluene dropwise to the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin crude product, heat up to 80°C, stir until the resin crude product is completely dissolved, and keep warm.

P8. Add 160g of 50wt% sodium hydroxide solution within 2h and keep it at 80℃ for 1h.

P9. After the heat preservation is over, add 360g of water, stir for 30min, and let stand for 30min; add 360g of water again, stir for 30min, stand for 30min, and recover the upper layer resin. The recovered resin is heated to 150°C to remove residual toluene to obtain phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin.

Example 2: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 2 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 1.

Table 1.

Example 3: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 3 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 2.

Table 2.

Example 4: Preparation of phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient

Example 4 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 3.

table 3.

Example 5: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 5 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 4.

Table 4.

Example 6: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 6 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 5.

table 5.

Example 7: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 7 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 6.

Table 6.

Example 8: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 8 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 7.

Table 7.

Example 9: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 9 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 8.

Table 8.

Example 10: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 10 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 9.

Table 9.

Example 11: Preparation of phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient

Example 11 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 10.

Table 10.

Example 12: Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin

Example 12 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 11.

Table 11.

Comparative example 1

An epoxy resin prepared by the following process: To a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 216g DOPO and 817g phenol novolac epoxy resin (Phenol Novoac Epoxy, EEW: 128g/eq) are added, After confirming dissolution at 110°C, 1000 ppm of imidazole catalyst was added. Stir thoroughly and disperse, heat to raise the temperature to 150°C. The equivalent is detected every hour, and when the theoretical equivalent is reached, the reaction is terminated and the solid is taken out to obtain a yellow solid epoxy resin.

Comparative example 2

An epoxy resin prepared by the following process: Into a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 324g DOPO-HQ and 1100g Bisphenol-A Epoxy (EEW: 187g/eq), after confirming the dissolution at 110°C, 1000ppm imidazole catalyst was added. Stir thoroughly and disperse, heat to raise the temperature to 150°C. The equivalent is detected every hour. When the theoretical equivalent is reached, the reaction is terminated and the solid is taken out to obtain a yellow solid epoxy resin.

Comparative example 3

An epoxy resin prepared by the following process: Add 358g DOPO-NQ and 1192g Bisphenol-A Epoxy (EEW) to a reactor equipped with a stirrer, thermometer, and reflux condenser: 187g/eq), after confirming the dissolution at 110°C, 1000ppm imidazole catalyst was added. Stir thoroughly and disperse, heat to raise the temperature to 150°C. The equivalent is detected every hour, and when the theoretical equivalent is reached, the reaction is terminated and the solid is taken out to obtain a yellow solid epoxy resin.

Note: DOPO, DOPO-HQ and DOPO-NQ are all phosphorus flame retardants,

The chemical formula of DOPO is,

The chemical formula of DOPO-HQ is,

The chemical formula of DOPO-NQ is,

In order to better test the performance of the prepared phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, the following uses the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention as a raw material to prepare an epoxy resin composition before performing performance testing. .

Production Example 1-12: Preparation of epoxy resin composition

Into a reactor equipped with a stirrer, a thermometer, and a reflux condenser, add the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin and phenol phenolic resin of Examples 1-12, and heat to 120°C to dissolve the added raw materials. After dissolving, add 0.2phr of curing catalyst, stir and mix thoroughly, and take it out. The mixture is completely cured at 180°C to produce a pure resin hardened product with a thickness of 2 (±0.5) mm.

Table 12 and Table 13 below show the amount of each substance used in the preparation process of the epoxy resin composition in Manufacturing Examples 1-12.

Table 12.

Table 13.

Comparative manufacturing example 1-3: Preparation of epoxy resin composition

Add the epoxy resin and phenol phenol resin of Comparative Example 1-3 into the reactor equipped with a stirrer, a thermometer, and a reflux condenser, and heat to 120°C and dissolve. After the dissolution is complete, add 0.2 phr of the curing catalyst, stir well and take out after mixing. The mixture is completely cured at 180°C to produce a pure resin cured product with a thickness of 2 (±0.5) mm.

Table 14 below shows the amount of each substance used in the preparation of pure resin hardened products in Comparative Manufacturing Examples 1-3.

Table 14.

Performance Testing

The physical properties of the resin hardened products prepared in Production Examples 1-12 and Comparative Production Examples 1-3 were tested according to the following methods, and the results were recorded in Table 15 and Table 16 below.

(1) Conduct flame retardancy test according to UL-94 method;

(2) Use a parallax thermal analyzer (DSC) for glass transition temperature (Tg) detection experiment (10°C/min);

(3) The decomposition temperature (Td) was measured using a thermogravimetric analyzer (TGA);

(4) According to JIS-C-6481 method, use Agilent E4991A RF Impedance/Material analyzer to measure dielectric constant (Dielectric Constant) and dissipation factor (Dissipation Factor, Df);

(5) The lead heat resistance test was carried out in accordance with the JIS-C-6481 method, and the state of the cured epoxy resin product immersed in a lead bath at 300°C for 120s was visually observed. Mark O when swelling and cracking are not observed by naked eyes, and X when observed;

(6) The peel strength (1/2 OZ Copper Peel Strength) was tested according to the GIS C-6417 method.

Table 15.

Table 16.

Comparing the data in Table 15 and Table 16, it can be seen that the traditional flame-retardant epoxy resins in Comparative Manufacturing Examples 1-3 have physical properties such as heat resistance, dielectric constant, dissipation factor, and adhesion, in addition to flame retardancy. There is no special advantage, and the total phosphorus content is also low.

Moreover, compared to the a1:50.83ppm and the expansion rate of 1.71% of Comparative Manufacturing Example 3, which is a traditional low thermal expansion coefficient and widely used, it can be found that Manufacturing Examples 1, 3, 4, 5, 6, 7, 11, 12 have the same or Better physical properties, and the increase in phosphorus content makes it have a better flame retardant effect.

At the same time, comparing the data in Table 15 and Table 16, it can be seen that compared with the hardened product of the traditional DOPO-NQ modified epoxy resin, the epoxy resin prepared by incorporating the phosphorus-containing flame-retardant low thermal expansion epoxy resin of the present invention The composition has a higher naphthalene content, so the glass transition temperature is higher, the dielectric constant is lower, and the thermal expansion coefficient is lower, and it is more suitable for achieving excellent low thermal expansion coefficient performance.

The phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention is a halogen-free compound, and can be used for high-reliability electrical and electronic materials, and can be used for requirements of excellent low thermal expansion coefficient, flame retardancy, heat resistance and low node characteristics PCB boards and insulating boards as well as other compatible materials, adhesives, coating agents, coatings and other fields that require related performance.

The above-mentioned specific embodiment is only an explanation of the present invention, and it is not a limitation of the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contribution as needed, but as long as the rights of the present invention All requirements are protected by patent law.

Claims

A phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient, as shown in chemical formula 1.

Wherein, m, n, o, p, q are integers selected from 0 to 5, m, n, o, p, q are not 0 at the same time, and m, q are not 0 at the same time;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , X, Y, and Z are independent of each other and represent each, among them

R 1 , R 2 , R 10 , and R 11 are the same or different, and are respectively selected from C1-C3 alkoxy, or C6-C10 aryl or aralkyl;

R 3 , R 4 , R 12 and R 13 are the same or different, and are selected from -H or C1-C3 hydrocarbon groups;

R 5 , R 7 , and R 8 are the same or different, and are respectively selected from -H, a C1-C3 hydrocarbon group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group;

R 6 , R 9 and Z are the same or different, and each represents a divalent aryl group;

X and Y are the same or different, and are respectively selected from chemical bonds, or —O—, or

Where R 0 represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl,
Wherein R 14 and R 15 are the same or different and are respectively selected from -H, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group.
A method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 1, characterized in that it comprises the following steps:

P1. According to the mass ratio of phosphorus-containing compound and solvent I of 1: (2.0-3.5), weigh the phosphorus-containing compound and solvent I, mix and heat to 50-100 ℃ to completely dissolve the phosphorus-containing compound to obtain a mixed solution ；

P2. Weigh the aromatic compounds according to the molar ratio of phosphorus-containing compounds and aromatic compounds of 1: (0.2-1.1), and put the weighed aromatic compounds into the mixed solution in batches;

P3. After the aromatic compound input is finished, reflux reaction at 50-100℃ and normal pressure for 4-8h to obtain the intermediate product;

P4. Calculated by mole, the intermediate product obtained by the reaction in step P3: epichlorohydrin=1: (2-7), weigh epichlorohydrin; in mass ratio, epichlorohydrin: solvent II =1: Weigh solvent II in a ratio of (0.3-0.6); add the weighed epichlorohydrin and solvent II to the intermediate product obtained by the reaction in step P3, heat up to 40～70℃, keep warm, and stir until epoxy Propane dissolves;

P5. According to the molar ratio of the intermediate product obtained by the reaction in step P3 and the alkali catalyst, the alkali catalyst is weighed at a ratio of 1:(1-2), and the alkali catalyst is added dropwise to the solution obtained in step P4 under stirring. The dripping is completed within ~5h, and the reaction mixture is obtained;

P6. Add water to the reaction mixture, let it stand, recover the upper resin, heat to ≥150°C to remove epichlorohydrin, and obtain phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 2, characterized in that the phosphorus-containing compound in step P1 is selected from one or more of the compounds shown in Chemical Formula 2 and Chemical Formula 3.

In chemical formula 3, R 16 and R 17 are independent of each other and represent each,

R 16 is -H, C1-C5 alkyl, C1-C5 alkoxy, C5-C6 cycloalkyl or C6-C18 aryl;

R 17 is -H, a C1-C5 alkyl group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 3, wherein the aromatic compound in step P2 is selected from one of quinone compounds, chemical formula 4 and chemical formula 5 Or more,

In Chemical Formula 4, R 18 and R 19 are independent of each other and represent each,

R 18 and R 19 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

In chemical formula 5, R 20 and R 21 are independent of each other and represent each,

R 20 and R 21 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

The quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 4, characterized in that: the raw materials added in step P4 also include the compounds shown in chemical formula 6 and chemical formula 7 as polymerized monomers, quinones Compound, one or more of the phosphorus-containing compounds shown in the chemical formula 2 and the chemical formula 3,

R 5 , R 7 , and R 8 are the same or different, and are respectively selected from -H, a C1-C3 hydrocarbon group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group;

R 6 and R 9 are the same or different, and each represents a divalent aryl group;

X and Y are the same or different, and are respectively selected from chemical bonds, or —O—, or

Where R 0 represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl,
Wherein R 14 and R 15 are the same or different and are respectively selected from -H, C1-C3 hydrocarbyl group, C5-C6 cycloalkyl group or C6-C18 aryl group;

The quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 5, characterized in that it further comprises the following steps:

P7. Add 50-200wt% of solvent III dropwise to the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, heat up to 75-85°C, keep warm and stir to make the phosphorus-containing flame retardant low thermal expansion coefficient epoxy The resin is completely dissolved;

P8. Add alkali catalyst under the condition of keeping warm and stirring at 75～85℃. The addition amount of alkali catalyst is 1-100wt% of the amount of alkali catalyst in step P5, and the addition is completed within 2～5h, and the refining reaction is carried out to obtain epoxy resin mixture;

P9. Add 50-200wt% of water to the epoxy resin mixture, which accounts for the mass of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, stir for 20-40 minutes, and then stand for 20-40 minutes to remove the lower layer of water;

P10. Repeat steps P9 1 to 5 times to recover the upper layer of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin;

P11. Heat the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P10 to ≥150°C, and remove the residual solvent III.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 6, wherein the solvent I and solvent III are both organic solvents and are selected from toluene, methyl isobutyl ketone, pyridine , 4-methyl-2-pentanone, butanol, ethylenediamine, acetic acid; the solvent II is one of water, isopropanol, butanol, ethylene glycol dimethyl ether or Many kinds.
The method for preparing phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin according to claim 6, wherein the alkali catalyst is sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and hydrogen carbonate. Sodium, sodium methoxide or sodium ethoxide.
An intermediate product for preparing the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of claim 1, characterized in that it is prepared through the following process:

P1. According to the mass ratio of phosphorus-containing compound and solvent I of 1: (2.0-3.5), weigh the phosphorus-containing compound and solvent I, mix and heat to 50-100 ℃ to completely dissolve the phosphorus-containing compound to obtain a mixed solution The phosphorus-containing compound is selected from one or more of the compounds shown in chemical formula 2 and chemical formula 3,

In chemical formula 3, R 16 and R 17 are independent of each other and represent each,

R 16 is -H, C1-C5 alkyl, C1-C5 alkoxy, C5-C6 cycloalkyl or C6-C18 aryl;

R 17 is -H, C1-C5 alkyl, C5-C6 cycloalkyl, or C6-C18 aryl;

P2. Weigh the aromatic compounds according to the molar ratio of phosphorus-containing compounds and aromatic compounds of 1: (0.2-1.1), and put the weighed aromatic compounds into the mixed solution in batches; the aromatic The compound is selected from one or more of quinone compounds, chemical formula 4 and chemical formula 5,

In Chemical Formula 4, R 18 and R 19 are independent of each other and represent each,

R 18 and R 19 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

In chemical formula 5, R 20 and R 21 are independent of each other and represent each,

R 20 and R 21 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;

The quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone;

P3. After the input of aromatic compound is finished, reflux reaction at 50-100°C and normal pressure for 4-8h to obtain intermediate product.
A phosphorous-containing flame-retardant low thermal expansion coefficient epoxy resin as claimed in claim 1 is used for the preparation of glue solution for the production of copper foil laminates, electrical and electrical insulating materials, electronic insulating materials, semiconductor packaging materials, fiber composite materials, and adhesives , Coating agent or coating application.