Emulsion type antioxidant and application thereof

Abstract

The invention provides an emulsion type antioxidant, the emulsion type antioxidant comprises a phosphite ester antioxidant and an emulsifier, the emulsion type antioxidant comprises a phosphite ester antioxidant and an emulsifier, and the phosphite ester antioxidant comprises a compound as shown in a formula I and / or a formula II. The invention also provides an application of the emulsion type antioxidant in synthesis of high polymer materials. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and specifically relates to an emulsion antioxidant containing a phosphite antioxidant and its application. Background Art

[0002] Phosphite antioxidants, also known as auxiliary antioxidants, are a type of antioxidant. Their main function is to generate stable inactive products by decomposing the hydroperoxides produced during the oxidation process, thereby delaying the oxidation process of polymer materials and extending the service life of the product. The generation and accumulation of hydroperoxides are the most critical steps in the degradation of organic polymer materials. When a certain concentration of hydroperoxides is generated, the free radical oxidation reaction will advance rapidly. Therefore, phosphite antioxidants are crucial to inhibit aging. At the same time, phosphite antioxidants have good color protection capabilities and can increase the processing temperature of polymers. They have synergistic effects with hindered phenol antioxidants, light stabilizers, etc.

[0003] Through the chemical structure of phosphite antioxidants, it can be found that most of the new structures of phosphites contain substituted aromatic rings, and the majority are pentaerythritol diphosphite spiro ring structure and bisphenol phosphite structure, indicating that the focus of phosphite auxiliary antioxidant technology development is on improving processing stability and improving hydrolysis stability. Phosphite antioxidants are very important polymer material processing stabilizers and are also a type of antioxidant with great market demand. However, because the molecular structure contains trivalent phosphorous structure, it will undergo hydrolysis reaction to generate phosphorous acid and its upstream synthetic raw materials when it comes into contact with water, thus limiting its application in the fields of emulsion polymerization or suspension polymerization and emulsion antioxidants.

[0004] However, in the high temperature stage after some emulsion polymerization or suspension polymerization (such as ABS, PVC, MBS, nitrile latex, etc.), phosphite antioxidants are needed to act strongly and quickly to protect the polymer from aging and degradation. However, the emulsion polymerization or suspension polymerization system generally has a high water content, and the addition of phosphite antioxidants is prone to hydrolysis. Therefore, it is industrially impossible to add phosphite antioxidants to this section, and it is impossible to protect the polymer from the beginning of the emulsion polymerization. Phosphites can only be added during the processing stage, resulting in only the main antioxidant effect in the high temperature stage between the emulsion polymerization or suspension polymerization and the processing stage, and it cannot well protect the polymer from high temperature aging and degradation.

[0005] Therefore, it is particularly important to develop a high temperature resistant composite emulsion antioxidant containing phosphite. At the same time, due to the easy hydrolysis of phosphite antioxidants, the emulsion antioxidant needs to have good stability, the pH change should not be too large, and the storage stability should be high, so that the composite emulsion antioxidant can better play the role of anti-aging and degradation. It can be seen that the preparation of a highly stable composite emulsion antioxidant containing phosphite is crucial for the use of emulsion polymerization or suspension polymer end. Summary of the invention

[0006] The present application provides an emulsion-type antioxidant, which is compounded with two phosphite antioxidants. At the same time, through the action of an emulsifier, the phosphite antioxidant is wrapped in the middle of a micelle, and the wrapping is relatively tight, reducing contact with water, thereby solving the problem that the phosphite antioxidant is easily hydrolyzed and ineffective in the field of aqueous emulsion-type antioxidants, and broadening the application of phosphites in the fields of emulsion polymerization and emulsion-type antioxidants.

[0007] According to one aspect of the present application, an emulsion-type antioxidant is provided, comprising a phosphite antioxidant and an emulsifier, wherein the phosphite antioxidant comprises a compound shown in the following formula I and / or formula II;

[0008]

[0009] In Formula I, R1 to R3 are each independently selected from an optionally substituted C5-C20 straight or branched alkyl group;

[0010] In Formula II, R4 is selected from an optionally substituted C1-C10 straight or branched alkylene group, R5 to R 12 are each independently selected from hydrogen or an optionally substituted C1-10 straight or branched chain alkyl group, R 13 To R 16 Each is independently selected from optionally substituted C5-C20 straight or branched chain alkyl groups.

[0011] In some embodiments, in Formula I, R1 to R3 are each independently selected from optionally substituted C6-C18 straight or branched alkyl groups. Preferably, R1 to R3 are each independently selected from C7-C14 straight or branched alkyl groups, such as octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl or tetradecyl.

[0012] In some embodiments, the compound represented by Formula I includes one or more of tri(tridecyl) phosphite, triisodecyl phosphite, tri(isooctyl) phosphite and tri(dodecyl) phosphite.

[0013] In some embodiments, in Formula II, R4 is selected from an optionally substituted C2-C8 straight or branched alkylene group, R5 to R 12 are each independently selected from hydrogen or an optionally substituted C1-C6 straight or branched chain alkyl group, R 13 To R 16 Each is independently selected from optionally substituted C6-C18 straight chain or branched alkyl groups.

[0014] In some embodiments, in Formula II, R4 is selected from a branched alkyl group selected from C3-C6, R5, R8, R 10 and R 11R6 and R9 are each independently selected from a C1-C3 straight chain alkyl group, R7 and R 12 Each independently selected from a C3-C6 branched alkyl group, R 13 To R 16 Each is independently selected from C7-C14 straight chain or branched chain alkyl.

[0015] In some embodiments, the compound represented by Formula II is selected from 4,4'-butylenebis-(3-methyl-6-tert-butylphenyl)-tetrakis(tridecyl) diphosphite.

[0016] In some embodiments, in the phosphite antioxidant, the mass ratio of the compound represented by Formula I to the compound represented by Formula II is 1:(0.05-20), for example, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:10, 1:15, 1:20 or any value therebetween. In some preferred embodiments, in the phosphite antioxidant, the mass ratio of the compound represented by Formula I to the compound represented by Formula II is 1:(0.1-10), more preferably 1:(0.2-5).

[0017] In some embodiments, the emulsion-type antioxidant further comprises a hindered phenol antioxidant.

[0018] In some embodiments, the hindered phenol antioxidant includes one or more compounds shown in Formula III, Formula IV and Formula V below;

[0019]

[0020] In Formula III, R 17 To R 19 Each is independently selected from optionally substituted C1-C10 straight or branched alkyl, and n is selected from an integer of 1-10;

[0021] In Formula IV, R 21 To R 25 Each is independently selected from optionally substituted C1-C10 straight or branched chain alkyl or alkylene;

[0022] In formula V, R 26 To R 28 Each is independently selected from an optionally substituted C1-C10 straight or branched alkyl or alkylene group, R 29 is selected from optionally substituted C5-30 straight or branched chain alkyl.

[0023] In some embodiments, in Formula III, R 17 is selected from optionally substituted C2-C6 branched alkyl, R 18 and R 19is selected from optionally substituted C1-C3 straight chain alkyl. In some embodiments, in Formula III, n is selected from an integer of 2-10, for example, 2, 4, 6, 8, 10 or any value therebetween.

[0024] In some embodiments, the compound represented by formula III is selected from p-cresol and dicyclopentadiene copolymer.

[0025] In some embodiments, in Formula IV, R 21 is selected from optionally substituted C2-C6 branched alkyl, R 22 is selected from optionally substituted C1-C3 straight chain alkyl, R 23 To R 25 Each is independently selected from optionally substituted C1-C3 straight or branched chain alkylene.

[0026] In some embodiments, the compound represented by formula IV is selected from triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate].

[0027] In some embodiments, in Formula V, R 26 and R 27 is selected from optionally substituted C2-C6 branched alkyl, R 28 is selected from optionally substituted C1-C5 straight chain alkylene, R 29 is selected from optionally substituted C7-18 straight or branched chain alkyl.

[0028] In some embodiments, the compound represented by formula V is selected from octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0029] In some embodiments, the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is 1:(0-30), preferably 1:(0.1-10). In some specific embodiments, the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:15, 1:20, 1:25, 1:30 or any value therebetween.

[0030] In some embodiments, the emulsifier includes a nonionic surfactant and an anionic surfactant.

[0031] In some embodiments, the nonionic surfactant includes one or more of fatty acid polyoxyethylene ether phosphate, polyoxyethylene alkylphenol ether phosphate, alkyl polyoxyethylene ether phosphite monoester and diester, polyoxyethylene carboxylic acid ester, polyol carboxylic acid ester, polyoxyethylene polyol carboxylic acid ester, polyoxyethylene alkylaryl ether, polyethylene alkyl ether, fatty alcohol polyoxyethylene ether or fatty alcohol and ethylene oxide condensate.

[0032] In some embodiments, the anionic surfactant includes one or more of fatty alcohol polyoxyethylene ether carboxylates, oleate soaps, ricinoleate soaps, rosin acid soaps, fatty acid soaps, polyoxyethylene alkylphenol ether sulfates, fatty alcohol polyoxyethylene ether sulfates, aralkylphenol polyoxyethylene ether sulfates, alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl succinate sulfonates, disodium succinate sulfonate mixture, fatty amide taurates, polyoxyethylene alkoxy ether sulfonates or fatty amide sarcosinates.

[0033] In some embodiments, the mass ratio of the total mass of the phosphite antioxidant and the hindered phenol antioxidant to the emulsifier is (1-500): 1, preferably (2-200): 1, and more preferably (3-50): 1. In some embodiments, in the emulsion antioxidant, the mass ratio of the total mass of the phosphite antioxidant and the hindered phenol antioxidant to the emulsifier is 1: 1, 2: 1, 5: 1, 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 100: 1, 150: 1, 200: 1, 300: 1, 400: 1, 500: 1 or any value therebetween.

[0034] In some embodiments, the mass ratio of the phosphite antioxidant to the emulsifier is (0.5-200): 1, preferably (1-50): 1. In some embodiments, the mass ratio of the phosphite antioxidant to the emulsifier is 0.5: 1, 1: 1, 2: 1, 5: 1, 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 100: 1, 150: 1, 200: 1 or any value therebetween.

[0035] In some embodiments, the mass ratio of the hindered phenol antioxidant to the emulsifier is (0.5-50): 1, preferably (1-20): 1. In some embodiments, the mass ratio of the phosphite antioxidant to the emulsifier is 0.5: 1, 1: 1, 2: 1, 5: 1, 10: 1, 20: 1, 30: 1, 40: 1, 50: 1 or any value therebetween.

[0036] In some embodiments, the mass ratio of the nonionic surfactant to the anionic surfactant in the emulsifier is (1-10):1, preferably (1-5:1). In some embodiments, the mass ratio of the nonionic surfactant to the anionic surfactant in the emulsifier is 1:1, 2:1, 4:1, 6:1, 8:1, 10:1 or any value therebetween.

[0037] In some embodiments, the emulsion antioxidant comprises, by weight, 0-60 parts of hindered phenol antioxidant, 2-60 parts of phosphite antioxidant and 0.3-20 parts of emulsifier.

[0038] In some embodiments, the emulsion antioxidant comprises, by weight, 0-60 parts of hindered phenol antioxidant, 10-60 parts of phosphite antioxidant and 1-20 parts of emulsifier.

[0039] In some embodiments, the emulsion antioxidant comprises 20-60 parts by weight of a hindered phenol antioxidant, 5-50 parts by weight of a phosphite antioxidant, and 3-15 parts by weight of an emulsifier.

[0040] In some embodiments, the emulsion antioxidant further comprises water. Preferably, the water accounts for 10-80% of the total mass of the emulsion antioxidant, for example, 10%, 20%, 40%, 60%, 80% or any value therebetween.

[0041] In some embodiments, the emulsion antioxidant further comprises additional antioxidants and / or additives.

[0042] In some embodiments, the additional antioxidants include tocopherols, phenolic forms, thioesters, phosphates, triazines, amines, benzyl compounds, and ascorbic acid.

[0043] In some embodiments, the additive includes one or more of a light stabilizer, a catalyst, a brightener, a thickener, a preservative, or an antifoaming agent.

[0044] According to another aspect of the present application, there is provided the use of the emulsion antioxidant described in the present application in the synthesis of polymer materials.

[0045] In some embodiments, the emulsion antioxidant is used in the emulsion polymerization and / or suspension polymerization of polymer materials.

[0046] In some embodiments, the polymer material includes an organic polymer or a polymeric rubber.

[0047] In some embodiments, the polymer material includes acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile-acrylate rubber copolymer (ASA), methyl methacrylate-butadiene-styrene copolymer (MBS), polyvinyl chloride (PVC), polymethacrylate and copolymers thereof, styrene-butadiene copolymer or its carboxylated derivatives, polybutadiene, isobutylene-isoprene copolymer, brominated isobutylene-isoprene copolymer, chlorinated isobutylene-isoprene copolymer, diene-C1-4-alkyl acrylate copolymer, polyvinyl acetate and copolymers thereof, polytetrafluoroethylene, styrene-butadiene rubber, nitrile rubber, partially or fully hydrogenated nitrile rubber, chloroprene rubber, acrylonitrile isoprene rubber, styrene isoprene rubber, styrene isoprene rubber, polyisoprene, natural rubber, epoxidized natural rubber, fixative latex, styrene-butadiene latex, styrene-butadiene latex, chloroprene latex, isoprene latex, and natural latex. One or more.

[0048] Compared with the prior art, this application has the following beneficial effects:

[0049] (1) The problem of phosphite antioxidants being easily hydrolyzed and ineffective in the field of aqueous emulsion antioxidants is solved. Through the action of the emulsifier, the phosphite antioxidants are wrapped in the middle of the micelles, and the wrapping is relatively tight, reducing contact with water, thereby broadening the application of phosphite in the field of emulsion polymerization and emulsion antioxidants;

[0050] (2) Adding a composite emulsion antioxidant containing phosphite after emulsion polymerization can effectively protect the polymer from the source and prevent the aging of the polymer caused by high temperature in the later stage;

[0051] (3) The composite emulsion antioxidant containing phosphite is added after emulsion polymerization, which eliminates the process of adding phosphite antioxidant in the subsequent processing stage and optimizes the process flow;

[0052] (4) The prepared composite emulsion antioxidant containing phosphite has good stability, small pH change after long-term placement, small emulsion particle size, and no clear liquid or precipitation after being placed for half a year;

[0053] (5) From the perspective of anti-aging effect, the combination of phosphite antioxidants and hindered phenol antioxidants has a synergistic anti-aging effect, has good color protection ability, can increase the processing temperature of the polymer, and can stabilize the polymer well in the high temperature stage between the emulsion polymerization and the processing stage. In addition, the combination of hindered phenol antioxidants and phosphite antioxidants can also reduce production costs. DETAILED DESCRIPTION

[0054] Phosphite antioxidants have the effect of strong and fast stabilizing polymers at high temperatures, but due to their structural characteristics, they are easily hydrolyzed when exposed to water, thus limiting their application in the fields of emulsion polymerization and emulsion antioxidants. However, the demand for water-based composite emulsion antioxidants containing phosphites in the actual polymer anti-aging field is very urgent, especially in the field of high-temperature anti-aging. The present application uses an emulsifier to encapsulate phosphite antioxidants to form tight micelles, reduces contact with water in an aqueous emulsion antioxidant system, prepares a composite emulsion antioxidant containing phosphites, expands the application field of phosphite antioxidants, and can effectively reduce the hydrolysis of phosphite antioxidants in water.

[0055] In the high-temperature stage after some emulsion polymerizations, phosphite antioxidants are required to act strongly and quickly to protect the polymer from aging and degradation. However, the water content of the emulsion polymerization system is generally very high, and the addition of phosphite antioxidants is prone to hydrolysis. Therefore, it is industrially impossible to add phosphite antioxidants to this section to protect the polymer from the beginning of the emulsion polymerization. Phosphites are only added in the processing stage, so that the high-temperature stage between the emulsion polymerization and the processing stage has only the main antioxidant effect, and cannot well protect the polymer from high-temperature aging and degradation. The emulsion-type antioxidant of the present application solves this problem.

[0056] In industry, for polymers prepared by emulsion polymerization, an emulsion antioxidant containing a primary antioxidant is generally added after the emulsion polymerization is completed, and a phosphite antioxidant is added in the later processing stage. The phosphite-containing composite antioxidant prepared in the present application contains the antioxidants added in the above two stages. A sufficient amount of the phosphite-containing composite antioxidant can be added after the emulsion polymerization to save the addition of materials in the later processing stage, thereby simplifying the production process, and the phosphite antioxidant can better protect the polymer.

[0057] The emulsion-type antioxidant containing phosphite antioxidants is not well coated with emulsifier micelles, which will cause the phosphite antioxidants to be exposed to water, thereby causing rapid hydrolysis and affecting the anti-aging performance. The phosphite antioxidant prepared in this application has good coating effect, high emulsion stability, and small pH change during long-term storage, which can have a good anti-aging effect. If the phosphite antioxidants are hydrolyzed in water to generate phosphorous acid and its upstream synthetic raw materials, the pH value of the emulsion-type antioxidant will change, and the emulsion antioxidant has a small particle size and a fast migration rate, and can enter the polymer micelles to target and prevent the aging of the polymer, which can have a good anti-aging effect.

[0058] From the anti-aging effect point of view, in the emulsion-type oxidant of the present application, the phosphite antioxidant and the hindered phenol antioxidant are combined, which has a synergistic anti-aging effect, has good color protection ability, and can increase the processing temperature of the polymer.

[0059] In some embodiments, the preparation method of the emulsion antioxidant of the present application comprises the following steps:

[0060] (1) adding an antioxidant to a reaction kettle, heating the reaction kettle to maintain the temperature at 50-180° C., stirring the reaction kettle at a low speed of 30-600 rpm to form an antioxidant melt;

[0061] (2) adding emulsifier into the reaction kettle and stirring at 30-600 rpm to uniformly mix it with the antioxidant melt;

[0062] (3) at 50-100° C., start high-speed stirring at a stirring rate of 300-3000 rpm, add 30-70 parts of water to the reaction kettle, and reduce the stirring rate to 30-600 rpm after the aqueous system becomes thin;

[0063] (4) After adding water, the aqueous emulsion is kept warm for 30 minutes and then cooled to below 50°C for discharging to obtain a highly stable composite emulsion antioxidant containing phosphite.

[0064] In some embodiments, the emulsion antioxidant may further include one or more additional antioxidants or synergists. Preferably, the additional antioxidants or synergists include one or more of tocopherol, phenolic aldehydes, thioesters, phosphates, triazines, amines, benzyl compounds and ascorbic acid. Preferably, the emulsion antioxidant may further include one or more additives, such as light stabilizers, catalysts and brighteners, which may also be mixed with these antioxidants and synergists.

[0065] In conventional industrial practice, it is desirable to use aqueous dispersions of the above-mentioned emulsion-type antioxidants to maximize compatibility and incorporation efficiency. A dispersion can be defined as a heterogeneous mixture of organic matter suspended in water. To provide this, more raw materials may be required, including one or more of the following: water, surfactants, thickeners, preservatives, and adjuvants such as antifoaming agents.

[0066] In some embodiments, the emulsion antioxidant of the present application can be used in the synthesis of polymer materials, especially in acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride PVC, methyl methacrylate-butadiene-styrene copolymer MBS, nitrile latex, etc.; and can be added in the initial stage of emulsion polymerization and suspension polymerization to better resist high temperature working conditions.

[0067] In some embodiments, the emulsion antioxidant of the present application can be used to stabilize a wide variety of rubbers and other polymer materials, including: nitrile rubber; partially or fully hydrogenated nitrile rubber; styrene-butadiene copolymers, including carboxylated derivatives thereof; polychloroprene; polybutadiene; isobutylene-isoprene copolymers; brominated isobutylene-isoprene copolymers; chlorinated isobutylene-isoprene copolymers; butadiene-C1-4-alkyl acrylate copolymers; acrylonitrile isoprene rubber; styrene isoprene rubber; styrene isoprene rubber; polyisoprene; natural rubber; epoxidized natural rubber; and mixtures thereof.

[0068] In some embodiments, the emulsion antioxidant of the present application can be used for organic polymer systems prepared by emulsion polymerization or suspension polymerization, mainly including polymers containing specific functional groups (including but not limited to ABS, ASA, MBS, polymethacrylate and copolymers thereof, polyvinyl chloride, polyvinyl acetate and copolymers thereof, polytetrafluoroethylene, etc.), emulsion polymerization rubber (including but not limited to latex polystyrene-butadiene rubber, nitrile rubber, chloroprene rubber, etc.), latex and its products (including but not limited to natural latex, nitrile latex, styrene-butadiene latex, styrene-butadiene latex, styrene-butadiene-pyridine latex, chloroprene latex, isoprene latex, natural latex, etc.), especially ABS, PVC and MBS, to prevent their aging and degradation.

[0069] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. The specific embodiments described herein are only used to explain the present application and are not intended to constitute any limitation to the present application. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concepts of the present disclosure. Such structures and technologies are also described in many publications.

[0070] Unless otherwise specified, the reagents and / or kits used in the following examples are commercially available or can be synthesized by known methods.

[0071] 4,4'-Butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite (AS-4500): CAS No. 13003-12-8

[0072] Potassium ricinoleate soap: CAS No.8013-05-6

[0073] Sodium alcohol polyoxyethylene ether sulfate (AES): CAS No.9004-82-4

[0074] Fatty alcohol polyoxyethylene ether (Peregal): CAS No.9002-92-0

[0075] p-Cresol and dicyclopentadiene copolymer (RIANOX CPL 650): CAS No.68610-51-5

[0076] Triisodecyl phosphite:CAS No.25448-25-3

[0077] Potassium oleate soap:CAS No.143-18-0

[0078] Sodium dodecyl sulfate(SDS):CAS No.151-21-3

[0079] Triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate](RIANOX 245): CAS No. 36443-68-2

[0080] Tridecyl phosphite: CAS No.77745-66-5

[0081] β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester (RIANOX 1076): CAS No. 2082-79-3

[0082] Tri(2-ethylhexyl)phosphite: CAS No.25103-12-2

[0083] Potassium rosin soap: CAS No.38592-41-5

[0084] Castor oil polyoxyethylene ether: CAS No.61791-12-6

[0085] Tris(nonylphenol)phosphite(TNPP):CAS No.26523-78-4

[0086] 2,6-Di-tert-Butyl-p-cresol(BHT):CAS No.128-37-0

[0087] Example 1

[0088] This embodiment provides an aqueous emulsion, and the specific preparation method is as follows:

[0089] a) adding 60 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite into a reaction kettle, heating the reaction kettle to maintain the temperature at 70°C, stirring the mixture at a low speed of 500 rpm to mix the mixture evenly;

[0090] b) adding 1 part of potassium ricinoleate soap, 1 part of sodium sulfate of fatty alcohol polyoxyethylene ether, and 1 part of fatty alcohol polyoxyethylene ether into the reaction kettle, stirring at 500 rpm to mix them with the antioxidant melt evenly, and the stirring time is 10 min;

[0091] c) at 70° C., start high-speed stirring at a stirring rate of 3000 rpm, add 37 parts of deionized water dropwise to the reaction kettle, and reduce the stirring rate to 500 rpm after the aqueous system becomes thin;

[0092] d) After adding water, keep the aqueous emulsion warm for 30 minutes, and then cool it to below 50°C before discharging it to obtain a highly stable aqueous emulsion antioxidant.

[0093] Example 2

[0094] This embodiment provides an aqueous emulsion, and the specific preparation method is as follows:

[0095] a) adding 60 parts of antioxidant p-cresol and dicyclopentadiene copolymer and 10 parts of triisodecyl phosphite into a reaction kettle, heating to 110° C., melting and mixing, and stirring evenly, and maintaining the temperature at 90° C.;

[0096] b) adding 1 part of potassium oleate soap, 1 part of sodium lauryl sulfate and 1 part of fatty alcohol polyoxyethylene ether into the reaction kettle, stirring at 600 rpm to mix them with the antioxidant melt evenly, and the stirring time is 40 min;

[0097] c) at 90° C., start high-speed stirring at a stirring rate of 2000 rpm, dropwise add 27 parts of deionized water into the reaction kettle, and reduce the stirring rate to 600 rpm after the aqueous system becomes thin;

[0098] d) After adding water, keep the aqueous emulsion warm for 30 minutes, and then cool it to below 50°C before discharging it to obtain a highly stable aqueous emulsion antioxidant.

[0099] Example 3

[0100] This embodiment provides a composite emulsion antioxidant containing phosphite, and the preparation method thereof is as follows:

[0101] a) Add 25 parts of triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] into the reaction kettle

[0102] Melt and mix with 25 parts of tri(tridecyl) phosphite at 80°C until uniform;

[0103] b) adding 8 parts of potassium ricinoleate soap, 4 parts of sodium sulfate of fatty alcohol polyoxyethylene ether, and 3 parts of fatty alcohol polyoxyethylene ether into a reaction kettle, and stirring at 300 rpm to mix them with the antioxidant melt uniformly for 30 min;

[0104] c) at 80° C., start high-speed stirring at a stirring rate of 1000 rpm, dropwise add 35 parts of deionized water into the reaction kettle, and reduce the stirring rate to 30 rpm after the aqueous system becomes thin;

[0105] d) After adding water, keep the aqueous emulsion warm for 30 minutes, and then cool it to below 50°C before discharging it to obtain a highly stable aqueous emulsion antioxidant.

[0106] Example 4

[0107] This embodiment provides a composite emulsion antioxidant containing phosphite, and the preparation method thereof is as follows:

[0108] a) Add 20 parts of triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] into the reaction kettle,

[0109] 20 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester and 10 parts of triisooctyl phosphite were melt mixed at 70°C;

[0110] b) adding 6 parts of potassium rosin soap and 4 parts of castor oil polyoxyethylene ether into the reaction kettle, stirring at 30 rpm to mix them with the antioxidant melt evenly, and the stirring time is 60 min;

[0111] c) at 80° C., start high-speed stirring at a stirring rate of 300 rpm, dropwise add 40 parts of deionized water into the reaction kettle, and reduce the stirring rate to 100 rpm after the aqueous system becomes thin;

[0112] d) After adding water, keep the aqueous emulsion warm for 30 minutes, and then cool it to below 50°C before discharging it to obtain a highly stable aqueous emulsion antioxidant.

[0113] Example 5

[0114] The aqueous emulsion antioxidant was prepared by the same method as in Example 1, except that in step a), 60 parts of antioxidant triisodecyl phosphite was added to the reactor. The other steps were the same as in Example 1 to prepare an aqueous emulsion antioxidant.

[0115] Example 6

[0116] The aqueous emulsion antioxidant was prepared by the same method as in Example 1, except that in step a), 30 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 30 parts of triisodecyl phosphite were added to the reaction kettle. The other steps were the same as in Example 1 to prepare an aqueous emulsion antioxidant.

[0117] Example 7

[0118] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 55 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 5 parts of triisodecyl phosphite were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0119] Example 8

[0120] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 40 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 20 parts of triisodecyl phosphite were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0121] Example 9

[0122] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 10 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 50 parts of triisodecyl phosphite were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0123] Example 10

[0124] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 4 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 56 parts of triisodecyl phosphite were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0125] Embodiment 11

[0126] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 15 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 15 parts of triisodecyl phosphite and 30 parts of p-cresol and dicyclopentadiene copolymer were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0127] Example 12

[0128] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 15 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 15 parts of triisodecyl phosphite and 30 parts of triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0129] Example 13

[0130] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 15 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 15 parts of triisodecyl phosphite and 20 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the reaction kettle; and in step c), 47 parts of deionized water were added dropwise to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0131] Embodiment 14

[0132] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 15 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 15 parts of triisodecyl phosphite and 30 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0133] Embodiment 15

[0134] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 3 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 2.45 parts of triisodecyl phosphite and 54.55 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0135] Example 16

[0136] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 1 part of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 1 part of triisodecyl phosphite and 58 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0137] Embodiment 17

[0138] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step b), 0.1 parts of potassium ricinoleate soap, 0.1 parts of sodium polyoxyethylene fatty alcohol ether sulfate, and 0.1 parts of polyoxyethylene fatty alcohol ether were added to the reaction kettle; and in step c), 49.7 parts of deionized water were added dropwise to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0139] Embodiment 18

[0140] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step b), 0.5 parts of potassium ricinoleate soap, 0.5 parts of sodium polyoxyethylene fatty alcohol ether sulfate, and 0.5 parts of polyoxyethylene fatty alcohol ether were added to the reaction kettle; and in step c), 48.5 parts of deionized water were added dropwise to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0141] Embodiment 19

[0142] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step b), 5 parts of potassium ricinoleate soap, 5 parts of sodium fatty alcohol polyoxyethylene ether sulfate, and 5 parts of fatty alcohol polyoxyethylene ether were added to the reaction kettle; and in step c), 35 parts of deionized water were added dropwise to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0143] Comparative Example 1

[0144] This embodiment provides an aqueous emulsion, and its preparation method is different from that of embodiment 1 in that: step a) is 60 parts of a copolymer of p-cresol and dicyclopentadiene.

[0145] Comparative Example 2

[0146] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 30 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite and 30 parts of tris(nonylphenol) phosphite were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0147] Comparative Example 3

[0148] The aqueous emulsion antioxidant was prepared by the same method as in Example 6, except that in step a), 15 parts of antioxidant 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)-tetra(tridecyl) diphosphite, 15 parts of triisodecyl phosphite and 30 parts of 2,6-di-tert-butyl-p-cresol were added to the reaction kettle. The other steps were the same as in Example 6 to prepare an aqueous emulsion antioxidant.

[0149] Test Case

[0150] The physical properties of the aqueous emulsion obtained in the above example were tested, and the testing method was as follows:

[0151] (1) Volume average particle size: Bettersize 2600 laser particle size distribution analyzer was used to test the particle size of aqueous emulsion;

[0152] (2) pH stability: dilute the emulsion antioxidant into a 1% aqueous solution and test its pH value at different times using a pH meter;

[0153] (3) Storage stability: Leave the emulsion at room temperature and observe whether there is clear liquid or sedimentation;

[0154] (4) Application performance evaluation: Add a certain amount of composite emulsion antioxidant containing phosphite in the late stage of PVC polymerization reaction according to the same solid content ratio, continue the reaction for about 1 hour, record the pressure drop of the kettle, and when the reaction pressure drop is stable, it means the reaction is over. Filter, wash and dry to obtain PVC powder. Take PVC powder and test the whiteness of PVC at 160℃ for 10 minutes according to GB / T 15595-2008; test its thermal stability time at 180℃ according to national standard GB / T 2917.1-2002.

[0155] The test results are shown in Table 1 below.

[0156] Table 1

[0157]

[0158]

[0159] The technical solution of the present application is not limited to the above-mentioned specific embodiments, and all technical variations made according to the technical solution of the present application fall within the protection scope of the present application.

Claims

1. An emulsion antioxidant, comprising a phosphite antioxidant and an emulsifier, wherein the phosphite antioxidant comprises a compound represented by the following formula I and / or formula II; In Formula I, R1 to R3 are each independently selected from an optionally substituted C5-C20 straight or branched alkyl group; In Formula II, R4 is selected from an optionally substituted C1-C10 straight or branched alkylene group, R5 to R 12 are each independently selected from hydrogen or an optionally substituted C1-10 straight or branched chain alkyl group, R 13 To R 16 Each is independently selected from optionally substituted C5-C20 straight or branched chain alkyl groups.

2. The emulsion antioxidant according to claim 1, characterized in that In Formula I, R1 to R3 are each independently selected from optionally substituted C6-C18 straight or branched alkyl groups, preferably, R1 to R3 are each independently selected from C7-C14 straight or branched alkyl groups; In Formula II, R4 is selected from an optionally substituted C2-C8 straight or branched alkylene group, R5 to R 12 are each independently selected from hydrogen or an optionally substituted C1-C6 straight or branched chain alkyl group, R 13 To R 16 Each is independently selected from an optionally substituted C6-C18 straight or branched alkyl group, preferably, R4 is selected from a branched alkyl group selected from C3-C6, R5, R8, R 10 and R 11 R6 and R9 are each independently selected from a C1-C3 straight chain alkyl group, R7 and R 12 Each independently selected from a C3-C6 branched alkyl group, R 13 To R 16 Each independently selected from C7-C14 straight or branched alkyl; More preferably, the compound represented by formula I comprises one or more of tri(tridecyl) phosphite, triisodecyl phosphite, tri(isooctyl) phosphite and tri(dodecyl) phosphite; More preferably, the compound represented by formula II is selected from 4,4'-butylenebis-(3-methyl-6-tert-butylphenyl)-tetrakis(tridecyl) diphosphite.

3. The emulsion antioxidant according to claim 1 or 2, characterized in that: In the phosphite antioxidant, the mass ratio of the compound represented by formula I to the compound represented by formula II is 1:(0.05-20), preferably 1:(0.1-10), and more preferably 1:(0.2-5).

4. The emulsion antioxidant according to any one of claims 1 to 3, characterized in that The emulsion-type antioxidant also includes hindered phenol antioxidants; Preferably, the hindered phenol antioxidant comprises one or more of the compounds shown in the following formula III, formula IV and formula V; In Formula III, R 17 To R 19 Each is independently selected from an optionally substituted C1-C10 straight or branched alkyl group, preferably, R 17 is selected from optionally substituted C2-C6 branched alkyl, R 18 and R 19 is selected from optionally substituted C1-C3 straight chain alkyl, n is selected from an integer of 1-10; In Formula IV, R 21 To R 25 Each is independently selected from an optionally substituted C1-C10 straight or branched alkyl or alkylene group, preferably, R 21 is selected from optionally substituted C2-C6 branched alkyl, R 22 is selected from optionally substituted C1-C3 straight chain alkyl, R 23 To R 25 Each is independently selected from optionally substituted C1-C3 straight or branched chain alkylene; In formula V, R 26 To R 28 are each independently selected from optionally substituted C1-C10 straight or branched alkyl or alkylene groups, R 29 is selected from optionally substituted C5-30 straight or branched alkyl groups, preferably, R 26 and R 27 is selected from optionally substituted C2-C6 branched alkyl, R 28 is selected from optionally substituted C1-C5 straight chain alkylene, R 29 Selected from optionally substituted C7-18 straight or branched chain alkyl; More preferably, the compound represented by formula III is selected from p-cresol and dicyclopentadiene copolymer; More preferably, the compound represented by formula IV is selected from triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate]; More preferably, the compound represented by formula V is selected from octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

5. The emulsion antioxidant according to claim 4, characterized in that The mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is 1:(0-30), preferably 1:(0.1-10).

6. The emulsion antioxidant according to any one of claims 1 to 5, characterized in that The emulsifier includes a nonionic surfactant and an anionic surfactant. Preferably, the nonionic surfactant comprises one or more of fatty acid polyoxyethylene ether phosphate, polyoxyethylene alkylphenol ether phosphate, alkyl polyoxyethylene ether phosphite monoester and diester, polyoxyethylene carboxylate, polyol carboxylate, polyoxyethylene polyol carboxylate, polyoxyethylene alkylaryl ether, polyethylene alkyl ether, fatty alcohol polyoxyethylene ether or fatty alcohol and ethylene oxide condensate; Preferably, the anionic surfactant includes one or more of fatty alcohol polyoxyethylene ether carboxylates, oleate soaps, ricinoleate soaps, rosin acid soaps, fatty acid soaps, polyoxyethylene alkylphenol ether sulfates, fatty alcohol polyoxyethylene ether sulfates, aralkylphenol polyoxyethylene ether sulfates, alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl succinate sulfonates, disodium succinate sulfonate mixture, fatty amide taurates, polyoxyethylene alkoxy ether sulfonates or fatty amide sarcosinates.

7. The emulsion antioxidant according to any one of claims 4 to 6, characterized in that The mass ratio of the phosphite antioxidant to the emulsifier is (0.5-200):1, preferably (1-50):1; and / or The mass ratio of the hindered phenol antioxidant to the emulsifier is (0.5-50):1, preferably (1-20):1; Preferably, the mass ratio of the total mass of the phosphite antioxidant and the hindered phenol antioxidant to the mass ratio of the emulsifier is (1-500):1, preferably (2-200):1, and more preferably (3-50):1; Preferably, in the emulsifier, the mass ratio of the nonionic surfactant to the anionic surfactant is (1-10):1, preferably (1-5):

1.

8. The emulsion antioxidant according to claim 4, characterized in that The emulsion antioxidant comprises, by weight, 0-60 parts of hindered phenol antioxidant, 2-60 parts of phosphite antioxidant and 0.3-20 parts of emulsifier; Preferably, the emulsion antioxidant comprises 0-60 parts by weight of a hindered phenol antioxidant, 10-60 parts by weight of a phosphite antioxidant and 1-20 parts by weight of an emulsifier; More preferably, the emulsion antioxidant comprises 20-60 parts by weight of hindered phenol antioxidant, 5-50 parts by weight of phosphite antioxidant and 3-15 parts by weight of emulsifier.

9. The emulsion antioxidant according to any one of claims 1 to 8, characterized in that The emulsion antioxidant further comprises water, preferably, the water accounts for 10-80% of the total mass of the emulsion antioxidant; Preferably, the emulsion antioxidant further comprises additional antioxidants and / or additives; More preferably, the additional antioxidants include tocopherols, phenolic forms, thioesters, phosphates, triazines, amines, benzyl compounds and ascorbic acid; More preferably, the additive comprises one or more of a light stabilizer, a catalyst, a brightener, a thickener, a preservative or an antifoaming agent.

10. Use of the emulsion antioxidant according to any one of claims 1 to 9 in the synthesis of polymer materials; Preferably, the emulsion antioxidant is used for emulsion polymerization and / or suspension polymerization of polymer materials. Preferably, the polymer material comprises an organic polymer or a polymerized rubber. More preferably, the polymer material includes acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile-acrylate rubber copolymer (ASA), methyl methacrylate-butadiene-styrene copolymer (MBS), polyvinyl chloride (PVC), polymethacrylate and copolymers thereof, styrene-butadiene copolymer or its carboxylated derivatives, polybutadiene, isobutylene-isoprene copolymer, brominated isobutylene-isoprene copolymer, chlorinated isobutylene-isoprene copolymer, diene-C1-4-alkyl acrylate copolymer, polyvinyl acetate and copolymers thereof, polytetrafluoroethylene, styrene-butadiene rubber, nitrile rubber, partially or fully hydrogenated nitrile rubber, chloroprene rubber, acrylonitrile isoprene rubber, styrene isoprene rubber, styrene isoprene rubber, polyisoprene, natural rubber, epoxidized natural rubber, fixative latex, styrene-butadiene latex, styrene-butadiene latex, chloroprene latex, isoprene latex, and natural latex. One or more.

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