Click chemistry modified polybutadiene polymer type P / S synergistic flame retardant as well as preparation method and application thereof

Abstract

The invention provides a preparation method and application of a chemically-modified polybutadiene (PB) polymer type P / S synergistic flame retardant, the chemically-modified PB polymer type P / S synergistic flame retardant is characterized in that an organic phosphorus small molecule compound is introduced to a side chain C = C of PB through a click reaction, and on the basis of maintaining the dielectric property, chemical resistance and the like of PB, the chemical property of the PB is improved, and the flame retardant efficiency is improved. The flame-retardant performance of PB is greatly improved, the glass-transition temperature (Tg) and strength of PB are improved, the processability is improved, the transparency of raw materials is kept, migration and precipitation of a small-molecule organic phosphorus flame retardant are limited, and the human body health and the natural environment are protected. The technical problems of poor flame retardant property, poor processability, gummosis and low glass transition temperature (Tg) of the PB resin are solved, meanwhile, the click reaction condition is mild, the reaction is rapid, the energy consumption is low, the energy consumption for preparing the polymer type flame retardant can be reduced, the cost is saved, and the carbon neutralization concept is met.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical modification of polymer materials, and in particular to a click-chemistry-modified polybutadiene (PB) polymer-type P / S synergistic flame retardant, a preparation method thereof, and applications thereof. Background Art

[0002] Polymer materials have been widely used in aerospace, electronic equipment, machinery, chemical industry and other fields due to their excellent chemical corrosion resistance, mechanical properties, transparency, insulation, heat resistance and light weight. However, most polymer materials are flammable or easily combustible in air, which brings convenience and huge benefits to people's production and life, but also puts people at risk of fire and even threatens their health. In recent decades, in order to better adapt to the rapid development of industry, polymer materials are required to meet the requirements of good flame retardancy, mechanical properties, and easy chemical modification. Therefore, the development of a new type of high-efficiency P / S synergistic polymer flame retardant is of great practical significance for achieving long-term flame retardancy of polymer materials, maintaining high transparency, ensuring personal safety and protecting the environment.

[0003] Polybutadiene (PB) is a type of polyolefin resin. Due to the low polarity of the CH bond in the molecular chain (the electronegativity of C is 2.5 and the electronegativity of H is 2.1), it has excellent properties such as low dielectric constant, dielectric loss and water absorption. It is widely used as a matrix material in microwave communication systems, military and civilian radar systems, automotive electronics and satellite broadcasting. For pure PB, due to its T g The low molecular weight polymer (MLM) is low. When used alone, it will have defects such as glue flow, poor flame retardancy, poor processing performance, poor thermal performance and poor mechanical properties, and the dielectric properties are unstable within a certain frequency range. Therefore, by chemically modifying the C=C side chain of PB and introducing organic phosphorus groups, the above defects are improved to enhance the comprehensive performance and expand its application range.

[0004] Among all types of flame retardants, phosphorus-based flame retardants occupy an important position. They not only overcome the defects of halogen-containing flame retardants in burning large amounts of smoke and releasing toxic and corrosive gases, but also improve the disadvantage of inorganic flame retardants that high addition levels seriously affect the physical and mechanical properties of the material. They achieve high flame retardancy, low toxicity, low smoke, and no corrosive gas generation with a small addition amount. To this end, phosphorus-based flame retardants are introduced into PB through chemical modification to obtain higher molecular weight polymer flame retardants. At the same time, they have difficulty penetrating cell membranes in organisms and participating in systemic circulation and metabolism, which effectively avoids bioaccumulation and greatly reduces environmental pollution.

[0005] Therefore, the research and development of PB polymer-type P / S synergistic flame retardants with excellent comprehensive performance has important practical significance for achieving long-term high-efficiency flame retardancy and high transparency of polymer materials, reducing economic costs and protecting the ecological environment. Summary of the Invention

[0006] To solve the above problems, the present invention provides a chemically modified PB polymer type P / S synergistic flame retardant, which introduces phosphorus, sulfur and / or benzene ring, phenanthrene ring and other groups into the PB side chain C=C by click chemistry, thereby solving the technical problems of flame retardant precipitation and frosting during use, and obtaining a composite resin matrix material with good compatibility and uniform dispersion. On the basis of maintaining the excellent dielectric properties of PB, the flame retardant properties and T of PB are greatly improved. g and processing performance, effectively reducing the migration of small molecule phosphorus and sulfur flame retardants, increasing the service life of composite resin matrix materials, and protecting the natural environment and people's life and health.

[0007] The first aspect of the present invention is to provide a click chemistry modified PB polymer type P / S synergistic flame retardant, which not only improves the flame retardant properties and T g and processing performance, and also solves the defects of small molecule phosphorus and sulfur flame retardants such as precipitation migration and poor dispersion.

[0008] The second aspect of the present invention is to provide a method for preparing a click chemistry modified PB polymer type P / S synergistic flame retardant, which has the characteristics of mild reaction conditions and rapid reaction.

[0009] The third aspect of the present invention is to provide an application of a click chemistry modified PB polymer type P / S synergistic flame retardant in the preparation of composite resin matrix materials, which can further improve the flame retardancy, dielectric properties, transparency and mechanical properties of the composite resin matrix materials.

[0010] In order to achieve the above-mentioned purpose of the present invention, the following experimental technology methods are adopted:

[0011] In a first aspect, the present invention provides a click chemistry modified PB polymer type P / S synergistic flame retardant having a structure represented by the following general formula (1):

[0012]

[0013] in,

[0014] x is selected from an integer of 1 to 60, preferably an integer of 1 to 50;

[0015] y is selected from an integer of 0 to 60, preferably an integer of 0 to 50;

[0016] z is selected from an integer of 1 to 60, preferably an integer of 1 to 50;

[0017] R is a substituent group, preferably a group having a phosphorus or sulfur heteroatom and a benzene ring or a phenanthrene ring.

[0018] Preferably, the click chemistry modified PB polymer type P / S synergistic flame retardant is PB-TBPO, which has the following structure:

[0019]

[0020] In the second aspect, the present invention provides a method for preparing the click chemistry modified PB polymer type P / S synergistic flame retardant described in the first aspect, which is prepared by a "thiol-ene" click reaction between PB and a sulfur-containing compound and a phosphorus-containing benzene ring and / or phenanthrene ring group compound, preferably in the presence of a photoinitiator and under ultraviolet light irradiation.

[0021] According to the present invention, the method comprises the following steps:

[0022] Step 1: dissolving a phosphorus-based flame retardant and an olefin with a hydroxyl group in an organic solvent, and subjecting the mixture to a free radical reaction to obtain the first product (HBPO);

[0023] Step 2: The hydroxyl group of the first step product is converted into a bromo group through the Appel-Lee reaction to obtain the second step product (BBPO);

[0024] Step 3: debrominating the product of the second step into a thiol group by using a sulfur-containing compound and an optional reactive reagent to obtain a sulfur-containing compound and an optional reactive reagent as a third product;

[0025] Step 4: Under room temperature, in the presence of a photoinitiator, PB and the product of the third step with different feed ratios are catalyzed by ultraviolet light irradiation, and the modified PB polymer type P / S synergistic flame retardant is obtained by post-treatment.

[0026] In step 1, the phosphorus-based flame retardant includes at least one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl hypophosphorous acid, dimethyl phosphite, ethyl hypophosphorous acid, triphenyl phosphate, propylbenzene phosphate, hypophosphorous acid, butylbenzene phosphate, phosphorous acid, diethyl phosphite, toluene diphenyl phosphate, and diphenyl phosphite.

[0027] The olefin with a hydroxyl group includes at least one of 2-propene-1-ol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7-octene-1-ol, 8-nonene-1-ol, 9-decene-1-ol, 10-undecene-1-ol, and 11-dodecene-1-ol, preferably 3-butene-1-ol.

[0028] In step 2, triphenylphosphine, carbon tetrabromide and HBPO are added to a solvent for reaction, and the molar ratio of triphenylphosphine and carbon tetrabromide to the molar ratio of the product of the first step is (1-10):1, preferably (1-5):1.

[0029] In step 3, a sulfur-containing compound, BBPO, and a reactive reagent are added to a solvent for reaction. The sulfur-containing compound is preferably bis(trimethylsilyl)sulfide, and the reactive reagent is preferably a tetraalkylammonium halide, such as tetrabutylammonium fluoride, tetrabutylammonium chloride, or tetrabutylammonium bromide. The molar ratio of the reactive reagent to the sulfur-containing compound to the molar ratio of BBPO is (1-15):1, preferably (1-9):1.

[0030] In step 4, PB, MBPO and a photoinitiator are added to a solvent and catalyzed by ultraviolet light irradiation. The PB is added in a certain molar ratio according to the side chain C=C and MBPO, preferably (1-10):1, more preferably (1-5):1, and the photoinitiator is preferably 2,2-dimethyl-2-phenylethanone (DMPA), and its amount is 1 to 30% by mass of PB, preferably 1 to 16%.

[0031] In a third aspect, the present invention provides an application of the click chemistry modified PB polymer type P / S synergistic flame retardant in the preparation of a composite resin matrix material.

[0032] Preferably, a modified PB polymer-type P / S synergistic flame retardant, bisphenol A formaldehyde novolac epoxy resin, and 4,4'-diaminodiphenylmethane are added to a solvent and dissolved, the solvent is removed, and the composite resin matrix material is obtained by temperature programming. The weight ratio of the 4,4'-diaminodiphenylmethane to the bisphenol A formaldehyde novolac epoxy resin is (5-30):60, preferably (10-25):60, and more preferably (13-20):60; the weight ratio of the PB-TBPO to the bisphenol A formaldehyde novolac epoxy resin is (1-20):100, preferably (2-10):100, and more preferably (3-7):100.

[0033] Compared with the existing technology, the present invention has at least the following beneficial effects:

[0034] (1) The click chemistry modified PB polymer type P / S synergistic flame retardant provided by the present invention catalyzes the reaction of PB and a phosphorus-based flame retardant with a thiol group, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, through a "thiol-ene" click reaction to obtain a PB polymer type P / S synergistic flame retardant (PB-TBPO). While maintaining the dielectric properties and mechanical properties of PB, it not only greatly improves its flame retardant properties, but also further improves T g , processing performance and mechanical properties.

[0035] (2) In the present invention, a synthetic route is designed using a "thiol-ene" click reaction. The reaction conditions are mild, the reaction is rapid, and PB containing phosphorus, sulfur, benzene ring and / or phenanthrene ring group side chains can be efficiently prepared. The preparation method is simple and easy to operate and implement.

[0036] (3) The click chemistry-modified PB polymer-type P / S synergistic flame retardant of the present invention can be applied to a variety of resin matrix materials, and can improve the flame retardancy, thermal stability, processing performance, mechanical properties and dielectric properties of composite resin matrix materials, maintain high transparency, and meet actual needs. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The infrared spectra of the small molecule compounds HBPO, BBPO, and MBPO in Example 1 are shown;

[0038] Figure 2 The infrared spectra of the products of PB-TBPO with different ratios in Example 2 are shown;

[0039] Figure 3 The DSC curves of PB-TBPO at different ratios in Example 2 are shown;

[0040] Figure 4 The UV-visible transmission spectra of the EP composite materials with different ratios of PB-TBPO in Experimental Examples 1-3 are shown. DETAILED DESCRIPTION

[0041] The technical solution of the present invention will be described in detail below, and the features and advantages of the present invention will become clearer and more distinct with the following description. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by other experimental technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0042] In a first aspect, the present invention provides a click chemistry modified PB polymer-type P / S synergistic flame retardant having a structure represented by the following general formula (1):

[0043]

[0044] in,

[0045] x is selected from an integer of 1 to 60, preferably an integer of 1 to 50, for example, x can be selected from 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50;

[0046] y is selected from an integer of 0 to 60, preferably an integer of 0 to 50, for example, y can be selected from 0, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50;

[0047] z is selected from an integer of 1 to 60, preferably an integer of 1 to 50, for example, z can be selected from 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50;

[0048] R is a substituent group, preferably having a phosphorus or sulfur heteroatom, and having a benzene ring and / or a phenanthrene ring group.

[0049] In a preferred embodiment, the click chemistry modified PB polymer type P / S synergistic flame retardant (PB-TBPO) is a compound having the following structure:

[0050]

[0051] Preferably, the number average molecular weight (Mn) of the click chemistry modified PB polymer type P / S synergistic flame retardant (PB-TBPO) is 600-40000 g / mol, preferably 3000-20000 g / mol, and more preferably 4000-15000 g / mol.

[0052] Preferably, the click chemistry modified PB polymer type P / S synergistic flame retardant is prepared by reacting PB with a sulfur-containing compound and a phosphorus-containing compound having a benzene ring and / or phenanthrene ring group.

[0053] The compound containing phosphorus-containing benzene ring and / or phenanthrene ring groups is at least one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl hypophosphorous acid, dimethyl phosphite, ethyl hypophosphorous acid, triphenyl phosphate, propylbenzene phosphate, hypophosphorous acid, butylbenzene phosphate, phosphorous acid, diethyl phosphite, toluene diphenyl phosphate, and diphenyl phosphite, preferably 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0054] The sulfur-containing compound can be selected from thiourea, bis(trimethylsilyl)sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., preferably bis(trimethylsilyl)sulfide.

[0055] The resulting P / S synergistic flame retardant (PB-TBPO) exhibits different number average or weight average molecular weights, PDIs, and the like depending on the molar ratio of the PB side chain C=C to TBPO when added to the raw materials during the preparation process, from which the parameters x, y, and z in the structural formula can be deduced. For example, when the molar ratio of the PB side chain C=C to TBPO is 1-5:1, such as 1:1, 2:1, 3:1, and 4:1, the resulting P / S synergistic flame retardant can have a number average molecular weight (Mn) of 4,500-12,000 g / mol, a weight average molecular weight (Mw) of 5,500-15,000 g / mol, and a PDI of 1.20-1.40, respectively.

[0056] In the second aspect of the present invention, a method for preparing the click chemistry-modified PB polymer-type P / S synergistic flame retardant is also provided. The method is prepared by reacting PB with a sulfur-containing compound, a phosphorus-containing benzene ring and / or phenanthrene ring group compound in the presence of a photoinitiator and under ultraviolet light irradiation through a "thiol-ene" click reaction.

[0057] The molar ratio of the PB to the compound containing phosphorus-containing benzene ring and / or phenanthrene ring groups is (1-50):1, preferably (1-20):1, more preferably (1-4):1, and the molar amount of PB is calculated based on the molar amount of the side chain C=C.

[0058] The photoinitiator can be, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-methylthiophenyl]-2-morpholinoacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 4-phenylbenzophenone, 2,2-dimethyl-2-phenylethanone, 2-vinylthioxanthone, preferably 2,2-dimethyl-2-phenylethanone (DMPA), and the amount of the photoinitiator is 1 to 30% of the mass of PB, preferably 1 to 16%, and more preferably 1 to 6%.

[0059] The method specifically comprises the following steps:

[0060] Step 1: The phosphorus-based flame retardant and the olefin with hydroxyl group are dissolved in an organic solvent, and the first step product (HBPO) is obtained through a free radical reaction.

[0061] According to a preferred embodiment of the present invention, in this step, the phosphorus-based flame retardant includes at least one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl hypophosphorous acid, dimethyl phosphite, ethyl hypophosphorous acid, triphenyl phosphate, propylbenzene phosphate, hypophosphorous acid, butylbenzene phosphate, phosphorous acid, diethyl phosphite, toluene diphenyl phosphate, and diphenyl phosphite, preferably 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0062] In the present invention, the olefin with a hydroxyl group includes at least one of 2-propene-1-ol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7-octene-1-ol, 8-nonene-1-ol, 9-decene-1-ol, 10-undecene-1-ol, and 11-dodecene-1-ol, preferably 3-butene-1-ol.

[0063] According to a preferred embodiment, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3-butene-1-ol, and azobisisobutyronitrile are added to a solvent and heated to react to obtain the product (HBPO).

[0064]

[0065] This step is, for example, the method described in reference [1] F. Bier, J. Six, A. Durand. DOPO-Based Phosphorus-Containing Methacrylic (Co) Polymers: Glass Transition Temperature Investigation [J]. Macromol. Mater. and Eng., 2019, 304, 1800645. Although the present invention refers to this preparation method, it has been optimized in many aspects.

[0066] The organic solvent is selected from one or more of ketone solvents, sulfone solvents, aromatic hydrocarbon solvents and amide solvents, preferably one or more of petroleum ether, N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide and xylene, more preferably tetrahydrofuran.

[0067] The reaction is carried out under a protective atmosphere, such as nitrogen or argon.

[0068] The amount of azobisisobutyronitrile used is 3% to 20% of the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, preferably 3% to 10%, and more preferably 3% to 5%.

[0069] The reaction temperature is 50-120° C., preferably 50-100° C., more preferably 60-80° C. The reaction time is 12-24 h, preferably 13-21 h, more preferably 15-19 h.

[0070] After the reaction, the product HBPO was obtained by column chromatography.

[0071] Step 2: The hydroxyl group of the product from the first step is converted into a bromo group through the Appel-Lee reaction to obtain the product from the second step.

[0072] According to a preferred embodiment of the present invention, in this step, triphenylphosphine, carbon tetrabromide and HBPO are added to a solvent to react, and the reaction is followed by treatment to obtain the product (BBPO).

[0073]

[0074] The solvent is an ether solvent, such as tetrahydrofuran or dioxane, preferably tetrahydrofuran.

[0075] The molar ratio of triphenylphosphine and carbon tetrabromide to the molar ratio of the product in the first step is 10:1, preferably 5:1, and more preferably 1:1.

[0076] The reaction is carried out at low temperature, preferably at a temperature maintained in an ice-water bath.

[0077] The reaction time is 8-24 hours, preferably 10-20 hours, more preferably 12-16 hours.

[0078] After the reaction, the reaction mixture was subjected to column chromatography to obtain the product BBPO.

[0079] Step 3: The product of the second step is debrominated and converted into a thiol group by using a sulfur-containing compound and an optional reactive reagent to obtain the product of the third step.

[0080] According to a preferred embodiment of the present invention, in this step, the sulfur-containing compound, BBPO and optional reactive reagent are added to a solvent to react, and the product (MBPO) is obtained by treatment after the reaction.

[0081]

[0082] The sulfur-containing compound is selected from thiourea, bis(trimethylsilyl) sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., and is preferably bis(trimethylsilyl) sulfide.

[0083] The reactive reagent can connect BBPO and the sulfur-containing compound with PB, and can be an alkylammonium salt, preferably a tetraalkylammonium halide salt, such as tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and more preferably tetrabutylammonium fluoride.

[0084] The molar ratio of the reactive reagent, the sulfur-containing compound and the BBPO is 1-15:1, preferably 1-9:1, and more preferably 1:1.

[0085] The solvent is an ether solvent, such as tetrahydrofuran or dioxane, preferably tetrahydrofuran.

[0086] The reaction is carried out at low temperature, preferably at a temperature maintained in an ice-water bath.

[0087] The reaction time is 5-24 hours, preferably 8-15 hours, more preferably 10-13 hours.

[0088] After the reaction, the reaction mixture was subjected to column chromatography to obtain the product MBPO.

[0089] Step 4: At room temperature, in the presence of a photoinitiator, PB and the product of the third step are catalytically reacted by ultraviolet light irradiation, and the modified PB polymer-type P / S synergistic flame retardant is obtained by post-treatment.

[0090] In step 4, the PB comprises a structure represented by the following general formula (2):

[0091]

[0092] in,

[0093] x is selected from an integer of 1 to 60, preferably an integer of 1 to 50;

[0094] w is selected from an integer of 1 to 120, preferably an integer of 1 to 100. Preferably, the relationship between w and y and z in formula (1) is: w=y+z.

[0095] According to a preferred embodiment, the ratio of the portion of butadiene polymerized at the 1,2 position (polymerization unit where w is located) to the total portion of the butadiene in the PB, that is, the sum of the portion polymerized at the 1,2 position and the portion polymerized at the 1,4 position (polymerization unit where x is located), that is, w / (x+w) can be 50-99%, preferably 75-98%, and more preferably 85-95%.

[0096] The number average molecular weight of the PB polymer is 400-6000 g / mol, preferably 900-4000 g / mol, more preferably 1000-3500 g / mol.

[0097] According to the present invention, the PB can be prepared according to the literature ([2] Yang Yongcheng, Wang Yurong, Gu Mingchu. Preparation of stereoblock polybutadiene [J]. Synthetic Rubber Industry, 1991, 14 (6): 413-416) or a known method, for example, it can be obtained by anionic polymerization of butadiene under the action of an initiator, or purchased from the market, for example, purchased from Japan Soda Co., Ltd., whose different models have a number average molecular weight of 1200-3200 g / mol, wherein the proportion of the 1,2-position polymerization part of butadiene to the sum of the 1,2-position and 1,4-position polymerization parts is between 85-92%.

[0098] According to a preferred embodiment of the present invention, in this step, PB and MBPO are added to a solvent with a photoinitiator, and a catalytic reaction is carried out under ultraviolet light irradiation. After the reaction, a click chemistry-modified PB polymer-type P / S synergistic flame retardant (PB-TBPO) is obtained by post-treatment.

[0099]

[0100] The PB is added in a certain molar ratio of side chain C=C and MBPO, preferably (1-10):1, more preferably (1-5):1, such as 1:1, 2:1, 3:1, 4:1.

[0101] The photoinitiator is selected from 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-methylthiophenyl]-2-morpholinoacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 4-phenylbenzophenone, 2,2-dimethyl-2-phenylethanone (DMPA), 2-vinylthioxanthone, preferably DMPA, and its usage is 1-30% of the mass of PB, preferably 1-16%, and more preferably 1-6%.

[0102] In the present invention, a 365nm ultraviolet lamp is used to provide ultraviolet light.

[0103] The reaction time is 1-24 hours, preferably 1-10 hours, more preferably 1-5 hours.

[0104] After the reaction, the mixture is precipitated with an alcohol solvent, preferably methanol, to obtain the final modified PB polymer type P / S synergistic flame retardant PB-TBPO.

[0105] The third aspect of the present invention further provides the use of the click chemistry modified PB polymer type P / S synergistic flame retardant for preparing a composite resin matrix material.

[0106] According to a preferred embodiment, modified PB polymer type P / S synergistic flame retardant (PB-TBPO), bisphenol A formaldehyde novolac epoxy resin, and 4,4'-diaminodiphenylmethane are added to a solvent and dissolved, the solvent is removed, the temperature is programmed, and the epoxy resin composite matrix material is cured.

[0107] The weight ratio of the 4,4'-diaminodiphenylmethane to the bisphenol A formaldehyde novolac epoxy resin is (5-30):60, preferably (10-25):60, and more preferably (13-20):60.

[0108] The mass ratio of the PB-TBPO to the bisphenol A formaldehyde novolac epoxy resin is (1-20):100, preferably (2-10):100, and more preferably (3-7):100.

[0109] Preferably, the solvent removal method is to remove the solvent by distillation under reduced pressure.

[0110] The curing is carried out under heating conditions, the curing temperature is 50-250° C., preferably 70-200° C., and the curing time is 5-12 hours, preferably 7-10 hours.

[0111] Preferably, the curing is carried out sequentially at 70-90° C. for 1-2 hours, at 110-140° C. for 2-6 hours, and at 160-200° C. for 2-5 hours.

[0112] Example

[0113] Example 1

[0114] Preparation of click chemistry modified PB polymer-type P / S synergistic flame retardant (PB-TBPO)

[0115] Weigh 5.00 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2.63 g of 3-butene-1-ol, 0.53 g of azobisisobutyronitrile, and 15 mL of tetrahydrofuran into a clean, dry three-necked flask. Reflux under nitrogen for 18 hours. Cool to room temperature and obtain 7.31 g of HBPO by column chromatography.

[0116] Weigh 5.10 g of HBPO, 8.8 g of carbon tetrabromide, 6.96 g of triphenylphosphine, and 20 mL of dichloromethane into a clean, dry three-necked flask and react in an ice-water bath for 12 hours. Column chromatography yielded 7.15 g of BBPO.

[0117] Weigh 6.30 g of BBPO, 6.08 g of tetrabutylammonium fluoride, 4.16 g of bis(trimethylsilyl)sulfide, and 30 mL of tetrahydrofuran into a clean, dry three-necked flask and react in an ice-water bath for 12 h. Column chromatography yielded 5.20 g of MBPO.

[0118] Taking the molar ratio of PB side chain C=C to MBPO as 1:1 as an example, 0.49 g PB (purchased from Japan Soda Co., Ltd., model B-2000, with a number average molecular weight of approximately 2000 g / mol, and the 1,2-position polymerization portion of butadiene accounts for approximately 90% of the sum of the 1,2-position and 1,4-position polymerization portions), 3.00 g MBPO, 0.07 g DMPA and 20 mL of dichloromethane were added to a dry and clean single-necked flask. The reaction was carried out under a 365 nm ultraviolet lamp at room temperature for 1 h, and the mixture was post-treated with methanol to obtain 3.42 g of a click chemistry modified PB polymer-type P / S synergistic flame retardant PB-TBPO. The results showed that its Mn was 11460 g / mol, the weight average molecular weight (Mw) was 14598 g / mol, and the PDI was 1.27.

[0119] The HBPO, BBPO, MBPO and PB-TBPO obtained above were characterized by infrared spectroscopy (FT-IR). The obtained infrared spectra are shown in the figure below. Figure 1 shown.

[0120] according to Figure 1 The infrared spectrum of HBPO is shown in Figure 2438cm -1 The stretching vibration peak of PH disappears at 3400 cm -1 The stretching vibration peak of -OH appears; for BBPO, 540 cm -1is the C-Br stretching vibration peak; for MBPO, at 2553 cm -1 The stretching vibration peak of -SH appears.

[0121] HBPO, BBPO, MBPO and PB-TBPO were tested by differential scanning calorimetry (DSC). The DSC graphs were as follows: Figure 3 shown.

[0122] Figure 3 The DSC test results show that the T g is 45℃, while the T g The T of PB-TBPO in this example is further verified. g With a substantial improvement.

[0123] Example 2

[0124] A click chemistry modified PB polymer type P / S synergistic flame retardant (PB-TBPO) was prepared as in Example 1, except that the molar ratio of the PB side chain C=C to MBPO was changed in the last step, and the preparation was carried out according to the ingredients in Table 1, and finally a click chemistry modified PB polymer type P / S synergistic flame retardant PB-TBPO was obtained. The Mn of the products PB-TBPO (2:1), PB-TBPO (3:1), and PB-TBPO (4:1) were 6829, 5312, and 4699 g / mol, respectively, and the Mw were 9266, 6750, and 5858 g / mol, respectively, and the PDI were 1.36, 1.27, and 1.25, respectively.

[0125] Table 1:

[0126]

[0127] The infrared spectra of the products prepared with different ratios of PB-TBPO are shown in Figure 2. Figure 2 shown.

[0128] according to Figure 2 The infrared spectrum of PB-TBPO (1:1) shows that the -1 The stretching vibration peak corresponding to -SH and 1640 cm -1 The stretching vibration peak corresponding to the C=C of the PB side chain disappears, and the peak at 1149 cm -1 The appearance of the stretching vibration peak of CSC proved that PB and MBPO successfully underwent the “thiol-ene” click reaction.

[0129] The DSC test results of other prepared products with different ratios of PB-TBPO are as follows: Figure 3 Its DSC characteristic data are shown in Table 2.

[0130] Table 2:

[0131]

[0132]

[0133] Experimental Example 1

[0134] Preparation of composite resin matrix material using PB-TBPO (1:1) I

[0135] 1.35g of PB-DBDPO, 45.00g of bisphenol A formaldehyde epoxy resin (EP), and 11.72g of 4,4'-diaminodiphenylmethane (DDM) were added to 200ml of butanone. Once completely dissolved, the solvent was completely removed by vacuum distillation. The mixture was immediately poured into the corresponding mold for testing and cured by a temperature-programmed reaction of 76°C / 1h, 127°C / 4h, and 170°C / 2h. Composite resin matrix I, designated EP / DDM / PB-TBPO (3phr), was obtained. Simultaneously, EP / DDM / PB (5phr) and EP / DDM / PB@MBPO (5phr) were temperature-programmed using the same conditions.

[0136] Microcombustion tests (MCC) were conducted on an FTT0001 microcalorimeter according to ASTM D7309-13. The results showed that the peak heat release rate (PHRR) of EP / DDM was 586.4 W / g, and the total heat release (THR) was 38.5 KJ / g. The PHRR of EP / DDM / PB (5 phr) was 574.3 W / g, and the THR was 40.8 KJ / g. The PHRR of EP / DDM / PB-TBPO (3 phr) was 565.4 W / g, and the THR was 36.1 KJ / g.

[0137] Vertical combustion tests (UL-94) were conducted in an M607B vertical combustion tester according to ASTM D3801-10. The test results showed that EP / DDM and EP / DDM / PB (5phr) exhibited violent combustion and were not flame retardant, while EP / DDM / PB-TBPO (3phr) achieved the highest UL-94 V-0 rating.

[0138] Bending properties were tested on an Instron 5869 electronic universal material testing machine according to GB / T9341-2008. The results showed that the flexural modulus of EP / DDM was 2567 MPa and the flexural strength was 54.0 MPa, the flexural modulus of EP / DDM / PB (5 phr) was 2022 MPa and the flexural strength was 40.1 MPa, the flexural modulus of EP / DDM / PB@MBPO (5 phr) was 2303 MPa and the flexural strength was 45.3 MPa, and the flexural modulus of EP / DDM / PB-TBPO (3 phr) was 3465 MPa and the flexural strength was 125.3 MPa.

[0139] The impact performance test was carried out using an XCJ-4 simply supported beam impact tester. The test standard was based on GB / T1843-2008. The experimental results showed that the impact strength of EP / DDM was 2.5KJ / m 2 The impact strength of EP / DDM / PB (5phr) is 4.2KJ / m 2 The impact strength of EP / DDM / PB@MBPO (5phr) is 10.2KJ / m 2 , while the impact strength of EP / DDM / PB-TBPO (3phr) is 11.9KJ / m 2 .

[0140] The dielectric properties of the composite resin matrix material were tested using an E5080B ENA network analyzer. The test results showed that at a frequency of 10 GHz, the dielectric constant (D k ) is 3.11, dielectric loss (D f ) is 0.0376, and the D k is 2.98, D f The D of EP / DDM / PB@MBPO(5phr) is 0.0341. k is 2.87, D f is 0.0320, while the D k is 2.37, D f is 0.0292; at a frequency of 20 GHz, the D k is 3.42, D f The D of EP / DDM / PB (5phr) is 0.0460. k is 2.86, D f The D of EP / DDM / PB@MBPO(5phr) is 0.0354. k is 2.63, D fis 0.0333, while the D k is 2.34, D f It is 0.0306.

[0141] The UV-visible transmittance spectra of the composite resin matrix materials were tested using a UV-3600 UV-visible spectrophotometer. The test results showed that the transmittance of EP / DDM at 800nm ​​was 88.11%, and the transmittance of EP / DDM / PB-TBPO (3phr) at 800nm ​​was 87.55%.

[0142] Experimental Example 2

[0143] Composite resin matrix material II (EP / DDM / PB-TBPO (5 phr)) was prepared according to the method of Experimental Example 1, except that the amount of PB-TBPO added in the curing reaction system was 2.25 g, and the amount of EP and DDM added remained unchanged.

[0144] Micro combustion test (MCC) was carried out on FTT0001 micro calorimeter. According to the experimental results, the PHRR of EP / DDM / PB-TBPO (5phr) was 549.6W / g, and the THR was 31.2KJ / g.

[0145] The vertical burning test (UL-94) was carried out in an M607B vertical burning tester. The test results showed that EP / DDM / PB-TBPO (5phr) can reach the highest level V-0 of UL-94.

[0146] The bending properties were tested on an Instron 5869 electronic universal material testing machine. The experimental results showed that the flexural modulus of EP / DDM / PB-TBPO (5phr) was 3886 MPa and the flexural strength was 164.1 MPa.

[0147] The impact performance test was carried out using an XCJ-4 simply supported beam impact tester. The experimental results showed that the impact strength of EP / DDM / PB-TBPO (5phr) was 18.3KJ / m 2 .

[0148] The dielectric properties of the composite resin matrix material were tested using an E5080B ENA network analyzer. The test results showed that at a frequency of 10 GHz, the D k is 2.35, D f is 0.0267; at a frequency of 20 GHz, the D k is 2.27, D f It is 0.0281.

[0149] The UV-visible transmission spectrum of the composite resin matrix material was tested using a UV-3600 UV-visible spectrophotometer. The test results showed that the transmittance of EP / DDM / PB-TBPO (5 phr) at 800 nm was 85.56%.

[0150] Experimental Example 3

[0151] Composite resin matrix material II (EP / DDM / PB-TBPO (7 phr)) was prepared according to the method of Experimental Example 1, except that the amount of PB-TBPO added in the curing reaction system was 3.15 g, and the amount of EP and DDM added remained unchanged.

[0152] Micro combustion test (MCC) was carried out on FTT0001 micro calorimeter. According to the experimental results, the PHRR of EP / DDM / PB-TBPO (7 phr) was 546.1 W / g, and the THR was 28.3 KJ / g.

[0153] The vertical burning test (UL-94) was carried out in an M607B vertical burning tester. The test results showed that EP / DDM / PB-TBPO (7phr) can reach the highest level V-0 of UL-94.

[0154] The bending properties were tested on an Instron 5869 electronic universal material testing machine. The experimental results showed that the flexural modulus of EP / DDM / PB-TBPO (7phr) was 3632 MPa and the flexural strength was 148.4 MPa.

[0155] The impact performance test was carried out using an XCJ-4 simply supported beam impact tester. The experimental results showed that the impact strength of EP / DDM / PB-TBPO (7phr) was 17.7KJ / m 2 .

[0156] The dielectric properties of the composite resin matrix material were tested using an E5080B ENA network analyzer. The test results showed that at a frequency of 10 GHz, the D k is 2.39, D f is 0.0273; at a frequency of 20 GHz, the D k is 2.29, D f It is 0.0297.

[0157] The UV-3600 UV-visible spectrophotometer was used to test the UV-visible transmission spectrum of the composite resin matrix material. The test results showed that the transmittance of EP / DDM / PB-TBPO (7 phr) at 800 nm was 83.88%.

[0158] From Experimental Examples 1-3, the micro combustion test (MCC) data of composite resin matrix materials with different PB-TBPO contents are summarized in Table 3 below:

[0159] Table 3:

[0160]

[0161] The vertical burning test (UL-94) data of composite resin matrix materials with different PB-TBPO contents are summarized in Table 4 below:

[0162] Table 4:

[0163]

[0164] The bending performance test and impact performance test data of composite resin matrix materials with different PB-TBPO contents are summarized in Table 5 below:

[0165] Table 5:

[0166]

[0167] The dielectric constant and dielectric loss data of composite resin matrix materials with different PB-TBPO contents are summarized in Table 6 below:

[0168] Table 6:

[0169]

[0170] The UV-visible transmittance data of the composite resin matrix materials with different PB-TBPO contents are summarized in Table 7 below.

[0171] Table 7:

[0172]

[0173]

[0174] The above description only describes the preferred embodiments of the present invention in detail, but does not limit the scope of protection of the present invention. Any person skilled in the art who, within the technical scope disclosed in the present invention, makes equivalent substitutions, improvements, or modifications based on the technical solutions and inventive concepts of the present invention shall fall within the scope of protection of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A click chemistry modified PB polymer type P / S synergistic flame retardant having a structure represented by general formula (1): in, x is an integer selected from 1 to 60; y is an integer selected from 0 to 60; z is an integer selected from 1 to 60; R is a substituted group, preferably a group having a phosphorus or sulfur heteroatom and having a benzene ring and / or a phenanthrene ring.

2. A click chemistry modified PB polymer type P / S synergistic flame retardant according to claim 1, which is PB-TBPO and has the following structure:

3. A click chemistry modified PB polymer type P / S synergistic flame retardant according to claim 1 or 2, characterized in that: The modified flame retardant is prepared by reacting PB with a sulfur-containing compound and a phosphorus-containing benzene ring and / or phenanthrene ring group compound. The compound containing phosphorus-containing benzene ring and / or phenanthrene ring groups is at least one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl hypophosphorous acid, dimethyl phosphite, ethyl hypophosphorous acid, triphenyl phosphate, propylbenzene phosphate, hypophosphorous acid, butylbenzene phosphate, phosphorous acid, diethyl phosphite, toluene diphenyl phosphate, and diphenyl phosphite. The sulfur-containing compound is selected from thiourea, bis(trimethylsilyl) sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., preferably bis(trimethylsilyl) sulfide.

4. A method for preparing the click chemistry modified PB polymer type P / S synergistic flame retardant according to any one of claims 1 to 3, characterized in that: The method is prepared by reacting PB with a sulfur-containing compound, a phosphorus-containing benzene ring and / or phenanthrene ring group compound in the presence of a photoinitiator and under ultraviolet light irradiation through a "thiol-ene" click reaction. Preferably, the molar ratio of PB to the compound containing phosphorus-containing benzene ring and / or phenanthrene ring groups is (1-50):1, preferably (1-20):

1.

5. The preparation method according to claim 4, characterized in that The method comprises the following steps: Step 1: dissolving a phosphorus-based flame retardant and an olefin with a hydroxyl group in an organic solvent, and subjecting the mixture to a free radical reaction to obtain the first product (HBPO); Step 2: The hydroxyl group of the first step product is converted into a bromo group through the Appel-Lee reaction to obtain the second step product (BBPO); Step 3: converting the second step product into a thiol group by debromination with a sulfur-containing compound and an optional reactive reagent to obtain the third step product (MBPO); Step 4: At room temperature, in the presence of a photoinitiator, PB and the product of the third step are catalyzed by ultraviolet light irradiation, and post-processed to obtain the modified PB polymer-type P / S synergistic flame retardant (PB-TBPO).

6. The preparation method according to claim 5, characterized in that In step 1, the phosphorus-based flame retardant is a compound containing a phosphorus-containing benzene ring and / or phenanthrene ring group, preferably 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the olefin with a hydroxyl group includes at least one of 2-propene-1-ol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 6-heptene-1-ol, 7-octen-1-ol, 8-nonene-1-ol, 9-decen-1-ol, 10-undecene-1-ol, and 11-dodecene-1-ol, preferably 3-butene-1-ol. In step 2, triphenylphosphine, carbon tetrabromide and HBPO are added to a solvent for reaction, and the molar ratio of triphenylphosphine and carbon tetrabromide to the molar ratio of the product of the first step is (1-10):1, preferably (1-5):

1.

7. The preparation method according to claim 5 or 6, characterized in that: In step 3, The sulfur-containing compound, BBPO and reactive reagent are added to a solvent for reaction. The sulfur-containing compound is selected from thiourea, bis(trimethylsilyl) sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., preferably bis(trimethylsilyl) sulfide. The reactive reagent is preferably a tetraalkylammonium halide salt, such as tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, The molar ratio of the reactive reagent, the sulfur-containing compound and the molar ratio of BBPO is (1-15):1, preferably (1-9):

1.

8. The preparation method according to any one of claims 5 to 7, characterized in that: In step 4, PB and MBPO are added to the solvent with photoinitiator and catalyzed by ultraviolet light. The PB is added in a certain molar ratio according to the side chain C=C and MBPO, preferably (1-10):1, more preferably (1-5):1, The photoinitiator is selected from 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-methylthiophenyl]-2-morpholinoacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzophenone, 4-phenylbenzophenone, 2,2-dimethyl-2-phenylethanone (DMPA), and 2-vinylthioxanthone, and its usage is 1 to 30% of the mass of PB, preferably 1 to 16%.

9. Use of the click chemistry modified PB polymer type P / S synergistic flame retardant according to any one of claims 1 to 3, characterized in that: Used to prepare composite resin matrix materials, Preferably, the modified PB polymer type P / S synergistic flame retardant, bisphenol A formaldehyde novolac epoxy resin, and 4,4'-diaminodiphenylmethane are added to a solvent for dissolution, the solvent is removed, and the composite resin matrix material is obtained by programmed temperature curing.

10. The use according to claim 9, characterized in that The mass ratio of the 4,4'-diaminodiphenylmethane to the bisphenol A formaldehyde novolac epoxy resin is (5-30):60, preferably (10-25):60, The mass ratio of the PB-TBPO to the bisphenol A formaldehyde novolac epoxy resin is (1-20):100, preferably (2-10):100.

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