CN102580471B - Preparation method of grafted quaternary phosphonate ionic liquid - Google Patents
Preparation method of grafted quaternary phosphonate ionic liquid Download PDFInfo
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- CN102580471B CN102580471B CN201210047045.5A CN201210047045A CN102580471B CN 102580471 B CN102580471 B CN 102580471B CN 201210047045 A CN201210047045 A CN 201210047045A CN 102580471 B CN102580471 B CN 102580471B
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Abstract
The invention relates to a preparation method of a grafted quaternary phosphonate ionic liquid. The preparation method comprises the following steps of: using 3-(chloropropyl)triethoxysilane and trioctylphosphine to react and generate a chlorinated quaternary phosphonate ionic liquid intermediate, then using the chlorinated ionic liquid intermediate and sodium fluoroborate to synthesize a tetrafluoroborate quaternary phosphonate ionic liquid intermediate, and finally using the tetrafluoroborate ionic liquid intermediate and silica to react and generate the grafted quaternary phosphonate ionic liquid. The grafted quaternary phosphonate ionic liquid provided by the preparation method of the grafted quaternary phosphonate ionic liquid can be used as the CO2 adsorbent alone and can also be used along with other adsorption materials; and compared with the silica gel supported 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid which is synthesized by the traditional immersion method and the silica gel supported 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid which is synthesized by the sol-gel method, the grafted quaternary phosphonate ionic liquid has larger cumulative specific surface area and better CO2 adsorption property.
Description
Technical field
the present invention relates to the preparation method of organic chemistry, field of chemical engineering intermediate ion liquid, especially a kind of preparation method of grafted quaternary phosphonate ionic liquid.
Background technology
along with industrial expansion, the mankind are discharged into the CO in atmosphere after using the fuel such as petrochemical industry
2
grow with each passing day, Global Environmental Problems is increasingly serious.Each state is all being devoted to control and reduce CO
2
discharge capacity, exploitation adsorbing separation CO
2
technology is the common focus of paying close attention in the whole world.Current CO
2
catching method mainly contains that solvent absorption, pressure-variable adsorption and film are separated etc., and wherein organic amine aqueous solution absorption process is the most general, but because the organic amine aqueous solution is volatile, easily produces the secondary pollution of VOCs.And absorption method separation of C O
2
technology because it is not moisture, low energy consumption, adsorbent is corrosion-free and the advantage that can use for a long time, becomes gradually competitive CO
2
separation and recovery technology.But traditional adsorbent adsorption efficiency is low, therefore in the urgent need to a kind of new material, carry out separation of C O effectively
2
.
ionic liquid is the organic salt that melts being in a liquid state under a kind of room temperature, for CO
2
the shortcoming that can avoid traditional absorbent to bring during absorption.If but ionic liquid is directly used in to CO
2
separation, because viscosity is large, specific area is little, is unfavorable for desorption and recovery, thereby is unfavorable for commercial Application.By ionic liquid supported on high-molecular organic material or inorganic porous material, the solid-loaded ionic-liquid making has the characteristic of ionic liquid and porous carrier materials concurrently, be conducive to expand specific area, shorten diffusion path, promote mass transfer and convenient recycling, and can adopt the method for pressure-variable adsorption to realize large-scale commercial Application.At present conventional physics infusion process is prepared solid-loaded ionic-liquid, cannot be packed into the space of carrier by customer service ionic liquid, and cause duct to be blocked, and hinders CO
2
transmission in duct also affects CO
2
adsorption efficiency, and between ionic liquid and carrier simple physical force a little less than, cause ionic liquid under Dynamic Adsorption state to have leakage.And using grafted quaternary phosphonate ionic liquid as novel CO
2
adsorbent has potential using value, about preparation and the CO thereof of such adsorbent
2
absorption property is rarely seen report especially.
Summary of the invention
in order to improve grafted quaternary phosphonate ionic liquid as novel CO
2
the using value of adsorbent, the invention provides a kind of preparation method of grafted quaternary phosphonate ionic liquid, and the method can be separately as CO
2
adsorbent is used, also can with other sorbing material compound uses, absorption property is better.
the technical solution adopted for the present invention to solve the technical problems is: the preparation method of grafted quaternary phosphonate ionic liquid comprises three steps:
(1) use 3-chloropropyl triethoxysilane and trioctylphosphine phosphorus reaction to generate chlorination season phosphine ionic liquid intermediate, requiring reaction condition is under inert gas shielding, the mol ratio of 3-chloropropyl triethoxysilane and trioctylphosphine phosphorus is 1:1.0～1.5,0.5～10 part of dry toluene of take is solvent, and at 25 ℃～120 ℃, stirring reaction is 1～24 hour;
(2) use chlorination ionic liquid intermediate and sodium tetrafluoroborate reaction to generate tetrafluoroborate season phosphine ionic liquid intermediate, requirement reaction condition is that the mol ratio of chlorination ionic liquid intermediate and sodium tetrafluoroborate is 1:1.0～1.5,1～15 part of acetonitrile of take is solvent, and at 25 ℃～60 ℃, stirring reaction is 1～48 hour;
(3) use tetrafluoroborate ion liquid intermediate and silicon dioxde reaction to generate grafted quaternary phosphonate ionic liquid; during reaction, silica is first calcined 1～6h at 100～550 ℃; requiring reaction condition is under inert gas shielding; the mol ratio of tetrafluoro boric acid ionic liquid intermediate and silica is 1:0.5～5.0; 0.5～50 part of dry toluene of take is solvent; 25 ℃～100 ℃ stirring reactions 1～12 hour, obtain grafted quaternary phosphonate ionic liquid.
the preparation method of grafted quaternary phosphonate ionic liquid involved in the present invention can represent with chemical equation below:
the invention has the beneficial effects as follows, the grafted quaternary phosphonate ionic liquid that the preparation method of this grafted quaternary phosphonate ionic liquid provides can be separately as CO
2
adsorbent is used, also can with other sorbing material compound uses, absorption property is better.Table 1 has provided under 0 ℃ and 0.1Mpa condition, grafted quaternary phosphonate ionic liquid 1, the traditional immobilized 1-butyl-3-of infusion process synthesized silicon rubber methylimidazole tetrafluoro boric acid ionic liquid 2, accumulative total specific area and the CO of 3, three kinds of ionic liquids of the immobilized 1-butyl-3-of sol-gel process synthesized silicon rubber methylimidazole tetrafluoro boric acid ionic liquid
2
the comparative analysis of absorption property, grafted quaternary phosphonate ionic liquid has larger accumulation specific area and good CO as can be seen here
2
absorption property.
the pore structure parameter of table 1 sample and CO
2
adsorbance
Accompanying drawing explanation
below in conjunction with drawings and Examples, the invention will be further described.
fig. 1 is the chemical structural formula of each compound of reaction.
fig. 2 is the synthetic chemistry equation schematic diagram of related grafted quaternary phosphonate ionic liquid.
in Fig. 1, formula (I) is 3-chloropropyl triethoxysilane, and formula (II) is chlorination season phosphine ionic liquid intermediate, and formula (III) is tetrafluoroborate season phosphine ionic liquid intermediate, and formula (IV) is grafted quaternary phosphonate ionic liquid.
The specific embodiment
synthesizing of embodiment 1 chlorination season phosphine ionic liquid intermediate (II)
20ml dry toluene is added in there-necked flask to N
2
protection; 3.0g 3-chloropropyl triethoxysilane (I) is added in toluene with syringe, and 6.0g trioctylphosphine phosphorus adds in the same manner immediately; In the oil bath of 120 ℃, add hot reflux, reaction 24h; Product is standing, and ionic liquid phase is got in layering, with ether washing three times, washes away toluene and unreacted reactant; Vacuum drying 24h at 80 ℃, obtains brown color chlorination season phosphine ionic liquid intermediate (II).
synthesizing of embodiment 2 tetrafluoro boric acid ionic liquid intermediates (III)
chlorination season phosphine ionic liquid intermediate (II) 1.9g of upper step gained is put into there-necked flask, then under continuous stirring condition, 0.6g(is excessive) sodium tetrafluoroborate adds in this flask, then adds the acetonitrile of 150 mL, stirring reaction 35 h; Two kinds of salt dissolve gradually and have new white precipitate to generate, and because the precipitation before and after reaction is white, course of reaction phenomenon is not obvious; Sedimentation and filtration is removed, in filtrate, added approximately 750 mL ether, adularescent crystallization generates; Filtration obtains this white precipitate, and at room temperature vacuum drying 10 h obtain tetrafluoro boric acid ionic liquid intermediate (III).
synthesizing of embodiment 3 grafted quaternary phosphonate ionic liquids (IV)
silica supports is calcined to 6h at 550 ℃, in flask, add 150ml toluene, tetrafluoro boric acid ionic liquid (III) 1.6 g are joined in toluene, use N
2
discharge air; Add 2.0 g carriers, reaction mixture stirs 3h at 90 ℃; Vacuum drying 2h at 110 ℃, obtains final products grafted quaternary phosphonate ionic liquid (IV) particulate.
Claims (1)
1. the preparation method of grafted quaternary phosphonate ionic liquid, is characterized in that described preparation method's concrete steps are as follows:
(1) chlorination season phosphine ionic liquid intermediate (II) is synthetic, use 3-chloropropyl triethoxysilane (I) and trioctylphosphine phosphorus reaction to generate chlorination season phosphine ionic liquid intermediate (II), requiring experiment condition is under inert gas shielding, the mol ratio of 3-chloropropyl triethoxysilane (I) and trioctylphosphine phosphorus is 1:1.0～1.5,0.5～10 part of dry toluene of take is solvent, normal temperature～120 ℃ stirring reaction 1～24 hour; (2) tetrafluoro boric acid ionic liquid intermediate is synthetic, use chlorination ionic liquid intermediate (II) and sodium tetrafluoroborate reaction to generate tetrafluoroborate season phosphine ionic liquid intermediate (III), requiring the mol ratio of chlorination ionic liquid intermediate (II) and sodium tetrafluoroborate is 1:1.0～1.5,1～15 part of acetonitrile of take is solvent, and at normal temperature～60 ℃, stirring reaction is 1～48 hour; (3) grafted quaternary phosphonate ionic liquid is synthetic; use tetrafluoroborate ion liquid intermediate (III) and silicon dioxde reaction to generate grafted quaternary phosphonate ionic liquid (IV); require silica first at 100～550 ℃, to calcine 1～6h; experiment condition is under inert gas shielding; the mol ratio of tetrafluoro boric acid ionic liquid intermediate (III) and silica is 1:0.5～5.0; 0.5～50 part of dry toluene of take is solvent; normal temperature～100 ℃ stirring reaction 1～12 hour, obtains grafted quaternary phosphonate ionic liquid (IV).
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