Semi-hindered phenolic antioxidant aqueous dispersion composition, semi-hindered phenolic antioxidant aqueous dispersion, and use thereof

Abstract

The application provides a semi-hindered phenolic antioxidant aqueous dispersion composition, a semi-hindered phenolic antioxidant aqueous dispersion and application thereof. The semi-hindered phenolic antioxidant aqueous dispersion composition comprises component A: a semi-hindered phenolic antioxidant, wherein the semi-hindered phenolic antioxidant has a structure shown in general formula I and / or general formula II; component B: a sulfonate emulsifying dispersant; and component C: a rosin acid salt emulsifying dispersant. The semi-hindered phenolic antioxidant can be stably dispersed in water by the sulfonate emulsifying dispersant and the rosin acid salt, the stability of the semi-hindered phenolic antioxidant aqueous dispersion is greatly improved, and the performance advantages of low toxicity and high efficiency of the semi-hindered phenolic antioxidant are well reserved.

Description

Technical Field

[0001] This invention relates to the field of polymer material additives, and more specifically, to an aqueous dispersion composition of a semi-hindered phenolic antioxidant, an aqueous dispersion of a semi-hindered phenolic antioxidant, and their applications. Background Technology

[0002] Semi-hindered phenolic antioxidants, as highly efficient antioxidants, are characterized by high antioxidant efficiency, low volatility, and significant synergistic effects with auxiliary antioxidants (such as thioester or phosphite antioxidants). When used in conjunction with light stabilizers, they impart excellent weather resistance to products. Semi-hindered phenolic antioxidants exhibit good polymer compatibility, high resistance to thermo-oxidative stress, low toxicity, and non-coloring properties, effectively preventing thermal oxidative degradation during processing and use, making them a mainstream antioxidant in the polymer materials field. However, semi-hindered phenolic antioxidants are typically organic solid powders, and their relatively large particle size and water insolubility limit their application in some areas. For example, when used as chain terminators in PVC polymerization, they must be readily soluble in water and able to be stably stored in aqueous solution. Water-insoluble organic antioxidant powders do not meet these requirements. Therefore, preparing a stable, non-precipitating antioxidant aqueous dispersion composition with a small particle size is crucial for broadening the application range of antioxidants, especially for their use as PVC chain terminators.

[0003] Currently, there are a few water-dispersible formulations of semi-hindered phenolic antioxidants on the market, but they are all limited by the suspension characteristics of the water-dispersible liquid itself, which makes them prone to precipitation and stratification after long-term storage. Summary of the Invention

[0004] The main objective of this invention is to provide an aqueous dispersion composition of a semi-hindered phenolic antioxidant, an aqueous dispersion of a semi-hindered phenolic antioxidant, and their applications, in order to solve the problem that semi-hindered phenolic antioxidants in the prior art cannot exist stably in aqueous solution, thus limiting their application scope.

[0005] To achieve the above objectives, according to one aspect of the present invention, an aqueous dispersion composition of a semi-hindered phenolic antioxidant is provided, comprising:

[0006] Component A: a semi-hindered phenolic antioxidant, wherein the semi-hindered phenolic antioxidant has the structure shown in general formula I and / or general formula II;

[0007] Component B: Sulfonate emulsifier and dispersant;

[0008] Component C: Rosin acid salt emulsifier and dispersant;

[0009]

[0010] In general formulas I and II, R1 and R2 in each general formula represent H or a C1-C4 alkyl group, and the other represents a C3-C4 alkyl group; x represents an integer from 0 to 3, y represents an integer from 1 to 7, "*" represents a bonding site with R3, n represents an integer from 1 to 4, R3 is an n-valent straight-chain, branched, or cycloalkyl group containing a triazine ring or ester group, and the alkylene group in R3 may optionally be replaced by -O-, -S-, -NH-, or -CO-.

[0011] Further, the sulfonate emulsifying dispersant is selected from one or more of fatty acid ester sulfonates, fatty amide sulfonates, alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates; preferably, the sulfonate emulsifying dispersant is selected from one or more of sodium butylnaphthalene sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium diisopropylnaphthalene sulfonate; more preferably, it is sodium butylnaphthalene sulfonate and / or sodium dodecylbenzene sulfonate.

[0012] Furthermore, the rosin acid salt emulsifying dispersant is selected from potassium rosinate and / or sodium rosinate.

[0013] Furthermore, R3 is C2~C 22 An n-valent straight-chain or branched alkyl group containing a triazine ring or ester group, or a C4-C6 group. 22 The R3 is an n-valent cycloalkyl group containing a triazine ring or an ester group, and the alkylene group in R3 may optionally be replaced by -O-, -S-, -NH- or -CO-; preferably, n is 2 or 3; preferably, R3 contains at least two ester groups or at least one triazine ring; more preferably, R3 is one of the following groups: Where m represents an integer between 1 and 3, q ​​represents an integer between 1 and 3, and R4 is a C1 to C4 alkylene group; more preferably, m represents 1 or 2, q represents 1 or 2, and R4 is methylene, ethylene, or propylene.

[0014] Furthermore, R1 and R2 in each general formula are each independently selected from methyl, ethyl, propyl, or butyl; preferably, each CxHy group independently represents H or methyl; more preferably, the semi-hindered phenolic antioxidant is...

[0015] and One or more of the following;

[0016] Most preferably, the semi-hindered phenolic antioxidant is

[0017] Further, the weight ratio of component A, component B and component C is (35-55):(0.5-5):(1-6), preferably (38-50):(1-4):(1-4); preferably, the semi-hindered phenolic antioxidant aqueous dispersion composition further includes an defoamer, preferably one or more of organosilicon defoamers, polysiloxane defoamers and polyether-modified organosilicon defoamers, more preferably organosilicon defoamers.

[0018] Further, the semi-hindered phenolic antioxidant aqueous dispersion composition comprises 35-55 parts of triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione or 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane; 0.5-5 parts of sodium dodecylbenzenesulfonate or sodium butylnaphthalenesulfonate or sodium diisopropylnaphthalenesulfonate; and 1-6 parts of sodium rosinate or potassium rosinate.

[0019] Furthermore, the semi-hindered phenolic antioxidant aqueous dispersion composition further includes water; preferably, the mass concentration of the semi-hindered phenolic antioxidant in the semi-hindered phenolic antioxidant aqueous dispersion composition is 35-55%, more preferably 38-50%; even more preferably, the mass concentration of the defoamer in the semi-hindered phenolic antioxidant aqueous dispersion composition is 0-1%.

[0020] According to another aspect of the present invention, an aqueous dispersion of a semi-hindered phenolic antioxidant is also provided, which is formed by dispersing the above-mentioned aqueous dispersion composition of the semi-hindered phenolic antioxidant via a dispersion device; preferably, the particle size of the solid particles in the aqueous dispersion of the semi-hindered phenolic antioxidant is 0.5 to 5 μm, more preferably 0.5 to 1.5 μm.

[0021] According to another aspect of the present invention, a polymeric material is also provided, comprising a polymeric substrate and an antioxidant dispersed therein, wherein the antioxidant comprises the above-mentioned semi-hindered phenolic antioxidant aqueous dispersion; preferably, the polymeric substrate is a plastic, rubber, or coating; more preferably, the polymeric substrate material is polystyrene, synthetic rubber, polyoxymethylene, polyurethane, polyamide, polyester, methyl methacrylate, or polyvinyl chloride; preferably, the polymeric substrate further disperses an ultraviolet absorber and / or a light stabilizer; more preferably, the ultraviolet absorber is selected from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-ditert-butyltriazole) One or more of the following: butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, 2-[4,6-di(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, and 2-hydroxy-4-n-octyloxybenzophenone Multiple light stabilizers are available, selected from poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]}, N,N”'-1,2-ethylenedimethyldi[N-[3-[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]amino]propyl]-N,N”-dibutyl- N,N”-Di(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, (C12-21 saturated, C18 unsaturated) fatty acids, 2,2,6,6-tetramethyl-4-piperidinyl esters, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; preferably, the antioxidant further includes thioester antioxidants; more preferably, the thioester antioxidants are selected from one or more of pentaerythritol tetra(3-lauryl thiopropionate), didodecyl thiodipropionate, and dioctadecyl thiodipropionate.

[0022] According to a third aspect of the invention, an aqueous dispersion of a semi-hindered phenolic antioxidant is also provided as a chain terminator for polymer (such as PVC) polymerization reactions.

[0023] This invention provides an aqueous dispersion composition for a semi-hindered phenolic antioxidant, comprising component A: a semi-hindered phenolic antioxidant having the structure shown in general formula I and / or general formula II; component B: a sulfonate emulsifying dispersant; and component C: a rosinate emulsifying dispersant. Through the sulfonate emulsifying dispersant and the rosinate, the semi-hindered phenolic antioxidant can be stably dispersed in water, greatly improving the stability of its aqueous dispersion, while perfectly preserving the low toxicity and high efficiency advantages of the semi-hindered phenolic antioxidant. Attached Figure Description

[0024] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0025] Figure 1 The image shown is a photograph of the antioxidant dispersion of Example 1 of the present invention after being stored stably for one month;

[0026] Figure 2 The image shown is a photograph of the antioxidant dispersion of Example 6 of the present invention after being stored stably for one month;

[0027] Figure 3 A photograph of the antioxidant dispersion of Comparative Example 1 after one month of stable storage is shown.

[0028] Figure 4 A photograph of the antioxidant dispersion of Comparative Example 2 after one month of stable storage is shown.

[0029] Figure 5 The diagram shows the particle size distribution data in the antioxidant dispersion of Example 1 of the present invention;

[0030] Figure 6 Another set of photographs is shown after the antioxidant dispersion of Example 1 of the present invention has been stored stably for 1 month;

[0031] Figure 7 A photograph shows the tilted state of the antioxidant dispersion of Example 1 of the present invention after being stored stably for one month;

[0032] Figure 8 A comparison chart of average pressure drop in reactors when using different terminators is shown;

[0033] Figure 9 The whiteness graphs of PVC corresponding to different terminators are shown;

[0034] Figure 10 The graph shows the PVC thermal stability time for different terminating agents. Detailed Implementation

[0035] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0036] As described in the background section of this invention, prior art semi-hindered phenolic antioxidants cannot exist stably in aqueous solution, thus limiting their application range. To address this problem, this invention provides an aqueous dispersion composition of a semi-hindered phenolic antioxidant, comprising: component A: a semi-hindered phenolic antioxidant having the structure shown in general formula I and / or general formula II; component B: a sulfonate emulsifying dispersant; and component C: a rosinate emulsifying dispersant.

[0037]

[0038] In general formulas I and II, R1 and R2 in each formula represent H or a C1-C4 alkyl group, and the other represents a C3-C4 alkyl group; x represents an integer from 0 to 3, y represents an integer from 1 to 7, "*" represents a bonding site with R3, and n represents an integer from 1 to 4. R3 is an n-valent straight-chain, branched, or cycloalkyl group containing a triazine ring or ester group, and the alkylene group in R3 may optionally be replaced by -O-, -S-, -NH-, or -CO-. Preferably, R1 and R2 are not the same.

[0039] By using sulfonate and rosinate emulsifying and dispersing agents, the aforementioned specific semi-hindered phenolic antioxidants can be stably dispersed in water, greatly improving the stability of their aqueous dispersions while perfectly preserving the low toxicity and high efficiency advantages of these antioxidants. This invention broadens the application range of semi-hindered phenolic antioxidants in polymers, while also offering the advantages of low volatility and no pollution.

[0040] It should be noted that the present invention uses a semi-hindered phenolic antioxidant with the above-mentioned structure. On the one hand, due to its special structure, it is easier to disperse in water. On the other hand, as a polymer (such as polyvinyl chloride PVC) terminator in the form of an aqueous dispersion, it has a more significant effect and can enter the polymer macromolecular particles to terminate the free radicals.

[0041] In a preferred embodiment, the sulfonate emulsifying dispersant is selected from one or more of fatty acid ester sulfonates, fatty amide sulfonates, alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. Using these sulfonate emulsifying dispersants in combination with rosin salts can better improve the dispersion stability of semi-hindered phenolic antioxidants in water, allowing them to be stored more stably as an aqueous dispersion. Furthermore, these sulfonate emulsifying dispersants also possess good surface activity and strong hydrophilicity, which can further effectively reduce the tension at the oil-water interface, achieving emulsification, and are cost-effective.

[0042] Preferably, the sulfonate emulsifying dispersant is selected from one or more of sodium butylnaphthalene sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium diisopropylnaphthalene sulfonate; more preferably, experiments have shown that the sulfonate emulsifying dispersant selected from sodium butylnaphthalene sulfonate and / or sodium dodecylbenzene sulfonate has the best effect, and the D50 particle size of the product is less than 0.75 μm. At the optimal ratio, the D50 particle size can reach less than 0.6 μm, and the stability is better.

[0043] In a preferred embodiment, the aforementioned rosin acid salt emulsifying dispersant is selected from potassium rosinate and / or sodium rosinate. Besides better performing the aforementioned functions, these rosin acid salt emulsifying dispersants also have the advantages of low cost and easy availability, and do not have any other adverse effects on the performance of the polymer in the application.

[0044] In a preferred embodiment, R3 is C2 to C3. 22 An n-valent straight-chain or branched alkyl group containing a triazine ring or ester group, or a C4-C6 group. 22 The R3 is an n-valent cycloalkyl group containing a triazine ring or ester group, and the alkylene group in R3 may optionally be replaced by -O-, -S-, -NH-, or -CO-; preferably, n is 2 or 3; preferably, R3 contains at least two ester groups or at least one triazine ring. The semi-hindered phenolic antioxidant corresponding to the above R3 exhibits better water dispersibility under the action of sulfonate emulsifying and dispersing agents and rosinate emulsifying and dispersing agents. Furthermore, considering further optimization of stability, antioxidant properties, and polymer chain termination performance, more preferably, R3 is one of the following groups: Where m represents an integer between 1 and 3, q ​​represents an integer between 1 and 3, and R4 is a C1 to C4 alkylene group; more preferably, m represents 1 or 2, q represents 1 or 2, and R4 is methylene, ethylene, or propylene.

[0045] More preferably, R1 and R2 in each general formula are each independently selected from methyl, ethyl, propyl or butyl; preferably, each CxHy group independently represents H or methyl.

[0046] For example, a semi-hindered phenolic antioxidant is (triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate), (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione) and One or more of (3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane); most preferably, the semi-hindered phenolic antioxidant is (Diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate).

[0047] To further improve water dispersion stability, in a preferred embodiment, the weight ratio of component A, component B, and component C is (35-55):(0.5-5):(1-6). For example, component A is 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, or 50 parts; component B is 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, 3.5 parts, 3.75 parts, 4 parts, 4.5 parts, or 5 parts; and component C is 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, 3.5 parts, 3.75 parts, 4 parts, 4.5 parts, or 5 parts. Preferably, the weight ratio of component A, component B, and component C is (38-50):(1-4):(1-4). Controlling the proportions of each component within the above range not only improves water dispersion stability but also helps maintain the antioxidant and terminator effects of the semi-hindered phenolic antioxidant.

[0048] In a preferred embodiment, the semi-hindered phenolic antioxidant aqueous dispersion composition comprises 35 to 55 parts of triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione or 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane; 0.5 to 5 parts of sodium dodecylbenzenesulfonate or sodium butylnaphthalenesulfonate or sodium diisopropylnaphthalenesulfonate; and 1 to 6 parts of sodium rosinate or potassium rosinate.

[0049] In actual preparation, the above composition only needs to be mixed and ground with water for dispersion. To make the dispersion process more efficient, the above semi-hindered phenolic antioxidant aqueous dispersion composition preferably also includes an antifoaming agent, preferably an organosilicon antifoaming agent, more preferably an organosilicon antifoaming agent, a polysiloxane antifoaming agent, or a polyether-modified organosilicon antifoaming agent. Adding this antifoaming agent is beneficial to the stability of the aqueous dispersion and also acts as a grinding aid, enabling the above composition to form an aqueous dispersion more quickly and efficiently during the dispersion process. More preferably, the mass concentration of the antifoaming agent in the semi-hindered phenolic antioxidant aqueous dispersion composition is 0-1%. For example, the organosilicon antifoaming agent can be selected from JS605 of Foshan Nanhai Datian Chemical Co., Ltd., the polysiloxane antifoaming agent can be selected from CK-0164 of Tianjin Gaotian New Material Technology Co., Ltd., and the polyether-modified organosilicon antifoaming agent can be selected from DT-1050 of Foshan Nanhai Datian Chemical Co., Ltd.

[0050] In a preferred embodiment, the semi-hindered phenolic antioxidant aqueous dispersion composition further includes water. Preferably, the mass concentration of the semi-hindered phenolic antioxidant in the semi-hindered phenolic antioxidant aqueous dispersion composition is 35-55%, more preferably 38-50%. Controlling the concentration within the above range is more conducive to improving the stability of the dispersion, while ensuring the effective amount for subsequent applications.

[0051] According to another aspect of the present invention, an aqueous dispersion of a semi-hindered phenolic antioxidant is also provided, which is formed by grinding the above-mentioned aqueous dispersion composition of a semi-hindered phenolic antioxidant using a grinding device. To obtain a stable, non-precipitating aqueous dispersion of a semi-hindered phenolic antioxidant, the present invention innovatively proposes the use of sulfonate emulsifiers and rosinate emulsifiers, which work together to prepare the antioxidant aqueous dispersion using wet grinding. The present invention successfully transforms the antioxidant from a large-particle-size organic powder into a small-particle-size aqueous dispersion, greatly improving the stability of the aqueous dispersion while perfectly preserving the low-toxicity and high-efficiency performance advantages of the antioxidant. Preferably, the particle size of the solid particles in the aqueous dispersion of the semi-hindered phenolic antioxidant is 0.5–5 μm, for example, 0.5 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm; more preferably, 0.5–1.5 μm.

[0052] The aforementioned grinding devices include, for example, ball mills, sand mills, homogeneous mixers, vertical bead mills, horizontal bead mills, pinbead mills, colloid mills, ultrafine grinding mills, ultra-high pressure homogenizers, and ultrasonic dispersion mixers.

[0053] According to another aspect of the present invention, a polymeric material is also provided, comprising a polymeric substrate and an antioxidant dispersed therein, wherein the antioxidant comprises the above-mentioned semi-hindered phenolic antioxidant aqueous dispersion; preferably, the polymeric substrate is a plastic, rubber, or coating; more preferably, the material of the polymeric substrate is polystyrene, synthetic rubber, polyoxymethylene, homopolymer and copolymer, polyurethane, polyamide, polyester, methyl methacrylate, or polyvinyl chloride; preferably, the polymeric substrate further disperses an ultraviolet absorber and / or a light stabilizer; more preferably, the ultraviolet absorber is selected from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy -3',5'-Di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-hydroxy-4-n-octyloxydi One or more of benzophenone, wherein the light stabilizer is selected from poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazin-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]}, N,N”'-1,2-ethylenedioxydi[N-[3-[[4,6-di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N The antioxidant comprises N”-dibutyl-N,N”-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, (C12-21 saturated, C18 unsaturated) fatty acids, 2,2,6,6-tetramethyl-4-piperidinyl esters, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis(1,2,2,6,6-pentamethyl-4–piperidinyl) sebacate; preferably, the antioxidant further comprises thioester antioxidants; more preferably, the thioester antioxidants are selected from one or more of pentaerythritol tetra(3-lauryl thiopropionate), disododecyl thiodipropionate, and disodadecyl thiodipropionate.

[0054] According to another aspect of the invention, the application of the above-mentioned semi-hindered phenolic antioxidant aqueous dispersion as a polymer polymerization reaction chain terminator is also provided. The polymer is preferably polyvinyl chloride (PVC).

[0055] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0056] Example 1

[0057] In a 500mL volumetric beaker, add 139g purified water, 2.5g sodium butylnaphthalene sulfonate, 7.5g potassium rosinate, and 100g of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (equivalent to an aqueous dispersion concentration of 44.2%, with a weight ratio of 50:1.25:3.75 between components A, B, and C), and mix thoroughly. Then, add the mixture to a vertical ball mill, add 275g of φ0.8mm zirconia beads to disperse and grind the mixture, adding 1g of silicone defoamer JS605 during grinding. Grind for 240 minutes to obtain an aqueous dispersion of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0058] Example 2

[0059] In a 500mL volumetric beaker, add 134g of purified water, 7.5g of sodium dodecylbenzenesulfonate, 7.5g of sodium rosinate, and 100g of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (equivalent to an aqueous dispersion concentration of 46.2%, with a weight ratio of 50:3.75:3.75 between components A, B, and C), and mix thoroughly. Then, add the mixture to a vertical ball mill, add 275g of φ0.8mm zirconia beads to disperse and grind the mixture, adding 1g of silicone defoamer JS605 during grinding. Grind for 240 minutes to obtain an aqueous dispersion of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0060] Example 3

[0061] In a 500mL volumetric beaker, add 139g purified water, 7.5g sodium dodecylbenzenesulfonate, 2.5g potassium rosinate, and 100g of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (equivalent to an aqueous dispersion concentration of 44.2%, with a weight ratio of 50:3.75:1.25 between components A, B, and C), and mix thoroughly. Then, add the mixture to a vertical ball mill, add 275g of φ0.8mm zirconia beads to disperse and grind the mixture, adding 1g of silicone defoamer JS605 during grinding. Grind for 240 minutes to obtain an aqueous dispersion of antioxidant diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0062] Example 4

[0063] The antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] in Example 1 was replaced with 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0064] Example 5

[0065] The antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] in Example 1 was replaced with 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0066] Example 6

[0067] The sodium butylnaphthalene sulfonate in Example 1 was replaced with sodium diisopropylnaphthalene sulfonate.

[0068] Example 7

[0069] The difference from Example 1 is that the total amount of components A, B and C remains the same, but the weight ratio of the three is adjusted to 55:0.5:6.

[0070] Example 8

[0071] The difference from Example 1 is that the total amount of components A, B and C remains the same, but the weight ratio of the three is adjusted to 35:5:1.

[0072] Example 9

[0073] The difference from Example 1 is that the total amount of components A, B and C remains the same, but the weight ratio of the three is adjusted to 35:0.5:0.8.

[0074] Example 10

[0075] The difference from Example 1 is that the water dispersion has a mass concentration of 38%.

[0076] Example 11

[0077] The difference from Example 1 is that the water dispersion has a mass concentration of 50%.

[0078] Example 12

[0079] The difference from Example 1 is that the water dispersion has a mass concentration of 55%.

[0080] Comparative Example 1

[0081] In a 500mL volumetric beaker, add 139g purified water, 2.5g sodium butylnaphthalene sulfonate, 7.5g glycerin, and 100g of antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and mix thoroughly. Then, add the mixture to a vertical ball mill, add 275g of φ0.8mm zirconia beads to disperse and grind the mixture. During grinding, add 1g of silicone defoamer JS605. Grind for 240 minutes to obtain an aqueous dispersion of antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0082] Comparative Example 2

[0083] In a 500mL beaker, add 139g of purified water, 2.5g of nonylphenol polyoxyethylene ether ammonium sulfate, 7.5g of potassium rosinate, and 100g of antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and mix thoroughly. Then, add the mixture to a vertical ball mill, add 275g of φ0.8mm zirconia beads to disperse and grind the mixture. During grinding, selectively add silicone defoamer JS605 as needed. Grind for 240 minutes to obtain an aqueous dispersion of antioxidant triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0084] Dispersion effect data:

[0085] Particle size determination: Particle size was obtained by wet testing using a laser particle size analyzer (Bettersize2600). Unless otherwise specified, the particle size of semi-hindered phenol aqueous dispersions was determined by light scattering (Dv). 50Value (volume diameter, with 50% of the population below this point and 50% of the population above this point). Particle size was determined in a suspension of a semi-hindered phenolic aqueous dispersion in water (ultrapure water (purified from Mili-Q)), preferably with a 5% opacity for particle size analyzer testing.

[0086] Stability determination: The stability of the dispersion was observed by standing at room temperature. The stability results are shown in the table below:

[0087] Table 1

[0088]

[0089]

[0090] Figure 5 The diagram shows the particle size distribution data of the dispersion in Example 1 of the present invention. It can be seen that the dispersion has uniform particle size and can be stored stably.

[0091] The dispersion in Example 1 was photographed after being stored stably for one month. Figure 6 and 7 As shown in the figure, there is no obvious stratification and no bottom settlement.

[0092] Application test of antioxidant dispersion as a terminator:

[0093] Terminator's main function is to stop polymerization in the later stages. Additionally, in emergency situations such as water or power outages during the reaction, the polymerization reaction must be stopped midway to avoid safety issues. Terminator can also function as a heat stabilizer and whitening agent, effectively improving the whiteness and thermal stability of the resin.

[0094] Because the termination rate and effectiveness of the terminator directly affect the safety of the polymerization production system, the termination effect of the terminator is one of the most fundamental and important evaluation factors. The greater the termination efficiency of the terminator, the greater the temperature drop and the smaller the pressure drop in the reactor under the same conditions.

[0095] When the product of Example 1 of this invention (denoted as B245D) and commercially available product 1 were used as PVC polymerization terminators, 5‰ terminator was added to the reactor during polymerization under the same conditions, and the pressure drop of the reactor was compared. The polymerization conditions were as follows: 1. Water, initiator azobisisobutyronitrile, dispersant polyvinyl alcohol, pH slow-release agent ammonium bicarbonate, and all other additives except monomers were added to the reactor; 2. Nitrogen gas was introduced to purge the air from the reactor, and the reactor was placed in liquid nitrogen for rapid freezing; 3. Vinyl chloride monomer was introduced through the gas phase valve; 4. The gas phase valve was tightened, stirring was started, and the temperature was raised to carry out the polymerization reaction. The temperature was stabilized at 40-50℃, and the overall pressure was <0.7MPa; 5. When the pressure drop of the reactor was observed, the terminator was injected through the liquid phase valve; 6. The reaction continued, and the pressure drop of the reactor was recorded; 7. When the reactor pressure stabilized, the reaction was completed. Unreacted monomers were directly released in a fume hood, and the polymer product was washed with water (100℃ / 30min) and dried at 40-50℃.

[0096] Test results:

[0097] 1) Comparison of pressure drop in the reactor: Figure 8 By comparing the average pressure drop of different terminating agents, it can be seen that when the water-dispersible composition in Example 1 of the present invention is used as a terminating agent, the termination is fast, there is no pressure drop, and the termination effect is better.

[0098] 2) Whiteness Comparison: After the terminator is added to the polymerization reactor and undergoes processes such as stripping and drying, the effective components remaining in the resin can absorb the HCl generated during PVC degradation, reducing the autocatalytic effect and improving the aging whiteness of the resin. The effect of the terminator can also be seen by testing the whiteness of the PVC using a colorimeter. Figure 9 The whiteness of PVC corresponding to different terminators is shown. It can be seen that when the water-dispersible composition in Example 1 of the present invention is used as a terminator, the resulting PVC product has higher whiteness and stronger anti-aging protection for the polymer.

[0099] 3) Comparison of thermal stability: Terminators are generally composite terminators, possessing functions such as terminating resin, anti-oxidation, improving thermal stability, and increasing resin whiteness. Therefore, resin thermal stability is also one of the important indicators for evaluating the effectiveness of terminators. This invention uses the Congo red method to evaluate the thermal stability of the resin. Figure 10 The results show the PVC thermal stability time corresponding to different terminators. It can be seen that when the water-dispersible composition in Example 1 of the present invention is used as a terminator, the PVC product obtained has a significantly longer thermal stability time, indicating that it has better thermal stability.

[0100] The antioxidant dispersions provided in the embodiments of the present invention and the above comparative examples were used as terminators for the above tests. It was found that the pressure drop of the reactor, the whiteness of the PVC product and the thermal stability of the embodiments were better than the test results of the comparative examples. Among them, the effects of Examples 2 to 5 and 10 were comparable to those of Example 1, while the effects of Examples 6 to 9 and 11 to 12 were slightly worse than those of Example 1.

[0101] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An aqueous dispersion composition of a semi-hindered phenolic antioxidant, characterized in that, include: Component A: A semi-hindered phenolic antioxidant, wherein the semi-hindered phenolic antioxidant is selected from triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione or 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane; Component B: Sulfonate emulsifying dispersant; the sulfonate emulsifying dispersant is selected from one or more of fatty acid ester sulfonates, fatty amide sulfonates, alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates; Component C: Rosin acid salt emulsifying and dispersing agent; the rosin acid salt emulsifying and dispersing agent is selected from potassium rosinate and / or sodium rosinate; The weight ratio of component A, component B and component C is (35~55):(0.5~5):(1~6).

2. The aqueous dispersion composition of the semi-hindered phenolic antioxidant according to claim 1, characterized in that, The sulfonate emulsifying dispersant is selected from one or more of sodium butylnaphthalene sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, and sodium diisopropylnaphthalene sulfonate.

3. The semi-hindered phenolic antioxidant aqueous dispersion composition according to claim 1, characterized in that, The sulfonate emulsifying dispersant is sodium butylnaphthalene sulfonate and / or sodium dodecylbenzene sulfonate.

4. The aqueous dispersion composition of the semi-hindered phenolic antioxidant according to claim 1, characterized in that, The semi-hindered phenolic antioxidant aqueous dispersion composition further includes water.

5. The semi-hindered phenolic antioxidant aqueous dispersion composition according to claim 4, characterized in that, The semi-hindered phenolic antioxidant has a mass concentration of 35-55% in the aqueous dispersion composition of the semi-hindered phenolic antioxidant.

6. The semi-hindered phenolic antioxidant aqueous dispersion composition according to claim 4, characterized in that, The semi-hindered phenolic antioxidant has a mass concentration of 38-50% in the aqueous dispersion composition of the semi-hindered phenolic antioxidant.

7. The semi-hindered phenolic antioxidant aqueous dispersion composition according to claim 1, characterized in that, The defoamer has a mass concentration of 0-1% in the aqueous dispersion composition of the semi-hindered phenolic antioxidant.

8. An aqueous dispersion of a semi-hindered phenolic antioxidant, characterized in that, The semi-hindered phenolic antioxidant aqueous dispersion is formed by dispersing the semi-hindered phenolic antioxidant aqueous dispersion composition according to any one of claims 1 to 7 using a dispersion device.

9. The semi-hindered phenolic antioxidant aqueous dispersion according to claim 8, characterized in that, The solid particles in the aqueous dispersion of the semi-hindered phenolic antioxidant have a particle size of 0.5~5μm.

10. The semi-hindered phenolic antioxidant aqueous dispersion according to claim 8, characterized in that, The solid particles in the aqueous dispersion of the semi-hindered phenolic antioxidant have a particle size of 0.5~1.5μm.

11. A polymer material, comprising a polymer substrate and an antioxidant dispersed therein, characterized in that, The antioxidant comprises an aqueous dispersion of a semi-hindered phenolic antioxidant as described in any one of claims 8 to 10.

12. The polymer material according to claim 11, characterized in that, The polymer substrate is plastic, rubber, or coating.

13. The polymer material according to claim 11, characterized in that, The polymer substrate is made of polystyrene, synthetic rubber, polyoxymethylene, polyurethane, polyamide, polyester, or polyvinyl chloride.

14. The polymer material according to claim 11, characterized in that, The polymer substrate also contains ultraviolet absorbers and / or light stabilizers.

15. The polymer material according to claim 14, characterized in that, The ultraviolet absorber is selected from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, 2-[4,6-di(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5- Octyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, and 2-hydroxy-4-n-octyloxybenzophenone, wherein the light stabilizer is selected from poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazin-2,4-diyl] [2-(2,2,6,6-Tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-Tetramethylpiperidinyl)-imino]}, N,N'''-1,2-Ethylenedi[N-[3-[[4,6-Di[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N,N'' One or more of the following: -dibutyl-N,N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine, (C12-21 saturated, C18 unsaturated) fatty acids, 2,2,6,6-tetramethyl-4-piperidinyl esters, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

16. The polymer material according to claim 15, characterized in that, The antioxidants also include thioester antioxidants.

17. The polymer material according to claim 16, characterized in that, The thioester antioxidants are selected from one or more of pentaerythritol tetra(3-lauryl thiopropionate), didodecyl thiodipropionate, and dioctadecyl thiodipropionate.

18. The use of a semi-hindered phenolic antioxidant aqueous dispersion according to any one of claims 8 to 10 as a polymer polymerization reaction chain terminator.

19. The application according to claim 18, characterized in that, The polymer is PVC.

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