CN107674154B - Preparation method of self-emulsifying wax - Google Patents
Preparation method of self-emulsifying wax Download PDFInfo
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- CN107674154B CN107674154B CN201711094974.0A CN201711094974A CN107674154B CN 107674154 B CN107674154 B CN 107674154B CN 201711094974 A CN201711094974 A CN 201711094974A CN 107674154 B CN107674154 B CN 107674154B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention provides a preparation method of self-emulsifying wax. 50-95 parts of wax, 0-20 parts of monomer I, 0-15 parts of monomer II, 0-15 parts of monomer III and 0.1-3 parts of initiator. The method adopts a bulk graft polymerization method, does not add any organic solvent, and has green and environment-friendly process; the self-emulsifying wax prepared by the invention exists in a solid form before use, can be stably stored at room temperature, and is convenient to store and transport; when the wax emulsion is used, an emulsifier is not required to be added, the self-emulsifying wax is only required to be melted and heated and stirred to obtain the wax emulsion, and the wax emulsion has the advantages of low preparation cost, simple process, convenience and easiness in operation.
Description
Technical Field
The invention belongs to the technical field of organic chemical materials, and relates to a preparation method of self-emulsifying wax.
Background
The wax emulsion is a liquid which can flow uniformly and has a stable state, does not need heating, melting or dissolving when in use, has uniform film formation and good coverage, is easy to be used with aqueous solution or emulsion of other substances in a composite way, has the advantages of safety, high efficiency, economy, convenience and the like, and is widely applied to the fields of leather, textile, artificial boards, papermaking, agriculture, building industry, petroleum, coating, printing ink, agriculture and the like.
Wax is an oily substance with strong cohesive force, is solid at normal temperature, is insoluble in water and difficult to emulsify, and can be dispersed into emulsion by reducing the surface tension by means of the directional adsorption of an emulsifier under the action of mechanical stirring. Although wax emulsions can be produced using this process, the process also has a number of disadvantages. Firstly, when the process is used for preparing wax emulsion, a large amount of emulsifier (the amount is 80-90% of the weight of the wax) is required to be added to emulsify the wax into emulsion. The use of a large amount of emulsifier leads to higher cost of the product due to higher price of the emulsifier; secondly, the wax emulsion prepared by the process has larger particle size and poorer stability, is not beneficial to storage, is easy to generate layering or precipitation phenomenon after being placed for a long time, and seriously influences the effect; thirdly, the effective solid content of the wax emulsion is usually less than 50%, that is, more than 50% of the wax emulsion is water, which makes the transportation extremely inconvenient, and more importantly, the transportation cost is greatly increased. The above disadvantages severely limit the range of applications of wax emulsions.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a solid self-emulsifying wax which does not need to be added with an emulsifier, is easy to store for a long time and is easy to transport, and a preparation method thereof.
The preparation method of the self-emulsifying wax provided by the invention comprises the following steps and conditions:
(1) raw materials:
the wax is any one of paraffin wax, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, oxidized paraffin wax, oxidized polyethylene wax, oxidized polypropylene wax and oxidized Fischer-Tropsch wax, the monomer I is maleic anhydride, maleic acid, itaconic anhydride, acrylic acid or methacrylic acid, the monomer II is any one or two of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, styrene, α -methyl styrene and acrylonitrile, the monomer III is any one or two of acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, the base is any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, copper hydroxide, ammonia water, diethylamine, triethylamine, triethanolamine and diethanolamine, the water is deionized water, the initiator is cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, dibenzoyl peroxide, dicyclohexyl peroxide, tert-butyl peroxide benzoate, tert-butyl peroxide, dimethylazodicarbonyl peroxide, dimethylazodicarbonamide, azodicarbonyl peroxide, azodicarbonyl, dimethyl peroxydicarbonate, azodicarbonyl, dimethyle or azodicarbonyl isobutyronitrile, azodicarbonyl, azo;
(2) the weight parts of the materials are as follows:
50-95 parts of wax, preferably 75-90 parts; 0-20 parts of monomer I, preferably 5-15 parts; 0-15 parts of monomer II, preferably 5-10 parts; 0-15 parts of monomer III, preferably 5-10 parts; 0.1-3 parts of initiator, preferably 0.5-2 parts;
(3) adding wax, a monomer I, a monomer II and a monomer III into a reaction kettle according to a ratio, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 100-200 ℃, preferably 120-160 ℃, adding an initiator after the wax is fully melted, and reacting for 1-8 hours at a constant temperature, preferably 3-6 hours; adding a prepared alkali aqueous solution into a reaction kettle, continuously reacting for 0.1-1 h, preferably 0.3-0.6 h, and removing water in a reactant in vacuum after the reaction is finished to obtain self-emulsifying wax;
the mass concentration of the alkaline water solution is 50%, the water is deionized water, and the molar ratio of the alkali to the monomer I is 8: 1-1: 3, preferably 4: 1-1: 2.
self-emulsifying property test of self-emulsifying wax: melting self-emulsifying wax in a kettle, then adding hot water for stirring, wherein the emulsifying temperature is 105-150 ℃, the stirring speed is 2000-8000 r/min, and continuously stirring for 15-60 min to obtain white wax emulsion with the solid content of 5-45% and the particle size of 500-5000 nm.
Has the advantages that: the invention provides a preparation method of self-emulsifying wax. The method adopts a bulk graft polymerization method, does not add any organic solvent, and has green and environment-friendly process; the self-emulsifying wax prepared by the invention exists in a solid form before use, can be stably stored at room temperature, and is convenient to store and transport; when the wax emulsion is used, an emulsifier is not required to be added, the self-emulsifying wax is only required to be melted and heated and stirred to obtain the wax emulsion, and the wax emulsion has the advantages of low preparation cost, simple process, convenience and easiness in operation.
Detailed Description
Example 1
Adding 85 parts of polyethylene wax, 15 parts of maleic anhydride, 5 parts of styrene and 5 parts of acrylamide into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 140 ℃, adding 0.5 part of cumene hydroperoxide after wax is fully melted, reacting for 3 hours at constant temperature, adding a prepared sodium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.3 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsified polyethylene wax.
The mass concentration of the sodium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the sodium hydroxide to the maleic anhydride is 2: 1.
and (3) testing the emulsifying property of the self-emulsifying polyethylene wax: melting self-emulsified polyethylene wax in a kettle, adding hot water, stirring, and stirring at 140 ℃ at 4000r/min for 30min to obtain white slightly blue wax emulsion with solid content of 40% and particle size of 500 nm-1000 nm, wherein the white slightly blue wax emulsion can be stably stored at room temperature.
Example 2
Adding 90 parts of Fischer-Tropsch wax, 5 parts of itaconic acid, 6 parts of methyl acrylate and 6 parts of methacrylamide into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 135 ℃, adding 1 part of di-tert-butyl peroxide after the wax is fully melted, reacting for 3.5 hours at constant temperature, adding a prepared potassium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in reactants in vacuum after the reaction is finished to obtain the self-emulsifying Fischer-Tropsch wax.
The mass concentration of the potassium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the potassium hydroxide to the itaconic acid is 1: 1.
testing the emulsifying property of the self-emulsifying Fischer-Tropsch wax: melting self-emulsifying Fischer-Tropsch wax in a kettle, adding hot water, stirring, and stirring at 130 ℃ for 35min at 3000r/min to obtain white light blue wax emulsion with solid content of 35% and particle size of 1000-1200 nm, wherein the white light blue wax emulsion can be stably stored at room temperature.
Example 3
Adding 80 parts of polypropylene wax, 10 parts of methacrylic acid, 7 parts of propylstyrene and 10 parts of hydroxyethyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 130 ℃, adding 1.2 parts of diisopropyl peroxydicarbonate after the wax is fully melted, reacting for 4 hours at constant temperature, adding a prepared calcium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.5 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying polypropylene wax.
The mass concentration of the calcium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the calcium hydroxide to the methacrylic acid is 1: 2.
emulsification performance testing of self-emulsifying polypropylene waxes: melting self-emulsifying polypropylene wax in a kettle, adding hot water, stirring at 110 ℃ for 25min at 2000r/min to obtain white wax emulsion with solid content of 30% and particle size of 3650-4000 nm, and stabilizing at room temperature for 30 days.
Example 4
Adding 95 parts of paraffin, 12 parts of itaconic anhydride, 8 parts of ethyl acrylate and 5 parts of hydroxypropyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 100 ℃, adding 1.4 parts of dicumyl peroxide after the paraffin is fully melted, reacting for 4.5 hours at constant temperature, adding a prepared triethanolamine aqueous solution into the reaction kettle, continuing to react for 0.6 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying paraffin.
The triethanolamine aqueous solution has a mass concentration of 50%, water is deionized water, and the molar ratio of triethanolamine to itaconic anhydride is 3: 2.
testing the emulsifying property of the self-emulsifying paraffin: melting the self-emulsified paraffin in a kettle, adding hot water, stirring at 120 ℃ at 7000r/min for 15min to obtain white slightly blue wax emulsion with solid content of 25% and particle size of 1200 nm-1700 nm, and storing at room temperature for a long time.
Example 5
Adding 75 parts of oxidized polyethylene wax, 13 parts of acrylic acid, 10 parts of ethyl acrylate and 8 parts of hydroxypropyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 125 ℃, adding 1.6 parts of azodiisobutyronitrile after the wax is fully melted, reacting for 5 hours at constant temperature, adding a prepared aqueous solution of diethanolamine into the reaction kettle, continuing to react for 0.3 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsified oxidized polyethylene wax.
The mass concentration of the aqueous solution of the diethanolamine is 50%, the water is deionized water, and the molar ratio of the diethanolamine to the acrylic acid is 3: 1.
and (3) testing the emulsifying property of the self-emulsifying oxidized polyethylene wax: melting the self-emulsified oxidized polyethylene wax in a kettle, adding hot water, stirring, and stirring at 125 ℃ for 45min at 5000r/min to obtain white slightly blue wax emulsion with the solid content of 35% and the particle size of 700-1500 nm, wherein the white slightly blue wax emulsion can be stored at room temperature for a long time.
Example 6
Adding 75 parts of oxidized paraffin, 14 parts of maleic anhydride, 9 parts of α -methyl styrene and 8 parts of hydroxyethyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 105 ℃, adding 1.8 parts of azodiisoheptonitrile after the wax is fully melted, reacting for 6 hours at constant temperature, adding a prepared diethylamine aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized paraffin.
The mass concentration of the diethylamine aqueous solution is 50%, the water is deionized water, and the molar ratio of the diethylamine to the maleic anhydride is 4: 1.
testing the emulsifying property of the self-emulsifying oxidized paraffin: melting the self-emulsifying oxidized paraffin in a kettle, adding hot water, stirring, and stirring at 6000r/min at 100 ℃ for 60min to obtain white wax emulsion with solid content of 15% and particle size of 2500 nm-3000 nm, wherein the white wax emulsion can be stabilized at room temperature for 120 days.
Example 7
Adding 85 parts of oxidized polypropylene wax, 11 parts of maleic acid, 8 parts of glycidyl methacrylate and 8 parts of a mixture of methacrylamide and hydroxyethyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 120 ℃, adding 2 parts of tert-butyl peroxypivalate after the wax is fully melted, reacting for 5.5 hours at constant temperature, adding a prepared triethylamine aqueous solution into the reaction kettle, continuing to react for 0.5 hour, and removing water in reactants in vacuum after the reaction is finished to obtain the self-emulsifying oxidized polypropylene wax.
The mass concentration of the triethylamine aqueous solution is 50%, water is deionized water, and the molar ratio of triethylamine to maleic acid is 2: 1.
testing the emulsifying property of the self-emulsifying oxidized paraffin: melting the self-emulsifying oxidized paraffin in a kettle, adding hot water, stirring, and stirring at 115 ℃ at 8000r/min for 30min to obtain white wax emulsion with solid content of 45% and particle size of 3000-3300 nm, wherein the white wax emulsion can be stabilized at room temperature for 80 days.
Example 8
Adding 80 parts of oxidized polyethylene wax, 6 parts of itaconic anhydride, 9 parts of acrylonitrile and 7 parts of acrylamide into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 140 ℃, adding 0.7 part of methyl ethyl ketone peroxide after the wax is fully melted, reacting for 3 hours at constant temperature, adding a prepared diethylamine aqueous solution into the reaction kettle, continuing to react for 0.6 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsified oxidized polyethylene wax.
The mass concentration of the ammonia water solution is 50%, the water is deionized water, and the molar ratio of the ammonia water to the itaconic anhydride is 3: 1.
and (3) testing the emulsifying property of the self-emulsifying oxidized polyethylene wax: melting the self-emulsified oxidized polyethylene wax in a kettle, adding hot water, stirring, and stirring at 5500r/min at 145 ℃ for 25min to obtain a white wax emulsion with the solid content of 15 and the particle size of 4000-4500 nm, wherein the white wax emulsion can be stabilized at room temperature for 10 days.
Example 9
Adding 75 parts of oxidized Fischer-Tropsch wax, 8 parts of maleic anhydride, 5 parts of methyl methacrylate and 8 parts of a mixture of acrylamide and hydroxypropyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 150 ℃, adding 0.7 part of cyclohexanone peroxide after the wax is fully melted, reacting for 5 hours at constant temperature, adding a prepared sodium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.3 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized Fischer-Tropsch wax.
The mass concentration of the sodium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of sodium hydroxide to maleic anhydride is 3: 2.
and (3) testing the emulsifying property of the self-emulsifying oxidized polyethylene wax: melting the self-emulsified oxidized polyethylene wax in a kettle, adding hot water, stirring, and stirring at 150 ℃ for 20min at 3500r/min to obtain white wax emulsion with solid content of 5 and particle size of 4300-4500 nm, wherein the white wax emulsion can be stabilized at room temperature for 10 days.
Example 10
Adding 90 parts of oxidized polypropylene wax, 7 parts of maleic acid, 6 parts of hexyl acrylate and 8 parts of hydroxyethyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 120 ℃, adding 0.9 part of dibenzoyl peroxide after the wax is fully melted, reacting for 3.5 hours at constant temperature, adding a prepared diethylamine aqueous solution into the reaction kettle, continuing to react for 0.5 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized polypropylene wax.
The mass concentration of the diethylamine aqueous solution is 50%, the water is deionized water, and the molar ratio of the diethylamine to the maleic acid is 1: 1.
emulsification Performance testing of self-emulsifying oxidized Polypropylene wax: melting the self-emulsifying oxidized polypropylene wax in a kettle, adding hot water, stirring, and stirring at the temperature of 130 ℃ and 4500r/min for 35min to obtain white wax emulsion with the solid content of 35% and the particle size of 700-1000 nm, wherein the white wax emulsion can be stably stored at room temperature.
Example 11
Adding 85 parts of oxidized polypropylene wax, 9 parts of methacrylic acid, 6 parts of butyl acrylate and 8 parts of acrylic acid into a reaction kettle of a mixture of hydroxypropyl methacrylate and hydroxyethyl acrylate according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 155 ℃, adding 1 part of benzoyl peroxide after the wax is fully melted, reacting for 5 hours at constant temperature, adding a pre-mixed potassium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.6 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized polypropylene wax.
The mass concentration of the potassium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of potassium hydroxide to methacrylic acid is 2: 3.
emulsification Performance testing of self-emulsifying oxidized Polypropylene wax: melting the self-emulsifying oxidized polypropylene wax in a kettle, adding hot water, stirring, and stirring at the temperature of 125 ℃ for 40min at 6500r/min to obtain white wax emulsion with the solid content of 10% and the particle size of 1300-1500 nm, wherein the white wax emulsion can be stably stored at room temperature.
Example 12
Adding 75 parts of oxidized polyethylene wax, 14 parts of acrylic acid, 7 parts of a mixture of methyl acrylate and ethyl acrylate and 8 parts of hydroxypropyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 130 ℃, adding 1.1 parts of azodicyclo cyano valeric acid after the wax is fully melted, reacting for 6 hours at constant temperature, adding a prepared copper hydroxide aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsified oxidized polyethylene wax.
The mass concentration of the copper hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the copper hydroxide to the acrylic acid is 1: 1.
and (3) testing the emulsifying property of the self-emulsifying oxidized polyethylene wax: melting the self-emulsified oxidized polyethylene wax in a kettle, adding hot water, stirring, and stirring at the temperature of 145 ℃ for 40min at 6500r/min to obtain white wax emulsion with the solid content of 10% and the particle size of 3500-3800 nm, wherein the white wax emulsion can be stored at room temperature for 60 days.
Example 13
Adding 75 parts of oxidized Fischer-Tropsch wax, 15 parts of itaconic acid, 7 parts of glycidyl methacrylate and 8 parts of the oxidized Fischer-Tropsch wax into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 150 ℃, adding 1.3 parts of peroxydicarbonate after the wax is fully melted, reacting for 4.5 hours at constant temperature, adding a prepared diethylamine aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized Fischer-Tropsch wax.
The mass concentration of the diethylamine aqueous solution is 50%, the water is deionized water, and the molar ratio of the diethylamine to the maleic anhydride is 2: 1.
testing the emulsifying property of the self-emulsifying oxidized Fischer-Tropsch wax: melting the self-emulsifying oxidized Fischer-Tropsch wax in a kettle, adding hot water, stirring at 120 ℃ for 35min at 7500r/min to obtain white wax emulsion with the solid content of 25% and the particle size of 2500-2800 nm, and storing at room temperature for 180 days.
Example 14
Adding 90 parts of polypropylene wax, 14 parts of maleic anhydride, 6 parts of butyl methacrylate and 7 parts of hydroxypropyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 120 ℃, adding 1.5 parts of tert-butyl peroxybenzoate after the wax is fully melted, reacting for 3 hours at constant temperature, adding a prepared calcium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.6 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying polypropylene wax.
The mass concentration of the calcium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the calcium hydroxide to the maleic anhydride is 1: 1.
emulsification performance testing of self-emulsifying polypropylene waxes: melting self-emulsifying polypropylene wax in a kettle, adding hot water, stirring, and stirring at 140 ℃ for 30min at 3500r/min to obtain white slightly blue wax emulsion with the solid content of 35% and the particle size of 600-800 nm, wherein the white slightly blue wax emulsion can be stably stored at room temperature.
Example 15
Adding 75 parts of oxidized paraffin, 10 parts of methacrylic acid, 9 parts of styrene and 8 parts of hydroxyethyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 110 ℃, adding 1.7 parts of azobutyronitrile formamide after the wax is fully melted, reacting for 4.5 hours at constant temperature, adding a prepared sodium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized paraffin.
The mass concentration of the sodium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the sodium hydroxide to the methacrylic acid is 3: 1.
self-emulsifying property test of the self-emulsifying oxidized paraffin: melting the self-emulsifying oxidized paraffin in a kettle, adding hot water, stirring, and stirring at 4000r/min at 125 ℃ for 45min to obtain white slightly blue wax emulsion with solid content of 40% and particle size of 900-1100 nm, wherein the white slightly blue wax emulsion can be stably stored at room temperature.
Example 16
Adding 85 parts of polypropylene wax, 15 parts of itaconic acid, 9 parts of methyl acrylate and 8 parts of methacrylamide into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 155 ℃, adding 1.9 parts of azodicyclohexyl carbonitrile after the wax is fully melted, reacting for 3.5 hours at constant temperature, adding a prepared aqueous solution of diethanolamine into the reaction kettle, continuing to react for 0.6 hour, and removing water in reactants in vacuum after the reaction is finished to obtain the self-emulsifying polypropylene wax.
The mass concentration of the aqueous solution of the diethanolamine is 50%, the water is deionized water, and the molar ratio of the diethanolamine to the maleic anhydride is 4: 1.
self-emulsifying property test of self-emulsifying polypropylene wax: melting self-emulsifying polypropylene wax in a kettle, adding hot water, stirring at 120 ℃ at 3000r/min for 15min to obtain white wax emulsion with solid content of 15% and particle size of 4000-4500 m, and storing at room temperature for 5 days.
Example 17
Adding 80 parts of polyethylene wax, 12 parts of maleic acid, 8 parts of α -methyl styrene and 8 parts of methacrylamide into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 135 ℃, adding 2 parts of azodiisobutyramidine hydrochloride after the wax is fully melted, reacting for 4 hours at constant temperature, adding a prepared aqueous solution of ammonia water into the reaction kettle, continuing to react for 0.5 hour, and removing water in reactants in vacuum after the reaction is finished to obtain the self-emulsified polyethylene wax.
The mass concentration of the ammonia water solution is 50%, the water is deionized water, and the molar ratio of the ammonia water to the maleic acid is 2: 3.
self-emulsifying property test of the self-emulsifying polyethylene wax: melting self-emulsified polyethylene wax in a kettle, adding hot water, stirring at 150 ℃ at 7000r/min for 25min to obtain white bluish wax emulsion with solid content of 25% and particle size of 2300-2400 nm, and stably storing at room temperature.
Example 18
Adding 75 parts of oxidized polyethylene wax, 13 parts of methacrylic acid, 9 parts of glycidyl methacrylate and 8 parts of hydroxyethyl methacrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 135 ℃, adding 0.5 part of dimethyl azodiisobutyrate after the wax is fully melted, reacting for 5.5 hours at constant temperature, adding a pre-compounded copper hydroxide aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized polyethylene wax.
The mass concentration of the copper hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of the copper hydroxide to the methacrylic acid is 2: 1.
and (3) testing the emulsifying property of the self-emulsifying oxidized polyethylene wax: melting the self-emulsified oxidized polyethylene wax in a kettle, adding hot water, stirring, and stirring at the temperature of 130 ℃ at 5000r/min for 35min to obtain a white bluish wax emulsion with the solid content of 30% and the particle size of 2400-2600 nm, wherein the white bluish wax emulsion can be stably stored at room temperature.
Example 19
Adding 85 parts of oxidized polypropylene wax, 14 parts of maleic acid, 9 parts of glycidyl methacrylate and 8 parts of acrylic acid into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 120 ℃, adding 2 parts of p-menthane hydroperoxide after the wax is fully melted, reacting for 6 hours at constant temperature, adding a pre-mixed diethylamine aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in a reactant in vacuum after the reaction is finished to obtain the self-emulsifying oxidized polypropylene wax.
The mass concentration of the aqueous solution of diethanolamine is 50%, the water is deionized water, and the molar ratio of diethylamine to maleic anhydride is 2: 3.
emulsification Performance testing of self-emulsifying oxidized Polypropylene wax: melting the self-emulsifying oxidized polypropylene wax in a kettle, adding hot water, stirring at 150 ℃ at 8000r/min for 20min to obtain white wax emulsion with solid content of 5% and particle size of 4000-4200 nm, and storing at room temperature for 10 days.
Example 20
Adding 75 parts of Fischer-Tropsch wax, 9 parts of maleic anhydride, 9 parts of glycidyl methacrylate and 8 parts of ethyl acrylate into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 160 ℃, adding 1.5 parts of azodiisovaleronitrile after the wax is fully melted, reacting for 3.5 hours at constant temperature, adding a pre-mixed potassium hydroxide aqueous solution into the reaction kettle, continuing to react for 0.4 hour, and removing water in reactants in vacuum after the reaction is finished to obtain the self-emulsifying Fischer-Tropsch wax.
The mass concentration of the potassium hydroxide aqueous solution is 50%, the water is deionized water, and the molar ratio of potassium hydroxide to maleic anhydride is 3: 1.
testing the emulsifying property of the self-emulsifying Fischer-Tropsch wax: melting self-emulsifying Fischer-Tropsch wax in a kettle, adding hot water, stirring at 135 ℃ at 4500r/min for 40min to obtain white wax emulsion with solid content of 15% and particle size of 2900-3100 nm, and storing at room temperature for 100 days.
Claims (5)
1. A preparation method of self-emulsifying wax is characterized by comprising the following steps and conditions:
(1) the raw materials are as follows:
the wax is any one of paraffin wax, polypropylene wax, Fischer-Tropsch wax, oxidized paraffin wax, oxidized polyethylene wax, oxidized polypropylene wax and oxidized Fischer-Tropsch wax, the monomer I is itaconic acid, itaconic anhydride, acrylic acid or methacrylic acid, the monomer II is any one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, styrene, α -methyl styrene and acrylonitrile, the monomer III is any one of acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, the base is any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, copper hydroxide, ammonia water, diethylamine, triethylamine, triethanolamine and diethanolamine, the water is deionized water, the initiator is cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, cyclohexanone peroxide or dimethyldicyclohexyl peroxide, dimethylazodicarbonamide, azodicarbonyl peroxide, azodicarbonyl chloride, azodicarbonyl isobutyronitrile, azodicarbonyl isobutyronitrile, azodicarbonyl, tert-butyl peroxyisobutyronitrile, tert-methyl ethyl ketone or dimethylene peroxide;
(2) the weight parts of the materials are as follows:
75-90 parts of wax, 5-15 parts of monomer I, 5-10 parts of monomer II, 5-10 parts of monomer III and 0.5-2 parts of initiator;
(3) adding wax, a monomer I, a monomer II and a monomer III into a reaction kettle according to the proportion, removing air in the reaction kettle by using nitrogen, heating the reaction kettle to 100-200 ℃, adding an initiator according to the proportion after the wax is fully melted, and reacting for 1-8 hours at constant temperature; adding a prepared alkali aqueous solution into a reaction kettle, continuously reacting for 0.1-1 h, and removing water in a reactant in vacuum after the reaction is finished to obtain self-emulsifying wax;
the mass concentration of the alkaline water solution is 50%, the water is deionized water, and the molar ratio of the alkali to the monomer I is 8: 1-1: 3.
2. the process of claim 1, wherein the molar ratio of base to monomer i is from 4: 1-1: 2.
3. the method according to claim 1, wherein the temperature of the reaction kettle is increased to 120-160 ℃ in step (3).
4. The method for preparing self-emulsifying wax according to claim 1, wherein the isothermal reaction of (3) is carried out for 3-6 hours.
5. The method according to claim 1, wherein the step (3) comprises adding a prepared aqueous alkali solution to the reaction vessel, and continuing the reaction for 0.3 to 0.6 hours.
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