Reactive phosphorus-containing polymer and preparation method, composition and plate thereof

Abstract

The invention provides a reactive phosphorus-containing polymer and a preparation method thereof, a composition and a plate, and relates to the field of materials.The polymer is a block polymer and comprises a segment A and a segment B; the segment A comprises a carbon chain A and a phosphorus-containing substituent group connected to the carbon chain A; the section B comprises a carbon chain B and a divinyl benzene substituent connected to the carbon chain B; the content of phosphorus in the polymer is not lower than 0.1 wt% and not higher than 10 wt% in percentage by mass; the number average molecular weight of the polymer is 1000 to 5000. The polymer provided by the technical scheme provided by the invention is a copolymer taking a carbon chain as a main chain, and a branch chain containing phosphorus and double bonds and a branch chain containing divinyl phenyl groups are formed on the main chain, so that the polymer has good flame retardance and extremely low dielectric loss, and is suitable for the field of high-frequency and high-speed communication.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and in particular to a reactive phosphorus-containing polymer and a preparation method, a composition and a plate thereof. Background Art

[0002] In recent years, with the rapid development of 5G communication technology, the Internet of Things, and automotive electronics, as well as the high functionality and miniaturization of electronic equipment, communication devices, personal computers, etc., the circuit boards used are also developing towards multi-layering, high-density wiring, and high-speed signal transmission. This puts forward higher requirements on the comprehensive performance of circuit substrates such as copper foil substrates, such as low dielectric constant and dielectric loss, good flame retardant properties, good heat resistance and dimensional stability.

[0003] Traditional halogen-containing flame retardants have high flame retardant efficiency and small dosage, but when they burn, they will produce dioxins and other difficult-to-degrade products, which are harmful to the environment and the health of citizens and do not meet the current green environmental protection requirements. If halogen-free flame retardant modification is adopted, there are usually two methods: one is to use halogen-free additive flame retardants. Such flame retardants are mostly powders. After addition, there are defects such as low compatibility with the matrix, poor durability, and long response time to achieve flame retardant effect when burning. The other is to add halogen-free reactive flame retardants, through the copolymerization of reactive monomers with other monomers, flame retardant elements such as phosphorus and nitrogen are embedded in the polymer molecular chain, thereby playing a flame retardant role. This type of addition method can effectively solve problems such as precipitation, surface whitening, and moisture absorption.

[0004] For example, patent CN113620994A discloses a reactive phosphorus-containing flame retardant and its preparation method and application. The invention uses DOPO-based flame retardant DOPO-HQ as a starting material and is chemically modified to obtain a reactive phosphorus-containing flame retardant. The molecular structure does not contain polar groups, so it is not easy to absorb moisture, easy to react, and not easy to migrate; it can react with polymer resins containing unsaturated double bonds and connect to the molecular chain of the polymer to achieve a flame retardant effect; it can be dissolved in ketone solvents and aromatic solvents. However, after the DOPO-based flame retardant mentioned in the invention is actually used to synthesize or modify polymer resins, the flame retardant effect, heat resistance and dielectric properties are significantly reduced, and it is difficult to meet the needs of 5G communications. In addition, patent CN117447521A also discloses a reactive phosphorus-containing flame retardant monomer and its preparation method and application, flame retardant polyacrylate and its preparation method. The invention mixes DOPO, a monomer containing two or more C=C double bonds, an inhibitor, a catalyst and an organic solvent for addition reaction to obtain a reactive phosphorus-containing flame retardant monomer. The invention, under the action of an inhibitor and a catalyst, causes the PH bond of DOPO to undergo an addition reaction with part of the C=C double bonds of a monomer containing two or more C=C double bonds, thereby obtaining a reactive flame retardant monomer having a DOPO structure. The reactive flame retardant monomer has free radical reaction activity and can be introduced into a polyacrylic acid resin by means of a free radical polymerization reaction to prepare a bulk flame retardant polymer material having excellent flame retardant properties. However, the dielectric constant of the obtained polyacrylic acid resin is about 2.94, and the dielectric loss is 0.04-0.06. Although it has been modified to contain phosphorus, which can significantly improve the flame retardancy, it cannot be used for the flame retardancy of organic materials in the field of high-frequency and high-speed electronic communications. The scope of application is limited and it can only be used for the preparation of fire retardant coatings. Summary of the invention

[0005] The purpose of the present invention is to provide a reactive phosphorus-containing polymer and a preparation method, a composition and a plate thereof; the polymer is a copolymer with a carbon chain as the main chain, and phosphorus-containing and double-bond-containing side chains and divinylbenzene-containing side chains are formed on the main chain, and has good flame retardancy and extremely low dielectric loss, and is suitable for the field of high-frequency and high-speed communications.

[0006] In a first aspect, an embodiment of the present invention provides a reactive phosphorus-containing polymer, which is a block polymer, comprising an A segment and a B segment; The A segment includes a carbon chain A and a phosphorus-containing substituent connected to the carbon chain A; the B segment includes a carbon chain B and a divinylbenzene substituent connected to the carbon chain B; The content of phosphorus in the polymer is not less than 0.1wt% and not more than 10wt% in terms of mass percentage; the number average molecular weight of the polymer is 1000-5000.

[0007] Furthermore, in some embodiments of the present application, the general chemical structure formula of the polymer is:

[0008] Wherein, n and m are natural numbers, and 10<m+n<60; R1 is a group containing phosphorus and double bonds, so that the phosphorus content in the polymer is not less than 0.1wt%, and R2 is selected from any one of hydrogen or hydrocarbon groups.

[0009] Further, in some embodiments of the present application, the chemical structure of the polymer is selected from any one of the following formulas I to V: Among them, R 11 Selected from , , , Any of R 12 Selected from , Any of R 13 , R 15 Independently selected from , Any of .

[0010] In a second aspect, the present application also provides a method for preparing the reactive phosphorus-containing polymer described in the first aspect, which is obtained by polymerization reaction of double bonds in phosphorus-containing and carbon-carbon double bond-containing monomers and carbon-carbon double bonds in divinylbenzene under the action of an initiator.

[0011] Furthermore, in some embodiments of the present application, the preparation method comprises the following steps: (1) taking a divinylbenzene monomer, a phosphorus-containing monomer containing a carbon-carbon double bond, an initiator and a solvent, wherein the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 100 parts by weight, and the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 65-90 parts by weight, 9.5-35 parts by weight and 0.01-0.5 parts by weight respectively; (2) mixing a phosphorus-containing and carbon-carbon double bond-containing monomer with a solvent, stirring and heating to 70°C-100°C under a protective gas environment; then slowly adding a divinylbenzene monomer and a solution formed by an initiator and a solvent at a uniform speed, and keeping the temperature for reaction for 2-5 hours to obtain a reaction system; (3) Concentrating and washing to obtain a reactive phosphorus-containing polymer.

[0012] Furthermore, in some embodiments of the present application, in the step (2), the addition time of the divinylbenzene monomer is not less than 30 minutes.

[0013] Further, in some embodiments of the present application, the mass fraction of the solvent is 2 to 20 times the sum of the mass fractions of the phosphorus-containing and carbon-carbon double bond-containing monomer and the divinylbenzene monomer; and / or The solvent is one or a mixture of acetone, butanone, benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, and butyl acetate; The initiator is a peroxide initiator or an azo initiator.

[0014] Further, in some embodiments of the present application, the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; and the azo initiator is azobisisobutyronitrile or azobisisoheptylonitrile.

[0015] In a third aspect, the present application also provides a resin composition, comprising: 10-30 parts by weight of reactive phosphorus-containing polymer; 20-40 parts by mass of hydrocarbon resin; Filler 30~60 parts by mass; The second initiator is 0.1%~1.0%; The reactive phosphorus-containing polymer is the reactive phosphorus-containing polymer described in any one of claims 1 to 3 or the reactive phosphorus-containing polymer prepared by the method for preparing the reactive phosphorus-containing polymer described in any one of claims 4 to 7.

[0016] Further, in some embodiments of the present application, the hydrocarbon resin is at least one of polybutadiene, styrene-butadiene-styrene copolymer, polyisoprene-styrene, and polystyrene-based norbornene; and / or The second initiator is a peroxide initiator or an azo initiator; wherein the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; the azo initiator is at least one of azobisisobutyronitrile or azobisisoheptylnitrile; and / or The filler is a silica filler which is at least one of a silica filler without surface treatment, a silica filler surface treated with a vinyl silane coupling agent, and silica particles.

[0017] In a fourth aspect, the present application also provides a board material, comprising a resin prepared from a reactive phosphorus-containing polymer prepared by the reactive phosphorus-containing polymer described in the first aspect or the reactive phosphorus-containing polymer prepared by the preparation method of the reactive phosphorus-containing polymer described in the second aspect, or a resin prepared from the resin composition described in the third aspect.

[0018] Furthermore, in some embodiments of the present application, the board material is a copper-clad board, an insulating board, or a laminate board.

[0019] The embodiment of the present application provides a reactive phosphorus-containing polymer, which is a copolymer with a carbon chain as the main chain, and has phosphorus-containing and double-bond-containing side chains and divinylbenzene-containing side chains connected to the main chain. During the curing process of the resin composition, the phosphorus-containing group that mainly plays a flame retardant effect is chemically bonded to the polymer, so that its flame retardant effect is fully exerted. In addition, its carbon-carbon double bonds can participate in the curing reaction and be chemically bonded to the reactive groups of other components in the resin composition. At the same time, the divinylbenzene groups in the reactive polymer react with other polymers to improve the heat resistance of the resin composition. The reactive polymer has a carbon chain as the main chain, and can also reduce the dielectric loss of the obtained material, especially in a high-frequency and high-speed environment, and its dielectric loss can also be kept at an extremely low level.

[0020] In addition, the polymer provided in the present application can participate in the polymerization reaction of the polymer as a reaction monomer, and the phosphorus-containing flame retardant is chemically bonded to the polymer, thereby avoiding the precipitation of small molecules. At the same time, it avoids the phenomenon of precipitation similar to that of additive flame retardants due to easy hydrolysis or easy solubility in water, thereby achieving high-efficiency flame retardancy.

[0021] The flame retardancy of the polymer provided by the present invention can reach V-0 level, and the flame retardancy stability can also reach V-0 level. At the same time, the dielectric loss (D f / 10G) is lower than 0.006, which meets the requirements of general high-frequency and high-speed materials. The preparation process is simple and the raw materials are easily available, which has broad prospects for industrial application.

[0022] The present application provides a method for preparing the reactive phosphorus-containing polymer, which is simple and easy to promote and apply. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The GPC spectrum of the reactive phosphorus-containing polymer provided in Example 1 of the present application; Figure 2 The GPC spectrum of the reactive phosphorus-containing polymer provided in Example 2 of the present application; Figure 3 The GPC spectrum of the reactive phosphorus-containing polymer provided in Example 3 of the present application; Figure 4 The GPC spectrum of the reactive phosphorus-containing polymer provided in Example 4 of the present application; Figure 5 The GPC spectrum of the polymer provided in Comparative Example 5 of the present application; Figure 6This is an infrared spectrum of the reactive phosphorus-containing polymer provided in Example 1 of the present application; Figure 7 This is an infrared spectrum of the reactive phosphorus-containing polymer provided in Example 2 of the present application; Figure 8 This is an infrared spectrum of the reactive phosphorus-containing polymer provided in Example 3 of the present application; Fig. 9 This is the infrared spectrum of the reactive phosphorus-containing polymer provided in Example 4 of the present application. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] In a first aspect, an embodiment of the present invention provides a reactive phosphorus-containing polymer, which is a block polymer, comprising an A segment and a B segment; The A segment includes a carbon chain A and a phosphorus-containing substituent connected to the carbon chain A; the B segment includes a carbon chain B and a divinylbenzene substituent connected to the carbon chain B; The content of phosphorus in the polymer is not less than 0.1wt% and not more than 10wt% in terms of mass percentage; the number average molecular weight of the polymer is 1000-5000.

[0026] It should be noted that the alkenyl groups on the divinylbenzene in the reactive phosphorus-containing polymer provided in the present application can chemically react with double bonds on other polymers, so that the polymer provided in the present application can be grafted onto the polymer as a whole to form an island-shaped flame retardant material located on the surface of the polymer, making its flame retardant effect more obvious; and the polymer provided in the present application itself can also undergo polymerization reaction to form a polymer with excellent flame retardant effect and low dielectric loss, but due to its block effect, and the phosphorus-containing substituent and the divinylbenzene group that undergoes polymerization reaction are located on different blocks, a network structure with uneven flame retardant effect and uneven cross-linking degree can be formed inside the polymer, thereby further improving the flame retardant effect and reducing the dielectric loss without the need for a higher phosphorus content.

[0027] In the polymer, the degree of polymerization of segment A is 1-21, and the degree of polymerization of segment B is 9-54; preferably, the degree of polymerization of segment A is 3-18, and the degree of polymerization of segment B is 10-50; more preferably, the degree of polymerization of segment A is 5-16, and the degree of polymerization of segment B is 12-48.

[0028] In the present application, the degree of polymerization of the A segment in the polymer should not be too low or too high, because if the degree of polymerization of the A segment is too low, it is easy to cause the phosphorus content to be too low, and the flame retardant effect is not good; if the degree of polymerization of the A segment is too high, although the phosphorus content is increased and the flame retardant effect is good, the dielectric loss is high, and it is not suitable for high-frequency and high-speed materials; the degree of polymerization of the B segment should not be too low or too high, because if the degree of polymerization of the B segment is too low, it is easy to cause the benzene rings on the polymer side chain to decrease, and the heat resistance of the material to deteriorate; and if the degree of polymerization of the B segment is too high, it is easy to cause the overall phosphorus content of the polymer to decrease, and the flame retardant effect is not good. The degree of polymerization of the polymer should not be too high or too low, because if the degree of polymerization is too low, the viscosity of the polymer is too low, which is easy to cause serious glue flow when pressing the copper foil substrate; and if the degree of polymerization is too high, its solubility is poor, the viscosity is too high, and it is easy to lack glue when pressing the copper foil substrate.

[0029] Preferably, the number average molecular weight of the polymer is 1000-5000.

[0030] In some embodiments, the chemical structure of the polymer is: ; Wherein, n and m are natural numbers, and 10<m+n<60; R1 is a group containing phosphorus and double bonds, so that the phosphorus content in the polymer is not less than 0.1wt%, and R2 is selected from any one of hydrogen or hydrocarbon groups.

[0031] Furthermore, n is selected from a natural number of 1 to 21, m is selected from a natural number of 6 to 54, and the value of n / m is 1 / 9 to 1 / 1.85. In the present application, the content (degree of polymerization) of the B segment in the polymer is preferably higher, because the A segment has a high content and good flame retardancy, but the molecular weight will be larger, the polymer solubility will deteriorate and the viscosity will be very high, resulting in poor fluidity of the resin composition during pressing, resulting in glue shortage, and the B segment content is low, resulting in fewer hydrocarbon segments, poor dielectric properties, and difficult to use in high-frequency and high-speed fields.

[0032] In some embodiments, the chemical structure of the polymer is selected from any one of the following Formula I to Formula V: Among them, R 11 Selected from , , , Any of R 12 Selected from , Any of R 13 , R 15 Independently selected from , Any of .

[0033] In a second aspect, the present application also provides a method for preparing the reactive phosphorus-containing polymer described in the first aspect, which is obtained by polymerization reaction of double bonds in phosphorus-containing and carbon-carbon double bond-containing monomers and carbon-carbon double bonds in divinylbenzene under the action of an initiator.

[0034] The phosphorus-containing and carbon-carbon double bond-containing monomer may be a compound represented by the following chemical structural formula:

[0035] In some embodiments, the preparation method comprises the following steps: (1) taking a divinylbenzene monomer, a phosphorus-containing monomer containing a carbon-carbon double bond, an initiator and a solvent, wherein the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 100 parts by weight, and the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 65-90 parts by weight, 9.5-35 parts by weight and 0.01-0.5 parts by weight respectively; (2) mixing a phosphorus-containing and carbon-carbon double bond-containing monomer with a solvent, stirring and heating to 70°C-100°C under a protective gas environment; then slowly adding a divinylbenzene monomer and a solution formed by an initiator and a solvent and a solution formed by a solvent at a uniform speed, and keeping the temperature for reaction for 2-5 hours to obtain a reaction system; (3) Concentrating and washing to obtain a reactive phosphorus-containing polymer.

[0036] During the preparation process, the double bonds in the phosphorus-containing and carbon-carbon double bond-containing monomer and the carbon-carbon double bonds in divinylbenzene generate free radicals under the initiation of the initiator and undergo free radical polymerization together, so that the flame retardant group is embedded in the macromolecular structure of the polymer through a stable chemical bond, thereby achieving flame retardant modification of the hydrocarbon resin. Therefore, in the reactive phosphorus-containing polymer provided by the present invention, the reactive flame retardant participates in the free radical polymerization reaction of divinylbenzene as a polymerization monomer, and finally exists in the polymer in the form of molecular chain fragments, avoiding the precipitation of small molecules, and also avoiding the phenomenon that the additive flame retardant is easily soluble in water and precipitates or hydrolyzes, while avoiding affecting the mechanical properties and dielectric properties of the polymer. The reactive phosphorus-containing polymer provided by the present invention can truly achieve an efficient and environmentally friendly flame retardant effect.

[0037] Exemplarily, the amount of the phosphorus-containing and carbon-carbon double bond-containing monomer can be 9.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight or 35 parts by weight, as well as specific values ​​between the above-mentioned points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0038] Exemplarily, the amount of the divinylbenzene monomer used can be 65 parts by weight, 68 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, and specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0039] Exemplarily, the amount of the initiator can be 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, and specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0040] Illustratively, the reaction temperature can be 71°C, 75°C, 79°C, 83°C, 85°C, 88°C, 90°C, 92°C, 94°C, 95°C, 98°C or 99°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0041] Exemplarily, the reaction time can be 2.5 h, 3 h, 3.5 h, 4 h or 4.5 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0042] In a specific embodiment, after the two monomers are dissolved in a solvent respectively, the solution containing divinylbenzene monomer and initiator is added to the solution containing phosphorus-containing and carbon-carbon double bond-containing monomer, wherein the concentration of the initiator in the solution containing divinylbenzene monomer and initiator is 0.01%~0.5% by mass fraction, and the concentration of the phosphorus-containing and carbon-carbon double bond-containing monomer in the solution containing phosphorus-containing and carbon-carbon double bond-containing monomer is 9.5~35% by mass fraction.

[0043] In some embodiments, in step (2), the divinylbenzene monomer is added for no less than 30 minutes, and the addition is required to be slow and uniform, and stirring and maintaining a protective gas environment during the addition process. The addition method can be batch addition, dropwise addition, or continuous addition. If batch addition is adopted, the number of batches is no less than 30 times. In addition, the protective gas can be nitrogen or an inert gas. Before the solution containing divinylbenzene monomer and initiator is added to the solution containing phosphorus and carbon-carbon double bond monomer, the protective gas is first introduced for at least 30 minutes to fully exclude oxygen.

[0044] In some embodiments, the mass fraction of the solvent is 2 to 20 times the sum of the mass fractions of the phosphorus-containing and carbon-carbon double bond-containing monomer and the divinylbenzene monomer; and / or The solvent is one or a mixture of acetone, butanone, benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, and butyl acetate; The initiator is a peroxide initiator or an azo initiator.

[0045] In some embodiments, the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; and the azo initiator is azobisisobutyronitrile or azobisisoheptylnitrile.

[0046] In step (3), the concentration is achieved by rotary evaporation, and before washing, a poor solvent is used to precipitate the crude product, and then the product is obtained by filtering and washing. The poor solvent is selected from a mixture of one or more of pentane, hexane, cyclohexane, petroleum ether, methanol, ethanol, and water, and the weight part of the poor solvent used is 1-80 parts by weight, based on 1 part by weight of the reactive phosphorus-containing polymer.

[0047] Exemplarily, the preparation route of the reactive phosphorus-containing polymer of Formula I is as follows:

[0048] Exemplarily, the preparation route of the reactive phosphorus-containing polymer of Formula II is as follows:

[0049] Exemplarily, the preparation route of the reactive phosphorus-containing polymer of formula III is as follows:

[0050] Exemplarily, the preparation route of the reactive phosphorus-containing polymer of Formula IV is as follows:

[0051] Exemplarily, the preparation route of the reactive phosphorus-containing polymer of Formula V is as follows:

[0052] In a third aspect, the present application also provides a resin composition, comprising: 10-30 parts by weight of reactive phosphorus-containing polymer; 20-40 parts by mass of hydrocarbon resin; Filler 30~60 parts by mass; The second initiator is 0.1%~1%; The reactive phosphorus-containing polymer is the reactive phosphorus-containing polymer mentioned above or a reactive phosphorus-containing polymer prepared by the method for preparing the reactive phosphorus-containing polymer mentioned above.

[0053] Wherein, the hydrocarbon resin is at least one of polybutadiene, styrene-butadiene-styrene copolymer, polyisoprene-styrene, and polystyrene-based norbornene; and / or The second initiator is a peroxide initiator or an azo initiator; wherein the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; the azo initiator is at least one of azobisisobutyronitrile or azobisisoheptylnitrile; and / or The filler is a silica filler which is at least one of a silica filler that has not been surface treated or a silica filler that has been surface treated with a vinyl silane coupling agent.

[0054] In a fourth aspect, the present application also provides a board material, comprising a resin prepared from a reactive phosphorus-containing polymer prepared by the reactive phosphorus-containing polymer described in the first aspect or the reactive phosphorus-containing polymer prepared by the preparation method of the reactive phosphorus-containing polymer described in the second aspect, or a resin prepared from the resin composition described in the third aspect.

[0055] The above-mentioned reactive phosphorus-containing polymer and its preparation method and plate of the present application will be described below in conjunction with specific examples. Those skilled in the art should understand that the examples are only to help understand the present invention and should not be regarded as specific limitations of the present application. If no specific technology or conditions are specified in the examples, the conventional technology or conditions in the art or the product instructions are used. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0056] In the following specific implementation of the present invention, the materials involved are as follows: Polybutadiene B-3000, number average molecular weight 3000, purchased from Japan Soda; The initiator azobisisobutyronitrile AIBN was purchased from Chengdu Kelong; Silica, HM102YJ, purchased from Jiangsu Huimai; Triphenyl phosphate, purity 98%, purchased from McLean; Methyl methacrylate, purity 98%, purchased from McLean; Styrene, reagent grade, was purchased from MacLean; N,N-dimethylformamide reagent grade, 99.5%, purchased from MacLean; Divinylbenzene, 55%, purchased from MacLean; Glass fiber cloth, 1080 glass fiber cloth treated with vinyl coupling agent, purchased from Shanghai Honghe; Flame retardant GU304, purchased from Chengdu Keyi; The conductive metal layer, brand HF2-TG-VSP, thickness 1OZ, was purchased from Tongguan.

[0057] Example 1 This embodiment provides a method for preparing a reactive phosphorus-containing polymer, and the reaction path is as follows:

[0058] The specific preparation method is: First, 30.01 g (0.1 mol) of the phosphorus-containing and carbon-carbon double bond-containing monomer in the above reaction path was stirred and dissolved in 200 g of N,N-dimethylformamide and placed in a reaction container. Separately, 0.19 g of azobisisobutyronitrile, 65.1 g (0.5 mol) of divinylbenzene monomer and 100 g of N,N-dimethylformamide were taken as an initiator and stirred until completely dissolved to obtain a divinylbenzene monomer solution for later use. The reaction vessel was purged with nitrogen for more than 30 minutes. Under the protection of nitrogen, stirring was maintained and the temperature was raised to 70° C. The divinylbenzene monomer solution was added dropwise to the system in the reaction vessel. The dropping time was controlled to be more than 30 minutes. The time was counted after the dropping was completed. The reaction time was 3 hours. After the reaction was completed, the reaction solution was subjected to reduced pressure rotary evaporation to remove most of the solvent. The rotary evaporation was stopped when about 100 g of concentrated solution remained. The concentrated solution was then added to 500 g of ethanol to precipitate a crude product. The crude product was then washed with ethanol for 3 times to finally obtain a reactive phosphorus-containing polymer A1, wherein m=50, n=10, refer to Figure 1 , Figure 6 .

[0059] Example 2 A reactive phosphorus-containing polymer with a DOPO group, the reaction pathway is as follows:

[0060] The preparation method is as follows: First, 31.43 g (0.03 mol) of phosphorus-containing and carbon-carbon double bond-containing monomer is stirred and dissolved in 300 g of toluene and placed in a reaction container. Separately take initiator: 0.44 g of azobisisobutyronitrile, 13.19 g (0.1 mol) of divinylbenzene monomer and 150 g of toluene, stir until completely dissolved, and obtain divinylbenzene monomer solution for standby use. Pass nitrogen through the reaction container for more than 30 minutes, keep stirring under nitrogen protection, heat to 80°C, and drop divinylbenzene monomer solution into the system in the reaction container. The dropping time is controlled to be more than 30 minutes. The timing is started after the dropwise addition is completed. The reaction time is 3.5 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure rotary evaporation to remove most of the solvent. The rotary evaporation is stopped when 50 g of concentrated solution remains. Then the concentrated solution is added to 600 g of methanol to precipitate a crude product. The crude product is washed with methanol 3 times to finally obtain a reactive phosphorus-containing polymer A2, whose m=45, n=15, refer to Figure 2 , Figure 7 .

[0061] Example 3 A reactive phosphorus-containing polymer with a nitrogen-phosphorus heterocycle, the reaction pathway is as follows:

[0062] The preparation method is as follows: First, 23.51 g (0.1 mol) of phosphorus-containing and carbon-carbon double bond-containing monomer is stirred and dissolved in 150 g of toluene in a reaction container. Separately take initiator: 0.15 g of azobisisobutyronitrile, 26.04 g (0.2 mol) of divinylbenzene monomer and 300 g of toluene, stir until completely dissolved, and obtain divinylbenzene monomer solution for standby use. Pass nitrogen through the reaction container for more than 30 minutes, keep stirring under nitrogen protection, heat to 95°C, and drop divinylbenzene monomer solution into the system. The dropping time is controlled to be more than 30 minutes. The timing is started after the dropwise addition is completed. The reaction time is 5.5 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure rotary evaporation to remove most of the solvent. The rotary evaporation is stopped when 60 g of concentrated solution is left. The concentrated solution is then added to 600 g of methanol to precipitate a crude product. The crude product is then washed with methanol 3 times to finally obtain a reactive phosphorus-containing polymer A3, whose m=40, n=20, see Figure 3 , Figure 8 .

[0063] Example 4 A reactive phosphorus-containing polymer with a DPO group, the reaction pathway is as follows:

[0064] The preparation method is as follows: First, 48.83 g (0.09 mol) of phosphorus-containing and carbon-carbon double bond-containing monomer is stirred and dissolved in 300 g of toluene and placed in a reaction container. Separately take initiator: 0.44 g of azobisisobutyronitrile, 70.30 g (0.54 mol) of divinylbenzene monomer and 150 g of toluene, stir until completely dissolved, and obtain divinylbenzene monomer solution for standby use. Pass nitrogen through the reaction container for more than 30 minutes, keep stirring under nitrogen protection, heat to 85°C, and drop divinylbenzene monomer solution into the system. The dropping time is controlled to be more than 30 minutes. The timing is started after the dropwise addition is completed. The reaction time is 4.5 hours. After the reaction is completed, the reaction solution is subjected to reduced pressure rotary evaporation to remove most of the solvent. The rotary evaporation is stopped when 140 g of concentrated solution remains. The concentrated solution is then added to 700 g of methanol to precipitate a crude product. The crude product is then washed with methanol 3 times to finally obtain a reactive phosphorus-containing polymer A4, whose m=54, n=9, see Figure 4 , Fig. 9 .

[0065] Comparative Example 1 The difference between this comparative example and Example 1 is that the phosphorus-containing and carbon-carbon double bond-containing monomer is replaced by an equal weight portion of methyl methacrylate.

[0066] Comparative Example 2 The difference between this comparative example and Example 1 is that equal weight parts of the phosphorus-containing and carbon-carbon double bond-containing monomer are replaced by triphenyl phosphate.

[0067] Comparative Example 3 The difference between this comparative example and Example 1 is that the phosphorus-containing and carbon-carbon double bond-containing monomer is replaced by an equal weight portion of styrene monomer.

[0068] Comparative Example 4 The difference between this comparative example and Example 1 is that the mass ratio of the phosphorus-containing and carbon-carbon double bond-containing monomer to the divinylbenzene monomer is 1:11, wherein m=55 and n=5.

[0069] Comparative Example 5 The difference between this comparative example and Example 1 is that the mass fraction ratio of the phosphorus-containing and carbon-carbon double bond-containing monomer to the divinylbenzene monomer is 1:3, wherein m=15, n=45, see Figure 5 .

[0070] Comparative Example 6 The difference between this comparative example and Example 1 is that the phosphorus-containing and carbon-carbon double bond-containing monomer and the divinylbenzene monomer are not added with an initiator, a solvent, or reacted, but are simply mixed together.

[0071] In order to better verify the performance of the reactive phosphorus-containing polymer provided in the present application in copper-clad laminates or other high-frequency and high-speed communication equipment, the reactive phosphorus-containing polymers A1 to A4 prepared above, and the comparative materials obtained in Comparative Examples 1 to 6 were reacted with hydrocarbon resins to prepare insulating resin films, which were further assembled to form copper-clad laminates. The formula of the insulating resin film is: 20 parts of reactive phosphorus-containing polymer or comparative material, 80 parts of hydrocarbon resin B-3000, 100 parts of silicon dioxide, 0.3 parts of initiator azobisisobutyronitrile AIBN, and 15 parts of flame retardant GU304.

[0072] The specific preparation method is as follows: (1) mixing the raw materials with butanone according to the formula to prepare a resin glue solution with a solid content of 55%; (2) applying the resin glue obtained in step (1) to the surface of the glass fiber cloth, and baking it in an oven at 130° C. for 4 min to remove the solvent, thereby obtaining a prepreg; (3) Ten prepregs obtained in step (2) were stacked and coated with HOZ HVLP2 copper foil on both sides at 210°C and 30kg / cm 2 , and hot pressing and curing under the conditions of 1000 μm and 1200 min to obtain the copper clad laminate.

[0073] The polymer materials or copper clad laminates corresponding to the comparative materials obtained in Examples 1 to 4 and Comparative Examples 1 to 6 were subjected to the following tests, respectively, and the specific methods are as follows: (1) Glass transition temperature Tg: tested using a dynamic mechanical analyzer (DMA) Rheometric RSAIII; (2) Flame retardancy: tested according to UL-94 standard; (3) Flame retardant stability: After soaking in water for 1 hour, dry it and measure its flammability again according to the UL-94 vertical burning test standard; (4) Dielectric constant Dk: measured using the split post dielectric resonator (SPDR) method with a dielectric analyzer (HP Agilent E4991A) at a frequency of 10 GHz. (5) Dielectric loss tangent Df: measured using the split post dielectric resonator (SPDR) method and a dielectric analyzer (HP Agilent E4991A) at a frequency of 10 GHz; (6) Peel strength PS: Tested according to IPC-TM-650 2.4.8C standard to test the peel strength between the copper foil and the circuit board after thermal stress; (7) PCT for moisture and heat resistance: PCT 6h, make three samples of 100mm×100mm size from the board after etching away the copper foil; steam the board sample in a pressure cooker at 105℃ and 103.4KPa for 360min, and then immerse it in a 288℃ tin furnace to test the delamination and bursting time. If it is less than 300s, record the specific time; stop the test after 5min, and record the time as ≥300s. √ means that the sample has no delamination and bursting within 300s, and the moisture and heat resistance has passed; × means that the sample has delamination and bursting within 300s, and the moisture and heat resistance test has not passed; (8) Chemical resistance (solvent resistance): Soak the board in toluene and place it at 25°C for one day, then take it out to dry the solvent and check whether the board surface is bubbling or disintegrating. If the board surface does not change, it means that the solvent resistance is good, marked with √; if it bubbles or disintegrates, it means that the solvent resistance is poor, marked with ×; (9) Molecular weight and its distribution were measured by gel permeation chromatography. The instrument used was an American company-type high performance gel permeation chromatograph, tetrahydrofuran (as solvent, monodisperse polystyrene as standard calibration sample; (10) Fourier transform infrared (FT-IR): Take an appropriate amount of sample and grind it with potassium bromide to make a pellet, and scan it in the range of 400-4000 cm-1.

[0074] The test results are shown in Table 1

[0075] From the data in Table 1, it can be seen that Examples 1 to 4 have both vinyl and phosphorus elements, and have significantly better flammability and flame retardant stability than Comparative Examples 1 and 6; Examples 1 to 3 have ester groups, and the dielectric properties are lower than that of Comparative Example 3, but the heat resistance and flammability are better than those of Comparative Example 3; The flame retardants in Examples 1 to 4 (the reactive phosphorus-containing polymers obtained in this application) are partly reactive and partly additive, and compared with Comparative Example 2, the flame retardants are all additive, and the flame retardant properties of the material in Comparative Example 2 are significantly reduced after boiling. Therefore, the flame retardant stability of Examples 1 to 4 is better; Comparative Examples 1 and 3 only have additive flame retardants, so the flame retardancy is worse than the others; in addition, the moisture and heat resistance and chemical resistance of Comparative Example 2 are slightly better than those of other examples; Compared with Example 1, the ratio of m and n in Comparative Examples 4 to 5 exceeds the range, resulting in the flame retardancy or dielectric constant of the material being slightly better than that of Example 1; The flame retardant and divinylbenzene in Comparative Example 6 are both directly added. Compared with Example 1, the examples have excellent dielectric properties, flame retardancy, flame retardant stability, moisture and heat resistance, chemical resistance, and excellent reliability.

[0076] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A reactive phosphorus-containing polymer, characterized in that: The polymer is a block polymer, including segment A and segment B; The A segment includes a carbon chain A and a phosphorus-containing substituent connected to the carbon chain A; the B segment includes a carbon chain B and a divinylbenzene substituent connected to the carbon chain B; The content of phosphorus in the polymer is not less than 0.1wt% and not more than 10wt% in terms of mass percentage; the number average molecular weight of the polymer is 1000-5000.

2. The reactive phosphorus-containing polymer according to claim 1, characterized in that The general chemical structure formula of the polymer is: ； Wherein, n and m are natural numbers, and 10<m+n<60; R1 is a group containing phosphorus and double bonds, so that the phosphorus content in the polymer is not less than 0.1wt%, and R2 is selected from any one of hydrogen or hydrocarbon groups.

3. The reactive phosphorus-containing polymer according to claim 1 or 2, characterized in that: The chemical structure of the polymer is selected from any one of the following formulas I to V: Among them, R 11 Selected from , , , Any of R 12 Selected from , Any of R 13 , R 15 Independently selected from , Any of .

4. The method for preparing a reactive phosphorus-containing polymer according to any one of claims 1 to 3, characterized in that: The product is obtained by polymerization reaction of double bonds in phosphorus-containing and carbon-carbon double bond-containing monomers and carbon-carbon double bonds in divinylbenzene under the action of an initiator.

5. The method for preparing a reactive phosphorus-containing polymer according to claim 4, characterized in that: The following steps are involved: (1) taking a divinylbenzene monomer, a phosphorus-containing monomer containing a carbon-carbon double bond, an initiator and a solvent, wherein the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 100 parts by weight, and the weight parts of the divinylbenzene monomer, the phosphorus-containing monomer containing a carbon-carbon double bond and the initiator are 65-90 parts by weight, 9.5-35 parts by weight and 0.01-0.5 parts by weight respectively; (2) mixing a phosphorus-containing and carbon-carbon double bond-containing monomer with a solvent, stirring and heating to 70°C-100°C under a protective gas environment; then slowly adding a divinylbenzene monomer and a solution formed by an initiator and a solvent at a uniform speed, and keeping the temperature for reaction for 2-5 hours to obtain a reaction system; (3) Concentrating and washing to obtain a reactive phosphorus-containing polymer.

6. The method for preparing a reactive phosphorus-containing polymer according to claim 5, characterized in that: In the step (2), the divinylbenzene monomer is added for no less than 30 minutes.

7. The method for preparing a reactive phosphorus-containing polymer according to claim 6, characterized in that: The mass fraction of the solvent is 2 to 20 times the sum of the mass fractions of the phosphorus-containing and carbon-carbon double bond-containing monomer and the divinylbenzene monomer; and / or The solvent is one or a mixture of acetone, butanone, benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, and butyl acetate; and / or The initiator is a peroxide initiator or an azo initiator; wherein the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; and the azo initiator is azobisisobutyronitrile or azobisisoheptylnitrile.

8. A resin composition, characterized in that include: 10-30 parts by weight of reactive phosphorus-containing polymer; 20-40 parts by mass of hydrocarbon resin; Filler 30~60 parts by mass; The second initiator is 0.1%~1%; The reactive phosphorus-containing polymer is the reactive phosphorus-containing polymer described in any one of claims 1 to 3 or the reactive phosphorus-containing polymer prepared by the method for preparing the reactive phosphorus-containing polymer described in any one of claims 4 to 7.

9. The resin composition according to claim 8, characterized in that The hydrocarbon resin is at least one of polybutadiene, styrene-butadiene-styrene copolymer, polyisoprene-styrene, and polystyrene-based norbornene; and / or The second initiator is a peroxide initiator or an azo initiator; wherein the peroxide initiator is selected from one of dibenzoyl peroxide, dodecyl peroxide, tert-butyl pervalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; the azo initiator is at least one of azobisisobutyronitrile or azobisisoheptylnitrile; and / or The filler is a silica filler which is at least one of a silica filler that has not been surface treated or a silica filler that has been surface treated with a vinyl silane coupling agent.

10. A plate material comprising a resin prepared from the reactive phosphorus-containing polymer according to any one of claims 1 to 3 or the reactive phosphorus-containing polymer prepared by the method for preparing a reactive phosphorus-containing polymer according to any one of claims 4 to 7, or a resin prepared from the resin composition according to any one of claims 8 to 9.

11. The sheet material according to claim 9, characterized in that The plate material is a copper-clad plate, an insulating plate or a laminate.

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