CN1126767C - Polymer of TEMPO contg. block polyether-polystyrene and its prepn. method - Google Patents
Polymer of TEMPO contg. block polyether-polystyrene and its prepn. method Download PDFInfo
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Abstract
The present invention relates to a synthetic method for polyethylene glycol oxide-polystyrene (PEO-PS) or polyoxytrimethylene-polystyrene (PPO-PS) with two blocks, three blocks, multiple blocks or multiple branches. At present, the polymer and a synthetic method thereof are not disclosed. The present invention has the technical scheme that the PEO or the PPO of 2, 2, 6, 6-tetramethyl oxidation piperidol (TEMPO) is used as a free radical capturing agent for macromolecules, so that the active polymerization of the free radicals of styrene is initiated by an initiating agent AIBN or an initiating agent BPO. The polyether with TEMPO is prepared by initiating oxidation olefine and epoxy group TEMPO copolymerization by TEMPO sodium salt or natrium phenolicum, and the molecular weight of the polyether and the position and the number of the TEMPO in a polyether chain can be controlled. The length and the branching degree of polystyrenes chain segments in obtained polymer can also be controlled.
Description
The present invention a kind ofly contains 2,2,6, the synthetic method of the polyoxyethylene-polystyrene (PEO-PS) of two blocks of 6-tetramethyl-oxidation piperidines alcohol (TEMPO), three blocks, many blocks or many branching, polyoxytrimethylene-polystyrene (PPO-PS) polymkeric substance.
(Macromolecules 1995 for Huang JL; 28:4421) wait ammonia alcohol initiation oxyethane under the Schiff's base protection earlier; under action of ultraviolet light, react the polyoxyethylene ether that makes end group band TEMPO then with the TEMPO nitroxyl free radical; last and vinylbenzene is total to the PEO-PS that heat makes two blocks; obviously reactions steps is long; the condition harshness is difficult to suitability for industrialized production.(China Synthetic Rubber Industry 1998 such as Liu Feng, 21 (5): 303) disclose the synthetic method of another kind of PS-PEO, they adopt polyoxyethylene ether and bromoacetyl bromide reaction, reaction product and copper halide, bipyridine and vinylbenzene mix, heterogeneous atom transition free radical polymerization reaction method takes place under violent stirring, disadvantage is the halogen-containing end group of product, and and copper halide, bipyridine separation difficulty.
The objective of the invention is to realize PEO-PS or the PPO-PS polymkeric substance and the synthetic method thereof of two blocks, three blocks, three blocks, many blocks or the many branching of a kind of TEMPO of containing.
The present invention is polyoxyethylene-polystyrene (PEO-PS) or the polyoxytrimethylene-polystyrene (PPO-PS) and the synthetic method thereof of two blocks, three blocks, many blocks or the many branching of a kind of TEMPO of containing.The present invention uses and is with 2,2,6, and the PEO of 6-tetramethyl-oxidation piperidines alcohol (TEMPO) or PPO cause vinylbenzene as the macromolecular radical trapping agent through initiator azo isobutyronitrile (AIBN) or benzoyl peroxide (BPO), and the radical living polymerization preparation takes place.The polyethers of this band TEMPO is by TEMPO sodium salt or phenol sodium initiated oxidation alkene and epoxy group(ing) TEMPO copolymerization preparation; The molecular weight of this polyethers, TEMPO position or the number in polyether chain, and the styrene chain segment length is controlled.
The polyoxyethylene or the polyoxytrimethylene preparation method that contain TEMPO disclose in applying for a patent 99113978.x, with itself and vinylbenzene at radical initiator AIBN or BPO initiated polymerization.The mol ratio of TEMPO group is 1 in radical initiator and the polyethers: (0.8～2), the mol ratio of initiator and styrene monomer is 1: (300～600), 95～140 ℃ of polymeric reaction temperatures, reacted under these conditions 6～16 hours, and can make the block PEO-PS or the PPO-PS that contain TEMPO.
The present invention causes oxyethane synthetic polyethers TEMPO as free radical scavenger with TEMPO sodium as initiator, makes two block PEO-PS, and its structural formula is:
Wherein n is 10～200, x=5～100.
During above-mentioned polymer manufacture, be initiator with TEMPO sodium, with reacting ethylene oxide, reaction conditions is that initiator and monomeric molar ratio are 1: 5～100,40～100 ℃ of temperature of reaction, and 12～30 hours time, making end group is the polyoxyethylene ether of TEMPO.
Polyoxyethylene ether with above-mentioned TEMPO is free radical scavenger, causes through radical initiator AIBN or BPO, and styrene polymerization, can make two block PEO-PS of said structure.
With phenol sodium is that initiator causes oxyethane and epoxy group(ing) TEMPO copolymerization, and synthetic polyethers TEMPO promptly makes two block PEO-PS as free radical scavenger, and its structure is:
Wherein n is 10～200, x=5～100.
During above-mentioned polymer manufacture, with phenol sodium is initiator, with reacting ethylene oxide, reaction conditions is that initiator and monomeric molar ratio are 1: 5～100,40～100 ℃ of temperature of reaction, add epoxy group(ing) TEMPO then at 12～30 hours time, continue reaction 5～20 hours at 60～100 ℃, making end group is the polyoxyethylene ether of TEMPO.
With above-mentioned end group is that the polyoxyethylene ether of TEMPO is free radical scavenger, causes through radical initiator AIBN or BPO, and styrene polymerization, can make two block PEO-PS of said structure.
The present invention causes propylene oxide synthetic polyethers TEMPO as free radical scavenger with TEMPO sodium as initiator, makes two block PPO-PS, and its structure is:
Wherein n is 10～200, x=5～100.
During above-mentioned polymer manufacture, be initiator with TEMPO sodium, with propylene oxide reaction, reaction conditions is that initiator and monomeric molar ratio are 1: 5～100,40～100 ℃ of temperature of reaction, and 12～30 hours time, making end group is the polyoxytrimethylene ether of TEMPO.
Polyoxytrimethylene ether with above-mentioned TEMPO is free radical scavenger, causes through radical initiator AIBN or BPO, and styrene polymerization, can make two block PPO-PS of said structure.
The present invention causes propylene oxide synthetic polyethers TEMPO as free radical scavenger with phenol sodium as initiator, makes two block PPO-PS, and its structure is:
Wherein n is 10～200, x=5～100.
During above-mentioned polymer manufacture, with phenol sodium is initiator, with propylene oxide reaction, reaction conditions is that initiator and monomeric molar ratio are 1: 5～100,40～100 ℃ of temperature of reaction, add epoxy group(ing) TEMPO then at 12～30 hours time, continue reaction 5～20 hours at 60～100 ℃, making end group is the polyoxytrimethylene ether of TEMPO.
With above-mentioned end group is that the polyoxytrimethylene ether of TEMPO is free radical scavenger, causes through radical initiator AIBN or BPO, and styrene polymerization, can make two block PPO-PS of said structure.
The present invention can make three block polyethers that contain TEMPO with following method: with TEMPO sodium or phenol sodium is initiator, react with olefin oxide, mainly be ethylene oxide and propylene oxide, reaction conditions is that initiator and monomeric mol ratio are 1: (5～100), temperature of reaction is 40～100 ℃, reaction times is 12～30 hours, the reaction back adds epoxy group(ing) TEMPO, if phenol sodium, then the mol ratio of it and epoxy group(ing) TEMPO is 1: 2, continue reaction 5～20 hours down at 60～100 ℃, make the polyethers that two end groups are TEMPO.
With above-mentioned end group is that the polyoxyethylene ether of TEMPO is free radical scavenger, cause through radical initiator AIBN or BPO, and styrene polymerization, polymerizing condition can make three block PEO-PS as hereinbefore.
The structure of the three block PS-PEO-PS that aforesaid method makes is as follows:
The structure of three block PS-PPO-PS is as follows:
M=10～200 wherein, n=10～200, x=5～100.
Above-mentioned triblock polymer, each section chain length scope preferably is: m=20～100, n=10～200, x=20～40.
The preparation method that the present invention contains many blocks of TEMPO or multi-branch polyether-poly styrene polymer makes agent TEMPO sodium or phenol sodium and oxyethane or propylene oxide 40～100 ℃ of reactions 12～30 hours down, the i.e. section of winning polyethers, the epoxy group(ing) TEMPO that adds metering, reacted 5～20 hours down at 60～100 ℃, promptly get second section, add oxyethane or propylene oxide again, continue reaction 8～10 hours under these conditions, get the 3rd section, adding epoxy group(ing) TEMPO, get the 4th section, and the like, promptly make the polyethers that has a plurality of TEMPO.
With above-mentioned end group is that the polyethers of TEMPO is a free radical scavenger, cause through radical initiator AIBN or BPO, and styrene polymerization, can make many blocks or many branching PEO-PS or PPO-PS.
Above-mentioned many blocks or multi-branch polyether-polystyrene polyreaction optimum reaction condition is that temperature of reaction is 110～130 ℃, and the reaction times is 8～14 hours.
The structure that the above-mentioned polyethers that contains a plurality of TEMPO makes many blocks or multi-branch polyether-poly styrene polymer is:
Wherein T is
K=0～5 wherein, l=10～200, m=10～200, n=10～200, x=5～100, y=5～100.In the said structure, the better content of each block is k=1～3, l=20～100, m=20～100, n=20～100, x=20～40, y=20～40.
The structure of the intermediate epoxy group(ing) TEMPO that the present invention uses in building-up process is as follows:
Promptly make with epoxy chloropropane and 4-hydroxyl TEMPO reaction by phase transfer method.Promptly add the catalyzer 4-butyl ammonium hydrogen sulfate 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).
Used phenol sodium among the present invention, 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.
Employed TEMPO sodium among the present invention refluxed in tetrahydrofuran solution 4～30 hours by 4-hydroxyl TEMPO and sodium Metal 99.5, and temperature is 40～100 ℃, filtered, and promptly made pink TEMPO sodium powder.
The present invention is the PEO-PS of a kind of novelty, practical two blocks, three blocks or many blocks or the preparation method of PPO-PS.At first synthesized the polyethers of band TEMPO by anionic ring-opening polymerization, its molecular weight distribution is less than 1.3; The polyethers of these TEMPO and vinylbenzene generation active free radical polymerization, the molecular weight distribution of the block chain that obtains is less than 1.5.These block polymer molecular structures can arbitrarily design, and are controlled in its intramolecularly polyethers section or polystyrene segment length, and this is brand-new series polymer, and are 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.The PPO-PS kind block polymer mixes ether as urethane, will increase the rigidity of elastomerics or foam largely.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
In dry peace a word used in place name bottle, add 0.1mol TEMPO sodium, add oxyethane 4mol, seal with syringe, reacted 12 hours down at 60 ℃, ring-opening reaction finishes the back and adds the methyl alcohol termination, and behind ether sedimentation, obtaining molecular weight is that 2000 end groups are the polyoxyethylene ether of TEMPO.Polyethers 0.012mol and 0.01mol AIBN, the 3mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 100 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got two block PEO-PS after 10 hours.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, obtaining molecular weight is the polyoxyethylene of 2000 end group band TEMPO.Polyethers 0.012mol and 0.01mol AIBN, the 3mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 130 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got two block PEO-PS after 6 hours.Example three
In dry peace a word used in place name 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, obtaining molecular weight is the polyoxytrimethylene of 2000 end group band TEMPO.Polyethers 0.012mol and 0.01mol AIBN, the 3mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 130 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got two block PPO-PS after 8 hours.Example four
In dry peace a word used in place name bottle, add 0.1mol TEMPO sodium, add propylene oxide 6mol, seal with syringe, reacted 8 hours down at 100 ℃, ring-opening reaction finishes the back and adds the methyl alcohol termination, and behind ether sedimentation, obtaining molecular weight is the polyoxytrimethylene of 3000 end group band TEMPO.Polyethers 0.012mol and 0.01mol AIBN, the 3mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 120 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got two block PPO-PS after 10 hours.Example five
In dry peace a word used in place name 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, obtaining molecular weight is the polyoxyethylene of two TEMPO of 2000 end group bands.Polyethers 0.024mol and 0.02mol AIBN, the 6mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 120 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got three block PS-PEO-PS after 14 hours.Example six
In dry peace a word used in place name 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 the methyl alcohol termination, and behind ether sedimentation, obtaining molecular weight is 3000 polyoxyethylenes with a plurality of TEMPO.Polyethers 0.036mol and 0.03molAIBN, the 9mol vinylbenzene of above-mentioned preparation are mixed, join in the reactor, after drum nitrogen is replaced oxygen, join in 120 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got the PS-PEO-PS of many blocks or many branching after 16 hours.Example seven
In dry peace a word used in place name 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 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 is 4000 and be embedded with the polyoxyethylene of a plurality of TEMPO.Polyethers 0.036mol with above-mentioned preparation, mix with 0.03mol AIBN, 9mol vinylbenzene, join in the reactor, after drum nitrogen is replaced oxygen, join in 130 ℃ of oil baths together with whole reactor, stirring down, reaction promptly got the controlled many blocks of molecular weight or the PS-PEO-PS of many branching after 16 hours.
Claims (13)
1. a preparation method who contains TEMPO block polyether-polystyrene polymkeric substance uses and is with 2,2,6, the polyoxyethylene or the propylene oxide of 6-tetramethyl-oxidation piperidines alcohol are made the macromolecular radical trapping agent, cause vinylbenzene through initiator, active free radical polymerization takes place, and it is characterized in that:
(1) radical initiator is azo isobutyronitrile or benzoyl peroxide;
(2) mol ratio of TEMPO nitroxyl free radical is 1 in radical initiator and the polyethers:
(0.8～2)；
(3) mol ratio of initiator and styrene monomer is 1: (300～600);
(4) polymeric reaction temperature is 95～140 ℃;
(5) reaction times is 6～16 hours.
2. the preparation method who contains the block polyether-polystyrene polymkeric substance of TEMPO according to claim 1, it is characterized in that causing oxyethane synthetic polyethers TEMPO as free radical scavenger with TEMPO sodium as initiator, the diblock PEO-PS structural formula that makes is as follows:
Wherein n is 10～200, x=5～100.
3. the preparation method who contains the block polyether-polystyrene polymkeric substance of TEMPO according to claim 1, it is characterized in that causing oxyethane and epoxy group(ing) TEMPO copolymerization as initiator with phenol sodium, synthetic polyethers TEMPO is as free radical scavenger, and the diblock PEO-PS structural formula that makes is as follows:
Wherein n is 10～200, x=5～100.
4. the preparation method who contains the block polyether-polystyrene polymkeric substance of TEMPO according to claim 1, it is characterized in that causing propylene oxide synthetic polyethers TEMPO as free radical scavenger with TEMPO sodium as initiator, the diblock PPO-PS structural formula that makes is as follows:
Wherein n is 10～200, x=5～100.
5. the preparation method who contains the block polyether-polystyrene polymkeric substance of TEMPO according to claim 1, it is characterized in that causing propylene oxide synthetic polyethers TEMPO as free radical scavenger with phenol sodium as initiator, the diblock PPO-PS structural formula that makes is as follows:
Wherein n is 10～200, x=5～100.
6. according to claim 2,3,4 or 5 each described preparation methods that contain the block polyether-polystyrene polymkeric substance of TEMPO, it is characterized in that making the PEO-PS of two blocks or the x=20 of PPO-PS～40, n=20～100.
7. a preparation method who contains the three block polyether-polystyrene polymkeric substance of TEMPO is characterized in that:
(1) be initiator with TEMPO sodium or phenol sodium, anti-with oxyethane or propylene oxide
Should, reaction conditions is: initiator and monomeric mol ratio are 1: (5～100),
40～100 ℃ of temperature of reaction, 12～30 hours reaction times;
(2) add epoxy group(ing) TEMPO, continue reaction 5～20 hours down at 60～100 ℃;
(3) be that the polyethers of TEMPO is a free radical scavenger with above-mentioned end group, through free radical
Initiator A IBN or BPO cause and styrene polymerization, promptly make three blocks
PS-PEO-PS or PS-PPO-PS.
8. the preparation method who contains the three block polyether-polystyrene polymkeric substance of TEMPO according to claim 7 is characterized in that the three block PS-PEO-PS structural formulas that make are as follows:
And the PS-PPO-PS structural formula is as follows:
M=10～200 wherein, n=10～200, x=5～100.
9. the preparation method who contains the three block polyether-polystyrene polymkeric substance of TEMPO according to claim 8 is characterized in that m=20～100, n=10～200, x=20～40.
10. preparation method who contains the many blocks of TEMPO or multi-branch polyether-poly styrene polymer is characterized in that:
(1) phenol sodium or TEMPO sodium and oxyethane or propylene oxide are at 40～100 ℃
Under reacted 12～30 hours, the section of winning contains the polyethers of TEMPO;
(2) add epoxy TEMPO and continue reaction 5～20 hours down at 60～100 ℃,
Second section;
(3) add oxyethane or propylene oxide and continue to react 8～10 little under these conditions
The time, get the 3rd section;
(4) add epoxy TEMPO again and continued under these conditions to react 8～10 hours,
The 4th section, and the like, make the multi-block polyether that contains a plurality of TEMPO;
(5) be that the polyethers of TEMPO is a free radical scavenger with above-mentioned end group, through free radical
Initiator causes, and styrene polymerization.
11. the many blocks of TEMPO or the preparation method of multi-branch polyether-poly styrene polymer of containing according to claim 10 is characterized in that polymeric reaction temperature is 110～130 ℃, the reaction times is 8～14 hours.
12. the many blocks of TEMPO or the preparation method of multi-branch polyether-poly styrene polymer of containing according to claim 10 is characterized in that the many blocks or many branching PEO-b (the g)-PS structural formula that make are as follows:
And many blocks or many branching PPO-b (g)-PS structural formula are as follows:
Wherein T is
K=0～5, l=10～200, m=10～200, n=10～200, x=5～100, y=5～100.
13. the preparation method who contains the polyether-polystyrene polymkeric substance of the many blocks of several TEMPO or many branching according to claim 12 is characterized in that k=1 in the structural formula～3, l=20～100, m=20～100, n=20～100, x=20～40, y=2040.
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| US7795347B2 (en) * | 2003-03-14 | 2010-09-14 | Mitsui Chemicals, Inc. | Multi-branched polymer, process for producing the same, and applications thereof |
| EP1877457B1 (en) * | 2005-05-03 | 2009-08-12 | Basf Se | Method of producing comb block-copolymers from epoxy-functionalized nitroxylethers and anionically polymerizable monomers |
| CN103030755B (en) * | 2013-01-18 | 2015-04-22 | 复旦大学 | Method for synthesizing block polymers by reversible addition-fragmentation chain transfer free radical polymerization |
| CN105153354B (en) * | 2015-10-18 | 2017-07-11 | 长春工业大学 | A kind of preparation method of hyper branched polymer |
| CN109575271A (en) * | 2018-06-23 | 2019-04-05 | 埃得新材料有限公司 | A kind of preparation method of smooth stabilized polyphenylene ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5610249A (en) * | 1995-01-24 | 1997-03-11 | Kansai Paint Co., Ltd. | Process for production of styrene or styrene derivative polymer of narrow molecular weight distrubition |
| CN1198750A (en) * | 1996-06-04 | 1998-11-11 | 埃勒夫阿托化学有限公司 | Method for preparing telechelic 1,3-diene oligomers by the controlled free radical polymerization of 1,3-dienes in presence of a stable free radical |
| CN1244547A (en) * | 1999-08-10 | 2000-02-16 | 复旦大学 | Polyether containing several TEMPO radicals and its preparation |
| CN1344547A (en) * | 2001-06-12 | 2002-04-17 | 衣宣凯 | Multieffect stomach-invigorating bolus |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5610249A (en) * | 1995-01-24 | 1997-03-11 | Kansai Paint Co., Ltd. | Process for production of styrene or styrene derivative polymer of narrow molecular weight distrubition |
| CN1198750A (en) * | 1996-06-04 | 1998-11-11 | 埃勒夫阿托化学有限公司 | Method for preparing telechelic 1,3-diene oligomers by the controlled free radical polymerization of 1,3-dienes in presence of a stable free radical |
| CN1244547A (en) * | 1999-08-10 | 2000-02-16 | 复旦大学 | Polyether containing several TEMPO radicals and its preparation |
| CN1344547A (en) * | 2001-06-12 | 2002-04-17 | 衣宣凯 | Multieffect stomach-invigorating bolus |
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