CN112062965B - Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof - Google Patents
Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN112062965B CN112062965B CN202010799403.2A CN202010799403A CN112062965B CN 112062965 B CN112062965 B CN 112062965B CN 202010799403 A CN202010799403 A CN 202010799403A CN 112062965 B CN112062965 B CN 112062965B
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- long
- chain alkyl
- preparation
- modified
- 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
Links
Classifications
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- 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
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The invention belongs to the field of emulsion, and particularly relates to long-chain alkyl and zwitterion co-modified silicone oil antibacterial emulsion and a preparation method thereof. The long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion disclosed by the invention improves the interaction force of silicone oil and fabric, enhances the water resistance, greatly improves the hand feeling and the hydrophilicity of the fabric, simultaneously reduces the yellowing degree of the fabric, and also endows the fabric with the characteristic of resisting virus and bacteria adsorption.
Description
Technical Field
The invention belongs to the field of emulsion, and particularly relates to long-chain alkyl and zwitter-ion co-modified silicone oil antibacterial emulsion and a preparation method thereof.
Background
The organic silicon material mainly refers to a polymer material which contains a polysiloxane (Si-O-Si) main chain and silicon atoms are directly connected with organic groups, and has the characteristics of excellent lubricating property, demoulding property, hydrophobicity, defoaming property, physiological inertia and the like. The organic silicon emulsion is stable emulsion obtained by dispersing silicon oil in water in the form of fine particles under the action of strong mechanical stirring and an emulsifier, can be used as a textile auxiliary to endow the fabric with the characteristics of excellent flexibility, antistatic property, hydrophobicity, crease resistance, antibiosis, deodorization and the like, and is an important auxiliary in textile processing.
The amino silicone oil emulsion is one of the most widely used organic silicon fabric finishing agents, the treated fabric has excellent softening smoothness, wrinkle resistance and antistatic property, but the fabric is easy to yellow and has poor hygroscopicity due to the existence of amino groups. In order to solve the problems, the modification of amino silicone oil usually comprises polyether modification, cation modification, alkylation modification and the like, and when the emulsion prepared from the modified silicone oil is used for treating fabrics, the defects of yellowing or poor hygroscopicity of products are improved to a certain extent, but the softness of the fabrics treated by the silicone oil is reduced. In addition, the interaction force of common modified amino silicone oil with polypropylene non-woven fabrics and melt-blown fabrics is weak, so that the application of the excellent performance of the organosilicon material in medical supplies such as masks and the like is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and the preparation method thereof.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion comprises the following steps:
(1) Preparing a novel end socket agent with one end being long-chain alkane and the other end being tertiary amine: under the protection of nitrogen, cooling 1,1,3,3-tetramethyldisiloxane to 0-20 ℃, adding 5-15ppm Kaersite catalyst, adding linear chain alpha olefin, and reacting at constant temperature for 0.5-3 hours; adding allyl substituted piperazine compound, continuing to react for 0.5-3 hours, then heating to 40-80 ℃ for 0.5-3 hours, then heating to 80-110 ℃, and removing unreacted low-boiling-point substances in vacuum to obtain long-chain alkane and amino modified novel end-capping agent;
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: mixing the end sealing agent and octamethylcyclotetrasiloxane in a molar ratio of 1:5-100, heating to 85-115 ℃, adding 20-100ppm of catalyst, reacting at constant temperature for 3-10 hours, heating to 150-180 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitter ion co-modified silicone oil: under reflux condensation and nitrogen protection, 0, mixing the silicone oil and the solvent according to the mass ratio of 1.2-5, heating to 25-75 ℃, and dropwise adding an amphoteric ionizing reagent; reflux reaction is carried out for 6 to 36 hours, and the solvent and low-boiling-point substances are removed in a vacuumizing mode to obtain the long-chain alkyl and zwitter-ion co-modified silicone oil;
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: at 25 ℃,30-60 parts by mass of silicone oil and 5-10 parts by mass of emulsifier are mixed by high-speed mechanical stirring, 25-65 parts by mass of water is added dropwise within 1-2 hours, and stable silicone oil emulsion is obtained after emulsification.
Preferably, the olefin in the step (1) is a linear alpha olefin containing 6 to 18 carbon atoms; the allyl substituted piperazine compounds are 1-allyl piperazine, 1-allyl-4-methyl piperazine, 1-allyl-4-ethyl piperazine and 1-allyl-4-aminoethyl piperazine; the mole ratio of the linear alpha olefin to 1,1,3,3-tetramethyldisiloxane is 0.1-1.1; the mol ratio of the allyl substituted piperazine compound to 1,1,3,3-tetramethyl disiloxane is 1-1.2:1.
preferably, the catalyst in step (2) is tetramethylammonium hydroxide alkali gel.
Preferably, the solvent in the step (3) is one or two mixed solvents of isopropanol, acetonitrile and N, N-dimethylformamide; the zwitterionic reagent is 1,3-propane sultone and 1,4-butane sultone, and the mass ratio of the zwitterionic reagent to silicone oil is 0.05-0.5.
Preferably, the emulsifier in the step (4) is one or a mixture of fatty alcohol-polyoxyethylene ether AEO-3 and AEO-7; the mechanical stirring speed in the step (4) is 1000-3000 r/min.
The long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion is applied to a fabric treating agent.
From the above description, it can be seen that the present invention has the following advantages:
in the emulsion prepared by the invention, the introduction of long-chain alkyl realizes that the modified silicone oil enhances the compatibility of hydrophobic materials such as polyolefin and the like; the introduction of zwitterions enhances the functions of hydrophilicity, yellowing resistance and hygroscopicity of the modified silicone oil, and meanwhile, the modified silicone oil has antibacterial capability, and the prepared emulsion is more stable.
Detailed Description
A specific embodiment of the present invention will be described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end being long-chain alkane and the other end being tertiary amine: under the protection of nitrogen, 268g of 1, 3-tetramethyldisiloxane is added into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device, the temperature is reduced to 0 ℃, 15ppm of Kaersite catalyst is added, 100.8g of n-octene is added at the rate of 5g/min, and the constant temperature reaction is carried out for 3 hours; 154g of 1-methyl 4-allyl piperazine is continuously added at the speed of 5g/min to continuously react for 3 hours, then the temperature is raised to 40 ℃ to react for 3 hours, the temperature is raised to 80 ℃, and the low-boiling-point substance is pumped out by vacuum pumping to obtain the long-chain alkyl and amino modified end sealing agent.
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 38.7g (0.1 mol) of the end sealing agent and 2960g (10 mol) of octamethylcyclotetrasiloxane, heating to 115 ℃, adding 50ppm of tetramethylammonium hydroxide alkali gel, reacting for 3 hours at constant temperature, heating to 180 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitterion co-modified silicone oil: under reflux condensation and nitrogen protection, 152g of the silicone oil and 760g of isopropanol are mixed, heated to 75 ℃, 7.6g of 1, 3-propane sultone is dripped at the speed of 1g/min, reflux reaction is carried out for 4 hours, and a vacuum pumping way is adopted to remove a solvent and low-boiling-point substances, so that the long-chain alkyl and zwitter-ion co-modified silicone oil with the viscosity of 1250cst is obtained.
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: at 25 ℃,30g of the silicone oil and 5g of emulsifier AEO-3 are mixed by high-speed mechanical stirring, the stirring speed is 3000 r/min, 65g of water is added dropwise within 2 hours, and stable silicone oil emulsion is obtained after emulsification.
Example 2:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end of long-chain alkane and the other end of tertiary amine: under the protection of nitrogen, adding 201g of 1, 3-tetramethyldisiloxane into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device, cooling to 10 ℃, adding 10ppm of Kaersite catalyst, adding 138.6g of n-dodecene at the speed of 5g/min, and reacting for 2 hours at constant temperature; continuing to add 94.5g of 1-allylpiperazine at the rate of 5g/min, continuing to react for 2 hours, then heating to 60 ℃ to react for 1 hour, then heating to 110 ℃, and vacuumizing to extract low-boiling-point substances to obtain a long-chain alkyl and amino modified end sealing agent;
(2) Preparing long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 42.8g (0.1 mol) of the end sealing agent and 148g (0.5 mol) of octamethylcyclotetrasiloxane, heating to 85 ℃, adding 50ppm of tetramethylammonium hydroxide alkali gel, reacting for 20 hours at constant temperature, heating to 150 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitter ion co-modified silicone oil: under the protection of reflux condensation and nitrogen, 190g of the silicone oil and 38g of isopropanol are mixed, heated to 25 ℃, 95g of 1, 3-propane sultone is dropwise added at the speed of 5g/min, reflux reaction is carried out for 36 hours, and the solvent and low-boiling-point substances are removed in a vacuum pumping manner, so that the long-chain alkyl and zwitterion co-modified silicone oil with the viscosity of 25cst is obtained.
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: at 25 ℃,60g of the silicone oil and 10g of emulsifier AEO-7 are mixed by high-speed mechanical stirring, the stirring speed is 1000 r/min, 30g of water is added dropwise in 1 hour, and stable silicone oil emulsion is obtained after emulsification.
Example 3:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end being long-chain alkane and the other end being tertiary amine: adding 134g of 1, 3-tetramethyldisiloxane into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device under the protection of nitrogen, preserving the temperature to 20 ℃, adding 5ppm of Kaersite catalyst, adding 252g of 1-octadecene at the speed of 5g/min, and reacting for 0.5 hour at constant temperature; continuously adding 169.4g 1-allyl-4-ethylpiperazine at the speed of 5g/min, continuously reacting for 0.5 hour, then heating to 80 ℃ for reacting for 0.5 hour, then heating to 110 ℃, vacuumizing and pumping out low-boiling-point substances to obtain long-chain alkyl and amino modified end sealing agent;
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 55.5g (0.1 mol) of the end sealing agent and 1480g (5 mol) of octamethylcyclotetrasiloxane, heating to 100 ℃, adding 50ppm of tetramethylammonium hydroxide alkali glue, reacting for 8 hours at constant temperature, heating to 150 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitter ion co-modified silicone oil: under reflux condensation and nitrogen protection, 200g of the silicone oil is mixed with 400g of isopropanol/acetonitrile (4, 1 w/w), the mixture is heated to 50 ℃, 20g of 1, 3-propane sultone is dropwise added at the speed of 5g/min, reflux reaction is carried out for 10 hours, and a solvent and low-boiling-point substances are removed in a vacuumizing mode, so that the long-chain alkyl and zwitter ion co-modified silicone oil with the viscosity of 580cst is obtained.
(4) Preparing long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion: 50g of the silicone oil and 8g of emulsifier AEO-3/AEO-7 (1:1) are mixed by high-speed mechanical stirring at 25 ℃, the stirring speed is 2000 r/min, 42g of water is added dropwise within 1 hour, and stable silicone oil emulsion is obtained after emulsification.
Example 4:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end of long-chain alkane and the other end of tertiary amine: adding 134g of 1, 3-tetramethyldisiloxane into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device under the protection of nitrogen, preserving the temperature to 5 ℃, adding 10ppm of Kaersite catalyst, adding 196g of 1-tetradecene at the speed of 5g/min, and reacting for 2 hours at constant temperature; continuing to add 202.8g of 1-allyl-4-aminoethyl piperazine at the rate of 5g/min, continuing to react for 2 hours, then heating to 60 ℃ for reaction for 2 hours, then heating to 100 ℃, vacuumizing and pumping out low-boiling-point substances to obtain the long-chain alkyl and amino modified end sealing agent;
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 49.9g (0.1 mol) of the end sealing agent and 1184g (4 mol) of octamethylcyclotetrasiloxane, heating to 110 ℃, adding 50ppm of tetramethylammonium hydroxide alkali gel, reacting at constant temperature for 6 hours, heating to 150 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitterion co-modified silicone oil: under reflux condensation and nitrogen protection, 200g of the silicone oil is mixed with 300g of isopropanol/N, N-dimethylformamide (4, w/w), the mixture is heated to 45 ℃, 25g of 1, 3-propane sultone is dropwise added at the speed of 5g/min, reflux reaction is carried out for 12 hours, and a solvent and low-boiling-point substances are removed in a vacuumizing mode, so that the long-chain alkyl and zwitterionic co-modified silicone oil with the viscosity of 495cst is obtained.
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: at 25 ℃,45g of the silicone oil and 7g of emulsifier AEO-3/AEO-7 (1:1) are mixed by high-speed mechanical stirring, the stirring speed is 2000 r/min, 48g of water is added dropwise within 1 hour, and stable silicone oil emulsion is obtained after emulsification.
Example 5:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end of long-chain alkane and the other end of tertiary amine: under the protection of nitrogen, 160.8g of 1, 3-tetramethyldisiloxane is added into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device, the temperature is kept to 5 ℃, 10ppm of Kaersite catalyst is added, 201.61-dodecene is added at the speed of 5g/min, and the constant temperature reaction is carried out for 2 hours; adding 221.8g of 1-allyl-4-ethylpiperazine at the rate of 5g/min, reacting for 2 hours, heating to 55 ℃, reacting for 2 hours, heating to 100 ℃, vacuumizing and pumping out low-boiling-point substances to obtain the long-chain alkyl and amino modified end sealing agent;
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 45.6g (0.1 mol) of the end sealing agent and 888g (3 mol) of octamethylcyclotetrasiloxane, heating to 110 ℃, adding 50ppm of tetramethylammonium hydroxide alkali gel, reacting at constant temperature for 6 hours, heating to 150 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitter ion co-modified silicone oil: under reflux condensation and nitrogen protection, 250g of the silicone oil and 360g of isopropanol are mixed, heated to 50 ℃,50g of 1, 4-propane sultone is dripped at the speed of 5g/min, reflux reaction is carried out for 12 hours, and a vacuum pumping way is adopted to remove a solvent and low-boiling-point substances, so that the long-chain alkyl and zwitter-ion co-modified silicone oil with the viscosity of 365cst is obtained.
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: 50g of the silicone oil and 8g of emulsifier AEO-3/AEO-7 (2:1) are mixed by high-speed mechanical stirring at 25 ℃, the stirring speed is 1500 r/min, 42g of water is added dropwise within 1 hour, and stable silicone oil emulsion is obtained after emulsification.
Example 6:
a long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and a preparation method thereof are disclosed, and the preparation method comprises the following steps:
(1) Preparing a novel end socket agent with one end being long-chain alkane and the other end being tertiary amine: under the protection of nitrogen, 234.5g of 1, 3-tetramethyldisiloxane is added into a reactor with the volume of 1L and provided with a thermometer, a reflux condenser tube and a stirring device, the temperature is kept to 10 ℃, 10ppm of Kaersite catalyst is added, 147g of n-hexene is added at the speed of 5g/min, and the constant temperature reaction is carried out for 2 hours; adding 260g of 1-allyl piperazine at the rate of 5g/min, reacting for 2 hours, heating to 50 ℃ for 3 hours, heating to 100 ℃, vacuumizing and pumping out low-boiling-point substances to obtain a long-chain alkyl and amino modified end sealing agent;
(2) Preparation of long-chain alkyl and tertiary amine modified silicone oil: uniformly mixing 34.4g (0.1 mol) of the end sealing agent and 592g (2 mol) of octamethylcyclotetrasiloxane, heating to 110 ℃, adding 50ppm of tetramethylammonium hydroxide alkali gel, reacting for 6 hours at constant temperature, heating to 150 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
(3) Preparing long-chain alkyl and zwitter ion co-modified silicone oil: under reflux condensation and nitrogen protection, 200g of the silicone oil and 200g of isopropanol are mixed, heated to 60 ℃,60g of 1, 4-propane sultone is dripped at the speed of 5g/min, reflux reaction is carried out for 10 hours, and a vacuum pumping way is adopted to remove a solvent and low-boiling-point substances, so that the long-chain alkyl and zwitter-ion co-modified silicone oil with the viscosity of 115cst is obtained.
(4) Preparing long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion: 60g of the silicone oil and 10g of emulsifier AEO-3/AEO-7 (1:2) are mixed by high-speed mechanical stirring at 25 ℃, the stirring speed is 1000 r/min, 30g of water is added dropwise within 1 hour, and stable silicone oil emulsion is obtained after emulsification.
The emulsions prepared in examples 1-6 have excellent stability, and when used for treating polypropylene non-woven fabrics, the treated fabrics have good yellowing resistance, the hand feeling of the fabrics is improved, and meanwhile, the emulsions have long-term antibacterial property.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be understood by those skilled in the art that the present invention may be modified and equivalents substituted for elements thereof to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (4)
1. A preparation method of a long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion is characterized in that the emulsion is prepared according to the following steps:
mixing 30-60 parts by mass of silicone oil and 5-10 parts by mass of emulsifier by high-speed mechanical stirring at 25 ℃, dropwise adding 25-65 parts by mass of water within 1-2 hours, and emulsifying to obtain stable silicone oil emulsion, wherein the silicone oil adopts long-chain alkyl and zwitter ion co-modified antibacterial silicone oil, and the mechanical stirring speed is 1000-3000 r/min;
the silicone oil is prepared according to the following steps:
under reflux condensation and nitrogen protection, mixing long-chain alkyl and amino modified silicone oil with a solvent according to a mass ratio of 1.2-5, heating to 25-75 ℃, and dropwise adding an amphoteric ionization reagent; carrying out reflux reaction for 6-36 hours, and removing the solvent and low-boiling-point substances in a vacuumizing mode to obtain long-chain alkyl and zwitter-ion co-modified silicone oil, wherein the mass ratio of the zwitter-ionization reagent to the silicone oil is 0.05-0.5; the solvent is one or two of isopropanol, acetonitrile and N, N-dimethylformamide, and the zwitterionic reagent is 1,3-propane sultone or 1,4-butane sultone;
the long-chain alkyl and amino modified silicone oil is prepared by the following steps:
long-chain alkane, an amino modified end-capping agent and octamethylcyclotetrasiloxane are mixed according to a molar ratio of 1:5-100, heating to 85-115 ℃, adding 20-100ppm of catalyst, reacting at constant temperature for 3-10 hours, heating to 150-180 ℃, and removing low-boiling-point substances under a vacuum condition to obtain long-chain alkyl and amino modified silicone oil;
the long-chain alkane and amino modified end socket agent is prepared by the following steps:
under the protection of nitrogen, cooling 1,1,3,3-tetramethyl disiloxane to 0-20 ℃, adding 5-15ppm Kaersite catalyst, adding linear chain alpha olefin, and reacting at constant temperature for 0.5-3 hours; adding allyl substituted piperazine compound, continuing to react for 0.5-3 hours, then heating to 40-80 ℃ for 0.5-3 hours, then heating to 80-110 ℃, and removing unreacted low-boiling-point substances in vacuum to obtain long-chain alkane and amino modified end-capping agent;
the olefin is a linear alpha olefin containing 6 to 18 carbon atoms; the allyl substituted piperazine compounds are 1-allyl piperazine, 1-allyl-4-methyl piperazine, 1-allyl-4-ethyl piperazine and 1-allyl-4-aminoethyl piperazine; the mole ratio of the linear alpha olefin to 1,1,3,3-tetramethyldisiloxane is 0.9-1.1; the molar ratio of the allyl substituted piperazine compound to 1,1,3,3-tetramethyldisiloxane is 1.0-1.2.
2. The preparation method of the long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion as claimed in claim 1, wherein the preparation method comprises the following steps: the emulsifier is one or two of fatty alcohol polyoxyethylene ether AEO-3 and AEO-7.
3. The preparation method of the long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion as claimed in claim 1, wherein the preparation method comprises the following steps: the catalyst is tetramethyl ammonium hydroxide alkali glue.
4. The application of the long-chain alkyl and zwitter-ion co-modified antibacterial silicone oil emulsion prepared by the preparation method of any one of claims 1 to 3 in a fabric treating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010799403.2A CN112062965B (en) | 2020-08-11 | 2020-08-11 | Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010799403.2A CN112062965B (en) | 2020-08-11 | 2020-08-11 | Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112062965A CN112062965A (en) | 2020-12-11 |
| CN112062965B true CN112062965B (en) | 2022-10-04 |
Family
ID=73661118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010799403.2A Active CN112062965B (en) | 2020-08-11 | 2020-08-11 | Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112062965B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11945950B2 (en) * | 2020-12-18 | 2024-04-02 | Hongrita Plastics Ltd. | Germ-repellent silicone rubber and preparation method and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124490A (en) * | 1999-10-26 | 2000-09-26 | Mona Industries, Inc. | Zwitterionic siloxane polymers and ionically cross-linked polymers formed therefrom |
| KR100419864B1 (en) * | 2001-11-15 | 2004-03-04 | 한국화학연구원 | New Cross-linker, and Cross-linkable Solid polymer Electrolytes using the same |
| CN1354189A (en) * | 2001-12-05 | 2002-06-19 | 中国化工建设总公司常州涂料化工研究院 | Stable organosilicon modified copolymer emulsion and its preparation method |
| CN103172867A (en) * | 2011-12-20 | 2013-06-26 | 江南大学 | Preparation method of long-chain alkane and epoxy co-modified amino-terminated silicone oil |
| CN102952273B (en) * | 2012-10-31 | 2016-12-21 | 上海氟聚化学产品有限公司 | Amphoteric ion type amido silicon oil and preparation method thereof |
| CN203393077U (en) * | 2013-07-31 | 2014-01-15 | 嘉兴联合化学有限公司 | Terminal epoxy-based polysiloxane production system |
| CN104558618A (en) * | 2013-10-17 | 2015-04-29 | 苏州联胜化学有限公司 | Block modified silicone as well as preparation method and application thereof |
| CN110172154A (en) * | 2019-06-03 | 2019-08-27 | 浙江工业大学 | A kind of amino-modified silicone oil and preparation method thereof containing chain alkyl |
-
2020
- 2020-08-11 CN CN202010799403.2A patent/CN112062965B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112062965A (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0659930B1 (en) | Process for softening textiles with reduced yellowing, in which a composition containing polyorganosiloxane is used | |
| EP1063344B1 (en) | Nitrogen atom-containing polysiloxanes, their preparation, and fiber and fabric finishing agent compositions | |
| US7790801B2 (en) | Organo-functional silicone in emulsion systems and process for preparing same | |
| EP0546231B1 (en) | Process for softening and providing hydrophilic textile material using a composition containing polyorganisiloxane | |
| US8742154B2 (en) | Block ABA silicone polyalkyleneoxicie copolymers, methods of preparation, and applications for employing the same | |
| US7896929B2 (en) | Treating textiles with silicone polyether-amide block copolymers | |
| CN112062965B (en) | Long-chain alkyl and zwitterion co-modified antibacterial silicone oil emulsion and preparation method thereof | |
| US8399591B2 (en) | Amino-mercapto functional organopolysiloxanes | |
| JPS584114B2 (en) | Preparation agent for pre-shrunk wool | |
| EP2617892B1 (en) | Textiles treated with copolymers of epoxy compounds and amino silanes | |
| KR101003798B1 (en) | Hydrophilic amino modified polysiloxane and method for preparing thereof | |
| CN101747511B (en) | Polysiloxane containing fluorine and application thereof | |
| US4049676A (en) | Sulfolanyloxyalkyl cyclic polysiloxanes | |
| US9012671B2 (en) | Process for preparing amino-mercapto functional organopolysiloxanes | |
| CN111978548B (en) | Long-chain alkyl and zwitter-ion co-modified silicone oil and preparation method thereof | |
| KR100777010B1 (en) | Amino oil having goods alkali resistance property | |
| EP1519996B1 (en) | Fire and stain resistant compositions | |
| JP2887337B2 (en) | Fiber treatment agent | |
| CN115400462B (en) | Organic silicon compound with special structure and preparation method thereof | |
| WO2004018562A1 (en) | Conpositions which comprise polyorganosiloxanes with quaternary ammonium groups | |
| US11401420B2 (en) | Composition, fiber treatment agent, fiber treatment method, and treated fiber | |
| CN117903456A (en) | Super-stable quaternary ammonium modified silicone oil emulsion with reticular structure and preparation method thereof | |
| CN115322382A (en) | Organic silicon emulsifier with special structure and preparation method and application thereof | |
| KR101283626B1 (en) | Silicon copolymer with 3 dimensional network structure, its manufacturing method and fabric softner using the same |
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 |