CN1244547A - Polyether containing several TEMPO radicals and its preparation - Google Patents
Polyether containing several TEMPO radicals and its preparation Download PDFInfo
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- CN1244547A CN1244547A CN 99113978 CN99113978A CN1244547A CN 1244547 A CN1244547 A CN 1244547A CN 99113978 CN99113978 CN 99113978 CN 99113978 A CN99113978 A CN 99113978A CN 1244547 A CN1244547 A CN 1244547A
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Abstract
The present invention relates to a kind of new polyether and a novel preparation process. Sodium phenoxide and TEMPO sodium as initiator is used to initiate the ring-opening polymerization or copolymerization of olefine oxide anion, the epoxy TEMPO is first synthesized, and multi-block polyether containing several TEMPO side radicals is then synthesized through multistage or simultaneous addition of this epoxy TEMPO as intermediate and olefine oxide so that the polyether with multi-blocks containing several TEMPO side radicals is synthesized. Because of containing several free radical capturing TEMPO radicals, this kind of polyethyer can be used to control the hot polymerization of free radicals of styrene to realize the polymerization of active free radicals. As complely new serial polymer, the block polymers contains polyether with designable molecular weight and polystyrene chain segments at the same time.
Description
The present invention is a kind of novel polyethers that contains several TEMPO radicals and preparation method thereof, and TEMPO is 2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical.
In polymer arts, Shang Weiyou contains the polyethers of several TEMPO radicals at present, and such polyethers can be realized active free radical polymerization, can also programmable polyethers of synthetic molecular weight and polystyrene segment.The intermediate epoxy group(ing) TEMPO that the present invention relates to, also with existing document propose different.Kobatake (Macromolecules 1997,30,4238～4242) is by the reaction of TEMPO and benzoyl peroxide (BPO), and the epoxy group(ing) TEMPO molecular structure that makes with epichlorohydrin reaction again after the hydrolysis is:
But its severe reaction conditions, step is long, and yield is low.U.S. Pat P2674619,2549439,2454434 and 2213447 has disclosed the preparation of polyoxygenated alkene.
The objective of the invention is to invent a kind of polyethers that contains several TEMPO radicals and preparation method thereof.
The present invention as initiator, reacts the polyethers that make following structure with olefin oxide, epoxy group(ing) TEMPO with phenol sodium:
Wherein T is
X and y are 5～100, and n is 0～5.
The present invention as initiator, reacts the polyethers that make following structure with olefin oxide, epoxy group(ing) TEMPO with TEMPO sodium:
Polyethers of the present invention is ABAB or AABBAA structure, and it is the polyethers that many blocks contain a plurality of TEMPO side groups, and this polyethers contains a plurality of radical-scavenging group TEMPO, therefore can control the thermopolymerization of vinylbenzene free radical, to realize active free radical polymerization.Use as the model polymkeric substance in the Polymer Physics research field, the special physicals that shows will greatly enrich the kind of macromolecular material.
The present invention (1) formula structure contain the several TEMPO polyethers, x, y are 20～40 in its common structure, n=1～3.
The present invention (2) formula structure contain the several TEMPO polyethers, x, y are 20～40 in its common structure, n=1～3.
In the composite structure formula is 1 o'clock, and initiator is a phenol sodium, i.e. sodium phenylate is to sylvan sodium and adjacent sylvan sodium.After in tetrahydrofuran solution, refluxing 4～30 hours by phenol and sodium Metal 99.5, filter, promptly make white phenol sodium powder.
The structure of the intermediate epoxy group(ing) TEMPO that uses in building-up process is as follows:
Make with epoxy chloropropane and 4-hydroxyl TEMPO reaction by phase transfer method.Promptly add catalyzer four butyl hydrogen sulfate hydrogen ammoniums under alkaline condition, add epoxy chloropropane or epoxy bromopropane again, mix the back and added 4-hydroxyl TEMPO in batches in 2～4 hours, reacted 20～26 hours, through extraction, recrystallization gets final product.Epoxy chloropropane and 4-hydroxyl TEMPO molar ratio are 1: (1～5).
Phenol sodium and olefin oxide reaction, 40～100 ℃ of temperature of reaction, add epoxy group(ing) TEMPO reaction, 60～100 ℃ of temperature of reaction, 5～20 hours time then at 12～30 hours time.Stop with alcoholic solvent when reaction finishes, general methyl alcohol get final product, adding precipitation agent such as ether get final product product of the present invention.
Add different olefin oxide oxyethane or propylene oxide by changing in the present invention by changing, can make polyethers,, promptly get polyoxyethylene ether if promptly add oxyethane with differing molecular link configuration, if the adding propylene oxide promptly gets polyoxytrimethylene ether.
By changing the ratio between initiator and olefin oxide such as oxyethane or propylene oxide, generally be 5～100 in the present invention, i.e. x in structural formula or y value can obtain the polyethers of different molecular weight, and molecular weight from 400 to 8000 does not wait.
In the present invention, by regulating the ratio between epoxy group(ing) TEMPO and the initiator, promptly the n value in structural formula generally is 0～5, can change number or position at the intramolecular TEMPO base of synthesizing polyether.
When composite structure formula 2, initiator is the TEMPO steel, refluxes in tetrahydrofuran solution 4～30 hours by 4-hydroxyl TEMPO and sodium Metal 99.5, and temperature is 40～100 ℃, filters, and promptly makes pink TEMPO sodium powder.
Be initiator with phenol sodium with TEMPO sodium be that other synthesis condition of initiator is identical.
In the present invention, the mode reinforced by segmentation realizes many block structures formula (1) or (2), and at first initiator and oxyethane are at 40～100 ℃ of reactions 12～30 hours, the i.e. section of winning polyethers, add metering epoxy TEMPO and reacted 5～20 hours down, promptly get second section at 60～100 ℃; Add oxyethane then and continue reaction under these conditions, promptly get three sections, add epoxy TEMPO again, promptly get four sections polyethers; And the like, can make the polyethers of many blocks.
Among the present invention, optimal reaction temperature is 50～70 ℃ for first section, and the time is 12～24 hours, and second section is 60～80 ℃, and the time is 5～10 hours.
In the present invention, realize many block structures formula (1) or (2), initiator and oxyethane and epoxy TEMPO are mixed with certain proportion by reinforced simultaneously copolymerization mode, general x is 5～100, and n is～5, at 40～100 ℃, reaction times is 12～30 hours, can make the polyethers of many blocks.
Among the present invention, during by copolymerization process composite structure formula (1) or (2), optimum temps is 60～80 ℃, and the time is 18～24 hours.
Structural formula of the present invention (1) or (2) polyethers be through after the conventional acidifying, as with 0.5～4M concentration hcl acidifying, promptly makes and contain quaternary nitrogen ionic tensio-active agent, and be of many uses.
Contain several TEMPO polyethers and novel preparation method thereof, realize by anionic ring-opening polymerization, the pfpe molecule amount that makes distributes less than 1.3, the molecular weight of block chain or molecular structure can arbitrarily design, this polyethers contains a plurality of radical-scavenging group TEMPO thereby can control the thermopolymerization of vinylbenzene free radical, realize active free radical polymerization, made the multipolymer of the many blocks of polyether-polystyrene or many branching simultaneously.Contain programmable polyethers of molecular weight and polystyrene segment in this kind block polymer simultaneously, this is brand-new series polymer, and is that the general polymerization method is difficult to make, and will greatly enrich the kind of macromolecular material; In the Polymer Physics research field, use as the model polymkeric substance; The special physicals that this kind block polymer shows can be used as the phase solvent of blend processing or dispersion agent etc.This polyethers can make the nonionic-cationic surfactant that contains quaternary ammonium cation through acidifying, and is used to field breakdown of emulsion, removal of impurities or separation such as oil field, chemical industry or water treatment.The inventive method is a kind of very convenient, practical and novel method, this method can also be in general laboratory or small chemical factory obtain implementing; The employed basic raw material of this method obtains on ordinary Chemical market easily or synthesizes easily.Example one:
P-cresol 1mol is dissolved in the 50ml anhydrous tetrahydro furan (THF), adds the sodium Metal 99.5 1.1mol that has been cut into fine strip shape, 60 ℃ of holding temperatures, and stirring is spent the night, and filters, and promptly gets white sodium cresylate anionic initiator.
Dissolving 0.5mol 4-hydroxyl TEMPO (or abbreviating HTEMPO as) in 50mlTHF under agitation slowly divides 4 batches to add the sodium silk, refluxes 24 hours, is chilled to 60 ℃ of reactions 24 hours, promptly gets pink TEMPO sodium salt.
Adding 50%NaOH 60ml and catalyzer are some in the 250ml flask, after stirring, slowly splash into epoxy chloropropane 50ml, in 2 hours, add HTEMPO in batches, 20 ℃ were reacted 24 hours down, after the dilution of 200ml water, add the 200ml chloroform extraction, promptly get reddish-brown epoxy TEMPO behind the recrystallization.Example two:
In dry ampere bottle, add the 0.1mol sodium cresylate, add oxyethane 4mol with syringe, seal, reacted 12 hours down at 60 ℃, add 0.1mol epoxy TEMPO, continue reaction 8 hours down at 70 ℃, ring-opening reaction end back adds methyl alcohol and stops, behind ether sedimentation, obtain molecular weight and be 2000 structural formula polyethers for (1).Example three:
In dry ampere bottle, add the 0.1mol sodium cresylate, add propylene oxide 4mol with syringe, seal, reacted 12 hours down at 80 ℃, add 0.1mol epoxy TEMPO, continue reaction 8 hours down at 90 ℃, ring-opening reaction end back adds methyl alcohol and stops, behind ether sedimentation, obtain molecular weight and be 2000 structural formula polyethers for (1).Example four:
In dry ampere bottle, add 0.1mol TEMPO sodium, add oxyethane 4mol with syringe, seal, reacted 12 hours down at 60 ℃, add 0.1mol epoxy TEMPO, continue reaction 10 hours down at 70 ℃, ring-opening reaction end back adds methyl alcohol and stops, behind ether sedimentation, obtain molecular weight and be 2000 structural formula polyethers for (2).Example five:
In dry ampere bottle, add 0.1mol TEMPO sodium, add propylene oxide 2mol with syringe, seal, reacted 12 hours down at 80 ℃, add 0.1mol epoxy TEMPO, continue reaction 5 hours down at 90 ℃, ring-opening reaction end back adds methyl alcohol and stops, behind ether sedimentation, obtain molecular weight and be 1000 structural formula polyethers for (2).Example six:
In dry ampere bottle, add the 0.1mol sodium cresylate, add oxyethane 4mol, seal with syringe, reacted 12 hours down at 60 ℃, add 0.1mol epoxy TEMPO, continue reaction 8 hours down at 70 ℃, add oxyethane 4mol with syringe again, seal, continue reaction 12 hours down, add 0.1mol epoxy TEMPO at 60 ℃, continue reaction 8 hours down at 70 ℃, ring-opening reaction finishes the back and adds methyl alcohol and stop, and behind ether sedimentation, obtains molecular weight and be 4000 the structural formula polyethers for (1).Example seven:
In dry ampere bottle, add 0.1mol TEMPO sodium, add oxyethane 4mol, seal with syringe, reacted 12 hours down at 60 ℃, add 0.1mol epoxy TEMPO, continue reaction 8 hours down at 70 ℃, add oxyethane 4mol with syringe again, seal, continue reaction 12 hours down, add 0.1mol epoxy TEMPO at 60 ℃, continue reaction 8 hours down at 70 ℃, ring-opening reaction finishes the back and adds methyl alcohol and stop, and behind ether sedimentation, obtains molecular weight and be 4000 the structural formula polyethers for (2).Example eight:
In dry ampere bottle, add 0.1mol sodium cresylate and 0.2mol epoxy TEMPO, add oxyethane 4mol, seal with syringe, reacted 12 hours down at 70 ℃, copolymerization finishes the back and adds methyl alcohol and stop, and behind ether sedimentation, obtains molecular weight and be 2000 the structural formula polyethers for (1).Example nine:
In dry ampere bottle, add 0.1mol TEMPO sodium and 0.3mol epoxy TEMPO, add oxyethane 6mol, seal with syringe, reacted 12 hours down at 70 ℃, copolymerization finishes the back and adds methyl alcohol and stop, and behind ether sedimentation, obtains molecular weight and be 3000 the structural formula polyethers for (1).
Claims (10)
1. polyethers that contains several TEMPO radicals, phenol sodium is initiator, its molecular structure is as follows:
Wherein T is
X and y are 5～100, and n is 0～5.
2. polyethers that contains several TEMPO radicals, TEMPO sodium is initiator, its molecular structure is as follows:
X and y are 5～100, and n is 0～5.
3. according to the right 1 described polyethers that contains several TEMPO radicals, it is characterized in that X or Y=20～40, n=1～3.
4. according to the right 2 described polyethers that contain several TEMPO radicals, it is characterized in that X or Y=20～40, n=1～3.
5. preparation method who contains the several TEMPO radicals polyethers, initiator is a phenol sodium, it is characterized in that: (1) makes phenol sodium initiator with phenol and sodium Metal 99.5; (2) make epoxy group(ing) TEMPO with epoxy chloropropane and 4-hydroxyl TEMPO reaction; (3) phenol sodium and olefin oxide reaction, temperature is 40～100 ℃, the time is 12～30 hours, is first section reaction; (4) step (3) reaction finishes back adding epoxy TEMPO reaction, and temperature is 60～100 ℃, and the time is 5～20 hours, is second section reaction; (5) use the alcoholic solvent termination reaction, add precipitation agent and get final product; (6) mol ratio of initiator and olefin oxide is 5～100, and the mol ratio of initiator and epoxy group(ing) TEMPO is 0～5; (7) first sections and second section reaction are overlapping carrying out.
6. preparation method who contains the several TEMPO radicals polyethers, initiator is a TEMPO sodium, it is characterized in that: (1) with sodium Metal 99.5 and 4-hydroxyl TEMPO back flow reaction in tetrahydrofuran solution, the time is 4～30 hours, and temperature is 40～100 ℃; (2) other step is identical with (2)～(7) of claim 5.
7. the preparation method who contains the several TEMPO radicals polyethers according to claim 5 is characterized in that first section temperature of reaction is 50～70 ℃, and the time is 12～24 hours, and second section temperature of reaction is 60～80 ℃, and the time is 5～10 hours.
8. preparation method who contains the several TEMPO radicals polyethers, it is characterized in that using phenol sodium or TEMPO sodium as initiator, add olefin oxide, add epoxy group(ing) TEMPO again, 40～100 ℃ of reaction copolymerization in 12～30 hours down, use the alcoholic solvent termination reaction, add precipitation agent and get final product, the mol ratio of initiator and olefin oxide is 5～100, and the mol ratio of initiator and epoxy group(ing) TEMPO is 0～5.
9. the described according to Claim 8 preparation method who contains the several TEMPO radicals polyethers, the temperature that it is characterized in that copolyreaction is 60～80 ℃, the reaction times is 18～24 hours.
10. the several TEMPO radicals polyethers that contains according to claim 1 and 2 is characterized in that this polyethers can acidifying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99113978 CN1126774C (en) | 1999-08-10 | 1999-08-10 | Polyether containing several TEMPO radicals and its preparation |
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| CN 99113978 CN1126774C (en) | 1999-08-10 | 1999-08-10 | Polyether containing several TEMPO radicals and its preparation |
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| CN1244547A true CN1244547A (en) | 2000-02-16 |
| CN1126774C CN1126774C (en) | 2003-11-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126767C (en) * | 1999-10-21 | 2003-11-05 | 复旦大学 | Polymer of TEMPO contg. block polyether-polystyrene and its prepn. method |
| CN105237660A (en) * | 2015-10-28 | 2016-01-13 | 复旦大学 | Polymer with stable nitroxide free radical as terminal group, and preparation method thereof |
| CN113307966A (en) * | 2021-05-31 | 2021-08-27 | 安徽师范大学 | Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof |
-
1999
- 1999-08-10 CN CN 99113978 patent/CN1126774C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126767C (en) * | 1999-10-21 | 2003-11-05 | 复旦大学 | Polymer of TEMPO contg. block polyether-polystyrene and its prepn. method |
| CN105237660A (en) * | 2015-10-28 | 2016-01-13 | 复旦大学 | Polymer with stable nitroxide free radical as terminal group, and preparation method thereof |
| CN105237660B (en) * | 2015-10-28 | 2018-06-12 | 复旦大学 | The polymer of a kind of end group for stable nitrogen-oxygen free radical and preparation method thereof |
| CN113307966A (en) * | 2021-05-31 | 2021-08-27 | 安徽师范大学 | Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof |
| CN113307966B (en) * | 2021-05-31 | 2023-04-25 | 安徽师范大学 | Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt, and preparation method and application thereof |
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| CN1126774C (en) | 2003-11-05 |
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