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

Abstract

The invention discloses a bio-based amino polyol brominated epoxy resin, and a preparation method and application thereof, the bio-based amino polyol brominated epoxy resin has the following structure: # imgabs0 #, in which R and R1 are both carbon pentadecyl, and R2 is amino polyol. The polyol provided by the invention can be used as a reactive flame retardant in polyurethane foam, and can maintain the mechanical properties of the material to the greatest extent; meanwhile, the processing technology is simple; and moreover, the amino polyol brominated epoxy resin containing the bio-based group contains a flame-retardant group (Br) which can be used as a polyurethane foam synthetic material and also can be used as a flame retardant, so that the flame-retardant property of the product is improved. In addition, the amino polyol structure contained in the bio-based amino polyol brominated epoxy resin can completely replace an amino catalyst in polyurethane foam synthesis, and multiple functions are integrated.

Description

Technical Field

[0001] The 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 repeated carbamate groups (-NHCOO-) in the polymer main chain structure. Polyurethane resin has very excellent physical and chemical properties, such as low thermal conductivity, high strength, excellent adhesion and mechanical properties. It is an important polymer foam material and is considered to be the "fifth most commonly used plastic" after polyethylene, polyvinyl chloride, polypropylene and polystyrene. It is widely used in construction, transportation, packaging, furniture and aviation industries. However, polyurethane has a large specific surface area, and the limiting oxygen index value (LOI) of polyurethane foam material without flame retardant modification is only 19%. It is highly flammable and burns quickly, releasing a large amount of heat and thick black smoke as well as toxic gases such as CO, NO, HCN, etc., which not only poses a huge safety hazard, but also easily causes serious loss of life and property. Therefore, it is of great significance to develop efficient flame retardant polyurethane foam materials.

[0003] At present, the flame retardant properties of polyurethane are generally improved by using additive flame retardants and flame retardant polyether polyols. Traditional additive flame retardants in the form of physical blending are prone to flame retardant migration and precipitation during the use of polyurethane products, which reduces the flame retardant properties of polyurethane foam and also reduces the physical properties of the material. Reactive flame retardants have the characteristics of good stability, low toxicity, and little effect on polymer properties. However, their operation and processing technology are complicated and are not as common as additive flame retardants in practical applications. Therefore, there is an urgent need for a product with a simple operation and processing technology that improves flame retardant properties while maintaining mechanical properties to the maximum extent. Summary of the invention

[0004] The first technical problem to be solved 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, which can maintain the mechanical properties of the material to the maximum extent; at the same time, the processing technology is simple; and the bio-based amino polyol brominated epoxy resin contains a flame retardant group (Br) and can be used as a polyurethane foam synthetic material and also as 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 synthesis of polyurethane foam, realizing multi-functions in one.

[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 carbon pentadecanyl, 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 brominated epoxy resin modified with cardanol;

[0017] S3, further reacting the aldehyde and the 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 terminated by epoxy groups at both ends are as follows:

[0019] 400-420g of epichlorohydrin and 390-410g of tetrabromobisphenol A are weighed and added into 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 performed for 2-3h, and the excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of solvent toluene is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is added evenly within 1h and stirred evenly, and the reaction is performed for 4-6h; then 280-320g of solvent toluene is added for extraction, and 300-500g of water is added for washing while hot to wash away the generated sodium chloride, and the mixture is separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the mixture is separated; the solvent toluene is removed by distillation under reduced pressure to obtain a brominated epoxy resin with epoxy groups capped at both ends.

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

[0021] Weigh 330-370g of the brominated epoxy resin with epoxy groups at both ends prepared in step S1, 330-340g of cardanol, and 0.6-1.0g of antioxidant into a four-necked flask, heat to 95-105°C, stir to dissolve, add 2-3.5g of triphenylphosphine catalyst into the reaction flask, continue to heat to 170-190°C, and react for 50-70min. After the reaction is completed, 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 into a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the brominated epoxy resin modified with cardanol obtained 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 polyformaldehyde.

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

[0026] 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 synthetic raw material for polyurethane foaming material with flame retardant properties.

[0028] As an implementation method, the flame retardant polyurethane foam material is made of 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 from the market, 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 uses cardanol as a nucleophilic reagent, and the phenolic hydroxyl group in cardanol attacks the carbon atom of the epoxy group in the brominated epoxy resin, causing the CO bond to break, so that the epoxy group is ring-opened, and connected with the phenolic hydroxyl group to prepare a cardanol-modified brominated epoxy resin. Then, the aldehyde and the amine group in the diethanolamine undergo a Mannich reaction, the carbonyl group of the aldehyde is protonated, and the amine undergoes nucleophilic addition to the carbonyl group. After deprotonation, electron transfer of nitrogen, and water leaving steps, an iminium ion intermediate is obtained, which acts as an electrophilic reagent to attack the ortho-para active hydrogen of cardanol in the brominated epoxy resin modified by cardanol, and then a bio-based amino polyol brominated epoxy resin is obtained.

[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 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 connects the cardanol structure and contains bromine (Br) flame retardant groups. It can be used as a polyurethane foam synthetic material and a flame retardant at the same time, 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 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 multi-functions in one flame-retardant polyurethane foam material, 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. It should be understood by those skilled in the art 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 unless otherwise specified.

[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, 4# rotor, purchased from Shanghai Lichen Bangxi Instrument Technology Co., Ltd.

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

[0060]

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

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

[0063]

[0064] Among many bio-based materials, the chemical structure of cardanol combines benzene ring structure, phenolic hydroxyl group and C15 unsaturated straight chain. Among them, the benzene ring is rigid and the carbon 15 straight chain has good toughness. It is precisely these rigid and flexible structural characteristics that cardanol has become 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, which has the advantages of abundant sources, low price and renewable. Usually cardanol is a mixture of four alkyl phenols with different saturations, which are 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 of the present invention 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 brominated epoxy resin modified with cardanol;

[0069] S3, further reacting the aldehyde and the 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 terminated by epoxy groups at both ends are as follows:

[0071] 400-420g of epichlorohydrin and 390-410g of tetrabromobisphenol A are weighed and added into 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 performed for 2-3h, and the excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of solvent toluene is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is added evenly within 1h and stirred evenly, and the reaction is performed for 4-6h; then 280-320g of solvent toluene is added for extraction, and 300-500g of water is added for washing while hot to wash away the generated sodium chloride, and the mixture is separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the mixture is separated; the solvent toluene is removed by distillation under reduced pressure to obtain a brominated epoxy resin with epoxy groups capped at both ends.

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

[0073] Weigh 330-370g of the brominated epoxy resin with epoxy groups at both ends prepared in step S1, 330-340g of cardanol, and 0.6-1.0g of antioxidant into a four-necked flask, heat to 95-105°C, stir to dissolve, add 2-3.5g of triphenylphosphine catalyst into the reaction flask, continue to heat to 170-190°C, and react for 50-70min. After the reaction is completed, 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 into a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the brominated epoxy resin modified with cardanol obtained 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 polyformaldehyde.

[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] As another aspect of the present invention, the present invention provides an application of the above-mentioned bio-based amino polyol brominated epoxy resin, using the bio-based amino polyol brominated epoxy resin as a synthetic raw material for a polyurethane foam material having flame retardant properties. The bio-based amino polyol brominated epoxy resin enables the polyurethane foam material to have flame retardant properties.

[0079] According to some embodiments of the present invention, the polyurethane foam material with flame retardant properties is made of 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 ester or tetrabromophthalic anhydride diol; wherein the halogenated phosphate ester 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 needed 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 reduced pressure distillation; 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 to wash while hot to wash away the generated sodium chloride, and separate the liquids; then add 400g of hot water at 60°C for two consecutive times to wash, and separate the liquids; remove the solvent toluene by reduced pressure distillation 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 brominated epoxy resin modified with cardanol:

[0089] 350 g of the brominated epoxy resin prepared in Example 1, 335 g of cardanol and 0.8 g of antioxidant were weighed and added to a four-necked flask, heated to 100° C., 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. and reacted for 60 min. After the reaction was completed, 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 has a wavelength of 3383.7 cm -1 The broad peak at 3008.2cm 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, 2926.1cm -1 、2852.0cm -1 Corresponding to the stretching vibration absorption peak of CH on methyl and methylene, 1583.7cm -1 、1488.6cm -1 、1449.4cm -1 Corresponding to the absorption peak of benzene ring skeleton vibration, 1254.7cm -1 、1155.5cm -1 It 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 polyformaldehyde were added to a flask, heated to 90°C for reaction 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 reduced pressure distillation to obtain bio-based amino polyol brominated epoxy resin.

[0096] The viscosity was 81410 cPs (25°C) after viscometer test. 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 characterized by infrared spectroscopy. The infrared spectra are shown in the attached figure. Figure 2 , 3 As shown. Figure 2 It can be found that 3297.3cm -1 The peak at 3108.5cm 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 100 nm increased, which was 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 45° 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 demonstrate the successful synthesis of bio-based amino polyol-based brominated epoxy resins.

[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 polyformaldehyde were added to a flask and heated to 90°C for reaction 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 reduced pressure distillation to obtain bio-based amino polyol brominated epoxy resin.

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

[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 polyformaldehyde were added to a flask, heated to 90°C for reaction 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 reduced pressure distillation to obtain 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 amine polyols is also demonstrated. The amount of polyol incorporated is demonstrated by calculation of the hydroxyl number.

[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 polyformaldehyde were added into a flask, heated to 90°C for reaction 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 reduced pressure distillation to obtain bio-based amino polyol brominated epoxy resin.

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

[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. The other steps were the same, and 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 actual performance of the cured product after curing should be examined to determine the best ratio.

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

[0116] Application Example 1

[0117] (1) Weigh 100 g of epoxy resin E51, place in a water bath at 80°C and heat for 30 min, and set aside;

[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 for later use;

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

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

[0121] Description: The polytetrafluoroethylene mold is provided 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 100g of epoxy resin E51, place it in a water bath at 80°C and heat it for 30min, and set it aside; and weigh 130g of bio-based amino polyol brominated epoxy resin (Example 4), place it in a water bath at 80°C and heat it for 30min, and set it aside; the other contents are exactly the same as those in Application Example 1 and will not be repeated here.

[0124] Application Example 3

[0125] Weigh 100g of epoxy resin E51, place it in a water bath at 80°C and heat it for 30min, and set it aside; and weigh 125g of bio-based amino polyol brominated epoxy resin (Example 5), place it in a water bath at 80°C and heat it for 30min, and set it aside; the other contents are exactly the same as those in Application Example 1 and will not be 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 sample so that the long axis of the sample is consistent with the tensile direction of the center line of the upper and lower clamps, continuously load at a certain speed until it is broken, and read the breaking load value. The loading speed is 2mm / min, and each group of samples is not less than 5. If the breaking point of the sample is not in the middle parallel part, the sample 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, introduce the polyether polyol in the formula into a disposable plastic cup, and put other reagents (except isocyanate) into the plastic cup, stir and mix evenly at a speed of about 1000r / min, and use it as white material for standby. Isocyanate itself is used as black material for standby. Set the temperature of the thermostat to the required temperature (T=25℃), and the constant material temperature T1=T2=T (if it is a water bath thermostat, pay attention to the protection of the raw materials from water absorption). Put the disposable cup on the balance and reset it; pour in the amount of white material designed in the formula and reset it. Add the amount of black material designed in the formula according to the ratio coefficient. First, stir the black and white material mixture slowly (start the stopwatch at the same time) to avoid splashing and affecting the ratio; after 2-3 seconds, stir at full speed for 8-10 seconds (try to shorten the operation time of the above two steps). Then quickly pour the stirred raw materials into a plastic cup or wooden box and let them foam freely. After the foaming stops, place it 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 limiting oxygen index of foam plastics).

[0139] According to the UL94 foam material test standard, the sample strip 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: Use a sample clamp to clamp a sample of a certain size vertically in a transparent combustion tube, in which there is an upward flow of oxygen and nitrogen mixed in a certain proportion. Light the upper end of the sample, observe the subsequent combustion phenomenon, and record the continuous combustion time or the distance burned. When the burning time of the sample exceeds 3 minutes or the flame front exceeds the 50mm mark, reduce the oxygen concentration. When the burning time of the sample is less than 3 minutes or the flame front does not reach the mark, increase the oxygen concentration. Repeat this operation, gradually approaching the specified value from the upper and lower sides 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 proportions of polyol, catalyst, flame retardant and Sb2O3. The LOI of each formula is shown in the following table.

[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] The flame retardant properties of amino polyol brominated epoxy resin containing flexible groups were studied in formulations 1# to 6#. The limiting oxygen index of formulation 2#, which only added 10g of amino polyol brominated epoxy resin, 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 dosage 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 with the increase of the addition amount of amino polyol brominated epoxy resin and Sb2O3, 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 situations.

[0155] Formula 7# and Formula 8# studied the flame retardant properties 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, 17g of amino polyol brominated epoxy resin was used to replace polyether polyol on the basis of formula 7, and the limiting oxygen index was 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 a flame retardant were studied in formulations 9# and 10#.

[0159] 9# formula added 10g of TCPP, and 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 the 11# formulation with 35.5g of amino polyol brominated epoxy resin (25.5g of which replaced the polyether polyol and 10g of which served as a 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 can achieve higher flame retardant properties under the synergistic effect of tetrabromophthalic anhydride diol and TCPP; not only that, the bio-based amino polyol brominated epoxy resin of the present invention can also be used as a flame retardant and an amine 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 a bio-based amino polyol brominated epoxy resin of the present invention as a polyurethane flame retardant material, a UL94 flame retardant test was carried out. As shown in Table 4 above, a bio-based amino polyol brominated epoxy resin of the present invention shows excellent flame retardant properties when used as a polyurethane flame retardant material.

[0167] In summary: the present invention uses cardanol as a nucleophilic reagent, and the phenolic hydroxyl group in cardanol attacks the carbon atom of the epoxy group in the brominated epoxy resin, causing the CO bond to break, so that the epoxy group is ring-opened, and after connecting with the phenolic hydroxyl group, a brominated epoxy resin modified by cardanol is prepared. Then, the aldehyde reacts with the amine group in the diethanolamine to undergo a Mannich reaction, the carbonyl group of the aldehyde is protonated, and the amine undergoes nucleophilic addition to the carbonyl group. After deprotonation, electron transfer of nitrogen, and water leaving steps, an iminium ion intermediate is obtained, which, as an electrophilic reagent, attacks the ortho-para active hydrogen of cardanol in the brominated epoxy resin modified by cardanol, and then a bio-based amino polyol brominated epoxy resin is obtained. The synthesized bio-based amino polyol brominated epoxy resin successfully connects the cardanol structure, and at the same time gives it the flexibility, low toxicity and low-temperature rapid curing brought by the unique long chain of cardanol. The bio-based amino polyol brominated epoxy resin provided in the present application has a simple operation process; the contained cardanol structure improves the flexibility of the product. Most importantly, the bio-based amino polyol brominated epoxy resin provided by the present application 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, and no amine catalyst needs to be added in the synthesis of polyurethane foam. When the amino polyol brominated epoxy resin product containing a flexible group with a hydroxyl group of 225-245mg KOH / g is used to flame retard polyurethane, it shows excellent flame retardant properties in terms of use as a flame retardant, partial replacement of polyether polyols, and complete replacement of amine catalysts, realizing multi-function in one.

[0168] Obviously, the above embodiments of the present invention are merely examples for clearly explaining the present invention, and are not intended to limit the implementation methods of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all implementation methods here. Any obvious changes or modifications derived from the technical solution of the present invention are still 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, R and R1 are both carbon pentadecanyl, and R2 is an amino polyol.

2. The bio-based amino polyol brominated epoxy resin according to claim 1, characterized in that: The R and R1 are bond-line structures shown in any one of the following formulas (I), (II), (III), and (IV):

3. The method for preparing a bio-based amino polyol brominated epoxy resin as claimed in any one of claims 1 to 2, comprising the following steps: 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 brominated epoxy resin modified with cardanol; S3, further reacting the aldehyde and the amino polyol with the brominated epoxy resin modified with cardanol obtained in step S2 to obtain a bio-based amino polyol brominated epoxy resin.

4. The preparation method according to claim 3, 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 into 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 performed for 2-3h, and the excess epichlorohydrin is removed by distillation under reduced pressure; the temperature is lowered to 55-65°C, 90-110g of solvent toluene is added, the mixture is stirred evenly, 20-30wt% sodium hydroxide solution is added evenly within 1h and stirred evenly, and the reaction is performed for 4-6h; then 280-320g of solvent toluene is added for extraction, and 300-500g of water is added for washing while hot to wash away the generated sodium chloride, and the mixture is separated; 300-500g of hot water at a temperature of 55-65°C is added twice for washing, and the mixture is separated; the solvent toluene is removed by distillation under reduced pressure to obtain a brominated epoxy resin with epoxy groups capped at both ends.

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

6. The preparation method according to claim 3, characterized in that: 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 into a flask, heat to 85-95°C and react for 1-3h; then add 125-135g of the brominated epoxy resin modified with cardanol obtained 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.

7. The preparation method according to claim 3, characterized in that: In step S3, the aldehyde is selected from one or more of formaldehyde, trioxymethylene and polyformaldehyde.

8. The preparation method according to claim 3, characterized in that: In step S3, the amino polyol is selected from one or more of ethanolamine, diethanolamine, and triethanolamine.

9. The use of the above-mentioned bio-based amino polyol brominated epoxy resin as described in any one of claims 1-2, 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.

10. The use according to claim 9, characterized in that: The flame retardant polyurethane foam material is made of the following raw materials: bio-based amino polyol brominated epoxy resin, polyether polyol, isocyanate, catalyst and foaming agent; Preferably, 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 TCPP (tris(2-chloropropyl) phosphate); Preferably, the catalyst is a tin catalyst and an amine catalyst; Preferably, the amine catalyst is a bio-based amino polyol brominated epoxy resin.

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