CN105566623A - Polycarbonate material and preparation method thereof - Google Patents
Polycarbonate material and preparation method thereof Download PDFInfo
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- CN105566623A CN105566623A CN201610132626.7A CN201610132626A CN105566623A CN 105566623 A CN105566623 A CN 105566623A CN 201610132626 A CN201610132626 A CN 201610132626A CN 105566623 A CN105566623 A CN 105566623A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
The invention provides a preparation method of a crystallizable polycarbonate material. The preparation method comprises the steps of performing copolymerization for carbon dioxide and an epoxy compound containing long-chain alkane substituent groups under a catalyst, so as to obtain the polycarbonate material. The catalyst used by the method is good in structure control ability, so that the polycarbonate material has a relatively high head-to-tail structure; the substituent groups of the epoxy compound is relatively long in alkyl chain, so that crystal is formed easily; in such a way, the polycarbonate material prepared by the method disclosed by the invention has crystallinity; on the other hand, by the method disclosed by the invention, the polycarbonate material can be prepared by only performing copolymerization for the carbon dioxide and the epoxy compound under the catalyst, and the epoxy compound is unnecessary to be separated or modified, so that the preparation method of the polycarbonate material is simple.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to a kind of polycarbonate material and preparation method thereof.
Background technology
Carbonic acid gas is a kind of greenhouse gases, is also a kind of rich reserves, cheap carbon resource simultaneously, gets more and more people's extensive concerning.The chemistry of carbonic acid gas is fixedly the important research field of Green Chemistry, wherein, carbonic acid gas and epoxy compounds copolymerization is prepared biodegradable polycarbonate, is a kind of effective way of chemical stabilizing carbon dioxide.
At present, there is a lot of patent report preparing polycarbonate about carbonic acid gas and epoxy alkane copolymerization both at home and abroad, the US Patent No. 3585168 that aboveground auspicious flat professor as Japan delivers, US3900424, US3953383, above-mentioned patent uses to prepare number-average molecular weight at the polycarbonate of more than 20kg/mol, urethane and polyethers based on the dual-component catalyst system of zinc alkyl(s).Japanese Patent JP2142824, JP2575199 describe catalysis of metalloporphyrin epoxy compounds and carbon dioxide copolymerization prepares polycarbonate, and catalytic capability reaches every mol catalyst catalysis 10
3~ 10
4gram polymkeric substance, but the number-average molecular weight of its polymkeric substance only has about 5kg/mol, and long reaction time, expensive.Wang Xianhong etc. application number be in the Chinese patent of 98125654.6,00136189.9 and 03105023.9 in describe a kind of three-way catalyst be made up of metal-salt, zinc alkyl(s) and glycerine, prepare high-molecular aliphatic polycarbonate, the catalytic efficiency of catalyzer is more than 8 × 10
4gram every mol catalyst of polymkeric substance, the number-average molecular weight of polymkeric substance is more than 30,000kg/mol, and in polymkeric substance, the content of carbonic acid gas unit is more than 40wt%, and alternating structure is greater than 95%.Nozaki seminar (the J.Am.Chem.S DEG C of .1999 of Japan, 121,11008-11009) and the Coates seminar (Chem.Common. of the U.S., 2000,2007-2008) Zn complex containing chiral carbon is utilized to be catalyzer respectively, catalysis carbonic acid gas and epoxy cyclohexane copolymerization, prepared the complete poly-cyclohexene carbonate with structure 60 ~ 80%, but new polymkeric substance is still unbodied.
The polymkeric substance with crystallizing power mainly relies on the symmetry of molecular chain repeating unit, polycarbonate is prepared for propylene oxide and carbonic acid gas alternating copolymerization, prepared by Lv little Bing teach problem group, the tacticity of polymkeric substance has reached more than 99% (Sci.ChinaChem., 2010,1646-1652), this polymkeric substance does not still have crystal property.In recent years, although there is the report about carbon dioxide copolymer crystallization, all the chiral catalyst catalysis of Structure of need complexity could realize.Therefore, be badly in need of at present providing a kind of preparation method simply to have the preparation method of the polycarbonate material of crystallizability.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method with the polycarbonate material of crystallizability.
In view of this, this application provides a kind of preparation method of polycarbonate material, comprising:
Under the effect of catalyzer, carbonic acid gas is carried out copolyreaction with containing the substituent epoxy compounds of long chain alkane, obtains polycarbonate material.
Preferably, described catalyzer is selected from the one in the first catalyst system of tetradentate schiff base cobalt complex and promotor, Cobalt Porphyrin and the second catalyst system of promotor and the 3rd catalyst system of porphyrin aluminium and promotor.
Preferably, the mol ratio of described tetradentate schiff base cobalt complex and promotor is 10:(1 ~ 20), the mol ratio of described Cobalt Porphyrin and promotor is 10:(1 ~ 20), the mol ratio of described porphyrin aluminium and promotor is 10:(1 ~ 20).
Preferably, promotor in promotor in described first catalyst system, the promotor in the second catalyst system and the 3rd catalyst system is quaternary ammonium salt, described quaternary ammonium salt be independently selected from two-(dihalotriphenylphosphoranes base) ammonium chloride, two-(dihalotriphenylphosphoranes base) brometo de amonio and two-(dihalotriphenylphosphoranes base) ammonium iodide one or more.
Preferably, described have structural formula as shown in formula I containing the substituent epoxy compounds of long chain alkane,
Wherein, 9 < n < 15.
Preferably, the described mol ratio containing the substituent epoxy compounds of long chain alkane and described catalyzer is (100 ~ 10000): 1.
Preferably, the temperature of described copolyreaction is 20 ~ 80 DEG C, and pressure is 1 ~ 6MPa, and the time is 5 ~ 48h.
Preferably, described copolyreaction is carried out in a solvent, described solvent be selected from methylene dichloride, toluene, 1,3-dioxolane, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran (THF) one or more.
Preferably, the described mass ratio containing the substituent epoxy compounds of long chain alkane and described solvent is 10:(1 ~ 10).
Present invention also provides a kind of polycarbonate material, under catalyst action, carried out copolyreaction by carbonic acid gas obtain with containing the substituent epoxy compounds of long chain alkane.
This application provides a kind of preparation method of crystallizability polycarbonate material, it is by carbonic acid gas and contains the substituent epoxy compounds of long chain alkane under the effect of catalyzer, carries out copolyreaction, obtains polycarbonate material.The catalyzer adopted due to the application has good structure control ability, polycarbonate material can be made to have higher head-to-tail structure, and the substituted radical alkyl chain of epoxy compounds is longer simultaneously, easily forms crystallization, therefore, the polycarbonate material that prepared by the application has crystallinity.On the other hand, carbonic acid gas and epoxy compounds only need be carried out copolyreaction by the application under the effect of catalyzer, can obtain polycarbonate material, do not need to split or trimming loop oxygen compound, and make the preparation method of polycarbonate material simple.
Accompanying drawing explanation
Fig. 1 is the DSC spectrogram of polycarbonate prepared by the embodiment of the present invention 1;
Fig. 2 is the XRD spectra of polycarbonate prepared by the embodiment of the present invention 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of polycarbonate material, comprising:
Carbonic acid gas is carried out copolyreaction with containing the substituent epoxy compounds of long chain alkane under the effect of catalyzer, obtains polycarbonate material.
The application is with carbonic acid gas and contain the substituent epoxy compounds of long chain alkane for raw material, under the effect of catalyzer, has synthesized polycarbonate material.Polycarbonate material prepared by the application has crystallinity, and constantly increases along with epoxy compounds side chain lengths, and the crystallizing power of polymkeric substance constantly strengthens.
The application is in the process preparing polycarbonate material, and described catalyzer is selected from the one in the first catalyst system of tetradentate schiff base cobalt complex and promotor, Cobalt Porphyrin and the second catalyst system of promotor and the 3rd catalyst system of porphyrin aluminium and promotor.Described tetradentate schiff base cobalt complex has the structure shown in formula II, described Cobalt Porphyrin has the structure shown in formula (III), in an embodiment, described Cobalt Porphyrin preferably has the structure shown in formula IV, described porphyrin aluminium has the structure shown in formula (V), in an embodiment, described porphyrin aluminium has the structure shown in formula VI, tetradentate schiff base cobalt complex described in the application, Cobalt Porphyrin and porphyrin aluminium are compound well known to those skilled in the art, its preparation method is according to technique means well known to those skilled in the art, this the application is had no particular limits.
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19and R
20independently be selected from hydrogen, halogen, alkyl, assorted alkyl, aryl or heteroaryl separately.
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19and R
20independently be selected from hydrogen, halogen, alkyl, assorted alkyl, aryl or heteroaryl separately.
In above-mentioned catalyst system, promotor in promotor in described first catalyst system, the promotor in the second catalyst system and the 3rd catalyst system is quaternary ammonium salt, and described quaternary ammonium salt is independently selected from two-(dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), two-(dihalotriphenylphosphoranes base) brometo de amonio (PPNBr) and one or more in two-(dihalotriphenylphosphoranes base) ammonium iodide (PPNI).Primary Catalysts porphyrin aluminium in Cobalt Porphyrin in Primary Catalysts tetradentate schiff base cobalt complex in first catalyst system described in the application and promotor, the second catalyst system and promotor and the 3rd catalyst system and promotor are all occur in pairs, Primary Catalysts is separately as the katalysis DeGrain of catalyzer, promotor is and the coordination of primary catalyst metal title complex, and then the initiation reaction of activation carbonic acid gas is carried out.The mol ratio of epoxy compounds described in the application and described catalyzer is preferably (100 ~ 10000): 1, and in an embodiment, the mol ratio of described epoxy compounds and described catalyzer is more preferably (200 ~ 5000): 1; The mol ratio of described Primary Catalysts and promotor is preferably 10:(1 ~ 20), be more preferably 1:1.
In the process preparing polycarbonate material, the structural formula containing the substituent epoxy compounds of long chain alkane described in the application is preferably formula I,
Wherein, 9 < n < 15.
Epoxy compounds described in the application is that side chain well known to those skilled in the art contains the substituent epoxy compounds of alkane, just the length of its side chain is longer, to make the polycarbonate of preparation have crystallinity, described in the application, the substituent carbonatoms of epoxy compounds side chain alkane is preferably greater than 9 and is less than 15.Copolyreaction described in the application can be carried out under condition of no solvent, also can carry out having under solvent condition, if but the side chain substituents of described epoxy compounds is greater than 14 carbon, described copolyreaction is preferably carried out having under solvent condition, and the application has no particular limits described solvent, is solvent well known to those skilled in the art, preferably, described solvent be preferably in methylene dichloride, toluene, 1,3-dioxolane, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran (THF) one or more.The mass ratio of described epoxy compounds and described solvent is preferably 10:(1 ~ 10), in an embodiment, the mass ratio of described epoxy compounds and described solvent is more preferably 1:1.
According to the present invention, in the process preparing polycarbonate, the temperature of described copolyreaction is preferably 2 ~ 40 DEG C, and the pressure of described copolyreaction is preferably 1.0 ~ 6.0MPa, and the time of described copolyreaction is preferably 5 ~ 48h.
Present invention also provides a kind of polycarbonate material, it is carried out copolyreaction by carbonic acid gas obtain with containing the substituent epoxy compounds of long chain alkane under catalyst action.
In the said products, the raw material wherein related to and reaction conditions such scheme are illustrated, no longer repeat herein.
The invention provides a kind of carbon dioxide-base polycarbonate material and preparation method thereof, carbonic acid gas and epoxy compounds are under the effect of binary catalyst system, under certain temperature and pressure condition, copolymerization certain hour, prepares the carbon dioxide-base polycarbonate material of Side chain crystallizable.Compared with prior art, the present invention makes catalyzer with cheap, the tetradentate schiff base cobalt complex of easily synthesis, Cobalt Porphyrin, porphyrin aluminium, and very common quaternary ammonium salt is as promotor; And epoxy monomer is modified without the need to carrying out or split, can obtain that there is crystalline polycarbonate.Experimental result shows, the alternately rate of polycarbonate prepared by the present invention is 100%, molecular weight is 6.4 ~ 22kg/mol, molecular weight distribution is 1.11 ~ 1.15, head-to-tail structure is 90 ~ 94%, fusing point is at-16 ~ 43 DEG C, and prepared polycarbonate is defined as crystallizable side chain type polymkeric substance through Temperature-dependent IR analysis.
In order to understand the present invention further, be described in detail to polycarbonate provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1 tetradentate schiff base cobalt complex (SalanCo
iIIcl) preparation of catalyzer
Step a) adds 3 successively in the 500mL there-necked flask being furnished with magnetic agitation, reflux condensing tube and constant pressure funnel, 5-di-tert-butyl salicylaldehyde (34.85g, 0.1mol) with 200mL ethanol, be heated to about 60 DEG C, stir and make it to dissolve completely; 1,2-cyclohexanediamine (5.7g, 0.05mol) is dissolved in 40mL ethanol, is slowly added drop-wise in the ethanolic soln of salicylic aldehyde, after dropwising, reflux 6h, cool to room temperature, placement is spent the night.Filtered by the mixture obtained and obtain yellow solid, then vacuum-drying at 40 DEG C, obtains Salen part.
Step b) under argon shield, in the 250mL there-necked flask being furnished with constant pressure funnel and magnetic agitation, add Salen part (3.65g, 6.67mmol) and the refining methylene dichloride of 25mL, stir and make it to dissolve.By anhydrous Co (AcO)
2ethanolic soln (1.42g, 8.0mmol, 30mL) be slowly added drop-wise in flask half an hour by constant pressure funnel.Along with Co (AcO)
2add, have a large amount of red solid to separate out.Dropwise, with the dichloromethane rinse constant pressure funnel that 5mL is refining, continue to stir 15min, adopt ice-water bath to make it temperature of reaction system and be down to 0 DEG C, keep 30min.Press filtration under argon shield, precipitation methanol wash several, then vacuum-drying at 40 DEG C, obtains SalenCo
iI.
Step c) p-methyl benzenesulfonic acid one water (0.599g, 3.15mmol) is dissolved in 50mL acetone, be then added drop-wise to SalenCo
iIdichloromethane solution in (1.81g, 3.0mmol, 100mL).Pass into dry oxygen, at room temperature stir and spend the night.Spin off solvent, with a small amount of n-hexane once, collected by filtration, further vacuum-drying, obtains blackish green pulverulent solids (Salen) Co
iIIoTs.
Steps d) by (Salen) Co of 2g
iIIoTs is dissolved in 150mL methylene dichloride, pour in 1000mL pear shape separatory funnel, with saturated sodium-chloride water solution concussion washing (6 × 100mL), after organic over anhydrous dried over sodium sulfate, spin off solvent, then use a small amount of n-hexane, collected by filtration, further vacuum-drying obtains blackish green pulverulent solids, i.e. tetradentate schiff base cobalt complex (SalanCo
iIIcl) catalyzer.Shown in structure formula II prepared by the present embodiment,
The preparation of embodiment 2 CoTPP
Step a) adds refining methylene dichloride 800mL, phenyl aldehyde (2.2g successively in the 1L there-necked flask being furnished with magnetic agitation, argon shield; 13mmol) with pyrroles (0.93mL; 13mmol), room temperature reaction, stirs and makes it to dissolve completely.Slowly be added drop-wise to by trifluoroacetic acid (0.93mL, 4mmol) in above-mentioned solution, after dropwising, reaction 1h, obtains reaction solution.DDQ (1.82g, 8mmol) is joined in reaction solution, continues reaction 1h, then filter, spin off solvent.Crude product neutral alumina column chromatography (elutriant is sherwood oil/methylene dichloride), obtains pure violet solid.
Step b) under argon shield; by previous step product (6.12g; 10mmol) join in dry 1L there-necked flask; add 500mLN; dinethylformamide is heated with stirring to backflow; add four hydration Cobaltous diacetates (2.99g) after dissolving completely, continue back flow reaction 1h.Reaction terminates rear cool to room temperature, pours frozen water into there-necked flask.By the suspension suction filtration of gained, filter cake washes with water, vacuum-drying 24h, namely obtains product Cobalt Porphyrin (II).
Step c) by previous step product (0.6g, 0.89mmol) be put in there-necked flask, the mixing solutions adding chloroform and methyl alcohol is stirred to dissolving, add 4.5mL concentrated hydrochloric acid subsequently, stir certain hour and add 100mL chloroform, with organic phase anhydrous magnesium sulfate drying after deionized water wash, filter, gained filtrate drained, vacuum-drying 48h, products therefrom is Cobalt Porphyrin catalyzer.Described in the present embodiment, catalyst structure is as shown in formula IV,
The preparation of embodiment 3 CoTPP
Step a) adds refining methylene dichloride 800mL, phenyl aldehyde (2.9g successively in the 1L there-necked flask being furnished with magnetic agitation, argon shield; 13mmol) with pyrroles (0.93mL; 13mmol), room temperature reaction, stirs and makes it to dissolve completely; obtain mixing solutions; trifluoroacetic acid (0.93mL, 4mmol) is slowly added drop-wise in mixing solutions, after dropwising; reaction 1h, obtains reaction solution.DDQ (1.82g, 8mmol) is joined in above-mentioned reaction solution, continue reaction 1h, then filter, spin off solvent.Crude product neutral alumina column chromatography (elutriant is sherwood oil/methylene dichloride), obtains pure violet solid.
Step b) under argon shield; by previous step product (0.81g; 1mmol) join in dry single port flask; add 10mL methylene dichloride to be stirred to and to dissolve completely, under room temperature, add the hexane solution (1M, 1mL) of diethyl aluminum chloride; reaction 2h; removal of solvent under reduced pressure, crude product neutral alumina column chromatography for separation (elutriant is methylene chloride/methanol), obtains purple porphyrin Al catalysts.Described in the present embodiment, catalyst structure is as shown in formula VI,
Embodiment 4
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 286mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:250 with this weighing bottle
iIIcl catalyzer and 257mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains 16 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, connection subsequently by catalyzer weighing bottle adds 30mL toluene in still, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 3.0MPa of polymerization, polymeric reaction temperature 25 DEG C, polymerization reaction time 10h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 18.8g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 11kg/mol, and molecular weight distribution is 1.10.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, and carry out nuclear-magnetism carbon spectrum analysis to product after purification, result shows, polymkeric substance head-to-tail structure 90% prepared by the present embodiment.Carry out dsc analysis result to product after purification to show, melting point polymer 43 DEG C, DSC spectrogram as indicated with 1.Carry out XRD analysis to product after purification, spectrogram as shown in Figure 2.
Embodiment 5
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 209mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:500 with this weighing bottle
iIIcl catalyzer and 187mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains ten carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure 4.0MPa of polymerization, polymeric reaction temperature 30 DEG C, polymerization reaction time 20h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 29.7g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 20kg/mol, and molecular weight distribution is 1.15.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 92% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer-16 DEG C.
Embodiment 6
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 151mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:600 with this weighing bottle
iIIcl catalyzer and 135mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains 12 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 2.0MPa of polymerization, polymeric reaction temperature 30 DEG C, polymerization reaction time 10h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 23.5g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 17kg/mol, and molecular weight distribution is 1.13.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 92% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 4 DEG C.
Embodiment 7
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 80mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:1000 with this weighing bottle
iIIcl catalyzer and 72mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains 14 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, then 30g methylene dichloride is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 1.0MPa of polymerization, polymeric reaction temperature 30 DEG C, polymerization reaction time 48h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 23.5g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 20kg/mol, and molecular weight distribution is 1.11.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 91% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 27 DEG C.
Embodiment 8
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 320mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:250 with this weighing bottle
iIIcl catalyzer and 288mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains 14 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, then 30g dioxolane is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 1.0MPa of polymerization, polymeric reaction temperature 25 DEG C, polymerization reaction time 22h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 23.5g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 20kg/mol, and molecular weight distribution is 1.11.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 91% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 27 DEG C.
Embodiment 9
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 91mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:1000 with this weighing bottle
iIIcl catalyzer and 81mgPPNCl, and add to weighing bottle the epoxy compounds that 30g contains 12 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, then 15g dioxane is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 1.0MPa of polymerization, polymeric reaction temperature 20 DEG C, polymerization reaction time 48h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 30.8g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 22kg/mol, and molecular weight distribution is 1.13.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 92% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 4 DEG C.
Embodiment 10
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 114mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:800 with this weighing bottle
iIIcl catalyzer and 109mgPPNBr, and add to weighing bottle the epoxy compounds that 30g contains 12 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, then 18g dioxane is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 3.0MPa of polymerization, polymeric reaction temperature 20 DEG C, polymerization reaction time 20h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 25.6g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 22kg/mol, and molecular weight distribution is 1.13.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 92% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 4 DEG C.
Embodiment 11
Tetradentate schiff base cobalt complex (SalanCo is prepared with reference to embodiment 1
iIIcl) catalyzer.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take the SalanCo of 320mg embodiment 1 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:250 with this weighing bottle
iIIcl catalyzer and 334mgPPNI, and add to weighing bottle the epoxy compounds that 30g contains 14 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, then 30g dioxolane is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 1.0MPa of polymerization, polymeric reaction temperature 25 DEG C, polymerization reaction time 22h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 20.5g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 20kg/mol, and molecular weight distribution is 1.11.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 91% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 27 DEG C.
Embodiment 12
Tetraphenylporphyrin cobalt catalyst is prepared with reference to embodiment 2.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take catalyzer and the 334mgPPNI of 352mg embodiment 2 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:250 with this weighing bottle, and add to weighing bottle the epoxy compounds that 30g contains 14 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100ml autoclave of room temperature, then 30g dioxolane is added, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 1.0MPa of polymerization, polymeric reaction temperature 25 DEG C, polymerization reaction time 22h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 21.5g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 22kg/mol, and molecular weight distribution is 1.11.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 92% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 27 DEG C.
Embodiment 13
Four (4-phenyl) porphyrin Al catalysts is prepared with reference to embodiment 3.
By weighing bottle at 80 DEG C, find time applying argon gas process 2h (inflating 6 times), and be cooled to room temperature, then take catalyzer and the 8mgPPNCl of 12mg embodiment 3 preparation by feed ratio (catalyzer: promotor: epoxy monomer) 1:1:10000 with this weighing bottle, and add to weighing bottle the epoxy compounds that 30g contains 12 carbon alkane chain substituents group under argon shield, obtain mixture, said mixture is added in advance at 80 DEG C, through the applying argon gas process 10h that finds time (inflating 6 times), and be cooled in the 100mL autoclave of room temperature, stir with the speed of 500rpm, in still, carbonic acid gas is passed into rapidly by pressurized carbon dioxide draught control mechanism, autoclave is inserted in thermostatic bath and is carried out polyreaction, the pressure carbon dioxide 3.0MPa of polymerization, polymeric reaction temperature 70 DEG C, polymerization reaction time 48h, after polyreaction terminates, the autoclave cooling bath of 0 ~ 5 DEG C is cooled to room temperature, the unreacted monomer of slow discharge and carbonic acid gas, residuum at 40 DEG C of vacuum drying oven inner dryings to constant weight, obtain polycarbonate 30.8g.
Utilize GPC to detect polycarbonate prepared by the present embodiment, relative molecular weight is 22kg/mol, and molecular weight distribution is 1.13.Carry out nucleus magnetic hydrogen spectrum analytical results to product after purification to show, polymkeric substance prepared by the present embodiment contains the carbonate unit being greater than 99%, carries out nuclear-magnetism carbon spectrum analysis result and shows, polymkeric substance head-to-tail structure 90% prepared by the present embodiment to product after purification.Carry out dsc analysis result to product after purification to show, melting point polymer 4 DEG C.
To sum up, carbon dioxide-base polycarbonate material that the invention provides a kind of Side chain crystallizable and preparation method thereof, carbonic acid gas and epoxy compounds form binary catalyst system at use tetradentate schiff base cobalt complex, Cobalt Porphyrin, porphyrin aluminium and quaternary ammonium salt, under certain temperature, pressure condition, copolymerization certain hour, successfully prepares the carbon dioxide-base polycarbonate material of Side chain crystallizable.Compared with prior art, the present invention makes catalyzer with cheap, the tetradentate schiff base cobalt complex of easily synthesis, Cobalt Porphyrin, porphyrin aluminium, and very common quaternary ammonium salt is co catalysis; And epoxy monomer is modified without the need to carrying out or is split.Experimental result shows, the alternately rate of polycarbonate prepared by the present invention is 100%, and molecular weight is 6.4 ~ 2.2kg/mol, and molecular weight distribution is 1.11 ~ 1.15, and head-to-tail structure is 90 ~ 94%, and fusing point is at-16 ~ 43 DEG C.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for polycarbonate material, comprising:
Under the effect of catalyzer, carbonic acid gas is carried out copolyreaction with containing the substituent epoxy compounds of long chain alkane, obtains polycarbonate material.
2. preparation method according to claim 1, it is characterized in that, described catalyzer is selected from the one in the first catalyst system of tetradentate schiff base cobalt complex and promotor, Cobalt Porphyrin and the second catalyst system of promotor and the 3rd catalyst system of porphyrin aluminium and promotor.
3. preparation method according to claim 2, it is characterized in that, the mol ratio of described tetradentate schiff base cobalt complex and promotor is 10:(1 ~ 20), the mol ratio of described Cobalt Porphyrin and promotor is 10:(1 ~ 20), the mol ratio of described porphyrin aluminium and promotor is 10:(1 ~ 20).
4. preparation method according to claim 2, it is characterized in that, promotor in promotor in described first catalyst system, the promotor in the second catalyst system and the 3rd catalyst system is quaternary ammonium salt, described quaternary ammonium salt be independently selected from two-(dihalotriphenylphosphoranes base) ammonium chloride, two-(dihalotriphenylphosphoranes base) brometo de amonio and two-(dihalotriphenylphosphoranes base) ammonium iodide one or more.
5. preparation method according to claim 1, is characterized in that, described have structural formula as shown in formula I containing the substituent epoxy compounds of long chain alkane,
Wherein, 9 < n < 15.
6. preparation method according to claim 1, is characterized in that, the described mol ratio containing the substituent epoxy compounds of long chain alkane and described catalyzer is (100 ~ 10000): 1.
7. preparation method according to claim 1, is characterized in that, the temperature of described copolyreaction is 20 ~ 80 DEG C, and pressure is 1 ~ 6MPa, and the time is 5 ~ 48h.
8. preparation method according to claim 1, is characterized in that, described copolyreaction is carried out in a solvent, described solvent be selected from methylene dichloride, toluene, 1,3-dioxolane, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran (THF) one or more.
9. preparation method according to claim 8, is characterized in that, the described mass ratio containing the substituent epoxy compounds of long chain alkane and described solvent is 10:(1 ~ 10).
10. a polycarbonate material, is characterized in that, is carried out copolyreaction by carbonic acid gas and obtains with containing the substituent epoxy compounds of long chain alkane under catalyst action.
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