CN116217798A - Process for preparing gas phase inversion amidino graft polymer stable miniemulsion - Google Patents
Process for preparing gas phase inversion amidino graft polymer stable miniemulsion Download PDFInfo
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- CN116217798A CN116217798A CN202211629334.6A CN202211629334A CN116217798A CN 116217798 A CN116217798 A CN 116217798A CN 202211629334 A CN202211629334 A CN 202211629334A CN 116217798 A CN116217798 A CN 116217798A
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 55
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000001409 amidines Chemical class 0.000 claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000000977 initiatory effect Effects 0.000 claims abstract description 9
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims description 11
- 230000005587 bubbling Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- -1 Amidinodecyl acrylamide Chemical compound 0.000 claims description 5
- 229940057995 liquid paraffin Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 125000000320 amidine group Chemical group 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
The invention relates to the fields of functional polymer synthesis, reversed-phase colloid, carbon dioxide utilization and the like. The invention discloses a method for preparing a stable miniemulsion of a gas phase inversion amidino graft polymer, which comprises the steps of mixing an initiator aqueous solution and an oily solvent, crushing at a certain temperature according to a set mode, maintaining ultrasonic waves, heating, adding a water-soluble monomer solution for polymerization, and forming the stable inverse miniemulsion of the water-soluble oligomer. The preparation method is placed in a reactor protected by carbon dioxide, and the reverse miniemulsion with stable amidine grafted polymer can be prepared at low temperature by slowly dripping amidine monomers and adopting a slow oxidation-reduction initiation mode. The gas-responsive amidine graft polymer stabilized miniemulsion may be passed through an inert gas or carbon dioxide to effect water/oil type inversion of the miniemulsion to oil/water or oil/water type inversion to water/oil type inversion.
Description
Technical Field
The present invention provides a gas phase inversion miniemulsion process for stabilizing amidine grafted polymers. The carbon dioxide is used for responding to the amidine graft polymer to stabilize the reverse phase miniemulsion, and inert gas is introduced to realize that the water/oil type phase inversion of the miniemulsion is changed into oil/water type, or carbon dioxide is introduced to realize that the oil/water type phase inversion of the miniemulsion is changed into water/oil type. The invention relates to the fields of functional polymer synthesis, reversed-phase colloid, carbon dioxide utilization and the like.
Background
Stimulus-responsive polymers are a class of intelligent macromolecular systems that can accept physical (temperature, optical radiation, electromagnetic fields, stress, etc.) or chemical (pH, ionic strength, redox agents, biomolecules, etc.) stimulus signals that cause changes in the configuration of the polymer units, chain structure, assembly morphology, resulting in abrupt changes in various macroscopic properties of the system, also known as environmentally-responsive polymers. Carbon dioxide stimulus-responsive polymers are a class of macromolecules that reversibly change in polymer properties upon external application and removal of carbon dioxide gas.
Amidines are also known as imidoamides, i.e. compounds in which the carbonyl oxygen atom of the amide molecule is replaced by an imino group. Polyamidine is a class of polymers containing amidine groups in the molecular chain. After carbon dioxide forms carbonic acid in water, guanidine and amidine groups are protonated to form corresponding salts, and the hydrophilicity and hydrophobicity of molecules are changed. And (3) discharging carbon dioxide in the inert gas solution under the heating condition, so that the molecules are deprotonated and restored to the initial state. The introduction of amidine groups into polymer systems and the development and use thereof have become an important point of technological development.
The carbon dioxide is used for responding to the amidine graft polymer to realize the stability of the miniemulsion, and carbon dioxide or nitrogen is introduced to realize the inversion of the oil/water type miniemulsion into the water/oil type or the water/oil type miniemulsion into the oil/water type. Relates to the fields of functional polymer synthesis, reversed phase colloid, carbon dioxide utilization and the like. The invention has definite practical value and innovation.
Disclosure of Invention
The invention aims to perform carbon dioxide response amidino grafted polymer to realize miniemulsion stabilization, and introducing carbon dioxide or inert gas to realize miniemulsion phase inversion.
A process for the stabilization of miniemulsions of gas-phase-inversion amidino graft polymers, carried out according to the following steps:
(1) Preparation of water-soluble oligomer stabilized inverse miniemulsion
At room temperature, mixing the initiator aqueous solution and the oily solvent, quickly transferring into an ultrasonic biological pulverizer, pulverizing at a certain temperature for a certain time in a set mode, maintaining ultrasonic waves, heating to a specified temperature, dripping the water-soluble monomer solution at a certain speed, and starting polymerization to form the water-soluble oligomer-stabilized inverse miniemulsion.
The initiator in the step (1) is potassium persulfate or ammonium persulfate and the like, and the mass concentration of the aqueous solution of the initiator is 0.5-1.0%; the water-soluble monomer refers to acrylamide, methacrylic acid (or methacrylate), acrylic acid (or acrylate), itaconic acid (or methylene succinate), styrenesulfonic acid or sodium vinylsulfonate and the like, and the mass concentration of the water-soluble monomer solution is 5.0-10.0%. The oily solvent refers to heavy liquid paraffin (density 0.860-0.890 g/cc) and the like. Mixing the water phase and the oil phase, and crushing for 10 minutes in a 70% power state by using a high-power 500W ultrasonic biological crusher at a temperature of 5 ℃; high-power crushing, low-power 200W power state, heating to 70-80 deg.c, dropping monomer water solution and maintaining ultrasonic treatment for 150 min. After the completion of the sonication, the reaction solution was cooled to room temperature.
The mass ratio of the water-soluble initiator solution to the oily solvent to the monomer aqueous solution in the step (1) is 5-10:100:50-100, and the dropping speed of the monomer aqueous solution is: 2% aqueous monomer solution mass/min.
(2) Preparation of stable inverse miniemulsion of amidine graft polymer
And (3) placing the water-soluble oligomer-stabilized reverse phase miniemulsion prepared in the quantitative step (1) into a stirred reactor under the protection of carbon dioxide at room temperature, and controlling the colloid temperature. And respectively adding amidino monomer, oxidant aqueous solution and reducer which forms a water-soluble oxidation-reduction grafting initiation system into the reactor by adopting a three-channel microsyringe. After the dripping is completed, the colloid temperature is continuously maintained for a certain time, and then the temperature is reduced to room temperature to complete the preparation of the reverse phase miniemulsion with stable amidine grafted polymer.
The amidino monomer in the process of step (2) is an N-amidinoalkylacrylamide, such as N-amidinodecylacrylamide. The oxidant aqueous solution is 1% mass concentration aqueous solution of cerium nitrate or cerium sulfate; the reducing agent for forming the water-soluble oxidation-reduction grafting initiation system is methanol, ethanol or propylene glycol, etc.
The mass ratio of the amidine monomer to the oxidant aqueous solution to the reducing agent forming the water-soluble oxidation system to the water-soluble oligomer inverse miniemulsion prepared in the step (2) is 5-10:1:1:100; the dripping speeds of the amidino monomer, the oxidant aqueous solution and the reducing agent forming the water-soluble oxidation system are all 10 percent of the mass/min of the dripped substances; the colloid is controlled at 40 ℃, and the colloid is kept at the temperature for 60-90 minutes after the dripping is completed.
(3) Gas phase inversion amidino graft polymer stabilized miniemulsion
At room temperature, introducing inert gas into the reactor (of water-in-oil type) filled with the reverse phase miniemulsion (of which the amidine grafted polymer is stable) prepared in the step (2) to bubble and raise the temperature for a certain time, layering the reverse phase miniemulsion in the reactor, and after crushing for a certain time by using an ultrasonic biological crusher, responding to the amidine grafted polymer by gas to invert the reverse phase miniemulsion, wherein the reverse phase miniemulsion (of which the water-in-oil type) inverts into miniemulsion (of which the water-in-oil type); stopping introducing inert gas, reducing the emulsion temperature, blowing carbon dioxide again, layering the miniemulsion in the reactor again, crushing for a certain time by using an ultrasonic biological crusher, and recovering the gas in response to the amidine grafted polymer phase inversion miniemulsion to the phase state of the step (2), so as to realize the purpose that the miniemulsion (oil-in-water) is phase-inverted into inverse miniemulsion (water-in-oil).
In the method in the step (3), the inert gas can be nitrogen or argon, the temperature is increased to 60-80 ℃, the air blowing time is 10 minutes, and the air flow is standard air pressure of 1 cubic centimeter per minute; stopping introducing inert gas, reducing the temperature of the emulsion to 20-40 ℃, and blowing for 10 minutes, wherein the gas flow is 1 cubic decimeter/min of standard gas pressure; high power 500W of the ultrasonic biological pulverizer pulverizes in a 70% power state for 5 minutes.
The invention stabilizes the reverse phase miniemulsion by prefabricating carbon dioxide in response to the amidino graft polymer, and introduces inert gas to realize the inversion of the miniemulsion or re-introduces carbon dioxide to recover the reverse phase state of the miniemulsion. The miniemulsion prepared by the method has potential application prospect in the fields of regulating and controlling carbon dioxide absorption, conversion and utilization, intelligent macromolecules and the like. The invention has the following advantages:
1. the water-soluble oligomer with 20-50 polymerization degree can be obtained by a reversed-phase miniemulsion polymerization method of dropwise adding water-soluble monomers;
2. the amidine grafted polymer can be prepared at low temperature by utilizing a slow dropwise adding amidine monomer and an oxidation-reduction slow initiation mode;
3. the amidine graft polymer has excellent stability, and under the action of the gas response amidine graft polymer, the reverse phase miniemulsion can be introduced with inert gas to change phase or carbon dioxide to restore the phase state.
Detailed Description
The invention will be described in further detail with reference to examples.
Example 1
(1) Preparation of water-soluble oligomer stabilized inverse miniemulsion
At room temperature, mixing 5 g of 0.5% potassium persulfate initiator aqueous solution with 100 g of heavy liquid paraffin (density 0.860 g/cubic centimeter) solvent, quickly transferring into an ultrasonic biological pulverizer, mixing water phase and oil phase, and pulverizing for 10 minutes in a 70% power state by using the ultrasonic biological pulverizer at a high power of 500W and a temperature of 5 ℃; after high-power crushing, the mixture is turned into a low-power 200W power state, the temperature is raised to 70 ℃, 50 g of 5.0% mass concentration water-soluble acrylamide aqueous solution is dripped at a speed of 1 g/min, polymerization is started, and ultrasonic treatment is maintained for 150 minutes. After the completion of the sonication, the reaction solution was cooled to room temperature. Forming a water-soluble oligomer-stabilized inverse miniemulsion. The average particle diameter of the reverse phase miniemulsion Z is 150 nanometers, and the standing stability time is more than 30 days.
(2) Preparation of stable inverse miniemulsion of amidine graft polymer
100 g of the water-soluble oligomer inverse miniemulsion prepared in the step (1) is placed in a stirred reactor under the protection of carbon dioxide at room temperature, and the colloid temperature is controlled to be 40 ℃.5 g of N-amidinodecyl acrylamide, 0.1 g of 1% strength by mass aqueous solution of cerium nitrate and 0.1 g of methanol reducing agent which forms a water-soluble oxidation-reduction grafting initiation system are respectively added into the reactor at a rate of 0.5 g/min by using a three-channel microsyringe. Continuing to maintain the colloid at 40 ℃ after the dripping is completed, and continuing to maintain the colloid for heat preservation for 60 minutes after the dripping is completed; the temperature is then reduced to room temperature to complete the preparation of the stable inverse miniemulsion of the amidine grafted polymer. The Z average particle diameter of the reverse miniemulsion stabilized by the amidine grafted polymer is 180 nanometers, and the standing stability time is more than 30 days.
(3) Gas phase inversion amidino graft polymer stabilized miniemulsion
And (3) at room temperature, introducing argon into the reverse phase miniemulsion reactor with the stable amidine grafted polymer prepared in the step (2), bubbling and raising the temperature to 60 ℃, wherein the bubbling time is 10 minutes, the gas flow is 1 cubic centimeter per minute of standard gas pressure, and the reverse phase miniemulsion in the reactor is layered and the bubbling time is 10 minutes. A gas-responsive amidino graft polymer phase inversion miniemulsion; stopping introducing inert gas, reducing the temperature of the emulsion to 20 ℃, and blowing carbon dioxide again, wherein the gas flow is standard gas pressure of 1 cubic centimeter per minute, the gas blowing time is 10 minutes, the fine emulsion in the reactor is layered again, and the ultrasonic biological pulverizer is crushed for 5 minutes in a power state of 70% at high power of 500W. The gas-responsive amidine graft polymer phase inversion miniemulsion returns to the step (2) phase state.
Example 2
(1) Preparation of water-soluble oligomer stabilized inverse miniemulsion
At room temperature, mixing 10 g of 1.0% ammonium persulfate initiator aqueous solution with 100 g of heavy liquid paraffin (density 0.890 g/cubic centimeter) solvent, quickly transferring into an ultrasonic biological pulverizer, mixing water phase and oil phase, and pulverizing for 10 minutes in a 70% power state by using high power 500W of the ultrasonic biological pulverizer at a temperature of 5 ℃; after high-power crushing, the mixture is turned into a low-power 200W power state, the temperature is raised to 80 ℃, 100 g of 10.0% mass concentration water-soluble methacrylic acid aqueous solution is dripped at a speed of 2 g/min, polymerization is started, and ultrasonic treatment is maintained for 150 minutes. After the completion of the sonication, the reaction solution was cooled to room temperature. Forming a water-soluble oligomer-stabilized inverse miniemulsion. The average particle diameter of the reverse phase miniemulsion Z is 180 nanometers, and the standing stability time is more than 30 days.
(2) Preparation of stable inverse miniemulsion of amidine graft polymer
100 g of the water-soluble oligomer inverse miniemulsion prepared in the step (1) is placed in a stirred reactor under the protection of carbon dioxide at room temperature, and the colloid temperature is controlled to be 40 ℃. 10 g of N-amidinodecyl acrylamide, 0.1 g/min of 1% strength by mass aqueous solution of 1 g of cerium sulfate and 0.1 g/min of reducing agents such as 1 g of ethanol which form a water-soluble oxidation-reduction grafting initiation system are respectively added into the reactor by adopting a three-channel microsyringe. Continuing to maintain the colloid at 40 ℃ after the dripping is completed, and continuing to maintain the colloid for 90 minutes after the dripping is completed; the temperature is then reduced to room temperature to complete the preparation of the stable inverse miniemulsion of the amidine grafted polymer. The Z average particle diameter of the reverse miniemulsion stabilized by the amidine grafted polymer is 230 nanometers, and the standing stability time is more than 30 days.
(3) Gas phase inversion amidino graft polymer stabilized miniemulsion
And (3) at room temperature, introducing nitrogen into the reverse phase miniemulsion reactor containing the amidine grafted polymer prepared in the step (2), bubbling and raising the temperature to 80 ℃, wherein the bubbling time is 10 minutes, the gas flow is 1 cubic decimeter per minute of standard gas pressure, and the reverse phase miniemulsion in the reactor is layered, and the bubbling time is 10 minutes. A gas-responsive amidino graft polymer phase inversion miniemulsion; stopping introducing inert gas, reducing the temperature of the emulsion to 40 ℃, and blowing carbon dioxide again, wherein the gas flow is standard gas pressure of 1 cubic centimeter per minute, the gas blowing time is 10 minutes, the fine emulsion in the reactor is layered again, and the ultrasonic biological pulverizer is crushed for 5 minutes in a power state of 70% at high power of 500W. The gas-responsive amidine graft polymer phase inversion miniemulsion returns to the step (2) phase state.
Example 3
(1) Preparation of water-soluble oligomer stabilized inverse miniemulsion
At room temperature, mixing 8 g of 0.7% ammonium persulfate initiator aqueous solution with 100 g of heavy liquid paraffin (density 0.870 g/cubic centimeter) solvent, quickly transferring into an ultrasonic biological pulverizer, mixing water phase and oil phase, and pulverizing at 70% power state for 10 min by using the ultrasonic biological pulverizer at 5 ℃; after high-power crushing, the mixture is transferred to a low-power 200W power state, the temperature is raised to 75 ℃, 75 g of 7.0 mass percent water-soluble sodium vinylsulfonate solution is added dropwise at the speed of 1.5 g/min to start polymerization, and the ultrasonic treatment is maintained for 150 minutes. After the completion of the sonication, the reaction solution was cooled to room temperature. Forming a water-soluble oligomer-stabilized inverse miniemulsion. The average particle diameter of the reverse phase miniemulsion Z is 160 nanometers, and the standing stability time is more than 30 days.
(2) Preparation of stable inverse miniemulsion of amidine graft polymer
100 g of the water-soluble oligomer-stabilized reverse phase miniemulsion prepared in the step (1) is placed in a stirred reactor under the protection of carbon dioxide at room temperature, and the colloid temperature is controlled. 8 g of N-amidinodecyl acrylamide, 0.1 g of 1% strength by mass aqueous solution of cerium nitrate and 0.1 g of reducing agent such as propylene glycol which forms a water-soluble oxidation-reduction grafting initiation system are respectively added into the reactor at a rate of 0.75 g/min by adopting a three-channel microsyringe. Continuing to maintain the colloid at 40 ℃ after the dripping is completed, and continuing to maintain the colloid for heat preservation for 80 minutes after the dripping is completed; the temperature is then reduced to room temperature to complete the preparation of the stable inverse miniemulsion of the amidine grafted polymer. The Z average particle diameter of the reverse miniemulsion stabilized by the amidine grafted polymer is 200 nanometers, and the standing stability time is more than 30 days.
(3) Gas phase inversion amidino graft polymer stabilized miniemulsion
And (3) at room temperature, introducing argon into the reverse phase miniemulsion reactor with the stable amidine grafted polymer prepared in the step (2), bubbling and raising the temperature to 70 ℃, wherein the bubbling time is 10 minutes, the gas flow is 1 cubic centimeter per minute of standard gas pressure, and the reverse phase miniemulsion in the reactor is layered and the bubbling time is 10 minutes. A gas-responsive amidino graft polymer phase inversion miniemulsion; stopping introducing inert gas, reducing the temperature of the emulsion to 30 ℃, and blowing carbon dioxide again, wherein the gas flow is standard gas pressure of 1 cubic centimeter per minute, the gas blowing time is 10 minutes, the miniemulsion in the reactor is layered again, and the ultrasonic biological pulverizer is crushed for 5 minutes in a power state of 70% at high power of 500W. The gas-responsive amidine graft polymer phase inversion miniemulsion returns to the step (2) phase state.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and modifications made to the present invention by those skilled in the art in light of the present disclosure should be included within the scope of the present invention.
Claims (10)
1. A gas phase inversion amidine graft polymer stabilized miniemulsion process characterized by: the method comprises the following specific steps:
(1) Preparation of water-soluble oligomer stabilized inverse miniemulsion
Mixing an initiator aqueous solution and an oily solvent at room temperature, then transferring the mixture into an ultrasonic biological pulverizer for pulverization, and dripping a water-soluble monomer solution to start polymerization to form a water-soluble oligomer-stabilized reverse phase miniemulsion;
(2) Preparation of stable inverse miniemulsion of amidine graft polymer
Placing the water-soluble oligomer inverse miniemulsion prepared in the step (1) in a reactor under the protection of carbon dioxide, controlling the colloid temperature, respectively adding an amidine monomer, an oxidant aqueous solution and a reducing agent for forming a water-soluble oxidation-reduction grafting initiation system into the reactor, dropwise adding, carrying out heat preservation reaction, and then reducing the temperature to room temperature to finish the preparation of the inverse miniemulsion with stable amidine grafted polymer;
(3) Gas phase inversion amidino graft polymer stabilized miniemulsion
Introducing inert gas into the reactor of the reverse phase miniemulsion of the amidine grafted polymer prepared in the step (2) at room temperature, bubbling and raising the temperature to 60-80 ℃, and bubbling for a certain time to enable the reverse phase miniemulsion in the reactor to be layered, and after crushing by an ultrasonic biological crusher, inverting the reverse phase miniemulsion of the amidine polymer stabilized by the inert gas; stopping introducing inert gas, reducing the temperature of the emulsion to 20-40 ℃, blowing carbon dioxide again, layering the miniemulsion in the reactor again, crushing the miniemulsion by using an ultrasonic biological crusher, and recovering the miniemulsion stabilized by the carbon dioxide phase-inversion amidino polymer to the phase state in the step (2).
2. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: the initiator in the step (1) is potassium persulfate or ammonium persulfate, and the mass concentration of the aqueous solution of the initiator is 0.5-1.0%; the water-soluble monomer is one or more of acrylamide, methacrylic acid, methacrylate, acrylic acid, acrylate, itaconic acid, methylene succinate, styrene sulfonic acid or sodium vinylsulfonate, and the mass concentration of the monomer aqueous solution is 5.0-10.0%; the oily solvent is heavy liquid paraffin.
3. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: mixing the initiator aqueous solution and the oily solvent, and transferring the mixture into an ultrasonic biological pulverizer under the pulverizing conditions that: crushing the powder for 10 minutes in a 70% power state at a high power of 500W and a temperature of 5 ℃; high-power crushing, low-power 200W power state, heating to 70-80 deg.c, dropping monomer water solution, maintaining ultrasonic for 150 min, and cooling the reacted liquid to room temperature.
4. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: the mass ratio of the water-soluble initiator solution to the oily solvent to the monomer aqueous solution in the step (1) is 5-10:100:50-100; the drop rate of the aqueous monomer solution was 2% mass/min.
5. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: step (2) amidino monomer isNAmidinoalkylacrylamides, in particularNAmidinodecyl acrylamide.
6. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: the oxidant aqueous solution is 1% mass concentration aqueous solution of cerium nitrate or cerium sulfate; the reducing agent of the water-soluble oxidation-reduction grafting initiation system is methanol, ethanol or propylene glycol.
7. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: the mass ratio of the amidine monomer to the oxidant aqueous solution to the reducing agent forming the water-soluble oxidation system to the water-soluble oligomer inverse miniemulsion prepared in the step (2) is 5-10:1:1:100; the dropping speeds of the amidine monomer, the aqueous oxidant solution and the reducing agent composing the water-soluble oxidation system are all 10% of the mass/min of the added substance.
8. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: and (2) controlling the colloid temperature to be 40 ℃, and carrying out heat preservation reaction for 60-90 minutes after dripping.
9. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: the inert gas in the step (3) is nitrogen or argon; the gas flow rate of the air blowing is 1 cubic decimeter/min of standard air pressure.
10. The method of claim 1, wherein the gas phase inversion amidine graft polymer is a stable miniemulsion comprising: and (3) crushing the materials for 5 minutes in a 70% power state under the condition of 500W of a ultrasonic biological crusher.
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