CN107805320B - A method of preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature - Google Patents

A method of preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature Download PDF

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CN107805320B
CN107805320B CN201711134723.0A CN201711134723A CN107805320B CN 107805320 B CN107805320 B CN 107805320B CN 201711134723 A CN201711134723 A CN 201711134723A CN 107805320 B CN107805320 B CN 107805320B
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sodium
aqueous
ether
acid
antioxidant
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CN107805320A (en
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张明耀
杜帅
刘伯军
罗雪妍
徐璐
白阳
李京桥
王猛
张金辉
王凯
王一凯
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Sinochem International Polymer Lianyungang Co Ltd
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Changchun University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical Kinetics & Catalysis (AREA)
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  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)

Abstract

A method of it preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature, belongs to antioxidant technical field.It is that 45~140g primary antioxidant, 15~40g auxiliary anti-oxidant and 0.3~1.2g defoaming agent are added in 100~300g solvent, is completely dissolved raw material under magnetic stirring；2.5~5g emulsifier and 0.5~1.5g dispersing agent are dissolved in 50~100g deionized water；By primary antioxidant solution under the conditions of 3000~9000 revs/min 10~20s of emulsification pretreatment, emulsifier solution is slowly added dropwise during emulsification pretreatment thereto, primary antioxidant is precipitated slowly from solvent, 10~120min is sheared under the conditions of 9000~23000 revs/min again, 0.2~1.5g thickener is added after being cooled to room temperature, stands that 5~20min is preferable up to partial size of the present invention, the aqueous antioxygen agent emulsion of high-melting-point.Operation of the present invention is simple, energy-efficient, solves the disadvantages of big energy consumption in industrial antioxidant emulsion preparation process, cumbersome.

Description

A method of preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature
Technical field
The invention belongs to antioxidant technical fields, and in particular to one kind prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature The antioxidant of method, selection is suitable for emulsion polymerization production technology.
Background technique
All very stringent to the control of oxygen in the synthesis process of most of polymer, having prevented may in polymerization process Lead to material aging factor, but oxygen air and heat, light and machinery are stored and can inevitably touched in Polymer Processing The generation of phenomena such as power, the passage of adjoint time, high molecular material will be with discoloration, the decline of various physical mechanical properties, most Use value is lost eventually.Since the oxidation of high molecular material is an irreversible process, and eventually result in the materials'use longevity Life shortens, and for the generation for slowing down oxidation reaction, antioxidant becomes indispensable during the machine-shaping of high molecular material Auxiliary agent.
Antioxidant is that one kind can inhibit polymeric inner that oxidation reaction, a substance of scavenging activated oxygen occurs, and is resisted Oxygen agent can capture the free free radical of activity so that it becomes nonactive free free radical, so that chain reaction be made to terminate；Or pass through The polymer hydroperoxides generated in oxidation process are decomposed, stable nonactive product are produced, thus middle chain-breaking reaction.Therefore It is widely used in the high molecular materials such as plastics, rubber, fiber, improves the ageing-resistant performance of high molecular material, to extends material Expect service life.
Butadiene is important polymer monomer, can be copolymerized with multiple compounds and manufacture various synthetic rubber and synthesis tree Rouge.In its every annual consumption, about 90% or more is used for synthetic rubber such as butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene Rubber, EP rubbers, in terms of synthetic resin, for producing ABS, BS, SBS, MBS, POLYBUTADIENE EPOXY RESIN, liquid fourth Diene oligomers etc..Wherein, butadiene is maximum component to be influenced by oxidation reaction, thus play certainly to the aging of integral material Qualitative effect, it is numerous studies have shown that due to butadiene molecule chain link have largely be easy to be broken isolated double bond, in material Aging occurs first for rubber particle under butadiene in material use process, makes the reduction of material toughness itself, and rigidity improves, macro manifestations Become fragile for material, appearance color gradually turns yellow and deepens.
Polymer work in-process is heated and oxygen contacts inevitable meeting and generates free polymer readical and react with oxygen, can not Both the meeting avoided generates oxyradical and peroxylradicals, removed by certain means, that is, the anti-of polymer can be improved Oxidability.
Want to improve the oxidation resistance of polymer or remove free radical, or removal generates the object of free free radical Matter, prevents the progress of autoxidation chain reaction, compound of the suitable antioxidant generally by a variety of with antioxygen row compound and At usually being compounded by primary antioxidant and auxiliary anti-oxidant, antioxidant theory thinks, phenolic antioxidant can be with during antioxygen Peroxylradicals are captured so that it becomes hydroperoxides, and hydroperoxides have autocatalysis to thermal oxidative degradation, so Exclusive use is difficult to reach ideal antioxidant effect, although auxiliary antioxidant cannot capture peroxylradicals, can decompose hydrogen mistake Oxide, so that polymer caused by self-catalyzed reaction be inhibited to degrade.Composition of raw materials of the present invention is resisted using primary antioxidant with auxiliary Oxygen agent is used cooperatively to reach ideal synergy.
Traditional antioxidant application method is to be added in reaction system with solidapowder form, but this is faced with antioxidant powder End disperses uneven situation in the polymer, and then influences the antioxygen property of naval stores, thus mostly uses and aqueous cream can be dispersed Liquid type antioxidant.And the preparation process of traditional aqueous emulsion type antioxidant is mostly by primary antioxidant powder and auxiliary anti-oxidant powder It is mixed to form liquid composition shear agitation with water, surfactant, wetting agent, pre-emulsification effect is reached after being sufficiently mixed, then Mechanical stirring homogeneous after addition water, dispersing agent, obtains antioxidant product emulsion；The production of suspension liquid emulsion need to use ball mill and surpass Micro- grater constantly grinds composite antioxidant using stone, ceramic bead or other similar hard material as abrasive media Mill, operation want repeatability entrain the pellets into milling zone, can reach needs particle size range be 1-10 micron, averagely grain Diameter is 3-5 microns, and the substances such as water, dispersing agent, wetting agent are added later, are adequately mixed；Or by composite antioxidant, water, dispersion The material mixings such as agent, wetting agent grind 16-20 hours in the ball mill, obtain product；Inverted emulsion method is first by compound antioxygen Emulsifier is added under mechanical agitation and carries out being dispersed into water-in-oil emulsion, adds water and passes through high-speed stirring for agent high temperature melting Reversed formation emulsion oil-in-water is mixed, Temperature fall under stirring condition obtains aqueous antioxidant product emulsion.
Though can be dispersed to antioxidant with upper type, its preparation process is many and diverse, and energy consumption is big, and the production cycle is long, invisible Middle increase production cost, is not easy to industrialized production.The present invention overcomes above many deficiencies, far below antioxidant fusing point it Under, using physical means, good dispersion is carried out to antioxidant.
Summary of the invention
It is an object of the present invention to provide it is a kind of overturn it is traditional aqueous antioxidant emulsion preparation method can be dispersed, overcome existing Technical restriction primary antioxidant and auxiliary anti-oxidant is made by a certain percentage multiple under room temperature far below antioxidant fusing point Distribution type antioxidant systems initiate Dynamic Precipitation method in aqueous antioxidant field, in homogenizer high speed shear and emulsification collective effect Under prepare the aqueous antioxidant product of stable homogeneous at room temperature.
The method of the present invention for preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature, its step are as follows:
1. 45~140g primary antioxidant, 15~40g auxiliary anti-oxidant and 0.3~1.2g defoaming agent are added to 100~300g In solvent, it is completely dissolved raw material under magnetic agitation (30~800 revs/min)；
2. 2.5~5g emulsifier and 0.5~1.5g dispersing agent are dissolved in 50~100g deionized water；
3. 1. solution that step is obtained 10~20s of emulsification pretreatment, emulsification pretreatment under the conditions of 3000~9000 revs/min 2. solution that step obtains is slowly added dropwise thereto in the process, primary antioxidant is precipitated slowly from solvent, obtains aqueous antioxygen Agent emulsion；
4. 3. aqueous antioxygen agent emulsion that step is obtained shears 10 under the conditions of 9000~23000 revs/min~ 120min, after being cooled to room temperature be added 0.2~1.5g thickener, stand 5~20min up to partial size of the present invention preferably, The aqueous antioxygen agent emulsion of high-melting-point.
Since the fusing point of antioxidant itself is higher (being greater than 100 DEG C), the aqueous antioxygen agent emulsion because obtained from has higher Fusing point.Used solvent such as ethyl alcohol, acetone etc. can dissolve each other completely with water during preparing antioxygen agent emulsion, in this way Promote the antioxygen agent emulsion prepared that can also be completely dispersed in water, because of the referred to herein as aqueous antioxygen agent emulsion of high-melting-point.
Above method step 1. described in primary antioxidant be paracresol and dicyclopentadiene butylation product (antioxygen Agent CPL, fusing point >=115 DEG C), bis- (2,4-DTBP) pentaerythritol diphosphites (antioxidant 626, fusing points 175 DEG C), 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol) (antioxidant 2246,120~133 DEG C of fusing point), paracresol and double One or more of butylation product (115 DEG C of antioxidant Wingstay-L fusing point) of dicyclopentadiene；Auxiliary anti-oxidant For β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isoctanol ester (liquid antioxidant 1135), three (nonyl is for phenyl) phosphorous Acid esters (liquid antioxidant TPP)；The double isomerous tridecanol esters (liquid antioxidant DTDTP) of thio-2 acid, diphosphorous acid double 18 The one or more of ester pentaerythritol ester (liquid antioxidant DPD).
Above method step 1. described in defoaming agent be silicone emulsion defoaming agent；Natural oil defoaming agent (vegetable oil)； Polyethers defoaming agent (GP type defoaming agent, GPE type defoaming agent, GPES type defoaming agent)；Silicon class defoaming agent (dimethyl silicone polymer, Polyether modified silicon oil)；High-carbon alcohol defoaming agent；Polyoxyethylene polyoxypropylene pentaerythrite ether；Polyoxyethylene polyoxy propyl alcohol amidogen ether； Polypropylene glycerol aether；Polyoxyethylene polyoxypropylene glycerin ether.
Above method step 1. described in solvent be water-soluble solvent such as dehydrated alcohol, propyl alcohol, acetone.
Above method step 2. described in emulsifier be Tween-40；Tween-60；Tween-80；Tween-85；Disproportionation pine Fragrant acid sodium；Heterogeneous ten alcohol polyoxyethylene ether；Isomery undecyl alcohol polyoxyethylene ether；Isomerous tridecanol polyoxyethylene ether；Alkyl phenol is poly- Ethylene oxide ether；Propylene glycol block ether；Polypropylene glycol；Dialkyl benzene sulfonic acids sodium；Sodium alklyarylsulfonate；Dodecyl benzene sulfonic acid Sodium；Octyl phenol polyoxyethylene ether；Double, tributyl phenol polyoxyethylene ether；Alkyl phenol polyoxyethylene ether polyethenoxy ether；Two, three benzyl Base phenol polyethenoxy ether；Coconut oleyl alcohol；Different tridecanol polyoxyethylene ether；Phenethyl phenol polyethenoxy ether；Polyoxyethylene oleic acid ester； Polyoxyethylene stearic acid ester；Polyoxylethylene abietate；Castor oil polyoxyethylene ether；Two polyglycereol and aliphatic ester；Diglycerol Polypropylene glycol ether；Glycerin polyoxyethylene ether polyoxypropylene ether fatty acid ester；Nekal；Sodium diisopropylnaphthalene sulfonate； Sodium metnylene bis-naphthalene sulfonate；Petroleum sodium sulfonate；Alkane sodium olefin sulfonate；Hydroxy alkyl sulfonic acid sodium；Dialkyl succinylsuccinate ester sodium sulfonate；Alkane Base phenol polyethenoxy ether succinate sulfonate；Benzyl naphthalene sulfonic acid-formaldehyde condensation product；Naphthalenesulfonic acid-formaldehyde condensate；Dibutyl naphthalene Sodium sulfonate formaldehyde condensation products；Methyl naphthalene sulfonate formaldehyde condensate；Sulfated castor oil；Turkey red oil；Aliphatic alcohol sulfate； Spermaceti alcohol radical sodium sulphate；Secondary alcohol groups sodium sulphate.
2. the dispersing agent is lead naphthenate to above method step；Sodium pyrophosphate；Sodium tartrate；Sodium orthophosphate；Sub- oil Sour sodium；Tannic acid；Calcium chloride；Strontium chloride；Sodium Polyacrylate；More sodium metaphosphates；Hexenyl bis-stearamides；Stearic acid list glycerol Ester；Glyceryl tristearate；Atoleine；Barium stearate；Magnesium stearate；Copper stearate；Polyethylene glycol.
4. the thickener is sodium carboxymethyl starch to above method step；Xanthan gum；Gelatin；Sodium alginate；Cluster bean Glue；Cycloheptaamylose；Carboxymethyl cellulose；Hydroxyethyl cellulose；Sodium Polyacrylate；Polyacrylamide；Polyethylene glycol oxide, card wave Resin, polyacrylic acid and Polyacrylate Emulsion；Hydroxypropyl methyl cellulose；Sodium carboxymethylcellulose.
Compared with prior art the invention has the advantages that
1, what the present invention was initiative is added the characteristics of water will be slow precipitation using antioxidant solid in organic solvent, in room Can be prepared by high-melting-point under temperature can be dispersed aqueous antioxygen agent emulsion, easy to operate, energy-efficient, solve industrial antioxidant cream Consume energy in liquid preparation process big, cumbersome the disadvantages of.
2, the present invention is used using the surfactant of non-toxic efficient and a certain amount of dispersant, using mechanical stirring Dispersed.Raw material proportioning is flexible and changeable, and the proportion of primary antioxidant and auxiliary anti-oxidant can be adjusted according to polymer raw material formula, with It is optimal antioxidant effect.It due to preparation method uniqueness, matches anyway, it is preferable to be made particle diameter distribution, and viscosity is suitable The aqueous antioxygen agent emulsion of middle stable homogeneous.
3, the present invention has good particle diameter distribution, and dispersion effect is good, and finished product is without further purification operations such as filterings It can be used directly.And antioxygenic effect is high, good using response type antioxidant and ABS latex polymerization compatibility, to product without Other adverse effects, anti-extraction, anti-tarnishing ability and thermal decomposition ability are outstanding, and can improve products machinery intensity.
4, the equal asepsis environment-protecting of raw material selected by the present invention, it is raw materials used to be recognized by U.S. Food and Drug Administration (FDA) Card, meets green chemical concept.
Specific embodiment
All antioxidant raw materials of the present invention are commercial product, and rank is industrial top grade: antioxidant CPL appearance is white powder End, 1135 appearances are colourless or weak yellow liquid.
Embodiment 1
100g dehydrated alcohol is added in 500mL beaker, is separately added into 50g primary antioxidant paracresol and dicyclopentadiene fourth Silicone emulsion is added dropwise in glycosylation reaction product and 17g auxiliary anti-oxidant β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isoctanol ester Defoaming agent 0.5g, is completely dissolved antioxidant by 400 revs/min of magnetic agitation.Separately take 200mL beaker by 3g Tween-80 emulsifier with 0.5g polyethylene glycol dispersing agent is dissolved in 50g deionized water.It, will be above-mentioned after antioxidant is dissolved completely in ethanol solution 500mL beaker transposition emulsification pretreatment under the conditions of 5000 revs/min of homogenizer, while will be dissolved with the aqueous solution of emulsifier and dispersing agent It is added drop-wise in the ethanol solution, in being added dropwise in 3min, adjustment homogenizer shear rate is that 12000 revs/min of high speeds are cut 35min is cut, is cooled to room temperature, sodium carboxymethyl cellulose thickener 0.2g is added, 5min is stood and obtains stable antioxygen agent emulsion 220g。
Through Haake viscosity apparatus, Ke Nike pH detector test: Malvern partial size tester uses and prepares high-melting-point at room temperature The method of aqueous antioxidant prepares aqueous antioxidant emulsion viscosity 330cps, and 1.1 μm of average grain diameter, pH=9.27.
Embodiment 2
300g dehydrated alcohol is added in 1000mL beaker, is separately added into 140g primary antioxidant paracresol and dicyclopentadiene Polyoxy third is added dropwise in butylation product and 40g auxiliary anti-oxidant β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isoctanol ester Alkene polyoxyethylene glycerol ether defoaming agent 1.2g, 600 revs/min of magnetic agitation.Separately take 200mL beaker by 5g Tween-80 and 1.5g points Powder lead naphthenate is dissolved in 100g deionized water, is dissolved completely in ethanol solution to antioxidant, by beaker transposition In 7000 revs/min of emulsification pretreatments of homogenizer, while dehydrated alcohol will be slowly dropped to dissolved with the aqueous solution of emulsifier and dispersing agent In solution.In being added dropwise in 5min, adjustment homogenizer shear rate is 17000 revs/min of high speed shear 40min, is cooled to room Thickener cycloheptaamylose 1.5g is added in temperature, stands 7min and obtains stable antioxygen agent emulsion 587g.
Through Haake viscosity apparatus, Ke Nike pH detector test: Malvern partial size tester uses and prepares high-melting-point at room temperature The method of aqueous antioxidant prepares aqueous antioxidant emulsion viscosity 370cps, and 1.4 μm of average grain diameter, pH=10.17.
Embodiment 3
300g dehydrated alcohol is added in 1000mL beaker, is separately added into 140g primary antioxidant paracresol and double polycyclopentadithio.henes The double isomerous tridecanol esters of the butylation product and 40g auxiliary anti-oxidant thio-2 acid of alkene, are added dropwise dimethyl silicone polymer and disappear Infusion 0.9g, 600 revs/min of magnetic agitation.Separately take 200mL beaker by 3.5g neopelex and 1.3g dispersing agent 16 Alcohol is dissolved in 100g deionized water, is dissolved completely in ethanol solution to antioxidant, by beaker transposition in homogenizer 6000 revs/min of emulsification pretreatments, while will be slowly dropped in ethanol solution dissolved with the aqueous solution of emulsifier and dispersing agent.In It is added dropwise in 5min, adjustment homogenizer shear rate is 17000 revs/min of high speed shear 45min, is cooled to room temperature, and is added and increases Thick agent carboxymethyl sodium starch 1.2g stands 8min and obtains stable antioxygen agent emulsion 585g.
Through Haake viscosity apparatus, Ke Nike pH detector test: Malvern partial size tester uses and prepares high-melting-point at room temperature The method of aqueous antioxidant prepares aqueous antioxidant emulsion viscosity 330cps, and 1.7 μm of average grain diameter, pH=10.24.
Embodiment 4
300g dehydrated alcohol is added in 1000mL beaker, is separately added into 60g primary antioxidant paracresol and dicyclopentadiene The butylation product and 25g auxiliary anti-oxidant three of butylation product, 70g primary antioxidant paracresol and double focusing cyclopentadiene (nonyl is for phenyl) phosphite ester, be added dropwise polyoxyethylene polyoxy Propanolamine ether defoaming agent 0.75g, 500 revs/min of magnetic agitation.Separately 200mL beaker is taken to be dissolved in 3.5g Arlacel-80 with 0.9g dispersing agent sodium pyrophosphate complete to antioxidant in 100g deionized water It is dissolved in ethanol solution, by beaker transposition in 6000 revs/min of emulsification pretreatments of homogenizer, while dissolved with emulsifier and will divide The aqueous solution of powder is slowly dropped in ethanol solution.It is added dropwise in 5min, adjustment homogenizer shear rate is 14000 Rev/min high speed shear 50min, is cooled to room temperature, and thickener Sodium Polyacrylate 0.5g is added, stand 10min obtain it is stable anti- Oxygen agent emulsion 560g.
Through Haake viscosity apparatus, Ke Nike pH detector test: Malvern partial size tester uses and prepares high-melting-point at room temperature The method of aqueous antioxidant prepares aqueous antioxidant emulsion viscosity 330cps, and 1.1 μm of average grain diameter, pH=9.25.
Embodiment 5
100g propyl alcohol is added in 500mL beaker, is separately added into 45g primary antioxidant cresols and dicyclopentadiene butylation is anti- Product and the double octadecyl ester pentaerythritol esters of 15g auxiliary anti-oxidant diphosphorous acid are answered, polypropylene glycerol aether defoaming agent 0.3g, magnetic is added dropwise Power stirs 350 revs/min.Separately take 200mL beaker that 2.5g disproportionated rosin acid sodium and 0.5g dispersing agent linoleic acid sodium are dissolved in 50g In ionized water, it is heated to 70 DEG C under mechanical stirring.Be dissolved completely in ethanol solution to antioxidant, by beaker transposition in 4000 revs/min of emulsification pretreatments of homogenizer, at the same it is molten by dehydrated alcohol is slowly dropped to dissolved with the aqueous solution of emulsifier and dispersing agent In liquid.In being added dropwise in 3min, adjustment homogenizer shear rate is 12000 revs/min of high speed shear 30min, is cooled to room temperature, Thickener sodium alginate 1.5g is added, stands 5min and obtains stable antioxygen agent emulsion 213g.
Through Haake viscosity apparatus, Ke Nike pH detector test: Malvern partial size tester uses and prepares high-melting-point at room temperature The method of aqueous antioxidant prepares aqueous antioxidant emulsion viscosity 370cps, and 1.1 μm of average grain diameter, pH=9.73.

Claims (7)

1. the method that one kind prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, its step are as follows:
45 ~ 140g primary antioxidant, 15 ~ 40g auxiliary anti-oxidant and 0.3 ~ 1.2g defoaming agent are added in 100 ~ 300g solvent, in magnetic Raw material is completely dissolved under power stirring；
2.5 ~ 5g emulsifier and 0.5 ~ 1.5g dispersing agent are dissolved in 50 ~ 100g deionized water；
1. solution that step is obtained 10 ~ 20s of emulsification pretreatment under the conditions of 3000~9000 revs/min, during emulsification pretreatment 2. solution that step obtains is slowly added dropwise thereto, primary antioxidant is precipitated slowly from solvent, obtains aqueous antioxygen agent emulsion；
3. aqueous antioxygen agent emulsion that step is obtained shears 10~120min under the conditions of 9000~23000 revs/min, cooling 0.2 ~ 1.5g thickener is added after to room temperature, stands 5 ~ 20min and obtains the aqueous antioxygen agent emulsion of high-melting-point.
2. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: main Antioxidant is paracresol and dicyclopentadiene butylation product, bis- (2,4- DI-tert-butylphenol compounds) pentaerythrite diphosphorous acids Ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), paracresol and double focusing cyclopentadiene butylation product in One or more, auxiliary anti-oxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isoctanol ester, three (nonyl is for benzene Base) phosphite ester, the double isomerous tridecanol ester of thio-2 acid, one of double octadecyl ester pentaerythritol esters of diphosphorous acid or several Kind.
3. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: disappear Infusion is silicone emulsion defoaming agent, natural oil defoaming agent, high-carbon alcohol defoaming agent, polyoxyethylene polyoxypropylene pentaerythrite Ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, one or more of polyoxyethylene polyoxypropylene glycerin ether.
4. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: molten Agent is one or more of dehydrated alcohol, propyl alcohol, acetone.
5. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: cream Agent is Tween-40, Tween-60, Tween-80, Tween-85, disproportionated rosin acid sodium, heterogeneous ten alcohol polyoxyethylene ether, isomery ten One alcohol polyoxyethylene ether, isomerous tridecanol polyoxyethylene ether, propylene glycol block ether, polypropylene glycol, dialkyl benzene sulfonic acids sodium, 12 Sodium alkyl benzene sulfonate, octyl phenol polyoxyethylene ether, double, tributyl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether polyoxypropylene Ether, two, tribenzyl phenol polyethenoxy ether, coconut oleyl alcohol, phenethyl phenol polyethenoxy ether, polyoxyethylene oleic acid ester, stearic acid are poly- Ethylene oxide ester, polyoxylethylene abietate, castor oil polyoxyethylene ether, two polyglycereol and aliphatic ester, diglycerol polypropylene glycol Ether, glycerin polyoxyethylene ether polyoxypropylene ether fatty acid ester, nekal, sodium diisopropylnaphthalene sulfonate, methylene two Sodium naphthalene sulfonate, petroleum sodium sulfonate, alkane sodium olefin sulfonate, hydroxy alkyl sulfonic acid sodium, dialkyl succinylsuccinate ester sodium sulfonate, alkyl phenol polyoxy Vinethene succinate sulfonate, benzyl naphthalene sulfonic acid-formaldehyde condensation product, naphthalenesulfonic acid-formaldehyde condensate, nekal first Aldehyde condensate, methyl naphthalene sulfonate formaldehyde condensate, sulfated castor oil, turkey red oil, aliphatic alcohol sulfate, spermaceti alcohol radical Sodium sulphate, one or more of secondary alcohol groups sodium sulphate.
6. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: point Powder is lead naphthenate, sodium pyrophosphate, sodium tartrate, sodium orthophosphate, linoleic acid sodium, tannic acid, calcium chloride, strontium chloride, poly- third Olefin(e) acid sodium, more sodium metaphosphates, hexenyl bis-stearamides, glyceryl monostearate, glyceryl tristearate, atoleine, firmly Resin acid barium, magnesium stearate, copper stearate, the one or more of polyethylene glycol.
7. the method that one kind as described in claim 1 prepares the aqueous antioxygen agent emulsion of high-melting-point at room temperature, it is characterised in that: increase Thick dose is sodium carboxymethyl starch, xanthan gum, gelatin, sodium alginate, guar gum, cycloheptaamylose, carboxymethyl cellulose, hydroxyl second Base cellulose, Sodium Polyacrylate, polyacrylamide, polyethylene glycol oxide, carbomer, polyacrylic acid and polyacrylate copolymerization cream Liquid, hydroxypropyl methyl cellulose, one or more of sodium carboxymethylcellulose.
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