CN108752578A - A kind of preparation method of polyether-based organic silicon surfactant - Google Patents
A kind of preparation method of polyether-based organic silicon surfactant Download PDFInfo
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Abstract
A kind of preparation method of polyether-based organic silicon surfactant, the preparation method include the following steps：（1）Mercapto propyl-siloxane, unsaturated polyether, solvent and dimethoxybenzoin are added in single-necked flask, mercapto alkene reaction is carried out, the reaction time is 30min ~ 4 hour；（2）The complete monomer of unreacted, solvent and residual initiator are removed after reaction, obtain polyether-based organic silicon surfactant.The present invention reacted with unsaturated polyether by Mercapto propyl silanes prepare have the active polyether-based organic silicon surfactant of good surface, this method has the advantages that raw material is cheap and easily-available, easy to operate, post-processing is simple, it avoids using expensive catalyst, is conducive to industrialized production and the application of polyether-based organic silicon surfactant.
Description
Technical field
The present invention relates to a kind of preparation methods of polyether-based organic silicon surfactant.
Background technology
Organic silicon surfactant is with silica/carbon alkane for hydrophobic chain link, connects one or more hydrophilic radicals compositions
A kind of new and effective surfactant.Not only there is the surface-active more excellent than alkanes surfactant and " super to sprawl "
Property, and the excellent performance such as high-low temperature resistant, weather-resistant, nontoxic physiological inertia for having organosilicon material.Such is organic
Silicon surface active agent is widely used in polyurethane foam, pesticide, textile auxiliary, day used additives, oil field with its excellent performance
The fields such as product.As organosilicon material further develops and to the deep exploitation of organosilicon downstream product, organosilyl surface work
The kind and preparation method of property agent also will constantly increase, and application field also can constantly expand, this is all surfactant
Developing direction and research hotspot.
Polyether type organic silicone surfactant is to apply most kinds, such as Silwet series at present, is mainly contained
Hydrogen silane or silicone oil carry out Si―H addition reaction under noble metal catalyst effect with unsaturated polyether and are prepared.Such as Chinese patent CN
107759792 A prepare agricultural organosilicone surfactant with more methylsiloxanes and allyl polyether using hydrosilylation
Agent.The preparation method reaction time it is long and need to using the noble metals such as platinum as catalyst under conditions of can carry out.Document（Organic
Letters,2011,13 (22) :6006-6009）Polyether type organic silicone surfactant is efficiently prepared using mercapto alkene reaction,
But it needs to prepare polyethers containing sulfydryl, unsuitable industrialized production.Therefore it develops efficient, high yield organosilicone surfactant
Synthetic method is very necessary.
Invention content
Its purpose of the invention, which is that, provides a kind of preparation method of polyether-based organic silicon surfactant, and the present invention passes through
Mercapto propyl silanes reacted with unsaturated polyether prepare have the active polyether-based organic silicon surfactant of good surface, the party
Method has the advantages that raw material is cheap and easily-available, easy to operate, post-processing is simple, avoids using expensive catalyst, be conducive to
The industrialized production of polyether-based organic silicon surfactant and application.
It adopts the technical scheme that achieve the above object, a kind of preparation side of polyether-based organic silicon surfactant
Method, the preparation method include the following steps：
（1）Mercapto propyl-siloxane, unsaturated polyether, solvent and dimethoxybenzoin are added in single-necked flask, it is anti-to carry out mercapto alkene
It answers, the reaction time is 30min ~ 4 hour；
（2）The complete monomer of unreacted, solvent and residual initiator are removed after reaction, obtain polyether-based organosilicone surfactant
Agent.
The mercapto propyl-siloxane is mercapto oxypropyl trimethyl silane, mercapto propyl-three (trimethylsiloxy group) silane, mercapto third
Base-two (trimethylsiloxy group) methyl-monosilane, mercapto propyl-two (trimethylsiloxy group) methyl-monosilane, (ethyl two of mercapto propyl-two
Methyl siloxy) methyl-monosilane, mercapto propyl-two (propyl-dimethyl siloxy) methyl-monosilane ,-two (Butyldimethyl of mercapto propyl
Siloxy) methyl-monosilane, mercapto propyl-two (pheiiyldimetliyl siloxy) methyl-monosilane, 1- mercapto propyl pentamethyl disiloxane, 1-
Mercapto propyl -3- ethyls tetramethyl disiloxane, 1- mercapto propyl -3- propyl tetramethyl disiloxane, 1- mercapto propyl -3- butyl tetramethyls
One kind in base disiloxane, 1- mercapto propyl -3- phenyl tetramethyl disiloxanes.
The unsaturated polyether is hydroxy-end capped unsaturated polyether and methyl blocking unsaturated polyether, wherein ethylene glycol chain link
Number can be 3 ~ 50, and propoxyl group chain number is 0 ~ 20.
The molar ratio of the mercapto propyl-siloxane and unsaturated polyether is 1 ~ 1.3：1.
The solvent is one in methanol, ethyl alcohol, tetrahydrofuran, isopropanol, butanol, acetonitrile, N,N-dimethylformamide
Kind or its mixed solvent.
The dimethoxybenzoin dosage is 1% ~ 5% mass fraction.
Advantageous effect
The present invention has the following advantages compared with prior art.
1. polyether-based organic silicon surfactant γ prepared by the present inventionCMCLess than 28 mN/m, there is high surface, and
Influence there is no isomer to its surface-active can be used for insecticides adjuvant, medicament slow release, functional nanomaterials, spinning
Knit the fields such as processing aid；
2. preparing polyether-based organic silicon surfactant compared to using Si―H addition reaction, the reaction time needed for mercapto alkene reaction significantly drops
It is low, and do not use noble metal catalyst, need not heat, isomer is not present, and more economical simple；
3. the polyethers raw material used in this method is market ripe, promotes the preparation method of the present invention more feasible, be easy to grasp
Make, is suitble to industrialized production and application.
Description of the drawings
Below in conjunction with attached drawing, the invention will be further described.
Fig. 1 is the view of the structural formula of polyether-based organic silicon surfactant obtained by the method for the present invention.
Specific implementation mode
A kind of preparation method of polyether-based organic silicon surfactant, as shown in Figure 1, the preparation method includes the following steps：
（1）Mercapto propyl-siloxane, unsaturated polyether, solvent and dimethoxybenzoin are added in single-necked flask, it is anti-to carry out mercapto alkene
It answers, the reaction time is 30min ~ 4 hour；
（2）The complete monomer of unreacted, solvent and residual initiator are removed after reaction, obtain polyether-based organosilicone surfactant
Agent.
The mercapto propyl-siloxane is mercapto oxypropyl trimethyl silane, mercapto propyl-three (trimethylsiloxy group) silane, mercapto third
Base-two (trimethylsiloxy group) methyl-monosilane, mercapto propyl-two (trimethylsiloxy group) methyl-monosilane, (ethyl two of mercapto propyl-two
Methyl siloxy) methyl-monosilane, mercapto propyl-two (propyl-dimethyl siloxy) methyl-monosilane ,-two (Butyldimethyl of mercapto propyl
Siloxy) methyl-monosilane, mercapto propyl-two (pheiiyldimetliyl siloxy) methyl-monosilane, 1- mercapto propyl pentamethyl disiloxane, 1-
Mercapto propyl -3- ethyls tetramethyl disiloxane, 1- mercapto propyl -3- propyl tetramethyl disiloxane, 1- mercapto propyl -3- butyl four
One kind in tetramethyldisiloxane, 1- mercapto propyl -3- phenyl tetramethyl disiloxanes.
The unsaturated polyether is hydroxy-end capped unsaturated polyether and methyl blocking unsaturated polyether, wherein ethylene glycol chain link
Number can be 3 ~ 50, and propoxyl group chain number is 0 ~ 20.
The molar ratio of the mercapto propyl-siloxane and unsaturated polyether is 1 ~ 1.3：1.
The solvent is one in methanol, ethyl alcohol, tetrahydrofuran, isopropanol, butanol, acetonitrile, N,N-dimethylformamide
Kind or its mixed solvent.
The dimethoxybenzoin dosage is 1% ~ 5% mass fraction.
Embodiment 1
（1）14.8 g mercaptos propyl-two (trimethylsiloxy group) methyl-monosilanes, 36.5g allyls are added in 100 ml single port bottles
Poly glycol monomethyl ether（Molecular mass is about 750 g/mol）, 0.99 g dimethoxybenzoins and 30 ml methanol, room temperature stir
It mixes and carries out mercapto alkene reaction；（2）Stop reaction after forty minutes, depressurize away unreacted monomer, solvent, initiator etc., cooling to obtain the final product
Trisiloxanes type nonionic surfactant.
Its yield is 98%, and hermetically drying preserves.Non-ionic silicone surfactant γCMCFor 22.4 mN/m.
Embodiment 2
（1）19.3 g mercaptos propyl-three (trimethylsiloxy group) silane, the poly- first of 50.0g allyls are added in 100 ml single port bottles
Ether（Molecular mass is about 1000 g/mol）, 1.34 g dimethoxybenzoins and 50 ml methanol, be stirred at room temperature that carry out mercapto alkene anti-
It answers；（2）Stop reaction after 1 hour, depressurize away unreacted monomer, solvent, initiator etc., cooling trisiloxanes type to obtain the final product it is non-from
Sub- surfactant.
Its yield is 97%, and hermetically drying preserves.Non-ionic silicone surfactant γCMCFor 21.6 mN/m.
Embodiment 3
（1）17.2 g mercaptos propyl-two (ethyl dimethylsilyl bis) methyl-monosilanes, 50.0g alkene are added in 100 ml single port bottles
Propyl polyethers（Molecular mass is about 1000 g/mol）, 1.21 g dimethoxybenzoins and 50 ml methanol, progress is stirred at room temperature
Mercapto alkene reaction；（2）Stop reaction after 1 hour, depressurizes away unreacted monomer, solvent, initiator etc., it is cooling up to containing ethyl three
Silicone-type nonionic surfactant.
Its yield is 95%, and hermetically drying preserves.Non-ionic silicone surfactant γCMCFor 25.3 mN/m.
Embodiment 4
（1）- two (pheiiyldimetliyl siloxy) methyl-monosilane of 17.2g mercaptos propyl, 40.0g allyls are added in 100 ml single port bottles
The poly- methyl ether of base（Molecular mass is about 1000 g/mol）, 1.42 g dimethoxybenzoins and 40 ml tetrahydrofurans, be stirred at room temperature
Carry out mercapto alkene reaction；（2）Stop reaction after 1.5 hours, depressurizes away unreacted monomer, solvent, initiator etc., it is cooling up to three
Silicone-type nonionic surfactant.
Its yield is 95%, and hermetically drying preserves.Non-ionic silicone surfactant γCMCFor 26.5 mN/m.
Embodiment 5
（1）7.9 g mercapto oxypropyl trimethyls silane, 12.5g allyl polyglycols are added in 100 ml single port bottles（Molecular mass
About 270 g/mol）, 0.31 g dimethoxybenzoins and 20 ml methanol, be stirred at room temperature and carry out mercapto alkene reaction；（2）40 minutes
Stop reaction afterwards, depressurizes away unreacted monomer, solvent, initiator etc., it is cooling up to trisiloxanes type non-ionic surface active
Agent.
Its yield is 99%, and hermetically drying preserves.Non-ionic silicone surfactant γCMCFor 21.5 mN/m.
Claims (6)
1. a kind of preparation method of polyether-based organic silicon surfactant, which is characterized in that the preparation method includes the following steps：
Mercapto propyl-siloxane, unsaturated polyether, solvent and dimethoxybenzoin are added in single-necked flask, mercapto alkene reaction is carried out,
Reaction time is 30min ~ 4 hour；The complete monomer of unreacted, solvent and residual initiator are removed after reaction, obtain polyether-based
Organic silicon surfactant.
2. a kind of preparation method of polyether-based organic silicon surfactant according to claim 1, which is characterized in that described
Mercapto propyl-siloxane is mercapto oxypropyl trimethyl silane, mercapto propyl-three (trimethylsiloxy group) silane ,-two (trimethyl silicane of mercapto propyl
Oxygroup) methyl-monosilane, mercapto propyl-two (trimethylsiloxy group) methyl-monosilane, mercapto propyl-two (ethyl dimethylsilyl bis) methyl
Silane, mercapto propyl-two (propyl-dimethyl siloxy) methyl-monosilane, mercapto propyl-two (Butyldimethylsilanyloxy) methyl-monosilane,
Mercapto propyl-two (pheiiyldimetliyl siloxy) methyl-monosilane, 1- mercapto propyl pentamethyl disiloxane, 1- mercapto propyl -3- ethyls four
Tetramethyldisiloxane, 1- mercapto propyl -3- propyl tetramethyl disiloxane, 1- mercapto propyl -3- butyl tetramethyl disiloxane, 1- mercaptos
One kind in propyl -3- phenyl tetramethyl disiloxanes.
3. a kind of preparation method of polyether-based organic silicon surfactant according to claim 1, which is characterized in that described
Unsaturated polyether is hydroxy-end capped unsaturated polyether and methyl blocking unsaturated polyether, and wherein glycol chain joint number can be 3 ~ 50,
Propoxyl group chain number is 0 ~ 20.
4. a kind of preparation method of polyether-based organic silicon surfactant according to claim 1, which is characterized in that described
The molar ratio of mercapto propyl-siloxane and unsaturated polyether is 1 ~ 1.3：1.
5. a kind of preparation method of polyether-based organic silicon surfactant according to claim 1, which is characterized in that described
Solvent is that methanol, ethyl alcohol, tetrahydrofuran, isopropanol, butanol, acetonitrile, one kind in N,N-dimethylformamide or its mixing are molten
Agent.
6. a kind of preparation method of polyether-based organic silicon surfactant according to claim 1, which is characterized in that described
Dimethoxybenzoin dosage is 1% ~ 5% mass fraction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109810131A (en) * | 2018-12-26 | 2019-05-28 | 福建拓烯新材料科技有限公司 | The preparation method and polyethers trisiloxanes of seven methyl -3- mercapto propyl trisiloxanes of 1,1,1,3,5,5,5- |
| CN111713493A (en) * | 2020-07-23 | 2020-09-29 | 陕西农塔生物数据研究有限公司 | Synergistic insecticidal auxiliary agent |
| CN112044353A (en) * | 2019-06-05 | 2020-12-08 | 新特能源股份有限公司 | Novel Gemini surfactant and preparation method thereof, novel comb-type surfactant and preparation method thereof |
| CN114805730A (en) * | 2022-06-07 | 2022-07-29 | 山东大学 | Silicone polyurethane foam formulation, polyether graft polysiloxane polyether block copolymer and preparation method thereof |
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| US20070043232A1 (en) * | 2005-08-17 | 2007-02-22 | Korea Institute Of Science And Technology | Omega -[2-(polyalkyleneoxy)ethylthio]alkylalkoxysilane derivative and preparation method thereof |
| CN105713204A (en) * | 2016-02-29 | 2016-06-29 | 东南大学 | Organosilicon surfactant and thiol-ene click chemistry process preparation method thereof |
| CN107868256A (en) * | 2017-12-13 | 2018-04-03 | 山东大学 | A kind of preparation method of silicone polyether surfactant |
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2018
- 2018-06-15 CN CN201810621911.4A patent/CN108752578A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070043232A1 (en) * | 2005-08-17 | 2007-02-22 | Korea Institute Of Science And Technology | Omega -[2-(polyalkyleneoxy)ethylthio]alkylalkoxysilane derivative and preparation method thereof |
| CN105713204A (en) * | 2016-02-29 | 2016-06-29 | 东南大学 | Organosilicon surfactant and thiol-ene click chemistry process preparation method thereof |
| CN107868256A (en) * | 2017-12-13 | 2018-04-03 | 山东大学 | A kind of preparation method of silicone polyether surfactant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109810131A (en) * | 2018-12-26 | 2019-05-28 | 福建拓烯新材料科技有限公司 | The preparation method and polyethers trisiloxanes of seven methyl -3- mercapto propyl trisiloxanes of 1,1,1,3,5,5,5- |
| CN112044353A (en) * | 2019-06-05 | 2020-12-08 | 新特能源股份有限公司 | Novel Gemini surfactant and preparation method thereof, novel comb-type surfactant and preparation method thereof |
| CN112044353B (en) * | 2019-06-05 | 2022-06-28 | 新特能源股份有限公司 | Novel Gemini surfactant and preparation method thereof, novel comb-type surfactant and preparation method thereof |
| CN111713493A (en) * | 2020-07-23 | 2020-09-29 | 陕西农塔生物数据研究有限公司 | Synergistic insecticidal auxiliary agent |
| CN114805730A (en) * | 2022-06-07 | 2022-07-29 | 山东大学 | Silicone polyurethane foam formulation, polyether graft polysiloxane polyether block copolymer and preparation method thereof |
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