CN104492341A - Method for preparing Bola ionic liquid type organosilicon surfactant - Google Patents
Method for preparing Bola ionic liquid type organosilicon surfactant Download PDFInfo
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- CN104492341A CN104492341A CN201410838176.4A CN201410838176A CN104492341A CN 104492341 A CN104492341 A CN 104492341A CN 201410838176 A CN201410838176 A CN 201410838176A CN 104492341 A CN104492341 A CN 104492341A
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Abstract
The invention discloses a method for preparing a Bola ionic liquid type organosilicon surfactant. The Bola ionic liquid type organosilicon surfactant has the Bola amphiphilic molecule structure characteristics, and is prepared from reaction of alpha, omega-dichloro propyl polysiloxane or alpha, omega-dichloro methyl polysiloxane and N-methylimidazole, N-methylpyrrolidine or pyridine. The method is simple in preparation step and easy to operate, and the prepared surfactant is excellent in surface activity, has certain sterilization property and can be used in fields such as medicine slow release, functional nano materials and textile processing additives.
Description
Technical field
The present invention relates to a kind of preparation method of Bola ion liquid type organic silicon surfactant, belong to the synthesis technical field of organic silicon surfactant.
Background technology
Organic silicon surfactant is hydrophobic chain link with silica/carbon alkane, connects the surfactant that a class of one or more hydrophilic radical composition is new and effective.Not only there is the surface-active more excellent than alkanes surfactant and " surpass and sprawl " property, and the performance that the high-low temperature resistant, weather-resistant, nontoxic physiological inertia etc. that possess organosilicon material are excellent.Such organic silicon surfactant with the performance of its excellence be widely used in polyurethane foam, agricultural chemicals, textile auxiliary, day used additives, the field such as oil field chemical.To further develop along with organosilicon material and to the deep exploitation of organosilicon downstream product, the kind of organic silicon surfactant also will constantly increase, and application also can constantly expand, and this is all developing direction and the study hotspot of surfactant.
Ionic liquid is made up of organic cation and inorganic anion, and the salt be in a liquid state under low temperature (<100 DEG C), also referred to as " room temperature molten salt ".Ionic liquid has the characteristics such as low volatility, liquid temperature wide ranges, Heat stability is good, low toxicity, have a wide range of applications at chemical science and many fields such as technology, medical industry, ionic liquid is receiving acceptance and the concern of countries in the world and petroleum chemical enterprise as eco-friendly " cleaning " solvent and new catalyst system and catalyzing simultaneously.Development of new has surface-active ionic liquid, not only can expand the application of ionic liquid self, can also improve the character of surfactant aggregates, expands its kind and range of application.
Parents' molecular structure of Bola type surfactant determines the performance of its uniqueness, as high-temperature stability and chemical stability good; Critical micelle concentration value is generally greater than traditional single parent's aqueous based surfactant; Critical solution temperature is lower in aqueous, has higher dissolubility under normal temperature; The number of aggregates formed in aqueous phase is less, can form state of aggregation micella that is spherical, bar-shaped, variform such as dish dress etc., can also interface and body mutually in be self-assembled into ordered molecular aggregation, as monomolecular film or vesica.So change Bola type surfactant two polar head-group or hydrophobic chain can make it have broad application prospects in nano material, medicament slow release, self assembly, fabrication of new materials and catalysis etc.
Although reported a lot of Bola type surfactant at present, its capillary ability reducing water is very undesirable, as the γ of Bola type surfactant 1,12-bis-glutamic acid base dodecyl diamine salts
cMCbe 50.5 mN/m, see fresh tree harmony, Master's thesis, Yangzhou University, 2010; Bola type polyurethane surfactant γ
cMCbe greater than 39.0 mN/m, see Zhang Jing, Master's thesis, Northcentral University, 2013; Hao Chuanming adopts Si―H addition reaction to prepare γ
cMCfor the Bola type organic silicon surfactant of 24.6mN/m, see Hao Chuanming, Cui Xiao, Li Junying, Chinese Chemical Society the 29th Annual Conference summary collection---the 26th branch: colloid and interface, 2014-8-4; But because Si―H addition reaction exists α and β addition reaction, thus synthesized out there is isomer, thus have impact on the activity of surfactant.
Because the research of people to Bola type organic silicon surfactant is at the early-stage, development of new structure has the Bola type organic silicon surfactant of high surface, studies its application performance in every field very necessary.The present invention directly and reactive tertiary amine direct by chloropropyl has prepared the ion liquid based Bola type organic silicon surfactant of a kind of high surface, thus avoids the impact of isomer.
Summary of the invention
The invention provides a kind of simple, safe and economic method preparing Bola ion liquid type organic silicon surfactant.
The preparation method of a kind of Bola ion liquid type of the present invention organic silicon surfactant, its structural formula is:
Preparation process is as follows:
Step 1, polymerisation
Drop into octamethylcy-clotetrasiloxane, 1 in the reactor, 3-bis-(chloropropyl) tetramethyl disiloxane or 1,3-bis-(chloromethyl) tetramethyl disiloxane, concentrated sulfuric acid catalyst, stirring at room temperature is after 2 ~ 4 hours, be washed to neutrality, de-low-boiling-point substance.Obtain the α that the degree of polymerization is n, ω-two Chloropropylpolysiloxanes or α, ω-dichloromethyl polysiloxanes.
Step 2, quaterisation
The product of step 1 is loaded in there-necked flask, adds tertiary amine, solvent, N
2under protection, system after 30 ~ 35 hours of reacting at 70 ~ 85 DEG C is down to room temperature.By ethyl acetate precipitation, pour out upper solution, precipitation is dissolved in methyl alcohol, then by ethyl acetate precipitation, repeat 4-8 time like this.0.1 MPa must be deposited in, 40 DEG C of dryings 2 days, after cooling Bola ion liquid type organic silicon surfactant.
Described polymerization degree n is 0 ~ 15, m is 0 or 3.
Described tertiary amine is: N-methylimidazole, N-crassitude or pyridine.
Described α, ω-two Chloropropylpolysiloxanes or α, ω-dichloromethyl polysiloxanes and tertiary amine mol ratio be 1:2 ~ 4.
Described solvent is isopropyl alcohol, butanols, acetonitrile or dimethyl formamide.
beneficial effect: Bola ion liquid type organic silicon surfactant γ prepared by the present invention
cMCbe less than 25 mN/m, there is high surface and there is not the impact of isomer, and there is excellent heat endurance and biocompatibility, can be used for the fields such as medicament slow release, functional nanomaterials, textile process auxiliary agent, and there is certain bactericidal properties.
Preparation method of the present invention is feasible, and processing step is easy, be easy to operation, is applicable to suitability for industrialized production application.
Detailed description of the invention
below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
embodiment 1
Drop in the reactor 6.0 g octamethylcy-clotetrasiloxanes, 2.9 g 1,3-bis-(chloropropyl) tetramethyl disiloxanes, concentrated sulfuric acid catalyst addition be 2%(mass fraction), stirring at room temperature, after 2 ~ 4 hours, is washed to neutrality, de-lowly to boil.α, ω-two Chloropropylpolysiloxanes, the degree of polymerization is 6.6.
In the 100ml there-necked flask of assembling condenser pipe, add 5.0 g α, ω-two Chloropropylpolysiloxanes, 6.0 g N-methylimidazoles, 10ml isopropyl alcohol, N
2in 85 DEG C of reactions 36 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 30 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml absolute methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by absolute methanol-ethyl acetate redissolve-precipitation 5 times.Product is in 0.1 MPa, and 40 DEG C of dryings obtained thickness imidazole radicals Bola ion liquid type organic silicon surfactant after 2 days, and productive rate is 93%.Hermetically drying is preserved.Tg is-45 DEG C, and First CMC is 0.03 g/L, and second CMC is 3.2 g/L, γ
cMCbe 24.3 mN/m.
embodiment 2
Drop in the reactor 6.0 g octamethylcy-clotetrasiloxanes, 2.9 g 1,3-bis-(chloropropyl) tetramethyl disiloxanes, concentrated sulfuric acid catalyst addition be 2%(mass fraction), stirring at room temperature, after 2 ~ 4 hours, is washed to neutrality, de-lowly to boil.α, ω-two Chloropropylpolysiloxanes, polymer is 6.6.
In 100 ml there-necked flasks of assembling condenser pipe, add 5.0 g α, ω-two Chloropropylpolysiloxanes, 6.2 g N-crassitudes, 10ml isopropyl alcohol, N
2in 80 DEG C of reactions 34 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 30 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml absolute methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by absolute methanol-ethyl acetate redissolve-precipitation 5 times.Product in 0.1 MPa, 40 DEG C of dryings 2 days, after thickness pyrrolidinyl Bola ion liquid type organic silicon surfactant, productive rate is 96%.Hermetically drying is preserved.Tg is-49 DEG C, and First CMC is 0.09 g/L, and second CMC is 1.2 g/L, γ
cMCbe 22.4 mN/m.
embodiment 3
Drop in the reactor 7.4 g octamethylcy-clotetrasiloxanes, 2.4 g 1,3-bis-(chloromethyl) tetramethyl disiloxanes, concentrated sulfuric acid catalyst addition be 2%(mass fraction), stirring at room temperature 2 ~ 4 hours, is washed to neutrality, de-lowly to boil.Obtain α, ω-dichloromethyl polysiloxanes, the degree of polymerization is 8.9.
In the 100ml there-necked flask of assembling condenser pipe, add 5.0 g α, ω-dichloromethyl polysiloxanes, 5.8 g N-methylimidazoles, 20 ml isopropyl alcohols, N
2in 80 DEG C of reactions 30 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 40 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml absolute methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by absolute methanol-ethyl acetate redissolve-precipitation 6 times.Product in 0.1 MPa, 40 DEG C of dryings 2 days, after cooling thickness imidazole radicals Bola ion liquid type organic silicon surfactant, productive rate is 95%.Hermetically drying is preserved.Tg is-52 DEG C, and First CMC is 0.1 g/L, and second CMC is 2.2 g/L, γ
cMCbe 24.0 mN/m.
embodiment 4
Drop in the reactor 7.4 g octamethylcy-clotetrasiloxanes, 2.4 g 1,3-bis-(chloromethyl) tetramethyl disiloxanes, concentrated sulfuric acid catalyst addition be 2%(mass fraction), stirring at room temperature 2 ~ 4 hours, is washed to neutrality, de-lowly to boil.Obtain α, ω-dichloromethyl polysiloxanes, the degree of polymerization is 8.9.
In the 100ml there-necked flask of assembling condenser pipe, add 5.0 g α, ω-dichloromethyl polysiloxanes, 4.2 g pyridines, 10 ml isopropyl alcohols, N
2in 70 DEG C of reactions 30 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 30 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml absolute methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by absolute methanol-ethyl acetate redissolve-precipitation 6 times.Product in 0.1 MPa, 40 DEG C of dryings 2 days, after cooling thickness imidazole radicals Bola ion liquid type organic silicon surfactant, productive rate is 89 %.Hermetically drying is preserved.Tg is-52 DEG C, and First CMC is 0.1 g/L, and second CMC is 1.9 g/L, γ
cMCbe 23.5 mN/m.
Claims (5)
1. a preparation method for Bola ion liquid type organic silicon surfactant, is characterized in that its structural formula is:
Preparation process is as follows:
Step 1, polymerisation
Drop into octamethylcy-clotetrasiloxane, 1 in the reactor, 3-bis-(chloropropyl) tetramethyl disiloxane or 1,3-bis-(chloromethyl) tetramethyl disiloxane, concentrated sulfuric acid catalyst, stirring at room temperature is after 2 ~ 4 hours, be washed to neutrality, de-low-boiling-point substance; Obtain the α that the degree of polymerization is n, ω-two Chloropropylpolysiloxanes or α, ω-dichloromethyl polysiloxanes;
Step 2, quaterisation
The α of step 1, ω-two Chloropropylpolysiloxanes or α, ω-dichloromethyl polysiloxanes is loaded in there-necked flask, adds tertiary amine, solvent, N
2under protection, react 30-35 hour at 70 ~ 85 DEG C after, system is down to room temperature; By ethyl acetate precipitation, pour out upper solution, precipitation is dissolved in methyl alcohol, then by ethyl acetate precipitation, repeat 4-8 time like this; Be precipitated in 0.1 MPa, 40 DEG C of dryings 2 days, obtained Bola ion liquid type organic silicon surfactant after cooling.
2. the preparation method of a kind of Bola ion liquid type organic silicon surfactant according to claim 1, is characterized in that described polymerization degree n be 0 ~ 15, m is 0 or 3.
3. the preparation method of a kind of Bola ion liquid type organic silicon surfactant according to claim 1, is characterized in that described tertiary amine can be N-methylimidazole, N-crassitude or pyridine.
4. the preparation method of a kind of Bola ion liquid type organic silicon surfactant according to claim 1, is characterized in that described α, and ω-two Chloropropylpolysiloxanes or α, ω-dichloromethyl polysiloxanes and tertiary amine mol ratio are 1:2 ~ 4.
5. the preparation method of a kind of Bola ion liquid type organic silicon surfactant according to claim 1, is characterized in that described solvent can be isopropyl alcohol, butanols, acetonitrile or dimethyl formamide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688741A (en) * | 2016-01-18 | 2016-06-22 | 沈阳药科大学 | Preparation method of amino acid type Bola surfactant |
| CN105727829A (en) * | 2016-01-25 | 2016-07-06 | 常熟理工学院 | Polysiloxane surface active ion liquid and preparation method thereof |
| CN107138176A (en) * | 2017-06-23 | 2017-09-08 | 广东工业大学 | A kind of preparation method of middle micro-diplopore lamella MFI molecular sieve catalysts |
| CN111992134A (en) * | 2020-09-22 | 2020-11-27 | 陕西科技大学 | Polycarboxyl amphoteric Bola type surfactant and preparation method thereof |
| CN115652661A (en) * | 2022-10-14 | 2023-01-31 | 上海源之美新材料科技有限公司 | Waterproof digital coating ink and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688741A (en) * | 2016-01-18 | 2016-06-22 | 沈阳药科大学 | Preparation method of amino acid type Bola surfactant |
| CN105688741B (en) * | 2016-01-18 | 2018-01-02 | 沈阳药科大学 | The preparation method of amino acid pattern Bola surfactants |
| CN105727829A (en) * | 2016-01-25 | 2016-07-06 | 常熟理工学院 | Polysiloxane surface active ion liquid and preparation method thereof |
| CN107138176A (en) * | 2017-06-23 | 2017-09-08 | 广东工业大学 | A kind of preparation method of middle micro-diplopore lamella MFI molecular sieve catalysts |
| CN107138176B (en) * | 2017-06-23 | 2020-02-07 | 广东工业大学 | Preparation method of medium-micro double-pore lamellar MFI molecular sieve catalyst |
| CN111992134A (en) * | 2020-09-22 | 2020-11-27 | 陕西科技大学 | Polycarboxyl amphoteric Bola type surfactant and preparation method thereof |
| CN115652661A (en) * | 2022-10-14 | 2023-01-31 | 上海源之美新材料科技有限公司 | Waterproof digital coating ink and preparation method thereof |
| CN115652661B (en) * | 2022-10-14 | 2024-03-26 | 上海源之美新材料科技有限公司 | Waterproof digital coating ink and preparation method thereof |
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