CN102146148A - Sulfonated crosslinked polystyrene spheres and application thereof in ring-opening reaction - Google Patents
Sulfonated crosslinked polystyrene spheres and application thereof in ring-opening reaction Download PDFInfo
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- CN102146148A CN102146148A CN 201110025752 CN201110025752A CN102146148A CN 102146148 A CN102146148 A CN 102146148A CN 201110025752 CN201110025752 CN 201110025752 CN 201110025752 A CN201110025752 A CN 201110025752A CN 102146148 A CN102146148 A CN 102146148A
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Abstract
The invention discloses sulfonated crosslinked polystyrene spheres and application thereof in ring-opening reaction, and belongs to the technical field of high polymer material application. The sulfonated crosslinked polystyrene spheres consist of a large-pore crosslinked polystyrene carrier and a sulfo group bonded to the carrier. The sulfonated crosslinked polystyrene spheres are prepared through suspension polymerization of styrene and divinylbenzene, and sulfonation preparation of the crosslinked spheres. The sulfonated crosslinked polystyrene spheres are used as a chain extender in the ring-opening reaction of octamethylcyclotetrasiloxane. When the sulfonated crosslinked polystyrene spheres are used as the chain extender, the ring-opening reaction conditions are mild, and the orderly increase of molecule chains of a produce can be controlled; moreover, the chain extender has high activity; and because the solid-phase sulfonated crosslinked polystyrene spheres have large volume, the sulfonated crosslinked polystyrene spheres are easy to separate in production and can be repeatedly utilized.
Description
Technical field
The invention belongs to the technical field that macromolecular material is used, particularly in D4 (octamethylcyclotetrasiloxane) ring-opening reaction, as the purposes of the big ball of crosslinked polystyrene in chain extending reaction of chainextender use.
Background technology
Nineteen fifty-nine, Hyed and Wehrly have found that a kind of new letex polymerization-(Patent 2891920,1959-6-23) in ion open loop letex polymerization, promptly use the cyclosilane monomer, under ionic emulsifying agent and acid or alkaline catalysts effect, in the aqueous phase ring-opening polymerization, directly synthetic polysiloxane emulsion.The Si-O key has part ion, so cyclosiloxane can be caused ring-opening polymerization by acid or alkali, the Siliciumatom electronegativity in the cyclosiloxane is little, easily is the alkali attack; The electronegativity of oxygen is big, easily be sour attack (Polymer International, 1994,35:179-188).With respect to the body or the solution ring-opening polymerization of cyclosiloxane, the ion open loop letex polymerization of carrying out at water has higher monomer conversion, and molecular weight height and narrow distribution.(dyeing and printing auxiliary, 2008,25 (1): 9-12).
Catalyzer difference according to using can be divided into the ionic emulsion polymerization of cyclosiloxane cation emulsion polymerization and anionic polymerization.The cation emulsion polymerization refers generally to carrying out under mineral acid (as HCl) and the anionic emulsifier, and negatively charged ion then is to be catalyzer with highly basic, the ring-opening polymerization that carries out under cationic emulsifier.
Liu Shufen (J.polymer Communication (China), 1981, (4): 257-262) people such as grade has carried out D4 (octamethylcyclotetrasiloxane) anionic polymerization under existing with dodecyl dimethyl Bian Ji ammonium halide and alkali, the earliest the cation emulsion polymerization mechanism of D4 is carried out big quantity research, the final transformation efficiency of letex polymerization is about 87%, infers the balance that exists ring body and simple linear polymer in letex polymerization equally.M.Barrere people such as (Polylner Chemistry Edition 198220:3351-3368) stung to react to returning of generation annular material and had carried out more careful research afterwards, obtained the monomeric amount of the ring in the mini-emulsion polymerization by testing and calculating two kinds of methods respectively, find back to sting the circlet shape monomer D4 that reaction generates, amount and the substance law of D5 (decamethylcyclopentaandoxane) are basic identical, but big cyclic monomer D6 (ten diformazan basic rings, six siloxanes), the amount of D7 (tetradecamethylcycloheptasiloxane) has but descended greatly, especially the above amount of D7 very few.This may be because annulation mainly occurs on the interface, the active centre is to exist with the right form of son there, the space resistance that antiparticle provides has limited the monomeric generation of big ring, they have also further studied catalyzer and gegenion influences polymeric, confirmed that reaction is what to carry out on the surface of micella and emulsion particle, and point out that micella and the new polymer beads that forms are main reaction zones, the monomer emulsion droplet then is accessory reaction zone.
Summary of the invention
The purpose of this invention is to provide the big ball of a kind of sulfonated crosslinked polystyrene as the acid chainextender in the D4 ring-opening reaction process, this chainextender divided ring reaction conditions gentleness has high reactivity, is easy to separate and can reuse.
Chainextender of the present invention is in the chain extending reaction of siloxanes, and usable viscosity method proof is recently controlled the orderly growth of product molecule segment by the mole of control short chain siloxanes and D4.
The big ball of sulfonated crosslinked polystyrene of the present invention is made up of wide-aperture crosslinked polystyrene carrier and the sulfonic group two portions that are bonded on the carrier; Size distribution is between 0.5～5 millimeter.The big ball of this sulfonated crosslinked polystyrene is made chainextender and is used in the octamethylcyclotetrasiloxane ring-opening reaction.
The method of the big ball of this novel chainextender of preparation that the present invention proposes is made of chemical reactions such as suspension polymerization, sulfonation reactions.Following two steps are specifically arranged:
(1) suspension polymerization of vinylbenzene and Vinylstyrene:
Raw material and feed ratio: with volume ratio is that 1～9: 1 vinylbenzene and Vinylstyrene are reactant; The volume ratio 4～8: 1 of distilled water and reactant; With the benzoyl peroxide is initiator, and the mass ratio of initiator and reactant is 1: 30～70; With the polyvinyl alcohol is dispersion agent, and the mass ratio of dispersion agent and reactant monomer is 1: 30～70.
Polymerization technique: polyvinyl alcohol is dissolved in the distilled water; add reactant and initiator mixing solutions; under nitrogen protection, stir and heat up; at 6～12 hours after-filtration of 60～90 ℃ of reactions; clean (respectively washing 3 times) with distilled water ethanol; resulting polymers vacuum-drying obtains size distribution between 0.5～5 millimeter, contains the big ball of crosslinked polystyrene (PS-st) of remaining double bond.
(2) sulfonation of crosslinked big ball:
Raw material and feed ratio: the mass ratio of the big ball of crosslinked polystyrene and the vitriol oil is 1: 1～15.
Production technique:, obtain the big ball of tart crosslinked polystyrene through ion-exchange with stirring 48 hours in the big ball immersion of the crosslinked polystyrene vitriol oil.With the excessive sulfuric acid of distilled water flush away, obtain the big ball of sulfonated crosslinked polystyrene (SPS-st).
The purposes of the big ball of a kind of sulfonated crosslinked polystyrene is made chainextender and is used in the octamethylcyclotetrasiloxane ring-opening reaction.
The reaction formula that the big ball of SPS-st is used as chainextender is as follows:
The detailed process of ring-opening reaction is:
Raw material and feed ratio: with mol ratio is that 1: 2～50 short chain siloxanes and octamethylcyclotetrasiloxane (D4) are reactant; With the big ball of sulfonated crosslinked polystyrene (SPS-st) is chainextender, and the mass ratio of chainextender and reactant is 1: 20～50.
Production technique: the big ball of short chain siloxanes, octamethylcyclotetrasiloxane (D4) and sulfonated crosslinked polystyrene (SPS-st) is added in the reaction unit; under nitrogen protection, stir and heat up; react 3～8 hours after-filtration down at 60～90 ℃, the adding mass percent is 1%～10% CaCO in the filtrate
3, to react 1～3 hour down at 50～90 ℃, the short chain siloxanes of chain extension is fully removed not in vacuum-drying again, obtains the long-chain siloxanes.
Described vacuum-drying can be used 80 ℃ of dryings of vacuum drying oven 2 hours.
Described short chain siloxanes, preferred tetramethyl-dihydro sily oxide.
The big ball of sulfonated crosslinked polystyrene is that the present invention initiates as the acid chainextender in the D4 ring-opening reaction process, and its beneficial effect is, the ring-opening reaction mild condition can be controlled the orderly growth of product molecule segment; And this chainextender has high reactivity; Because the volume of the big ball of sulfonated crosslinked polystyrene of solid phase is bigger, be easy to aborning separate, can reuse.
Description of drawings:
Fig. 1 is the infrared comparison diagram of big ball of PS-st of the present invention and the big ball of SPS-st.
SPS-st is at 1006cm among Fig. 1
-1And 1127cm
-1Sulfonic charateristic avsorption band has all appearred in the place.
Fig. 2 is that the TGA of big ball of PS-st of the present invention and the big ball of SPS-st compares.
As seen from Figure 2, the thermal weight loss temperature of the big ball 5% of PS-st is 380 ℃, and the thermal weight loss temperature of the big ball 5% of SPS-st is 404 ℃.
Fig. 3 is the proton nmr spectra data of the two hydrogen end socket siloxanes (tetramethyl-dihydro sily oxide) of the raw materials used short chain of the present invention.(1H NMR, CDCl
3, chemical shift δ): 4.63～4.73 (m, Si-H, 2H); 0.17～0.20 (d, Si-CH
3, 12H)
Fig. 4 be the big ball of SPS-st of the present invention as chainextender, short chain siloxanes and D4 mol ratio are the proton nmr spectra data of the two hydrogen end socket siloxanes of 3.25 o'clock prepared long-chains.(1H NMR, CDCl
3, chemical shift δ): 4.67～4.74 (m, Si-H, 2H); 0.17～0.19 (d, end group Si-CH
3, 12H); 0.05～0.09 (d, Si-CH
3, 90H).
Si-CH in the two hydrogen end socket siloxanes of long-chain is described
3, the content of H increases to 102 from 12, and product contains 15 Si-O segments.
Specific embodiments:
Embodiment 1:
The 0.4g polyvinyl alcohol is dissolved in the 120ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.3g benzoyl peroxide is joined in the mixed solution of 18ml vinylbenzene and 2ml Vinylstyrene, inject above-mentioned there-necked flask, 4～5 revolutions per seconds of control stirring velocitys, intensification is reacted 10 hours after-filtration down at 85 ℃, product cleans 3 times with distilled water and ethanol successively, and 50 ℃ of dryings of vacuum drying oven 12 hours get the big ball of PS, particle diameter is 2mm, and the swelling phenomenon is arranged in solvent.
Embodiment 2:
The 0.3g polyvinyl alcohol is dissolved in the 120ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.6g benzoyl peroxide is joined in the mixed solution of 18ml vinylbenzene and 2ml Vinylstyrene, this mixed solution is joined in the above-mentioned there-necked flask, 4～5 revolutions per seconds of control stirring velocitys, intensification is reacted 10 hours after-filtration down at 85 ℃, product cleans 3 times with distilled water and ethanol successively, and 50 ℃ of dryings of vacuum drying oven 12 hours get the big ball of PS-st, particle diameter is 2mm, and the swelling phenomenon is arranged in solvent.
Embodiment 3:
The 0.4g polyvinyl alcohol is dissolved in the 120ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.4g benzoyl peroxide is joined in the mixed solution of 16ml vinylbenzene and 4ml Vinylstyrene, this mixed solution is joined in the above-mentioned there-necked flask, 4～5 revolutions per seconds of control stirring velocitys, intensification is reacted 10 hours after-filtration down at 85 ℃, product cleans 3 times with distilled water and ethanol successively, and 50 ℃ of dryings of vacuum drying oven 12 hours get the big ball of PS-st, particle diameter is 2mm, is insoluble to general organic solvent.
Embodiment 4:
The 0.6g polyvinyl alcohol is dissolved in the 120ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.4g benzoyl peroxide is joined in the mixed solution of 10ml vinylbenzene and 10ml Vinylstyrene, this mixed solution is joined in the above-mentioned there-necked flask, 3 revolutions per seconds of control stirring velocitys, intensification is reacted 8 hours after-filtration down at 85 ℃, product cleans 3 times with distilled water and ethanol successively, and 50 ℃ of dryings of vacuum drying oven 12 hours get the big ball of PS-st, particle diameter is 5mm, is insoluble to general organic solvent.
Embodiment 5:
The 0.4g polyvinyl alcohol is dissolved in the 160ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.4g benzoyl peroxide is joined in the mixed solution of 16ml vinylbenzene and 4ml Vinylstyrene, this mixed solution is joined in the above-mentioned there-necked flask, 8 revolutions per seconds of control stirring velocitys, intensification is reacted 6 hours after-filtration down at 90 ℃, product cleans 3 times with distilled water and ethanol successively, and 50 ℃ of dryings of vacuum drying oven 12 hours get the big ball of PS-st, particle diameter is 0.5mm, and the swelling phenomenon is arranged in solvent.
Embodiment 6:
The 0.4g polyvinyl alcohol is dissolved in the 80ml distilled water, and not molten part is heated to whole dissolvings, injects there-necked flask and feeds nitrogen.The 0.4g benzoyl peroxide is joined in the mixed solution of 16ml vinylbenzene and 4ml Vinylstyrene, this mixed solution is joined in the above-mentioned there-necked flask, and 8 revolutions per seconds of control stirring velocitys heat up and react 6 hours after-filtration down at 60 ℃, particle diameter is 0.5mm, and the swelling phenomenon is arranged in solvent.
Synthesizing of the big ball of embodiment 7:SPS-st
The big ball 2g of PS-st that gets among the embodiment 3 immerses in the 10ml vitriol oil, and magnetic agitation was poured in the water and filtered after 48 hours, cleaned 3 times with distilled water, got the big ball of SPS-st.
Embodiment 8:
The big ball 2g of PS-st that gets among the embodiment 3 immerses in the 2ml vitriol oil, and magnetic agitation was poured in the water and filtered after 48 hours, cleaned 3 times with distilled water, got the big ball of SPS-st.
Embodiment 9:
The big ball 2g of PS-st that gets among the embodiment 3 immerses in the 30ml vitriol oil, and magnetic agitation was poured in the water and filtered after 48 hours, cleaned 3 times with distilled water, got the big ball of SPS-st.
Embodiment 10:
Getting the mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 joins tetramethyl-dihydro sily oxide and D4 is in the reaction system of forming at 1: 2 (wherein the D4 add-on is 33.3g), heats up at 60 ℃ of 5 hours after-filtration of reaction down.CaCO with filtrate adding 1%
3In the solution, be warming up to 50 ℃, react after 1 hour, put into vacuum drying oven, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.With Ubbelohde viscometer toluene is that solvent is measured its viscosity, is 0.08.
Embodiment 11:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 11.5 the reaction system (wherein the D4 add-on is 46g), heat up and react 5 hours after-filtration down at 60 ℃.CaCO with filtrate adding 1%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.With Ubbelohde viscometer toluene is that solvent is measured its viscosity, is 0.27.
Embodiment 12:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 22.5 the reaction system (wherein the D4 add-on is 47.87g), heat up and react 5 hours after-filtration down at 60 ℃.CaCO with filtrate adding 1%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.With Ubbelohde viscometer toluene is that solvent is measured its viscosity, is 0.47.
Embodiment 13:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 2 the reaction system (wherein the D4 add-on is 33.3g), heat up and react 5 hours after-filtration down at 70 ℃.CaCO with filtrate adding 1%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.
Embodiment 14:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 2 the reaction system (wherein the D4 add-on is 33.3g), heat up and react 5 hours after-filtration down at 90 ℃.CaCO with filtrate adding 1%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.
Embodiment 15:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 2 the reaction system (wherein the D4 add-on is 33.3g), heat up and react 5 hours after-filtration down at 60 ℃.CaCO with filtrate adding 5%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.
Embodiment 16:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 2 the reaction system (wherein the D4 add-on is 33.3g), heat up and react 5 hours after-filtration down at 60 ℃.CaCO with filtrate adding 10%
3In the solution, 50 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours.Obtain the siloxanes of the hydrogeneous double-seal head of long-chain.
Embodiment 17:
Get mol ratio that the big ball 1.5g of SPS-st among the embodiment 7 adds tetramethyl-dihydro sily oxide and D4 and be in 1: 2 the reaction system (wherein the D4 add-on is 33.3g), heat up and react 5 hours after-filtration down at 60 ℃.CaCO with filtrate adding 10%
3In the solution, heat up 90 ℃ down reaction put into vacuum drying oven after 1 hour, 80 ℃ of dryings 2 hours obtain the siloxanes of the hydrogeneous double-seal head of long-chain.
Claims (4)
1. the big ball of sulfonated crosslinked polystyrene is characterized in that, is made up of crosslinked polystyrene carrier and the sulfonic group two portions that are bonded on the carrier; Size distribution is between 0.5～5 millimeter.
2. the preparation method of the big ball of sulfonated crosslinked polystyrene of a claim 1 has two steps of suspension polymerization and sulfonation reaction,
Described suspension polymerization is, is that 1～9: 1 vinylbenzene and Vinylstyrene are reactant with volume ratio; The volume ratio 4～8: 1 of distilled water and reactant; With the benzoyl peroxide is initiator, and the mass ratio of initiator and reactant is 1: 30～70; With the polyvinyl alcohol is dispersion agent, and the mass ratio of dispersion agent and reactant monomer is 1: 30～70; Polyvinyl alcohol is dissolved in the distilled water, adds reactant and initiator mixing solutions, under nitrogen protection, stir and heat up, at 6～12 hours after-filtration of 60～90 ℃ of reactions, clean with distilled water ethanol respectively, resulting polymers vacuum-drying obtains containing the big ball of crosslinked polystyrene of remaining double bond;
Described sulfonation reaction is with stirring 48 hours in the big ball immersion of the crosslinked polystyrene vitriol oil, to obtain the big ball of tart crosslinked polystyrene through ion-exchange; Use the excessive sulfuric acid of distilled water flush away again, obtain the big ball of sulfonated crosslinked polystyrene; Wherein the mass ratio of the big ball of crosslinked polystyrene and the vitriol oil is 1: 1～15.
3. the purposes of the big ball of sulfonated crosslinked polystyrene of a claim 1 is made chainextender and is used in the octamethylcyclotetrasiloxane ring-opening reaction.
4. the purposes of the big ball of sulfonated crosslinked polystyrene according to claim 3 is characterized in that, the detailed process of described ring-opening reaction is, is that 1: 2～50 short chain siloxanes and octamethylcyclotetrasiloxane are reactant with mol ratio; With the big ball of sulfonated crosslinked polystyrene is chainextender, and the mass ratio of chainextender and reactant is 1: 20～50; Reactant and chainextender are added in the reaction unit; under nitrogen protection, stir and heat up; react 3～8 hours after-filtration down at 60～90 ℃; the adding mass percent is 1%～10% CaCO3 in the filtrate; reacted 1～3 hour down at 50～90 ℃; the short chain siloxanes of chain extension is fully removed not in vacuum-drying again, obtains the long-chain siloxanes.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059190A (en) * | 2013-01-16 | 2013-04-24 | 吉林大学 | Resin ball capable of swelling and adsorbing aromatic hydrocarbon in hydrocarbon mixture and preparation method of resin ball |
| CN106749826A (en) * | 2016-12-21 | 2017-05-31 | 河南中帅医药科技股份有限公司 | A kind of preparation method of pharmaceutical grade Multifunctional tree lipid microspheres |
| CN109593155A (en) * | 2018-12-11 | 2019-04-09 | 怀化学院 | Sulfonated polystyrene tiny balloon, preparation method and application |
| CN113578383A (en) * | 2021-08-09 | 2021-11-02 | 江南大学 | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere |
-
2011
- 2011-01-24 CN CN 201110025752 patent/CN102146148A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《离子交换与吸附树脂》 19950228 何炳林等 离子交换与吸附树脂 上海科技教育出版社 38-39 1 , * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059190A (en) * | 2013-01-16 | 2013-04-24 | 吉林大学 | Resin ball capable of swelling and adsorbing aromatic hydrocarbon in hydrocarbon mixture and preparation method of resin ball |
| CN103059190B (en) * | 2013-01-16 | 2014-07-23 | 吉林大学 | Resin ball capable of swelling and adsorbing aromatic hydrocarbon in hydrocarbon mixture and preparation method of resin ball |
| CN106749826A (en) * | 2016-12-21 | 2017-05-31 | 河南中帅医药科技股份有限公司 | A kind of preparation method of pharmaceutical grade Multifunctional tree lipid microspheres |
| CN109593155A (en) * | 2018-12-11 | 2019-04-09 | 怀化学院 | Sulfonated polystyrene tiny balloon, preparation method and application |
| CN109593155B (en) * | 2018-12-11 | 2021-05-28 | 怀化学院 | Sulfonated polystyrene hollow microsphere, preparation method and application |
| CN113578383A (en) * | 2021-08-09 | 2021-11-02 | 江南大学 | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere |
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Application publication date: 20110810 |