CN1412212A - Preparation method of double functionality lithium system initiator - Google Patents
Preparation method of double functionality lithium system initiator Download PDFInfo
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- CN1412212A CN1412212A CN 01136233 CN01136233A CN1412212A CN 1412212 A CN1412212 A CN 1412212A CN 01136233 CN01136233 CN 01136233 CN 01136233 A CN01136233 A CN 01136233A CN 1412212 A CN1412212 A CN 1412212A
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Abstract
In the mixed solvent using non-polar solvent as main component the metal lithium and alpha-methylstyrene or isoprene are reacted to directly prepare bifunctionality anionic oligomer. Its mixed solvent uses arene or paraffine or their mixture as main component, contains ether or amine or both mixture, in which arene and paraffine content is 50-99.9% (valoume) and ether and amine content is 0.1-50% (valume), the conjugated arene and metal lithium are reacted for 1-6 hr. under the condition of -50- -50 deg.C to obtain reactino product, said product is filtered to obtain bifunctionality initiator.
Description
Technical field:
The present invention relates to the preparation method of a kind of negatively charged ion method synthetic polymer with initiator.Preparation especially for the double functionality lithium system initiator of synthetic segmented copolymer or telechelic polymer.
Background technology:
Basic metal and condensed-nuclei aromatics can form homogeneous complex in ether solvent, this complex compound activity is high, can generate the difunctionality anionic initiator with diolefine or styrene monomer reaction, but the formation reaction speed of this complex compound and peak concentration increase and increase according to solvent polarity, so must be prepared and store for solvent as tetrahydrofuran (THF) (THF) and glycol dimethyl ether (DMF) with polar ethers molecule.And a large amount of polar molecules existence will produce following negative impact: 1. conjugated diene polymer side group content is too big, and second-order transition temperature raises, and does not reach the performance requriements of rubber.2. the polar solvent price is more expensive, causes the increase of initiator cost.3. the initiator instability has negative reaction.Above-mentioned reason makes this complex compound not become the initiator with industrial significance so far.
In order to develop qualified double functionality lithium system initiator by complex compound, US3,377,404 and US3,388,178, West German Examin Appl.No.1768188, WestGerman Published Appl.No.1817478 etc. has invented and has at first allowed diolefine (divinyl, isoprene) and naphthalene lithium complex react in ether solvent, aggregates into two lithium oligopolymers of certain-length, then distills metathetical technology with non-polar solvent.According to the rubber performance requirement, the content of anionic polymerization initiator Semi-polarity material is low as far as possible, thus adopt the distillation method of replacement, but but cause the initiator cost to rise simultaneously, and cause the loss of functionality.92110152.X employing non-polar solvent by the applicant's application is that main mixed solvent reacts metallic lithium and condensed-nuclei aromatics, and it is very low-level that polar solvent content is reduced to, and can be adjustable within the specific limits.But this initiator system product is the mixture of lithium complex and high reactivity lithium powder how, and being used for anionoid polymerization needs at first to generate oligopolymer with the conjugated diene reaction, further polymerization then.The shortcoming of this method also is to contain a large amount of deleterious condensed-nuclei aromaticss in the system, causes that finally this compound is also arranged in the polymkeric substance, and is difficult to remove, and causes environmental pollution.US4,075,253 make alpha-methyl styrene and metallic lithium reaction form the pairs of anion of alpha-methyl styrene oligopolymer short chain and the balanced solution of α-Jia Jibenyixidanti in tetrahydrofuran (THF), add monomer reactions such as diolefine then and obtain the neat multipolymer of difunctionality negative ion, at last, carry out the non-polar solvent displacement.Though this method has been got rid of the condensed ring arene compound, complicated distil process becomes the obstacle of its practical application again.
Summary of the invention:
The present invention is directed to the deficiencies in the prior art, the subject matter that solve is: the polar solvent content during control preparation initiator, and do not contain fused ring compound, and make the preparation technology of this initiator simple simultaneously, cost reduces.Thereby propose a kind ofly based on non-polar solvent, metallic lithium and alpha-methyl styrene and/or isoprene direct reaction prepare the method for difunctionality anionic oligomer thing initiator.
The present invention forms mixed solvent based on non-polar solvent C with D, and wherein C is aromatic hydrocarbons or alkane, or both mixing; D is ether or amine, or both is mixed, the content 50～99.9% (volume) of C wherein, D content is 0.1～50% (volume), adding conjugated alkene and metallic lithium reacted 1～6 hour under-50～50 ℃ of temperature in this solvent, wherein the metallic lithium add-on is 0.25～2 with respect to the mol ratio of conjugated alkene, and reactant obtains bifunctional initiator after filtration.
Above-mentioned conjugated alkene comprises α alkyl-substituted styrene (substituting group is the alkyl of n=0～3 carbon atoms) or conjugated diene and both mixtures thereof, and its conjugated diene structural formula can be expressed as: CR
1H=CR
2-CR
3=CR
4H, wherein R
1, R
2, R
3, R
4Be H or CH
3, can be identical or different.
Regulate the content that D content can be controlled polar material in the above-mentioned mixed solvent, wherein C content is preferably 70～99.5% (volumes), and the content of D is preferably 0.5～30% (volume).
In the above-mentioned mixed solvent, alkane contains a kind of hexanaphthene, hexane at least.Aromatic hydrocarbons contains a kind of benzene, toluene at least.
In the above-mentioned mixed solvent, ether, amine compound contain a kind of tetrahydrofuran (THF), ether, dioxane, methyl-phenoxide, triethylamine, Tetramethyl Ethylene Diamine at least.Above-mentioned α substituted phenylethylene contains a kind of vinylbenzene, alpha-methyl styrene, α-ethyl styrene at least.
Above-mentioned conjugated diene contains a kind of divinyl, isoprene, 1,3-pentadiene at least.
The difunctionality lithium initiator of method for preparing is conjugated diene oligomers or conjugated diene and the cinnamic segmented copolymer of alpha-substitution, and structure is LiABALi, and wherein A is a poly-conjugated-diolefin, and B is poly-alpha-substitution vinylbenzene.
Effect of the present invention: the preparation method of initiator of the present invention be metallic lithium and alpha-methyl styrene and (or) isoprene equiconjugate diolefine directly generates the oligopolymer short chain in non-polar solvent is main mixed solvent, therefore:
1, raw material of the present invention for alpha-methyl styrene commonly used and (or) isoprene equiconjugate diolefine, do not contain the material that condensed-nuclei aromatics etc. works the mischief to environment, and its source is abundant, with low cost.Therefore the initiator comprehensive cost of preparation greatly reduces.
2, the present invention realized in based on the mixed solvent of non-polar solvent metallic lithium and alpha-methyl styrene and (or) the isoprene direct reaction prepares oligopolymer, thereby simplified bifunctional initiator preparation technology, guaranteed the initiator functionality.
3, initiator system Semi-polarity substances content is in very large range adjustable, can be lower than 1% of solvent, also can be higher.Therefore, the polydiolefin rubber that this invention initiator can be used for low side group content synthesizes, and has good stability, and speed of response is moderate, the characteristics that are easy to control.Compare with the butyllithium of present industrial employing, because the reaction times of the present invention is short, synthesis temperature is low, and is simple for process.
Based on These characteristics of the present invention, this new lithium series initiators has the bright prospects of industrial application.For example: 1. can adopt this invention initiator to replace butyllithium to simplify the polymerization technique of SBS, SIS etc.2. synthetic polymkeric substance as types such as PMMA-PB-PMMA, thus the performance of raising thermoplastic elastomer satisfies particular requirement.
Bifunctional initiator of the present invention can be used in divinyl, isoprene, vinylbenzene to carry out homopolymerization and copolymerization and obtains corresponding product.
Utilize above-mentioned initiator system can synthesize diolefine and/or styrene monomer is main chain, the distant pawl prepolymer of two ends hydroxyl, carboxyl, halogen, sulfydryl.
Embodiment:
Embodiment 1: in the three-necked bottle of 100ml, put into 50ml toluene and 1ml tetrahydrofuran (THF), add 1g dispersive metallic lithium and 15g alpha-methyl styrene then, 40～50 ℃ of reactions reduced the temperature to below-20 ℃ after half an hour reacts 30min, adds a small amount of isoprene reaction after-filtration half an hour.With determination of acid-basetitration spike concentration is 0.7mol/L.
Get in the 250ml polymerization bottle that above-mentioned initiator 0.9ml is added to 10g divinyl and 100ml cyclohexane solution, 50 ℃ of polymerizations 2 hours, after finishing, polymerization stops with methyl alcohol, and polymer precipitation is separated dry, recording the polyhutadiene relative molecular mass with GPC is 30000, and relative molecular mass is distributed as 1.27.
Embodiment 2
Add 30ml hexanaphthene and 20ml methyl-phenoxide 1mlTHF and 1g metallic lithium at the 100ml Wolff bottle, add then to reduce the temperature to below-20 ℃ after 40～50 ℃ of 15g alpha-methyl styrenes reaction half an hour and react 30min, add a small amount of isoprene reaction after-filtration half an hour.With determination of acid-basetitration spike concentration is 0.7mol/L.
Embodiment 3
In the 100ml three-necked bottle, add 35mlTHF, the 25ml hexanaphthene, 1g disperses lithium, drips isoprene 16ml about 30 ℃ in 2 hours, records the double functionality lithium system initiator that spike concentration is 0.85ml/L after the filtration.
Embodiment 4
The initiator 1.17ml that gets embodiment 3 gained joins in the solution of 30g divinyl 700ml hexanaphthene 50 ℃ of reactions 2 hours, add 20g vinylbenzene 300ml cyclohexane solution then and continue reaction 1 hour, stop reactive polymer, the dry SBS triblock copolymer that gets of precipitate and separate.This polymkeric substance relative molecular mass is 100000, and relative molecular mass is distributed as 1.27, polyhutadiene section 1,2-structural content 30%, tensile strength 16.8Mpa.
Claims (8)
1, a kind of preparation method of double functionality lithium system initiator, react in solvent by conjugated alkene and metallic lithium, it is characterized in that, based on non-polar solvent C, form mixed solvent with D, wherein C is aromatic hydrocarbons or alkane, or both mixing, D is ether or amine, or both is mixed, wherein the content 50～99.9% (volume) of C, D content is 0.1～50% (volume), in this solvent, add conjugated alkene and metallic lithium and under-50～50 ℃ of temperature, reacted 1～6 hour, wherein the metallic lithium add-on with respect to mol ratio be 0.25～2, reactant obtains bifunctional initiator after filtration.
2, preparation method according to claim 1, it is characterized in that conjugated alkene comprises α alkyl-substituted styrene or conjugated diene, or both mixtures, wherein α alkyl-substituted styrene substituting group is the alkyl of n=0～3 carbon atoms, and the conjugated diene structural formula can be expressed as: CR
1H=CR
2-CR
3=CR
4H, wherein R
1, R
2, R
3, R
4Be H or CH
3
3, preparation method according to claim 1 is characterized in that, C content is 70～99.5% (volumes) in the mixed solvent, and the content of D is 0.5～30% (volume).
4, preparation method according to claim 1 is characterized in that, contains following a kind of alkane in the mixed solvent at least: hexanaphthene, hexane.
5, preparation method according to claim 1 is characterized in that, contains following a kind of aromatic hydrocarbons in the mixed solvent at least: benzene, toluene.
6, preparation method according to claim 1 is characterized in that, in the mixed solvent, ether, amine compound contain a kind of of following compound at least: tetrahydrofuran (THF), ether, dioxane, methyl-phenoxide, triethylamine, Tetramethyl Ethylene Diamine.Above-mentioned α substituted phenylethylene contains a kind of vinylbenzene, alpha-methyl styrene, α-ethyl styrene at least.
7, preparation method according to claim 1 is characterized in that, conjugated diene contains a kind of divinyl, isoprene, 1,3-pentadiene at least.
8, preparation method according to claim 1, it is characterized in that the double functionality lithium system initiator of preparation is conjugated diene oligomers or conjugated diene and the cinnamic segmented copolymer of alpha-substitution, structure is LiABALi, wherein A is a poly-conjugated-diolefin, and B is poly-alpha-substitution vinylbenzene.
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| CN 01136233 CN1131253C (en) | 2001-10-11 | 2001-10-11 | Preparation method of double functionality lithium system initiator |
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| CN 01136233 CN1131253C (en) | 2001-10-11 | 2001-10-11 | Preparation method of double functionality lithium system initiator |
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| CN1131253C CN1131253C (en) | 2003-12-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294119C (en) * | 2005-10-18 | 2007-01-10 | 大庆油田有限责任公司 | Method for synthesizing bifunctionality initiator DIOOH |
| CN100339366C (en) * | 2005-10-18 | 2007-09-26 | 大庆油田有限责任公司 | Synthesis of di-functionality initiator 2,5-MONO |
| CN100371356C (en) * | 2006-06-23 | 2008-02-27 | 北京化工大学 | Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate |
| CN101045756B (en) * | 2006-03-30 | 2011-01-12 | 北京化工大学 | Preparation method of multifunction organic metal initiator for anionic polymerization |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102065130B1 (en) * | 2016-01-25 | 2020-01-10 | 주식회사 엘지화학 | Novel lithium compound and preparation method thereof |
-
2001
- 2001-10-11 CN CN 01136233 patent/CN1131253C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294119C (en) * | 2005-10-18 | 2007-01-10 | 大庆油田有限责任公司 | Method for synthesizing bifunctionality initiator DIOOH |
| CN100339366C (en) * | 2005-10-18 | 2007-09-26 | 大庆油田有限责任公司 | Synthesis of di-functionality initiator 2,5-MONO |
| CN101045756B (en) * | 2006-03-30 | 2011-01-12 | 北京化工大学 | Preparation method of multifunction organic metal initiator for anionic polymerization |
| CN100371356C (en) * | 2006-06-23 | 2008-02-27 | 北京化工大学 | Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate |
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|---|---|
| CN1131253C (en) | 2003-12-17 |
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