CN107522726A - A kind of amino-acid modified trisiloxane surfactant and preparation method thereof - Google Patents
A kind of amino-acid modified trisiloxane surfactant and preparation method thereof Download PDFInfo
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- -1 amino-acid modified trisiloxane Chemical class 0.000 title claims abstract description 63
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 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 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 230000002779 inactivation Effects 0.000 claims abstract description 12
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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
- 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
- 230000035484 reaction time Effects 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
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical class [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- MNJJTHFKDZQVKH-UHFFFAOYSA-N n'-[3-(diethoxymethylsilyl)propyl]ethane-1,2-diamine Chemical compound CCOC(OCC)[SiH2]CCCNCCN MNJJTHFKDZQVKH-UHFFFAOYSA-N 0.000 claims description 3
- XFFPIAQRIDTSIZ-UHFFFAOYSA-N n'-[3-(dimethoxymethylsilyl)propyl]ethane-1,2-diamine Chemical compound COC(OC)[SiH2]CCCNCCN XFFPIAQRIDTSIZ-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
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000693 micelle Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- GOCRPOKWZIVUQG-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propan-1-amine Chemical compound CCOC(OCC)[SiH2]CCCN GOCRPOKWZIVUQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 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
- 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000012827 research and development Methods 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
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
- 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
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- 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
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
A kind of amino-acid modified trisiloxane surfactant and preparation method thereof, belongs to organic silicon surfactant and its preparing technical field.Step：Using amino dialkoxymethyl silane and HMDO as raw material, using catalyst reaction, make catalyst inactivation, air-distillation removes excess raw material, then is evaporated under reduced pressure to obtain amino modified trisiloxanes；Using obtained amino modified trisiloxanes 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 trisiloxanes；Aminopropanoate type trisiloxanes 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, obtains amino-acid modified trisiloxane 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 three silicon
Oxygen alkane surfactant, and further relate to its preparation method.
Background technology
Organic silicon surfactant is a kind of important novel surfactant, and it is unique that its unique molecular structure assigns it
Performance, such as there is very high surface-active, is sprawled and wettability with excellent, it is nontoxic, skin etc. will not be stimulated.These
Unique performance makes it in the field such as polyurethane foam products, weaving, paint and coating, cosmetics and agricultural chemicals have widely should
With.Trisiloxane surfactant is one kind of organic silicon surfactant, due to ultra-low surface tension, super permeability,
The particular advantages such as super wetting and spreadability, obtain the extensive concern of domestic and international researcher.Chinese patent CN101653709A is synthesized
A kind of trisiloxane surfactant containing amino and ethyoxyl；Chinese patent CN103585926B has synthesized a kind of acid and alkali-resistance
Polyether-modified trisiloxane surfactant；Chinese patent CN106554496A has synthesized a kind of phosphate type trisiloxanes surface
Activating agent.But the hydrophilic group of foregoing synthesized trisiloxane surfactant is polyethers, carbohydrate.
Amino acid surfactant is due to properties of product are gentle, toxicity is relatively low, nonirritant, biological degradability and ring
Border compatibility is very good, it is had very big application prospect in the industries such as food, medicine, cosmetics.Research and development at present
It is N- alkyl amino acids surfactant and N- acyl amino acid surfactants to compare more amino acid surfactants, but
The hydrophobic grouping of above-mentioned amino acid surfactant is alkane chain.
Therefore, in view of existing prepare the problems such as amino-acid modified trisiloxane surfactant is of less types, exploitation is new
Amino-acid modified trisiloxane 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 trisiloxane surfactant.
The present invention another task be to provide a kind of preparation method of amino-acid modified trisiloxane surfactant,
This method technical process is brief, it is cheap to prepare cost, can meet industrial amplification production requirement, and the ammonia prepared by this method
The modified trisiloxane surfactant of base acid has excellent surface-active and can be gathered into micella in aqueous and be answered
For such as recovering the oil, weaving, in the field of biology and medicine etc.
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
Trisiloxane surfactant, its general structure are as follows：
R is in formula:CH2CH2COONa、CH2CH2NHCH2CH2COONa
In one particular embodiment of the present invention, the aqueous solution of the amino-acid modified trisiloxane surfactant
Lowest surface tension is 23 and 25mN/m；Critical micelle concentration is 75 and 182mg/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 three silicon
The preparation method of oxygen alkane surfactant, comprises the following steps：
(1) preparation of amino modified trisiloxanes
Using amino dialkoxymethyl silane and HMDO as raw material, using catalyst reaction and control anti-
After answering temperature and control reaction time, reaction to terminate, make catalyst inactivation, air-distillation removes excess raw material, then is evaporated under reduced pressure
Obtain amino modified trisiloxanes；
(2) preparation of aminopropanoate type trisiloxanes
The amino modified trisiloxanes 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 trisiloxanes；
(3) preparation of amino-acid modified trisiloxane surfactant
By step (2) obtain aminopropanoate type trisiloxanes 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 trisiloxane surfactant.
In another specific embodiment of the present invention, the amino dialkoxymethyl silane described in step (1), pregnancy
The mol ratio of base disiloxane and catalyst three are 1:5-20:0.01-0.1；Described controlling reaction temperature is to react
Temperature control is 60-120 DEG C；It is described control the reaction time be by reaction time control be 3-30h.
In another specific embodiment of the present invention, described amino dialkoxymethyl silane is aminopropyl dimethoxy
Butyldimethylsilyl, aminopropyl diethoxymethylsilane, aminoethylaminopropyl dimethoxymethylsilane or aminoethylaminopropyl
Diethoxymethylsilane.
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
During any one in alkali metal hydroxide and silicon alkoxide, add acid and catalyst is neutralized and makes catalyst inactivation, and when urging
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 catalysis
Agent inactivates.
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 trisiloxanes 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 3-30h；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 three 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 1-10h to answer time control；The low-carbon alcoholic solvent is methanol, ethanol, propyl alcohol or isopropanol.
Amino-acid modified trisiloxane surfactant provided by the invention is as a kind of new organic silicon surfactant
And the species of abundant organic silicon surfactant is able to, extend use range；Because preparation process letter is without tired, and make
Standby cost is cheap, thus can meet industrial amplification production requirement and the amino-acid modified trisiloxanes surface of acquisition can be made to live
Property agent possess excellent surface-active and micella can be gathered into aqueous, so as to applied to recover the oil, weaving, biotechnology
In medicine and other fields.
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 trisiloxane 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 trisiloxanes
Aminopropyl dimethoxy methyl-monosilane 16.3Kg (100mol), HMDO are added in a kettle
81.1Kg (500mol), TMAH 0.45Kg (5mol), dissolve by heating, temperature control is reacted 30 hours at 60 DEG C
Afterwards, heating makes catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified three silicon
Oxygen alkane 27.3Kg (98mol).
The preparation of amino acid methyl ester type trisiloxanes
Above-mentioned amino modified trisiloxanes 13.9Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using methanol as solvent, 3h is reacted at a reflux temperature, steams solvent methanol, obtain the silica of amino acid methyl ester type three
Alkane 18.2Kg (50mol).
The preparation of amino-acid modified trisiloxane surfactant
Above-mentioned amino acid methyl ester type trisiloxanes 18.2Kg (50mol) and 25% sodium hydroxide solution are added in a kettle
8Kg (50mol), using ethanol as solvent, reacts 10h at a reflux temperature, steams ethanol, and obtaining amino acid after vacuum drying changes
Property trisiloxane surfactant 18.6Kg (50mol), the lowest surface tension of its aqueous solution surveyed with K12 surface tension instruments is
23mN/m, critical micelle concentration 75mg/L.
Embodiment 2
The preparation of amino modified trisiloxanes
Aminopropyl diethoxymethylsilane 19.1Kg (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 90 DEG C
Acid neutralizes, and makes catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified three silicon
Oxygen alkane 27.0Kg (96.9mol).
The preparation of amino acid methyl ester type trisiloxanes
Above-mentioned amino modified trisiloxanes 13.9Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using ethanol as solvent, 30h is reacted at a reflux temperature, steams etoh solvent, obtain the silicon of amino acid methyl ester type three
Oxygen alkane 18.2Kg (50mol).
The preparation of amino-acid modified trisiloxane surfactant
Above-mentioned amino acid methyl ester type trisiloxanes 18.2Kg (50mol) and 50% sodium hydroxide solution are added in a kettle
4Kg (50mol), using methanol as solvent, reacts 1h at a reflux temperature, steams methanol, and obtaining amino acid after vacuum drying changes
Property trisiloxane surfactant 18.6Kg (50mol), the lowest surface tension of its aqueous solution surveyed with K12 surface tension instruments is
23mN/m, critical micelle concentration 75mg/L.
Embodiment 3
The preparation of amino modified trisiloxanes
Aminoethylaminopropyl dimethoxymethylsilane 20.6Kg (100mol), the silica of hexamethyl two are added in a kettle
Alkane 324.8Kg (2000mol), tetramethyl silanol ammonium 0.35Kg (1mol), dissolve by heating, for temperature control at 120 DEG C, reaction 30 is small
Shi Hou, heating make catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino modified three
Siloxanes 31.5Kg (98mol).
The preparation of amino acid methyl ester type trisiloxanes
Above-mentioned amino modified trisiloxanes 16.1Kg (50mol), methyl acrylate 4.3Kg are added in a kettle
(50mol), using propyl alcohol as solvent, 15h is reacted at a reflux temperature, steam solvent propyl alcohol, obtain the silicon of amino acid methyl ester type three
Oxygen alkane 20.4Kg (50mol).
The preparation of amino-acid modified trisiloxane surfactant
Above-mentioned amino acid methyl ester type trisiloxanes 20.4Kg (50mol) and 40% sodium hydroxide solution are added in a kettle
5Kg (50mol), using isopropanol as solvent, reacts 5h at a reflux temperature, steams isopropanol, amino is obtained after vacuum drying
The modified trisiloxane surfactant 20.8Kg (50mol) of acid, the minimum surface for its aqueous solution surveyed with K12 surface tension instruments
Power is 25mN/m, critical micelle concentration 182mg/L.
Embodiment 4
The preparation of amino modified trisiloxanes
Aminoethylaminopropyl diethoxymethylsilane 23.4Kg (100mol), the silica of hexamethyl two are added in a kettle
Alkane 129.9Kg (800mol), trimethyl silicane sodium alkoxide 0.22Kg (2mol), dissolve by heating, for temperature control at 100 DEG C, reaction 20 is small
Shi Hou, acid adding, which neutralizes, makes catalyst inactivation；Air-distillation goes out excessive HMDO, then rectification under vacuum obtains amino and changed
Property trisiloxanes 31.2Kg (97mol).
The preparation of amino acid methyl ester type trisiloxanes
Above-mentioned amino modified trisiloxanes 16.1Kg (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
Trisiloxanes 20.4Kg (50mol).
The preparation of amino-acid modified trisiloxane surfactant
Above-mentioned amino acid methyl ester type trisiloxanes 20.4Kg (50mol) and 30% sodium hydroxide solution are added in a kettle
6.7Kg (50mol), using propyl alcohol as solvent, reacts 5h at a reflux temperature, steams propyl alcohol, amino acid is obtained after vacuum drying
Modified trisiloxane surfactant 20.8Kg (50mol), the lowest surface tension for its aqueous solution surveyed with K12 surface tension instruments
For 25mN/m, critical micelle concentration 182mg/L.
Claims (9)
1. a kind of amino-acid modified trisiloxane 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 trisiloxane surfactant according to claim 1, it is characterised in that the amino
The lowest surface tension of the aqueous solution of the modified trisiloxane surfactant of acid is 23 and 25mN/m；Critical micell in aqueous
Concentration is 75 and 182mg/L.
A kind of 3. preparation method of amino-acid modified trisiloxane surfactant as claimed in claim 1, it is characterised in that
Comprise the following steps：
(1) preparation of amino modified trisiloxanes
Using amino dialkoxymethyl 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 trisiloxanes；
(2) preparation of aminopropanoate type trisiloxanes
The amino modified trisiloxanes 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 trisiloxanes；
(3) preparation of amino-acid modified trisiloxane surfactant
Step (2) is obtained into aminopropanoate type trisiloxanes 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 trisiloxane surfactant of acid.
4. a kind of preparation method of amino-acid modified trisiloxane surfactant according to claim 3, its feature exist
Amino dialkoxymethyl silane, HMDO and the mol ratio of catalyst three described in step (1) are
1:5-20:0.01-0.1；Described controlling reaction temperature is to control reaction temperature for 60-120 DEG C；When described control is reacted
Between be by the reaction time control be 3-30h.
5. a kind of preparation method of amino-acid modified trisiloxane surfactant according to claim 3 or 4, its feature
It is described amino dialkoxymethyl silane for aminopropyl dimethoxy methyl-monosilane, aminopropyl diethoxymethyl silicon
Alkane, aminoethylaminopropyl dimethoxymethylsilane or aminoethylaminopropyl diethoxymethylsilane.
6. a kind of preparation method of amino-acid modified trisiloxane surfactant according to claim 3, its feature exist
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 any one in alkali metal hydroxide and silicon alkoxide,
Acid is added to neutralize catalyst and make catalyst inactivation, and when catalyst is quaternary ammonium base, quaternary phosphonium hydroxides, silanol quaternary ammonium salt and silanol season
During any one in phosphonium salt, carry out heat resolve and make catalyst inactivation.
7. a kind of preparation method of amino-acid modified trisiloxane 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 trisiloxane surfactant according to claim 3, its feature exist
The mol ratio of amino modified trisiloxanes 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
3-30h；The low-carbon alcoholic solvent is methanol, ethanol, propyl alcohol or isopropanol.
9. a kind of preparation method of amino-acid modified trisiloxane surfactant according to claim 3, its feature exist
The mol ratio of aminopropanoate type trisiloxanes 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 1-10h；The low-carbon alcoholic solvent is methanol, second
Alcohol, propyl alcohol or isopropanol.
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| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
| CN111072754A (en) * | 2019-12-04 | 2020-04-28 | 常熟理工学院 | Trisiloxane modified carnosine and preparation method thereof |
| CN111548501A (en) * | 2020-06-02 | 2020-08-18 | 四川达威科技股份有限公司 | Preparation method of organic silicon surfactant containing amino acid |
| US11008348B2 (en) | 2019-08-22 | 2021-05-18 | Advansix Resins & Chemicals Llc | Siloxane derivatives of amino acids having surface-active properties |
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| US11008348B2 (en) | 2019-08-22 | 2021-05-18 | Advansix Resins & Chemicals Llc | Siloxane derivatives of amino acids having surface-active properties |
| CN111072754A (en) * | 2019-12-04 | 2020-04-28 | 常熟理工学院 | Trisiloxane modified carnosine and preparation method thereof |
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