Preparation and application of P / N / S-containing multifunctional polybutadiene polymer type flame retardant capable of shielding ultraviolet light and harmful blue light

Abstract

The invention provides a P / N / S-containing multifunctional polybutadiene polymer type flame retardant capable of shielding ultraviolet light and harmful blue light as well as a preparation method and application of the flame retardant, the flame retardant is prepared through a'thiol-ene 'click chemical reaction, the problem that a micromolecular flame retardant is easy to migrate and separate out is solved, the flame retardant property is improved, and the flame retardant efficiency is improved. The preparation method has the characteristics of mild reaction temperature, simple operation, rapid reaction, high yield and the like, energy consumption is saved, the idea of'carbon neutralization 'is achieved, the flame retardant is used in a composite resin matrix material, the mechanical property is further improved, due to close packing of benzene rings, biphenyl rings and phenanthrene rings, ultraviolet light and blue light which are harmful to human beings can be shielded, and the flame retardant can be used in the composite resin matrix material. The optical transparency and the light stability are relatively good.

Description

Technical Field

[0001] The present invention relates to the preparation and application of a P / N / S multifunctional polybutadiene polymer flame retardant capable of shielding ultraviolet light and harmful blue light. The flame retardant can impart high flame retardancy, mechanical strength and high-efficiency shielding properties of ultraviolet light and harmful blue light to the composite material with a low addition amount. Background Art

[0002] With the rapid development of modern technology and changes in people's lifestyles, prolonged exposure to electronic screens and strong outdoor lighting has become the norm, leading to increasing concerns about UV and blue light damage. To address this challenge, new multifunctional materials have emerged to protect against UV and blue light, providing strong protection for people's health and safety. At the same time, flammable materials pose a threat to human health and hinder socioeconomic development, making new, multifunctional and highly effective flame-retardant materials particularly important.

[0003] Polybutadiene (PB) has excellent dielectric properties and is widely used as a substrate material in aerospace, electronic and electrical equipment, microwave communications, and other applications. However, PB is flammable, with a limiting oxygen index of approximately 20%. Its molten droplet characteristics can easily cause secondary fires. Furthermore, when used alone, it can suffer from a series of defects, such as glue flow and poor processing properties. These limitations significantly limit its application. Therefore, the development of multifunctional polybutadiene polymer flame retardants is essential.

[0004] Phosphorus-based flame retardants are characterized by high flame retardancy, low toxicity, and low smoke, making phosphorus a key element in the preparation of halogen-free flame retardants. Synergistic flame retardants such as polymeric phosphorus, nitrogen, sulfur, and silicon are typically combined within a single molecular structure, or one of the sources is designed as a hyperbranched macromolecule and then compounded with the other two. The use of polymeric flame retardants can avoid the reduction in thermal stability caused by small molecule additives and improve compatibility and dispersibility with the matrix, allowing the flame retardant to fully function during combustion. Furthermore, polymeric flame retardants have a relatively minimal impact on the overall performance of composite materials, providing guidance in practical applications. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a P / N / S multifunctional polybutadiene polymer flame retardant with the function of shielding ultraviolet light and harmful blue light, and a preparation method and application thereof. It is prepared through a "thiol-ene" click chemistry reaction, which not only solves the problem of easy migration and precipitation of small molecule flame retardants, but also improves the flame retardant performance. The preparation method has the characteristics of mild reaction temperature, simple operation, rapid reaction, high yield, etc., saves energy consumption, and achieves the concept of "carbon neutrality". The flame retardant is used in composite resin matrix materials to further improve the mechanical properties. Due to the close stacking of benzene rings, biphenyl rings and phenanthrene rings, it can shield ultraviolet light and blue light that are harmful to humans, and has good optical transparency and light stability, thereby completing the present invention.

[0006] Therefore, according to the present invention, a multifunctional polybutadiene polymer flame retardant containing P / N / S with the ability to shield ultraviolet light and harmful blue light is provided, abbreviated as PB-TMAPO. The flame retardant is a PB polymer-type P / N / S synergistic flame retardant modified by click chemistry, and is mainly prepared by reacting polybutadiene (PB) with phosphorus-containing benzene ring, phenanthrene ring group compounds, sulfur-containing compounds, nitrogen-containing compounds and biological matrices.

[0007] Preferably, the structural formula of the P / N / S multifunctional polybutadiene polymer flame retardant is as follows:

[0008]

[0009] in,

[0010] m is selected from an integer of 1 to 60, preferably an integer of 1 to 50; n is selected from an integer of 0 to 60, preferably an integer of 0 to 50;

[0011] p is selected from integers of 1-60, preferably integers of 1-50.

[0012] The number average molecular weight of the PB is 400-6000 g / mol, preferably 900-4000 g / mol, and more preferably 1000-3500 g / mol.

[0013] According to the present invention, a preparation method of the P / N / S multifunctional polybutadiene polymer flame retardant (PB-TMAPO) with the ability to shield ultraviolet light and harmful blue light is also provided. The flame retardant is mainly prepared by reacting PB with phosphorus-containing benzene rings, phenanthrene ring group compounds, sulfur-containing compounds, nitrogen-containing compounds and biological matrices.

[0014] According to a preferred embodiment, the preparation method comprises the following steps:

[0015] Step 1: Add the biological matrix and nitrogen-containing compounds into a container, add an alcohol solvent, and then add phosphorus-containing benzene ring and phenanthrene ring group compounds to react, and obtain the first step product through post-treatment.

[0016] In this step, the phosphorus-containing benzene ring and phenanthrene ring group compound 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.

[0017] The nitrogen-containing compound is ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 9-amino-1-nonanol, 10-amino-1-decanol, 11-amino-1-undecanol, 12-amino-1-dodecanol, 13-amino-1-tridecanol, 14-amino-1-tetradecanol, 15-amino-1-pentadecanol and the like, including all amino alcohols, preferably ethanolamine and 3-amino-1-propanol.

[0018] The biological matrix includes cardanol, lignin, vanillin (3-methoxy-4-hydroxybenzaldehyde), tannic acid, vegetable oil, ramie oil, etc. and related derivatives, preferably 3-methoxy-4-hydroxybenzaldehyde, namely vanillin.

[0019] The reaction formula of this step is as follows:

[0020]

[0021] According to a preferred embodiment, in step 1, a certain amount of 3-methoxy-4-hydroxybenzaldehyde and ethanolamine are added to a dry and clean three-necked flask, and a certain amount of ethanol is added at the same time. The temperature is raised for a period of time under nitrogen protection, and then a certain amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is added. The reaction is continued for a period of time, and the reaction liquid is cooled to room temperature and concentrated by rotary evaporation to obtain the first step product.

[0022] In step 1, the molar ratio of 3-methoxy-4-hydroxybenzaldehyde:ethanolamine:ethanol:DOPO is 1:1-2:4-8:1-1.6.

[0023] In step 1, the reaction temperature is 30° C. to 80° C., the reaction time is 5 to 13 hours, and the reaction time after adding DOPO is 8 to 16 hours.

[0024] Step 2: The alcoholic hydroxyl group of the product from the first step is converted into bromine through a reaction to obtain the product from the second step.

[0025] In step 2, preferably, the alcoholic hydroxyl group of the product from the first step is converted into bromine by adding triphenylphosphine and carbon tetrabromide.

[0026] The reaction formula of this step is as follows:

[0027]

[0028] According to a preferred embodiment, the molar ratio of the first step product: triphenylphosphine: carbon tetrabromide is 1:1-3:1-3.

[0029] Step 3: The product of the second step is debrominated and converted into a thiol group by using a quaternary ammonium salt and a sulfur-containing compound to obtain the product of the third step.

[0030] In step 3, preferably, the quaternary ammonium salt is preferably tetrabutylammonium fluoride, and the sulfur-containing compound is selected from thiourea, bis(trimethylsilyl) sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., preferably bis(trimethylsilyl) sulfide bis(trimethylsilyl) sulfide.

[0031] The reaction formula of this step is as follows:

[0032]

[0033] According to a preferred embodiment, the molar ratio of the second step product: tetrabutylammonium fluoride: bis(trimethylsilyl) sulfide is 1:1-3:1-3.

[0034] Step 4: Through the "thiol-ene" click reaction, PB and the product of the third step are fed differently to obtain a P / N / S multifunctional polybutadiene polymer flame retardant with the function of shielding ultraviolet light and harmful blue light.

[0035] According to the present invention, the PB comprises a structure represented by the following formula:

[0036]

[0037] in,

[0038] x is selected from an integer of 1 to 60, preferably an integer of 1 to 50, and preferably, its relationship with m in the above formula is: x=m;

[0039] w is selected from an integer of 1 to 120, preferably an integer of 1 to 100. Preferably, its relationship with n and p in the above formula is: w=n+p.

[0040] According to a preferred embodiment, in the PB, the ratio of the 1,2-polymerized portion of butadiene (the polymerization unit where w is located) to the whole, that is, the sum of the 1,2-polymerized portion and the 1,4-polymerized portion (the polymerization unit where x is located), that is, w / (x+w) can be 50-99%, preferably 75-98%, and more preferably 85-95%.

[0041] The number average molecular weight of the PB is 400-6000 g / mol, preferably 900-4000 g / mol, and more preferably 1000-3500 g / mol.

[0042] The PB can be prepared according to the literature ([1] Yang Yongcheng, Wang Yurong, Gu Mingchu. Preparation of stereoblock polybutadiene [J]. Synthetic Rubber Industry, 1991, 14(6): 413-416) or known methods, for example, by anionic polymerization of butadiene under the action of an initiator, or purchased from the market, for example, from Japan Soda Co., Ltd., whose different models have a number average molecular weight ranging from 1200 to 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%.

[0043] The reaction formula of this step is as follows:

[0044]

[0045] In step 4, the molar ratio of the third step product to PB (side chain C=C) is 1:1-40.

[0046] By the above method of the present invention, a click chemistry modified PB polymer type P / N / S synergistic flame retardant (PB-TMAPO) is finally prepared. Preferably, its number average molecular weight (Mn) is 800-50000 g / mol, preferably 2000-30000 g / mol, and more preferably 5000-18000 g / mol.

[0047] According to the present invention, there is also provided a use of the P / N / S multifunctional polybutadiene polymer flame retardant (PB-TMAPO) having the ability to shield ultraviolet light and harmful blue light, preferably in a composite resin matrix material, and the application method thereof is as follows:

[0048] A certain amount of bisphenol A formaldehyde novolac epoxy resin (EP), PB-TMAPO, and 4,4-diaminodiphenylmethane (DDM) were added to a solvent and dissolved, and the solvent was removed by rotary evaporation. The composite resin matrix material was obtained by programmed temperature curing according to the curing kinetics results.

[0049] Furthermore, the multifunctional P / N / S ternary synergistic polybutadiene polymer flame retardant provided by the present invention forms phosphoric acid and polyphosphoric acid on the surface of the condensed phase. Dehydration promotes the formation of a carbon layer, reducing heat conduction and isolating oxygen to prevent further flame spread. Simultaneously, the generated nitrogen- and sulfur-containing non-combustible gases dilute combustibles, achieving highly efficient synergistic flame retardancy. Furthermore, the densely packed benzene, biphenyl, and phenanthrene rings shield against harmful ultraviolet (UVA, UVB, and UVC) and blue light, while also exhibiting excellent optical transparency and photostability.

[0050] Compared with the existing technology, the present invention has at least the following advantages:

[0051] (1) The present invention provides a P / N / S multifunctional polybutadiene polymer flame retardant with the ability to shield ultraviolet light and harmful blue light. The synthesis conditions are mild and the operation is simple, which improves the comprehensive performance of PB and expands the scope of application.

[0052] (2) The present invention provides a P / N / S multifunctional polybutadiene polymer flame retardant with the ability to shield ultraviolet light and harmful blue light. When applied to epoxy resin, the flame retardant efficiency can be improved through the P / N / S ternary synergistic flame retardant mechanism, and the mechanical properties, dielectric properties, thermal stability, etc. of the composite resin matrix material are improved.

[0053] (3) The present invention provides a P / N / S multifunctional polybutadiene polymer flame retardant with the ability to shield ultraviolet light and harmful blue light, which can effectively shield ultraviolet light and harmful blue light, thereby realizing a multifunctional new material that is resistant to ultraviolet light, harmful blue light and highly flame-retardant. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The right figure is the infrared spectra of the small molecule compounds VHAPO, BBAPO, and MMAPO in Example 1. For comparison, Figure 1 The left figure shows the infrared spectra of VHAPO, DOPO, Vanilin, and MEA;

[0055] Figure 2 The infrared spectra of PB-TMAPO and PB and MMAPO in different ratios prepared in Examples 1-4;

[0056] Figure 3 The DSC curves of PB-TMAPO and PB prepared in different ratios in Examples 1-4 are shown, and their respective T g ;

[0057] Figure 4(a) UV-visible transmission spectra of the composite resin matrix materials containing PB-TMAPO prepared in Examples 5-7, compared with EP / DDM, EP / DDM / PB (6 phr), and EP / DDM / PB@MMAPO (6 phr);

[0058] Figure 4 (b) is the UV-visible transmission spectrum of the composite resin matrix material containing PB-TMAPO after continuous irradiation with 365nm UV light for 48h, and is compared with EP / DDM, EP / DDM / PB (6phr), and EP / DDM / PB@MMAPO (6phr). DETAILED DESCRIPTION

[0059] The technical solution of the present invention will be described in detail below. The described embodiments are part of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by other experimental technicians in this field without making creative work are within the scope of protection of the present invention.

[0060] (1) The synthesis example of the P / N / S multifunctional polybutadiene polymer flame retardant having the function of shielding ultraviolet light and harmful blue light of the present invention is as follows

[0061] Example 1

[0062] First, 6.00 g of 3-methoxy-4-hydroxybenzaldehyde and 2.92 g of ethanolamine were weighed and added to a dry, clean three-necked flask. Then, 40 mL of anhydrous ethanol was added and the mixture was refluxed under nitrogen for 12 h. Subsequently, 9.67 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added and the mixture was refluxed under nitrogen for 12 h. After cooling to room temperature, 16.73 g of VHAPO was obtained by column chromatography.

[0063] Subsequently, 10.00 g of VHAPO, 8.04 g of triphenylphosphine, and 10.16 g of carbon tetrabromide were weighed and added to a dry, clean three-necked flask. 30 mL of dichloromethane was also added. The mixture was reacted in an ice-water bath for 12 h, and 11.03 g of BBAPO was obtained by column chromatography.

[0064] Finally, 10.33 g of BBAPO, 5.55 g of tetrabutylammonium fluoride, 3.79 g of bis(trimethylsilyl)sulfide, and 40 mL of tetrahydrofuran were weighed and added into a dry and clean three-necked flask. The mixture was reacted in an ice-water bath for 12 h, and 8.56 g of MMAPO was obtained by column chromatography.

[0065] With a molar ratio of PB side chain C=C to MMAPO of 1:1, 0.50g PB (purchased from Japan Soda Co., Ltd., model B-2000, with a number average molecular weight of approximately 2000g / 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), 3.70g MMAPO, 0.21g DMPA and 20mL dichloromethane were added to a dry and clean single-necked flask, and the reaction was carried out under a 365nm UV lamp at room temperature for 1h. After post-treatment with methanol, 4.05g of a P / N / S multifunctional polybutadiene polymer flame retardant PB-TMAPO (1:1) was obtained. The Mn, Mw and PDI of the obtained mixture were determined to be 16455g / mol, 43248g / mol and 2.63.

[0066] The VHAPO, BBAPO, MMAPO and PB-TMAPO (1:1) obtained above were characterized by infrared spectroscopy (FT-IR). Figure 1 and Figure 2 shown.

[0067] according to Figure 1 The infrared spectrum of VHAPO is shown in Figure 2438cm -1 The corresponding PH bond absorption disappears, and the characteristic peaks of P-Ar, P=O and POC appear at 1600 cm -1 、1202cm -1 and 922cm -1 The absorption vibration peak of CN appears at 1056 cm -1 Compared with VHAPO, BBAPO is at 540 cm -1 The absorption vibration peak at 2592 cm-1 is stronger, indicating the conversion of alkyl alcohol C-OH to C-Br. Compared with BBAPO, MMAPO has a stronger absorption vibration peak at 2592 cm-1. -1 There is a new absorption vibration peak at , indicating the conversion from C-Br to C-SH.

[0068] according to Figure 2 The infrared spectrum of MMAPO is shown in Figure 1. -1 The characteristic peak at 1640 cm is CSC, and the PB-TMAPO with a ratio of 1:1 is at 1640 cm -1 The characteristic peak of 910cm -1 The characteristic absorption peak of POC is 1590 cm -1 is the characteristic absorption peak of P-Ar, proving that PB and MMAPO successfully carried out the "thiol-ene" click reaction.

[0069] Example 2

[0070] With the molar ratio of PB side chain C=C to MMAPO being 2:1, 0.50 g PB, 1.85 g MMAPO, 0.12 g DMPA and 20 mL dichloromethane were weighed and added to a dry and clean single-necked flask. The mixture was irradiated with a 365 nm UV lamp for 1 h at room temperature. After post-treatment with methanol, 2.20 g of a P / N / S multifunctional polybutadiene polymer flame retardant PB-TMAPO (2:1) was obtained. The Mn, Mw and PDI of the obtained product were 7696 g / mol, 11628 g / mol and 1.51, respectively. The obtained product was characterized by infrared spectroscopy (FT-IR). Figure 2 As shown (labeled as 2:1PB-TMAPO).

[0071] Example 3

[0072] With a molar ratio of PB side chain C=C to MMAPO of 3:1, 1.00 g PB, 2.47 g MMAPO, 0.17 g DMPA and 20 mL dichloromethane were weighed and added to a dry and clean single-necked flask. The mixture was irradiated with a 365 nm UV lamp for 1 h at room temperature and post-treated with methanol to obtain 3.19 g of a P / N / S multifunctional polybutadiene polymer flame retardant PB-TMAPO (3:1). The results showed that its Mn was 6180 g / mol, Mw was 8424 g / mol, and PDI was 1.36. The FT-IR spectra were characterized as follows: Figure 2 As shown (labeled as 3:1PB-TMAPO).

[0073] Example 4

[0074] With the molar ratio of PB side chain C=C to MMAPO being 4:1, 1.00 g PB, 1.85 g MMAPO, 0.14 g DMPA and 20 mL dichloromethane were weighed and added to a dry and clean single-necked flask. The mixture was irradiated with a 365 nm UV lamp for 1 h at room temperature and post-treated with methanol to obtain 2.51 g of a P / N / S multifunctional polybutadiene polymer flame retardant PB-TMAPO (4:1). The results showed that its Mn was 5356 g / mol, Mw was 8927 g / mol, and PDI was 1.67. The FT-IR was used for characterization, as shown in FIG. Figure 2 As shown (labeled as 4:1PB-TMAPO).

[0075] according to Figure 2 The infrared spectrum of -1 The characteristic peak at 1640 cm is CSC, and the PB-TMAPO with a ratio of 2:1, 3:1 and 4:1 has a peak at 1640 cm -1 There is a characteristic peak of C=C of PB side chain at 910cm -1The characteristic absorption peak of POC is 1590 cm -1 is the characteristic absorption peak of P-Ar, which further indicates the successful preparation of PB-TMAPO with different ratios.

[0076] The T values ​​of the PB-TMAPO products with different ratios prepared in Examples 1-4 were tested by DSC. g and compared with unmodified PB, the results are as follows Figure 3 shown.

[0077] Depend on Figure 3 It can be seen that the T of unmodified PB g At -20℃, the T of the modified PB-TMAPO g Both were improved, and the T g is 80℃, which increases by 100℃. The T g was 71℃, which was increased by 91℃. The T g was 60℃, which increased by 80℃. The T g The temperature of the heat exchanger is 43℃, which is an increase of 630℃, further expanding its application range.

[0078] (2) Applying the P / N / S multifunctional polybutadiene polymer flame retardant of the present invention to epoxy resin

[0079] Example 5

[0080] Preparation of composite resin matrix material using PB-TMAPO (1:1) I

[0081] 0.61 g of PB-TMAPO prepared in Example 1, 20.00 g of bisphenol A formaldehyde novolac epoxy resin (EP), and 5.20 g of 4,4'-diaminodiphenylmethane (DDM) were added to 200 ml of butanone. After complete dissolution, the solvent was completely removed by vacuum distillation. The mixture was immediately poured into a corresponding mold and cured by a temperature program of 72°C / 1 h+124°C / 4 h+163°C / 2 h to obtain a composite resin matrix material I, named EP / DDM / PB-TMAPO (3 phr).

[0082] At the same time, EP / DDM / PB (6 phr) and EP / DDM / PB@MMAPO (6 phr) were cured under the same conditions as above, where PB@MMAPO was prepared by adding PB and MMAPO, respectively, and the mass of the added MMAPO was the same as the molar amount of sulfur in EP / DDM / PB-TMAPO (6 phr).

[0083] 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 (6phr) exhibited violent combustion and produced a large amount of molten droplets, indicating that they were not flame retardant. However, EP / DDM / PB-TMAPO (3phr) achieved the highest UL-94 V-0 rating.

[0084] 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 2599 MPa and the flexural strength was 55.2 MPa, the flexural modulus of EP / DDM / PB (6 phr) was 2008 MPa and the flexural strength was 38.5 MPa, the flexural modulus of EP / DDM / PB@MMAPO (6 phr) was 2854 MPa and the flexural strength was 65.7 MPa, and the flexural modulus of EP / DDM / PB-TMAPO (3 phr) was 3601 MPa and the flexural strength was 151.9 MPa.

[0085] The UV-3600 UV-visible spectrophotometer was used to test the UV-visible transmission spectrum of the composite resin matrix material. Figure 4 As shown in (a). EP / DDM has a shielding efficiency of 79.47% against ultraviolet light (400nm) and a shielding efficiency of 31.08% against harmful blue light (450nm). EP / DDM / PB (6phr) has a shielding efficiency of 83.64% against ultraviolet light and a shielding efficiency of 51.26% against harmful blue light. EP / DDM / PB@MMAPO (6phr) has a shielding efficiency of 90.61% against ultraviolet light and a shielding efficiency of 75.99% against harmful blue light. EP / DDM / PB-TMAPO (3phr) has a shielding efficiency of 99.03% against ultraviolet light and a shielding efficiency of 84.75% against harmful blue light.

[0086] The light stability test of the composite resin matrix material I was carried out. After continuous irradiation with 365nm ultraviolet light for 48 hours, the shielding efficiency against ultraviolet rays was 98.80%, and the shielding efficiency against harmful blue light was 82.65%. Figure 4 (b) shown.

[0087] Example 6

[0088] Composite resin matrix material II (EP / DDM / PB-TMAPO (6phr)) was prepared according to the method of Example 5, except that the amount of PB-TMAPO added to the curing reaction system was 1.25 g, the amount of DDM added was 5.19 g, and the amount of EP added remained unchanged.

[0089] A vertical burning test (UL-94) was conducted in an M607B vertical burning tester according to ASTM D3801-10. The test results showed that EP / DDM / PB-TMAPO (6phr) can achieve the highest UL-94 V-0 grade.

[0090] Bending properties were tested using an Instron 5869 electronic universal testing machine according to GB / T9341-2008. The experimental results showed that the flexural modulus of EP / DDM / PB-TMAPO (6phr) was 3932 MPa and the flexural strength was 174.0 MPa.

[0091] The UV-3600 UV-visible spectrophotometer was used to test the UV-visible transmission spectrum of the composite resin matrix material. Figure 4 (a) As shown. EP / DDM / PB-TMAPO (6phr) has a shielding efficiency of 99.78% against ultraviolet light and 96.15% against harmful blue light. The photostability test of composite resin matrix material II showed that after continuous irradiation with 365nm ultraviolet light for 48 hours, the shielding efficiency against ultraviolet light was 99.76% and the shielding efficiency against harmful blue light was 95.68%. Figure 4 (b) shown.

[0092] Example 7

[0093] Composite resin matrix material III (EP / DDM / PB-TMAPO (9 phr)) was prepared according to the method of Example 5, except that the amount of PB-TMAPO added to the curing reaction system was 1.92 g, the amount of DDM added was 5.20 g, and the amount of EP added remained unchanged.

[0094] Vertical burning tests (UL-94) were conducted in an M607B vertical burning tester according to ASTM D3801-10. The UL-94 data for composite resin matrices containing varying PB-TMAPO contents are summarized in Table 1. The test results demonstrate that EP / DDM / PB-TMAPO (9 phr) achieves the highest UL-94 rating of V-0.

[0095] Flexural properties were tested using an Instron 5869 electronic universal testing machine according to GB / T9341-2008. The flexural performance data for composite resin matrices containing different PB-TMAPO contents are summarized in Table 2. The results show that the flexural modulus of EP / DDM / PB-TMAPO (9 phr) was 3741 MPa and the flexural strength was 161.2 MPa.

[0096] The UV-3600 UV-visible spectrophotometer was used to test the UV-visible transmission spectrum of the composite resin matrix material. Figure 4 (a) is shown. The UV-visible transmittance data of composite resin matrix materials with different PB-TMAPO contents are summarized in Table 3 below. The shielding efficiency of EP / DDM / PB-TMAPO (9 phr) against ultraviolet rays is 99.97%, and the shielding efficiency against harmful blue light is 99.36%. The photostability test of composite resin matrix material III was carried out. After continuous irradiation with 365 nm ultraviolet light for 48 hours, the shielding efficiency against ultraviolet rays was 99.96%, and the shielding efficiency against harmful blue light was 99.27%. Figure 4 As shown in (b), the above results indicate that the material has high photostability.

[0097] Table 1: Summary of vertical burning test (UL-94) data for composite resin matrix materials with different PB-TMAPO contents

[0098]

[0099]

[0100] Table 2: Summary of flexural properties test data of composite resin matrix materials with different PB-TMAPO contents

[0101]

[0102] Table 3: Summary of UV-Vis transmission data for composite resin matrix materials with different PB-TMAPO contents

[0103]

[0104]

[0105] Finally, it should be noted that the above embodiments are intended only to illustrate the technical solutions of the present invention and are not intended to 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 multifunctional polybutadiene polymer flame retardant containing P / N / S that can shield ultraviolet light and harmful blue light. The flame retardant is a PB polymer-type P / N / S synergistic flame retardant modified by click chemistry, and is mainly prepared by reacting PB with phosphorus-containing benzene ring and phenanthrene ring group compounds, sulfur-containing compounds, nitrogen-containing compounds and biological matrices.

2. The flame retardant according to claim 1, characterized in that The flame retardant has the structure shown below: and / or in, m is an integer selected from 1 to 60; n is an integer selected from 0 to 60; p is selected from integers of 1-60.

3. A method for preparing the P / N / S multifunctional polybutadiene polymer flame retardant according to claim 1 or 2, characterized in that: The steps include: Step 1: Add the biological matrix and nitrogen-containing compound into a container, add an alcohol solvent, and then add a phosphorus-containing benzene ring or phenanthrene ring group compound to react, and obtain the first step product through post-treatment; Step 2: The alcoholic hydroxyl group of the product from the first step is converted into bromine by addition reaction to obtain the product from the second step; Step 3: converting the product of the second step into a thiol group by debromination with a quaternary ammonium salt and a sulfur-containing compound to obtain the product of the third step; Step 4: Through the "thiol-ene" click reaction, PB and the product of the third step are fed differently to obtain the P / N / S multifunctional polybutadiene polymer flame retardant.

4. The preparation method according to claim 3, characterized in that In step 1, The phosphorus-containing benzene ring and phenanthrene ring group compound 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; The nitrogen-containing compound is ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 9-amino-1-nonanol, 10-amino-1-decanol, 11-amino-1-undecanol, 12-amino-1-dodecanol, 13-amino-1-tridecanol, 14-amino-1-tetradecanol, 15-amino-1-pentadecanol and the like, including all amino alcohols, preferably ethanolamine and 3-amino-1-propanol; The biological matrix includes cardanol, lignin, vanillin (3-methoxy-4-hydroxybenzaldehyde), tannic acid, vegetable oil, ramie oil, etc., preferably 3-methoxy-4-hydroxybenzaldehyde.

5. The preparation method according to claim 3 or 4, characterized in that In step 1, A certain amount of 3-methoxy-4-hydroxybenzaldehyde and ethanolamine were added to a dry and clean three-necked flask, and a certain amount of ethanol was added at the same time. The temperature was raised for a period of time under nitrogen protection. Then, a certain amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was added and the reaction was continued for a period of time. The reaction solution was cooled to room temperature and concentrated by rotary evaporation to obtain the first step product. The molar ratio of 3-methoxy-4-hydroxybenzaldehyde:ethanolamine:ethanol:DOPO is 1:1-2:4-8:1-1.6; The reaction temperature is 30° C. to 80° C., the reaction time is 5 to 13 hours, and the reaction time after adding DOPO is 8 to 16 hours.

6. The preparation method according to any one of claims 3 to 5, characterized in that: In step 2, The first step product is reacted by adding triphenylphosphine and carbon tetrabromide to convert the alcoholic hydroxyl group into bromine. Preferably, the molar ratio of the first step product: triphenylphosphine: carbon tetrabromide is 1:1-3:1-3.

7. The preparation method according to any one of claims 3 to 6, characterized in that: In step 3, The quaternary ammonium salt is tetrabutylammonium fluoride, The sulfur-containing compound is selected from thiourea, bis(trimethylsilyl) sulfide, potassium hydrogensulfide, potassium thioacetate, carbon disulfide, etc., preferably bis(trimethylsilyl) sulfide. Preferably, the molar ratio of the second step product: tetrabutylammonium fluoride: bis(trimethylsilyl) sulfide is 1:1-3:1-3.

8. The preparation method according to any one of claims 3 to 7, characterized in that: In step 4, the molar ratio of the third step product to PB (side chain C=C) is 1:1-40.

9. Use of the P / N / S multifunctional polybutadiene polymer flame retardant according to claim 1 or 2, preferably in composite resin matrix materials.

10. The use according to claim 9, wherein the application method is as follows: A certain amount of bisphenol A formaldehyde novolac epoxy resin (EP), PB-TMAPO, and 4,4-diaminodiphenylmethane (DDM) were added to a solvent and dissolved, the solvent was removed by rotary evaporation, and programmed temperature curing was performed to obtain a composite resin matrix material.

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