CN101274984A - Dihydroxyl-terminated polydimethylsiloxane and preparation thereof - Google Patents
Dihydroxyl-terminated polydimethylsiloxane and preparation thereof Download PDFInfo
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- CN101274984A CN101274984A CNA200810015223XA CN200810015223A CN101274984A CN 101274984 A CN101274984 A CN 101274984A CN A200810015223X A CNA200810015223X A CN A200810015223XA CN 200810015223 A CN200810015223 A CN 200810015223A CN 101274984 A CN101274984 A CN 101274984A
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Abstract
The invention provides a new method for preparing single-ended double-hydroxyl alkyl polydimethylsiloxane and the preparation method of the invention is different from prior synthetic methods. The preparation method takes D3 (Hexamethylcyclotrisiloxane), allyl glycidyl ether and methylaminoethanol as starting raw materials which go through three-step reactions of anion ring-opening polymerization, hydrosilylation and epoxy ring-opening to synthesize the target product of the single-ended double-hydroxyl alkyl polydimethylsiloxane of which the product purity is over 98 percent. The invention has the advantages of simple and convenient reaction steps, easily accessible raw materials, low production cost, high product yield, high purity, etc.
Description
Technical field:
The present invention relates to a kind of novel method of synthetic dihydroxyl-terminated polydimethylsiloxaneand.This method is with D
3, glycidyl allyl ether and methylethylolamine be starting raw material, through anionic ring-opening polymerization, the addition of silicon hydrogen and epoxy addition three-step reaction synthesising target compound dihydroxyl-terminated polydimethylsiloxaneand.
Background technology:
Dihydroxyl-terminated polydimethylsiloxaneand is a kind of intermediate of important organosilicon grafted and modified high molecular polymer, because two hydroxyls of these type of silicoorganic compound are more active, can utilize its reactive behavior that some synthetic resins (as urethane, polyester etc.) is carried out graft modification, thereby improve the surface property of resin.
European patent EP 0 356 963 (1989) discloses the synthetic method of dihydroxyl-terminated polydimethylsiloxaneand.Basic step is: (1) with hexamethyldisilazane or trimethylchlorosilane to 2-ethyl-2-[(2-propenyl oxygen base) methyl]-1, the hydroxyl in the ammediol is protected; (2) synthetic single-ended hydrogen polydimethylsiloxane; (3) unsaturated compound behind the hydroxyl protection and single-ended hydrogen polydimethylsiloxane carry out addition reaction of silicon with hydrogen; (4) polymkeric substance that previous step is obtained carries out the deprotection reaction of hydroxyl.U.S. Pat 5,059,707 (1991) disclose the another kind of synthetic method of dihydroxyl-terminated polydimethylsiloxaneand, and basic step is identical with European patent, difference is: the unsaturated compound that contains two hydroxyls changes 2-methylene radical-1, ammediol into.
In the synthetic method that above-mentioned two pieces of patents are reported, all have following shortcoming: (1) unsaturated compound that contains two hydroxyls that synthesising target compound adopted is not easy to obtain, and costs an arm and a leg.(2) synthetic method adopts hexamethyldisilazane or trimethylchlorosilane as protecting group, and cost is higher.(3) protection of hydroxyl and deprotection reaction have increased reactions steps, make the total reaction time of synthesising target compound elongated.More than three shortcomings make dihydroxyl-terminated polydimethylsiloxaneand industrialization cost up, the market value height is unfavorable for the broadened application field.
Summary of the invention:
The objective of the invention is to simplify the synthesis step of dihydroxyl-terminated polydimethylsiloxaneand, improve yield, select cheap starting material for use, reduce production costs.
Feature of the present invention is: with D
3, glycidyl allyl ether and methylethylolamine be starting raw material, through anionic ring-opening polymerization, the addition of silicon hydrogen and epoxy addition three-step reaction synthesising target compound dihydroxyl-terminated polydimethylsiloxaneand, synthesis step tails off, simple to operation, starting raw material is cheap and easy to get, target compound is easily purified, the yield height.
Reaction formula of the present invention is as follows:
The main contents of this synthetic method are described below:
D
3Anionic ring-opening polymerization reaction be with D
3Prepare single-ended hydrogen polydimethylsiloxane, D with initiator ring-opening polymerization in organic solvent
3Decide on the polymerization degree with the ratio of initiator.Feeding mode is earlier with D
3Be dissolved in the organic solvent, join in the reaction flask that anhydrous and oxygen-free was handled, inject anionic initiator (n-Butyl Lithium) and promotor (tetrahydrofuran (THF)) back and under 20～50 ℃ of conditions, carry out the anionic ring-opening polymerization reaction, reaction 4～12h, inject the end-capping reagent dimethylchlorosilane, filter the back underpressure distillation and remove low-boiling-point substance, get single-ended hydrogen polydimethylsiloxane, above-mentioned organic solvent is meant any one in benzene,toluene,xylene, the hexanaphthene.
Addition reaction of silicon with hydrogen is that the aqueous isopropanol with Platinic chloride is a catalyzer, and single-ended hydrogen polydimethylsiloxane dropwise is added in the toluene solution of glycidyl allyl ether, protects with nitrogen in the reaction process.Molar ratio is: single-ended hydrogen polydimethylsiloxane: glycidyl allyl ether=1: 1.5～5, temperature of reaction is 80～110 ℃, reaction times is: 8～12h, low-boiling-point substance is removed in underpressure distillation, obtains single-ended epoxy alkyl polydimethylsiloxane after the filtration.
Epoxy addition reaction is that the above-mentioned single-ended epoxy alkyl polydimethylsiloxane that obtains dropwise is added in the organic solvent of methylethylolamine in 60～90 ℃ of reaction 5～8h, molar ratio is: single-ended epoxy alkyl polydimethylsiloxane: methylethylolamine=1: 1.5～5, be cooled to room temperature, low-boiling-point substance is removed in underpressure distillation, promptly obtain the target compound dihydroxyl-terminated polydimethylsiloxaneand, used organic solvent is meant any one in methyl alcohol, ethanol, n-propyl alcohol and the trimethyl carbinol.
The present invention compared with prior art has the following advantages:
1. synthetic route of the present invention does not relate to the protection and the deprotection of hydroxyl, and synthesis step is reduced, and operation becomes simple, thereby can improve the yield of target compound to a certain extent.Compare with the synthetic route of bibliographical information, the shortening that present method is bigger the reaction times, reduced energy consumption.
2. the back two-step reaction in the synthetic route does not have by product to produce, the yield height, and respectively go on foot reactor product and be easy to separate and purify.
3. used raw material is easy to get in the synthetic route of the present invention, and production cost is low.
Embodiment:
In order to be easy to further understand the present invention, the following example has been set forth more specific details.
Embodiment 1
Anionic ring-opening polymerization reaction: in the 200ml reaction flask after handling, add D through anhydrous and oxygen-free
3Benzole soln (19.52g) and 0.014mol n-Butyl Lithium, stir 0.5h under the room temperature, add the 60ml tetrahydrofuran (THF) then, stir down at 25 ℃, reaction 8h, add the end-capping reagent dimethylchlorosilane, after the end, filter out the lithium chloride of generation, low-boiling-point substance is removed in underpressure distillation, cooling gets the single-ended hydrogen polydimethylsiloxane of colourless transparent liquid 20.68g, yield 98%.
Addition reaction of silicon with hydrogen: in the 100ml four-hole boiling flask, the toluene solution and the appropriate amount of catalysts (aqueous isopropanol of Platinic chloride) that add glycidyl allyl ether (2.78g), after feeding nitrogen 0.5h, continue ventilation and to the reaction system heat temperature raising, treat stable after 100 ℃, stir, dropwise add single-ended hydrogen polydimethylsiloxane (7.33g), reaction 8h, cooling, low-boiling-point substance is removed in underpressure distillation, filter the single-ended epoxy alkyl of little light yellow transparent liquid polydimethylsiloxane (7.10g), yield 90%.
Epoxy addition reaction: in the 100ml there-necked flask, the ethanolic soln that adds methylethylolamine (1.28g), heat temperature raising to 70 ℃, stirring also dropwise adds single-ended epoxy alkyl polydimethylsiloxane (5.51g), under this reaction conditions, and reaction 10h, cooling, low-boiling-point substance is removed in underpressure distillation, gets yellow transparent liquid dihydroxyl-terminated polydimethylsiloxaneand (5.53g), yield 95%.
Embodiment 2
Change the ethanol in the reaction of embodiment 1 epoxy addition into methyl alcohol, temperature of reaction becomes 65 ℃, and other reaction conditionss get the target compound dihydroxyl-terminated polydimethylsiloxaneand, yield 95% as described in example 1 above.
Embodiment 3
Change the ethanol in the reaction of embodiment 1 epoxy addition into n-propyl alcohol, temperature of reaction becomes 90 ℃, and other reaction conditionss get the target compound dihydroxyl-terminated polydimethylsiloxaneand, yield 92% as described in example 1 above.
Embodiment 4
With D in the reaction of embodiment 1 anionic ring-opening polymerization
3Add-on becomes 17.68g, and n-Butyl Lithium 0.02mol, other reaction conditionss get single-ended hydrogen polydimethylsiloxane 18.68g, yield 92% as described in example 1 above.The condition of addition reaction of silicon with hydrogen and epoxy addition reaction gets the target compound dihydroxyl-terminated polydimethylsiloxaneand that molecular weight is different from embodiment 1, yield 96% as described in example 1 above.
Claims (4)
1. the synthetic method of dihydroxyl-terminated polydimethylsiloxaneand is characterized in that: with D
3(hexamethyl cyclotrisiloxane), glycidyl allyl ether and methylethylolamine are starting raw material, through anionic ring-opening polymerization, and the addition of silicon hydrogen, epoxy addition three-step reaction synthesising target compound dihydroxyl-terminated polydimethylsiloxaneand.
2. synthetic method according to claim 1 is characterized in that: D
3Anionic ring-opening polymerization reaction be with D
3Prepare single-ended hydrogen polydimethylsiloxane, D with initiator ring-opening polymerization in organic solvent
3Decide on the polymerization degree with the ratio of initiator.Feeding mode is earlier with D
3Be dissolved in the organic solvent, join in the reaction flask after anhydrous and oxygen-free is handled, inject anionic initiator (n-Butyl Lithium) and promotor (tetrahydrofuran (THF)), temperature of reaction: 20～50 ℃, polymerization 4～12h injects the end-capping reagent dimethylchlorosilane, filters, low-boiling-point substance is removed in underpressure distillation, obtains single-ended hydrogen polydimethylsiloxane.Above-mentioned organic solvent is meant any one in benzene,toluene,xylene, the hexanaphthene.
3. synthetic method according to claim 1; it is characterized in that: addition reaction of silicon with hydrogen is that the aqueous isopropanol with Platinic chloride is a catalyzer; single-ended hydrogen polydimethylsiloxane dropwise is added in the toluene solution of glycidyl allyl ether, protects with nitrogen in the reaction process.Molar ratio is: single-ended hydrogen polydimethylsiloxane: glycidyl allyl ether=1: 1.5～5, temperature of reaction is: 80～110 ℃, the reaction times is: 8～12h obtains single-ended epoxy alkyl polydimethylsiloxane.
4. synthetic method according to claim 1 is characterized in that: the ring-opening reaction of single-ended epoxy alkyl polydimethylsiloxane is that above-mentioned single-ended epoxy alkyl polydimethylsiloxane is dropwise joined in the organic solvent of methylethylolamine.Molar ratio is: single-ended epoxy alkyl polydimethylsiloxane: methylethylolamine=1: 1.5～5, temperature of reaction is: 60～90 ℃, reaction 5～8h, be cooled to room temperature, low-boiling-point substance is removed in underpressure distillation, promptly obtain the target compound dihydroxyl-terminated polydimethylsiloxaneand, above-mentioned organic solvent is meant any one in methyl alcohol, ethanol, n-propyl alcohol and the trimethyl carbinol.
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| CN110922600B (en) * | 2019-10-22 | 2021-05-25 | 武汉大学 | Hydroxyalkyl organosilicon compounds, and preparation method and application thereof |
| CN111576036A (en) * | 2020-05-20 | 2020-08-25 | 浙江海明实业有限公司 | Nano antifouling, antibacterial and breathable environment-friendly fabric and preparation process thereof |
| CN116446215A (en) * | 2023-03-22 | 2023-07-18 | 冠宏化工（扬州）有限公司 | Whitening sizing agent for papermaking and preparation method thereof |
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