CN101942097B - Method for preparing glycosyl amide modified polysiloxane - Google Patents
Method for preparing glycosyl amide modified polysiloxane Download PDFInfo
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- CN101942097B CN101942097B CN2010102914254A CN201010291425A CN101942097B CN 101942097 B CN101942097 B CN 101942097B CN 2010102914254 A CN2010102914254 A CN 2010102914254A CN 201010291425 A CN201010291425 A CN 201010291425A CN 101942097 B CN101942097 B CN 101942097B
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- acid amides
- modified polyorganosiloxane
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- silanol
- glycosyl
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- -1 glycosyl amide Chemical class 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title abstract description 12
- 229920001296 polysiloxane Polymers 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 16
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010025 steaming Methods 0.000 claims description 9
- 229920013822 aminosilicone Polymers 0.000 claims description 8
- 230000009849 deactivation Effects 0.000 claims description 8
- UNYNVICDCJHOPO-UHFFFAOYSA-N quabalactone III Natural products CC1OC(=O)C(O)=C1C UNYNVICDCJHOPO-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 230000002779 inactivation Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- ZRBPLFDXISTAAG-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](OC)(CCCN)OC ZRBPLFDXISTAAG-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical group CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- GOCRPOKWZIVUQG-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propan-1-amine Chemical compound CCOC(OCC)[SiH2]CCCN GOCRPOKWZIVUQG-UHFFFAOYSA-N 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 3
- WERJVTRSPUFCRW-UHFFFAOYSA-N NCC[SiH](C(OCC)OCC)CCCN Chemical compound NCC[SiH](C(OCC)OCC)CCCN WERJVTRSPUFCRW-UHFFFAOYSA-N 0.000 claims description 3
- NTSNXSJENBZFSF-UHFFFAOYSA-N [Na+].[SiH3][O-] Chemical group [Na+].[SiH3][O-] NTSNXSJENBZFSF-UHFFFAOYSA-N 0.000 claims description 3
- YAGNBBKTVGENKK-UHFFFAOYSA-N azane methoxy(trimethyl)silane Chemical group CO[Si](C)(C)C.N YAGNBBKTVGENKK-UHFFFAOYSA-N 0.000 claims description 3
- ZBBKCJXETVKDOI-UHFFFAOYSA-N butylphosphanium;hydroxide Chemical class [OH-].CCCC[PH3+] ZBBKCJXETVKDOI-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000000415 inactivating effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 229910021529 ammonia Inorganic materials 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000003918 potentiometric titration Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000008101 lactose Substances 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 229940099563 lactobionic acid Drugs 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention discloses a method for preparing glycosyl amide modified polysiloxane. The method comprises the following steps of: reacting cyclosiloxane, hexamethyldisiloxane and aminosilane serving as raw materials under the action of a catalyst at the temperature of between 30 and 220 DEG C for 4 to 8 hours, wherein the molar ratio of the cyclosiloxane to the aminosilane to the hexamethyldisiloxane is 0.25-2.25:3-5:1; the molar ratio of the catalyst to the sum of the cyclosiloxane, the aminosilane and the hexamethyldisiloxane is 0.1 to 1; inactivating the catalyst after the reaction is finished; performing reduced pressure distillation to obtain the amino-polysiloxane; reacting the amino-polysiloxane and glycosyl lactone or saccharic acid in low-carbon alcohol serving as a solvent at the temperature of between 30 and 200 DEG C for 5 to 10 hours, wherein the molar ratio of primary amine of the amino-polysiloxane to the glycosyl lactone or saccharic acid is 1-5:1; and evaporating off the solvent to obtain the glycosyl amide modified polysiloxane after the reaction is finished. The method has the advantages of low cost, no toxicity and large-scale industrialization.
Description
Technical field
The present invention relates to a kind of preparation method of glycosyl acid amides modified polyorganosiloxane.
Background technology
The method of the glycosyl acid amides modified polyorganosiloxane of existing preparation; Like Feng Shengyu (Carbohydrate Polymer, 2006,65; 321) reported a kind of method of glycosyl acid amides modified polyorganosiloxane of preparation; Through again hydroxyl being protected after Gluconolactone and the allyl amine reaction, then carry out addition reaction of silicon with hydrogen with hydrogen containing siloxane again, go protection to obtain glycosyl acid amides modified polyorganosiloxane again.German patent DE 4,318,539 have reported a kind of method for preparing glycosyl acid amides modified polyorganosiloxane, through aminosiloxane and sugar lactone reaction, obtain product.But aminosiloxane is to be obtained through hydrosilation reaction by allyl amine.Wagner R. (Applied Organometallic Chemistry; 1996; 10,421) reported a kind of method for preparing glycosyl acid amides modified polyorganosiloxane, obtained epoxy-modified polysiloxane through hydrogen containing siloxane and glycidyl allyl ether reaction; Obtain amino modified polysiloxane with excessive reacting ethylenediamine again, then reaction obtains product with sugar lactone.
These method synthetic glycosyl acid amides modified polyorganosiloxanes all have addition reaction of silicon with hydrogen in its building-up process, this reaction catalyst system therefor Platinic chloride price is more expensive; And the method that has needs protection and goes to protect step, makes reaction process tediously long; The allyl amine toxicity that the method that has is used is very big.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of cost low, nontoxic and have a preparation method of the glycosyl acid amides modified polyorganosiloxane of heavy industrialization.
The molecular structural formula of a kind of glycosyl acid amides modified polyorganosiloxane of the present invention is following:
Wherein R is:
or
The preparation method of glycosyl acid amides modified polyorganosiloxane of the present invention may further comprise the steps:
(1) be raw material by cyclosiloxane, SWS-F 221, aminosilane, at catalyst action, reaction is 4-8 hour under 30-220 ℃ condition; Wherein the mol ratio of cyclosiloxane, aminosilane and SWS-F 221 is 0.25-2.25: 3-5: 1; The mole dosage of catalyzer is the 0.1-1% of cyclosiloxane, aminosilane and SWS-F 221 mole sum; Reaction makes catalyst deactivation after finishing, and underpressure distillation obtains amino silicones;
(2) amino silicones and sugar lactone or saccharic acid are made solvent with low-carbon alcohol, and reaction is 5-10 hour under 30-200 ℃ situation, and wherein the mol ratio of the primary amine of amino silicones and sugar lactone or saccharic acid is 1-5: 1; After reaction was accomplished, steaming desolventized and obtains glycosyl acid amides modified polyorganosiloxane.
Temperature of reaction is preferably 70-100 ℃ in the step (1) as stated.The mole proportioning of cyclosiloxane, aminosilane and SWS-F 221 is preferably 0.5-2 in the step (1): 3-4: 1.The proportioning of amino silicones and sugar lactone or saccharic acid is preferably 1-4 in the step (2): 1.
Aforesaid aminosilane comprises: aminopropyl dimethoxy-methyl silane, aminopropyl diethoxymethyl silane, aminoethyl aminopropyl dimethoxy-methyl silane or aminoethyl aminopropyl diethoxymethyl silane etc.
Aforesaid catalyzer can comprise: alkali metal hydroxide such as sodium hydroxide, Pottasium Hydroxide etc.; Silicon alkoxide such as sodium silanolate, silanol potassium etc.; Quaternary ammonium hydroxide such as TMAH etc.; quaternary phosphonium hydroxide is like four butyl phosphonium hydroxides etc., silanol quaternary ammonium salt such as tetramethyl-silanol ammonium etc., silanol quaternary alkylphosphonium salt such as tetrabutyl silanol Phosphonium etc.
The aforesaid catalyst deactivation that makes is when catalyzer is alkali metal hydroxide, silanol, adds sour catalyst neutralisation, makes it inactivation and filters out; When catalyzer was quaternary ammonium hydroxide 、 quaternary phosphonium hydroxide, silanol quaternary ammonium salt, silanol quaternary alkylphosphonium salt, thermal degradation made it inactivation and underpressure distillation is come out.
Aforesaid low-carbon alcohol can comprise: methyl alcohol, ethanol, Virahol etc.
The glycosyl acid amides modified polyorganosiloxane that the present invention is prepared, the lowest surface tension of its aqueous solution are at 20-28mN/m, and micelle-forming concentration is 10-200mg/L.It can form vesica class aggregate in the aqueous solution.Because ZGK 5 all is environmentally friendly material with sugar, shows that it can be used as pharmaceutical carrier and in the medicine transmission system, uses.
The glycosyl acid amides modified polyorganosiloxane that the present invention is prepared; Its advantage is the deficiency that has overcome original technology, has avoided the addition reaction of silicon with hydrogen step in original technology, has reduced reaction process; Also avoided using the very big allyl amine of toxicity; And catalyzer is cheap, and cost is low, helps industriallization.
Embodiment
Below in conjunction with embodiment the present invention is made an explanation.
Embodiment 1
In reaction kettle, add octamethylcyclotetrasiloxane 5.93kg, aminoethyl aminopropyl dimethoxy-methyl silane 6.18kg, SWS-F 221 1.62kg; TMAH 10.9g, heating for dissolving, temperature are controlled at 30 ℃; React after 5 hours, be warming up to 135 ℃, make catalyst deactivation.Obtain aminoethyl aminopropyl ZGK 5 after the rectification under vacuum, record uncle's ammonia value with potentiometric titration.Mole number according to uncle's ammonia value adds equimolar glucose lactone, makees solvent with methyl alcohol, is to react 6 hours under 70 ℃ of conditions in temperature.Steaming desolventizes methyl alcohol, obtains product glucamide modification aminoethyl aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 23mN/m, micelle-forming concentration is 35mg/L.
Embodiment 2
In reaction kettle, add octamethylcyclotetrasiloxane 2.97kg, aminopropyl diethoxymethyl silane 5.74kg, SWS-F 221 1.62kg; Pottasium Hydroxide 112g, heating for dissolving, temperature are controlled at 220 ℃; React after 7 hours, add the acetic acid catalyst neutralisation, make it inactivation and filter out.Obtain the aminopropyl ZGK 5 after the rectification under vacuum, record the ammonia value with potentiometric titration.Adding the glucose lactone of three times of moles according to the mole number of ammonia value, make solvent with ethanol, is reaction 5 hours under 30 ℃ of conditions in temperature.Steaming desolventizes ethanol, obtains product glucamide modification aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 24mN/m, micelle-forming concentration is 23mg/L.
Embodiment 3
In reaction kettle, add hexamethyl cyclotrisiloxane 1.12kg, aminopropyl dimethoxy-methyl silane 2.45kg, SWS-F 221 0.81kg; Si butyl phosphonium hydroxides 104.5g, heating for dissolving, temperature are controlled at 80 ℃; React after 8 hours, heat up and be heated to 110 ℃, make catalyst deactivation.Rectification under vacuum obtains the aminopropyl ZGK 5, records the ammonia value with potentiometric titration.Adding the lactobionic acid of twice mole according to the mole number of ammonia value, make solvent with Virahol, is reaction 10 hours under 90 ℃ of conditions in temperature.Steaming desolventizes Virahol, obtains product lactose amide modification aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 26mN/m, micelle-forming concentration is 74mg/L.
Embodiment 4
In reaction kettle, add octamethylcyclotetrasiloxane 7.41kg, aminoethyl aminopropyl diethoxymethyl silane 6.18kg, SWS-F 221 1.62kg; Silanol potassium 546g, heating for dissolving, temperature are controlled at 90 ℃; React after 5 hours, add the acetic acid catalyst neutralisation, make it inactivation and filter out.Rectification under vacuum obtains aminoethyl aminopropyl ZGK 5, records uncle's ammonia value with potentiometric titration.Adding the lactobionic acid of four times of moles according to the mole number of uncle's ammonia value, make solvent with ethanol, is reaction 7 hours under 50 ℃ of conditions in temperature.Steaming desolventizes ethanol, obtains product lactose amide modification aminoethyl aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 25mN/m, micelle-forming concentration is 183mg/L.
Embodiment 5
In reaction kettle, add hexamethyl cyclotrisiloxane 5.93kg, aminopropyl dimethoxy-methyl silane 9.8kg, SWS-F 221 3.24kg; Tetramethyl-silanol ammonium 190.4g, heating for dissolving, temperature are controlled at 60 ℃; React after 4 hours, heat up and be heated to 130 ℃, make catalyst deactivation.Rectification under vacuum obtains the aminopropyl ZGK 5, records the ammonia value with potentiometric titration.Mole number according to the ammonia value adds equimolar glucose lactone, makees solvent with Virahol, is to react 8 hours under 60 ℃ of conditions in temperature.Steaming desolventizes Virahol, promptly gets product glucamide modification aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 27mN/m, micelle-forming concentration is 30mg/L.
Embodiment 6
In reaction kettle, add octamethylcyclotetrasiloxane 18.54kg, aminoethyl aminopropyl dimethoxy-methyl silane 30.9kg, SWS-F 221 8.1kg; Tetrabutyl silanol Phosphonium 3.78kg, heating for dissolving, temperature are controlled at 70 ℃; React after 5 hours, heat up and be heated to 110 ℃, make catalyst deactivation.Rectification under vacuum obtains aminoethyl aminopropyl ZGK 5, records uncle's ammonia value with potentiometric titration.Mole number according to uncle's ammonia value adds equimolar glucose lactone, makees solvent with methyl alcohol, is to react 9 hours under 70 ℃ of conditions in temperature.Steaming desolventizes methyl alcohol, obtains product glucamide modification aminoethyl aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 28mN/m, micelle-forming concentration is 44mg/L.
Embodiment 7
In reaction kettle, add six basic ring trisiloxanes 9.3kg, aminoethyl aminopropyl dimethoxy-methyl silane 15.5kg, SWS-F 221 4.05kg; Sodium hydroxide 120g, heating for dissolving, temperature are controlled at 110 ℃; React after 4 hours, add the acetic acid catalyst neutralisation, make it inactivation and filter out.Rectification under vacuum obtains aminoethyl aminopropyl ZGK 5, records uncle's ammonia value with potentiometric titration.Adding five times lactose lactone according to the mole number of uncle's ammonia value, make solvent with Virahol, is reaction 4 hours under 100 ℃ of conditions in temperature.Steaming desolventizes methyl alcohol, obtains product lactose amide modification aminoethyl aminopropyl ZGK 5 after the vacuum-drying.Use the lowest surface tension of its aqueous solution of K12 surface tension instrument survey to be 27mN/m, micelle-forming concentration is 67mg/L.
Claims (10)
1. the preparation method of a glycosyl acid amides modified polyorganosiloxane is characterized in that comprising the steps:
(1) be raw material by cyclosiloxane, SWS-F 221, aminosilane, at catalyst action, reaction is 4-8 hour under 30-220 ℃ condition; Wherein the mol ratio of cyclosiloxane, aminosilane and SWS-F 221 is 0.25-2.25: 3-5: 1; The mole dosage of catalyzer is the 0.1-1% of cyclosiloxane, aminosilane and SWS-F 221 mole sum; Reaction makes catalyst deactivation after finishing, and underpressure distillation obtains amino silicones;
(2) amino silicones and sugar lactone or saccharic acid are made solvent with low-carbon alcohol, and reaction is 5-10 hour under 30-200 ℃ situation, and wherein the mol ratio of the primary amine of amino silicones and sugar lactone or saccharic acid is 1-5: 1; After reaction was accomplished, steaming desolventized and obtains glycosyl acid amides modified polyorganosiloxane.
2. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that temperature of reaction is 70-100 ℃ in the above step (1).
3. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that the mole proportioning of cyclosiloxane, aminosilane and SWS-F 221 in the step (1) is 0.5-2: 3-4: 1.
4. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that the proportioning of the middle amino silicones of step (2) and sugar lactone or saccharic acid is 1-4: 1.
5. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that described aminosilane is aminopropyl dimethoxy-methyl silane, aminopropyl diethoxymethyl silane, aminoethyl aminopropyl dimethoxy-methyl silane or aminoethyl aminopropyl diethoxymethyl silane.
6. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that described catalyzer is alkali metal hydroxide, silicon alkoxide, quaternary ammonium hydroxide Huo quaternary phosphonium hydroxide.
7. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 6; It is characterized in that described alkali metal hydroxide is sodium hydroxide or Pottasium Hydroxide; Silicon alkoxide is sodium silanolate, silanol potassium, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt; Quaternary ammonium hydroxide is that TMAH ， quaternary phosphonium hydroxide is a Si butyl phosphonium hydroxides.
8. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 7 is characterized in that described silanol quaternary ammonium salt is a tetramethyl-silanol ammonium, and the silanol quaternary alkylphosphonium salt is a tetrabutyl silanol Phosphonium.
9. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1; It is characterized in that the described catalyst deactivation that makes is when catalyzer is alkali metal hydroxide, sodium silanolate or silanol potassium; Add sour catalyst neutralisation, make it inactivation and filter out; When catalyzer was quaternary ammonium hydroxide 、 quaternary phosphonium hydroxide, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt, thermal degradation made it inactivation and underpressure distillation is come out.
10. the preparation method of a kind of glycosyl acid amides modified polyorganosiloxane as claimed in claim 1 is characterized in that described low-carbon alcohol is methyl alcohol, ethanol or Virahol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102914254A CN101942097B (en) | 2010-09-20 | 2010-09-20 | Method for preparing glycosyl amide modified polysiloxane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102914254A CN101942097B (en) | 2010-09-20 | 2010-09-20 | Method for preparing glycosyl amide modified polysiloxane |
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| Publication Number | Publication Date |
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| CN101942097A CN101942097A (en) | 2011-01-12 |
| CN101942097B true CN101942097B (en) | 2012-09-05 |
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| CN102614807A (en) * | 2012-03-07 | 2012-08-01 | 中国日用化学工业研究院 | Tetrasiloxane contained dimeric glycosyl surfactant and synthesis method |
| CN103772708B (en) * | 2013-12-30 | 2016-05-04 | 上海发凯化工有限公司 | Glycosyl modified polyorganosiloxane silicone softening agent and preparation method thereof |
| CN104231274B (en) * | 2014-08-21 | 2017-03-29 | 中国日用化学工业研究院 | A kind of synthetic method of surface-active room temperature silicone ionic liquid |
| CN104610338B (en) * | 2015-01-13 | 2017-07-14 | 常熟理工学院 | Glycosyl amide is modified tetrasiloxane and preparation method thereof |
| CN105273198A (en) * | 2015-07-07 | 2016-01-27 | 常熟理工学院 | Preparation method of Gemini type glycosyl modified polysiloxane |
| CN106565514A (en) * | 2016-10-11 | 2017-04-19 | 沈阳化工大学 | Process method for catalytic synthesis of beta-hydroxyalkyl amide by using tetramethylammonium hydroxide |
| CN106986786A (en) * | 2017-02-27 | 2017-07-28 | 沈阳化工大学 | A kind of process of synthesis β hydroxyalkyl amides |
| CN107602862A (en) * | 2017-09-13 | 2018-01-19 | 常熟理工学院 | A kind of amino-acid modified polysiloxane surfactant and preparation method thereof |
| CN107599096A (en) * | 2017-09-20 | 2018-01-19 | 安徽三和工艺品有限公司 | A kind of processing method for improving wood surface wearability |
| CN107815678A (en) * | 2017-10-23 | 2018-03-20 | 安徽屹翔滤材有限公司 | A kind of stainless steel sieve surface passivation method for anticorrosion treatment |
| CN108409968A (en) * | 2018-03-29 | 2018-08-17 | 中国日用化学研究院有限公司 | A kind of preparation method of high grafting rate combed organosilicon glucoheptose sugar acidamide surfactant |
| CN116119879A (en) * | 2023-03-02 | 2023-05-16 | 常熟理工学院 | Treatment method of heavy metal-containing smelting flue gas acid making wastewater |
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| DE4318539A1 (en) * | 1993-06-04 | 1994-12-08 | Bayer Ag | Anionic siloxanyl modified polyhydroxylated hydrocarbons |
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
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| DE4318539A1 (en) * | 1993-06-04 | 1994-12-08 | Bayer Ag | Anionic siloxanyl modified polyhydroxylated hydrocarbons |
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
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