CN117004178A

CN117004178A - Toughened and modified compound and its preparing process

Info

Publication number: CN117004178A
Application number: CN202210477921.1A
Authority: CN
Inventors: 巫胜彦; 陈子方; 曾柏凯; 许喻傑; 李德傑; 余少维
Original assignee: Jiangxi Lianmao Electronic Technology Co ltd
Current assignee: Jiangxi Lianmao Electronic Technology Co ltd
Priority date: 2022-04-29
Filing date: 2022-04-29
Publication date: 2023-11-07

Abstract

The application provides a toughened and modified compound and a manufacturing method thereof, wherein the toughened and modified compound comprises the following components: a polybenzoxazine compound; a toughening agent comprising an anhydride grafted olefin polymer; and a modifier, which comprises diisocyanate compound; wherein the diisocyanate of the modifier is bonded with the polybenzoxazine compound and the anhydride of the toughening agent respectively. The application has high toughness and excellent mechanical property, thus having wide application range in the fields of electronics, aerospace and the like.

Description

Toughened and modified compound and its preparing process

Technical Field

The present application relates to a toughened and modified compound and a manufacturing method thereof, particularly to a polybenzoxazine compound with olefinic polymer modification.

Background

Polybenzoxazines are thermosetting resins containing nitrogen and having a phenolic resin-like structure, and are superior in performance to conventional phenolic resins, and benzoxazine compounds are generally compounds prepared from phenolic compounds, primary amines and formaldehyde compounds by Mannich (Mannich) reaction, which is heated or catalyzed to ring-open polymerize a phenolic resin-like network, called benzoxazine resin (benzoxazine resin).

Benzoxazine resins have many superior properties compared to traditional phenolic resins, such as: the polymerization process has no release of small molecule byproducts and low volume shrinkage; the moisture absorption rate is low; the heat resistance, mechanical property, electrical property and flame retardant property are all good. Therefore, benzoxazine resins are widely used in the fields of composite matrix resins, solvent-free impregnating varnishes, electronic packaging materials, flame-retardant materials, electrical insulating materials and the like.

Although benzoxazine resins have many of the above advantages, benzoxazines have brittle mechanical properties after thermal ring-opening polymerization, which is a barrier to be overcome in application development.

Disclosure of Invention

In view of this, it is one of the problems to be solved by the present application how to improve the mechanical properties of the existing polybenzoxazines to enhance the processability.

The main objective of the present application is to provide a toughened and modified compound, which comprises: a polybenzoxazine compound; a toughening agent comprising an anhydride grafted olefin polymer; and a modifier, which comprises diisocyanate compound; wherein the diisocyanate of the modifier forms a bond with the polybenzoxazine compound and the anhydride of the toughening agent, respectively.

In a preferred embodiment, the toughening agent comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.

In a preferred embodiment of the present application, the modifier is selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, etc., 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.

In a preferred embodiment, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a diamine type polybenzoxazine.

In a preferred embodiment, the polybenzoxazine compound is selected from the group consisting of bisphenol A type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzoxazine, diaminodiphenylmethane type benzoxazine, diaminodiphenyl ether type benzoxazine and polyimide type benzoxazine.

In a preferred embodiment, the toughened and modified compound is selected from the group consisting of a modified poly (benzoxazine) compound selected from the group consisting of an isophorone diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened poly (benzoxazine) compound, a methylene dicyclohexyl diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened poly (benzoxazine) compound, a hexamethylene diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened poly (benzoxazine) compound, an isophorone diisocyanate modified polypropylene grafted maleic anhydride toughened poly (benzoxazine) compound, a methylene dicyclohexyl diisocyanate modified polypropylene grafted maleic anhydride toughened poly (benzoxazine) compound, a hexamethylene diisocyanate polypropylene grafted maleic anhydride toughened poly (benzoxazine) compound, an isophorone diisocyanate modified poly (ethylene) grafted maleic anhydride toughened poly (benzoxazine) compound, a methylene dicyclohexyl diisocyanate modified poly (ethylene) grafted maleic anhydride poly (benzoxazine) compound, and a hexamethylene diisocyanate grafted poly (ethylene) maleic anhydride toughened poly (benzoxazine) compound.

Another object of the present application is to provide a method for preparing the toughened and modified compound as described above, comprising: (a) Adding a polybenzoxazine compound and a solvent to a reaction flask, heating to about 50 to 80 ℃, and stirring; (b) Gradually adding an anhydride grafted olefin polymer into the solution in the step (a) under stirring, and raising the temperature to 80-100 ℃ to completely dissolve the anhydride grafted olefin polymer so as to form a synthetic solution; (c) Adding diisocyanate compound, heating and gradually heating the synthesized solution to 120-150 ℃ and reacting for 0.5-2 hours; and (d) stopping heating and cooling to room temperature to obtain the toughened and modified compound.

In a preferred embodiment, the solvent is selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

In a preferred embodiment, the temperature of step (a) is raised to 55 to 65℃and the temperature of step (b) is raised to 85 to 95 ℃.

In a preferred embodiment, step (c) is heated to 130℃and reacted for 1 hour.

Therefore, the toughened and modified compound and the manufacturing method thereof provided by the application are to toughen and modify the polybenzoxazine compound by using olefin polymer, and bond is formed between the compound and diisocyanate compound, so that the compound has good heat resistance and mechanical property and low water absorption. Therefore, the application is more suitable for being applied to composite materials and electronic circuit materials, and the resin material can be applied to the wide fields of aerospace, electronic motors, automobile industry and the like.

Drawings

The details of one or more embodiments of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter of the present description will become apparent from the description, the drawings, and the claims, wherein:

FIG. 1 is a schematic representation of the reaction scheme of a preferred embodiment of the present application.

Wherein, the reference numerals:

100: toughening modified compound

110: bisphenol A type polybenzoxazine

120: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride

130: isofordone diisocyanate

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. As used in the present application, the following terms have the following meanings.

As used herein, terms such as "first," "second," "third," "fourth," and "fifth," etc., describe various elements, components, regions, layers and/or sections that are not limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another. Unless the context clearly indicates otherwise, terms such as "first", "second", "third", "fourth" and "fifth" as used herein do not imply a sequence or order.

The term "or" as used herein means "and/or" unless otherwise indicated. The terms "comprises" or "comprising" when used herein are intended to exclude the presence of, or the addition to, one or more other elements, steps, operations, and/or components; similarly, the terms "include", "contain", "include", "have" and "have" as used herein are interchangeable and are not limiting. "a" or "an" means that the grammatical object of the article is one or more (i.e., at least one). As used herein and in the claims, the singular forms "a", "an", and "the" include plural referents.

The present application is a toughened and modified compound comprising: a polybenzoxazine compound; a toughening agent; a modifying agent.

The "polybenzoxazine compound (abbreviated herein as BZ)" described herein is a thermosetting resin containing nitrogen and having a phenolic resin-like structure, and the benzoxazine compound is a six-membered heterocyclic compound system composed of an oxygen atom and a nitrogen atom, typically a compound obtained by Mannich (Mannich) reaction of a phenol compound, a primary amine and a formaldehyde compound, which is ring-opening polymerized under the action of heat or a catalyst to form a phenolic resin-like network structure, which may also be referred to as a benzoxazine resin. In a preferred embodiment, the polybenzoxazine compound is a bisphenol type polybenzoxazine or a diamine type polybenzoxazine. In a more preferred embodiment, the polybenzoxazine compound is at least one selected from the group consisting of bisphenol A type benzoxazine (BPA-BZ), bisphenol F type benzoxazine (BPF-BZ), bisphenol S type benzoxazine (BPS-BZ), diaminodiphenyl methane type benzoxazine (DDM-BZ), diaminodiphenyl ether type benzoxazine (ODA-BZ) and polyimide type benzoxazine (polybenzoxazine with polyimide).

As used herein, a "toughening agent" is an olefin polymer comprising anhydride grafts, which has excellent electrical properties and good impact properties; preferably, the olefin polymer of the toughening agent is grafted with maleic anhydride, has good compatibility with base material resin, and achieves the modification effect. In a preferred embodiment, the toughening agent is such as, but not limited to: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA), polypropylene grafted maleic anhydride (PP (Poly Propylene) -g-MA) or polyethylene grafted maleic anhydride (PE (Poly Ethylene) -g-MA).

The term "modifier" as used herein includes diisocyanate compounds wherein the diisocyanate forms a bond with the polybenzoxazine compound and the anhydride of the toughening agent, respectively, to achieve chemical modification. The cyanate ester compound can increase the reactive functional groups in the resin structure, thereby improving the crosslinking density of the epoxy cured product and improving the heat resistance. For example, the cyanate ester compound may be a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, for example: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate and the like, 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and the like. In a preferred embodiment, the modifier comprises: isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (Methylene dicyclohexyldiisocyanate or hydrogenated MDI, HMDI), or Hexamethylene Diisocyanate (HDI)).

In a preferred embodiment, the toughened and modified compound of the present application is a composition comprising a polymer selected from the group consisting of a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (IPDI/SEBS-g-MA/BZ), a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (HMDI/SEBS-g-MA/BZ), a modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound (HDI/SEBS-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (IPDI/PP-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (HMDI/PP-g-MA/BZ), a modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound (HDI/PP-g-MA/BZ), a modified polypropylene toughened polystyrene/PP-g-MA/BZ, and a modified polypropylene toughened polybenzoxazine compound (HDI/PP-g-MA/BZ), the group consisting of a methylene dicyclohexyl diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound (HMDI/PE-g-MA/BZ) and a hexamethylene diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound (HDI/PE-g-MA/BZ).

Furthermore, the present application also relates to a method for preparing the toughening modified compound as described above, which comprises the following steps (a) to (d).

Step (a): a polybenzoxazine compound and a solvent are added to a reaction flask, heated to about 50 to 80℃and stirred well. In the step (a), the reaction is heated to 50 to 80 ℃, such as but not limited to: 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any two values between the two. In a more preferred embodiment, step (a) is performed by heating to 55 to 65 ℃, such as, but not limited to: 55 ℃, 57 ℃, 59 ℃, 61 ℃, 63 ℃, 65 ℃ or any two values between the two values.

As used herein, "solvent" refers to any solvent that can dissolve or disperse the components in solution, but does not react with the components. In a preferred embodiment, the solvent may be selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

Step (b): gradually (e.g., within 20 minutes) adding an anhydride grafted olefin polymer to the solution of step (a) with stirring, and raising the temperature to 80 to 100 ℃ to completely dissolve the polymer, thereby forming a synthetic solution. In the step (b), the reaction is heated to 80 to 100 ℃, for example but not limited to: 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or any two values between the two values. In a more preferred embodiment, the temperature of step (b) is raised to 85 to 95 ℃, such as but not limited to: 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ or any two values between the two.

Step (c): the diisocyanate compound was added, the synthetic solution was heated and gradually warmed to 120 to 150 ℃ and reacted for 0.5 to 2 hours. In the step (c), the reaction is heated to 120 to 150 ℃, such as but not limited to: 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or any two values between the two values; the reaction time is 0.5 to 2 hours, such as but not limited to: 0.5 hours, 1 hour, 1.5 hours, 2 hours or between the two time points. In a more preferred embodiment, step (c) is heated to 130℃and reacted for 1 hour.

Step (d): stopping heating and cooling to room temperature to obtain the toughened and modified compound.

The application not only forms the chemical modification of polyimide bond through the reaction of isocyanate and anhydride, but also achieves the effect of toughening and improving through the modification of the toughening agent and the polybenzoxazine compound, so that the application has high toughness and excellent mechanical property. Further, if the present application is blended with other materials, a composite material having excellent properties can be further formed.

Examples

The present application will be further described in terms of detailed description and embodiments, however, it should be understood that these embodiments are merely used to facilitate easier understanding of the present application and to clarify aspects of the present application and the benefits achieved thereby, and are not intended to limit the scope of the present application.

Example 1

6 toughened and modified compounds (example compounds A-F) were prepared according to the present application. Metal foil laminates were then prepared using the example compounds a-F.

Examples Compound A

Referring to the exemplary reaction scheme of fig. 1, m, n, X, Y in fig. 1 is the same or different positive integer. 200 g of bisphenol A benzoxazine (BPA-BZ) 110 and 600 g of toluene were added to a 3 liter four port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride (SEBS-g-MA) 120 was gradually added to the toluene solution over 20 minutes, at which time the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of isophorone diisocyanate (IPDI) 130 was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound A of the embodiment, namely the toughened and modified compound 100.

Examples compound B

200 g of ODA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, and cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound B of the example.

Examples compound C

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of PP-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound C of the example.

Examples compound D

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of PE-g-MA were gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of IPDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound D of the example.

Examples Compound E

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 grams of HMDI was added, the synthesis solution was heated and gradually warmed to about 130 ℃, and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound E of the example.

Examples compound F

200 g of BPA-BZ and 600 g of toluene were added to a 3 liter four-port separable reaction flask equipped with a heating device, thermometer, stirrer, cooling tube, heated to about 60℃and stirred uniformly. With stirring, 20 g of SEBS-g-MA was gradually added to the toluene solution over 20 minutes, at which point the temperature of the synthesis solution was raised to 90℃to allow complete dissolution. Next, about 5 g of HDI was added, the synthesis solution was heated and gradually warmed to about 130℃and reacted for 1 hour. And then stopping heating and cooling to room temperature to obtain the compound F of the example.

Material

BPA-BZ and ODA-BZ are manufactured by Yuanhong corporation; SEBS-g-MA is produced by Taiwan Li Changrong company; PP-g-MA is produced by ExxonMobil chemical company, product model Exxelor ^TM PO1015; PE-g-MA is produced by Exxelor, product model Exxelor ^TM pE1040。

Table 1 below shows the preparation ingredients and contents of the compounds A to F of the examples.

TABLE 1

Example 2

The following provides a non-limiting method of preparing the toughened and modified compounds of the present application into metal foil laminate. Ten non-limiting example laminates (example laminates 1-10) and six comparative example laminates (comparative example laminates 1-6) were prepared with example compounds according to a method similar to the method disclosed below. However, the specific methods of preparing the example laminate plates 1 to 10 and the comparative example laminate plates 1 to 6 will generally differ in one or more respects from the methods disclosed below.

Example laminate 1

Preparation of a resin composition: the solution of compound a of the above example was taken at 30 g, 5 g of thermosetting resin (BMI), 25 g of CNE epoxy resin and 40 g of solvent (butanone, MEK) were added, and the mixture was uniformly mixed with a homogenizing mixer to dissolve the components. After the resin was completely dissolved, 40 g of silica was added, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.

Preparing a prepreg: the reinforcing material Glass fiber cloth (base material E-Glass) was impregnated or coated with the varnish-liquid resin composition, and the impregnated or coated base material was dried at 80℃for 3 minutes and at 180℃for 7 minutes, whereby a prepreg in a semi-cured state (B-stage) was obtained.

Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5 oz of metal foil (copper foil) was laminated on each of the outermost layers on both sides, followed by hot press curing at high temperature. The hot pressing conditions are as follows: the temperature is raised to 200 ℃ to 220 ℃ at a heating rate of 3.0 ℃/min, and the copper foil laminated plate is prepared by hot pressing for 180 minutes at a pressure of 15 kg/square centimeter (8 kg/square centimeter at initial pressure) at the temperature.

Examples laminate panels 2-10

The example laminate sheets 2-10 were prepared according to a method similar to that of example laminate sheet 1, however, example laminate sheets 2-10 may differ in one or more respects, with the specific differences shown in table 2 below.

Table 2 shows the results of measuring the preparation components and contents of the laminate sheets 1 to 10, and the adhesion strength, the thermal expansion coefficient in the Z-axis direction, and the heat resistance.

TABLE 2

Remarks: EG in the Table represents E-Glass. The units of addition of each component in the table are grams.

Comparative example laminate 1

Preparation of a resin composition: 30 g of non-toughened and modified BPA-BZ was added with 5 g of thermosetting resin (BMI), 25 g of epoxy resin, 2 g of toughening resin and 40 g of solvent (butanone, MEK) and mixed uniformly by a homogenizing mixer to dissolve the components. After the resin was completely dissolved, 40 g of silica was added, and the mixture was uniformly mixed with a homogenizing mixer and dispersed in a solvent to prepare a varnish-like resin composition.

Preparing a metal foil laminated plate: four prepregs were laminated, and 0.5 oz of copper foil was laminated on each of the outermost layers on both sides, followed by hot press curing at high temperature. The hot pressing conditions are as follows: the temperature was raised to 200℃to 220℃at a heating rate of 3.0℃per minute, and hot-pressed at this temperature for 180 minutes at a pressure of 15 kg/cm (initial pressure of 8 kg/cm). To obtain a copper foil laminate.

Comparative example laminate 2-6

Comparative example laminate sheets 2-6 were prepared in a similar manner to comparative example laminate sheet 1, however comparative example laminate sheets 2-6 may differ in one or more respects, the specific differences being disclosed in Table 3 below.

Table 3 shows the results of measuring the preparation components and contents of the laminate sheets 1 to 6 of comparative examples, and the adhesion strength, the thermal expansion coefficient in the Z-axis direction, and the physical properties such as heat resistance.

TABLE 3 Table 3

Remarks: CSR in the table is core-shell rubber. Ricon100 is a butadiene-styrene copolymer. EG represents E-Glass. The units of addition of each component in the table are grams.

Material

BPA-BZ and ODA-BZ are manufactured by Yuanhong corporation; filler SiO ₂ Is 10um cut manufactured by Sibiraex; the thermosetting resin BMI (KI-70) is produced by Dai and Chemie; CNE epoxy resin is prepared from long chainSpring manufactured by Artificial resin company; the reinforcing material is E-Glass cloth 2116 produced by Taibo Glass company; the toughening resin is Ricon100 manufactured by CSR, polyscope company manufactured by Kaneka company; the copper foil was H1.5. 0.5 OZ from Nanya.

Characterization test

CTE test: according to IPC-TM-650.2.4.24.5 specifications, the coefficient of thermal expansion (coefficient of thermal exapansion, CTE) change rate (total Z-CTE) in the Z-axis direction of a sample to be measured at a temperature lower than the glass transition temperature (Tg) is measured using a thermo-mechanical analyzer (thermal mechanical analyzer, TMA). Z-CTE is measured in% over a temperature range of 50 ℃ to 260 ℃.

And (3) adhesive strength test: the adhesion strength refers to the adhesion of the metal foil to the laminated prepreg, and in this test, the adhesion is expressed by the amount of force required by a 1/8 inch wide copper foil that is peeled vertically from the board surface. Tear strength is in pounds force per inch (1 bf/in).

Heat resistance test: immersing the dried metal foil laminate in a soldering bath at 288 ℃ and 300 ℃ for 100 seconds, repeating the process for 3 times, showing excellent heat resistance, and recording as "O"; when the appearance had a bubbling bulge, it was recorded as "×" indicating that the heat resistance was poor.

From the above results, it is understood that the crosslinked and brittle mechanical properties are inferior to those of the comparative example laminate sheets 1 to 6 containing the non-toughening-modified polybenzoxazine compound, and that even if a large amount of toughening agent or rubber is added externally, the example laminate sheets 1 to 10 containing the toughening-modified compound of the present application exhibit good mechanical properties and heat resistance. Therefore, the application is more suitable for being applied to the wide fields of composite materials, electronic circuit materials and the like.

In summary, the present application provides a toughened and modified compound and a method for preparing the same, wherein an olefin polymer is used to toughen and modify a polybenzoxazine compound, and a diisocyanate compound is used to form a chemical bond with the compound, so that the compound has good mechanical properties and heat resistance. Therefore, compared with the characteristic that the mechanical property of the polybenzoxazine compound is fragile after the thermal ring-opening polymerization reaction in the prior art, the resin material using the toughened and modified compound is more suitable for being applied to composite materials, electronic circuit materials and the like, and can be applied to the wide fields of aerospace, electronic motors, automobile industry and the like.

The terms "substantially" and "about" are used herein and are not otherwise defined as describing or claiming small variations. When combined with an event or circumstance, the term can include the exact whereabouts of the event or circumstance and the whereabouts of the event or circumstance to a close approximation. For example, when combined with a numerical value, the term can include a variation of less than or equal to + -10%, such as less than or equal to + -5%, less than or equal to + -4%, less than or equal to + -3%, less than or equal to + -2%, less than or equal to + -1%, less than or equal to + -0.5%, less than or equal to + -0.1%, or less than or equal to + -0.05% of the numerical value.

The foregoing has outlined the components of several embodiments so that those skilled in the art may better understand the concepts of the embodiments of the application. It will be appreciated by those skilled in the art that the embodiments of the application may be used as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art to which the application pertains will also appreciate that such equivalent constructions do not depart from the spirit and scope of the application and that they may make various changes, substitutions and other selections herein without departing from the spirit and scope of the application. Accordingly, the scope of the application is defined by the claims.

Claims

1. A toughened and modified compound, comprising:

a polybenzoxazine compound;

a toughening agent comprising an anhydride grafted olefin polymer; and

A modifier including diisocyanate;

wherein the diisocyanate of the modifier is bonded with the polybenzoxazine compound and the anhydride of the toughening agent respectively.

2. The toughening modified compound of claim 1, wherein the toughening agent comprises: styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride or polyethylene grafted maleic anhydride.

3. The toughening modifying compound according to claim 1, wherein the modifier is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and the like, 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methylene dicyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.

4. The toughening modified compound of claim 1, wherein the polybenzoxazine compound is a bisphenol-type polybenzoxazine or a bis-amine-type polybenzoxazine.

5. The toughening modified compound of claim 1, wherein the polybenzoxazine compound is selected from the group consisting of bisphenol a type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzoxazine, diaminodiphenylmethane type benzoxazine, diaminodiphenyl ether type benzoxazine, and polyimide type benzoxazine.

6. The toughened modified compound of claim 1, wherein the toughened modified compound is a group comprising a polybenzoxazine compound selected from the group consisting of a styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened by isophorone diisocyanate, a methylene dicyclohexyl diisocyanate grafted maleic anhydride toughened polybenzoxazine compound, a hexamethylene diisocyanate modified styrene-ethylene/butylene-styrene copolymer grafted maleic anhydride toughened polybenzoxazine compound, an isophorone diisocyanate modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound, a methylene dicyclohexyl diisocyanate grafted maleic anhydride toughened polybenzoxazine compound, a hexamethylene diisocyanate modified polypropylene grafted maleic anhydride toughened polybenzoxazine compound, an isophorone diisocyanate modified polyethylene grafted maleic anhydride toughened polybenzoxazine compound, a methylene dicyclohexyl diisocyanate grafted maleic anhydride toughened polybenzoxazine compound, and a hexamethylene diisocyanate polyethylene grafted maleic anhydride toughened polybenzoxazine compound.

7. A method of producing the toughening modified compound according to any one of claims 1 to 6, comprising:

(a) Adding a polybenzoxazine compound and a solvent into a reaction bottle, heating to 50-80 ℃, and stirring;

(b) Gradually adding an anhydride grafted olefin polymer into the solution in the step (a) under the condition of stirring, and raising the temperature to 80-100 ℃ at the moment to completely dissolve the anhydride grafted olefin polymer so as to form a synthetic solution;

(c) Adding diisocyanate compound, heating and gradually heating the synthesized solution to 120-150 ℃ and reacting for 0.5-2 hours; and

(d) Stopping heating and cooling to room temperature to obtain the toughened and modified compound.

8. The method of claim 7, wherein the solvent is selected from the group consisting of toluene, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof.

9. The method of claim 7, wherein the step (a) is heating to 55 to 65 ℃ and the step (b) is heating to 85 to 95 ℃.

10. The method of claim 7, wherein the step (c) is performed by heating to 130℃and reacting for 1 hour.