Organic phosphine compound, flame-retardant fiber, composite material composition and application thereof

Abstract

The invention relates to the technical field of flame retardance, in particular to an organic phosphine compound, a flame-retardant fiber, a composite material composition and application thereof, and the organic phosphine compound is a compound obtained by reacting a P OH bond of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound with an epoxy group of furan methyl glycidyl ether. The organic phosphine compound provided by the invention contains phosphaphenanthrene and furan ring structures, and has good char forming property and flame retardance. The flame retardant containing the organic phosphine compound can be coated on the surface of fiber tows and / or fiber fabrics to prepare flame-retardant fibers.

Description

Technical Field

[0001] The invention relates to the field of flame retardant technology, and in particular to an organic phosphine compound, a flame retardant fiber, a composite material composition and applications thereof. Background Art

[0002] Fiber-reinforced resin-based composite materials have the advantages of light weight, high strength, corrosion resistance, and fatigue resistance. They have broad application prospects in the manufacturing of transportation vehicles such as aircraft, automobiles, trains, and ships. Fire resistance is a basic issue that must be considered in the selection and use of materials in these fields. Epoxy resin is a commonly used resin matrix for fiber-reinforced composite materials. It has good comprehensive mechanical properties and cost-effectiveness, but its flame retardant performance is poor, and the limiting oxygen index is only about 20%. Therefore, the flame retardant modification of epoxy resin has always been a hot topic in the industry. The common flame retardant modification method of epoxy resin is to add inorganic or organic flame retardants. Inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and zinc borate are added in large amounts, have poor flame retardant efficiency, and have a significant impact on the molding processability and final mechanical properties of composite materials; there are many types of organic flame retardants, mainly halogen, phosphine, nitrogen, silicon, etc. Among them, organic phosphine flame retardants have the advantages of high flame retardant efficiency, low smoke, and non-toxicity. It is one of the most widely used halogen-free flame retardants.

[0003] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a highly efficient reactive organic phosphine flame retardant. The PH group in its molecular structure can react with the epoxy group in the epoxy resin to obtain a flame-retardant modified epoxy resin. However, the viscosity of the epoxy resin after the reaction increases significantly, which makes it difficult to meet the requirements of vacuum infusion, winding, pultrusion and other liquid molding processes for resin viscosity. Patent application CN201110346692.1 uses DOPO organic solution to modify the surface of natural fibers for flame retardancy, and the prepared flame-retardant natural fiber reinforced phenolic resin composite material has a flame retardant grade of UL94 V-0. Patent application CN202211672083.X uses DOPO to react with epoxy resin and active diluent to obtain a flame-retardant modified epoxy resin, and the prepared glass fiber reinforced composite material has a flame retardant grade of UL94 V-0. Summary of the invention

[0004] One of the technical problems to be solved by the present invention is that in the prior art, the addition of an organic phosphine flame retardant during flame retardant modification of fiber composite materials will lead to an increase in the viscosity of the resin system and fail to meet the process requirements of liquid molding processes such as vacuum infusion, winding, and pultrusion, and the flame retardant efficiency is poor. An organic phosphine compound and a preparation method thereof are provided. The organic phosphine compound is used as a flame retardant, coated on the surface of a fiber (such as a fiber bundle, a fiber product), and then the fiber is composited with a resin matrix to prepare a fiber composite material, thereby avoiding direct flame retardant modification of the resin matrix or reducing the amount of flame retardant added to the resin matrix, thereby solving the technical problem that it is difficult to balance processability and flame retardancy in the prior art.

[0005] The second technical problem to be solved by the present invention is to provide a flame retardant fiber corresponding to the first technical problem to be solved, and a preparation method and application thereof.

[0006] In order to achieve the above object, the first aspect of the present invention provides an organic phosphine compound, which is a compound obtained by reacting the POH bond of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound with the epoxy group of furan methyl glycidyl ether.

[0007] The second aspect of the present invention provides a method for preparing the organic phosphine compound of the present invention, the method comprising:

[0008] In the presence of a catalyst, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound represented by formula (II) is contacted with the furan methyl glycidyl ether represented by formula (III);

[0009] The catalyst is selected from at least one of triphenylphosphine, quaternary phosphonium salt and quaternary ammonium salt;

[0010]

[0011] Among them, in formula (II) and formula (III), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro.

[0012] The third aspect of the present invention provides a use of the organic phosphine compound of the present invention in flame retardancy.

[0013] A fourth aspect of the present invention provides a flame retardant fiber, the flame retardant fiber comprising:

[0014] Fiber tows and / or fiber fabrics;

[0015] and, an organic phosphine flame retardant coated on the surface of the fiber tow and / or fiber fabric;

[0016] The organic phosphine flame retardant accounts for 5wt%-30wt% of the mass of the fiber tow and / or fiber fabric;

[0017] The organic phosphine flame retardant contains the organic phosphine compound of the present invention.

[0018] A fifth aspect of the present invention provides a method for preparing the flame-retardant fiber of the present invention, the method comprising:

[0019] (1) dispersing an organic phosphine flame retardant in water to obtain a suspension;

[0020] (2) removing water after first contacting the fiber tow and / or fiber fabric with the suspension;

[0021] The organic phosphine flame retardant contains the organic phosphine compound of the present invention.

[0022] A sixth aspect of the present invention provides a use of the flame retardant fiber of the present invention in preparing a flame retardant fiber composite material.

[0023] A seventh aspect of the present invention provides a flame retardant fiber composite material composition, the composition comprising:

[0024] Organic resin and the flame retardant fiber of the present invention;

[0025] The mass ratio of the flame retardant fiber to the organic resin is 20-80:80-20.

[0026] An eighth aspect of the present invention provides a method for preparing a flame retardant fiber composite material, the method comprising: mixing the flame retardant fiber of the present invention with an organic resin matrix, and curing to obtain the flame retardant fiber composite material.

[0027] A ninth aspect of the present invention provides a flame retardant fiber composite material prepared by the method for preparing the flame retardant fiber composite material of the present invention.

[0028] A tenth aspect of the present invention provides an application of the composite material of the present invention in the preparation of one or more products of automobiles, high-speed railways, aviation, and ships.

[0029] Through the above technical scheme, the organic phosphine compound provided by the present invention contains phosphaphenanthrene and furan ring structures and has good charring property and flame retardancy.

[0030] The flame retardant containing the organic phosphine compound of the present invention can be coated on the surface of fiber bundles and / or fiber fabrics to prepare flame-retardant fibers.

[0031] In the prior art, when preparing fiber composite materials, organic phosphine flame retardants are usually added to the organic resin matrix to modify the organic resin matrix to be flame retardant, but this process will increase the viscosity of the resin system and fail to meet the process requirements of liquid molding processes such as vacuum infusion, winding, and pultrusion, and the flame retardant efficiency is poor. When the flame-retardant fiber of the present invention is used to prepare a fiber composite material, after the flame-retardant fiber is in contact with the organic resin matrix, the flame retardant coated on the surface of the flame-retardant fiber can be dissolved in the organic resin matrix during the heating and curing process, thereby avoiding the flame retardant powder particles from forming stress concentration points in the composite material, resulting in a decrease in the mechanical properties of the composite material.

[0032] The use of the flame-retardant fiber of the present invention to prepare fiber composite materials can reduce the amount of flame retardant added to the organic resin matrix or directly use a non-flame-retardant organic resin matrix, while ensuring the processability during the preparation of the flame-retardant composite material and its products while having good flame retardancy. DETAILED DESCRIPTION

[0033] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0034] A first aspect of the present invention provides an organic phosphine compound, which is a compound obtained by reacting a POH bond of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound with an epoxy group of a furan methyl glycidyl ether.

[0035] According to a preferred embodiment of the present invention, the structural formula of the organic phosphine compound is as shown in formula (I);

[0036]

[0037] In formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro;

[0038] According to a preferred embodiment of the present invention, R1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 All are hydrogen, R 9 , R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro.

[0039] According to a preferred embodiment of the present invention, the structural formula of the organic phosphine compound is as shown in formula (I-1);

[0040]

[0041] The organic phosphine compounds having the aforementioned structural formula can achieve the purpose of the present invention, and there is no special requirement for their preparation methods. According to a preferred embodiment of the present invention, the second aspect of the present invention provides a method for preparing the organic phosphine compound of the present invention, the method comprising:

[0042] In the presence of a catalyst, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound represented by formula (II) is contacted with the furan methyl glycidyl ether represented by formula (III);

[0043] The catalyst is selected from at least one of triphenylphosphine, quaternary phosphonium salt and quaternary ammonium salt;

[0044]

[0045] Among them, in formula (II) and formula (III), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro.

[0046] In the present invention, the contact conditions have a wide range of optional options. According to a preferred embodiment of the present invention, the contact conditions include: a temperature of 100°C-180°C; the contact time can be reasonably adjusted according to actual needs. According to a preferred embodiment of the present invention, the contact time is 1-8h.

[0047] In the present invention, the amount of the catalyst can be selected in a wide range. According to a preferred embodiment of the present invention, the amount of the catalyst is 0.01 to 1 wt % of the mass of furan methyl glycidyl ether.

[0048] According to a preferred embodiment of the present invention, the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound to furan methyl glycidyl ether is 0.5-2:1.

[0049] According to a preferred embodiment of the present invention, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).

[0050] According to a preferred embodiment of the present invention, the furan methyl glycidyl ether is furan methyl glycidyl ether.

[0051] The third aspect of the present invention provides an application of the organic phosphine compound of the present invention in flame retardancy. The organic phosphine compound provided by the present invention contains phosphaphenanthrene and furan ring structures and has good charring properties and flame retardancy.

[0052] A fourth aspect of the present invention provides a flame retardant fiber, the flame retardant fiber comprising:

[0053] Fiber tows and / or fiber fabrics;

[0054] and, an organic phosphine flame retardant coated on the surface of the fiber tow and / or fiber fabric;

[0055] The organic phosphine flame retardant accounts for 5wt%-30wt% of the fiber tow and / or fiber fabric mass;

[0056] The organic phosphine flame retardant contains the organic phosphine compound of the present invention. The flame retardant containing the organic phosphine compound of the present invention can be coated on the surface of fiber tow and / or fiber fabric to prepare flame-retardant fiber.

[0057] In the present invention, there are a wide variety of fibers that can be selected. The following is an exemplary description of the embodiments of the present invention, but the present invention is not limited to this scope.

[0058] According to one embodiment of the present invention, the fiber is selected from at least one of carbon fiber, glass fiber, basalt fiber, aramid fiber and ultra-high molecular weight polyethylene fiber.

[0059] In the present invention, there is no special requirement for the form of the fiber fabric, for example, the fabric form is one or more of plain, twill or satin.

[0060] According to a preferred embodiment of the present invention, the D 90Less than or equal to 0.1mm. For example, crush the organic phosphine flame retardant to D 90 The powder does not exceed 0.1mm, controlling the average particle size of the organic phosphine flame retardant particles.

[0061] According to a preferred embodiment of the present invention, the flame retardant fiber also includes a suspension aid coated on the surface of the fiber tow and / or fiber fabric, selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, lignin sulfonate, sodium carboxymethyl cellulose, sodium carboxyethyl cellulose methyl cellulose, and polyacrylic acid salt.

[0062] According to a preferred embodiment of the present invention, the content of the suspension aid is 0.5wt%-10wt% of the mass of the organic phosphine flame retardant.

[0063] A fifth aspect of the present invention provides a method for preparing the flame-retardant fiber of the present invention, the method comprising:

[0064] (1) dispersing an organic phosphine flame retardant in water to obtain a suspension;

[0065] (2) removing water after first contacting the fiber tow and / or fiber fabric with the suspension;

[0066] The organic phosphine flame retardant contains the organic phosphine compound of the present invention. The preparation method of the flame retardant fiber provided by the present invention is simple and easy to realize industrial production.

[0067] In the present invention, step (1) further comprises adding a suspension aid.

[0068] In the present invention, in step (1), the type of the suspension aid can be selected from a wide range. According to a preferred embodiment of the present invention, the suspension aid is selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, lignin sulfonate, sodium carboxymethyl cellulose, sodium carboxyethyl cellulose, methyl cellulose, and polyacrylic acid salt.

[0069] In the present invention, in step (1), the amount of the suspension aid can be selected in a wide range. According to a preferred embodiment of the present invention, the amount of the suspension aid is 0.5wt%-10wt% of the mass of the organic phosphine flame retardant.

[0070] In the present invention, in step (1), the optional range of the dosage ratio of the organic phosphine flame retardant to deionized water is relatively wide. According to a preferred embodiment of the present invention, the mass ratio of the organic phosphine flame retardant to deionized water is 1:1-10.

[0071] In the present invention, in step (2), there is no particular requirement for the form of the first contact, as long as the organic phosphine flame retardant can be coated on the surface of the fiber bundle and / or fiber fabric; according to a preferred embodiment of the present invention, the fiber bundle and / or fiber fabric is passed through the suspension.

[0072] In the present invention, in step (2), there is no particular requirement for the method of removing moisture. For example, the moisture can be removed by heating. According to a preferred embodiment of the present invention, the moisture is removed by heating at 60-120°C.

[0073] A sixth aspect of the present invention provides a use of the flame retardant fiber of the present invention in preparing a flame retardant fiber composite material.

[0074] When the flame-retardant fiber of the present invention is used to prepare a fiber composite material, after the flame-retardant fiber contacts an organic resin matrix, the flame retardant coated on the surface of the flame-retardant fiber can be dissolved in the organic resin matrix during the heating and curing process, thereby preventing the flame retardant powder particles from forming stress concentration points in the composite material, resulting in a decrease in the mechanical properties of the composite material.

[0075] The flame-retardant fiber of the present invention can be used to prepare flame-retardant fiber composite materials and products thereof through molding processes such as prepreg, winding, pultrusion, vacuum infusion, and resin transfer molding. Not only can the amount of flame retardant added to the organic resin matrix be reduced or a non-flame-retardant organic resin matrix can be directly used, but also the processability during the preparation of the flame-retardant composite material and its products can be ensured while having good flame retardancy.

[0076] A seventh aspect of the present invention provides a flame retardant fiber composite material composition, the composition comprising:

[0077] Organic resin and the flame retardant fiber of the present invention;

[0078] The mass ratio of the flame retardant fiber to the organic resin is 20-80:80-20.

[0079] In the present invention, the type of the organic resin can be selected from a wide range. According to a preferred embodiment of the present invention, the organic resin is selected from at least one of epoxy resin, polyurethane resin, unsaturated resin, vinyl ester resin, phenolic resin, cyanate resin, polyimide resin and benzoxazine resin, preferably epoxy resin.

[0080] An eighth aspect of the present invention provides a method for preparing a flame retardant fiber composite material, the method comprising: mixing the flame retardant fiber of the present invention with an organic resin matrix, and curing to obtain the flame retardant fiber composite material.

[0081] In the present invention, there is no particular limitation on the conditions for mixing the flame retardant fiber with the organic resin matrix, and the purpose of the present invention can be achieved by conventional technical means in the art.

[0082] In the present invention, there is no particular limitation on the curing conditions, and the purpose of the present invention can be achieved by conventional technical means in the art.

[0083] A ninth aspect of the present invention provides a flame retardant fiber composite material prepared by the method for preparing the flame retardant fiber composite material of the present invention.

[0084] A tenth aspect of the present invention provides an application of the composite material of the present invention in the preparation of one or more products of automobiles, high-speed railways, aviation, and ships.

[0085] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0086] Preparation Example 1

[0087] (1) Under nitrogen protection, furan methyl glycidyl ether is heated to 130° C., DOPO in an equal molar ratio to furan methyl glycidyl ether is added under stirring, and then a catalyst triphenylphosphine (the amount used is 0.5% of the mass of furan methyl glycidyl ether) is added. After keeping warm for 4 hours, an organic phosphine compound P11 is obtained, the structural formula of which is shown in formula (I-1).

[0088] Preparation Example 2

[0089] (1) Under nitrogen protection, furanyl glycidyl ether is heated to 100° C., DOPO is added under stirring (the molar ratio of DOPO to furanyl glycidyl ether is 2:1), and then a catalyst triphenylphosphine is added (the amount is 0.2% of the mass of furanyl glycidyl ether). After keeping the temperature for 8 hours, an organic phosphine compound P12 is obtained, the structural formula of which is shown in Formula (I-1).

[0090] Preparation Example 3

[0091] (1) Under nitrogen protection, furan methyl glycidyl ether is heated to 180° C., DOPO is added under stirring (the molar ratio of DOPO to furan methyl glycidyl ether is 1:2), and then a catalyst triphenylphosphine is added (the amount is 0.5% of the mass of furan methyl glycidyl ether). After keeping the temperature for 1 hour, an organic phosphine compound P13 is obtained, the structural formula of which is shown in formula (I-1).

[0092] Preparation Example 4

[0093] The method of Preparation Example 1 is followed, except that the compound represented by formula (III-1) is used to replace furanyl glycidyl ether;

[0094] Formula (III-1): In formula (III), R11 The remaining conditions are the same as those in Preparation Example 1 to obtain an organic phosphine compound P14, the structural formula of which is shown in Formula (I-2);

[0095] Formula (I-2), in Formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 All are hydrogen, R 11 It is methyl.

[0096] Preparation Example 5

[0097] The method of Preparation Example 1 is followed, except that the compound represented by formula (III-2) is used to replace furanyl glycidyl ether;

[0098] Formula (III-2): In formula (III), R 11 The remaining conditions are the same as those in Preparation Example 1 to obtain an organic phosphine compound P15, the structural formula of which is shown in Formula (I-3);

[0099] Formula (I-3), in formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 All are hydrogen, R 11 For Cl.

[0100] Preparation Example 6

[0101] The method of Preparation Example 1 is followed, except that the compound represented by formula (III-3) is used to replace furanyl glycidyl ether;

[0102] Formula (III-3): In formula (III), R 11 The remaining conditions are the same as those in Preparation Example 1 to obtain an organic phosphine compound P16, the structural formula of which is shown in Formula (I-4);

[0103] Formula (I-4), in formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 , R 9 , R 10 All are hydrogen, R 11 For nitro.

[0104] In the following examples, the organic phosphine compound powder is the organic phosphine compound P11 pulverized into powder with an average particle size not exceeding 0.01 mm.

[0105] Example 1

[0106] (1) dispersing the organic phosphine compound powder obtained in Preparation Example 1 in deionized water containing polyvinyl alcohol to prepare a suspension, wherein the mass ratio of the organic phosphine compound to the deionized water is 1:2, and the amount of polyvinyl alcohol added is 3.5% of the mass of the organic phosphine compound;

[0107] (2) The fiber surface density of the fiber woven from Shanghai Petrochemical SCF35s-12K carbon fiber is 400g / m 2 The plain fabric is impregnated in the suspension of step (2), taken out and squeezed to remove the excess suspension, and heated and dried in an oven at 80° C. to remove moisture, thereby obtaining a flame retardant carbon fiber fabric SCF35s-PW400-FR, wherein the mass content of the organic phosphine flame retardant is 23.1%;

[0108] (3.1) Preparation of resin matrix: 75 parts of bisphenol F epoxy resin, 25 parts of ethylene glycol diglycidyl ether and 21.5 parts of 1,3-cyclohexanedimethylamine were mixed evenly, and the viscosity at 25°C was 80-120 mPa·s;

[0109] (3.2) The flame retardant carbon fiber fabric SCF35s-PW400-FR was cut into 300mm×300mm squares, 5 layers were stacked together, and the composite laminate was prepared by vacuum infusion process. The organic content of the prepared composite laminate was 50%, and phosphorus accounted for 2.51% of the organic matter. The curing system of the laminate was step-by-step curing, 40℃, 80℃ and 120℃ for 2 hours each.

[0110] The composite laminate was cut into strips with length × width of 130 mm × 13 mm and 20 mm × 10 mm, and subjected to vertical burning test and interlaminar shear strength test respectively. The flame retardant grade was UL94 V-0 and the interlaminar shear strength was 54.1 MPa.

[0111] Embodiment 2-4

[0112] The method of Example 1 is followed, except that the mass ratio of the organic phosphine compound to deionized water is different, and the other conditions are the same as Example 1; the feeding and the vertical combustion test and interlaminar shear strength test results of the composite laminate are shown in Table 1.

[0113] Table 1

[0114]

[0115] Example 5

[0116] (1) dispersing an organic phosphine compound powder in deionized water containing polyvinyl alcohol to prepare a suspension, wherein the mass ratio of the organic phosphine compound to the deionized water is 1:6, and the amount of polyvinyl alcohol added is 3.5% of the mass of the organic phosphine compound;

[0117] (2) passing the Shanghai Petrochemical SCF35s-12K carbon fiber tow through an organic phosphine flame retardant aqueous suspension, squeezing the excess suspension with a roller, drying it at 80° C. with a heating device, removing moisture, and then winding it up to obtain a flame-retardant carbon fiber SCF35s-12K-FR, wherein the mass content of the organic phosphine flame retardant is 14.5%;

[0118] (3.1) Preparation of resin matrix: 75 parts of bisphenol F epoxy resin, 25 parts of ethylene glycol diglycidyl ether and 27 parts of diethyltoluenediamine were mixed evenly, and the viscosity at 25°C was 200-400 mPa·s;

[0119] (3.2) Composite laminates were prepared by winding molding process, and the curing system was step temperature curing: 100℃, 150℃ and 180℃ for 2 hours each. The organic content of the prepared composite laminates was 36.3%, and phosphorus accounted for 2.5% of the organic matter in the composite laminates;

[0120] The composite laminate was cut into strips with length × width of 130 mm × 13 mm and 20 mm × 10 mm, and subjected to vertical burning test and interlaminar shear strength test respectively. The flame retardant grade was UL94 V-0 and the interlaminar shear strength was 78.2 MPa.

[0121] Example 6

[0122] The difference from Example 5 is that SCF35s-48K large tow carbon fiber is used to prepare flame-retardant carbon fiber, the mass content of organic phosphine flame retardant in the prepared flame-retardant carbon fiber is 16.4%, the organic matter content in the prepared composite laminate is 39.6%, the phosphorus element accounts for 2.5% of the amount of organic matter in the composite laminate, the flame retardant grade of the composite material is UL94 V-0, and the interlaminar shear strength is 75.8 MPa.

[0123] Example 7

[0124] (1) dispersing an organic phosphine compound powder in deionized water containing polyvinyl alcohol to prepare a suspension, wherein the mass ratio of the organic phosphine compound to the deionized water is 1:4, and the amount of polyvinyl alcohol added is 3.5% of the mass of the organic phosphine compound;

[0125] (2) The fiber surface density of the fiber woven from Shanghai Petrochemical SCF35s-12K carbon fiber is 400g / m 2 The plain fabric is immersed in the above-mentioned organic phosphine flame retardant aqueous suspension, taken out and squeezed to remove the excess suspension, and heated in an oven at 80°C to dry and remove moisture to obtain a flame retardant carbon fiber fabric SCF35s-PW400-FR, wherein the mass content of the organic phosphine flame retardant is 16.4%;

[0126] The composite laminate is prepared using the prepreg process, and the specific steps are as follows:

[0127] (3.1) Preparation of prepreg resin film: SCR2201 prepreg resin produced by Sinopec (Shanghai) Petrochemical Research Institute Co., Ltd. is used to prepare the resin film. The resin is a non-flame retardant resin, mainly composed of bisphenol A epoxy resin, dicyandiamide, and substituted urea. The resin coating temperature is 70°C, and the resin film surface density is 94g / m 2 ;

[0128] (3.2) Prepreg preparation: The flame-retardant carbon fiber fabric SCF35s-PW400-FR and the above two layers of resin film are used to prepare the prepreg, and the resin content of the prepared prepreg is 40%;

[0129] (3.3) Preparation of composite laminates: The prepreg was cut into 300 mm × 300 mm squares, 5 layers were stacked together, and the composite laminates were prepared by vacuum bag pressing process, and the curing system was 120° C. for 2 hours. The phosphorus element in the prepared composite laminate accounted for 2.47% of the organic matter.

[0130] The composite laminate was cut into strips with length × width of 130 mm × 13 mm and 20 mm × 10 mm, and subjected to vertical burning test and interlaminar shear strength test respectively. The flame retardant grade was UL94 V-0 and the interlaminar shear strength was 56.6 MPa.

[0131] Example 8

[0132] The preparation method of Example 1 is followed, except that the organic phosphine compound prepared in Preparation Example 4 is used instead of the organic phosphine compound obtained in Preparation Example 1, and the other conditions are the same as in Example 1.

[0133] The flame retardant grade of the composite material is UL94 V-0, and the interlaminar shear strength is 52.9MPa.

[0134] Example 9

[0135] The preparation method of Example 1 is followed, except that the organic phosphine compound prepared in Preparation Example 5 is used instead of the organic phosphine compound obtained in Preparation Example 1, and the other conditions are the same as in Example 1.

[0136] The flame retardant grade of the composite material is UL94 V-0, and the interlaminar shear strength is 53.1MPa.

[0137] Example 10

[0138] The preparation method of Example 1 is followed, except that the organic phosphine compound prepared in Preparation Example 5 is used instead of the organic phosphine compound obtained in Preparation Example 1, and the other conditions are the same as in Example 1.

[0139] The flame retardant grade of the composite material is UL94 V-0, and the interlaminar shear strength is 52.6MPa.

[0140] Comparative Example 1

[0141] (1) Preparation of resin matrix: 75 parts of bisphenol F epoxy resin, 25 parts of ethylene glycol diglycidyl ether and 26 parts of DOPO were mixed at 110°C, cooled to below 30°C, and then 21.5 parts of 1,3-cyclohexanedimethylamine were added and mixed evenly. The viscosity of the mixture at 25°C was 600-800 mPa·s, and the phosphorus content of the mixture was 2.53%;

[0142] (2) Carbon fiber fabric SCF35s-PW400 was cut into 300 mm × 300 mm squares, 5 layers were stacked together, and composite laminates were prepared by vacuum infusion process. The resin mass content in the composite laminates was controlled to be 50%, and the curing system was step-by-step curing at 40°C, 80°C and 120°C for 2 hours each.

[0143] The composite laminate was cut into strips with length × width of 130 mm × 13 mm and 20 mm × 10 mm, and subjected to vertical burning test and interlaminar shear strength test respectively. The flame retardant grade was UL94 V-1 and the interlaminar shear strength was 48.2 MPa.

[0144] Comparative Example 2

[0145] The flame retardant DOPO was directly dissolved in the epoxy resin matrix, and then the composite laminate was prepared by winding molding process using Shanghai Petrochemical SCF35s-12K carbon fiber. The steps for preparing the composite material are as follows:

[0146] (1) Preparation of resin matrix: 75 parts of bisphenol F epoxy resin, 25 parts of ethylene glycol diglycidyl ether and 27 parts of DOPO were mixed at 110° C., cooled to below 30° C., and then 27 parts of diethyltoluenediamine were added and mixed evenly. The viscosity of the mixture at 25° C. was 600-800 mPa·s, and the phosphorus content in the mixture was 2.51%;

[0147] (2) Composite laminates were prepared by winding SCF35s-12K carbon fiber, and the curing system was step-by-step curing: 100°C, 150°C and 180°C for 2 hours each. The organic matter content of the prepared composite laminates was 32.1%.

[0148] The composite laminate was cut into strips with length × width of 130 mm × 13 mm and 20 mm × 10 mm, and subjected to vertical burning test and interlaminar shear strength test respectively. The flame retardant grade was UL94 V-1 and the interlaminar shear strength was 58.2 MPa.

[0149] Comparative Example 3

[0150] DOPO was crushed and ground into powder. According to the method of Example 1, DOPO powder was used to replace P11. The flame retardant grade of the composite laminate was UL94 V-1, and the interlaminar shear strength was 48.6 MPa.

[0151] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An organic phosphine compound, characterized in that The organic phosphine compound is a compound obtained by reacting the POH bond of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound with the epoxy group of furan methyl glycidyl ether.

2. The organic phosphine compound according to claim 1, wherein The structural formula of the organic phosphine compound is shown in formula (I); In formula (I), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro; Preferably, R1, R2, R3, R4, R5, R6, R7, R8 are all hydrogen, R9, R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro.

3. The compound according to claim 1 or 2, wherein The structural formula of the organic phosphine compound is shown in formula (I-1); 4. A method for preparing an organic phosphine compound according to any one of claims 1 to 3, characterized in that: The method includes: In the presence of a catalyst, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound represented by formula (II) is contacted with the furan methyl glycidyl ether represented by formula (III); The catalyst is selected from at least one of triphenylphosphine, quaternary phosphonium salt and quaternary ammonium salt; Among them, in formula (II) and formula (III), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 Each is independently selected from one of H, C1-C3 alkyl, halogen and nitro.

5. The preparation method according to claim 4, wherein The contact conditions include: a temperature of 100°C to 180°C; preferably, a time of 1 to 8 hours; and / or The amount of the catalyst is 0.01 to 1 wt% of the mass of furan methyl glycidyl ether; and / or The molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compounds to furan methyl glycidyl ether is 0.5-2:

1.

6. Use of the organic phosphine compound according to any one of claims 1 to 3 in flame retardancy.

7. A flame retardant fiber, characterized in that: The flame retardant fiber includes: Fiber tows and / or fiber fabrics; and, an organic phosphine flame retardant coated on the surface of the fiber tow and / or fiber fabric; The organic phosphine flame retardant accounts for 5wt%-30wt% of the fiber tow and / or fiber fabric mass; The organic phosphine flame retardant contains the organic phosphine compound according to any one of claims 1 to 3.

8. The flame-retardant fiber according to claim 7, wherein: The fiber is selected from at least one of carbon fiber, glass fiber, basalt fiber, aramid fiber and ultra-high molecular weight polyethylene fiber; and / or The organic phosphine flame retardant particles have a D 90 Less than or equal to 0.1mm; Preferably, the flame retardant fiber further comprises a suspension aid coated on the surface of the fiber tow and / or fiber fabric, selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, lignin sulfonate, sodium carboxymethyl cellulose, sodium carboxyethyl cellulose methyl cellulose, and polyacrylic acid salt; More preferably, the content of the suspension aid is 0.5 wt% to 10 wt% of the mass of the organic phosphine flame retardant.

9. The method for preparing the flame-retardant fiber according to claim 7 or 8, characterized in that: The method includes: (1) dispersing an organic phosphine flame retardant in water to obtain a suspension; (2) removing water after first contacting the fiber tow and / or fiber fabric with the suspension; The organic phosphine flame retardant contains the organic phosphine compound according to claim 1 or 2.

10. The preparation method according to claim 9, wherein: In step (1), a suspension aid is further added, preferably, the suspension aid is selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, lignin sulfonate, sodium carboxymethyl cellulose, sodium carboxyethyl cellulose methyl cellulose, polyacrylic acid salt; preferably, the amount of the suspension aid is 0.5wt%-10wt% of the mass of the organic phosphine flame retardant; and / or The mass ratio of the organic phosphine flame retardant to deionized water is 1:1-10.

11. Use of the flame retardant fiber according to any one of claims 6 to 8 in preparing a flame retardant fiber composite material.

12. A flame retardant fiber composite material composition, characterized in that: The composition comprises: An organic resin and the flame retardant fiber according to claim 7 or 8; The mass ratio of the flame retardant fiber to the organic resin is 20-80:80-20.

13. The composite material according to claim 12, wherein: The organic resin is selected from at least one of epoxy resin, polyurethane resin, unsaturated resin, vinyl ester resin, phenolic resin, cyanate resin, polyimide resin and benzoxazine resin, preferably epoxy resin.

14. A method for preparing a flame retardant fiber composite material, characterized in that: The method includes: The flame retardant fiber according to claim 7 or 8 is mixed with an organic resin matrix and cured to obtain a flame retardant fiber composite material.

15. The flame retardant fiber composite material prepared by the preparation method according to claim 14.

16. Use of the composite material according to claim 15 in the preparation of one or more products selected from the group consisting of automobiles, high-speed railways, aviation, and ships.

Images