CN113461970B - Organic silicon wax emulsion and preparation method thereof - Google Patents

Organic silicon wax emulsion and preparation method thereof Download PDF

Info

Publication number
CN113461970B
CN113461970B CN202110843169.3A CN202110843169A CN113461970B CN 113461970 B CN113461970 B CN 113461970B CN 202110843169 A CN202110843169 A CN 202110843169A CN 113461970 B CN113461970 B CN 113461970B
Authority
CN
China
Prior art keywords
organic silicon
heating
surfactant
silicon wax
wetting agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110843169.3A
Other languages
Chinese (zh)
Other versions
CN113461970A (en
Inventor
李庆
李遵陕
吴翠
刘继
邵月刚
汪宏冠
姜哲
余声
杨旭
喻琮惠
陆建明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Xinan Chemical Industrial Group Co Ltd
Original Assignee
Zhejiang Xinan Chemical Industrial Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Xinan Chemical Industrial Group Co Ltd filed Critical Zhejiang Xinan Chemical Industrial Group Co Ltd
Priority to CN202110843169.3A priority Critical patent/CN113461970B/en
Publication of CN113461970A publication Critical patent/CN113461970A/en
Application granted granted Critical
Publication of CN113461970B publication Critical patent/CN113461970B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention provides a preparation method of an organic silicon wax emulsion, which comprises the following steps: s1) heating and mixing the organic silicon wax, the surfactant, the wetting agent and water to obtain a mixed solution; s2) homogenizing the mixed solution under high pressure to obtain the organic silicon wax emulsion. Compared with the prior art, the silicone wax emulsion is prepared by a one-pot method, emulsification is performed without dripping water, the preparation method is simple, the process conditions are mild, the production efficiency of the emulsion is greatly improved, the energy consumption is greatly reduced, the production device is simple, and the industrial continuous production of the silicone wax emulsion is facilitated; meanwhile, the obtained organic silicon wax emulsion has the advantages of proper viscosity, strong stability and uniform texture, and can be widely applied to the fields of demolding of metal die-casting devices such as alloys and the like, cosmetics, textiles, coatings and the like.

Description

Organic silicon wax emulsion and preparation method thereof
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to an organic silicon wax emulsion and a preparation method thereof.
Background
At present, the preparation technology of the organic silicon wax emulsion basically continues the traditional mechanical emulsification method, and the O/W type organic silicon wax emulsion is prepared by using a reversal method.
Chinese patent publication No. CN107216458A discloses an organosilicon wax emulsion and a preparation method thereof, wherein the organosilicon wax emulsion comprises octadecyl organosilicon wax, and the octadecyl organosilicon wax is prepared by the following method: firstly, mixing D4H and hydrogen-terminated silicone oil, reacting under the action of a catalyst sulfonated cationic resin, carrying out reduced pressure distillation and filtering to obtain hydrogen-terminated silicone oil with a side chain containing active hydrogen, then mixing the hydrogen-terminated silicone oil with a side chain containing active hydrogen with 1-octadecene, carrying out hydrosilylation reaction for 6-10 h at 90-130 ℃ under the action of a catalyst chloroplatinic acid, and carrying out reduced pressure distillation after the reaction is finished to obtain the octadecyl organosilicon wax. Mixing octadecyl organosilicon wax and emulsifier, heating in water bath until completely dissolved to obtain oil phase; and (2) emulsifying by adopting a high-shear dispersion emulsifying machine, dripping water into an oil phase under the water bath stirring state of 75-85 ℃, and emulsifying for 90-180 s after dripping to obtain the octadecyl silicone wax emulsion.
Chinese patent publication No. CN110283336A discloses a preparation and application of silicone wax emulsion for moisturizing cosmetics, the preparation method comprising the following steps: respectively weighing the following components in percentage by mass as 35%: putting 65% of oil phase and water phase into two containers, heating to 65 ℃ simultaneously, maintaining the temperature, adding the water phase into the oil phase under the condition of stirring the oil phase until the water phase and the oil phase are completely mixed to prepare uniform and stable O/W type organosilicon wax emulsion, namely the organosilicon wax emulsion for the moisturizing cosmetic; the oil phase is organic silicon wax and a composite emulsifier, the composite emulsifier is cetearyl olive oil ester/sorbitan olive oil ester, and the mass of the composite emulsifier accounts for 20% of that of the oil phase; the aqueous phase is water. The finally prepared O/W type organic silicon wax emulsion has the particle size smaller than 1 mu m, and has small average particle size, narrow particle size distribution, high centrifugal stability and more uniform texture compared with common commercial organic silicon wax emulsion. But the organic silicon wax emulsion prepared by the method has low solid content, the silicon wax content is only 35 percent, and the traditional phase inversion emulsification method is also continued, so the production energy consumption is higher.
Chinese patent publication No. CN101260236A discloses a formulation and preparation method of silicone wax emulsion for polyurethane water-based release agent, heating the mixed component wax of silicone wax above the melting point of 10-30 ℃ in a stirred sealed pressure reaction kettle to form emulsion, keeping the temperature at the highest temperature for 10-15 min, and keeping stirring and cooling. The wax in the aforementioned silicone wax component is characterized by at least including oxidized polyethylene wax and/or synthetic ester wax and/or synthetic acid wax, the silicone is characterized by a silicone polymer with hydroxyl groups, nonylphenol polyoxyethylene ether (or polyoxyethylene tallow amide), and the mass ratio of KOH (or glacial acetic acid), water in the mixed component to silicone wax in the aforementioned silicone wax mixed component is 0.5: 1-20: 1. however, the silicone wax emulsion prepared by the method is actually a mixture of a silicone oil emulsion and an aliphatic hydrocarbon emulsion, and is not an emulsion of aliphatic hydrocarbon-based modified silicone oil, so that the excellent moisture retention and lubricity of the aliphatic hydrocarbon-based modified silicone oil emulsion cannot be achieved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a silicone wax emulsion and a preparation method thereof, wherein the preparation method is simple, and the obtained silicone wax emulsion is a micron-sized emulsion and has characteristics of appropriate viscosity, strong stability and uniform texture.
The invention provides a preparation method of an organic silicon wax emulsion, which comprises the following steps:
s1) heating and mixing the organic silicon wax, the surfactant, the wetting agent and water to obtain a mixed solution;
s2) homogenizing the mixed solution under high pressure to obtain an organic silicon wax emulsion;
the wetting agent is represented by the formula (I):
Figure BDA0003179608570000021
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group.
Preferably, R is-R' O (R "O)mH, wherein R 'and R' are respectively and independently selected from C2-C5 alkyl; m is an integer of 10 to 30.
Preferably, R 'and R' are independently selected from C2-C3 alkyl.
Preferably, the wetting agent is prepared according to the following method:
A1) mixing octamethylcyclotetrasiloxane, high-hydrogen silicone oil, hexamethyldisiloxane and an acidic catalyst, heating for reaction, neutralizing, filtering, heating for removing low hydrogen silicone oil;
A2) and mixing the low-hydrogen-content silicone oil, the terminal alkenyl polyether and the platinum catalyst, heating for reaction, and heating to remove the low content to obtain the wetting agent.
Preferably, the temperature of the heating reaction in the step A1) is 35-45 ℃; the heating reaction time is 4-7 h; the temperature for heating and removing is 130-140 ℃; the heating and reducing time is 2-5 h;
the heating reaction temperature in the step A2) is 70-120 ℃; the heating reaction time is 60-200 min; the temperature for heating and removing is 130-140 ℃; the heating and reducing time is 2-5 h.
Preferably, the silicone wax is selected from compounds represented by formula (II) and/or formula (III):
Figure BDA0003179608570000031
wherein n, p and q are polymerization degrees, and n, p and q are respectively an integer of 10-200;
R1、R2and R3Each independently is a substituted or unsubstituted C8-C30 alkyl group; and the substituent in the substituted C8-C30 alkyl is phenyl.
Preferably, said R is1、R2And R3Each independently is a substituent of formula (IV):
Figure BDA0003179608570000032
wherein a and b are integers, and a + b is 8-30;
R4is H or methyl.
Preferably, the surfactant is a cationic surfactant or an anionic surfactant; the cationic surfactant is selected from one or more of fatty amine salt, ethanolamine salt, stearic acid amide salt and polyethylene polyamine salt; the anionic surfactant is selected from one or more of anionic polyacrylamide, fatty acid salt, sulfonate, sulfate and phosphate;
the mass ratio of the organic silicon wax, the surfactant, the wetting agent and the water is (10-50): (1-15): (1-5): (35-89);
the temperature for heating and mixing in the step S1) is 40-100 ℃; the heating and mixing time is 30-180 min;
the pressure for high-pressure homogenization in the step S2) is 30-1200 bar; the temperature of high-pressure homogenization is 50-90 ℃.
The invention also provides an organic silicon wax emulsion which is prepared by homogenizing the following raw materials under high pressure;
the raw materials comprise organic silicon wax, a surfactant, a wetting agent and water;
the wetting agent is represented by the formula (I):
Figure BDA0003179608570000041
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group.
The invention also provides a wetting agent, which is shown as the formula (I):
Figure BDA0003179608570000042
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group.
The invention provides a preparation method of an organic silicon wax emulsion, which comprises the following steps: s1) heating and mixing the organic silicon wax, the surfactant, the wetting agent and water to obtain a mixed solution; s2) homogenizing the mixed solution under high pressure to obtain an organic silicon wax emulsion; the wetting agent is shown as a formula (I); wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group. Compared with the prior art, the preparation method is carried out by a one-pot method, the organic silicon wax, the surfactant, the deionized water and the self-made wetting agent are heated, dissolved and mixed at one time under the synergistic action of the ionic surfactant and the specific wetting agent, and after materials in a kettle are completely dissolved and uniformly mixed, the materials are introduced into a high-pressure homogenizer for homogenization and emulsification to obtain the organic silicon wax emulsion with micron-sized particle size, and the emulsion is emulsified without dripping water; meanwhile, the obtained organic silicon wax emulsion has the advantages of proper viscosity, strong stability and uniform texture, and can be widely applied to the fields of demolding of metal die-casting devices such as alloys and the like, cosmetics, textiles, coatings and the like.
Drawings
FIG. 1 is an infrared spectrum of a low hydrogen silicone oil and a high hydrogen silicone oil in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a low hydrogen silicone oil, allyl polyether and wetting agent in example 1 of the present invention;
FIG. 3 is a GPC gel chromatography test chart of the low hydrogen-containing silicone oil obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a wetting agent, which is shown as a formula (I):
Figure BDA0003179608570000051
wherein x and y are polymerization degrees, and x is 10-50; in embodiments provided herein, x is specifically 10, 20, 25, 15, 30, or 50;
y is 10-70; in embodiments provided herein, y is specifically 15, 10, 20, 70, or 50;
x + y is 15-100, preferably 20-100, and more preferably 25-100;
r is a polyether radical, preferably-R' O (R "O)mH; wherein, R 'and R' are respectively and independently preferably C2-C5 alkyl, more preferably C2-C4 alkyl, and even more preferably C2-C3 alkyl; m is preferably an integer of 10-30; in the embodiments provided by the present invention, m is specifically 10, 14, 20, 30 or 25.
In the present invention, the most preferablePreferably, R is-CH2CH2CH2O(CH2CH2O)mH。
The invention also provides a preparation method of the wetting agent, which comprises the following steps: A1) mixing octamethylcyclotetrasiloxane, high-hydrogen silicone oil, hexamethyldisiloxane and an acidic catalyst, heating for reaction, neutralizing, filtering, heating for removing low hydrogen silicone oil; A2) and mixing the low-hydrogen-content silicone oil, the terminal alkenyl polyether and the platinum catalyst, heating for reaction, and heating to remove the low content to obtain the wetting agent.
Mixing octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil, hexamethyldisiloxane and an acidic catalyst, and heating for reaction; the high hydrogen-containing silicone oil is preferably 202 high hydrogen-containing silicone oil; the mass ratio of the octamethylcyclotetrasiloxane to the high-hydrogen-content silicone oil to the hexamethyldisiloxane is preferably 1:10: 0.01-7: 1: 0.5; in the embodiment provided by the invention, the mass ratio of the octamethylcyclotetrasiloxane, the high hydrogen-containing silicone oil and the hexamethyldisiloxane is specifically 5.14: 1: 0.23; the acidic catalyst is preferably concentrated sulfuric acid; the addition amount of the acidic catalyst is preferably 2-4% of the total mass of the octamethylcyclotetrasiloxane, the high hydrogen-containing silicone oil and the hexamethyldisiloxane, and more preferably 2-3%; the temperature of the heating reaction is preferably 35-45 ℃; the heating reaction time is preferably 4-7 h.
After the reaction, neutralizing, filtering, and heating for removing low content; the neutralization is preferably carried out with sodium carbonate; the temperature for heating and removing the low temperature is preferably 130-140 ℃; the time for heating and reducing is preferably 2-5 h; and finally cooling to room temperature to obtain the low hydrogen-containing silicone oil.
Mixing the low-hydrogen-content silicone oil, the terminal alkenyl polyether and a platinum catalyst, and heating for reaction; the alkenyl-terminated polyether is preferably allyl-terminated polyether; the mass ratio of the low-hydrogen silicone oil to the terminal alkenyl polyether is preferably 1: 1-10, more preferably 1:1 to 5, preferably 1: 1-3; in the embodiment provided by the invention, the mass ratio of the low hydrogen-containing silicone oil to the terminal alkenyl polyether is specifically 1: 1.2; the platinum catalyst is preferably an isopropanol-chloroplatinic acid solution; the mass percentage of platinum in the isopropanol-chloroplatinic acid solution is preferably 3000 PPM-8000 PPM; the addition amount of the platinum catalyst (based on the mass of platinum) is preferably 1.5-8 ppm, more preferably 3-8 ppm, even more preferably 4-6 ppm, and most preferably 5ppm of the total mass of the low hydrogen-containing silicone oil and the terminal alkenyl polyether; the temperature of the heating reaction is preferably 70-120 ℃, more preferably 70-100 ℃, and further preferably 75-90 ℃; the heating reaction time is preferably 60-200 min, more preferably 80-180 min, still more preferably 100-140 min, and most preferably 120 min.
After the reaction is finished, heating and removing; the temperature for heating and removing the low temperature is preferably 130-140 ℃; the time for heating and removing is preferably 2-5 h, and more preferably 3-4 h; and finally cooling to room temperature to obtain the wetting agent.
The invention also provides an organic silicon wax emulsion which is prepared by homogenizing the following raw materials under high pressure;
the raw materials comprise organic silicon wax, a surfactant, a wetting agent and water;
the wetting agent is represented by the formula (I):
Figure BDA0003179608570000061
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group.
In the invention, the raw material preferably comprises 10-50 parts by weight of organic silicon wax; 1-15 parts by weight of a surfactant; 1-5 parts by weight of a wetting agent; 35-89 parts of water.
According to the invention, the content of the organic silicon wax in the raw materials is preferably 15-50 parts by weight, and more preferably 20-50 parts by weight; in the examples provided by the invention, the content of the organic silicon wax is specifically 25 parts by weight, 50 parts by weight or 20 parts by weight; the organic silicon wax can be divided into two types of terminal long-chain alkyl organic silicon wax with two end-capped long-chain alkyl groups at two ends and trimethyl end-capped long-chain alkyl organic silicon wax with long-chain alkyl groups on side chains according to the position of the long-chain alkyl, and in the invention, the organic silicon wax is preferably a compound shown in a formula (II) and/or a formula (III):
Figure BDA0003179608570000071
wherein n, p and q are polymerization degrees, and each of n, p and q is an integer of 10-200 independently; in the invention, n is preferably an integer of 20 to 200, more preferably an integer of 30 to 200; in the embodiments provided by the present invention, n is specifically 30, 50, 100, 120 or 200; in embodiments provided herein, p is specifically 150, 200, 10, or 30; in the examples provided by the present invention, q is specifically 10, 70, 150 or 200.
R1、R2And R3Each independently is a substituted or unsubstituted C8-C30 alkyl group; the substituent of the substituted C8-C30 alkyl group is preferably phenyl. In the present invention, most preferably, R is1、R2And R3Each independently is a substituent of formula (IV):
Figure BDA0003179608570000072
wherein a and b are integers, and a + b is 8-30; the preferable range of a is 0-30; in the embodiments provided by the present invention, a is specifically 5, 8, 7, 15, 30, 18, 10, 0 or 20; b is preferably an integer of 0-30; b is specifically 8, 0, 4, 15, 10, 30 or 8; in the examples provided by the present invention, said a + b is in particular 13, 8, 12, 30, 11, 18, 10 or 23.
R4Is H or methyl.
The content of the surfactant is preferably 2.5-15 parts by weight; in the examples provided by the present invention, the content of the surfactant is specifically 2.5 parts by weight, 10 parts by weight, 5 parts by weight, 15 parts by weight, or 6 parts by weight; the surfactant is preferably a cationic surfactant or an anionic surfactant; the cationic surfactant is preferably one or more of fatty amine salt, ethanolamine salt, stearic acid amide salt and polyethylene polyamine salt, and more preferably one or more of polyethylene polyamine salt (N7), dodecylamine acetate, stearic acid amidopropyl dimethylamine lactate and dodecyl benzene sulfonic acid triethanolamine salt; the anionic surfactant is preferably one or more of anionic polyacrylamide, fatty acid salt, sulfonate, sulfate ester salt and phosphate ester salt, and more preferably one or more of polyacrylamide, sodium dodecyl benzene sulfonate, castor oil phosphate salt and sodium dodecyl sulfate salt.
In the examples provided by the present invention, the content of the wetting agent is specifically 1 part by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight.
The content of the water is preferably 35 to 85 parts by weight, more preferably 35 to 80 parts by weight, and still more preferably 35 to 74 parts by weight; in the examples provided by the invention, the content of the water is specifically 62.5 parts by weight, 40 parts by weight, 45 parts by weight, 35 parts by weight, 74 parts by weight or 70 parts by weight; the water is preferably deionized water.
The invention also provides a preparation method of the organic silicon wax emulsion, which comprises the following steps: s1) heating and mixing the organic silicon wax, the surfactant, the wetting agent and water to obtain a mixed solution; s2) homogenizing the mixed solution under high pressure to obtain an organic silicon wax emulsion;
the wetting agent is represented by the formula (I):
Figure BDA0003179608570000081
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is a polyether group.
Heating and mixing organic silicon wax, a surfactant, a wetting agent and water to obtain a mixed solution; the types of the organic silicon wax, the surfactant, the lubricant and the water are the same as those described above, and are not described again; the mass ratio of the organic silicon wax, the surfactant, the wetting agent and the water is preferably (10-50): (1-15): (1-5): (35-89), more preferably (15-50): (1-15): (1-5): (35-85), and more preferably (20-50): (2.5-15): (1-5): (35-80), most preferably (20-50): (2.5-15): (1-5): (35-74); in the embodiment provided by the invention, the mass ratio of the organic silicon wax, the surfactant, the wetting agent and the water is specifically as follows: 25: 2.5: 1: 62.5, 50: 10: 2.5: 40. 50: 5: 3: 45. 50: 15: 3.5: 35. 20: 6: 4: 74. 25: 5: 4.5: 70. 50: 15: 5: 35. 20: 6: 3: 74 or 25: 5: 3.5: 70; the heating and mixing temperature is preferably 40-100 ℃; the heating and mixing time is 30-180 min; fully dissolving and uniformly mixing to obtain a mixed solution.
Homogenizing the mixed solution under high pressure to obtain an organic silicon wax emulsion; the high-pressure homogenization is preferably carried out in a high-pressure homogenizer; the temperature of the high-pressure homogenization is preferably 50-90 ℃; in the embodiment provided by the invention, the high-pressure homogenization temperature is specifically 50 ℃, 70 ℃, 75 ℃ or 90 ℃; the pressure for high-pressure homogenization is preferably 30-1200 bar; in the embodiment provided by the invention, the high-pressure homogenizing pressure is specifically 100bar, 300bar, 400bar, 1200bar, 600bar, 800bar or 500 bar; the number of times of high-pressure homogenization is preferably 1-5 times.
The silicone wax emulsion is prepared by a one-pot method, through the synergistic effect of an ionic surfactant and a specific wetting agent, the silicone wax, the surfactant, deionized water and a self-made wetting agent are heated, dissolved and mixed at one time, and after materials in a kettle are completely dissolved and uniformly mixed, the materials are introduced into a high-pressure homogenizer for homogenization and emulsification to obtain the silicone wax emulsion with micron-sized particle size, and the silicone wax emulsion is emulsified without dripping water; meanwhile, the obtained organic silicon wax emulsion has the advantages of proper viscosity, strong stability and uniform texture, and can be widely applied to the fields of demolding of metal die-casting devices such as alloys and the like, cosmetics, textiles, coatings and the like.
Moreover, the preparation method has the advantages of small equipment investment, no need of dropwise adding water, one-time addition, reduction of equipment investment of pump equipment and a water heating kettle, reduction of space required by production equipment, no need of equipment to be pressurized, normal-pressure operation, low process temperature and reduction of production safety and equipment investment.
In order to further illustrate the present invention, the following will describe a silicone wax emulsion and a preparation method thereof in detail with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 adding 201.6g of octamethylcyclotetrasiloxane, 39.2g of high hydrogen silicone oil (202), 9.1g of hexamethyldisiloxane and 5.5g of concentrated sulfuric acid into a reactor, heating to 45 ℃, preserving heat for 4 hours, adding a sodium carbonate neutralizer, filtering, heating to 140 ℃, removing low hydrogen silicone oil for 2 hours, cooling and cooling to obtain low hydrogen silicone oil;
1.2 adding 250g of the prepared low-hydrogen silicone oil, 300g of allyl-terminated polyether and 0.55g of platinum catalyst (isopropanol-chloroplatinic acid solution, platinum mass concentration is 5000ppm) into a reactor, heating to 75 ℃ under normal pressure, carrying out heat preservation reaction for 120min, heating to 130 ℃ for removing the catalyst for 3h, and cooling to obtain the wetting agent.
The raw material high hydrogen silicone oil (202) and the low hydrogen silicone oil obtained in example 1 were analyzed by infrared spectroscopy to obtain an infrared spectrum thereof, as shown in FIG. 1. As can be seen from FIG. 1, 1089cm-1A characteristic absorption multiplet of-Si-O-Si-is nearby; 1266cm-1Is represented by-Si-CH3Characteristic absorption peak of (a); 2166cm-1The absorption peaks of Si-H bond stretching vibration appear in the infrared spectra of the low-hydrogen silicone oil and the high-hydrogen silicone oil respectively, but are relative to 2960cm-1And the peak value of the low hydrogen-containing silicone oil is smaller than that of the high hydrogen-containing silicone oil. In summary, it can be confirmed that the reaction for preparing the low hydrogen-containing silicone oil by using the high hydrogen-containing silicone oil is completed.
The low hydrogen silicone oil, allyl polyether and wetting agent obtained in example 1 were analyzed by infrared spectroscopy, and the infrared spectrum thereof was as shown in fig. 2. In FIG. 2, 1640cm-1C ═ C stretching vibration absorption peak of polyether; 2166cm-1The absorption peak is the Si-H bond stretching vibration absorption peak in the low hydrogen-containing silicone oil, the C ═ C stretching vibration absorption peak and the Si-H bond of the polyether in the infrared spectrogram of the product wetting agent become weak peaks, and most of the silicon hydride addition is finishedThe reaction is finished, the product is colorless to golden yellow transparent liquid, and the original insoluble turbid state is changed into uniform transparent liquid, which indicates that the reaction is finished.
The low hydrogen silicone oil has viscosity of 25.5cp (25 deg.C) measured by rotational viscometer, hydrogen content of 0.24%, Si-H chain number of 7, Si-O chain number of 34, and GPC gel chromatography test result shown in figure 3.
The hydrogen content test method comprises the following steps:
1. the required silicone oil weight was weighed out with an analytical balance and dissolved in an iodine vial to an accuracy of 0.0001 g.
2. 20mL of pure carbon tetrachloride was measured in an iodine measuring flask using a graduated cylinder. Shaking to dissolve the oil completely.
3. 10mL of the bromoacetic acid solution was pipetted into an iodometric vial. Shaking, sealing with water, and standing in dark for 30 min.
4. Adding 25ml of LKI solution, shaking for 2-3 minutes, and shaking up.
5. Titration was performed with 0.1N sodium thiosulfate standard solution (brown burette). When the iodine is dripped, the iodine in the carbon tetrachloride is completely put into the aqueous solution by violent vibration.
6. Titration to light yellow, about 2mL of starch solution is added, and titration is continued until the blue color disappears, namely the titration end point is reached.
7. A blank of 1 part was prepared and the procedure was as described above except that the silicone oil was not added.
8. Three experiments were performed in parallel. After titration, the waste liquid is poured into a waste liquid cylinder so as to recover carbon tetrachloride.
Example 2
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000111
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000112
(n＝30) wherein R is1Is composed of
Figure BDA0003179608570000113
(a＝0，b＝8，R4Is H), wherein R2Is composed of
Figure BDA0003179608570000114
(a＝5，b＝8，R4Is H)); the surfactant is lauryl amine acetate; wetting agents of formula (I) (x ═ 10, y ═ 15, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝10)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 40 ℃, stirring for 60min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 1 time at the homogenizing temperature of 50 ℃ and the homogenizing pressure of 100bar to obtain the organic silicon wax emulsion.
Example 3
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials in parts by weight:
Figure BDA0003179608570000115
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000121
(n-50) wherein R is
Figure BDA0003179608570000122
(a＝10，b＝8，R4Is H), R2Is composed of
Figure BDA0003179608570000123
(a＝8，b＝0，R4Is H); the surfactant is stearic acid amidePropyl dimethylamine lactate; wetting agents of formula (I) (x ═ 20, y ═ 15, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝14)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 60 ℃, stirring for 100min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 70 ℃ and the homogenization pressure of 300bar to obtain the silicone wax emulsion.
Example 4
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000124
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000125
(n-100), wherein R1Is composed of
Figure BDA0003179608570000126
(a＝7，b＝4，R4Is H), R2Is composed of
Figure BDA0003179608570000127
(a＝15，b＝15，R4Is H); the surfactant is triethanolamine salt of dodecyl benzene sulfonic acid; wetting agents of formula (I) (x ═ 25, y ═ 10, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝20)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 60 ℃, stirring for 100min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 70 ℃ and the homogenization pressure of 300bar to obtain the silicone wax emulsion.
Example 5
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials in parts by weight:
Figure BDA0003179608570000131
wherein the structural formula of the organosilicon silicone wax is as follows:
Figure BDA0003179608570000132
(n-120), wherein R1Is composed of
Figure BDA0003179608570000133
(a＝7，b＝4，R4Is H), R2Is composed of
Figure BDA0003179608570000134
(a＝30，b＝0，R4Is H); the surfactant is polyacrylamide; a wetting agent of formula (I) (x ═ 15, y ═ 15, and R is-CH)2CH2CH2O(CH2CH2O)mH，m＝20)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 60 ℃, stirring for 120min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenizing temperature of 75 ℃ and the homogenizing pressure of 400bar to obtain the silicone wax emulsion.
Example 6
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000141
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000142
(n-200) wherein R1Is composed of
Figure BDA0003179608570000143
(a＝18，b＝0，R4Is methyl), R2Is composed of
Figure BDA0003179608570000144
(a＝10，b＝0，R4Is H); the surfactant is sodium dodecyl benzene sulfonate; a wetting agent of formula (I) (x ═ 20, y ═ 20, and R is-CH)2CH2CH2O(CH2CH2O)mH，m＝30)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 40 ℃, stirring for 180min, fully dissolving and uniformly mixing;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 5 times at the homogenizing temperature of 50 ℃ and the homogenizing pressure of 1200bar to obtain the silicone wax emulsion.
Example 7
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000145
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000151
(q-10, p-150), wherein R3Is composed of
Figure BDA0003179608570000152
(b＝8，a＝0，R4Is H); the surfactant is a castor oil phosphate and dodecyl sodium sulfate compound (the mass ratio is 1: 2); wetting agents of formula (I) (x ═ 30, y ═ 15, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝25)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 50 ℃, stirring for 80min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 70 ℃ and the homogenization pressure of 600bar to obtain the silicone wax emulsion.
Example 8
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000153
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000154
(q-70, p-200), wherein R3Is composed of
Figure BDA0003179608570000155
(b＝20，a＝10，R4Is H); the surfactant is polyacrylamide; wetting agents of formula (I) (x ═ 30, y ═ 70, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝30)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 100 ℃, stirring for 150min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 70 ℃ and the homogenization pressure of 800bar to obtain the silicone wax emulsion.
Example 9
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000161
wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000162
(q 150, p 10), wherein R3Is composed of
Figure BDA0003179608570000163
(a＝0，b＝30，R4Is H); the surfactant is sodium dodecyl benzene sulfonate; wetting agents of formula (I) (x ═ 50, y ═ 50, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝20)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 40 ℃, stirring for 180min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 5 times at the homogenizing temperature of 50 ℃ and the homogenizing pressure of 1200bar to obtain the silicone wax emulsion.
Example 10
The embodiment provides an organic silicon wax emulsion, which comprises the following raw materials:
Figure BDA0003179608570000171
wherein the structural formula of the organosilicon silicone wax is as follows:
Figure BDA0003179608570000172
(q 200, p 30), wherein R3Is composed of
Figure BDA0003179608570000173
(a＝8，b＝15，R4Is H); the surfactant is castor oil phosphate; wetting agents of formula (I) (x ═ 10, y ═ 15, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝10)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 80 ℃, stirring for 180min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 90 ℃ and the homogenization pressure of 500bar to obtain the silicone wax emulsion.
Comparative example 1
The comparative example provides an organosilicon wax emulsion, the raw materials for preparation of which comprise the following components:
10 parts by weight of silicone wax
1 part by weight of a surfactant
89 parts by weight of deionized water
Wherein the structural formula of the organic silicon wax is as follows:
Figure BDA0003179608570000181
(n-10), wherein R1、R2Are all made of
Figure BDA0003179608570000182
(a＝0，b＝30，R4Is H); the surfactant is polyethylene polyamineSalt (N7) and dodecylamine acetate complex (mass ratio 1: 2).
The preparation method comprises the following steps:
(1) measuring the organic silicon wax, the surfactant and the deionized water according to a set proportion, adding the measured organic silicon wax, the surfactant and the deionized water into a reaction kettle, starting to heat to 40 ℃, stirring for 30min, fully dissolving the organic silicon wax, the surfactant and the deionized water, and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 1 time at the homogenizing temperature of 50 ℃ and the homogenizing pressure of 30bar to obtain the organic silicon wax emulsion.
Comparative example 2
The comparative example provides an organosilicon wax emulsion, the raw materials for preparation of which comprise the following components:
Figure BDA0003179608570000183
wherein the structural formula of the organosilicon silicone wax is as follows:
Figure BDA0003179608570000184
(n-50), wherein R1Is composed of
Figure BDA0003179608570000185
(a＝10，b＝8，R4Is H), R2Is composed of
Figure BDA0003179608570000186
(a＝8，b＝0，R4Is H); the surfactant is stearic acid amide propyl dimethylamine lactate; wetting agents of formula (I) (x ═ 70, y ═ 80, R is-CH)2CH2CH2O(CH2CH2O)mH，m＝60)。
The preparation method comprises the following steps:
(1) adding the organic silicon wax, the surfactant, the wetting agent and the deionized water into a reaction kettle after metering according to a set proportion, starting to heat to 60 ℃, stirring for 100min, fully dissolving and uniformly mixing to obtain a mixed solution;
(2) and introducing the mixed solution which is fully dissolved and uniformly mixed into a high-pressure homogenizer, and homogenizing for 3 times at the homogenization temperature of 70 ℃ and the homogenization pressure of 300bar to obtain the silicone wax emulsion.
And (3) performance testing:
the silicone wax emulsions obtained in examples 2-10 and comparative examples 1-2 were tested according to emulsion stability (GB/T1603-2001) and skin moisturizing performance (QB/T4256-2011), and the results are shown in Table 1.
Table 1 emulsion stability and skin moisturizing performance test results
Serial number Viscosity of emulsion Sense of particle Emulsion stability Skin moisture content/% (2h)
Comparative example 1 / / Non-emulsifying /
Example 2 Is suitable for The emulsion is fine and smooth and has no particles Not layering 46.19
Example 3 Is suitable for The emulsion is fine and smooth and has no particles Not layering 48.22
Example 4 Is suitable for The emulsion is fine and smooth and has no particles Not layering 48.10
Example 5 Is suitable for The emulsion is fine and smooth and has no particles Without delamination 47.47
Example 6 Is suitable for The emulsion is fine and smooth and has no particles Not layering 48.15
Example 7 Is suitable for The emulsion is fine and smooth and has no particles Not layering 47.82
Example 8 Is suitable for The emulsion is fine and smooth and has no particles Not layering 47.63
Example 9 Is suitable for The emulsion is fine and smooth and has no particles Not layering 46.87
Example 10 Is suitable for The emulsion is fine and smooth and has no particles Not layering 47.92
Comparative example 2 / / Non-emulsifying /
The silicone wax emulsions obtained in examples 2-10 and comparative examples 1-2 were tested according to ASTM D3108-2001 Standard test method for coefficient of Friction between yarn and solid Material, and the results are shown in Table 2.
TABLE 2 Friction coefficient test results
Figure BDA0003179608570000191
Figure BDA0003179608570000201
Note: comparative example 3 is the coefficient of friction of sewing thread without the addition of silicone wax emulsion.

Claims (6)

1. A method for preparing an organosilicon wax emulsion, comprising:
s1) heating and mixing the organic silicon wax, the surfactant, the wetting agent and water to obtain a mixed solution;
s2) homogenizing the mixed solution under high pressure to obtain an organic silicon wax emulsion;
the wetting agent is represented by the formula (I):
Figure FDA0003685566340000011
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is-R 'O (R' O)mH; r 'and R' are each independently C2-C5 alkyl; m is an integer of 10-30;
the organic silicon wax is selected from compounds shown in a formula (II) and/or a formula (III):
Figure FDA0003685566340000012
wherein n, p and q are polymerization degrees, and n, p and q are respectively an integer of 10-200;
the R is1、R2And R3Each independently is a substituent of formula (IV):
Figure FDA0003685566340000013
wherein a and b are integers, and a + b is 8-30;
R4is H or methyl;
the surfactant is a cationic surfactant or an anionic surfactant; the cationic surfactant is selected from one or more of fatty amine salt, ethanolamine salt, stearic acid amide salt and polyethylene polyamine salt; the anionic surfactant is selected from one or more of anionic polyacrylamide, fatty acid salt, sulfonate, sulfate and phosphate;
the mass ratio of the organic silicon wax, the surfactant, the wetting agent and the water is (10-50): (1-15): (1-5): (35-89).
2. The method of claim 1, wherein R' and R "are each independently selected from C2-C3 alkyl groups.
3. The method of claim 1, wherein the wetting agent is prepared by the following method:
A1) mixing octamethylcyclotetrasiloxane, high-hydrogen silicone oil, hexamethyldisiloxane and an acidic catalyst, heating for reaction, neutralizing, filtering, heating for removing low hydrogen silicone oil;
A2) and mixing the low-hydrogen-content silicone oil, the terminal alkenyl polyether and the platinum catalyst, heating for reaction, and heating to remove the low content to obtain the wetting agent.
4. The preparation method according to claim 3, wherein the temperature of the heating reaction in the step A1) is 35 to 45 ℃; the heating reaction time is 4-7 h; the temperature for heating and removing is 130-140 ℃; the heating and reducing time is 2-5 h;
the heating reaction temperature in the step A2) is 70-120 ℃; the heating reaction time is 60-200 min; the temperature for heating and removing is 130-140 ℃; the heating and reducing time is 2-5 h.
5. The method according to claim 1,
the temperature for heating and mixing in the step S1) is 40-100 ℃; the heating and mixing time is 30-180 min;
the pressure for high-pressure homogenization in the step S2) is 30-1200 bar; the temperature of high-pressure homogenization is 50-90 ℃.
6. An organic silicon wax emulsion is characterized by being prepared by homogenizing the following raw materials under high pressure;
the raw materials comprise organic silicon wax, a surfactant, a wetting agent and water;
the wetting agent is represented by the formula (I):
Figure FDA0003685566340000021
wherein x and y are polymerization degrees, and x is 10-50; y is 10-70; x + y is 15-100; r is-R 'O (R' O)mH; r 'and R' are each independently C2-C5 alkyl; m is an integer of 10-30;
the organic silicon wax is selected from compounds shown in a formula (II) and/or a formula (III):
Figure FDA0003685566340000022
wherein n, p and q are polymerization degrees, and n, p and q are respectively an integer of 10-200;
the R is1、R2And R3Each independently is a substituent of formula (IV):
Figure FDA0003685566340000031
wherein a and b are integers, and a + b is 8-30;
R4is H or methyl;
the surfactant is a cationic surfactant or an anionic surfactant; the cationic surfactant is selected from one or more of fatty amine salt, ethanolamine salt, stearic acid amide salt and polyethylene polyamine salt; the anionic surfactant is selected from one or more of anionic polyacrylamide, fatty acid salt, sulfonate, sulfate and phosphate;
the mass ratio of the organic silicon wax, the surfactant, the wetting agent and the water is (10-50): (1-15): (1-5): (35-89).
CN202110843169.3A 2021-07-26 2021-07-26 Organic silicon wax emulsion and preparation method thereof Active CN113461970B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110843169.3A CN113461970B (en) 2021-07-26 2021-07-26 Organic silicon wax emulsion and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110843169.3A CN113461970B (en) 2021-07-26 2021-07-26 Organic silicon wax emulsion and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113461970A CN113461970A (en) 2021-10-01
CN113461970B true CN113461970B (en) 2022-07-12

Family

ID=77882357

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110843169.3A Active CN113461970B (en) 2021-07-26 2021-07-26 Organic silicon wax emulsion and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113461970B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114808461A (en) * 2022-05-16 2022-07-29 泰州万诺纺织科技有限公司 Non-aqueous silicon wax finishing agent for polyamide filament sewing thread, preparation method and application thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351900A (en) * 1999-06-14 2000-12-19 Shin Etsu Chem Co Ltd Organopolysiloxane emulsion and its preparation
CN101081899A (en) * 2006-05-29 2007-12-05 深圳市海川实业股份有限公司 Preparation method of polyoxyalkylenes ether grafted polysiloxane
CN101298027A (en) * 2008-01-18 2008-11-05 滁州四新科技有限责任公司 Method for dispersing highly viscous organosilicon mixture
CN103182271A (en) * 2011-12-27 2013-07-03 广东标美硅氟新材料有限公司 Organosilicon surfactant and preparation method and application thereof
CN103755961A (en) * 2013-12-20 2014-04-30 中科院广州化学有限公司 Polysiloxane microemulsion, and preparation method and application thereof
CN106687508A (en) * 2014-07-23 2017-05-17 道康宁公司 Silicone emulsions
CN109400913A (en) * 2018-10-17 2019-03-01 南京瑞思化学技术有限公司 A kind of preparation method of organosilicon emulsion
CN109867790A (en) * 2018-12-24 2019-06-11 南京美思德新材料有限公司 A kind of organic silicon polyether copolymer and preparation method thereof
CN109929120A (en) * 2019-01-03 2019-06-25 南京瑞思化学技术有限公司 A kind of organic silicon emulsion
CN110256692A (en) * 2019-06-21 2019-09-20 南京澳莉峰环保科技有限公司 A method of improving stability of organic silicone emulsion
CN110283336A (en) * 2019-07-01 2019-09-27 广州大学 A kind of preparation and application of the Organosilicon wax lotion for moisturizing cosmetic
CN111234698A (en) * 2020-01-15 2020-06-05 启东曦瑞新材料科技有限公司 Preparation method of modified organic silicon wax emulsion brightener

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000351900A (en) * 1999-06-14 2000-12-19 Shin Etsu Chem Co Ltd Organopolysiloxane emulsion and its preparation
CN101081899A (en) * 2006-05-29 2007-12-05 深圳市海川实业股份有限公司 Preparation method of polyoxyalkylenes ether grafted polysiloxane
CN101298027A (en) * 2008-01-18 2008-11-05 滁州四新科技有限责任公司 Method for dispersing highly viscous organosilicon mixture
CN103182271A (en) * 2011-12-27 2013-07-03 广东标美硅氟新材料有限公司 Organosilicon surfactant and preparation method and application thereof
CN103755961A (en) * 2013-12-20 2014-04-30 中科院广州化学有限公司 Polysiloxane microemulsion, and preparation method and application thereof
CN106687508A (en) * 2014-07-23 2017-05-17 道康宁公司 Silicone emulsions
CN109400913A (en) * 2018-10-17 2019-03-01 南京瑞思化学技术有限公司 A kind of preparation method of organosilicon emulsion
CN109867790A (en) * 2018-12-24 2019-06-11 南京美思德新材料有限公司 A kind of organic silicon polyether copolymer and preparation method thereof
CN109929120A (en) * 2019-01-03 2019-06-25 南京瑞思化学技术有限公司 A kind of organic silicon emulsion
CN110256692A (en) * 2019-06-21 2019-09-20 南京澳莉峰环保科技有限公司 A method of improving stability of organic silicone emulsion
CN110283336A (en) * 2019-07-01 2019-09-27 广州大学 A kind of preparation and application of the Organosilicon wax lotion for moisturizing cosmetic
CN111234698A (en) * 2020-01-15 2020-06-05 启东曦瑞新材料科技有限公司 Preparation method of modified organic silicon wax emulsion brightener

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
复合型硅蜡乳液的乳化工艺研究;吕敏等;《中国皮革》;20160803(第08期);全文 *
聚醚侧链接枝密度对聚醚硅油性能的影响;刑炜等;《有机硅材料》;全文 *
聚醚改性硅油表面性质的研究;王文宗等;《精细化工》;20100315(第03期);全文 *

Also Published As

Publication number Publication date
CN113461970A (en) 2021-10-01

Similar Documents

Publication Publication Date Title
CN1125843C (en) Method for preparing water-covered siloxane emulsion
JP5312654B2 (en) Emulsion of silicone and non-aqueous hydroxyl solvent
CN113461970B (en) Organic silicon wax emulsion and preparation method thereof
US7683119B2 (en) Process for making silicone emulsions
US1970578A (en) Assistants for the textile and related industries
JP4843020B2 (en) Silicone emulsion, method of preparing the same, and cosmetic ingredients
WO2010108781A1 (en) Process for making stable high viscosity amino silicone emulsion
CN108484933B (en) Organic silicon emulsion and production process thereof
JPH11292970A (en) Elastomer dispersion having unique particle size distribution
CN109487560A (en) Complex wax microemulsion composition and its preparation method and application
CN106065527A (en) Polyester filament FDY spinning oil and preparation method thereof
WO2012095374A1 (en) Silicone emulsions and method for producing same
CN109550282B (en) High-temperature-resistant integral power plant desulfurization defoaming agent and preparation method thereof
EP0967239B1 (en) Process for the preparation of cured silicone powder
CN112006923B (en) High internal phase emulsion stabilized by low-content surfactant and preparation method thereof
US6174983B1 (en) Silicone terpolymers with high refractive indices
EP3452173B1 (en) Aqueous emulsions containing amino-functional organopolysiloxanes and non-ionic emulsifiers
CN106675875B (en) A kind of ceramics paraffin removal cleaning agent and preparation method thereof
DE3427496A1 (en) METHOD FOR PRODUCING A POLYSILOXANE BLOCK POLYMERISATE
CN115124721B (en) Modified gelatin for coating printing and dyeing adhesive as well as preparation method and application thereof
CN109280171A (en) Small particle amido silicone oil microemulsion and its preparation method and application
CN107759806A (en) A kind of moisturizing lubricating type polysiloxanes Pickering emulsions and preparation method thereof
CN110885559A (en) High-viscosity dimethyl silicone oil emulsion and preparation method thereof
JP6652240B2 (en) Cosmetics
TWI695016B (en) Dyeing composition of wool fiber material and dyeing method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant