CN1439452A - Organic silicon anionic surfctant and its synthesis - Google Patents
Organic silicon anionic surfctant and its synthesis Download PDFInfo
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- CN1439452A CN1439452A CN02136615.2A CN02136615A CN1439452A CN 1439452 A CN1439452 A CN 1439452A CN 02136615 A CN02136615 A CN 02136615A CN 1439452 A CN1439452 A CN 1439452A
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Abstract
An anionic organosilicon surfactant is prepared through synthesizing alkylhydroxy polysiloxane and condensing reacting to introduce hydrophilic group to the alkylhydroxy polysiloxane, and has the emulsifying, dispersing, wetting, antistatic, defoaming, foam stabilizing, foaming and smoothing functions. Its advantages are easily available raw materials, low cost, high output rate, and broad-spectrum application.
Description
Technical field
The present invention relates to a kind of novel organic silicon anionic surfctant and synthetic method thereof, particularly be the anion surfactant and the synthetic method thereof of sulfonic acid type.
Background technology
As everyone knows, surfactant is that the hydrophobic grouping and the hydrophilic radical that contain silane, silicon methylene or siloxanes are formed, and has higher surface tension.It can be that low molecule also can be a high polymer.Surfactant can be divided into cationic by the kind of its hydrophilic group, anionic and amphoteric ion type, and wherein organic silicon surfactant also is classification like this.
Organic silicon surfactant has good performance, and its hydrophobic grouping is that the alkylsiloxane chain is formed, and has than the stronger surface-active of hydrocarbon chain class surfactant; In solution, has lower surface tension with isoconcentration.Such special construction is also given the resistant of high or low temperature that silicone surfactant has silicide, resistance to ag(e)ing, and flatness is coated with levelling, nontoxic non-corrosiveness, features such as physiology inertia; The same with hc-surfactant again, have emulsibility, dispersiveness, wetability, antistatic behaviour, froth breaking, steady bubble, performances such as foaming.
Along with the development of the synthesising chemical technology and the formula technique of siloxanes, organic silicon surfactant plays an important role in fields such as orderization, food, bioengineering, light industry, weaving, petrochemical industry, electronics, medicine, agricultural chemicals.
Organic silicon surfactant is polyether-modified polysiloxanes of nonionic at the surfactant great majority, and its general formula is: (CH
3)
3SiO[-(CH
3)
2SiO-]
m-[RSiO-]
n-Si (CH
3)
3, R: polyether chain, m=5-400, n＞1, (as German patent DE 1444555), and the anionic organic silicon surfactant is less, but its scope of application is wider.The anionic organic silicon surfactant is comprising carboxylic acid type, sulfonic acid type, and sulfuric acid type, phosphate type etc., they can be by obtaining with the unsaturated strong hydrocarbon corresponding esters and the hydrosilylation of containing hydrogen silicone oil; As also carrying out the anionic surfactant that hydrosilylation is made the band carboxyl by acrylate, undecylate and containing hydrogen silicone oil.Organophosphorus ester can improve hydroxyl on the silicone oil molecule and the reaction of phosphorus pentoxide and condensed phosphate obtains by polyethers.Organosilicon sulfonate epoxy available improves silicone oil and the sodium hydrogensulfite reaction obtains; Compare with lauryl sodium sulfate with the anionic surfactant that the method is synthetic, surface tension reduces greatly.
More than the synthesising method reacting condition of these anionic organic silicon surfactants relatively harsh, hydrosilylation will can carry out (Japan, spy open flat 11-140370) as the condition of catalyst at platinic acid; The cost of platinic acid is higher; Polyethers improves the production of silicone oil will under high pressure use oxirane and expoxy propane, and epoxy improves the production of silicone oil also will under high pressure carry out, and therefore, the synthetic method of these anionic organic silicon surfactants has certain limitation.
At this situation, the objective of the invention is to invent the synthetic method of a kind of novel sulfonic acid type anionic organic silicon surfactant and synthetic this novel sulfonic acid type anionic organic silicon surfactant, to overcome
The shortcoming of prior art.
Summary of the invention
The general structure of organic silicon anionic surfctant of the present invention is as follows:
In the formula: m=10-2000, n=1-200
R＝CH
2CH
2CH
2NHZ
CH
2NHCH
2CH
2NHZ
CH
2CH
2CH
2NHCH
2CH
2NHZ
(CH
2)
3NHCH
2CH
2NHCH
2CH
2NHZ
Z＝CH
2CHOHCH
2SO
3M
C
2H
4SO
3M
CH
2CHOHCH
2OPO
3M
CH
2CH
2CH
2SO
3M
M＝Na，K，NH
4
Wherein preferable scope:
m＝50-800，n＝5-80，M＝Na
The synthetic method of organic silicon anionic surfctant of the present invention comprises the steps: synthetic ammonia alkyl polysiloxanes, through condensation reaction ammonia alkyl polysiloxanes is introduced hydrophilic group, wherein:
(1) synthetic method of ammonia alkyl polysiloxanes is:
With D
4(octamethylcy-clotetrasiloxane), amino silicane coupling agent, MM (HMDO) catalyst (KOH), promoter (dimethyl sulfoxide (DMSO)) is 80-150 ℃ in temperature and reacted 1-15 hour down, neutralize with equimolar inorganic acid and organic acid, obtain ammonia alkyl polysiloxanes, its mol ratio that feeds intake is: D
4(octamethylcy-clotetrasiloxane): amino silicane coupling agent: MM (HMDO) catalyst (KOH): promoter (dimethyl sulfoxide (DMSO))=1: (0.05-0.45): (0.02-0.35): (0.001-0.008): (0.0009-0.008), optimum mole ratio is: D
4(octamethylcy-clotetrasiloxane): amino silicane coupling agent: MM (HMDO) catalyst (KOH): promoter (dimethyl sulfoxide (DMSO))=1: (0.1-0.35): (0.08-0.35): (0.004-0.006): (0.001-0.006), its optimal reaction temperature is: 90-130 ℃, and optimum reacting time: 8-12 hour.The used inorganic acid that neutralizes is a watery hydrochloric acid, and dilute sulfuric acid or phosphoric acid, organic acid are formic acid or acetate or propionic acid or butyric acid or valeric acid, and ammonia value scope is: 0.1-0.9.Amino silicane coupling agent is: γ-aminopropyl methyldiethoxysilane or γ-aminopropyl methyl dimethoxysilane or N-(β-aminoethyl)-aminomethyl methyl dimethoxysilane or N-(β-aminoethyl)-aminomethyl methyldiethoxysilane or γ-diethylenetriamine propyl group methyl dimethoxysilane
(2) ammonia alkyl polysiloxanes introducing hydrophilic group synthetic method is:
Thereby a, with epoxychloropropane and sodium hydrogensulfite 15 ℃ of 80-1 down reaction generated γ-chloro-beta-hydroxy propane sulfonic acid salt in 1-15 hour, wherein: sodium hydrogensulfite is 50% the aqueous solution, its mol ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.5, optimum mole ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.1.
C, ammonia alkyl polysiloxanes and γ-chloro-beta-hydroxy propane sulfonic acid salt were generated organic silicon anionic surfctant at 80-95 ℃ of following condensation reaction 1-15 hour, used solvent is a dioxane, its mol ratio is: γ-chloro-beta-hydroxy propane sulfonic acid salt: amino silicane coupling agent=1: 1.2, optimum response 6-8 hour.
Ammonia alkyl polysiloxanes introduce the hydrophilic group synthetic method also can for:
(1) bromoethyl sodium sulfonate and the condensation reaction of ammonia alkyl polysiloxanes generated anion surfactant, and γ-chloro-beta-hydroxy propane sulfonic acid salt and ammonia alkyl polysiloxanes were generated the sulfonic acid organic silicon anionic surfctant at 80-95 ℃ of following condensation reaction 1-15 hour;
Or (2) are with 1,3-trimethylene base sulfinic acid lactone and ammonia alkyl polysiloxanes generated the sulfonic acid anion surfactant at 80-90 ℃ of following condensation reaction 2-15 hour, used solvent is a dioxane, optimum response 6-8 hour, its mol ratio is: 1, and 3-trimethylene base sulfinic acid lactone: amino silicane coupling agent=1: 1.2.
Ammonia alkyl polysiloxanes is introduced the hydrophilic group synthetic method can also introduce the phosphate hydrophilic group for ammonia alkyl polysiloxanes:
(1) thus with epoxychloropropane and sodium hydrogensulfite 80-115 ℃ down reaction generated γ-chloro-beta-hydroxy third phosphate in 1-1.5 hour, sodium hydrogensulfite is 50% the aqueous solution, its mol ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.5;
(2) condensation reaction generation in 1-15 hour phosphate anionic organic silicon surfactant is taken place down at 80-95 ℃ in γ-chloro-beta-hydroxy third phosphate and ammonia alkyl polysiloxanes, used solvent is a dioxane, its mol ratio is: γ-chloro-beta-hydroxy third phosphate: amino silicane coupling agent=1: 1.2, optimum response 6-8 hour.
Being described as follows of the main Points of the synthetic method of organic silicon anionic surfctant of the present invention:
Mass polymerization prepares the route of ammonia alkyl polysiloxane backbone:
X=H, CH
2CH
2NH
2(1) selection of catalysts
Si-O key in the siloxanes ring body is a polar bond, and Si band portion positive charge is subject to the attack of nucleophilicity base reagent; Oxygen atom band portion negative electricity, can with proton in the acid in conjunction with causing the Si-O bond fission.So soda acid all can cause the polymerisation of siloxanes ring body.Consider the alkalescence of amino silicon monomer, should select base catalyst for use, as alkali metal hydroxide, TMAH, tetrabutylammonium hydroxide phosphine, butyl lithium, tertiary amine etc.
During alkali as a catalyst, alkalescence is strong more, and catalyst activity is high more, and the speed of initiated polymerization is just big more.Make catalyst as KOH, NaOH, LiOH,
The hydroxide form alkali as a catalyst, it is actual that what play catalytic action is silicon alkoxide, the present invention select KOH as catalyst, KOH is made silanol sylvite carries out catalysis.(2) reaction temperature
Reaction temperature mainly influences reaction speed, and temperature raises, and polymerization rate is accelerated.But the anionic polymerisation that has the chain shift factor, temperature can influence the degree of polymerization of polymerisation.Therefore, temperature major control of the present invention is at 80-150 ℃.(3) HMDO MM consumption is to the influence of mean molecule quantity
MM is D
4Effective end-capping reagent of polymerisation can stop the polymerisation chain growth, generally works to regulate molecular weight in reaction, and the MM consumption increases, and the mean molecule quantity of polysiloxanes descends.(4) amino silicane coupling agent
Amino silicon chain link mainly comes from the amino silicon monomer of raw material in the ammonia alkyl polysiloxane molecule, i.e. amino silicane coupling agent changes itself and D
4Molar ratio, the ammonia value of ammonia alkyl polysiloxane chain will change thereupon, like this can be so that introduce the variation of hydrophilic radical.(5) neutralization
Ammonia alkyl polysiloxanes will neutralize with equimolar inorganic acid and organic acid, the used inorganic acid that neutralizes is watery hydrochloric acid or dilute sulfuric acid or phosphoric acid, organic acid is formic acid or acetate or propionic acid or butyric acid or valeric acid etc., also have the anion sulfoacid resin, but generally all adopt small molecular organic acid to neutralize.
The ammonia value of the resulting ammonia alkyl of the present invention polysiloxanes, the mM number of the contained amino of every gram ammonia alkyl polysiloxanes, with purple as indicator in the crystalline ester, available perchloric acid-acetate standard solution (0.1mol/L) is demarcated.
The relative molecular weight of ammonia alkyl polysiloxanes can use gel permeation chromatograph to measure.(6) hydrophilic radical of being introduced
The hydrophilic radical that the present invention introduced has: the bromoethyl sodium sulfonate, 1,3-trimethylene base sulfinic acid lactone, γ chloro-beta-hydroxy propane sulfonic acid, γ chloro-beta-hydroxy third phosphate etc., general comparatively commonly used be γ-chloro-beta-hydroxy propane sulfonic acid, generally be the aqueous solution that it is made into 40-60%, then with ammonia alkyl polysiloxanes generation condensation reaction.(7) primary condition of condensation reaction
The solvent that reacts used is ethanol, isopropyl alcohol, the tert-butyl alcohol, ethyl cellosolve, methyl cellosolve, oxolane, dioxane, N, dinethylformamide, 1,2-dichloroethanes etc.The effect of solvent is the compatibility of ammonia alkyl polysiloxanes and hydrophilic compounds.
The consumption of solvent is the 10-80% of raw material consumption, and preferable consumption is 20-40%,, temperature is 50-125 ℃, and the time of reaction is 4-8 hour, and temperature is higher, and the time can shorten.After reaction finished, solvent can reclaim.
It is sodium carbonate, sodium carbonate, potash that bromoethyl sodium sulfonate, γ chloro-beta-hydroxy propane sulfonic acid, γ chloro-beta-hydroxy third phosphate etc. carry out the used acid binding agent of condensation reaction, sodium acetate, sodium formate etc.
The surfactant that the present invention synthesized can be that oily molten type surfactant also can be water-soluble type surfactant.
The surface tension of the surfactant that the present invention synthesized can reach 20mN.m
-1Below, have functions such as wetting preferably, emulsification, dispersion, washing, sterilization, antistatic, softness, can be used for fields such as daily use chemicals, food, bioengineering, light industry, weaving, petrochemical industry, electronics, medicine, agricultural chemicals.
The advantage of the inventive method is the reaction condition gentleness, and is simple, and yield is higher, is easy to suitability for industrialized production, and the raw material of usefulness is easy to get, and is cheap.Can be used for various aspects such as washing, emulsification, infiltration, wetting, diffusion, promptly at numerous areas such as daily use chemicals, light industry, weavings.
Innovation part of the present invention is to utilize D
4(octamethylcy-clotetrasiloxane), different amino silicane coupling agents, MM (HMDO) generate under the condition of gentleness and contain amino modified polyorganosiloxane chain under the effect of catalyst (KOH) and promoter (dimethyl sulfoxide (DMSO)).Utilize easy condensation reaction with hydrophilic radical, introduce the side chain of modified polyorganosiloxane chain, thereby form anion surfactant as sulfonic group, phosphate.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
(1) ammonia alkyl polysiloxanes is synthetic:
At first get the there-necked flask that condenser pipe, churned mechanically 250ml are housed ready, carry out drying in advance and dewater, feed N
2(nitrogen), totally three times, then with 62gD
4(octamethylcy-clotetrasiloxane), 4.1gKH-Si-602 (aminoethyl aminopropyl methyl dimethoxysilane), 0.4g MM (HMDO), 0.6g silanol potassium promoter 0.4g add successively, feed N
2(nitrogen) protection was reacted 8 hours down at 120 ℃, and decompression removes low-boiling-point substance, reduces to room temperature, added the neutralization of 1.0g acetic acid, and the pH value is 7.5, filters, and got transparency liquid and was aminoethyl aminopropyl dimethyl silicone polymer.Ammonia value: 0.55mmol/g; Viscosity: 1.530Pa.s.(2) introduce hydrophilic radical
With ammonia alkyl polysiloxanes (60g) and γ chloro-beta-hydroxy propane sulfonic acid (0.035mol, 6.5g) be dissolved in the 100ml dioxane, be heated to 80 ℃, refluxed 4 hours, after reaction is finished, be cooled to 50 ℃, add 10ml sodium carbonate liquor (50%) again, reacted 5 hours, after reaction is finished, the dioxane aqueous solution steams recovery, the rest is product.
Embodiment 2
(1) the alkyl polysiloxanes is synthetic:
At first get the there-necked flask that condenser pipe, churned mechanically 250ml are housed ready, carry out drying in advance and dewater, feed N
2(nitrogen), totally three times, then with 62gD
4(octamethylcy-clotetrasiloxane), 4.3g aminopropyl methyl dimethoxysilane, 0.4g MM (HMDO), 0.65g silanol potassium, promoter 0.4g adds successively, feeds N
2(nitrogen) protection was reacted 8 hours down at 120 ℃, and decompression removes low-boiling-point substance, reduces to room temperature, added the neutralization of 1.0g acetic acid, and the pH value is 7.5, filters, and got transparency liquid and was aminopropyl methyl dimethyl silicone polymer.Ammonia value: 0.31mmol/g; Viscosity: 0.222Pa.s.(2) introduce hydrophilic radical
With ammonia alkyl polysiloxanes (60g) and bromoethyl sodium sulfonate (0.018mol, 3.8g) be dissolved in 100ml dioxane-ethanol, be heated to 82 ℃, refluxed 4.5 hours, after reaction is finished, be cooled to 50 ℃, add 10ml sodium carbonate liquor (50%) again, reacted 5 hours, after reaction is finished, dioxane-ethanol water steams recovery, the rest is product.
Embodiment 3
At first get the there-necked flask that condenser pipe, churned mechanically 250ml are housed ready, carry out drying in advance and dewater, feed N
2, totally three times, then with 62gD
4(octamethylcy-clotetrasiloxane), 4.3g N-(β-aminoethyl)-aminomethyl methyldiethoxysilane, 0.41g MM (HMDO), 0.61g silanol potassium, promoter 0.42g adds successively, feeds N
2(nitrogen) protection was reacted 8 hours down at 120 ℃, and decompression removes low-boiling-point substance, reduces to room temperature, added the neutralization of 1.0g acetic acid, and the pH value is 7.5, filters, and got transparency liquid and was aminopropyl methyl dimethyl silicone polymer.Ammonia value: 0.35mmol/g; Viscosity: 0.262Pa.s.
With ammonia alkyl polysiloxanes (60g) and bromoethyl sodium sulfonate (0.018mol, 3.8g) be dissolved in 100ml dioxane-oxolane, be heated to 82 ℃, refluxed 4.5 hours, after reaction is finished, be cooled to 50 ℃, add 10ml sodium carbonate liquor (50%) again, reacted 5 hours, after reaction is finished, dioxane-tetrahydrofuran aqueous solution steams recovery, the rest is product.
Embodiment 4
(1) ammonia alkyl polysiloxanes is synthetic:
At first get the there-necked flask that condenser pipe, churned mechanically 250ml are housed ready, carry out drying in advance and dewater, feed N
2(nitrogen), totally three times, then with 65gD
4(octamethylcy-clotetrasiloxane), 4.2g γ-diethylenetriamine aminopropyl methyl dimethoxysilane, 0.44gMM (HMDO), 0.7g silanol potassium promoter 0.45g add successively, feed N
2(nitrogen) protection was reacted 7 hours down at 120 ℃, and decompression removes low-boiling-point substance, reduces to room temperature, added the neutralization of 1.2g acetic acid, and the pH value is 8.5, filters, and got transparency liquid and was diethylenetriamine aminopropyl methyl dimethyl silicone polymer.Ammonia value: 0.65mmol/g; Viscosity: 1.630Pa.s.
Ammonia hydrocarbon polysiloxanes (62g) and γ chloro-beta-hydroxy propane sulfonic acid sodium (0.039mol, 7.6g) be dissolved in 100ml dioxane-oxolane, be heated to 85 ℃, refluxed 4.5 hours, after reaction is finished, be cooled to 50 ℃, add 10ml sodium carbonate liquor (50%) again, reacted 5 hours, after reaction is finished, dioxane-tetrahydrofuran aqueous solution steams recovery, the rest is product.
Embodiment 5
(1) ammonia alkyl polysiloxanes is synthetic:
At first get the there-necked flask that condenser pipe, churned mechanically 250ml are housed ready, carry out drying in advance and dewater, feed N
2(nitrogen), totally three times, then with 62gD
4(octamethylcy-clotetrasiloxane), 4.1gKH-Si-602 (aminoethyl aminopropyl methyl dimethoxysilane), 0.4gMM (HMDO), 0.6g silanol potassium promoter 0.4g add successively, feed N
2(nitrogen) protection was reacted 8 hours at 120 ℃, and decompression removes low-boiling-point substance, reduces to room temperature, added the neutralization of 1.0g acetic acid, and the pH value is 7.5, filters, and got transparency liquid and was aminoethyl aminopropyl dimethyl silicone polymer.Ammonia value: 0.55mmol/g; Viscosity: 1.530Pa.s.(2) introduce hydrophilic radical
Ammonia alkyl polysiloxanes (60g) is dissolved in the 100ml dioxane, slowly drips 1,3-trimethylene base sulfinic acid lactone (0.035mol, 7.9g), be heated to 50 ℃, added in 30 minutes, keep 50 ℃ of temperature, reacted 4 hours, after reaction is finished, be cooled to 40 ℃, add 10ml sodium carbonate liquor (50%) again, reacted 2 hours, after reaction is finished, the dioxane aqueous solution steams recovery, the rest is product.
Claims (9)
1. organic silicon anionic surfctant is characterized in that having following general structure:
In the formula: m=10-2000, n=1-200
R＝CH
2CH
2CH
2NHZ
CH
2NHCH
2CH
2NHZ
CH
2CH
2CH
2NHCH
2CH
2NHZ
(CH
2)
3NHCH
2CH
2NHCH
2CH
2NHZ
Z＝CH
2CHOHCH
2SO
3M
C
2H
4SO
3M
CH
2CHOHCH
2OPO
3M
CH
2CH
2CH
2SO
3M
M＝Na、K，NH
4
2. organic silicon anionic surfctant according to claim 1 is characterized in that: in the described general structure preferably: m=50-800, n=5-80
M＝Na
3. as the synthetic method of organic silicon anionic surfctant as described in the claim 1,2, it is characterized in that comprising the steps: synthetic ammonia alkyl polysiloxanes, ammonia alkyl polysiloxanes is introduced hydrophilic group through condensation reaction, wherein:
(1) synthetic method of ammonia alkyl polysiloxanes is:
With D
4(octamethylcy-clotetrasiloxane), amino silicane coupling agent, MM (HMDO) catalyst (KOH), promoter (dimethyl sulfoxide (DMSO)) is 80-150 ℃ in temperature and reacted 1-15 hour down, neutralize with equimolar inorganic acid and organic acid, obtain ammonia alkyl polysiloxanes, its mol ratio that feeds intake is: D
4(octamethylcy-clotetrasiloxane): amino silicane coupling agent: MM (HMDO) catalyst (KOH): promoter (dimethyl sulfoxide (DMSO))=1: (0.05-0.45): (0.02-0.35): (0.001-0.008): (0.0009-0.008), the used inorganic acid that neutralizes is watery hydrochloric acid or dilute sulfuric acid or phosphoric acid, organic acid is formic acid or acetate or propionic acid or butyric acid or valeric acid, and ammonia value scope is: 0.1-0.9
(2) ammonia alkyl polysiloxanes introducing hydrophilic group synthetic method is:
Thereby a, with epoxychloropropane and sodium hydrogensulfite 80-115 ℃ down reaction generated γ-chloro-beta-hydroxy propane sulfonic acid salt in 1-15 hour, wherein: sodium hydrogensulfite is 50% the aqueous solution, its mol ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.5;
B, ammonia alkyl polysiloxanes and γ-chloro-beta-hydroxy propane sulfonic acid salt were generated organic silicon anionic surfctant at 80-95 ℃ of following condensation reaction 1-15 hour, used solvent is a dioxane, its mol ratio is: γ-chloro-beta-hydroxy propane sulfonic acid salt: amino silicane coupling agent=1: 1.2, optimum response 6-8 hour.
4. the synthetic method of organic silicon anionic surfctant according to claim 3, the synthetic used amino silicane coupling agent that it is characterized in that described ammonia alkyl polysiloxanes is: γ-aminopropyl methyldiethoxysilane or γ-aminopropyl methyl dimethoxysilane or N-(β-aminoethyl)-aminomethyl methyl dimethoxysilane or N-(β-aminoethyl)-aminomethyl methyldiethoxysilane or γ-diethylenetriamine propyl group methyl dimethoxysilane
5, the synthetic method of organic silicon anionic surfctant according to claim 3 is characterized in that the synthetic optimum mole ratio that feeds intake of described ammonia alkyl polysiloxanes is: D
4(octamethylcy-clotetrasiloxane): amino silicane coupling agent: MM (HMDO): catalyst (KOH): promoter (dimethyl sulfoxide (DMSO))=1: (0.1-0.35): (0.08-0.35): (0.004-0.006): (0.001-0.006), its optimal reaction temperature is: 90-130 ℃, and optimum reacting time: 8-12 hour.
6, the synthetic method of organic silicon anionic surfctant according to claim 3 is characterized in that the optimum mole ratio of described ammonia alkyl polysiloxanes introducing hydrophilic group synthetic method is: epoxychloropropane: sodium hydrogensulfite=1: 1.1.
7, the synthetic method of organic silicon anionic surfctant according to claim 3, it is characterized in that described ammonia alkyl polysiloxanes introduce the hydrophilic group synthetic method also can for:
(1) bromoethyl sodium sulfonate and the condensation reaction of ammonia alkyl polysiloxanes generated anion surfactant, and γ-chloro-beta-hydroxy propane sulfonic acid salt and ammonia alkyl polysiloxanes were generated the sulfonic acid organic silicon anionic surfctant at 80-95 ℃ of following condensation reaction 1-15 hour; Perhaps
(2) with 1,3-trimethylene base sulfinic acid lactone and ammonia alkyl polysiloxanes generated the sulfonic acid anion surfactant at 80-90 ℃ of following condensation reaction 2-15 hour, used solvent is a dioxane, optimum response 6-8 hour, its mol ratio is: 1, and 3-trimethylene base sulfinic acid lactone: amino silicane coupling agent=1: 1.2;
8, the synthetic method of organic silicon anionic surfctant according to claim 3 is characterized in that described ammonia alkyl polysiloxanes introducing hydrophilic group synthetic method can also be that ammonia alkyl polysiloxanes is introduced the phosphate hydrophilic group:
(1) thus with epoxychloropropane and sodium hydrogensulfite 80-115 ℃ down reaction generated γ-chloro-beta-hydroxy third phosphate in 1-1.5 hour, sodium hydrogensulfite is 50% the aqueous solution, its mol ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.5;
(2) condensation reaction generation in 1-15 hour phosphate anionic organic silicon surfactant is taken place down at 80-95 ℃ in γ-chloro-beta-hydroxy third phosphate and ammonia alkyl polysiloxanes, used solvent is a dioxane, its mol ratio is: γ-chloro-beta-hydroxy third phosphate: amino silicane coupling agent=1: 1.2, optimum response 6-8 hour
9, the synthetic method of organic silicon anionic surfctant according to claim 8 is characterized in that described ammonia alkyl polysiloxanes introducing phosphate hydrophilic group synthetic method, and its optimum mole ratio is: epoxychloropropane: sodium hydrogensulfite=1: 1.1.
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| CN115044044B (en) * | 2022-07-13 | 2023-04-14 | 枣阳市华威硅氟材料有限公司 | Sulfonic group modified silicone oil and preparation method and application thereof |
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