CN106632909B - A method of reducing polystyrene melt viscosity - Google Patents
A method of reducing polystyrene melt viscosity Download PDFInfo
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- CN106632909B CN106632909B CN201610907364.7A CN201610907364A CN106632909B CN 106632909 B CN106632909 B CN 106632909B CN 201610907364 A CN201610907364 A CN 201610907364A CN 106632909 B CN106632909 B CN 106632909B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08L25/04—Homopolymers or copolymers of styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
A method of polystyrene melt viscosity is reduced, chemical industry and field of material technology are belonged to.First by electrostatic interaction, the cationic chain transfer agents containing three thioester groups are modified on multi-metal oxygen cluster surface, multi-metal oxygen cluster compound is obtained；In turn, it by reversible addion-fragmentation chain transfer polymerization reaction, by polystyrene graft to the periphery of above-mentioned compound, obtains using multi-metal oxygen cluster as core, using polymer as the star-type polymer of arm；Finally, being combined in polystyrene matrix using star-type polymer as nanofiller by solution blended process, the reduction of melt viscosity is realized.The principle of this method is the compatibility by multi-metal oxygen cluster surface polymer chain and polystyrene matrix, and star-type polymer is introduced polystyrene entanglement network, promotes polystyrene chain that disentanglement occurs in a shear condition, to reduce polystyrene melt viscosity.This method can be effectively reduced polystyrene melt and be switched to 10 from zero in shear rate5rad·S‑1Under the conditions of viscosity.
Description
Technical field
The invention belongs to chemical industry and field of material technology, and in particular to a kind of using multi-metal oxygen cluster as the star-type polymer of core
The method for promoting polystyrene chain that disentanglement occurs as nanofiller and reducing its melt viscosity.
Background technique
Polymer material includes plastics, rubber, fiber, coating etc., has become the development of the national economy and the daily life of the people
Essential important materials in work.Polymer material needs to obtain required shape, structure and property by machine-shaping
Can, become product with practical value.Common forming method has extrusion, injection molding, calendering etc., and realizing these processes is to pass through
What the flowing of polymer melt was completed.Therefore, polymer melt viscosity is most important to its processing conditions is designed, and viscosity reduction has
Help flowing and filling of the polymer melt in mold cavity.
Polystyrene is a kind of thermoplastic polymer, since its is cheap and has excellent insulation, insulation and transparent
Property, be widely applied.For the melt viscosity for reducing polystyrene and improve its processing performance, researcher has carried out not
Same trial.The common method of industry is to soften plasticizer using small molecule to reduce the interaction of polystyrene interchain, from
And improve its fluidity of molten.In recent years, the nanometer that size is less than polymeric matrix mean square radius of gyration is filled out in researcher's discovery
Expect (also referred to as extra small nanofiller), after being combined to polymeric matrix by method appropriate, can play reduces matrix melt
The effect of viscosity.Its mechanism promotees mainly since these extra small nanofillers are able to enter in the entanglement network of polymer chain
Make polymer chain that disentanglement occur under the conditions of external shearing, so as to cause the decline of polymer melt viscosity.It is basic herein
On, researcher has developed different types of nanofiller to reduce the melt viscosity of polystyrene, the polystyrene including crosslinking
The Fe of bead (A.Tuteja, M.E.Mackay, Macromolecules.2005,38,8000), oleic acid modified3O4Nanoparticle
(A.Tuteja, P.M.Duxbury, M.E.Mackay, Macromolecules.2007,40,9427) etc..The study found that passing through
Extra small nanofiller is composite modified to be expected to become a kind of promising new method for reducing polymer melt viscosity.However, at present
The research in the field is badly in need of the extra small nanofiller system that development has independent intellectual property right also in the initial stage.
Summary of the invention
It is reduced by the star-type polymer of core of multi-metal oxygen cluster as nanofiller the object of the present invention is to provide a kind of
The method of polystyrene melt viscosity.This method can be effectively reduced the zero-shear viscosity of polystyrene melt, and it is poly- to can be used as improvement
Styrene processing conditions provides new way.
In the present invention, it a kind of is filled out using multi-metal oxygen cluster as the star-type polymer of core as extra small nanometer it is proposed that using
Material, is combined in polystyrene matrix by the method for solution blending, so that realizing reduces polystyrene melt viscosity
Method.Multi-metal oxygen cluster is the inorganic cluster compound of unimolecule being formed by connecting by early transition metal atom by oxygen atom ligand,
Aperture can change in range from 0.5nm to 5nm, the skeleton structure with chemical constituent abundant and form of diverse.
The present invention is achieved by the following technical solutions：Firstly, three thioester groups will be contained by electrostatic interaction
Cationic chain transfer agents modify on multi-metal oxygen cluster surface, obtain multi-metal oxygen cluster compound；In turn, added by reversible
At-fracture chain transfer polymerization reaction, by polystyrene graft to the periphery of above-mentioned compound, obtain using multi-metal oxygen cluster as core,
Using polymer as the star-type polymer of arm；Finally, using star-type polymer as nanofiller, it is by solution blended process that its is compound
Into polystyrene matrix, the reduction of melt viscosity is realized.The principle of this method is by multi-metal oxygen cluster surface polymer chain
With the compatibility of polystyrene matrix, star-type polymer is introduced into polystyrene entanglement network, polystyrene chain is promoted to shear
Under the conditions of disentanglement occurs, to reduce polystyrene melt viscosity.This method can be effectively reduced polystyrene melt and cut
Cutting speed rate is switched to 10 from zero5rad·S-1Under the conditions of viscosity, be expected to be applied to polystyrene manufacture field.
The present invention includes following technology segment：(1) preparation of cationic chain transfer agents；(2) multi-metal oxygen cluster compound
Preparation；(3) preparation of star-type polymer；(4) star-type polymer and polystyrene is compound and viscosity modified.
1, the preparation of cationic chain transfer agents
3~5g of n-butyl mercaptan and 3~6g of triethylamine is taken to be dissolved in 50~200mL methylene chloride, in ice-water bath and nitrogen
Under protective condition, 3~5g of carbon disulfide is taken to be add to the above mixed solution, 20~30min is stirred under the conditions of ice-water bath, takes 2-
5~9g of bromo-propionic acid is added in above-mentioned solution, stirs 3~5h at room temperature；Product is re-dissolved in just after rotary evaporation removes solvent
In pentane, crude product is dissolved in pentane after rotary evaporation removes solvent, and the mass fraction for adding 150~250mL is
Then 10%~20% hydrochloric acid acidification is washed to neutrality with secondary, crude product is in petroleum ether after rotary evaporation removes solvent
Recrystallization, obtains pure product A；
11- 1~3g of bromo- 1- undecyl alcohol is taken, dissolution in ethanol, takes 1~3g of tri-n-octyl amine, is added to the bromo- 1- 11 of 11-
It in the ethanol solution of alcohol, is condensed back under the conditions of 70~80 DEG C of oil bath, 48~72h is reacted, after rotary evaporation removes solvent
Crude product recrystallizes in ether, and pure product B can be obtained；
Take 1~3g product A and 2~9g product B co-dissolve in the methylene chloride of 50~200mL, in the item of ice-water bath
20~30min is stirred under part, the dicyclohexylcarbodiimide of 1~4g is added into the solution, stirs 20~30min；Take 4- bis-
30~60mg of methylamino pyridine is added in the reaction system, is stirred 20~30min, is removed ice-water bath, stirred at room temperature to molten
Liquid color is glassy yellow stopping；It is filtered to remove precipitating, column chromatography for separation obtains pure cationic chain transfer agents, structural formula
As follows：
Specific example is referring to embodiment 1.
2, the preparation of multi-metal oxygen cluster compound
Multi-metal oxygen cluster K6CoW12O40According to document synthesis (C.W.B.Louis, P.M.Thomas,
J.Am.Chem.Soc.1956,78,4503)。
Cationic chain transfer agents prepared in step 1 are dissolved in the chloroform of 50~100mL, concentration 2
~4mg/mL；Multi-metal oxygen cluster is dissolved in 50~100mL secondary water, concentration is 1.5~3mg/mL；In violent stirring bar
Under part, the chloroform soln of cationic chain transfer agents is added in the aqueous solution of multi-metal oxygen cluster, cationic chain tra nsfer
The molar ratio of reagent and multi-metal oxygen cluster is 5~5.8：1, it is ensured that cationic chain transfer agents are totally consumed in reaction process；
After stirring 0.5~2h, stop reaction, stratification, organic phase, to neutrality, is taken out organic phase, led to secondary water washing 3~5 times
Rotation evaporation of solvent is crossed to get pure multi-metal oxygen cluster compound is arrived.
Specific example is referring to embodiment 2-1.
3, the preparation of star-type polymer
Multi-metal oxygen cluster compound 0.2g prepared in step 2 is taken, styrene 1~6mL and N, N- dimethyl formyl are taken
2~2.5mL of amine is uniformly mixed, and is completely dissolved multi-metal oxygen cluster compound with the mixed solution, is then added to 2~6mg azo
In bis-isobutyronitrile, it is uniformly mixed；In confined conditions, above-mentioned reaction system is carried out freezing-vacuumizing-inflated with nitrogen operation, instead
It is 3~5 times multiple, the air in reaction system is replaced into nitrogen completely；Then under the conditions of nitrogen protection, oil bath heating to 65~
75 DEG C, reaction 8~for 24 hours；After reaction, it is cooled down rapidly in liquid nitrogen, terminates reaction, while removing nitrogen protection, will slightly produce
Object is precipitated in 100~200mL methanol, and product washs 3~5 times with methanol after centrifugation, then in anhydrous ether repeatedly
3~5 times are precipitated to get pure star-type polymer is arrived.
Specific example is referring to embodiment 3-1,3-2,3-3.
4, star-type polymer and polystyrene is compound and viscosity modified
1~40mg of star-type polymer prepared in step 3 is taken, the chloroform of 0.2~0.5mL is dissolved completely in
In；Polystyrene (molecular weight is 80000~400000) 50mg is taken, is dissolved completely in the chloroform of 0.5~1mL；
The chloroform soln of star-type polymer is added dropwise in the chloroform soln of polystyrene, 0.5~2h of stirring is continued,
It is uniformly mixed it；Mixed solution is laid on polyimide substrate, under room temperature condition and chloroform atmosphere, makes solvent
Slowly volatilization 48~72h formed laminated film, then be placed in vacuum oven completely remove solvent to get to star-type polymer with
The composite material of polystyrene, to realize the reduction of polystyrene matrix melt viscosity.
Specific example is referring to embodiment 4-1,4-2,4-3.
Detailed description of the invention：
Fig. 1：Star-type polymer and the compound and viscosity modified process schematic of polystyrene；
Fig. 2：The structural formula and nuclear-magnetism figure of cationic chain transfer agents；
Fig. 3：Star-type polymer CoW12The mass spectrogram of-PS-1；
Fig. 4：Star-type polymer CoW12The mass spectrogram of-PS-2；
Fig. 5：Star-type polymer CoW12The mass spectrogram of-PS-3；
Fig. 6：Polystyrene (molecular weight 168000) and star-type polymer CoW12The rheometer test curve of the compound front and back-PS-1；
Fig. 7：Polystyrene (molecular weight 168000) and star-type polymer CoW12The rheometer test curve of the compound front and back-PS-3；
Fig. 8：Polystyrene (molecular weight 86500) and star-type polymer CoW12The rheometer test curve of the compound front and back-PS-3；
Fig. 1 describes multi-metal oxygen cluster 11 and cationic chain transfer agents 12 and forms compound 13 by electrostatic interaction, so
Afterwards by the way that star-type polymer 15 is prepared in 13 surface aggregate graft phenylethene 14 of compound, finally star-type polymer 15 is made
Be introduced into polystyrene entanglement network for extra small nanofiller, thus realize star-type polymer 15 and polystyrene compound 16 and
It is viscosity modified.
Fig. 2 is the structural formula and nuclear magnetic spectrogram of cationic chain transfer agents.
Fig. 3 is star-type polymer CoW12The mass spectrogram of-PS-1, mass-to-charge ratio is normal distribution, CoW in figure12- PS-1 is star-like
The degree of polymerization of polymer is 10 or so.
Fig. 4 is star-type polymer CoW12The mass spectrogram of-PS-2, mass-to-charge ratio is normal distribution, CoW in figure12- PS-2 is star-like
The degree of polymerization of polymer is 20 or so.
Fig. 5 is star-type polymer CoW12The mass spectrogram of-PS-3, mass-to-charge ratio is normal distribution, CoW in figure12- PS-3 is star-like
The degree of polymerization of polymer is 30 or so.
Fig. 6 is polystyrene (molecular weight 168000) and star-type polymer CoW12The rheometer test of the compound front and back-PS-1
Curve, the zero-shear viscosity of compound preceding polystyrene are 7.5 × 104Pas, the CoW for being 2% containing mass fraction12The polyphenyl of-PS-3
The zero-shear viscosity of ethylene composite material is 5.1 × 104Pas, viscosity reduce about 32%.
Fig. 7 is polystyrene (molecular weight 168000) and star-type polymer CoW12The rheometer test of the compound front and back-PS-3
Curve, the zero-shear viscosity of compound preceding polystyrene are 7.5 × 104Pas, the CoW for being 3% containing mass fraction12The polyphenyl of-PS-3
The zero-shear viscosity of ethylene composite material is 2.2 × 104Pas, viscosity reduce about 70%.
Fig. 8 is polystyrene (molecular weight 86500) and star-type polymer CoW12The rheometer test of the compound front and back-PS-3 is bent
Line, the zero-shear viscosity of compound preceding polystyrene are 6.7 × 103Pas, the CoW for being 3% containing mass fraction12The polyphenyl second of-PS-3
The zero-shear viscosity of alkene composite material is 2.7 × 103Pas, viscosity reduce about 60%.
Specific embodiment
Following specific embodiment has made further explaination to the present invention, successively carries out to the present invention without representative
Limitation.
1, the preparation of cationic chain transfer agents
Principle：It by esterification, will be covalently attached on hydroxy halogeno alkane, then pass through containing trithiocarbonic acid ester group
To the quaternization of halo groups, cation chain transfer agents are made.
Embodiment 1：11- (2- (positive fourth trithiocarbonate) propionic acid)-N, N, -11 ester -1- bromination of N- trioctylphosphine hendecane
The preparation of ammonium (BPOA)
4.5g n-butyl mercaptan and 5.6g triethylamine is taken to be dissolved in 100mL methylene chloride, in the protection of ice-water bath and nitrogen
Under the conditions of, it will be added dropwise in above-mentioned mixed solution dissolved with the 20mL dichloromethane solution of 4.2g carbon disulfide；Continue to stir
It after mixing 20min, will be added dropwise in above-mentioned reaction solution, drip dissolved with the 20mL dichloromethane solution of the 2 bromopropionic acid of 8.4g
After adding, ice-water bath is removed, is restored to room temperature, continues to stir 3h；Stop reaction, rotary evaporation removes solvent and obtains crude product；
Crude product is dissolved in the pentane of 100mL, it is acidified with the hydrochloric acid that the mass fraction of 180mL is 10%, in three times；
Then extra hydrochloric acid is washed away with secondary water, until pH value is neutrality；Rotary evaporation removes solvent, then that crude product is completely molten
Solution is uniformly spread in the beaker of 500mL in 50mL petroleum ether, after crystal precipitation, is filtered, and with the petroleum ether of 10mL
It rinses 3 times, available pure product --- 2- (positive fourth trithiocarbonate) propionic acid (BCTA), yield is about 83%.
The bromo- 1- undecyl alcohol of the 11- of 2.13g is taken to be added in round-bottomed flask, the ethyl alcohol that 25mL is added is completely dissolved, to
2g tri-n-octyl amine is wherein added to be condensed back under the conditions of 80 DEG C of oil bath after mixing, stops reaction after reacting 48h；Rotation
Turn evaporating ethanol and obtain crude product, crude product is recrystallized in the ether of frost, obtains pure production repeatedly for three times
Object --- 11- hydroxy-n, N, N- trioctylphosphine -1- ammonium bromide (HODA), yield is about 60%.
The HTOA of the BCTA and 2.54g of 1g is taken to be dissolved in 100mL methylene chloride；It is stirred under conditions of ice-water bath
After 30min, 1.03g dicyclohexylcarbodiimide is added into solution, the color of solution becomes brick-red from yellow；Continue to stir
After 20min, it will be added in reaction solution dissolved with the 10mL dichloromethane solution of the 4-dimethylaminopyridine of 60mg；Stir 30min
Ice-water bath is removed in recession, continues to stir at room temperature, until the color of solution becomes glassy yellow from brick-red, stops reaction；
It is filtered to remove precipitating, rotary evaporation removes solvent and obtains crude product, is dissolved in the ether of the frost of 100mL, removes precipitating；
Rotary evaporation removes solvent, is dissolved with a small amount of chloroform, and crude product is packed into silicagel column and carries out column chromatography for separation (eluent
The lesser impurity of depolarization first is removed with chloroform, after to be separated, change polarity is chloroform：Methanol=15：1), isolated pure
Net product --- 11- (2- (positive fourth trithiocarbonate) propionic acid)-N, N, -11 ester -1- ammonium bromide of N- trioctylphosphine hendecane produce
Rate is 75%, and product structure formula and nuclear magnetic spectrogram are shown in Figure of description 2, shows the product for having obtained target structure.
2, the preparation of multi-metal oxygen cluster compound
Principle：Surface counter ion counterionsl gegenions can dissociate multi-metal oxygen cluster in aqueous solution, form the cluster anions for having negative electrical charge,
It is compound by electrostatic with cationic surfactant, stable compound is formed, and be thus transferred in organic phase.
Embodiment 2-1：K6CoW12O40With the preparation of cationic chain transfer agents compound
Take the K of multi-metal oxygen cluster 0.14g6CoW12O40It is dissolved in the water of 70mL, takes 0.2g cation chain transfer agents
BPOA is dissolved in the chloroform of 70mL, and the molar ratio of cationic chain transfer agents and multi-metal oxygen cluster is 5.5：1；Violent
Under conditions of stirring, the chloroform soln of surfactant is added dropwise in the aqueous solution of multi-metal oxygen cluster, is dripped
Quan Hou continues strong stirring 1h；Stop stirring, stratification, for organic phase with secondary water washing 3 times until neutral, taking-up is organic
The sample of phase, rotary evaporation remove the available pure K of solvent chloroform6CoW12O40It is compound with cationic chain transfer agents
Object.Product quality is 0.3g.
3, the preparation of star-type polymer
Principle：The trithiocarbonic acid ester group of multi-metal oxygen cluster compound periphery can be used as chain tra nsfer group, by it is reversible/
Addition is broken chain transfer polymerization reaction, and monomer is grafted on compound, is formed using multi-metal oxygen cluster as core, is with polystyrene
The star-type polymer of arm.
Embodiment 3-1：K6CoW12O40Grafted polystyrene star-type polymer (CoW12- PS-1) preparation
The compound prepared in 0.2g embodiment 2-1 is taken, 1.86mL styrene and the n,N-Dimethylformamide of 2mL are taken,
It is uniformly mixed, compound is completely dissolved with mixed solution, 2.67mg azodiisobutyronitrile is taken to be added to reaction vessel ampoule bottle
In, then the mixed solution of compound is added in ampoule bottle, is uniformly mixed；It carries out freezing-taking out under conditions of closed true
Air in system is replaced into nitrogen by sky-inflated with nitrogen, repeatedly for three times, each 30min completely, will under the conditions of nitrogen protection
Ampoule bottle, which is placed in 65 DEG C of oil bath, reacts 10h；After reaction, it cools down ampoule bottle rapidly in liquid nitrogen, terminates reaction, together
When remove nitrogen protection, reaction solution is precipitated in 100mL methanol, centrifugation obtain crude product, washed three times, removed with methanol
Remove azo and isobutyronitrile；Then it is recrystallized in anhydrous ether, separating-purifying product, it is linearly poly- to remove polystyrene of autohemagglutination etc.
Close object.Pure star-type polymer, product quality 0.2g can be obtained.
Embodiment 3-2：K6CoW12O40Grafted polystyrene star-type polymer (CoW12- PS-2) preparation
The compound prepared in 0.2g embodiment 2-1 is taken, 3.73mL styrene and the n,N-Dimethylformamide of 2mL are taken,
It is uniformly mixed, compound is completely dissolved with mixed solution, 2.67mg azo-bis-isobutyl cyanide is taken to be added to reaction vessel ampoule bottle
In, then the mixed solution of compound is added in ampoule bottle, is uniformly mixed；It carries out freezing-taking out under conditions of closed true
Air in system is replaced into nitrogen by sky-inflated with nitrogen, repeatedly for three times, each 30min completely, will under the conditions of nitrogen protection
Ampoule bottle, which is placed in 65 DEG C of oil bath, reacts 10h；After reaction, it cools down ampoule bottle rapidly in liquid nitrogen, terminates reaction, together
When remove nitrogen protection, reaction solution is precipitated in 200mL methanol, centrifugation obtain crude product, washed three times, removed with methanol
Remove azo and isobutyronitrile；Then it is recrystallized in anhydrous ether, separating-purifying product, it is linearly poly- to remove polystyrene of autohemagglutination etc.
Close object.Pure star-type polymer, product quality 0.31g can be obtained.
Embodiment 3-3：K6CoW12O40Grafted polystyrene star-type polymer (CoW12- PS-3) preparation
The compound prepared in 0.2g embodiment 2-1 is taken, 5.58mL styrene and the n,N-Dimethylformamide of 2mL are taken,
It is uniformly mixed, compound is completely dissolved with mixed solution, 2.67mg azodiisobutyronitrile is taken to be added to reaction vessel ampoule bottle
In, then the mixed solution of compound is added in ampoule bottle, is uniformly mixed；It carries out freezing-taking out under conditions of closed true
Air in system is replaced into nitrogen by sky-inflated with nitrogen, repeatedly for three times, each 30min completely, will under the conditions of nitrogen protection
Ampoule bottle, which is placed in 65 DEG C of oil bath, reacts 10h；After reaction, it cools down ampoule bottle rapidly in liquid nitrogen, terminates reaction, together
When remove nitrogen protection, reaction solution is precipitated in 200mL methanol, centrifugation obtain crude product, washed three times, removed with methanol
Remove azo and isobutyronitrile；Then it is recrystallized in anhydrous ether, separating-purifying product, it is linearly poly- to remove polystyrene of autohemagglutination etc.
Close object.Pure star-type polymer, product quality 0.45g can be obtained.
4, star-type polymer and polystyrene is compound and viscosity modified
Principle：Star-type polymer can enter in the entanglement network structure of polymer as extra small nanoparticle, cause to gather
It closes object and disentanglement occurs under conditions of external shearing, so as to cause the reduction of polystyrene melt viscosity.
Embodiment 4-1：Polystyrene (molecular weight 168000) and star-type polymer CoW12The compound and viscosity of-PS-1 changes
Property
50mg polystyrene (molecular weight 168000) is taken, is dissolved completely in the chloroform of 0.8mL, is taken
4.45mg star-type polymer CoW12- PS-1, inorganic clusters mass fraction are 2%, are dissolved completely in the chloroform of 0.2mL
In, under agitation, the chloroform soln of star-type polymer is added dropwise in the chloroform soln of polystyrene,
Continue to stir 1h, be uniformly mixed；Mixed solution is laid in 2 × 2m2Kapton on, in room temperature condition and three chloromethanes
Under alkane atmosphere, so that solvent is slowly volatilized after 48h and form laminated film, by the film of preparation be placed in vacuum oven one week it is left
The right side completely removes solvent to get poly styrene composite material, product quality 50.28mg is arrived.
Embodiment 4-2：Polystyrene (molecular weight 168000) and star-type polymer CoW12The compound and viscosity of-PS-3 changes
Property
50mg polystyrene (molecular weight 168000) is taken, is dissolved completely in the chloroform of 0.8mL, is taken
16.7mg star-type polymer CoW12- PS-3, inorganic clusters mass fraction are 3%, are dissolved completely in the chloroform of 0.2mL
In, under agitation, the chloroform soln of star-type polymer is added dropwise in the chloroform soln of polystyrene,
Continue to stir 1h, be uniformly mixed；Mixed solution is laid in 2 × 2m2Kapton on, in room temperature condition and three chloromethanes
Under alkane atmosphere, so that solvent is slowly volatilized after 48h and form laminated film, by the film of preparation be placed in vacuum oven one week it is left
The right side, completely removing solvent to get the quality to poly styrene composite material, product is 62.14mg.
Embodiment 4-3：Polystyrene (molecular weight 86500) and star-type polymer CoW12The compound and viscosity of-PS-3 changes
Property
50mg polystyrene (molecular weight 86500) is taken, is dissolved completely in the chloroform of 0.8mL, is taken
16.7mg star-type polymer CoW12- PS-3, inorganic clusters mass fraction are 3%, are dissolved completely in the chloroform of 0.2mL
In, under agitation, the chloroform soln of star-type polymer is added dropwise in the chloroform soln of polystyrene,
Continue to stir 1h, be uniformly mixed；Mixed solution is laid in 2 × 2m2Kapton on, in room temperature condition and three chloromethanes
Under alkane atmosphere, so that solvent is slowly volatilized after 48h and form laminated film, by the film of preparation be placed in vacuum oven one week it is left
The right side, completely removing solvent to get the quality to poly styrene composite material, product is 62.22mg.
Claims (3)
1. a kind of method for reducing polystyrene melt viscosity, its step are as follows：
(1) preparation of multi-metal oxygen cluster compound
Cationic chain transfer agents are dissolved in the chloroform of 50~100mL, concentration is 2~4mg/mL；By multi-metal oxygen
Cluster is dissolved in 50~100mL secondary water, and concentration is 1.5~3mg/mL；Under violent stirring condition, by cationic chain tra nsfer
The chloroform soln of reagent is added in the aqueous solution of multi-metal oxygen cluster, and cationic chain transfer agents and multi-metal oxygen cluster rub
You are than being 5~5.8：1, it is ensured that cationic chain transfer agents are totally consumed in reaction process；After stirring 0.5~2h, stop anti-
It answers, stratification, organic phase, to neutrality, is taken out organic phase, remove solvent by rotary evaporation, i.e., with secondary water washing 3~5 times
Obtain pure multi-metal oxygen cluster compound；
(2) preparation of star-type polymer
Multi-metal oxygen cluster compound 0.2g prepared in step (1) is taken, 1~6mL of styrene and n,N-Dimethylformamide 2 are taken
~2.5mL is uniformly mixed, and is completely dissolved multi-metal oxygen cluster compound with the mixed solution, it is different to be then added to 2~6mg azo two
In butyronitrile, it is uniformly mixed；In confined conditions, above-mentioned reaction system freeze-vacuumize-inflated with nitrogen operates, repeatedly 3~
5 times, the air in reaction system is replaced into nitrogen completely；Then under the conditions of nitrogen protection, oil bath heating to 65~75 DEG C,
Reaction 8~for 24 hours；After reaction, it is cooled down rapidly in liquid nitrogen, terminates reaction, while removing nitrogen protection, crude product is existed
It is precipitated in 100~200mL methanol, product washs 3~5 times with methanol after centrifugation, then repeated precipitation 3 in anhydrous ether
~5 times to get arrive pure star-type polymer；
(3) star-type polymer and polystyrene is compound and viscosity modified
1~40mg of star-type polymer prepared in step (2) is taken, the chloroform of 0.2~0.5mL is dissolved completely in
In；Polystyrene 50mg is taken, is dissolved completely in the chloroform of 0.5~1mL；The chloroform of star-type polymer is molten
Liquid is added dropwise in the chloroform soln of polystyrene, continues 0.5~2h of stirring, is uniformly mixed it；By mixed solution
Be laid on polyimide substrate, under room temperature condition and chloroform atmosphere, make solvent slowly volatilize 48~72h formed it is compound
Film, then be placed in vacuum oven and completely remove solvent to get the composite material for arriving star-type polymer and polystyrene, thus
Realize the reduction of polystyrene matrix melt viscosity；
The structural formula of the cation chain transfer agents is as follows：
The preparation step of the cation chain transfer agents is as follows,
1. 3~5g of n-butyl mercaptan and 3~6g of triethylamine is taken to be dissolved in 50~200mL methylene chloride, protected in ice-water bath and nitrogen
Under the conditions of shield, 3~5g of carbon disulfide is taken to be add to the above mixed solution, 20~30min is stirred under the conditions of ice-water bath, takes 2- bromine
5~9g of propionic acid is added in above-mentioned solution, stirs 3~5h at room temperature；Crude product is dissolved in positive penta after rotary evaporation removes solvent
In alkane, the hydrochloric acid acidification of 150~250mL, mass fraction 10~20% is added, is then washed to neutrality with secondary, rotation is steamed
Crude product recrystallizes in petroleum ether after hair removes solvent, obtains pure product A；
2. taking 11- 1~3g of bromo- 1- undecyl alcohol, dissolution in ethanol, takes 1~3g of tri-n-octyl amine, is added to the bromo- 1- undecyl alcohol of 11-
Ethanol solution in, be condensed back under the conditions of 70~80 DEG C of oil bath, react 48~72h, rotary evaporation removes thick after solvent
Product recrystallizes in ether, and pure product B can be obtained；
3. taking 1~3g product A and 2~9g product B co-dissolve in the methylene chloride of 50~200mL, in the condition of ice-water bath
The dicyclohexylcarbodiimide of 1~4g is added into the solution by 20~30min of lower stirring, stirs 20~30min；Take 4- diformazan
30~60mg of aminopyridine is added in the reaction system, is stirred 20~30min, is removed ice-water bath, stirred at room temperature to solution
Color is glassy yellow stopping；It is filtered to remove precipitating, column chromatography for separation obtains pure cationic chain transfer agents.
2. a kind of method for reducing polystyrene melt viscosity as described in claim 1, it is characterised in that：Institute in step (1)
The multi-metal oxygen cluster stated is K6CoW12O40。
3. a kind of method for reducing polystyrene melt viscosity as described in claim 1, it is characterised in that：Institute in step (3)
The molecular weight for the polystyrene stated is 80000~400000.
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