CN100347220C - Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same - Google Patents
Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same Download PDFInfo
- Publication number
- CN100347220C CN100347220C CNB200610031223XA CN200610031223A CN100347220C CN 100347220 C CN100347220 C CN 100347220C CN B200610031223X A CNB200610031223X A CN B200610031223XA CN 200610031223 A CN200610031223 A CN 200610031223A CN 100347220 C CN100347220 C CN 100347220C
- Authority
- CN
- China
- Prior art keywords
- novel composite
- preparation
- composite initiator
- initiator
- iodine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyethers (AREA)
Abstract
The present invention discloses a method for preparing a novel combined initiator and initiating the copolymerization of epoxy compounds and cyclic ether and the homopolymerization of epoxy compounds. The copolymerization of epoxy compounds and cyclic ether, and the homopolymerization of epoxy compounds are initiated by the present invention using the combined initiator of hydrocarbyl lithium and an iodine onium salt. The polymerization speed of the present invention is rapid as compared with polymerization speed by using single hydrocarbyl lithium or a single iodine onium salt as an initiator. An initiation system has the advantages of favorable initiation effect, simple preparation, etc.
Description
Technical field
The present invention relates to a kind of initiator of polyreaction and application thereof.
Background technology
Because oxygen or sulphur atom give polyethers very big kindliness on the macromolecular main chain, so polyethers has elastic behavior.This elastic behavior makes the polymkeric substance of cyclic ether monomers homopolymerization or copolymerization gained such as polyethers and polyether glycol at aspect of performance many unique distinctions be arranged, and is used widely in real life.For example epoxypropane polymer or propylene oxide and ethylene oxide copolymer are the main productss of present polyether glycol; Polyethers is to contain [C-O-C-] in the macromolecular chain
nThe polymkeric substance of ehter bond is a main raw material by oxyethane (EO), propylene oxide (PO), butylene oxide ring (BO) or tetrahydrofuran (THF) etc. usually, open loop homopolymerization or copolymerization and make.Polyethers has the dual performance of high molecular characteristic and tensio-active agent concurrently as polymeric surface active agent.Tetrahydrofuran (THF)-propylene oxide copolymerization glycol is that ring-opening polymerization under the katalysis of lewis acid makes by tetrahydrofuran (THF) and propylene oxide, and this polymkeric substance is specially adapted to make low temperature resistant polyurethane material (resist cold and can reach-200 ℃).
Two kinds of methods that obtain polyethers or polyether glycol are arranged: a kind of is the cationoid polymerisation that cationic initiator causes, and another kind is the anionoid polymerization that anionic initiator causes.
Common common hot cationic initiator has protonic acid such as oleum, fluosulfonic acid in the cyclic ether monomers polymerization; Lewis acid such as BF
3, SnCl
4, SbCl
5Deng and various salt such as quaternary ammonium salt, pyridinium salt, trityl hexafluoro antimonate.Patent U.S.Pat.No.3 for example, 712,930 have provided with oleum as the Preparation of Catalyst polyether glycol, but the molecular weight of products obtained therefrom is lower than 1000.Patent U.S.2,751,419, U.S.5,393,866 and JP 52-32799 provide with fluosulfonic acid and cause method prepare polyether glycol, but the further hydrolysis of these method needs just can obtain polyether glycol, and fluosulfonic acid costs an arm and a leg, and produces a large amount of spent acid.Patent U.S.Pat.No.5,149,862 have provided use ZrO etc. and as the Preparation of Catalyst polyether glycol, but speed of reaction is slow, needs to add acetic acid/acetic anhydride and comes accelerated reaction.Patent U.S.4,120,903 use Nafion.RTM.resin to make catalyzer, but resins is difficult for and unstable properties.Patent EP-A-286454 adopts Lewis acid or protonic acid to make initiator, as antimony pentachloride, and trifluoromethanesulfonic acid, patent JP 45-13940; Adopt perchloric acid-diacetyl oxide; Patent WP52-32797 uses boron trifluoride-diacetyl oxide; But the acidity of these acid is crossed strong excessive to the corrodibility of equipment.Patent JP 63-30931, JP 63-30932, U.S.4,568,775 and US 4,658,065 use heteropolyacid to make polyether glycol, but the solubility property of heteropolyacid in organism is poor, the aftertreatment complexity.
Except hot cationic initiator, also have the light cationic initiator, this class initiator mainly contains salt compounded of iodine and sulfosalt.Salt compounded of iodine and sulfosalt take place to decompose rapidly under UV-irradiation, produce positively charged ion, initiation reaction.This light-initiated cationoid polymerisation can cause under UV-irradiation under low temperature or the normal temperature fast, but needs specific equipment.
Salt compounded of iodine is the cationoid type initiator that the James.V.Crievello by the U.S. invented in later 1970s.In general, salt compounded of iodine can only be used as cationic photoinitiator, and seldom as cationic thermal initiator, its reason may be because its better heat stability is difficult to decompose.
In the cyclic ethers anionoid polymerization, generally use potassium alcoholate as initiator.In the polymerization of alkene, hydrocarbyl lithium is a kind of good anionic polymerization initiator, but in synthesis of epoxy compounds, hydrocarbyl lithium just can not effectively cause, because can only observe elicitation procedure usually, and not having propagation process, this is because the strong congregation of lithium ion and chain end oxygen causes.
With regard to the present technology of announcing, in cationic polymerization, normally a kind of stopper of anionic species and terminator.So, to the anionicsite in the cationic initiator, require its alkalescence quite a little less than, generally be superpower acid radical anion as PF
6 -, SbF
6 -, BF
4 -...In like manner, in anionic polymerisation, cationic species is a kind of stopper and terminator.So, to the cationic moiety in the anionic initiator, require its acidity quite a little less than, generally all be alkali metal cation.Therefore anionic initiator and cationic initiator generally can not occur in same system.As for cationic polymerization, the moieties of hydrocarbyl lithium is an anionic species, and normally a kind of stopper of anionic species and chain terminator.In like manner, for general anionic polymerisation, salt compounded of iodine is a cationic species, also is a kind of stopper and chain terminator.
Summary of the invention
The purpose of this invention is to provide the polymerization of cyclic ethers initiator that has very fast polymerization velocity under a kind of moderate temperature.
The objective of the invention is to realize in the following way: in the preparation of novel composite initiator, salt compounded of iodine is dissolved in organic solvent, combines with hydrocarbyl lithium solution then, and the mol ratio of salt compounded of iodine and hydrocarbyl lithium is more than or equal to 1;
Wherein the salt compounded of iodine general formula is:
Ar
1-I
+-Ar
2X
- (I)
In the formula:
Ar
1, Ar
2Be the aromatic nucleus of aromatic nucleus or replacement, as phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring etc., or the phenyl ring of its replacement, naphthalene nucleus, anthracene nucleus, phenanthrene ring etc.;
X
-Be the super acids radical ion, as: PF
6 -, SbF
6 -, BF
4 -, AsF
6 -Deng;
The general formula of hydrocarbyl lithium is:
R-Li (II)
In the formula:
R is aromatic hydrocarbyl, alicyclic alkyl or aliphatic alkyl.
Organic solvent is hydro carbons or ether solvent.
-60 ℃ to 100 ℃ and stir under, hydrocarbyl lithium solution is slowly splashed in the iodized salt solution insulated and stirred 2-60 minute then.
The novel composite initiator of this method preparation is used for the copolymerization of epoxy compounds and cyclic ethers and the homopolymerization of epoxy compounds, and its polymeric reaction temperature is between 0-250 ℃.
The present invention has following beneficial effect, in the present invention, selected the combination of salt compounded of iodine cationic initiator and hydrocarbyl lithium anionic initiator dexterously, form a kind of novel initiator system---zwitterion composite initiator, creatively salt compounded of iodine is mixed generating composite initiator with hydrocarbyl lithium with suitable proportion.The preparation method is simple for this initiator, causes effective.This initiator can not only cause monomeric homopolymerization of cyclic ethers class and copolymerization effectively under moderate temperature, and polymerization rate uses salt compounded of iodine more merely or use hydrocarbyl lithium fast merely; And its speed is accelerated with the concentration of hydrocarbyl lithium in the initiator system; The molecular weight of resulting polymers is also satisfactory.
Following example is described further for the present invention, but the present invention is not limited to following example:
Embodiment
Example 1: under inert atmosphere be dissolved in 12ml tetrahydrofuran (THF) to the benzyl diphenyl iodine hexafluorophosphate 1mmol (0.516g), drip the n-Butyl Lithium hexane solution of 0.5mmol (0.2ml 2.5M) then, stirring at room 30 minutes gets xanchromatic composite initiator solution.
Example 2: under inert atmosphere be dissolved in 12ml tetrahydrofuran (THF) to the benzyl diphenyl iodine hexafluorophosphate 1mmol (0.516g), drip the n-Butyl Lithium hexane solution of 0.75mmol (0.3ml 2.5M) then, stirring at room 30 minutes gets xanchromatic composite initiator solution.
Example 3: under inert atmosphere be dissolved in 12ml tetrahydrofuran (THF) to the benzyl diphenyl iodine hexafluorophosphate 1mmol (0.516g), drip the n-Butyl Lithium hexane solution of 1.5mmol (0.6ml 2.5M) then, stirring at room 30 minutes gets xanchromatic composite initiator solution.
Example 4: under inert atmosphere be dissolved in 12ml dioxane to the benzyl diphenyl iodine hexafluorophosphate 1mmol (0.516g), drip the n-Butyl Lithium hexane solution of 0.5mmol (0.2ml 2.5M) then, 40 ℃ were stirred 30 minutes, got xanchromatic composite initiator solution.
Example 5: under inert atmosphere, be dissolved in 1mmol (0.426g) diphenyl iodine hexafluorophosphate in the 12ml tetrahydrofuran (THF), drip the n-Butyl Lithium hexane solution of 0.75mmol (0.3ml 2.5M) then, stirring at room 30 minutes gets xanchromatic composite initiator solution.
Example 6: under inert atmosphere, be dissolved in 1mmol (0.561g) [4-(4-benzyl chloride base)] diphenyl iodine hexafluorophosphate in the 12ml tetrahydrofuran (THF), drip the phenyl lithium solution of 0.75mmol (0.3ml 1.0M) then, stirring at room 30 minutes gets xanchromatic composite initiator solution.
Example 7: under inert atmosphere, be dissolved in 1mmol (0.534g) [4-(3-luorobenzyl)] diphenyl iodine hexafluorophosphate in the 12ml tetrahydrofuran (THF), drip the cyclohexyl lithium solution of 0.5mmol (0.5ml 1.0M) then, the chamber is wet stirred 30 minutes, got xanchromatic composite initiator solution.
Application example:
Example 8: in reaction flask, add 18.7g trityl glycidyl ether and 50ml tetrahydrofuran (THF), inert atmosphere adds down the prepared initiator solution of 6ml example 1, under 80 ℃ of conditions, stirs polymerase 17 hour, resulting polymers, pour in the methyl alcohol centrifugation, drying into, obtain polymkeric substance 25g, it is trityl glycidyl ether and tetrahydrofuran copolymer through nuclear magnetic resonance measuring, and wherein trityl glycidyl ether transformation efficiency reaches 83%, and it is 55000 that GPC measures its weight-average molecular weight.
Example 9: in reaction flask, add 18.7g trityl glycidyl ether and 50ml tetrahydrofuran (THF), inert atmosphere adds down the prepared initiator solution of 6ml example 2, under 80 ℃ of conditions, stirs polymerase 17 hour, resulting polymers, pour in the methyl alcohol centrifugation, drying into, obtain polymkeric substance 31g, it is trityl glycidyl ether and tetrahydrofuran copolymer through nuclear magnetic resonance measuring, and wherein trityl glycidyl ether transformation efficiency reaches 96%, and it is 68000 that GPC measures its weight-average molecular weight.
Example 10: in reaction flask, add 10ml propylene oxide and 10ml tetrahydrofuran (THF), inert atmosphere adds down the prepared initiator solution of 6ml example 2, under 80 ℃ of conditions, stir polymerase 17 hour, resulting polymers, refining, dry, obtain polymkeric substance 11g, it is propylene oxide and tetrahydrofuran copolymer through nuclear magnetic resonance measuring, and it is 32000 that GPC measures its weight-average molecular weight.
Example 11: add 18.7g trityl glycidyl ether and 50ml tetrahydrofuran (THF) in reaction flask, inert atmosphere adds the prepared initiator solution of 6ml example 3 down, under 80 ℃ of conditions, stirs polymerase 17 hour, pours in the methyl alcohol no polymerisate into.
Example 12: in reaction flask, add the 20g phenyl glycidyl ether, inert atmosphere adds down the prepared initiator solution of 6ml example 4, under 100 ℃ of conditions, stir polymerase 17 hour, resulting polymers, refining, dry, obtain polyphenyl glycidyl ether 14g,, it is 18000 that GPC measures its weight-average molecular weight.
Example 13: in reaction flask, add 10ml propylene oxide and 10ml tetrahydrofuran (THF), inert atmosphere adds down the prepared initiator solution of 6ml example 7, under 80 ℃ of conditions, stir polymerase 17 hour, resulting polymers, refining, dry, obtain polymkeric substance 13g, it is propylene oxide and tetrahydrofuran copolymer through nuclear magnetic resonance measuring, and it is 35000 that GPC measures its weight-average molecular weight.
Comparison example
Example 14: in reaction flask, add 10ml propylene oxide and 10ml tetrahydrofuran (THF), the pure cyclohexyl lithium solution of used cyclohexyl lithium lithium equal quantities is made initiator solution in following adding of inert atmosphere and example 7 initiators, under 80 ℃ of conditions, stir polymerase 17 hour, no polymerisate.
Example 15: in reaction flask, add 10ml propylene oxide and 10ml tetrahydrofuran (THF), inert atmosphere add down with example 7 initiators in used [4-(3-luorobenzyl)] diphenyl iodine hexafluorophosphate equal quantities pure [4-(3-luorobenzyl) diphenyl iodine hexafluorophosphate is made initiator, under 80 ℃ of conditions, stir polymerase 17 hour, get polymerisate 2.8g, it is 3700 that GPC measures its weight-average molecular weight.
The present invention obtains National Natural Science Foundation of China (NSFC) and subsidizes and (to subsidize number: 20472069).
Claims (8)
1, a kind of preparation of novel composite initiator is characterized in that, salt compounded of iodine is dissolved in organic solvent, combines with hydrocarbyl lithium solution then, and the mol ratio of salt compounded of iodine and hydrocarbyl lithium is more than or equal to 1.
2, the preparation of a kind of novel composite initiator according to claim 1 is characterized in that: salt compounded of iodine is the diaryl group iodized salt of being described by (I) formula;
Ar
1-I
+-Ar
2X
- (I)
In the formula:
Ar
1, Ar
2Be aromatic group, aryl can have substituting group, also can not have substituting group.
3, the preparation of a kind of novel composite initiator according to claim 1 is characterized in that: hydrocarbyl lithium is the hydrocarbyl lithium of being described by (II) formula
R-Li (II)
R is aromatic hydrocarbyl, alicyclic alkyl or aliphatic alkyl.
4, the preparation of a kind of novel composite initiator according to claim 1 is characterized in that: the anionicsite X of salt compounded of iodine
-It is superpower acid group.
5, the preparation of a kind of novel composite initiator according to claim 1 is characterized in that: organic solvent is hydro carbons or ether solvent.
6, the preparation of a kind of novel composite initiator according to claim 1 is characterized in that :-60 ℃ to 100 ℃ and stir under, hydrocarbyl lithium solution is slowly splashed in the iodized salt solution insulated and stirred 2-60 minute then.
7, cause epoxy compounds and the copolymerization of cyclic ethers and the homopolymerization of epoxy compounds with the described novel composite initiator of claim 1, with synthetic corresponding polymer.
8, according to claim 7, cause epoxy compounds and the copolymerization of cyclic ethers and the homopolymerization of epoxy compounds with the described novel composite initiator of claim 1, with synthetic corresponding polymer, its polymeric reaction temperature is between 0-250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610031223XA CN100347220C (en) | 2006-02-14 | 2006-02-14 | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610031223XA CN100347220C (en) | 2006-02-14 | 2006-02-14 | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844190A CN1844190A (en) | 2006-10-11 |
| CN100347220C true CN100347220C (en) | 2007-11-07 |
Family
ID=37063160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610031223XA Expired - Fee Related CN100347220C (en) | 2006-02-14 | 2006-02-14 | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100347220C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10476105B2 (en) * | 2017-08-18 | 2019-11-12 | GM Global Technology Operations LLC | Self-healing gel-type electrolyte composite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242388A (en) * | 1998-07-17 | 2000-01-26 | 中国科学院化学研究所 | Polysiloxane having silazane structure on its main chain |
| CN1388175A (en) * | 2001-05-25 | 2003-01-01 | 北京航空材料研究院 | Thermoplastic resin modified electron beam cured composite material epoxy resin matrix |
| CN1513884A (en) * | 2002-12-18 | 2004-07-21 | 株式会社德山 | Photopolymerization initiator and composition capable of photopolymerization |
| CN1615115A (en) * | 2002-01-15 | 2005-05-11 | 3M创新有限公司 | Ternary photoinitiator system for cationically polymerizable resins |
-
2006
- 2006-02-14 CN CNB200610031223XA patent/CN100347220C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242388A (en) * | 1998-07-17 | 2000-01-26 | 中国科学院化学研究所 | Polysiloxane having silazane structure on its main chain |
| CN1388175A (en) * | 2001-05-25 | 2003-01-01 | 北京航空材料研究院 | Thermoplastic resin modified electron beam cured composite material epoxy resin matrix |
| CN1615115A (en) * | 2002-01-15 | 2005-05-11 | 3M创新有限公司 | Ternary photoinitiator system for cationically polymerizable resins |
| CN1513884A (en) * | 2002-12-18 | 2004-07-21 | 株式会社德山 | Photopolymerization initiator and composition capable of photopolymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1844190A (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102718945B (en) | Itaconic acid-based epoxy resin composition and method for preparing cured substance | |
| JP3989548B2 (en) | Polymerization of cyclic ethers | |
| CN113105611A (en) | Polymerization method for ring-opening alternating copolymerization of anhydride compound and epoxy compound | |
| CN110283314A (en) | A method of preparing hyperbranched poly thioether | |
| CN102532365B (en) | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof | |
| CN100347220C (en) | Preparation of novel composite initiator and copolymerization of epoxide and cyclic ether and homopolymerization of epoxide initiated by same | |
| US3850857A (en) | Process for the polymerization of epihalohydrin employing a trialkyl oxonium salt of an hmf6 acid as catalyst | |
| CN114437020A (en) | Preparation method of glycolide | |
| CN102351970A (en) | Method for preparing poly-1,3-pentadiene | |
| CN100379789C (en) | Polyether polymer and process for producing the same | |
| CN102432861A (en) | Branched polyether macromonomer and preparation method thereof | |
| CN112126054A (en) | Method for preparing polyalkylene carbonate resin | |
| CN110283279A (en) | Copolymer, preparation method and the rubber composition of 1,3- butadiene and 1- butylene | |
| CN102399308B (en) | Cationic polymerization method | |
| CN101557017A (en) | Full solid state polymer electrolyte used for lithium sulphur battery and preparation thereof | |
| JP2012214792A (en) | Polyether compound composition and electrolyte | |
| CN103044292B (en) | Sulfonated aromatic compound, polyketone with sulfonated aromatic groups and methods for preparing sulfonated aromatic compound and polyketone with sulfonated aromatic groups | |
| CN1166842A (en) | Polyether glycols and alcohols derived from 3,4-epoxy-1-butene, tetrahydrofuran and initiator | |
| CN105295011B (en) | Preparation method of poly alpha-hydroxy acid | |
| CN108456266A (en) | Catalyst for compound stereoscopic regularity polyvinylpyridine and application | |
| CN1194994C (en) | Method for preparing hyperbranched polymers and its preparing method | |
| CN113354804B (en) | Fatty alcohol polyoxypropylene ether oxyacid and salt thereof | |
| CN1276383A (en) | Method for preparing polymer | |
| CN115403984B (en) | Cationic curable composition | |
| CN101607212B (en) | Binary alkyl benzene sulfonic acid rare earth catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071107 Termination date: 20100214 |