CN116003805B - Preparation method of anionic block silicone oil - Google Patents
Preparation method of anionic block silicone oil Download PDFInfo
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- CN116003805B CN116003805B CN202310134584.0A CN202310134584A CN116003805B CN 116003805 B CN116003805 B CN 116003805B CN 202310134584 A CN202310134584 A CN 202310134584A CN 116003805 B CN116003805 B CN 116003805B
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 90
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 42
- 229920000570 polyether Polymers 0.000 claims abstract description 42
- 239000004593 Epoxy Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229940124277 aminobutyric acid Drugs 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 4
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 18
- 239000004744 fabric Substances 0.000 abstract description 8
- 238000003287 bathing Methods 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000006081 fluorescent whitening agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920013822 aminosilicone Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- YFDKVXNMRLLVSL-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O YFDKVXNMRLLVSL-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 anionic salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention provides a preparation method of anionic block silicone oil, which comprises the following steps: s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 4-8 hours at 25-40 ℃ under the catalysis of concentrated sulfuric acid, then adding sodium bicarbonate, neutralizing for 3-5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids by suction to obtain double-end hydrogen-containing silicone oil; s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether and a solvent, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting for 3-5 hours at 80-140 ℃ to obtain an epoxy polyether silicone oil intermediate; s3, adding the anionic monomer into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 80-100 ℃, adding the anionic aqueous solution into the reaction bottle, and reacting for 7-9 hours under heat preservation to obtain the anionic block silicone oil. The anionic block silicone oil prepared by the invention has better stability, can realize dyeing and bathing in the same time, and reduces the damage of fabrics.
Description
Technical Field
The invention relates to a preparation method of anionic block silicone oil.
Background
The printing and dyeing auxiliary agent can endow the fabric with the characteristics of smoothness, ventilation, plumpness, softness, hydrophilicity and the like, greatly improve the comfort and the functionality of the fabric, and well meet the living demands of human beings. Most of the currently mainstream organosilicon block silicone oil printing and dyeing auxiliary agents are cationic block silicone oil, which brings rich style characteristics to fabrics, but the cationic groups in the emulsion structure of the organosilicon block silicone oil printing and dyeing auxiliary agents are easy to flocculate with dye dispersants under high-salt and high-alkalinity conditions, so that demulsification and oil drifting phenomena are caused.
The traditional anionic silicone oil mostly adopts an emulsion polymerization method, uses anionic emulsifiers such as dodecyl benzene sulfonic acid (sodium) and the like, uses octamethyl cyclotetrasiloxane and a silane coupling agent as monomers to prepare the anionic silicone oil emulsion, and the scheme has a complex main chain structure, does not have an anionic structure on an organosilicon chain segment, has high ring body content in the emulsion and has poor hydrophilicity and compatibility.
In the prior art, binary anhydride is adopted to modify amino silicone oil to prepare anionic silicone oil containing carboxyl, so that the hydrophilicity and whiteness of the amino silicone oil are improved, but the binary anhydride has high activity, and gel and other phenomena are easy to occur if the reaction condition is improper, so that the production is not facilitated.
The existing textile dyeing and finishing process is complex and lengthy, the dyeing and finishing process is effectively shortened, the production efficiency can be improved, the enterprise cost is reduced, the water consumption and the sewage discharge can be reduced, and the environment protection effect can be achieved. However, in dyeing processes, such as dyeing of polyester fibers, it is generally necessary to treat the fibers at high temperatures, high salt and high alkalinity. At present, the ternary block silicone oil with good stability is difficult to meet the requirement of dyeing in the same bath, and can only be used after the dyed fiber is washed, otherwise, demulsification and oil drifting phenomena can occur. If the dyeing auxiliary agent can realize dyeing and one-bath, the processing flow can be shortened, the water consumption is reduced, the cost is reduced, the contact damage of equipment to the dyeing cloth in the dyeing process can be reduced, and the dyeing processability is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of anionic block silicone oil, and the prepared anionic block silicone oil has better stability, can realize dyeing and one bath, and reduces fabric damage.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the anionic block silicone oil comprises the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 4-8 hours at 25-40 ℃ under the catalysis of concentrated sulfuric acid, then adding sodium bicarbonate, neutralizing for 3-5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids by suction to obtain double-end hydrogen-containing silicone oil;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether and a solvent, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting for 3-5 hours at 80-140 ℃ to obtain an epoxy polyether silicone oil intermediate;
s3, adding the anionic monomer into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 80-100 ℃, adding the anionic aqueous solution into the reaction bottle, and reacting for 7-9 hours under heat preservation to obtain the anionic block silicone oil.
The chemical reaction process of the preparation method of the anionic block silicone oil is as follows:
S1:
S2：
S3：
in the step S1, the mass concentration of the concentrated sulfuric acid is 98%, and the weight ratio of the octamethyl cyclotetrasiloxane, the hydrogen-containing double seal heads, the concentrated sulfuric acid and the sodium bicarbonate is (50-120) 1 (1-4.8) 1.5-7.2.
Further, in the step S2 of the invention, the molecular weight of the allyl epoxy polyether is 500-1500g/mol.
Further, in the step S2 of the present invention, the solvent is one or a combination of several of isopropanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and isohexylene glycol.
Further, in the step S2, the weight ratio of the double-end hydrogen-containing silicone oil, the allyl epoxy polyether, the solvent and the chloroplatinic acid obtained in the step S1 is 200 (20-30): 140-150): 0.003.
Further, in the step S3 of the present invention, the anionic monomer is one of sodium sulfamate, sodium sulfanilate, sodium metasulfamate, aminobutyric acid, and sodium cyclohexylsulfamate.
In the step S3, the weight ratio of the anionic monomer to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is (2-6): 6-18): 200.
The anionic block silicone oil prepared by the invention can be prepared into anionic block silicone oil emulsion, and the specific steps are as follows: mixing anionic block silicone oil with an emulsifier and water, and stirring and emulsifying to obtain anionic block silicone oil emulsion; the emulsifier is one or the combination of more of XP30, XP50, TO7, TO9 and N19, and the solid content of the anionic block silicone oil is 30-40%.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention uses some anionic monomers containing reactive amino groups and anions (or anionic salts) on the structure to react with the epoxy-terminated polyether silicone oil intermediate under certain conditions to prepare the anionic block silicone oil, and the anionic groups and the polyether hydrophilic chain segments are connected into the organic silicon chain segments, so that the anionic block silicone oil has good hydrophilicity, high temperature resistance, alkali resistance, salt resistance and anion resistance, can meet the stability of partial dyeing in the same bath, can reduce the dyeing steps, simultaneously can increase the hand feeling of the fabric, can reduce the mechanical damage of the fabric in the dyeing process, and can also be used as a fuzzing agent.
2) The invention has simple operation, safe and stable process and easy mass production.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments and descriptions of the present invention are provided for the purpose of illustration and are not intended to be limiting.
Example 1
The anionic block silicone oil is prepared according to the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 6 hours at 30 ℃ under the catalysis of concentrated sulfuric acid with the mass concentration of 98%, then adding sodium bicarbonate, neutralizing for 4 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids to obtain double-end hydrogen-containing silicone oil, wherein the weight ratio of octamethyl cyclotetrasiloxane to the hydrogen-containing double-end socket to the concentrated sulfuric acid to the sodium bicarbonate is 58.6:1:1.5:2.25;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether with the molecular weight of 500g/mol and isopropanol, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting at 130 ℃ for 4 hours to obtain an epoxy polyether silicone oil intermediate, wherein the weight ratio of the double-end hydrogen-containing silicone oil obtained in the step S1 to the allyl epoxy polyether, the isopropanol and the chloroplatinic acid is 200:25.3:150.2:0.003;
s3, adding sodium sulfanilate into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 90 ℃, adding the anionic aqueous solution into the reaction bottle, and carrying out heat preservation reaction for 8 hours to obtain anionic block silicone oil, wherein the weight ratio of the sodium sulfanilate to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is 5.2:15.6:200.
Example 2
The anionic block silicone oil is prepared according to the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 8 hours at 25 ℃ under the catalysis of concentrated sulfuric acid with the mass concentration of 98%, then adding sodium bicarbonate, neutralizing for 3 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids to obtain double-end hydrogen-containing silicone oil, wherein the weight ratio of octamethyl cyclotetrasiloxane to the hydrogen-containing double-end socket to the concentrated sulfuric acid to the sodium bicarbonate is 73.4:1.85:2.77;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether with the molecular weight of 1000g/mol and ethylene glycol monobutyl ether, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting at 120 ℃ for 3 hours to obtain an epoxy polyether silicone oil intermediate, wherein the weight ratio of the double-end hydrogen-containing silicone oil obtained in the step S1 to the allyl epoxy polyether to the ethylene glycol monobutyl ether to the chloroplatinic acid is 200:20.3:146.8:0.003;
s3, adding sodium metaaminobenzene sulfonate into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 80 ℃, adding the anionic aqueous solution into the reaction bottle, and carrying out heat preservation reaction for 9 hours to obtain anionic block silicone oil, wherein the weight ratio of the sodium metaaminobenzene sulfonate to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is 4.25:12.75:200.
Example 3
The anionic block silicone oil is prepared according to the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 4 hours at 40 ℃ under the catalysis of concentrated sulfuric acid with the mass concentration of 98%, then adding sodium bicarbonate, neutralizing for 5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids to obtain double-end hydrogen-containing silicone oil, wherein the weight ratio of octamethyl cyclotetrasiloxane to the hydrogen-containing double-end socket to the concentrated sulfuric acid to the sodium bicarbonate is 110.9:1:2.78:4.17;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether with the molecular weight of 1500g/mol and diethylene glycol monobutyl ether, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting at 80 ℃ for 5 hours to obtain an epoxy polyether silicone oil intermediate, wherein the weight ratio of the double-end hydrogen-containing silicone oil obtained in the step S1 to the allyl epoxy polyether to the diethylene glycol monobutyl ether to the chloroplatinic acid is 200:26.9:151.3:0.003;
s3, adding sodium sulfamate into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 80 ℃, adding the anionic aqueous solution into the reaction bottle, and carrying out heat preservation reaction for 8 hours to obtain anionic block silicone oil, wherein the weight ratio of the sodium sulfamate to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is 2.84:8.52:200.
Comparative example: the silicone copolymer prepared in example 1 of the patent application 201410315223.7 belongs to cationic block silicone oils.
Experimental example
The anionic block silicone oils prepared in examples 1 to 3 were diluted with water to an emulsion of 30% by mass, and the comparative examples were diluted with the same emulsification method to an emulsion of 30% by mass, and then tested for high temperature stability, alkali stability, salt stability, and anion stability, respectively. The test results are shown in tables 1 to 5:
TABLE 1 high temperature stability
| 50℃ | 70℃ | 80℃ | 100℃ | |
| Comparative example | Transparent, stable | Transparent, stable | Become muddy, drift oil | - |
| Example 1 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 2 | Transparent, stable | Transparent, stable | Transparent and stableFixing device | Transparent, stable |
| Example 3 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
Note that: during testing, the test pieces are stored for 60 minutes at different temperatures.
TABLE 2 alkali resistance stability
| 50℃ | 60℃ | 70℃ | 80℃ | |
| Comparative example | Transparent, stable | Slightly muddy and slightly floating | Bleaching oil | Bleaching oil |
| Example 1 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 2 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 3 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
Note that: during testing, storing for 60min at different temperatures; the alkali used for testing is sodium hydroxide, and the solid-to-liquid ratio of the sodium hydroxide to the emulsion is 20g/L.
TABLE 3 salt tolerance stability
Note that: during testing, storing for 60min at different temperatures; the salt for testing is anhydrous sodium sulfate, and the solid-liquid ratio of the anhydrous sodium sulfate to the emulsion is 20g/L, 40g/L and 60g/L.
TABLE 4 anion stability-Ma Bingshui resistance solution
| 50℃ | 60℃ | 70℃ | 80℃ | |
| Comparative example | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 1 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 2 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 3 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
Note that: during testing, storing for 60min at different temperatures; the test anion was Ma Bingshui solution, which Ma Bingshui solution consisted of a Maropropion copolymer and water at a concentration of 10g/L and a volume ratio of Ma Bingshui solution to emulsion of 1:1.
TABLE 5 anionic stability-fluorescent whitening Agents
| 50℃ | 60℃ | 70℃ | 80℃ | |
| Comparative example | Cloudy and flossing | - | - | - |
| Example 1 | Transparent, stable | Transparent, stable | Transparent, stable | Slightly muddy |
| Example 2 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
| Example 3 | Transparent, stable | Transparent, stable | Transparent, stable | Transparent, stable |
Note that: during testing, storing for 60min at different temperatures; the test anion was fluorescent whitening agent 4BK, and the solid-to-liquid ratio of fluorescent whitening agent 4BK to emulsion was 5g/L.
As can be seen from tables 1 to 5, the high temperature resistance stability, the alkali resistance stability, the salt resistance stability and the anion resistance stability of the examples 1 to 3 are all superior to those of the comparative examples, and the anionic block silicone oil prepared by the invention has better stability.
Example 4
The anionic block silicone oil is prepared according to the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 5 hours at 35 ℃ under the catalysis of concentrated sulfuric acid with the mass concentration of 98%, then adding sodium bicarbonate, neutralizing for 3.5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids to obtain double-end hydrogen-containing silicone oil, wherein the weight ratio of octamethyl cyclotetrasiloxane to the hydrogen-containing double-end socket to the concentrated sulfuric acid to the sodium bicarbonate is 50:1:1.5;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether with the molecular weight of 1000g/mol and isohexide, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting at 140 ℃ for 3.5 hours to obtain an epoxy polyether silicone oil intermediate, wherein the weight ratio of the double-end hydrogen-containing silicone oil obtained in the step S1 to the allyl epoxy polyether to the isohexide to the chloroplatinic acid is 200:20:140:0.003;
s3, adding the aminobutyric acid into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 100 ℃, adding the anionic aqueous solution into the reaction bottle, and carrying out heat preservation reaction for 7 hours to obtain anionic block silicone oil, wherein the weight ratio of the aminobutyric acid to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is 2:6:200.
Example 5
The anionic block silicone oil is prepared according to the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 7 hours at 30 ℃ under the catalysis of concentrated sulfuric acid with the mass concentration of 98%, then adding sodium bicarbonate, neutralizing for 4.5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids to obtain double-end hydrogen-containing silicone oil, wherein the weight ratio of octamethyl cyclotetrasiloxane to the hydrogen-containing double-end socket to the concentrated sulfuric acid to the sodium bicarbonate is 120:1:4.8:7.2;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether with the molecular weight of 500g/mol and ethylene glycol monobutyl ether, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting at 100 ℃ for 4.5 hours to obtain an epoxy polyether silicone oil intermediate, wherein the weight ratio of the double-end hydrogen-containing silicone oil obtained in the step S1 to the allyl epoxy polyether to the ethylene glycol monobutyl ether to the chloroplatinic acid is 200:30:150:0.003;
s3, adding sodium cyclohexylsulfamate into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 85 ℃, adding the anionic aqueous solution into the reaction bottle, and reacting for 8.5 hours under heat preservation to obtain anionic block silicone oil, wherein the weight ratio of the sodium cyclohexylsulfamate to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is 6:18:200.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (4)
1. A preparation method of anionic block silicone oil is characterized by comprising the following steps: the method comprises the following steps:
s1, putting octamethyl cyclotetrasiloxane and a hydrogen-containing double-end socket into a reaction bottle, reacting for 4-8 hours at 25-40 ℃ under the catalysis of concentrated sulfuric acid, then adding sodium bicarbonate, neutralizing for 3-5 hours at room temperature to obtain a reaction solution, and filtering the reaction solution to remove solids by suction to obtain double-end hydrogen-containing silicone oil; the mass concentration of the concentrated sulfuric acid is 98%, and the weight ratio of the octamethyl cyclotetrasiloxane to the hydrogen-containing double seal head to the concentrated sulfuric acid to the sodium bicarbonate is (50-120) 1 (1-4.8) 1.5-7.2;
s2, mixing the double-end hydrogen-containing silicone oil obtained in the step S1, allyl epoxy polyether and a solvent, stirring and heating to 40 ℃, adding chloroplatinic acid, and reacting for 3-5 hours at 80-140 ℃ to obtain an epoxy polyether silicone oil intermediate; the weight ratio of the double-end hydrogen silicone oil, allyl epoxy polyether, solvent and chloroplatinic acid obtained in the step S1 is 200 (20-30) (140-150) (0.003);
s3, adding an anionic monomer into water, uniformly mixing to obtain an anionic aqueous solution, adding the epoxy polyether silicone oil intermediate obtained in the step S2 into a reaction bottle, heating to 80-100 ℃, adding the anionic aqueous solution into the reaction bottle, and reacting for 7-9 hours under heat preservation to obtain anionic block silicone oil; the weight ratio of the anionic monomer to the water to the epoxy polyether silicone oil intermediate obtained in the step S2 is (2-6): 6-18): 200.
2. The method for preparing anionic block silicone oil according to claim 1, characterized in that: in the step S2, the molecular weight of the allyl epoxy polyether is 500-1500g/mol.
3. The method for preparing anionic block silicone oil according to claim 1, characterized in that: in the step S2, the solvent is one or a combination of several of isopropanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and isohexylene glycol.
4. The method for preparing anionic block silicone oil according to claim 1, characterized in that: in the step S3, the anionic monomer is one of sodium sulfamate, sodium sulfanilate, sodium metasulfamate, aminobutyric acid and sodium cyclohexylsulfamate.
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