Bio-based amino polyol brominated epoxy resin, preparation method and application

Abstract

The present invention discloses a bio-based amino polyol brominated epoxy resin, a preparation method, and applications. The bio-based amino polyol brominated epoxy resin has the following structure: wherein R and R1 are both a carbon pentadecanyl group, and R2 is an amino polyol. The polyol of the present invention can be used as a reactive flame retardant in polyurethane foam, which can maximize the mechanical properties of the material; at the same time, the processing technology is simple; and the bio-based amino polyol brominated epoxy resin contains a flame retardant group (Br), which can be used as a polyurethane foam synthetic material and a flame retardant, thereby improving the flame retardant properties of the product. In addition, the amino polyol structure contained in the bio-based amino polyol brominated epoxy resin can completely replace the amino catalyst in the polyurethane foam synthesis, realizing multifunctionality in one.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and in particular relates to a bio-based amino polyol brominated epoxy resin, a preparation method and an application thereof. Background Art

[0002] Polyurethane (PU) is a polymer with repeating carbamate groups (-NHCOO-) within its backbone structure. Polyurethane resins possess exceptional physical and chemical properties, such as low thermal conductivity, high strength, excellent adhesion, and mechanical properties. They are an important polymer foam material, considered the fifth most commonly used plastic after polyethylene, polyvinyl chloride, polypropylene, and polystyrene, and are widely used in the construction, transportation, packaging, furniture, and aviation industries. However, polyurethane has a large specific surface area, and unflammable polyurethane foams have a limiting oxygen index (LOI) of only 19%. They are highly flammable and burn rapidly, releasing large amounts of heat, thick black smoke, and toxic gases such as CO, NO, and HCN. This poses significant safety risks and can easily lead to serious loss of life and property. Therefore, the development of highly effective flame-retardant polyurethane foams is of great significance.

[0003] Currently, the flame retardancy of polyurethane is generally improved by using additive flame retardants and flame retardant polyether polyols. Traditional additive flame retardants, which are physically blended, are prone to problems such as flame retardant migration and precipitation during the use of polyurethane products, reducing the flame retardancy of polyurethane foam and also reducing the physical properties of the material. Reactive flame retardants have the characteristics of good stability, low toxicity, and minimal impact on polymer properties. However, their operation and processing technology are complex and are not as common as additive flame retardants in actual applications. Therefore, there is an urgent need for a product with simple operation and processing technology that improves flame retardancy while maintaining mechanical properties to the greatest extent possible. Summary of the Invention

[0004] The first technical problem addressed by the present invention is to provide a bio-based amino polyol brominated epoxy resin. The polyol of the present invention can be used as a reactive flame retardant in polyurethane foam, maximizing the mechanical properties of the material. The processing is simple. Furthermore, the bio-based amino polyol brominated epoxy resin contains flame-retardant groups (Br), allowing it to function as both a polyurethane foam synthetic material and a flame retardant, improving the product's flame retardancy. Furthermore, the amino polyol structure contained in the bio-based amino polyol brominated epoxy resin can completely replace amino catalysts in polyurethane foam synthesis, achieving multifunctionality.

[0005] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned bio-based amino polyol brominated epoxy resin.

[0006] The third technical problem to be solved by the present invention is to provide an application of the above-mentioned bio-based amino polyol brominated epoxy resin.

[0007] In order to solve the above-mentioned first technical problem, the present invention adopts the following technical solution:

[0008] A bio-based amino polyol brominated epoxy resin having the structure shown below:

[0009]

[0010] Wherein, R and R1 are both pentadecyl groups, and R2 is an amino polyol.

[0011] As an embodiment, R and R1 are bond-line structures shown in any one of the following formulas (I), (II), (III), and (IV):

[0012]

[0013] In order to solve the above second technical problem, the present invention adopts the following technical solution:

[0014] The present invention provides a method for preparing a bio-based amino polyol brominated epoxy resin, comprising the following steps:

[0015] S1, reacting tetrabromobisphenol A and epichlorohydrin in the presence of a catalyst to obtain a brominated epoxy resin having epoxy groups capped at both ends;

[0016] S2, reacting cardanol with the brominated epoxy resin obtained in step S1 to obtain a cardanol-modified brominated epoxy resin;

[0017] S3. Further reacting the aldehyde and amino polyol with the brominated epoxy resin modified with cardanol obtained in step S2 to obtain a bio-based amino polyol brominated epoxy resin.

[0018] As an embodiment, in step S1, the specific preparation steps of the brominated epoxy resin with epoxy groups capped at both ends are as follows:

[0019] 400-420g of epichlorohydrin and 390-410g of tetrabromobisphenol A are weighed and added to a four-necked flask, a reflux condenser and a thermometer are installed, heating is started, benzyltriethylammonium chloride is added, the temperature is raised to 85-95°C with stirring, the reaction is carried out for 2-3h, and excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of toluene solvent is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is evenly added over 1h and stirred evenly, and the reaction is carried out for 4-6h; then 280-320g of toluene solvent is added for extraction, and 300-500g of water is added while hot to wash off the generated sodium chloride, and the liquids are separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the liquids are separated; the toluene solvent is removed by distillation under reduced pressure to obtain a brominated epoxy resin end-capped with epoxy groups at both ends.

[0020] As an embodiment, in step S2, the specific preparation steps of the cardanol-modified brominated epoxy resin are as follows:

[0021] Weigh 330-370g of the brominated epoxy resin (end-capped with epoxy groups) prepared in step S1, 330-340g of cardanol, and 0.6-1.0g of an antioxidant into a four-necked flask. Heat to 95-105°C and stir to dissolve. Add 2-3.5g of triphenylphosphine catalyst to the reaction flask, continue heating to 170-190°C, and react for 50-70 minutes. After the reaction is complete, a brominated epoxy resin modified with cardanol is obtained.

[0022] As an embodiment, in step S3, the specific preparation steps of the bio-based amino polyol brominated epoxy resin are as follows:

[0023] Add 14-17g of amino polyol and 4-5g of aldehyde to a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the cardanol-modified brominated epoxy resin prepared in step 2, continue to react at 85-95°C for 4-6h, and then remove water and unreacted amino polyol by reduced pressure distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0024] As an embodiment, in step S3, the aldehyde is selected from one or more of formaldehyde, trioxymethylene, and paraformaldehyde.

[0025] As an embodiment, in step S3, the amino polyol is selected from one or more of ethanolamine, diethanolamine, and triethanolamine.

[0026] In order to solve the third technical problem mentioned above, the present invention adopts the following technical solution:

[0027] An application of the above-mentioned bio-based amino polyol brominated epoxy resin is to use the bio-based amino polyol brominated epoxy resin as a raw material for synthesizing polyurethane foam material with flame retardant properties.

[0028] As an embodiment, the flame-retardant polyurethane foam material is made from the following raw materials: bio-based amino polyol brominated epoxy resin, polyether polyol, isocyanate, catalyst and foaming agent;

[0029] As an embodiment, the raw materials further include a synergistic flame retardant; the synergistic flame retardant is a halogenated phosphate or tetrabromophthalic anhydride diol; wherein the halogenated phosphate is TCPP;

[0030] As an embodiment, the catalyst is a tin catalyst and an amine catalyst;

[0031] As an embodiment, the amine catalyst is a bio-based amino polyol brominated epoxy resin.

[0032] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0033] Unless otherwise specified, all raw materials in the present invention can be purchased commercially, and the equipment used in the present invention can adopt conventional equipment in the relevant field or refer to the existing technology in the relevant field.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1) First, the present invention utilizes cardanol as a nucleophilic reagent. The phenolic hydroxyl group in cardanol attacks the carbon atom of the epoxy group in the brominated epoxy resin, causing the C-O bond to break, opening the epoxy group and connecting with the phenolic hydroxyl group to prepare a cardanol-modified brominated epoxy resin. Then, an aldehyde undergoes a Mannich reaction with the amine group in diethanolamine. The carbonyl group of the aldehyde is protonated, and the amine undergoes nucleophilic addition to the carbonyl group. After deprotonation, electron transfer from nitrogen, and water removal, an iminium ion intermediate is obtained. This iminium ion intermediate acts as an electrophilic reagent to attack the active hydrogen atoms of the ortho-para positions of the cardanol in the cardanol-modified brominated epoxy resin, thereby obtaining a bio-based amino polyol brominated epoxy resin.

[0036] 2) The bio-based cardanol raw material of the present invention has the advantages of being cheap, abundant in source, non-toxic and biodegradable.

[0037] 3) The synthesized bio-based amino polyol brominated epoxy resin successfully connects to the cardanol structure, while giving it the benzene ring and long chain structure of cardanol, bringing flexibility, low toxicity, water resistance and high temperature resistance.

[0038] 4) The synthesized bio-based amino polyol brominated epoxy resin successfully connected to the cardanol structure contains brominated (Br) flame retardant groups, which can be used as a polyurethane foam synthetic material and also as a flame retardant, thereby improving the flame retardant properties of the product.

[0039] 5) A bio-based amino polyol brominated epoxy resin contains an R2 amino polyol structure and can be used as an amino catalyst in the synthesis of flame-retardant polyurethane polymer materials. Compared with the traditional synthesis of flame-retardant polyurethane foaming polymer materials, the use of the bio-based amino polyol brominated epoxy resin of this patent does not require the addition of an additional amine catalyst in the synthesis of flame-retardant polyurethane foaming polymer materials.

[0040] 6) The synthesized bio-based amino polyol brominated epoxy resin can achieve multifunctionality in flame-retardant polyurethane foam materials, while reducing costs and having excellent flame retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0042] Figure 1 This is the infrared spectrum of the bio-based brominated epoxy resin prepared in Example 2;

[0043] Figure 2 is the infrared spectrum of diethanolamine;

[0044] Figure 3 This is the infrared spectrum of the bio-based amino polyol brominated epoxy resin prepared in Example 3;

[0045] Figure 4 This is the infrared spectrum of the bio-based amino polyol brominated epoxy resin prepared in Example 4;

[0046] Figure 5 This is the infrared spectrum of the bio-based amino polyol brominated epoxy resin prepared in Example 5. DETAILED DESCRIPTION

[0047] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the following specific description is illustrative rather than restrictive and should not be used to limit the scope of protection of the present invention.

[0048] Unless otherwise specified, the methods used in the present invention are all conventional methods; the raw materials and devices used are all conventional commercially available products.

[0049] TCPP and cardanol were purchased from Zhejiang Wansheng Co., Ltd.;

[0050] Isocyanate was purchased from Wanhua Chemical Group Co., Ltd.

[0051] Polyether polyol and water-soluble silicone oil were purchased from Changzhou Zhuolian Zhichuang Polymer Material Technology Co., Ltd.

[0052] Acetone and diethanolamine were purchased from Tianjin Damao Chemical Reagent Factory;

[0053] Triethylenediamine was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0054] Paraformaldehyde was purchased from Tianjin Yongda Chemical Reagent Co., Ltd.

[0055] Defoamer B-459 was purchased from Guangdong Zhonglianban Fine Chemical Co., Ltd.;

[0056] Tetrabromophthalic anhydride diol was purchased from Shandong Runke Chemical Co., Ltd.;

[0057] Antimony trioxide was purchased from Hunan Jinbo New Material Technology Co., Ltd.;

[0058] The viscometer model is NDJ-8S, with a 4# rotor, purchased from Shanghai Lichen Bangxi Instrument Technology Co., Ltd.

[0059] As one aspect of the present invention, the present invention provides a bio-based amino polyol brominated epoxy resin having the structure shown below:

[0060]

[0061] Wherein, R and R1 are both pentadecyl groups, and R2 is an amino polyol.

[0062] According to certain embodiments of the present invention, R and R1 are bond-line structures represented by any one of the following formulas (I), (II), (III), and (IV):

[0063]

[0064] Among many bio-based materials, the chemical structure of cardanol combines a benzene ring structure, a phenolic hydroxyl group, and a C15 unsaturated straight chain. Among them, the benzene ring is rigid, and the C15 straight chain has good toughness. It is precisely these rigid and flexible structural characteristics that have made cardanol a research hotspot in the field of bio-based materials in recent years. As an agricultural by-product, cardanol is extracted from natural cashew nut shell oil and has the advantages of abundant sources, low prices, and renewable nature. Usually, cardanol is a mixture of four alkylphenols with different degrees of saturation, namely, about 3% saturated hydrocarbon cardanol, about 42% monoolefin cardanol, about 17% diene cardanol, and about 38% triolefin cardanol. Its structural diagram is as follows:

[0065]

[0066] As another aspect of the present invention, a method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0067] S1, reacting tetrabromobisphenol A and epichlorohydrin in the presence of a catalyst to obtain a brominated epoxy resin having epoxy groups capped at both ends;

[0068] S2, reacting cardanol with the brominated epoxy resin obtained in step S1 to obtain a cardanol-modified brominated epoxy resin;

[0069] S3. Further reacting the aldehyde and amino polyol with the brominated epoxy resin modified with cardanol obtained in step S2 to obtain a bio-based amino polyol brominated epoxy resin.

[0070] According to certain embodiments of the present invention, in step S1, the specific preparation steps of the brominated epoxy resin capped at both ends with epoxy groups are as follows:

[0071] 400-420g of epichlorohydrin and 390-410g of tetrabromobisphenol A are weighed and added to a four-necked flask, a reflux condenser and a thermometer are installed, heating is started, benzyltriethylammonium chloride is added, the temperature is raised to 85-95°C with stirring, the reaction is carried out for 2-3h, and excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of toluene solvent is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is evenly added over 1h and stirred evenly, and the reaction is carried out for 4-6h; then 280-320g of toluene solvent is added for extraction, and 300-500g of water is added while hot to wash off the generated sodium chloride, and the liquids are separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the liquids are separated; the toluene solvent is removed by distillation under reduced pressure to obtain a brominated epoxy resin end-capped with epoxy groups at both ends.

[0072] According to certain embodiments of the present invention, in step S2, the specific preparation steps of the cardanol-modified brominated epoxy resin are as follows:

[0073] Weigh 330-370g of the brominated epoxy resin (end-capped with epoxy groups) prepared in step S1, 330-340g of cardanol, and 0.6-1.0g of an antioxidant into a four-necked flask. Heat to 95-105°C and stir to dissolve. Add 2-3.5g of triphenylphosphine catalyst to the reaction flask, continue heating to 170-190°C, and react for 50-70 minutes. After the reaction is complete, a brominated epoxy resin modified with cardanol is obtained.

[0074] According to certain embodiments of the present invention, in step S3, the specific preparation steps of the bio-based amino polyol brominated epoxy resin are as follows:

[0075] Add 14-17g of amino polyol and 4-5g of aldehyde to a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the cardanol-modified brominated epoxy resin prepared in step 2, continue to react at 85-95°C for 4-6h, and then remove water and unreacted amino polyol by reduced pressure distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0076] According to some embodiments of the present invention, in step S3, the aldehyde is selected from one or more of formaldehyde, trioxymethylene, and paraformaldehyde.

[0077] According to some embodiments of the present invention, in step S3, the amino polyol is selected from one or more of ethanolamine, diethanolamine, and triethanolamine.

[0078] In another aspect of the present invention, the bio-based amino polyol brominated epoxy resin is used as a raw material for synthesizing a polyurethane foam material having flame retardant properties. The bio-based amino polyol brominated epoxy resin imparts flame retardancy to the polyurethane foam material.

[0079] According to certain embodiments of the present invention, the flame-retardant polyurethane foam material is made from the following raw materials: bio-based amino polyol brominated epoxy resin, polyether polyol, isocyanate, catalyst and foaming agent;

[0080] According to certain embodiments of the present invention, the raw materials further include a synergistic flame retardant; the synergistic flame retardant is a halogenated phosphate or tetrabromophthalic anhydride diol; wherein the halogenated phosphate is TCPP;

[0081] According to certain embodiments of the present invention, the catalyst is a tin catalyst and an amine catalyst;

[0082] According to certain embodiments of the present invention, the amine catalyst is a brominated epoxy resin containing a bio-based amino polyol; that is, no additional amine catalyst is required in the reaction raw materials.

[0083] Example 1

[0084] Synthesis of brominated epoxy resin:

[0085] Weigh 410g of epichlorohydrin and 400g of tetrabromobisphenol A into a four-necked flask, install a reflux condenser and a thermometer, start heating, add benzyltriethylammonium chloride, stir and heat to 90°C, react for 2.5h, and remove excess epichlorohydrin by distillation under reduced pressure; cool to 60°C, add 100g of solvent toluene, stir evenly, add 25% sodium hydroxide solution evenly within 1h and stir evenly, and react for 5h; then add 300g of solvent toluene for extraction, and add 400g of water for washing while hot to wash away the generated sodium chloride, and separate the liquids; then add 400g of hot water at 60°C for washing twice in a row, and separate the liquids; remove the solvent toluene by distillation under reduced pressure to obtain a brominated epoxy resin.

[0086] Through experimental testing (hydrochloric acid-acetone method), it was found that the epoxy equivalent of the brominated epoxy resin was 350 g / equivalent.

[0087] Example 2

[0088] Synthesis of cardanol-modified brominated epoxy resin:

[0089] 350 g of the brominated epoxy resin prepared in Example 1, 335 g of cardanol, and 0.8 g of an antioxidant were weighed and added to a four-necked flask. The mixture was heated to 100°C and stirred to dissolve. 2.8 g of triphenylphosphine catalyst was added to the reaction flask, and the temperature was continued to rise to 180°C. The reaction was allowed to proceed for 60 minutes. After the reaction, a brominated epoxy resin modified with cardanol was obtained.

[0090] Through experimental testing (hydrochloric acid-acetone method), it was found that the epoxy equivalent of the brominated epoxy resin modified with cardanol was 6250 g / equivalent.

[0091] Infrared detection: The brominated epoxy resin modified with cardanol obtained in Example 2 was detected at 3383.7 cm -1 The broad peak at 3008.2 cm is the absorption peak of the phenolic hydroxyl group of excess cardanol and the new hydroxyl -OH absorption peak generated by the ring opening reaction of cardanol and brominated epoxy resin. -1 is the stretching vibration peak of the olefin chain in the side chain, 2926.1 cm -1 、2852.0cm -1 The corresponding CH stretching vibration absorption peak on methyl and methylene is 1583.7 cm -1 、1488.6cm -1 、1449.4cm -1 Corresponding to the benzene ring skeleton vibration absorption peak, 1254.7cm -1 、1155.5cm -1 is the stretching vibration peak of CO.

[0092] The above results indicate the successful synthesis of brominated epoxy resin modified with cardanol.

[0093] Example 3

[0094] A method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0095] 15.75 g of diethanolamine and 4.5 g of paraformaldehyde were added to a flask and heated to 90°C for 2 h. Then, 130.9 g of brominated epoxy resin modified with cardanol was added and the reaction was continued at 90°C for 4.5 h. Finally, water and unreacted diethanolamine were removed by vacuum distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0096] The viscosity was measured by a viscometer and was 81410 cPs (25°C). The experimental test found that the hydroxyl value was 207 mg KOH / g. In order to further confirm the synthesis of the bio-based amino polyol brominated epoxy resin, diethanolamine and the bio-based amino polyol brominated epoxy resin prepared in Example 3 were subjected to infrared characterization. The infrared spectrum is shown in the attached figure. Figure 2 、 3 As shown. Figure 2 It can be found that 3297.3cm -1 The peak at 3108.5 cm is the stretching vibration of -OH. -1 The peak at 2922.5cm corresponds to the stretching vibration of NH, and the stretching vibration absorption peak of CH on the methylene group is at 2922.5cm -1 and 2846.2cm -1 , 1047.2cm -1 The stretching vibration of CN indicates that the product is indeed diethanolamine. Figure 1 In comparison, Figure 3 At 3343.5cm -1 The -OH stretching vibration peak at 1047.6 cm -1 The peak at the upper and lower ends increases, which is due to the increase of -OH and CN after the introduction of diethanolamine. Figure 2 In comparison, Figure 3 At 3108.5cm -1 The peak at 300 nm disappears, which is due to the disappearance of NH after the amino group of diethanolamine undergoes dehydration by Mannich reaction with formaldehyde.

[0097] The above results indicate the successful synthesis of bio-based amino polyol brominated epoxy resin.

[0098] Example 4

[0099] A method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0100] 24.15 g of diethanolamine and 6.3 g of paraformaldehyde were added to a flask and heated to 90°C for 2 hours. Then, 130.9 g of brominated epoxy resin modified with cardanol was added and the reaction was continued at 90°C for 4.5 hours. Finally, water and unreacted diethanolamine were removed by vacuum distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0101] The viscosity of the composite was 62870 cPs (25° C.) and the hydroxyl value was 233 mg KOH / g.

[0102] Infrared results and attached Figure 3 Similarly, the successful synthesis of brominated epoxy resins containing bio-based amino polyols was also demonstrated. The amount of polyol introduced was confirmed by calculating the hydroxyl value.

[0103] Example 5

[0104] A method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0105] 34.65 g of diethanolamine and 9.3 g of paraformaldehyde were added to a flask and heated to 90°C for 2 h. Then, 130.9 g of brominated epoxy resin modified with cardanol was added and the reaction was continued at 90°C for 4.5 h. Finally, water and unreacted diethanolamine were removed by vacuum distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0106] The viscosity of the product was 56250 cPs (25°C) after viscometer test. The hydroxyl value was 241 mg KOH / g after experimental test. Figure 3 Similarly, the synthesis of brominated epoxy resins containing bio-based amino polyols is also demonstrated. The amount of polyol incorporated is confirmed by calculating the hydroxyl value.

[0107] Example 6

[0108] A method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0109] 12.6 g of diethanolamine and 3.3 g of paraformaldehyde were added to a flask and heated to 90°C for 2 hours. Then, 130.9 g of brominated epoxy resin modified with cardanol was added and the reaction was continued at 90°C for 4.5 hours. Finally, water and unreacted diethanolamine were removed by vacuum distillation to obtain a bio-based amino polyol brominated epoxy resin.

[0110] The viscosity of the composite was 97320 cPs (25° C.) and the hydroxyl value was 145 mg KOH / g.

[0111] Example 7

[0112] A method for preparing a bio-based amino polyol brominated epoxy resin comprises the following steps:

[0113] Example 3-5 was repeated, and diethanolamine was replaced by ethanolamine or triethanolamine. Other steps were the same. The obtained bio-based amino polyol brominated epoxy resin showed similar effects to Example 3-6.

[0114] During use, the theoretical dosage and hydroxyl value are only a reference value. The two need to be combined and the performance of the cured product after actual curing should be examined to determine the best ratio.

[0115] In this application, different application examples were prepared according to the hydroxyl value of each example and the -CNO ratio in T-100 at a molar ratio of 1:1, and were used as flame-retardant polyurethane materials, respectively, and their physical properties were tested by tensile and unnotched impact tests.

[0116] Application Example 1

[0117] (1) Weigh 100 g of epoxy resin E51 and heat it in a water bath at 80°C for 30 min.

[0118] (2) 150 g of the bio-based amino polyol brominated epoxy resin (Example 3) was placed in a water bath at 80° C. and heated for 30 min.

[0119] (3) Place the polytetrafluoroethylene mold in a drying oven and preheat to 80°C for later use;

[0120] (4) Pour the curing agent heated in a water bath into the epoxy resin mixture, add 0.2 g of defoaming agent B-459 and 2-3 g of dibutyltin dilaurate (diluted in a certain proportion with acetone), stir thoroughly, and pour into a polytetrafluoroethylene mold. Then, place the mold in an oven at 80°C for 2 hours and take it out. After curing at room temperature for 4 hours, wait for the cured material in the mold to slowly cool to room temperature and then demold and take it out to obtain a tensile test specimen and a notched impact test specimen.

[0121] Description: The PTFE mold is equipped with a cavity that matches the shape and size of the tensile test specimen and the unnotched impact test specimen.

[0122] Application Example 2

[0123] Weigh 100 g of epoxy resin E51, place it in a water bath at 80° C. and heat it in a water bath for 30 min, and set aside; and weigh 130 g of bio-based amino polyol brominated epoxy resin (Example 4), place it in a water bath at 80° C. and heat it in a water bath for 30 min, and set aside; the other contents are exactly the same as those in Application Example 1 and are not repeated here.

[0124] Application Example 3

[0125] Weigh 100 g of epoxy resin E51, place it in a water bath at 80° C. and heat it in a water bath for 30 min, and set aside; and weigh 125 g of bio-based amino polyol brominated epoxy resin (Example 5), place it in a water bath at 80° C. and heat it in a water bath for 30 min, and set aside; the other contents are exactly the same as those in Application Example 1 and are not repeated here.

[0126] Tensile tests were performed on the tensile test specimens prepared in the above application examples 1 to 3 respectively. in:

[0127] 1. Tensile test

[0128] Test standard for tensile test: "Determination of tensile properties of plastics" (GB / T 2567-2021).

[0129] Sample size: Prepare according to GB / T 2567-2021. The sample needs to be made into a dumbbell shape.

[0130] Test method: Clamp the specimen so that the long axis of the specimen is aligned with the tension direction of the centerline of the upper and lower clamps. Load continuously at a certain speed until failure, and read the failure load value. Loading speed is 2mm / min, and each group of specimens is no less than 5. If the specimen's fracture point is not in the middle parallel part, the specimen is invalid. The average value of all test data is the final test result. The test results are shown in the table below.

[0131] Table 1 Tensile test results of application examples 1-3

[0132] Application Examples Tensile strength MPa Maximum elongation% Application Example 1 6.5 51 Application Example 2 8.6 33 Application Example 3 9.6 28

[0133] It can be found from Table 1 above that as the amount of paraformaldehyde and diethanolamine added increases, the tensile strength of Application Examples 1-3 gradually increases, and the maximum force elongation gradually decreases.

[0134] 2. Polyurethane foaming test

[0135] Preparation of foaming material:

[0136] Turn on the balance and preheat it for more than 5 minutes. Calibrate it if necessary and place a film plastic bag in the wooden box.

[0137] First, add the polyether polyol in the recipe to a disposable plastic cup. Add the other reagents (except the isocyanate) and stir at approximately 1000 rpm to mix thoroughly. This will be used as the white material. The isocyanate itself will be used as the black material. Set the thermostat to the desired temperature (T = 25°C), maintaining a constant material temperature of T1 = T2 = T (if using a water bath, ensure the raw materials are protected from water absorption). Place the disposable cup on a scale and reset the balance. Pour in the amount of white material specified in the recipe and reset the balance. Add the amount of black material specified in the recipe according to the mixing coefficient. Stir the black and white material mixture slowly (while starting a stopwatch) to prevent splashing and affecting the ratio. After 2-3 seconds, stir at full speed for 8-10 seconds (try to minimize the time required for these two steps). Then quickly pour the stirred ingredients into a plastic cup or wooden box and allow them to foam freely. Once foaming stops, allow them to stand in a natural environment and continue to react for 24 hours.

[0138] According to the LOI foam material test standard, the sample size (length, width and thickness) should be 70-150mm×10±0.5mm×10±0.5mm; (Test standard: GB / T2406-93 standard, determination of the limiting oxygen index of foam plastics).

[0139] According to the UL94 foam material test standard, the sample size (length, width and thickness) should be 150mm×50mm×thickness 3-13mm (10mm is used in this application) (test standard: UL94 foam material test standard).

[0140] Test method: A sample of a certain size is clamped vertically in a transparent combustion tube, where an upward flow of oxygen and nitrogen mixed in a specific ratio is present. Light the top of the sample and observe the subsequent combustion phenomenon. The duration of combustion or the distance burned is recorded. If the sample's combustion time exceeds 3 minutes or the flame front exceeds the 50mm mark, the oxygen concentration is reduced. If the sample's combustion time is less than 3 minutes or the flame front does not reach the mark, the oxygen concentration is increased. Repeat this operation, gradually approaching the specified value from the top and bottom, until the concentration difference between the two is less than 0.5%.

[0141] Table 2 Basic formula of flame retardant-free polyurethane foam

[0142] formula phr polyether polyols 100 triethylenediamine 0.3 Dibutyltin dilaurate 0.3 Water-soluble silicone oil 2 distilled water 2.5 PAPI 100

[0143] Based on the above formula, the flame retardancy of polyurethane foam was studied by studying different ratios of polyol, catalyst, flame retardant, and Sb2O3. The LOI of each formula is shown in the table below.

[0144] Table 3 Polyurethane foam flame retardant system formula

[0145]

[0146] Table 3 studies the flame retardant properties of polyurethane materials with different formulations, among which,

[0147] The limiting oxygen index of the 1# formula flame retardant-free polyurethane rigid foam is 18%.

[0148] Formulas 1#-6# studied the flame retardant properties of amino polyol brominated epoxy resin containing flexible groups as flame retardants. The limiting oxygen index of formula 2# with only 10g of amino polyol brominated epoxy resin added was 18.2%, which was not much improved.

[0149] When 4g Sb2O3 was added, the limiting oxygen index of formula 3# was significantly improved to 19.7%.

[0150] With the increase of the amount of amino polyol brominated epoxy resin and Sb2O3, its limiting oxygen index is significantly improved.

[0151] in,

[0152] The limiting oxygen index of 10g amino polyol brominated epoxy resin + 20g Sb2O3 is 21.5%; the limiting oxygen index of 20g amino polyol brominated epoxy resin + 4g Sb2O3 is 21.1%;

[0153] The limiting oxygen index of 20g amino polyol brominated epoxy resin + 20g Sb2O3 is the highest, which is 22.5%.

[0154] This shows that as the addition amount of amino polyol brominated epoxy resin and Sb2O3 increases, the limiting oxygen index also gradually increases. However, considering the cost issue, the appropriate formula should be selected according to the required flame retardancy in actual practice.

[0155] Formula 7# and Formula 8# studied the flame retardancy of the most commonly used catalyst (tetrabromophthalic anhydride diol) on the market. Formula 7# added 10g of tetrabromophthalic anhydride diol and 3g of Sb2O3, and the limiting oxygen index was 20.7%;

[0156] In formula 8#, which uses 17g of amino polyol brominated epoxy resin instead of polyether polyol on the basis of formula 7#, the limiting oxygen index is increased to 21.6%;

[0157] This indicates that the amino polyol brominated epoxy resin of this patent has a certain synergistic effect with the flame retardant tetrabromophthalic anhydride diol, which can further improve the flame retardant properties of the polyurethane foam material.

[0158] The flame retardant properties of polyurethane foam when TCPP was used as flame retardant were studied in 9# and 10# formulations.

[0159] When 10g of TCPP was added to the 9# formula, the limiting oxygen index test was 21.4;

[0160] On this basis, the limiting oxygen index of formula 10# was increased to 21.9% after using 17g of amino polyol brominated epoxy resin to replace polyether polyol;

[0161] This indicates that the amino polyol brominated epoxy resin of this patent also has a certain synergistic effect with the flame retardant TCPP.

[0162] Finally, the limiting oxygen index of the polyurethane foam material of formula 11# with 35.5g of amino polyol brominated epoxy resin (25.5g of which replaced polyether polyol and 10g was used as flame retardant) was 22.0%.

[0163] The above results show that the bio-based amino polyol brominated epoxy resin of the present invention can partially replace polyether polyols and achieve higher flame retardant properties in synergy with tetrabromophthalic anhydride diol and TCPP. In addition, the bio-based amino polyol brominated epoxy resin of the present invention can also be used as a flame retardant and amino catalyst, and can also achieve excellent flame retardant properties.

[0164] Table 4 Polyurethane foam flame retardant system UL94

[0165]

[0166] In order to further study the flame retardant properties of the bio-based amino polyol brominated epoxy resin of the present invention as a polyurethane flame retardant material, a UL94 flame retardant test was conducted. As shown in Table 4 above, the bio-based amino polyol brominated epoxy resin of the present invention exhibited excellent flame retardant properties when used as a polyurethane flame retardant material.

[0167] In summary, the present invention utilizes cardanol as a nucleophilic reagent. The phenolic hydroxyl group in cardanol attacks the carbon atom of the epoxy group in the brominated epoxy resin, causing the C-O bond to break, opening the epoxy group and connecting it to the phenolic hydroxyl group, thereby preparing a cardanol-modified brominated epoxy resin. Subsequently, an aldehyde undergoes a Mannich reaction with the amine group in diethanolamine. The carbonyl group of the aldehyde protonates, and the amine undergoes nucleophilic addition to the carbonyl group. After deprotonation, electron transfer from the nitrogen, and water removal, an iminium ion intermediate is obtained. This iminium ion intermediate acts as an electrophilic reagent to attack the active hydrogen atoms of the ortho- and para-positions of the cardanol in the cardanol-modified brominated epoxy resin, thereby producing a bio-based amino polyol brominated epoxy resin. The synthesized bio-based amino polyol brominated epoxy resin successfully connects to the cardanol structure, while also endowing it with the flexibility, low toxicity, and low-temperature rapid curing properties inherent to the unique long chain of cardanol. The bio-based amino polyol brominated epoxy resin provided in this application has a simple operation process; the cardanol structure enhances the product's flexibility. Most importantly, the bio-based amino polyol brominated epoxy resin provided herein contains a flame-retardant group (Br) that can be used as a flame retardant while serving as a polyurethane foam synthetic material, thereby improving the flame retardant properties of the product. In addition, the amino polyol structure contained in the bio-based amino polyol brominated epoxy resin can completely replace the amino catalyst in the synthesis of polyurethane foam, without the need to add an amine catalyst in the synthesis of polyurethane foam. When a hydroxyl group-containing amino polyol brominated epoxy resin product containing a flexible group of 225-245mg KOH / g is used to flame-retard polyurethane, it shows excellent flame retardant properties as a flame retardant, partially replaces polyether polyols, and completely replaces amine catalysts, achieving multi-functionality in one.

[0168] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications based on the above description are possible. It is not possible to enumerate all embodiments here. Any obvious variations or modifications arising from the technical solution of the present invention remain within the scope of protection of the present invention.

Claims

1. A bio-based amino polyol brominated epoxy resin, characterized in that: Has the following structure: Wherein, R2 is an amino polyol; R and R1 are bond-line structures represented by any one of the following formulas (I), (II), (III), and (IV): The bio-based amino polyol brominated epoxy resin is prepared by the following method: S1, reacting tetrabromobisphenol A and epichlorohydrin in the presence of a catalyst to obtain a brominated epoxy resin having epoxy groups capped at both ends; S2, reacting cardanol with the brominated epoxy resin obtained in step S1 to obtain a cardanol-modified brominated epoxy resin; S3. Further reacting the aldehyde and amino polyol with the brominated epoxy resin modified with cardanol obtained in step S2 to obtain a bio-based amino polyol brominated epoxy resin.

2. The bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: In step S1, the specific preparation steps of the brominated epoxy resin with epoxy groups capped at both ends are as follows: 400-420g of epichlorohydrin and 390-410g of tetrabromobisphenol A are weighed and added to a four-necked flask, a reflux condenser and a thermometer are installed, heating is started, benzyltriethylammonium chloride is added, the temperature is raised to 85-95°C with stirring, the reaction is carried out for 2-3h, and excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of toluene solvent is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is evenly added over 1h and stirred evenly, and the reaction is carried out for 4-6h; then 280-320g of toluene solvent is added for extraction, and 300-500g of water is added while hot to wash off the generated sodium chloride, and the liquids are separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the liquids are separated; the toluene solvent is removed by distillation under reduced pressure to obtain a brominated epoxy resin end-capped with epoxy groups at both ends.

3. The bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: In step S2, the specific preparation steps of the cardanol-modified brominated epoxy resin are as follows: Weigh 330-370 g of the brominated epoxy resin end-capped with epoxy groups prepared in step S1, 330-340 g of cardanol, and 0.6-1.0 g of an antioxidant, add them to a four-necked flask, heat to 95-105 ° C, stir to dissolve, add 2-3.5 g of triphenylphosphine catalyst to the reaction flask, continue to heat to 170-190 ° C, react for 50-70 minutes, and after the reaction is completed, obtain a brominated epoxy resin modified with cardanol.

4. The bio-based amino polyol brominated epoxy resin according to claim 1, wherein: In step S3, the specific preparation steps of the bio-based amino polyol brominated epoxy resin are as follows: Add 14-17g of amino polyol and 4-5g of aldehyde to a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the cardanol-modified brominated epoxy resin prepared in step 2, continue to react at 85-95°C for 4-6h, and then remove water and unreacted amino polyol by reduced pressure distillation to obtain a bio-based amino polyol brominated epoxy resin.

5. The bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: In step S3, the aldehyde is selected from one or more of formaldehyde, trioxymethylene, and paraformaldehyde.

6. The bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: In step S3, the amino polyol is selected from one or more of ethanolamine, diethanolamine, and triethanolamine.

7. The use of the bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: The bio-based amino polyol brominated epoxy resin is used as a raw material for synthesizing a polyurethane foam material with flame retardant properties.

8. The use according to claim 7, characterized in that: The polyurethane foam material with flame retardancy is made from the following raw materials: bio-based amino polyol brominated epoxy resin, polyether polyol, isocyanate, catalyst and foaming agent.

9. The use according to claim 8, characterized in that: The raw materials also include a synergistic flame retardant; the synergistic flame retardant is a halogenated phosphate or tetrabromophthalic anhydride diol; wherein the halogenated phosphate is tris (2-chloropropyl) phosphate.

10. The use according to claim 8, characterized in that: The catalyst is a tin catalyst and an amine catalyst.

11. The use according to claim 10, characterized in that: The amine catalyst is a bio-based amino polyol brominated epoxy resin.

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