Phosphite antioxidant based on bio-based lignin phenol as well as preparation method and application of phosphite antioxidant

Abstract

The invention belongs to the field of bio-based high polymer material auxiliaries, and relates to a phosphite antioxidant based on bio-based lignin phenol as well as a preparation method and application of the phosphite antioxidant. According to the invention, a green renewable biomass resource lignin oxidative degradation product is taken as a raw material, structural design is carried out, the lignin phenol-based phosphite antioxidant is synthesized, and the lignin phenol-based phosphite antioxidant can be used for replacing an antioxidant 168 type traditional phosphite antioxidant to be applied to a high polymer material, and can be used for preparing a high polymer material. The thermal stability and the oxidation resistance of the high polymer material are improved, and the dependence on fossil resources caused by traditional antioxidant production is avoided. Meanwhile, the invention explores a new way for high-value utilization of lignin. The structure of the lignin phenol-based phosphite antioxidant is as shown in a formula I in the specification. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of bio-based polymer material additives, and relates to a phosphite antioxidant based on bio-based lignin phenol, and a preparation method and application thereof. Background Art

[0002] During the processing, molding, storage and use of most polymer products, they are affected by many factors such as light, high temperature and mechanical processing. The macromolecular chains in the materials will undergo a series of complex and harmful chain breaking or cross-linking processes, which manifests as the surface of the material becoming sticky, discolored, cracked, brittle, etc., affecting the normal use of the material and thus shortening the service life of the material.

[0003] With the rapid development of the domestic petrochemical industry, a large number of polyolefin plant projects have been completed and put into production, which has promoted the prosperity of the antioxidant market. Phosphite antioxidants from traditional petrochemical products, such as triphenyl phosphite, trimethyl phosphite, and antioxidant 168, which has the largest demand in the market, have become mainstream products in this field. In particular, antioxidant 168, due to its wide range of applications, meets the stability requirements of various polymer materials.

[0004] However, with the continuous development of society, people's demand and dependence on chemical products have increased significantly, and the consumption of petrochemical products has reached an unprecedented level. Although the use of petroleum resources has brought convenience to industry and daily life, it has also caused serious environmental pollution and excessive resource consumption. At present, about 92% of the world's chemical products rely on fossil fuels. With the decreasing non-renewable resources and in line with the global environmental protection trend, it is urgent to develop a green and renewable phosphite antioxidant that can completely replace traditional phosphite antioxidants. People began to turn their attention to renewable biomass resources. Turning to biomass resources can not only alleviate the problem of resource shortage, but also reduce the negative impact on the environment and promote sustainable development.

[0005] Renewable biomass lignin is a natural aromatic polymer with a three-dimensional network structure in plants. It is a biopolymer formed by three phenylpropane units connected by ether bonds and carbon-carbon bonds. It contains rich aromatic ring structures, aliphatic and aromatic hydroxyl groups, and quinone groups and other active groups. It mainly exists in the secondary layer of plant cell walls. As a green renewable resource, lignin has many advantages such as wide sources, light weight, high biological efficiency, and wide ecological adaptability. In recent years, researchers have been working hard to find suitable renewable raw materials for the production of polymers. In particular, the development and application of lignin depolymerization monomer compounds have gained great interest, including vanillin, vanillin, guaiacol, eugenol and eugenol depolymerization monomers, which are widely used in food, beverage, perfume and pharmaceutical industries due to their unique fragrance and excellent antioxidant and antibacterial properties. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide two types of phosphite antioxidants IA and IB based on bio-based lignin phenol in view of the deficiencies of the prior art.

[0007] The technical problem that the present invention also aims to solve is to provide a method for preparing the above two types of bio-based ligninphenol-based phosphite antioxidants IA and IB.

[0008] Furthermore, the technical problem to be solved by the present invention is to provide the application of the above two types of bio-based ligninphenol-based phosphite antioxidants IA and IB in materials.

[0009] Invention idea: The present invention uses lignin oxidation degradation products as starting materials for structural design, and synthesizes two types of phosphite antioxidants IA and IB based on green renewable bio-based lignin phenol, thereby avoiding the dependence and consumption of fossil resources caused by the production of traditional phosphite antioxidants, as well as the pollution of the environment caused by their degradation products. In particular, a large number of aromatic rings are introduced into the structure IB type antioxidants. The aromatic ring structure is rigid and has large steric hindrance. The increase in aromatic ring structures further improves the thermal stability and antioxidant properties of the material.

[0010] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0011] The present invention discloses a compound as shown in formula I;

[0012]

[0013] in,

[0014] R3, R6 are independently selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0015] R1, R2, R4, R5 are independently selected from H or -OCH3;

[0016] R is selected from phenyl or R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0017] R7, R8 are independently selected from H or -OCH3;

[0018] R1 and R4 can be connected by -CH(R 10 )-connected into a ring; where R 10 Selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3. In some embodiments, preferably,

[0019] R3, R6 are independently selected from -CH2-CH2-CH3, and / or

[0020] R9 is selected from -CH2-CH2-CH3, and / or

[0021] R1 and R4 can be connected by -CH(R 10 )-connected into a ring; where R 10 Selected from H.

[0022] In some embodiments, further preferably, the compound of formula I is as follows:

[0023]

[0024] in,

[0025] R1, R2, R4, R5 are independently selected from H or -OCH3;

[0026] R is selected from phenyl or R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R9 is selected from -CH2-CH2-CH3;

[0027] R7 and R8 are independently selected from H or -OCH3.

[0028] In some embodiments, it is further preferred that the compound of formula I is as shown in formula IAi:

[0029]

[0030] in,

[0031] R1, R2, R4, R5 are independently selected from H or -OCH3;

[0032] R7, R8 are independently selected from H or -OCH3;

[0033] R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R9 is selected from -CH2-CH2-CH3. In some embodiments, more preferably, the compound of formula I is as shown in formula IA-ii:

[0034]

[0035] Wherein, R1, R2, R4, and R5 are independently selected from H or -OCH3.

[0036] In some embodiments, further preferably, the compound of formula I is as follows:

[0037]

[0038] in,

[0039] R2, R5 are independently selected from H or -OCH3;

[0040] R is selected from phenyl or

[0041] R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R9 is selected from -CH2-CH2-CH3;

[0042] R7, R8 are independently selected from H or -OCH3;

[0043] R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R 10 It is selected from H or -CH3, and more preferably H.

[0044] In some embodiments, more preferably, the compound of formula I is as shown in formula IBi:

[0045]

[0046] in,

[0047] R2, R5 are independently selected from H or -OCH3;

[0048] R7, R8 are independently selected from H or -OCH3;

[0049] R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R9 is selected from -CH2-CH2-CH3;

[0050] R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R 10 It is selected from H or -CH3, and more preferably H.

[0051] In some embodiments, more preferably, the compound of formula I is as shown in formula IB-ii:

[0052]

[0053] in,

[0054] R2, R5 are independently selected from H or -OCH3;

[0055] R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; preferably, R 10It is selected from H or -CH3, and more preferably H.

[0056] In some embodiments, the compound represented by formula I is tris(4-ethylphenyl)phosphite, tris(4-ethyl-2-methoxyphenyl)phosphite, tris(4-ethyl-2,6-dimethoxyphenyl)phosphite, bis(4-ethylphenyl)phenylphosphite, bis(4-ethyl-2-methoxyphenyl)phenylphosphite, bis(4-ethyl-2,6-dimethoxyphenyl)phenylphosphite, 2,10-diethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 2,10-diethyl-4,8-dimethoxy-12-methyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, g][1,3,2]dioxaphosphocyanine, 2,10-diethyl-4,8-dimethoxy-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 2,10-diethyl-6-(4-ethyl-2-methoxyphenoxy)-4,8-dimethoxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 2,10-diethyl-4,8-dimethoxy-6-(4-propylphenoxy)-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 2,10-diethyl-6-(4-ethyl-2,6-dimethoxyphenoxy)-4,8-dimethoxy 1,3,2]dioxophosphocyanine, tris(2-methoxy-4-methylphenyl)phosphite, tris(2,6-dimethoxy-4-methylphenyl)phosphite, bis(2-methoxy-4-methylphenyl)phenylphosphite, bis(2,6-dimethoxy-4-methylphenyl)phenylphosphite, 2,10-dimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 4,8-dimethoxy-2,10-dimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 4,8-dimethoxy-2,10-dimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, ,12-trimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 4,8-dimethoxy-2,10-dimethyl-6-(p-tolyloxy)-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 4,8-dimethoxy-6-(2-methoxy-4-methylphenoxy)-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine or 6-(2,6-dimethoxy-4-methylphenoxy)-4,8-dimethoxy-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine.

[0057] In some embodiments, preferably, the compound represented by formula I is any one of the compounds represented by the following structures:

[0058]

[0059] In some embodiments, it is further preferred that the compound represented by formula I is any one of the compounds represented by the following structures:

[0060]

[0061] In some embodiments, more preferably, the compound represented by formula I is a compound represented by the following structure:

[0062]

[0063] Furthermore, the present invention discloses a method for preparing the compound represented by the above formula I, which is selected from one of the following synthetic routes:

[0064] Synthetic route 1:

[0065] Compound 1 and compound 2 undergo a first reaction under the action of a first catalyst to obtain compound IA;

[0066]

[0067] in,

[0068] R1=R4, R2=R5, R3=R6;

[0069] R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0070] R1, R2 are independently selected from H or -OCH3;

[0071] R' is selected from Cl or phenyl;

[0072] R is selected from phenyl or

[0073] R7=R1, R8=R2, R9=R3;

[0074] or,

[0075] Synthetic route 2:

[0076] Compound 3 and compound 4 undergo a second reaction under the action of a second catalyst to obtain intermediate 5; intermediate 5 and compound 6 continue to undergo a third reaction under the action of a third catalyst to obtain compound IBa;

[0077]

[0078] in,

[0079] R2=R5、R3=R6;

[0080] R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0081] R2 is selected from H or -OCH3;

[0082] R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0083] R" is selected from phenyl;

[0084] R is selected from phenyl;

[0085] or,

[0086] Synthetic route 3:

[0087]

[0088] in,

[0089] R2=R5、R3=R6;

[0090] R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0091] R2 is selected from H or -OCH3;

[0092] R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0093] R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3;

[0094] R7, R8 are independently selected from H or -OCH3;

[0095] R is selected from

[0096] In some embodiments, in synthetic route 1, the first catalyst is any one or a combination of triethylamine, pyridine, diisopropylamine, D301 resin and dodecyl dimethyl tertiary amine, preferably any one or a combination of triethylamine and dodecyl dimethyl tertiary amine, and more preferably triethylamine; the molar ratio of -OH in the compound 1 to -Cl in the compound 2 is 1.00:(1.00-1.30), preferably 1.00:1.15; the molar ratio of the compound 2 to the first catalyst is 1.0:(2.0-3.5), Preferably it is 1.0:(2.3~3.3); the first solvent used in the first reaction is any one or a combination of toluene, xylene and chloroform, preferably toluene; the mass volume ratio of the compound 1 and the first solvent is 1g:(15~30)mL, preferably 1g:20mL; the reaction temperature of the first reaction is 30~90℃, preferably 40~90℃, further preferably 50~90℃; the reaction time of the first reaction is 1~5h; the first reaction is carried out under the protection of an inert gas; the inert gas is preferably nitrogen.

[0097] In some embodiments, in Synthesis Route 2, the second catalyst is any one or a combination of sodium hydroxide, potassium hydroxide, cesium hydroxide and 1,8-diazabicyclo (5,4,0)-7-undecene, preferably sodium hydroxide; the molar ratio of compound 3 to compound 4 is 2.00:(1.00-1.30), preferably 2.00:(1.15-1.25); the molar ratio of compound 3 to the second catalyst is 1.0:(0.3-0.4); the second catalyst is fed in the form of an aqueous solution, and the mass concentration of the second catalyst in the solution is 30%-35%; the reaction temperature of the second reaction is 100°C-150°C, preferably 120°C; the reaction time of the second reaction is 2-5h, preferably 3h;

[0098] In some embodiments, in synthetic route 2, the third catalyst is any one or a combination of triethylamine, pyridine, diisopropylamine, D301 resin and dodecyldimethylamine, preferably any one or a combination of triethylamine and dodecyldimethylamine, and further preferably triethylamine; the molar ratio of the intermediate 5 to the compound 6 is 1.00:(1.00-1.30), preferably 1.00:1.15; the molar ratio of the compound 6 to the third catalyst is 1.0:(2.0-2.5), preferably 1.0:2.3; the second solvent used in the third reaction is any one or a combination of toluene, xylene and chloroform, preferably toluene; the mass volume ratio of the intermediate 5 to the second solvent is 1g:(15-30)mL, preferably 1g:20mL; the reaction temperature of the third reaction is 40°C-80°C, preferably 60°C; the reaction time of the third reaction is 1-4h, preferably 2h.

[0099] Furthermore, the use of the above-mentioned compounds as antioxidants is also within the protection scope of the present invention; preferably, the use is the use of the compounds as antioxidants in the preparation of polymer materials with thermal stability and / or oxidation resistance; further preferably, the use is the use of the compounds as antioxidants in the preparation of polyolefin materials with thermal stability and / or oxidation resistance; further preferably, the use is the use of the compounds as antioxidants in the preparation of polypropylene materials with thermal stability and / or oxidation resistance.

[0100] Specifically, the above-mentioned compound is used as an antioxidant, the compound is mixed with a polymer raw material and then extruded through a twin-screw extruder to obtain a polymer material with thermal stability and / or antioxidant properties.

[0101] Specifically, the mass of the compound accounts for 0.2% to 1.0% of the mass of the polymer raw material, preferably 0.2% to 0.8%, and more preferably 0.4% to 0.8%.

[0102] Beneficial effects:

[0103] (1) The present invention uses the oxidative degradation product of lignin, a green renewable biomass resource with abundant sources, as raw materials, performs structural design, and synthesizes a phosphite antioxidant based on lignin phenol, which can be used to replace traditional phosphite antioxidants such as antioxidant 168 in polymer materials, avoiding the dependence on fossil resources caused by traditional antioxidant production, and is conducive to sustainable development. At the same time, the present invention explores a new path for the high-value utilization of lignin.

[0104] (2) The preparation method of the bio-based lignin phenol-based phosphite antioxidant provided by the present invention is simple to operate and has a mature production process, which can bring better economic and environmental benefits.

[0105] (3) The two types of phosphite antioxidants prepared by the method of the present invention have better thermal stability and antioxidant properties than the traditional antioxidant 168. Among them, when added in the same mass ratio, the oxidation induction time of the type Ⅰ-A antioxidant is better than that of the traditional antioxidant 168, and the type IB antioxidant is more than 3 times longer.

[0106] (4) The phosphite antioxidant prepared by the present invention can be applied not only to plastics such as polypropylene, polyethylene, polyvinyl chloride, polystyrene, etc., but also to various rubber materials such as butadiene styrene, butadiene styrene, ethylene propylene diene monomer, and other types of polymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0107] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0108] Figure 1 This is the carbon NMR spectrum of compound Ⅰ-A-2 prepared in Example 1.

[0109] Figure 2 This is the H NMR spectrum of compound Ⅰ-A-2 prepared in Example 1.

[0110] Figure 3 This is the mass spectrum of compound Ⅰ-A-2 prepared in Example 1.

[0111] Figure 4 This is the carbon NMR spectrum of compound Ⅰ-A-5 prepared in Example 2.

[0112] Figure 5 This is the H NMR spectrum of compound Ⅰ-A-5 prepared in Example 2.

[0113] Figure 6 This is the mass spectrum of compound Ⅰ-A-5 prepared in Example 2.

[0114] Figure 7 This is the carbon NMR spectrum of 6,6'-methylenebis(2-methoxy-4-propylphenol) prepared in Example 3.

[0115] Figure 8 This is the H NMR spectrum of 6,6'-methylenebis(2-methoxy-4-propylphenol) prepared in Example 3.

[0116] Fig. 9This is the mass spectrum of 6,6'-methylenebis(2-methoxy-4-propylphenol) prepared in Example 3.

[0117] Fig.10 This is the NMR carbon spectrum of compound IB-8 prepared in Example 4.

[0118] Fig.11 This is the H NMR spectrum of compound IB-8 prepared in Example 4.

[0119] Fig.12 This is the mass spectrum of compound IB-8 prepared in Example 4. DETAILED DESCRIPTION

[0120] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0121] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0122] The polypropylene raw material (K8303) used in the embodiment of the present invention is provided by China Petrochemical Corporation, and the weight average molecular weight is about 500,000; the antioxidant 168 is provided by Guangdong Kangjin Chemical.

[0123] Example 1: Preparation of antioxidant tris(2-methoxy-4-propylphenyl)phosphate (I-A-2)

[0124] The reaction route is as follows:

[0125]

[0126] Add lignin depolymerization monomer propyl guaiacol (1 g, 6 mmol) into the reaction bottle, then add 20 mL of reaction solvent toluene, then add acid binding agent triethylamine (0.77 g, 7.59 mmol), and then stir and mix evenly with a magnetic stirrer; measure PCl3 (0.32 g, 2.3 mmol) and mix evenly with a small amount of solvent toluene to obtain a toluene solution containing PCl3; fix the reaction bottle and build a condensation reflux device, use nitrogen to remove the air in the reaction bottle, slowly add the toluene solution containing PCl3 into the reaction liquid at 30°C and stir continuously, after the addition is complete, heat to 60°C for reaction for 2 hours, and then heat to 90°C for reaction for 3 hours. After the reaction, the reaction solution was cooled and filtered to remove the by-product triethylamine hydrochloride, the reaction solvent toluene and the incompletely reacted triethylamine were removed by rotary evaporation, and the compound tri(2-methoxy-4-propylphenyl) phosphate was separated and purified by column chromatography (ethyl acetate / n-hexane), recorded as compound Ⅰ-A-2, with a yield of 75%.

[0127] The NMR carbon spectrum of compound Ⅰ-A-2 is as follows Figure 1 As shown, the hydrogen spectrum is Figure 2 As shown in the mass spectrum Figure 3 The NMR and mass spectrometry data of compound Ⅰ-A-2 are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.20 (dd, J=8.0, 1.2Hz, 3H), 6.77 (d, J=2.0Hz, 3H), 6.72 (dd, J= 8.1,2.0Hz,3H),3.77(s,9H),2.61–2.55(m,6H),1.67(q,J=7.5Hz,6H),0.98(t,J=7.3Hz,9H); 13 C NMR (101MHz, Chloroform-d) δ150.75,139.44,139.01,122.09,120.49,112.79,55.87,37.89,24.71,13.83; MSI-MS: [M+H] + :527.35.

[0128] Example 2: Preparation of antioxidant bis(2-methoxy-4-propylphenyl)phenylphosphinoic acid ester (I-A-5)

[0129] The reaction route is as follows:

[0130]

[0131] Add lignin depolymerization monomer propyl guaiacol (1 g, 6 mmol) into the reaction bottle, then add 20 mL of reaction solvent toluene, then add acid binding agent triethylamine (0.80 g, 7.93 mmol), and then stir and mix evenly by magnetic stirring; measure phenyl phosphorus dichloride (DCPP, 0.62 g, 3.45 mmol) and mix evenly with a small amount of solvent toluene to obtain a toluene solution containing DCPP; fix the reaction bottle and build a condensation reflux device, use nitrogen to remove the air in the reaction bottle, slowly add the toluene solution containing DCPP into the reaction liquid at room temperature and stir continuously, and after the addition is completed, heat to 50°C and react for 2 hours. After the reaction is completed, the reaction solution is cooled and filtered to remove the by-product triethylamine hydrochloride, and the reaction solvent toluene and the incompletely reacted triethylamine are removed by rotary evaporation. The obtained crude product is slurried with n-hexane, and then the n-hexane is removed by oil filtration. The obtained white solid is freeze-dried to obtain the compound bis(2-methoxy-4-propylphenyl)phenylphosphinoylate, which is recorded as compound Ⅰ-A-5 with a yield of 89%.

[0132] The NMR carbon spectrum of compound Ⅰ-A-5 is as follows Figure 4 As shown, the hydrogen spectrum is Figure 5 As shown in the mass spectrum Figure 6 The NMR and mass spectrometry data of compound Ⅰ-A-5 are as follows: 1 H NMR (400MHz, DMSO-d6) δ7.86 (tdd, J=6.6, 3.3, 1.8Hz, 2H), 7.56–7.49 (m, 3H), 7.02 (dd, J=8.0, 1.4Hz, 2H), 6.88 (d, J= 2.0Hz,2H),6.68(dd,J=8.1,1.9Hz,2H),3.71(s,6H),2.50(s,4H),1.57(dt,J=8.9,7.3Hz,4H),0.88(t,J=7.3Hz,6H); 13 C NMR (101MHz, DMSO-d6) δ150.78,142.65,139.23,131.10,130.19,128.68,121.34,120.67,113.42,56.12,37.48,24.61,14.09; MSI-MS: [M+H] + :439.27.

[0133] Example 3: Preparation of bisphenol compound 6,6'-methylenebis(2-methoxy-4-propylphenol)

[0134] The reaction route is as follows:

[0135]

[0136] Propyl guaiacol (1g, 6mmol), 37% formaldehyde solution (0.281g, 3.45mmol) and 0.3mL 30% NaOH solution were added to the pressure bottle respectively, and placed in an oil bath pot at 120°C for 3h. After the reaction, the reaction solution was cooled to room temperature, and then an appropriate amount of ethyl acetate was poured into the obtained mixture to dissolve, and the mixture was repeatedly extracted with water three times. The obtained ethyl acetate solution was dried with anhydrous sodium sulfate, and then the ethyl acetate was removed by rotary evaporation. The obtained crude product was separated and purified by column chromatography (ethyl acetate / n-hexane) on silica gel to obtain a bisphenol compound 6,6'-methylenebis(2-methoxy-4-propylphenol) with a yield of 85%.

[0137] The NMR carbon spectrum of 6,6'-methylenebis(2-methoxy-4-propylphenol) is as follows Figure 7 As shown, the H NMR spectrum is Figure 8 As shown in the mass spectrum Fig. 9 As shown. The NMR and mass spectrometry data of 6,6'-methylenebis(2-methoxy-4-propylphenol) are: 1 HNMR(400MHz,DMSO-d6)δ8.22(s,2H),6.61(d,J=2.0Hz,2H),6.40(d,J=2.0Hz,2H),3.76 (d,J=2.4Hz,8H),2.36(dd,J=8.5,6.7Hz,4H),1.65–1.31(m,4H),0.84(t,J=7.3Hz,6H); 13 C NMR (101MHz, DMSO-d6) δ147.51,142.20,132.47,127.55,122.24,110.05,56.17,37.58,29.20,24.83,14.07; MSI-MS: [MH]-:343.3339.

[0138] Example 4: Preparation of antioxidant 4,8-dimethoxy-6-phenyl-2,10-dipropyl-12H-dibenzo[d,g][1,3,2]dioxaphosphoanthene (IB-8)

[0139] The reaction route is as follows:

[0140]

[0141] At room temperature, 6,6'-methylenebis(2-methoxy-4-propylphenol) (1 g, 2.906 mmol) and triethylamine (0.776 g, 7.687 mmol) prepared in Example 3 were added to 20 mL of toluene solution and stirred to mix evenly, and then a toluene solution containing DCPP (0.598 g, 3.342 mmol) was slowly added dropwise to the reaction solution, and the temperature was raised to 60°C for 2 h to complete the reaction. After the reaction was completed, the triethylamine hydrochloride generated in the reaction was removed by oil pump filtration, and then the reaction solvent toluene and the unreacted triethylamine were removed by rotary evaporation. The residue was washed with ethanol and filtered to obtain a white filter cake, which was dried at room temperature for 48 h to obtain a clean product, and the antioxidant 4,8-dimethoxy-6-phenyl-2,10-dipropyl-12H-dibenzo[d,g][1,3,2]dioxaphosphoranthene was obtained, which was recorded as compound IB-8 with a yield of 82%.

[0142] The NMR carbon spectrum of compound IB-8 is as follows Fig.10 As shown, the hydrogen spectrum is Fig.11 As shown in the mass spectrum Fig.12 The NMR and mass spectrometry data of compound IB-8 are: 1 H NMR(400MHz,Chloroform-d)δ8.10(td,J=6.2,3.1Hz,2H),7.65–7.50(m,3H),6.80(d,J=1.9Hz,2H),6.71–6.56(m,2H),4.54(dd,J=12 .7,3.7Hz,1H),3.83(s,6H),3.40(d,J=12.7Hz,1H),2.55(tt,J=9.4,4.9Hz,4H),1.65(dp,J=11.4,7.1Hz,4H),0.97(t,J=7.3Hz,6H); 13 C NMR(101MHz,Chloroform-d)δ151.77,140.98,139.48,136.58,130.61,129.78,1 29.65,128.40,121.32,110.80,56.04,38.07,33.56,24.62,13.86; MSI-MS: [M+H] + :451.26.

[0143] Example 5-7: Preparation of antioxidant / polypropylene (PP) composite materials

[0144] The PP masterbatch (polypropylene masterbatch) was placed in a vacuum drying oven at 60°C for dehydration treatment before processing to eliminate residual moisture. Subsequently, antioxidant Ⅰ-A-2 (prepared in Example 1), antioxidant Ⅰ-A-5 (prepared in Example 2) and antioxidant IB-8 (prepared in Example 4) with a total mass fraction of 0.2% of the PP masterbatch were weighed and mixed with the PP masterbatch in a mixer. Then, the mixed samples with different antioxidants were mixed and extruded at a speed of 50rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. Then the extruded antioxidant Ⅰ-A-2 / PP composite material, antioxidant Ⅰ-A-5 / PP composite material, and antioxidant IB-8 / PP composite material were pelletized for use.

[0145] Examples 8-10: Preparation of antioxidant / polypropylene (PP) composite materials

[0146] The PP masterbatch (polypropylene masterbatch) was placed in a vacuum drying oven at 60°C for dehydration treatment before processing to eliminate residual moisture. Subsequently, antioxidant Ⅰ-A-2 (prepared in Example 1), antioxidant Ⅰ-A-5 (prepared in Example 2) and antioxidant IB-8 (prepared in Example 4) with a total mass fraction of 0.4% of the PP masterbatch were weighed and mixed with the PP masterbatch in a mixer. Then, the mixed samples with different antioxidants were mixed and extruded at a speed of 50rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. Then the extruded antioxidant Ⅰ-A-2 / PP composite material, antioxidant Ⅰ-A-5 / PP composite material, and antioxidant IB-8 / PP composite material were pelletized for use.

[0147] Examples 11-13: Preparation of antioxidant / polypropylene (PP) composite materials

[0148] The PP masterbatch (polypropylene masterbatch) was placed in a vacuum drying oven at 60°C for dehydration treatment before processing to eliminate residual moisture. Subsequently, antioxidant Ⅰ-A-2 (prepared in Example 1), antioxidant Ⅰ-A-5 (prepared in Example 2) and antioxidant IB-8 (prepared in Example 4) with a total mass fraction of 0.6% of the PP masterbatch were weighed and mixed with the PP masterbatch in a mixer. Then, the mixed samples with different antioxidants were mixed and extruded at a speed of 50rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. Then the extruded antioxidant Ⅰ-A-2 / PP composite material, antioxidant Ⅰ-A-5 / PP composite material, and antioxidant IB-8 / PP composite material were pelletized for use.

[0149] Examples 14-16: Preparation of antioxidant / polypropylene (PP) composite materials

[0150] The PP masterbatch (polypropylene masterbatch) was placed in a vacuum drying oven at 60°C for dehydration treatment before processing to eliminate residual moisture. Subsequently, antioxidant Ⅰ-A-2 (prepared in Example 1), antioxidant Ⅰ-A-5 (prepared in Example 2) and antioxidant IB-8 (prepared in Example 4) with a total mass fraction of 0.8% of the PP masterbatch were weighed and mixed with the PP masterbatch in a mixer. Then, the mixed samples with different antioxidants were mixed and extruded at a speed of 50rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. Then the extruded antioxidant Ⅰ-A-2 / PP composite material, antioxidant Ⅰ-A-5 / PP composite material, and antioxidant IB-8 / PP composite material were pelletized for use.

[0151] Comparative Example 1: Preparation of blank polypropylene (PP) composite material

[0152] The PP masterbatch was placed in a vacuum drying oven at 60°C for dehydration before processing to eliminate residual moisture. Subsequently, the blank PP masterbatch was mixed and extruded at a speed of 50 rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C, and 180°C, respectively. The extruded blank PP composite material was then pelletized for use.

[0153] Comparative Example 2: Preparation of antioxidant 168-polypropylene (PP) composite material

[0154] The PP masterbatch was placed in a vacuum drying oven at 60°C for dehydration before processing to eliminate residual moisture. Subsequently, 0.2% of the total mass fraction of the PP masterbatch antioxidant 168 was weighed and mixed evenly with the PP masterbatch in a mixer. Then, the mixed sample with the addition of antioxidant 168 was mixed and extruded at a speed of 50 rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. The extruded antioxidant 168 / PP composite material was then pelletized for use.

[0155] Comparative Example 3: Preparation of antioxidant 168-polypropylene (PP) composite material

[0156] The PP masterbatch was placed in a vacuum drying oven at 60°C for dehydration before processing to eliminate residual moisture. Subsequently, 0.4% of the total mass fraction of the PP masterbatch antioxidant 168 was weighed and mixed evenly with the PP masterbatch in a mixer. Then, the mixed sample with the addition of antioxidant 168 was mixed and extruded at a speed of 50 rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. The extruded antioxidant 168 / PP composite material was then pelletized for use.

[0157] Comparative Example 4: Preparation of antioxidant 168-polypropylene (PP) composite material

[0158] The PP masterbatch was placed in a vacuum drying oven at 60°C for dehydration before processing to eliminate residual moisture. Subsequently, 0.6% of the total mass fraction of the PP masterbatch was weighed as antioxidant 168, and it was mixed evenly with the PP masterbatch in a mixer. Then, the mixed sample with the addition of antioxidant 168 was mixed and extruded at a speed of 50 rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. The extruded antioxidant 168 / PP composite material was then pelletized for use.

[0159] Comparative Example 5: Preparation of Antioxidant 168-Polypropylene (PP) Composite Material

[0160] The PP masterbatch was placed in a vacuum drying oven at 60°C for dehydration before processing to eliminate residual moisture. Subsequently, 0.8% of the total mass fraction of the PP masterbatch antioxidant 168 was weighed and mixed evenly with the PP masterbatch in a mixer. Then, the mixed sample with the addition of antioxidant 168 was mixed and extruded at a speed of 50 rpm using a micro twin-screw extruder (Wuhan Ruiming Plastics Machinery Co. Ltd.). The four-stage extrusion temperatures of the micro twin-screw extruder were set to 190°C, 185°C, 185°C and 180°C, respectively. The extruded antioxidant 168 / PP composite material was then pelletized for use.

[0161] Embodiment 17:

[0162] The composite materials obtained from the above examples and comparative examples were tested:

[0163] (1) TGA test: The thermal gravimetric loss of different antioxidant-PP composite materials was measured by DZ-TGA300 thermogravimetric analyzer. The results are shown in the table. The measurement was carried out in accordance with the national standard GB / T 27761-2011.

[0164] (2) DSC test: The oxidation induction test of different antioxidant-PP composite materials was carried out, and the oxidation induction time (OIT) was measured by DZ-DSC300 differential scanning calorimeter. The results are shown in the table. The measurement was carried out in accordance with the national standard GB / T19466.6-2009.

[0165] Table 1 Thermogravimetric data of antioxidant / PP composite materials of Examples 8 to 10, Comparative Example 1 and Comparative Example 3

[0166]

[0167] Note: 5％ 、T 50％ and T max Indicates the temperature at which the sample loses 5%, 50% and the maximum weight loss rate in the thermogravimetric analysis test;

[0168] Table 2 Oxidation induction time of antioxidant / PP composite materials of Examples 5 to 16 and Comparative Examples 1 to 5 (unit: min)

[0169]

[0170]

[0171] The experimental results in Table 1 and Table 2 show that the thermal stability of the Ⅰ-A-2 / PP and Ⅰ-A-5 / PP composites represented by Ⅰ-A antioxidants is better than that of the traditional antioxidant 168 / PP composite, especially under O2 atmosphere. 5％ and T 50％ Compared with the traditional antioxidant 168 / PP composite material, the T 5％ and T 50％ Compared with the traditional antioxidant 168 / PP composite material, the oxidation induction time was increased by 10°C and 7°C respectively. At the same time, the oxidation induction time of the Ⅰ-A-2 / PP and Ⅰ-A-5 / PP composite materials with different concentrations of antioxidants was greatly improved compared with the traditional antioxidant 168 / PP composite material. Among them, the composite materials with 0.4wt% of antioxidants Ⅰ-A-2 and Ⅰ-A-5 increased by about 5min compared with the composite material with 0.4wt% of antioxidant 168.

[0172] The IB-8 / PP composite material represented by IB antioxidants performed best. In N2 atmosphere, its T 5％ 、T 50％ and T max Compared with the antioxidant 168 / PP composite material, the T of IB-8 / PP composite material increased by 48℃, 9℃ and 5℃; in O2 atmosphere, the T 5％ 、T 50％ and T max Compared with 168 / PP, the OIT of the composite material with 0.4wt% antioxidant IB-8 / PP increased by 17℃, 10℃ and 12℃. The OIT of the composite material with 0.4wt% antioxidant IB-8 / PP increased by about 3 times compared with the composite material with 168 / PP, while the OIT of the composite material with 0.6wt% antioxidant IB-8 / PP increased by about 5 times compared with the composite material with 168 / PP.

[0173] The above experimental results show that the three phosphite antioxidants based on green renewable biomass ligninphenol when applied to materials all exhibit better thermal stability and antioxidant effects than traditional phosphite antioxidants.

[0174] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

[0175] The present invention provides a phosphite antioxidant based on bio-based lignin phenol and a preparation method and application thereof. There are many methods and approaches to implement the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

Claims

1. A compound as shown in formula I; in, R3, R6 are independently selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R1, R2, R4, R5 are independently selected from H or -OCH3; R is selected from phenyl or R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R7, R8 are independently selected from H or -OCH3; R1 and R4 can be connected by -CH(R 10 )-connected into a ring; where R 10 Selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3.

2. The compound according to claim 1, characterized in that R3, R6 are independently selected from -CH2-CH2-CH3, and / or R9 is selected from -CH2-CH2-CH3, and / or R1 and R4 can be connected by -CH(R 10 )-connected into a ring; where R 10 Selected from H.

3. The compound according to claim 1, characterized in that The compound represented by formula I is tris(4-ethylphenyl)phosphite, tris(4-ethyl-2-methoxyphenyl)phosphite, tris(4-ethyl-2,6-dimethoxyphenyl)phosphite, bis(4-ethylphenyl)phenylphosphite, bis(4-ethyl-2-methoxyphenyl)phenylphosphite, bis(4-ethyl-2,6-dimethoxyphenyl)phenylphosphite, 2,10-diethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 2,10-diethyl-4,8-dimethoxy-12-methyl-6-phenyl-12H-dibenzo[d,g][1,3 ,2] dioxaphosphocyanine, 2,10-diethyl-4,8-dimethoxy-6-phenyl-12H-dibenzo[d,g][1,3,2] dioxaphosphocyanine, 2,10-diethyl-6-(4-ethyl-2-methoxyphenoxy)-4,8-dimethoxy-12H-dibenzo[d,g][1,3,2] dioxaphosphocyanine, 2,10-diethyl-4,8-dimethoxy-6-(4-propylphenoxy)-12H-dibenzo[d,g][1,3,2] dioxaphosphocyanine, 2,10-diethyl-6-(4-ethyl-2,6-dimethoxyphenoxy)-4,8-dimethoxy-12 H-dibenzo[d,g][1,3,2]dioxophosphocyanine, tris(2-methoxy-4-methylphenyl)phosphite, tris(2,6-dimethoxy-4-methylphenyl)phosphite, bis(2-methoxy-4-methylphenyl)phenylphosphite, bis(2,6-dimethoxy-4-methylphenyl)phenylphosphite, 2,10-dimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 4,8-dimethoxy-2,10-dimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxophosphocyanine, 4,8-dimethoxy-2,10,1 2-Trimethyl-6-phenyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 4,8-dimethoxy-2,10-dimethyl-6-(p-tolyloxy)-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine, 4,8-dimethoxy-6-(2-methoxy-4-methylphenoxy)-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine or 6-(2,6-dimethoxy-4-methylphenoxy)-4,8-dimethoxy-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocyanine.

4. The compound according to claim 1, characterized in that The compound represented by formula I is any one of the compounds represented by the following structures: Preferably, the compound represented by formula I is any one of the compounds represented by the following structures: More preferably, the compound represented by formula I is a compound represented by the following structure:

5. A method for preparing the compound represented by formula I in claim 1, characterized in that: Select one of the following synthetic routes: Synthetic route 1: Compound 1 and compound 2 undergo a first reaction under the action of a first catalyst to obtain compound IA; in, R1=R4, R2=R5, R3=R6; R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R1, R2 are independently selected from H or -OCH3; R' is selected from Cl or phenyl; R is selected from phenyl or R7=R1, R8=R2, R9=R3; or, Synthesis route 2: Compound 3 and compound 4 undergo a second reaction under the action of a second catalyst to obtain intermediate 5; intermediate 5 and compound 6 continue to undergo a third reaction under the action of a third catalyst to obtain compound IBa; in, R2=R5、R3=R6; R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R2 is selected from H or -OCH3; R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R" is selected from phenyl; R is selected from phenyl; or, Synthetic route 3: in, R2=R5、R3=R6; R3 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R2 is selected from H or -OCH3; R 10 is selected from H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R9 is selected from -H, -CH3, -CH2-CH3 or -CH2-CH2-CH3; R7, R8 are independently selected from H or -OCH3; R is selected from 6. The preparation method according to claim 5, characterized in that: In synthetic route 1, the first catalyst is any one or a combination of triethylamine, pyridine, diisopropylamine, D301 resin and dodecyl dimethyl tertiary amine, preferably any one or a combination of triethylamine and dodecyl dimethyl tertiary amine, and more preferably triethylamine; the molar ratio of -OH in the compound 1 to -Cl in the compound 2 is 1.00:(1.00-1.30), preferably 1.00:1.15; the molar ratio of the compound 2 to the first catalyst is 1.0:(2.0-3.5), preferably 1 .0: (2.3~3.3); the first solvent used in the first reaction is any one or a combination of toluene, xylene and chloroform, preferably toluene; the mass volume ratio of the compound 1 and the first solvent is 1g: (15~30)mL, preferably 1g: 20mL; the reaction temperature of the first reaction is 30~90℃, preferably 40~90℃, and further preferably 50~90℃; the reaction time of the first reaction is 1~5h; the first reaction is carried out under the protection of an inert gas; the inert gas is preferably nitrogen.

7. The preparation method according to claim 5, characterized in that: In synthetic route 2, the second catalyst is any one or a combination of sodium hydroxide, potassium hydroxide, cesium hydroxide and 1,8-diazabicyclo (5,4,0)-7-undecene, preferably sodium hydroxide; the molar ratio of compound 3 to compound 4 is 2.00:(1.00-1.30), preferably 2.00:(1.15-1.25); the molar ratio of compound 3 to the second catalyst is 1.0:(0.3-0.4); the second catalyst is fed in the form of an aqueous solution, and the mass concentration of the second catalyst in the solution is 30%-35%; the reaction temperature of the second reaction is 100°C-150°C, preferably 120°C; the reaction time of the second reaction is 2-5h, preferably 3h; In synthetic route 2, the third catalyst is any one or a combination of triethylamine, pyridine, diisopropylamine, D301 resin and dodecyldimethylamine, preferably any one or a combination of triethylamine and dodecyldimethylamine, and more preferably triethylamine; the molar ratio of the intermediate 5 to the compound 6 is 1.00:(1.00-1.30), preferably 1.00:1.15; the molar ratio of the compound 6 to the third catalyst is 1.0:(2.0-2.5), preferably 1.0:2.3; the second solvent used in the third reaction is any one or a combination of toluene, xylene and chloroform, preferably toluene; the mass volume ratio of the intermediate 5 to the second solvent is 1g:(15-30)mL, preferably 1g:20mL; the reaction temperature of the third reaction is 40°C-80°C, preferably 60°C; the reaction time of the third reaction is 1-4h, preferably 2h.

8. Use of the compound described in any one of claims 1 to 4 as an antioxidant; preferably, the use is the use of the compound as an antioxidant in the preparation of a polymer material having thermal stability and / or oxidation resistance; further preferably, the use is the use of the compound as an antioxidant in the preparation of a polyolefin material having thermal stability and / or oxidation resistance; further preferably, the use is the use of the compound as an antioxidant in the preparation of a polypropylene material having thermal stability and / or oxidation resistance.

9. The use according to claim 8, characterized in that: The compound described in any one of claims 1 to 4 is used as an antioxidant, the compound is mixed with a polymer raw material and then extruded through a twin-screw extruder to obtain a polymer material with thermal stability and / or antioxidant properties.

10. The use according to claim 9, characterized in that: The mass of the compound accounts for 0.2% to 1.0% of the mass of the polymer raw material, preferably 0.2% to 0.8%, and more preferably 0.4% to 0.8%.

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