CN107698615A - A kind of amino-acid modified tetrasiloxane surfactant and preparation method thereof - Google Patents
A kind of amino-acid modified tetrasiloxane surfactant and preparation method thereof Download PDFInfo
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- CN107698615A CN107698615A CN201710821908.2A CN201710821908A CN107698615A CN 107698615 A CN107698615 A CN 107698615A CN 201710821908 A CN201710821908 A CN 201710821908A CN 107698615 A CN107698615 A CN 107698615A
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- -1 amino-acid modified tetrasiloxane Chemical class 0.000 title claims abstract description 82
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 230000002779 inactivation Effects 0.000 claims abstract description 13
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 12
- KTYVHLCLTPLSGC-UHFFFAOYSA-N amino propanoate Chemical compound CCC(=O)ON KTYVHLCLTPLSGC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 9
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 3
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 3
- SYKCSZUMAHWVJM-UHFFFAOYSA-N CCCCO[Si](CCCC)(CCCC)CCCC.P Chemical group CCCCO[Si](CCCC)(CCCC)CCCC.P SYKCSZUMAHWVJM-UHFFFAOYSA-N 0.000 claims description 2
- NTSNXSJENBZFSF-UHFFFAOYSA-N [Na+].[SiH3][O-] Chemical group [Na+].[SiH3][O-] NTSNXSJENBZFSF-UHFFFAOYSA-N 0.000 claims description 2
- ZBBKCJXETVKDOI-UHFFFAOYSA-N butylphosphanium;hydroxide Chemical class [OH-].CCCC[PH3+] ZBBKCJXETVKDOI-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229940017219 methyl propionate Drugs 0.000 claims 1
- 150000004714 phosphonium salts Chemical class 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- YAGNBBKTVGENKK-UHFFFAOYSA-N azane methoxy(trimethyl)silane Chemical group CO[Si](C)(C)C.N YAGNBBKTVGENKK-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
A kind of amino-acid modified tetrasiloxane surfactant and preparation method thereof, belongs to organic silicon surfactant and its preparing technical field.Step：Using amino-trialkoxy silane and HMDO as raw material, using catalyst reaction, after reaction terminates, make catalyst inactivation, air-distillation removes excess raw material, then is evaporated under reduced pressure to obtain amino modified tetrasiloxane；Using obtained amino modified tetrasiloxane and methyl acrylate as raw material, reacted in the presence of low-carbon alcoholic solvent, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtain aminopropanoate type tetrasiloxane；Aminopropanoate type tetrasiloxane will be obtained to react in the presence of low-carbon alcoholic solvent with sodium hydroxide solution, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtain amino-acid modified tetrasiloxane surfactant.Extend use range.Without tired, preparation cost is cheap for technical process letter.
Description
Technical field
The invention belongs to organic silicon surfactant and its preparing technical field, and in particular to a kind of amino-acid modified four silicon
Oxygen alkane surfactant, and further relate to its preparation method.
Background technology
Because amino acid surfactant has, properties of product are gentle, toxicity is relatively low, nonirritant, biological degradability and ring
The features such as border compatibility is good, thus have good application prospect in the industries such as food, medicine, cosmetics.Study and open at present
The more amino acid surfactant of hair is N- alkyl amino acids surfactant and N- acyl amino acid surfactants, so
And the hydrophobic grouping of foregoing amino acid surfactant is alkane chain.
Organic silicon surfactant is good to sprawl and the spy such as wetability and thermostabilization due to low surface tension
Point, it is set to be obtained a wide range of applications in polyurethane foam products, weaving, paint and coating, cosmetics and pesticide field.Four
Silicone surfactant is one kind of organic silicon surfactant, due to ultra-low surface tension, super permeability, super wetting
With the particular advantages such as spreadability, the extensive concern of domestic and international researcher is obtained.Chinese patent CN104072563A has synthesized one kind
Tetrasiloxane surfactant containing sugared amide groups；Chinese patent CN104610338B has synthesized a kind of glycosyl amide and has been modified four silicon
Oxygen alkane surfactant；What Chinese patent CN104072562A had synthesized that a kind of ethyoxyl is modified contains sugared amide groups tetrasiloxane table
Face activating agent；But the hydrophilic group of foregoing synthesized tetrasiloxane surfactant is sugar.
Therefore, in view of existing prepare the problems such as amino-acid modified tetrasiloxane surfactant is of less types, exploitation is new
Amino-acid modified tetrasiloxane surfactant simultaneously studies its preparation method and has positive effect, technical side described below
Case is caused under this background.
The content of the invention
Top priority of the present invention is that providing one kind contributes to abundant novel organosilicon kinds of surfactants and structure
Novel amino-acid modified tetrasiloxane surfactant.
The present invention another task be to provide a kind of preparation method of amino-acid modified tetrasiloxane surfactant,
This method technical process is brief, technical factor is not harsh and it is cheap to prepare cost, is satisfied industrial amplification production requirement,
And the amino-acid modified tetrasiloxane surfactant prepared by this method has excellent surface-active and can be in the aqueous solution
In be gathered into aggregation and be able to be applied to medicine and the field such as biology.
To embody the top priority for completing the present invention, concrete technical scheme provided by the invention is：It is a kind of amino-acid modified
Tetrasiloxane surfactant, its general structure are as follows：
R is in formula:CH2CH2COONa、CH2CH2NHCH2CH2COONa
In the specific embodiment of the present invention, the aqueous solution of the amino-acid modified tetrasiloxane surfactant
Lowest surface tension be 21 and 24mN/m；Critical micelle concentration is 65 and 113mg/L in aqueous.
To embody another task for completing the present invention, technical scheme provided by the invention is：A kind of amino-acid modified four silicon
The preparation method of oxygen alkane surfactant, comprises the following steps：
(1) preparation of amino modified tetrasiloxane
Using amino-trialkoxy silane and HMDO as raw material, using catalyst reaction and reaction temperature is controlled
Degree and control reaction time, after reaction terminates, make catalyst inactivation, air-distillation removes excess raw material, then is evaporated under reduced pressure to obtain
Amino modified tetrasiloxane；
(2) preparation of aminopropanoate type tetrasiloxane
The amino modified tetrasiloxane and methyl acrylate obtained using step (1) is raw material, in the presence of low-carbon alcoholic solvent
Reaction, and the reaction temperature in the presence of low alcoholic solvent and reaction time are controlled, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtains
To aminopropanoate type tetrasiloxane；
(3) preparation of amino-acid modified tetrasiloxane surfactant
By step (2) obtain aminopropanoate type tetrasiloxane and sodium hydroxide solution in the presence of low-carbon alcoholic solvent it is anti-
Should, and the reaction temperature in the presence of low alcoholic solvent and reaction time are controlled, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtains
Amino-acid modified tetrasiloxane surfactant.
In another specific embodiment of the present invention, amino-trialkoxy silane, hexamethyl described in step (1)
The mol ratio of disiloxane and catalyst three are 1:9-40:0.01-0.1；Described controlling reaction temperature is by reaction temperature
Degree control is 60-100 DEG C；It is described control the reaction time be by reaction time control be 5-50h.
In another specific embodiment of the present invention, described amino-trialkoxy silane is aminopropyl trimethoxy
Silane, aminopropyl triethoxysilane, aminoethylaminopropyl trimethoxy silane or aminoethylaminopropyl triethoxysilane.
In another specific embodiment of the present invention, catalyst described in step (1) is alkali metal hydroxide, silicon
Alkoxide, quaternary ammonium base, quaternary phosphonium hydroxides, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt；Described refers to catalyst inactivation：When catalyst is alkali
During any one in metal hydroxides and silicon alkoxide, add acid and catalyst is neutralized and makes catalyst inactivation, and when catalysis
When agent is any one in quaternary ammonium base, quaternary phosphonium hydroxides, silanol quaternary ammonium salt and silanol quaternary alkylphosphonium salt, carries out heat resolve and make catalyst
Inactivation.
In the also specific embodiment of the present invention, described alkali metal hydroxide is sodium hydroxide or hydrogen-oxygen
Change potassium；Described silicon alkoxide is sodium silanolate or silanol potassium；Described quaternary ammonium base is TMAH；The quaternary phosphonium hydroxides are
Si butyl phosphonium hydroxides；Described silanol quaternary ammonium salt is tetramethyl silanol ammonium；Described silanol quaternary alkylphosphonium salt is tetrabutyl silanol Phosphonium.
The present invention's and then in a specific embodiment, the amino modified tetrasiloxane and third described in step (2)
The mol ratio of e pioic acid methyl ester is 1:1；Reaction temperature and reaction time in the presence of described control low-carbon alcoholic solvent are to react
Temperature control is the reflux temperature of solvent, will be controlled in the reaction time as 2-20h；The low-carbon alcoholic solvent is methanol, ethanol, propyl alcohol
Or isopropanol.
The present invention again more and a specific embodiment in, the silicon of aminopropanoate type four described in step (3)
The mol ratio of oxygen alkane and sodium hydroxide is 1:1；The quality % specific concentrations of the sodium hydroxide solution are 25% to 50%；Described
Control the reaction temperature in the presence of low-carbon alcoholic solvent and the reaction time is reflux temperature by reaction temperature control for solvent, will be anti-
It is 1-30h to answer time control；The low-carbon alcoholic solvent is methanol, ethanol, propyl alcohol or isopropanol.
Novel amino provided by the invention is modified tetrasiloxane surfactant and lived as a kind of new organosilyl surface
Property agent and be able to the species of abundant organic silicon surfactant, extend use range.Because preparation process letter is without tired, and
And preparation cost is cheap, thus industrial amplification production requirement can be met and the amino-acid modified tetrasiloxane table of acquisition can be made
Face activating agent possesses excellent surface-active and can be gathered into aggregation in aqueous, so as to applied to medical, biological skill
In the fields such as art.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The present invention and be not limited to limit the scope of the present invention, all equivalent transformations done according to spirit of the invention or modification, all should
It is included within the scope of the present invention.The implementation condition used in embodiment can do further tune according to actual conditions
Whole, unreceipted implementation condition is usually the condition in normal experiment.
The amino-acid modified tetrasiloxane surfactant for preparing structures shown below formula is added by four embodiments respectively
With explanation.
Wherein R is:CH2CH2COONa、CH2CH2NHCH2CH2COONa
Embodiment 1
The preparation of amino modified tetrasiloxane
Aminopropyl trimethoxysilane 17.9Kg (100mol), HMDO 146.1Kg are added in a kettle
(900mol), tetramethyl silanol ammonium 0.35Kg (1mol), dissolve by heating, temperature control is at 60 DEG C, and after reacting 50 hours, heating makes
Catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified tetrasiloxane
34.4Kg(97.5mol)。
The preparation of amino acid methyl ester type tetrasiloxane
Above-mentioned amino modified tetrasiloxane 17.6Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using ethanol as solvent, 2h is reacted at a reflux temperature, steams etoh solvent, obtain the silica of amino acid methyl ester type four
Alkane 21.9Kg (50mol)
The preparation of amino-acid modified tetrasiloxane surfactant
Above-mentioned amino acid methyl ester type tetrasiloxane 21.9Kg (50mol) and 25% sodium hydroxide solution are added in a kettle
8Kg (50mol), using methanol as solvent, reacts 30h at a reflux temperature, steams methanol, and obtaining amino acid after vacuum drying changes
Property tetrasiloxane surfactant 22.3Kg (50mol), the lowest surface tension of its aqueous solution surveyed with K12 surface tension instruments is
21mN/m, critical micelle concentration 65mg/L.
Embodiment 2
The preparation of amino modified tetrasiloxane
Aminopropyl triethoxysilane 22.1Kg (100mol), HMDO 243.6Kg are added in a kettle
(1500mol), trimethyl silicane sodium alkoxide 0.22Kg (2mol), dissolving by heating, temperature control is at 100 DEG C, after reacting 5 hours, acid adding
Neutralization makes catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified four silica
Alkane 34.7Kg (98.3mol),
The preparation of amino acid methyl ester type tetrasiloxane
Above-mentioned amino modified tetrasiloxane 17.6Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using methanol as solvent, 20h is reacted at a reflux temperature, steams solvent methanol, obtain the silicon of amino acid methyl ester type four
Oxygen alkane 21.9Kg (50mol)
The preparation of amino-acid modified tetrasiloxane surfactant
Above-mentioned amino acid methyl ester type tetrasiloxane 21.9Kg (50mol) and 50% sodium hydroxide solution are added in a kettle
4Kg (50mol), using ethanol as solvent, reacts 1h at a reflux temperature, steams ethanol, and obtaining amino acid after vacuum drying changes
Property tetrasiloxane surfactant 22.3Kg (50mol), the lowest surface tension of its aqueous solution surveyed with K12 surface tension instruments is
21mN/m, critical micelle concentration 65mg/L.
Embodiment 3
The preparation of amino modified tetrasiloxane
Aminoethylaminopropyl triethoxysilane 26.4Kg (100mol), HMDO are added in a kettle
649.5Kg (4000mol), TMAH 0.45Kg (5mol), dissolve by heating, for temperature control at 90 DEG C, reaction 20 is small
Shi Hou, heating make catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified four
Siloxanes 38.35Kg (96.8mol),
The preparation of amino acid methyl ester type tetrasiloxane
Above-mentioned amino modified tetrasiloxane 19.8Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using isopropanol as solvent, 10h is reacted at a reflux temperature, steam solvent isopropanol, obtain amino acid methyl ester type
Tetrasiloxane 24.1Kg (50mol)
The preparation of amino-acid modified tetrasiloxane surfactant
Above-mentioned amino acid methyl ester type tetrasiloxane 24.1Kg (50mol) and 30% sodium hydroxide solution are added in a kettle
6.7Kg (50mol), using propyl alcohol as solvent, reacts 15h at a reflux temperature, steams propyl alcohol, amino acid is obtained after vacuum drying
Modified tetrasiloxane surfactant 24.5Kg (50mol), the lowest surface tension for its aqueous solution surveyed with K12 surface tension instruments
For 24mN/m, critical micelle concentration 113mg/L.
Embodiment 4
The preparation of amino modified tetrasiloxane
Aminoethylaminopropyl trimethoxy silane 26.4Kg (100mol), HMDO are added in a kettle
162.4Kg (1000mol), sodium hydroxide 0.4Kg (10mol), dissolve by heating, temperature control after reacting 15 hours, adds at 80 DEG C
Acid, which neutralizes, makes catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified four silicon
Oxygen alkane 38.51Kg (97.2mol),
The preparation of amino acid methyl ester type tetrasiloxane
Above-mentioned amino modified tetrasiloxane 19.8Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using propyl alcohol as solvent, 5h is reacted at a reflux temperature, steam solvent propyl alcohol, obtain the silica of amino acid methyl ester type four
Alkane 24.1Kg (50mol)
The preparation of amino-acid modified tetrasiloxane surfactant
Above-mentioned amino acid methyl ester type tetrasiloxane 24.1Kg (50mol) and 40% sodium hydroxide solution are added in a kettle
5.0Kg (50mol), using isopropanol as solvent, reacts 15h at a reflux temperature, steams isopropanol, ammonia is obtained after vacuum drying
The modified tetrasiloxane surfactant 24.5Kg (50mol) of base acid, the minimum surface for its aqueous solution surveyed with K12 surface tension instruments
Tension force is 24mN/m, critical micelle concentration 113mg/L.
Claims (9)
1. a kind of amino-acid modified tetrasiloxane surfactant, it is characterised in that its general structure is as follows：
R is in formula:CH2CH2COONa、CH2CH2NHCH2CH2COONa。
A kind of 2. amino-acid modified tetrasiloxane surfactant according to claim 1, it is characterised in that the amino
The lowest surface tension of the aqueous solution of the modified tetrasiloxane surfactant of acid is 21 and 24mN/m；Critical micell in aqueous
Concentration is 65 and 113mg/L.
A kind of 3. preparation method of amino-acid modified tetrasiloxane surfactant as claimed in claim 1, it is characterised in that
Comprise the following steps：
(1) preparation of amino modified tetrasiloxane
Using amino-trialkoxy silane and HMDO as raw material, using catalyst reaction and controlling reaction temperature and
After controlling reaction time, reaction to terminate, make catalyst inactivation, air-distillation removes excess raw material, then is evaporated under reduced pressure to obtain amino
Modified tetrasiloxane；
(2) preparation of aminopropanoate type tetrasiloxane
The amino modified tetrasiloxane and methyl acrylate obtained using step (1) reacts as raw material in the presence of low-carbon alcoholic solvent,
And the reaction temperature in the presence of low alcoholic solvent and reaction time are controlled, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtains amino
Methyl propionate type tetrasiloxane；
(3) preparation of amino-acid modified tetrasiloxane surfactant
Step (2) is obtained into aminopropanoate type tetrasiloxane to react in the presence of low-carbon alcoholic solvent with sodium hydroxide solution,
And the reaction temperature in the presence of low alcoholic solvent and reaction time are controlled, after the completion of reaction, low-carbon alcoholic solvent is evaporated off, obtains amino
The modified tetrasiloxane surfactant of acid.
4. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 3, its feature exist
The mol ratio of amino-trialkoxy silane, HMDO and catalyst three described in step (1) is 1:9-
40:0.01-0.1；Described controlling reaction temperature is to control reaction temperature for 60-100 DEG C；The described control reaction time is
It will control in the reaction time as 5-50h.
5. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 3 or 4, its feature
It is described amino-trialkoxy silane for aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminoethyl ammonia third
Base trimethoxy silane or aminoethylaminopropyl triethoxysilane.
6. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 3, its feature exist
The catalyst described in step (1) is alkali metal hydroxide, silicon alkoxide, quaternary ammonium base, quaternary phosphonium hydroxides, silanol quaternary ammonium salt or silanol season
Phosphonium salt；Described refers to catalyst inactivation：When catalyst is any one in alkali metal hydroxide and silicon alkoxide, add
Enter acid to neutralize catalyst and make catalyst inactivation, and when catalyst is quaternary ammonium base, quaternary phosphonium hydroxides, silanol quaternary ammonium salt and silanol quaternary phosphine
During any one in salt, carry out heat resolve and make catalyst inactivation.
7. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 6, its feature exist
In described alkali metal hydroxide be sodium hydroxide or potassium hydroxide；Described silicon alkoxide is sodium silanolate or silanol potassium；It is described
Quaternary ammonium base be TMAH；The quaternary phosphonium hydroxides are Si butyl phosphonium hydroxides；Described silanol quaternary ammonium salt is tetramethyl
Base silanol ammonium；Described silanol quaternary alkylphosphonium salt is tetrabutyl silanol Phosphonium.
8. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 3, its feature exist
The mol ratio of amino modified tetrasiloxane and methyl acrylate described in step (2) is 1:1；Described control low-carbon alcohols are molten
It by reaction temperature control is the reflux temperature of solvent that reaction temperature and reaction time in the presence of agent, which are, will control in the reaction time and be
2-20h；The low-carbon alcoholic solvent is methanol, ethanol, propyl alcohol or isopropanol.
9. a kind of preparation method of amino-acid modified tetrasiloxane surfactant according to claim 3, its feature exist
The mol ratio of aminopropanoate type tetrasiloxane and sodium hydroxide described in step (3) is 1:1；The sodium hydroxide is molten
The quality % specific concentrations of liquid are 25% to 50%；Reaction temperature and reaction time in the presence of described control low-carbon alcoholic solvent are
It is the reflux temperature of solvent by reaction temperature control, will controls in the reaction time as 1-30h；The low-carbon alcoholic solvent is methanol, second
Alcohol, propyl alcohol or isopropanol.
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