WO2021027202A1

WO2021027202A1 - Chelating macromolecular anti-oxidation stabilising agent, preparation method therefor, and application thereof

Info

Publication number: WO2021027202A1
Application number: PCT/CN2019/124727
Authority: WO
Inventors: 毛丽娟; 尹奇伟; 王以菲; 赵城世; 罗瑞; 王纪江; 陈秀颖; 刘树柏
Original assignee: 绍兴瑞康生物科技有限公司
Priority date: 2019-08-13
Filing date: 2019-12-12
Publication date: 2021-02-18
Also published as: CN110437838A

Abstract

A chelating anti-oxidation stabilising agent, a preparation method therefor, and an application thereof in macromolecular material, playing a dual protective role. The preparation method comprises: (1) adding compound 1 and epichlorohydrin, slowly adding sodium hydroxide or potassium hydroxide in batches, maintaining the temperature and reacting until the reaction of compound 1 is complete, and adding 1L MTBE or DCM or DCE to obtain a colourless oily compound 2; (2) adding mercaptan, adding a solvent, stirring for 30 min, adding compound 2 at 5-10℃ under the protection of nitrogen, implementing an ice bath for half an hour, and slowly adding sodium hydroxide or potassium hydroxide to obtain compound 3 or compound 4. The prepared chelating anti-oxidation stabilising agent has a thioether long-acting high-temperature anti-oxidation activity functional group, and also has the function of forming sulphur and hydroxyl coordinated five-membered cyclic complexing metal ions, said function playing a role in complexing and eliminating metal ions that catalyse the degradation of macromolecular materials.

Description

[Name of invention formulated by ISA according to Rule 37.2] 　Chelating polymer antioxidant stabilizer and its preparation method and application

Technical field

The invention belongs to the preparation field of polymer material functional additives, and in particular relates to a novel chelating type antioxidant stabilizer and a preparation method thereof.

Background technique

Antioxidant stabilizers for polymer materials, also known as antioxidants, are a class of functional additives that can quickly help capture and neutralize free radicals when polymer materials are oxidized, so as to remove free radicals and prevent oxidative degradation of polymer materials. When it exists in a small amount in the polymer system, it can delay or inhibit the progress of the polymer oxidation process, thereby preventing the aging of the polymer, maintaining its original various properties, and designing or extending its service life as required. Sulfur-containing organic compound auxiliary antioxidants have become a very important long-acting high-temperature antioxidant among auxiliary antioxidants because they can effectively decompose hydroperoxides.

Polymer materials are often due to the source of the material, its polymer additives and processing methods. The finished product will bring some metals or metal ions, such as Cr, Cu, Zn, Fe, etc., these variable trace metals or metal ions can It is used as a catalyst to catalyze the degradation of polymer materials, thereby accelerating the oxidative degradation process of polymer materials. This not only seriously affects the function and life of polymer materials, increases environmental pollution, but also poses a potential threat to our life safety. If such metals or metal ions are complexed into complexes, the catalysis of the Lewis acid of the metal or metal ions is greatly reduced, and the catalytic oxidation process is greatly inactivated, which plays an important role in the protection of polymer materials. effect. In addition, some metal complexes have the function of heat stabilizer in some polymer materials. These complexes have the same effect as the anti-heat aging stabilizer of metal chelate commonly used in polymer materials.

Summary of the invention

The impurity metal ion in the polymer material catalyzes the degradation of the polymer material is one of the important factors that must be considered to protect the polymer material. In order to solve the deficiencies in the prior art, the present invention provides an antioxidant stabilizer with chelating function and The preparation method and the specific scheme are as follows:

A chelating anti-oxidant stabilizer whose general structure is:

Wherein R ₁ is phenyl, biphenyl, isocyanuric acid, diphenylmethane, diphenyldimethylmethane, diphenylsulfone, alkyl or substituted acrylate group; R and R ₂ are C6～C20 straight Chain or branched alkanes; m=0,1,2,3,4; n=0,2,3,4, and m and n can be the same or different, but m and n are not 0 at the same time.

The general formula of the chemical reaction is:

A preparation method of chelating antioxidant stabilizer includes the following steps:

(1) Add compound 1 and epichlorohydrin, add a reflux tube, N2 protection, heat and stir, when the internal temperature reaches 65°C, slowly add sodium hydroxide in 4 batches, keep the temperature for the reaction until the reaction of compound 1 is complete, and cool to 50 1L MTBE was added after the temperature, and the insoluble matter was filtered. The filtrate was decompressed to recover MTBE and epichlorohydrin to obtain compound 2 as a colorless oil, which was directly used in the next step without further purification.

(2) Add mercaptan, add solvent, stir under the protection of nitrogen and lower the temperature to 5-15°C, add compound 2, keep the temperature in an ice bath for half an hour, and slowly add sodium hydroxide or potassium hydroxide to obtain compound 3 or compound 4.

The solvent in the step (2) is anhydrous dichloromethane or dichloroethane or acetone or ethanol or isopropanol or methanol.

In the step (2), after sodium hydroxide is slowly added, the temperature is naturally raised to room temperature, and the temperature is kept and stirred for 4-18 hours. It is detected that the thiol reaction is complete, and the alkali and impurities are washed with water and the solvent is removed under reduced pressure to obtain compound 3 or compound 4.

The molar ratio of compound 1 to epichlorohydrin in step (1) is 1:2-15.

The molar ratio of mercaptan and compound 2 in step (2) is 1:1.5-7.

The above-mentioned chelating anti-oxidation stabilizer is used in polymer materials as an anti-oxidation stabilizing additive for maintaining quality, color and maintaining various physical functions of the material.

The synthesis of the chelating antioxidant of the present invention utilizes alcohol, phenol or acid hydroxyl groups to introduce epoxy functional groups, and the epoxy functional groups further undergo a ring-opening addition reaction with mercaptans under alkaline conditions, thereby obtaining a new type of ortho The thioether long-acting high-temperature antioxidant stabilizer with hydroxyl functional group has a certain metal chelating function ligand structure; the present invention can be used as a dual-function unique antioxidant stabilizer under certain conditions. Under different application conditions, It provides a new choice for the development of innovative polymer materials industry.

The antioxidant of the present invention not only has the long-lasting high-temperature antioxidant active functional group of thioether, but also has the function of forming thioether and the coordinated five-membered cyclic complex metal ion of the ortho-hydroxyl group. This function can catalyze polymer materials. The degraded metal ions play a role of complexing and eradicating, thereby playing a more effective protective role for polymer materials. In addition, if this chelating long-acting high-temperature antioxidant chelates with heat-stable metal ions, a heat-stable metal ion complex is formed, which has better compatibility and matching with polymers, so that Improved protection of molecular materials. This patent also relates to the preparation method of chelating long-acting antioxidant, and its application as a new material antioxidant stabilizing additive in polymer materials. It can be used in polymer materials as antioxidant, anti-yellowing, and maintain its High-performance anti-oxidation stabilized additive with mechanical properties. This type of chelating high-performance antioxidant can be used in a series of polymer products such as plastics, rubber, fibers, coatings, and paints.

detailed description

Example 1

Structure of target product 1

Synthesis of target product 1:

Step (1): Preparation of bisphenol A diglycidyl ether (compound 2);

Add 1mol (228g) bisphenol A and 2.8mol (260g) epichlorohydrin to a 2-liter three-necked flask, add reflux tube, N2 protection, and heat and stir at 70°C. When the internal temperature reaches 65°C, divide into 4 batches Slowly add 2.05mol (ie 82g) sodium hydroxide, add heat preservation reaction to completion of the bisphenol A reaction, add 1L MTBE after cooling to 50℃, filter the insoluble matter, and recover the MTBE and epichlorohydrin from the filtrate under reduced pressure to obtain colorless The oily substance, 306 g of bisphenol A diglycidyl ether, was used directly in the next step without further purification.

Step (2) Synthesis of target product 1;

When compound 2 is bisphenol A dihydroglycerol ether, the thiol is n-dodecanethiol.

Add 0.20mol of n-dodecanethiol (38.2g), 120ml of anhydrous dichloromethane or dichloroethane or acetone or ethanol into a 250ml reaction flask, stir for 30min, and add 0.1mol( 34g) Bisphenol A dihydroglycerol ether, ice bath for half an hour, slowly add 2.5mmol (ie 0.1g) sodium hydroxide, naturally warm to room temperature, keep warm and stir for 12 hours, detect that the thiol reaction is complete, wash with water The solvent was removed under reduced pressure with impurities to obtain 69 g of a transparent oily substance with a yield of 95.6%. ESI/MS ⁺ : 745.32, 543.39; ¹ H-NMR/400MHz, CDCl ₃ : δ7.22–7.04(m,1H), 6.95–6.76(m,1H), 4.20–3.96(m,1H), 2.99– 2.43(m,1H),1.60(d,J=22.5Hz,2H),1.26(s,5H),0.88(t,J=6.7Hz,1H))

Example 2

2 examples of chemical synthesis target product synthesis steps:

Target product 2 structure

Target product 2 synthesis steps:

When compound 2 is bisphenol F dihydroglyceride, the thiol is n-dodecanethiol, if m=2.0, n=0. The reaction steps are: add 313 grams of bisphenol F glycerol ether, 1200 ml of anhydrous dichloromethane or dichloroethane or acetone or acetonitrile to a 2.5L reaction flask, stir until it is clear, and add n-dodecanethiol 405 Gram, nitrogen protection, ice bath for half an hour, slowly add 5 grams of sodium hydroxide, naturally warm to room temperature and keep stirring for 20 hours. It is detected that the mercaptan reaction is complete. The dichloromethane is recovered under reduced pressure and frozen to obtain 715 grams of white solid. The rate is 99.6%.

(ESI/MS+: 493.71, 515, 739.6, 827.5, 1029.48; ¹ H-NMR/400MHZ, CDCl ₃ : δ7.11–7.03 (m, 1H), 6.83 (ddd, J = 8.6, 4.3, 2.2 Hz, 1H ),4.05–3.89(m,2H),2.75–2.55(m,1H),2.58–2.47(m,1H),1.58(q,J=7.4Hz,1H),1.35(d,J=7.1Hz, 1H),1.32–1.25(m,2H),1.26(s,9H),0.88(t,J=6.8Hz,2H).)

Example 3

Chemical synthesis of the target product 3 example synthesis steps:

Target product 3 structure

n=1, m=2;

or

n=0, m=3.

Target product 3 synthesis steps:

When compound 2 is triglycidyl isocyanurate (TGIC) and the mercaptan is n-dodecanethiol, add 29.7g of TGIC, 120ml of anhydrous ethyl acetate or anhydrous dichloromethane or anhydrous dichloromethane to a 250ml reaction flask Chloroethane, stir until it is clear, add 60.7 g of n-dodecanethiol, nitrogen protection, slowly add 0.5 g of sodium hydroxide, stir at room temperature for 16 hours, detect that the mercaptan reaction is complete, filter to obtain 90 g of white solid, yield 99.6%.

ESI/MS+: 904.52,701.98; ¹ H-NMR/400MHZ, CDCl ₃ : δ6.54(s,1H), 4.18–3.80(m,1H), 2.79–2.37(m,1H), 1.98(s,1H) ), 1.51 (p, J = 7.4 Hz, 1H), 1.19 (s, 6H), 0.81 (t, J = 6.7 Hz, 1H).

Example 4

Target product 4 structure

Target product 4 synthesis steps

When compound 2 is glycidyl methacrylate and the mercaptan is n-dodecanethiol, m=2 or 1; add 20 g of glycidyl methacrylate and 120 ml of dichloromethane to a 250 ml reaction flask, and stir until it is clear , Add 56.8 grams of n-dodecanethiol, nitrogen protection, ice bath for half an hour, slowly add 1 gram of sodium hydroxide, naturally warm to room temperature and keep stirring for 12 hours. It is detected that the thiol reaction is complete, and the dichloromethane is recovered under reduced pressure. 75 g of transparent oily substance was obtained, and the yield was 97.7%.

1H-NMR (400MHz, Chloroform-d) δ 3.87–3.72 (m, 2H), 3.57 (dd, J = 11.1, 5.9 Hz, 1H), 1.67–1.52 (m, 2H), 0.90 (t, J = 6.8Hz, 3H). MS/ESI+: 569.32 (M+Na ⁺ ), 344.93.

Example 5

Target product 5 structure

Target product 5 synthesis steps

Reaction of bisphenol S epoxy resin intermediate with dodecanethiol

When compound 2 is bisphenol S dihydroglyceride, the mercaptan is n-dodecanethiol, m=1.3

Add 50g of bisphenol S glycerol ether, 120ml of dichloroethane or acetonitrile or ethanol to a 250ml reaction flask, stir until it is clear, add 36g of n-dodecanethiol, nitrogen protection, ice bath for half an hour, slowly 0.5 g of sodium hydroxide was added, the temperature was naturally raised to room temperature, and the temperature was kept and stirred for 12 hours. It was detected that the thiol reaction was complete, and dichloromethane was recovered under reduced pressure to obtain 80 g of a transparent oil with a yield of 93.1%.

1H-NMR (400MHz, Chloroform-d) δ 7.90--7.83 (m, 1H), 7.03--6.96 (m, 1H), 2.79--2.66 (m, 3H), 2.63--2.51 (m, 1H), 1.67-- 1.54 (m, 2H), 0.98-0.82 (m, 3H). ESI/MS ⁺ : 766.91; ESI/MS ^- : 764.91,507.24.

Claims

An anti-oxidant stabilizer with chelating function is characterized in that it can form a chelate structure with metal ions, passivating metal ions in polymer materials to catalyze polymer degradation, while maintaining excellent anti-oxidation functions. Its structural formula for:

Where X = O, N, NH; R 1 is phenyl, biphenyl, isocyanurate, diphenylmethane, diphenyldimethylmethane, diphenylsulfone, alkyl or substituted acrylate; R And R 2 are C6-C20 linear or branch-containing alkane groups; m=0,1,2,3,4; n=0,2,3,4, and m and n are not 0 at the same time.
A method for preparing the antioxidant stabilizer according to claim 1, wherein the general chemical reaction formula is:

Where X = O, N, NH; R 1 is benzene, biphenyl, isocyanuric acid, diphenylmethane, diphenyldimethylmethane, diphenylsulfone, alkyl or substituted acrylate group; R and R 2 is C6-C20 straight chain or branched alkanes; m=0,1,2,3,4; n=0,2,3,4, m and n cannot be 0 at the same time.
The method for preparing an antioxidant stabilizer according to claim 2, characterized in that it comprises the following steps:

(1) Add compound 1 and epichlorohydrin, add a reflux tube, N2 protection, heat and stir, when the internal temperature reaches 65°C, slowly add sodium hydroxide in batches, keep the temperature for the reaction until the reaction of compound 1 is complete, and cool to 50°C Then add 1L MTBE, or ethyl acetate, or dichloromethane or petroleum ether, filter the insoluble matter, and recover the solvent and excess epichlorohydrin from the filtrate under reduced pressure to obtain the colorless oil compound 2, which is used directly without further purification Next step.

(2) Add mercaptan, add dichloromethane, or acetone, or ethyl acetate, or ethanol, or methanol solvent, stir and reduce the temperature to 0-15°C under nitrogen protection, add compound 2, and keep the temperature in an ice bath for half an hour. Sodium hydroxide is slowly added in batches to obtain compound 3 or compound 4.
The method for preparing an antioxidant stabilizer according to claim 3, characterized in that it comprises the following steps: the solvent of the step (2) is anhydrous dichloromethane, dichloroethane, acetone or ethanol or acetic acid Ethyl or methanol or tetrahydrofuran.
The method for preparing an antioxidant stabilizer according to claim 3, characterized in that it comprises the following steps: the step (2) slowly adds sodium hydroxide in batches, then naturally warms to room temperature and keeps stirring for 3-24 After hours, it was detected that the thiol reaction was complete, and the solvent was removed by washing with water to remove alkali and impurities under reduced pressure to obtain compound 3 or compound 4.
The preparation method of an antioxidant stabilizer according to claim 3, characterized in that it comprises the following steps: the molar ratio of compound 1 to epichlorohydrin in the step (1) is 1:2-15.
The method for preparing an antioxidant stabilizer according to claim 3, which is characterized in that it comprises the following steps: the molar ratio of mercaptan to compound 2 in the step (2) is 1:1.5-7.
An antioxidant stabilizer according to claim 1 applied to polymer materials, as a long-lasting high-temperature antioxidant function, passivating metal ions to catalyze polymer price reduction, and form a complex heat stabilizer with certain metal ions, It is an anti-oxidation stabilized additive for polymer materials to maintain quality, color and maintain functions.