CN101070367B - Method for preparing block copolymer containing polyvinylpyridine in non-polarized solution - Google Patents
Method for preparing block copolymer containing polyvinylpyridine in non-polarized solution Download PDFInfo
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- CN101070367B CN101070367B CN2007100995908A CN200710099590A CN101070367B CN 101070367 B CN101070367 B CN 101070367B CN 2007100995908 A CN2007100995908 A CN 2007100995908A CN 200710099590 A CN200710099590 A CN 200710099590A CN 101070367 B CN101070367 B CN 101070367B
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Abstract
The invention relates to a method of preparing block copolymers comprising p-vinyl pyridines in nonpolar solvents, which relates to the field of macromolecular compound composition. The method uses negative ion polymerization to prepare block copolymers comprising polar monomer vinyl pyridine polymer chain, in non-polar solvents, such as cyclohexane, etc. The polymeric process has two steps of feeding raw materials, i.e. firstly, organolithium is used to initiate the polymerization of non-polar monomers, such as styrene, butadiene, isoprene, etc., and then alkyl aluminum, alkyl magnesium, etc. is used to reduce the activity of the polymer, and finally, vinyl pyridine monomer is fed to polymerize. The polymeric method is negative ion dispersion polymerization, and its products are microspheres formed by diblock copolymers. The polymer has broad uses, such as material surface modification, high-molecular material compatilizer. Moreover, the microsphere could be a new kind of reinforcing filler.
Description
Technical field
The present invention relates to macromolecular compound synthetic field, particularly anionic polymerization method.
Background technology
Anionic polymerization is the good method of preparation segmented copolymer.The anionic polymerization control techniques of non-polar monomer such as vinylbenzene, divinyl, isoprene etc. is very ripe, and has multiple segmented copolymer product to emerge.At present, the amphiphilic segmented copolymer of polar-nonpolar has Application Areas widely.But it is bigger to adopt the preparation of anionic polymerization method to contain polar block multipolymer difficulty, and this is because the anionic polymerization requirement condition of polar monomer is harsher.It is quite fast to show as polymerization velocity like the anionic polymerization of vinyl pyridine, is difficult to control, and has side reaction.In addition, the polymkeric substance of vinyl pyridine is insoluble to non-polar solvents such as hexanaphthene.So adopt the anionic polymerization preparation to contain the segmented copolymer of polyvinylpyridine, its reaction is mainly carried out in polar solvent.Robert
etc. 9: 1 must/THF in preparation contain the segmented copolymer (macromolecules of poly 4 vinyl pyridine; 1997; 30 (1), 5596).Sometimes in order to reduce side reaction, also need, and must adopt ' attaching the names of pre-determined candidates ' technology (polymer, 1998,39 (12), 2615) in lesser temps reaction (as-78 ℃).Some researchists attempt in non-polar solvent, realizing 2-vinyl pyridine anionic polymerization, but selected solvent mainly contains (macromolecules, 2001,34,1192) such as benzene, toluene.These solvent toxicity are big, in industry, use and have any problem.We adopt the mode that reduces initiating activity through organometallic compound, in hexanaphthene, hexane, have realized containing the preparation of the segmented copolymer of polyvinylpyridine, and this compound method is a kind of negative ion dispersion polymerization, and polymerization process directly forms polymer microballoon.
Amphiphilic segmented copolymer is one type of broad-spectrum material, like modification of the compatilizer between the various polymerization thing, material surface etc.Amphiphilic polymkeric substance has selectivity to solvent, therefore can carry out self-assembly, forms type material.In addition, we directly form micro-sphere structure at the preparation process, and skin is an elastomeric material, and inner polyvinylpyridine second-order transition temperature is a kind of potential elastomeric material strengthening agent than higher.
Summary of the invention
The objective of the invention is to be implemented in the segmented copolymer for preparing non-polar monomer and vinyl pyridine in the non-polar solvent, and form hud typed Nano microsphere.
The present invention is in drying, anaerobic, is equipped with and adds initiator and monomer in the reaction vessel of organic solvent and carry out polymerization at a certain temperature and realize.
The invention provides in a kind of non-polar solvent the segmented copolymer method that preparation contains polyvinylpyridine, it is characterized in that, may further comprise the steps:
1) in organic solvent, adds organolithium and cause non-polar monomer polymerization, 50 ℃-90 ℃ of polymerization temperatures, polymerization time 0.5-4 hour; Wherein: organolithium is lithium alkylide or phenyl lithium or benzyl lithium or allyl group lithium; Non-polar monomer has vinylbenzene, divinyl, isoprene;
2) add additive aluminum alkyls or alkyl magnesium, stirred 1-10 minute;
3) add the polar monomer vinyl pyridine 20 ℃-50 ℃ polymerization 10-40 minute, obtain the polar-nonpolar di-block copolymer.
The polar monomer vinyl pyridine has 4-vinylpridine and 2-vinyl pyridine, and polar monomer concentration is 3～21%wt; Organic solvent is hexanaphthene, hexane or the mixture of the two.
Initiator of the present invention is lithium alkylide, phenyl lithium, benzyl lithium, allyl group lithium etc., and consumption is the per 100 gram monomer total amounts of 0.5-15mmol.Use different organolithium (RLi), non-polar monomer and vinyl pyridine, can polymerize the segmented copolymer of different molecular weight and MWD.
Non-polar monomer of the present invention is vinylbenzene, divinyl, isoprene, and polar monomer is 4-vinylpridine, 2-vinyl pyridine.Wherein, polar monomer accounts for the 70%-5%wt of monomer total amount.
The additive that the present invention adopts is aluminum alkyls or alkyl magnesium, is preferably triethyl aluminum, di-n-butyl magnesium, triisobutyl aluminium etc., and the mol ratio of itself and initiator is 0.2-2.0, is preferably 0.5-1.2.
This system is a solution polymerization system, and solvent comprises that hexanaphthene, normal hexane reach by the mixed solvent of these two kinds of solvent compositions.The concentration of polar monomer is 5-30%wt.
Effect of the present invention: the present invention adopts the mode of adding aluminum alkyls or alkyl magnesium to reduce initiating activity; Realized in non-polar solvent control to the vinyl pyridine anionic polymerization; Synthesize the nonpolar di-block copolymer of polarity; Its aggregate is the core-shell type nano microballoon, and microsphere diameter is at 20-1000nm.
Embodiment
Technological process of the present invention is that example is summarized as follows with isoprene and 4-vinylpridine: at first adopt n-Butyl Lithium to cause isoprene polymerization in hexanaphthene, 50 ℃-90 ℃ of polymerization temperatures; Add aluminum alkyls after polymerization is accomplished, add 4-vinylpridine then 20 ℃ of-50 ℃ of polymerizations.Stop with ethanol at last.Get TR 301-poly 4 vinyl pyridine segmented copolymer through post precipitation vacuum-drying, its state of aggregation is the outer TR 301 shell that is, inner Nano microsphere for poly 4 vinyl pyridine nuclear.
The use gel permeation chromatograph is analyzed the Mn and the MWD of polymer samples, and nucleus magnetic resonance (NMR) characterizes the monomer ratio and the microtexture of polymer samples.Sample is dissolved in organic solvent, can adopts laser particle size analyzer its particle diameter of test and distribution thereof.
Following instance supplies to further specify the usefulness of method of the present invention, but should not be so limited.
Instance 1: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 50ml hexanaphthene, 5 gram isoprene 0.2mmol n-Butyl Lithiums add the 0.2mmol triethyl aluminum then and stirred 5 minutes 60 ℃ of following polymerizations two hours, add 2 gram 4-vinylpridines at last 30 ℃ of following polymerizations 40 hours.It is blood red transparent that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 3.5 ten thousand, MWD 1.2, monomer conversion 99.8%.
Instance 2: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 250ml, add the 140ml hexanaphthene, 5 gram divinyl 0.035mmol n-Butyl Lithiums add the 0.07mmol triethyl aluminum then and stirred 1 minute 60 ℃ of following polymerizations two hours, add 2 gram 4-vinylpridine polymerizations 40 minutes at last.It is blood red that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 200,000, MWD 1.3, monomer conversion 99.2%.
Instance 3: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 25ml hexanaphthene, 5 gram vinylbenzene 1.5mmol n-Butyl Lithiums polymerization half a hour under 60 ℃ of temperature add the 1.2mmol triethyl aluminum then and stirred 10 minutes, add 5 gram 4-vinylpridine polymerizations 40 minutes at last.It is blood red that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 0.7 ten thousand, MWD 1.38, monomer conversion 100%.
Instance 4: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 50ml hexanaphthene, the polymerization two hours under 60 ℃ of temperature of 2.1 gram isoprene 0.2mmol n-Butyl Lithiums adds 0.4mmol di-n-butyl magnesium then and stirred 10 minutes, adds 4.9 gram 4-vinylpridine polymerizations 40 minutes at last.It is blood red transparent that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 3.2 ten thousand, MWD 1.2, monomer conversion 98.6%.
Instance 5: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 60ml hexanaphthene, the polymerization two hours under 60 ℃ of temperature of 5.7 gram isoprene 0.2mmol n-Butyl Lithiums adds the 0.2mmol triisobutyl aluminium then and stirred 5 minutes, adds 0.3 gram 4-vinylpridine polymerization 10 minutes at last.It is blood red transparent that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 3.0 ten thousand, MWD 1.2, monomer conversion 99.9%.
Instance 6: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 250ml, add the 100ml hexanaphthene, the polymerization two hours under 60 ℃ of temperature of 5 gram vinylbenzene 0.3mmol n-Butyl Lithiums adds the 0.2mmol triethyl aluminum then and stirred 5 minutes, adds 10 gram 4-vinylpridine polymerizations 40 minutes at last.It is blood red that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 5.0 ten thousand, MWD 1.30 monomer conversions 99.8%.
Instance 7: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 50ml hexanaphthene, the polymerization two hours under 60 ℃ of temperature of 5 gram isoprene 0.2mmol n-Butyl Lithiums adds the 0.2mmol triethyl aluminum then and stirred 5 minutes, adds 2 gram 4-vinylpridine polyase 13s at last 0 minute.It is blood red transparent that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 3.5 ten thousand, MWD 1.15, monomer conversion 99.6%.
Instance 8: used glass reaction container in baking oven under 120 ℃ of conditions more than the baking 4h, before the reaction container vacuumize-toast-fill nitrogen, three times repeatedly, polyreaction is carried out in nitrogen atmosphere.Get the polymerization bottle of a 100ml, add the 50ml hexane, the polymerization two hours under 60 ℃ of temperature of 5 gram isoprene 0.2mmol n-Butyl Lithiums adds 0.2mmol di-n-butyl magnesium then and stirred 5 minutes, adds 2 gram 4-vinylpridine polyase 13s at last 0 minute.It is blood red transparent that polymeric solution is.Stop with small amount of methanol, a large amount of ethanol sedimentations, vacuum-drying gets polymkeric substance in order to test.The molecular weight Mn that records resulting polymers is 3.5 ten thousand, MWD 1.2, monomer conversion 99.7%.
Claims (4)
1. preparation contains the method for the segmented copolymer of polyvinylpyridine in the non-polar solvent, it is characterized in that, may further comprise the steps:
1) in non-polar organic solvent, adds organolithium and cause non-polar monomer polymerization, 50 ℃-90 ℃ of polymerization temperatures, polymerization time 0.5-4 hour; Wherein: organolithium is lithium alkylide or phenyl lithium or benzyl lithium or allyl group lithium, and consumption is the per 100 gram monomer total amounts of 0.5-15mmol; Non-polar monomer has vinylbenzene, divinyl or isoprene;
2) add additive aluminum alkyls or alkyl magnesium, stirred 1-10 minute;
3) add the polar monomer vinyl pyridine 20 ℃-50 ℃ polymerization 10-40 minute, polar monomer concentration is 3%～21%wt; Obtain the polar-nonpolar di-block copolymer;
Wherein polar monomer accounts for the 70%-5%wt of monomer total amount, and the concentration of polar monomer is 5-30%wt.
2. preparation contains the method for the segmented copolymer of polyvinylpyridine in a kind of non-polar solvent according to claim 1, and it is characterized in that: the polar monomer vinyl pyridine has 4-vinylpridine and 2-vinyl pyridine.
3. preparation contains the method for the segmented copolymer of polyvinylpyridine in a kind of non-polar solvent according to claim 1, and it is characterized in that: non-polar organic solvent is hexanaphthene, hexane or the mixture of the two.
4. preparation contains the method for segmented copolymer of polyvinylpyridine in a kind of non-polar solvent according to claim 1, and it is characterized in that: additive is triethyl aluminum, di-n-butyl magnesium, triisobutyl aluminium, and the mol ratio of itself and initiator is 0.2-2.0.
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| CN2007100995908A CN101070367B (en) | 2007-05-25 | 2007-05-25 | Method for preparing block copolymer containing polyvinylpyridine in non-polarized solution |
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