CN1305925C - A soft and hard multi-block polymer and its synthesis method - Google Patents
A soft and hard multi-block polymer and its synthesis method Download PDFInfo
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- CN1305925C CN1305925C CNB2005100276027A CN200510027602A CN1305925C CN 1305925 C CN1305925 C CN 1305925C CN B2005100276027 A CNB2005100276027 A CN B2005100276027A CN 200510027602 A CN200510027602 A CN 200510027602A CN 1305925 C CN1305925 C CN 1305925C
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Abstract
The present invention belongs to the technical field of electroluminescent material, more specifically a novel modified soft and hard multi-block polymer and a method for synthesizing the polymer. The present invention adopts monomers, such as substituted aromatic rings, acrylic acid, methacrylic acid, vinyl carbazole, caprolactone, etc., as raw materials to synthesize a series of block polymers through reactions, such as organic metal coupling, atom transfer radical polymerization, etc., and the block polymers are composed of conjugated oligomers and flexible water soluble/ oil soluble soft segments. The structures of the soft segments are adjusted to adjust the solubility and other physicochemical properties of the block polymer, and the block polymer is used for luminescent layers made of organic electroluminescent material (OLED), bioluminescence detectors, etc. Simultaneously, the aggregation structure is improved, so that the luminous efficacy of devices is improved, and the self-assembly of the polymer on a molecular level is realized.
Description
Technical field
The invention belongs to the technical field of electroluminescent novel material and self-assembled material, be specifically related to a kind of soft and hard multi-block polymer and synthetic method thereof.
Technical background
Because some special propertys that novel organic photoelectric luminescent materials such as conjugated polymers have, for example: solubilized, easily process, be easy to modification etc., make them aspect organic luminescent device, field effect transistor, chemistry and the bio-sensing wide application prospect arranged.Thereby, traditional conjugated polymers brings certain difficulty for the relation of research chemical structure and performance but having chemical imperfection usually.The present invention is by synthetic conjugation oligomer with fixed sturcture, and it is modified into suitable initiator; With atom transition free radical polymerization reaction (ATRP) or the ring-opening polymerization controlled introducing modification groups of method such as (ROP), thereby can very easily groups such as water-soluble, electrons/transmission, liquid crystal liquid crystal property be introduced in the conjugated polymers; And the clear and definite conjugated polymers of these structures carried out research on the performance.The multicomponent polymeric that will contain luminescent material simultaneously carries out self-assembly and realizes ordered 3 D structure, and studies the relation of its structure and performance.
Summary of the invention
The objective of the invention is to propose a kind of novel soft and hard multi-block polymer, and provide their synthetic method.
The present invention adopts steps such as protective group, organo-metallic catalytic coupling, deprotection, and synthetic one section has certain molecular weight and the oligomer of compound with regular structure; And connect at its symmetry centre place have liquid crystal liquid crystal property, the flexible polymer of performance such as water-soluble or electrons/transmission.
Because the present invention has adopted different flexible groups, these novel multi-block polymers have different self-assembly behaviors in different solvents, can obtain different micellar conformations, thereby adjust the luminosity of hard end (conjugated polymers section).By introducing the electronics injection balance that electronics or hole mobile material can improve polymkeric substance, improve luminescent properties.Also can come the self-assembly behavior of telomerized polymer or reach biology/chemical detection simultaneously by the group of adjusting compliant section.
Novel soft and hard multi-block polymer provided by the invention, its molecular structure is as follows:
Wherein
Ar can be an oligomerization benzene, oligo-thiophenes, oligomerization fluorenes, oligomerization benzyne, the support of oligomerization vinylbenzene, the support of oligomerization phenylacetylene, the perhaps multipolymer that is formed by above conjugated polymers monomer;
A, B are simple functional group, or the homopolymer or a plurality of monomeric multipolymer that are formed by monomer polymerizations such as acrylic acid or the like, methacrylic, vinylcarbazole, caprolactones;
In the polymkeric substance of the present invention, more following compounds have special structure formation and Practical significance:
I.Ar is the oligomerization fluorenes, and A is a methoxyl group, and B is the polymethylmethacrylate that contains the cyanobiphenyl liquid crystal unit; Its structural formula is as follows:
Wherein R is a hexyl; M=2,3,4 N=10,20,30,40
Wherein, the chemical structure of oligomerization fluorenes is clear and definite, and textural defect is few, and spectrum stability is good; Secondly the liquid crystal unit in the soft segment makes flexible chain have certain rigid, gives whole molecule simultaneously and has liquid crystal liquid crystal property.
II.Ar is the oligomerization fluorenes, and A is a methoxyl group, and B is PEG or polycaprolactone; Its structure is as follows:
Wherein R is a hexyl; M=2,3,4 N=10,20,30,40
The difference of these two kinds of structures and routine I is that mainly left example has biodegradability and biocompatibility in the design to flexible chain, and right example has water-soluble and good crystal property.Be on the polymerization process that left example is utilized the ring-opening polymerization of caprolactone, right example utilizes succinyl oxide that two kinds of polymkeric substance or oligomer are carried out coupling.
III.Ar is the oligomer of being made up of thiophene phenol and fluorenes, and A is a methoxyl group, and B is an Ionomer; Its structure is as follows:
Wherein R is a hexyl; N=10,20,30,40
Wherein, the oligomer that main chain is made of fluorenes and thiophene phenol, soft segment are to have water miscible ammonium salt ion, make whole molecule have water-soluble and bio-sensing.
IV.Ar is the oligomerization fluorenes, and A, B are the polymethylmethacrylate that contains the cyanobiphenyl liquid crystal unit;
Wherein R is a hexyl; M=2,3,4 N=10,20,30,40
Compare with I, its chemical structure is characterised in that flexible chain is symmetrically distributed in the both sides of stiff chain.
The synthetic method of polymkeric substance provided by the invention is as follows:
Synthesizing of the multipolymer of I, main chain oligomerization fluorenes or oligomerization thiophene phenol, oligomerization fluorenes and oligomerization benzyne:
1) protective group: brominated monomer is dissolved in the tetrahydrofuran (THF), adds the n-Butyl Lithium reaction down after 45-90 minute at subzero 78 ℃, adds the trimethyl silane afterreaction 30-120 minute; Separation obtains product through chromatography column;
(2) functional group go the protection: utilize ICl that the blocking group of trimethyl silane is removed, obtaining with I is end capped monomer;
(3) boration reaction: will have monomer to be dissolved in the tetrahydrofuran (THF) with Br or I functional group, add n-Butyl Lithium reaction 45-90 minute down at subzero 78 ℃, add the monomer that obtains having boric acid functional group after the reaction of trimethyl-boron acid esters or triisopropyl boric acid ester is spent the night;
(4) Suzuki metal linked reaction: the monomer that will have boric acid functional group and Br of halogen functional group or I carries out coupling under alkaline condition and under the catalysis of triphenyl phosphorus palladium, obtain corresponding oligomer;
II. the synthetic method of block polymer:
(1) atom transfer radical polymerization method:
To be dissolved in the orthodichlorobenzene by macromole evocating agent and the polymerization single polymerization monomer that oligomer is made, add ligand 1 then, 1,4,7,10,70-hexamethyl triethyl four ammoniums and catalyzer cuprous bromide are 60-90 ℃ in temperature, reaction back 3-10 hour, after the end, reactant is dissolved in tetrahydrofuran (THF), and with neutral alumina elimination mantoquita, with methyl alcohol polymkeric substance is settled then, and wash products therefrom with normal hexane;
(2) ring-opening polymerization method:
With the oligomer of hydroxyl and caprolactone at Sn (Oct)
2Under the catalysis, be to carry out mass polymerization under 120-140 ℃ in temperature, product precipitates in methyl alcohol and washs.
Description of drawings
Fig. 1 is the GPC of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5) figure among the embodiment among the present invention.
Fig. 2 is OFB initiator, a P1 infrared spectra among the embodiment among the present invention.
Fig. 3 is OFB initiator (Fig. 3 (A)), a P1 proton nmr spectra (Fig. 3 (B)) among the embodiment among the present invention.
Fig. 4 is OFB initiator (Fig. 4 (A)), a P1 carbon-13 nmr spectra (Fig. 4 (B)) among the embodiment among the present invention.
Fig. 5 is for the second time heating curve (Fig. 5 (A)) and a temperature lowering curve (Fig. 5 (B)) for the first time of the DSC thermodynamics of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5) among the embodiment among the present invention, heats up and the speed of lowering the temperature is 10 ℃/min.
Fig. 6 is the phase transition temperature of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5) and the relation of molecular weight among the embodiment among the present invention.
Fig. 7 is the texture under polarizing microscope of polymer P 1 among the embodiment among the present invention.
Fig. 8 is uv-absorbing (Fig. 8 (A)) and the fluorescence emission spectrum (Fig. 8 (B)) (excitation wavelength be 297nm) of polymkeric substance OFB PCBHMA (P1, P2, P3, P4, P5) in dilute solution among the embodiment among the present invention.
Fig. 9 is the optical emission spectroscopy of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5) in solid film among the embodiment among the present invention, and excitation wavelength is respectively 297nm (Fig. 9 (A)) and 370nm (Fig. 9 (B)).
Embodiment
In order to understand content of the present invention better, come the bright technical scheme of the present invention of further condition below by concrete example and legend.Example is the OFB-PCBHMA multipolymer, and its structural formula is as follows:
N=10 wherein, 20,30,40,50
Concrete synthetic schemes is shown in following schema:
Synthesizing of OFB-PCBHMA block polymer
I. the main chain oligomer is synthetic:
2,7-two bromo-9, synthesizing of 9-hexyl-fluorenes (1): in single neck bottle of 250ml, add 2,7-dibromo fluorenes 10g (0.031mol), bromohexane 12.74g (0.077mol), methyl-sulphoxide 45ml, with sodium hydroxide 12.43ml (50%, W/W) and a spot of catalyzer tetrabutylammonium chloride (TBACL).After reaction is at room temperature carried out 5 hours, wash, extract with methylene dichloride then with an amount of water.Remove with distillation after the saturated common salt water washing organic phase three times and to desolvate, the method by column chromatography for separation and recrystallization obtains product 13.9g at last, and productive rate is 90%.
2-bromo-7-TMS-9,9-dihexyl-fluorenes (2) synthetic: in the single neck bottle of 250ml, add 1 (10g, 0.0204mol), tetrahydrofuran (THF) 140ml, (1.6M is dissolved in normal hexane 12.8ml to n-Butyl Lithium, 0.0204mol), under-78 ℃, reacted one hour.(0.02448mol 3.08ml), and is raised to room temperature gradually with temperature of reaction, continues reaction half an hour to add trimethylchlorosilane then.Send out should finish after, with using petroleum ether extraction after a large amount of water washings.Organic phase is through the saturated common salt water washing, and anhydrous sodium sulfate drying by column chromatography for separation, obtains colourless liquid 8.64g, productive rate 87.8% at last at last.
2-boric acid-9, synthesizing of 9-dihexyl-7-(TMS)-fluorenes (3): in single neck bottle of 250ml, add 2 (8g, 16.53mmol), THF50ml, (1.6M is dissolved in normal hexane, 12.6ml) at temperature-78 a ℃ following adding n-Butyl Lithium, after reaction is carried out one hour, add triisopropyl boric acid ester (8.26ml); Continuing reaction at room temperature spends the night.After reaction finished, the water washing product with a large amount of extracted with ether then; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain white powder 5.23g by column chromatography for separation at last, productive rate 71%.
2-bromo-9,9-dihexyl-fluorenes (4) synthetic: in the two-neck bottle of 250ml, add 2-bromine fluorenes 10g (0.0408mol), bromohexane 20.14ml, methyl-sulphoxide 50ml, NaOH (50%, W/W) 20ml, catalyzer TBACL, reaction is 6 hours when temperature is 70 ℃.Reaction washes with water after finishing, and extracts with methylene dichloride then; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain light yellow liquid 15.6g by column chromatography for separation at last, productive rate is 92.3%.
2-boric acid-9,9-dihexyl-fluorenes (5) synthetic: method is 67% with (3) productive rate.
2-TMS-dimerization fluorenes (6) synthetic: in the two-neck bottle of 250ml, add 5 (5g, 13.2mol), 2 (5g, 10.33mmol), the triphenyl phosphorus palladium (400mg, 34.4mmol) and TBACL, toluene 50ml, 2.0M solution of potassium carbonate 50ml; In temperature is 90 ℃, unglazed according under the condition light, reacts two days.Reaction is used the petroleum ether extraction head product after finishing; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain colourless liquid 5.94g by column chromatography for separation at last, productive rate 78%.
Synthesizing of 2-iodo-dimerization fluorenes (7): in single neck bottle of 150ml, add 6, CCl
4(40ml), then when temperature is 0 ℃, (1.0M is dissolved in methylene dichloride, and 7.59ml 7.59mmol) dropwise drips in the reaction system and goes, and at room temperature reacts then 4 hours with ICl.After reaction finishes, with a large amount of Na
2S
2O
3Solution is removed excessive iodine; Back dichloromethane extraction crude product.Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Most of solvent is removed in distillation, obtains yellow crude product; To go out the crude product washing with methyl alcohol earlier, and carry out recrystallization then and obtain preceding yellow powder 4.6g, productive rate is 76.5%.
Synthesizing of 2-boric acid-dimerization fluorenes (8): method is with (3), and productive rate is 50%.
1-(4-brombutyl)-4-anisole (9) synthetic: in the round-bottomed flask of 500ml, add the 4-methoxyphenol (10g, 0.08mol) and potassium hydroxide (4.6g, 0.8mol), ethanol 200ml, reflux half an hour.(51.7g 28.6ml) adds, and continues reaction 4 hours with the 1.4-dibromobutane then.After reaction finished, most of ethanol was removed in distillation, washes and use chloroform extraction then with water; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain white crystal 14g by column chromatography for separation at last, productive rate 70%.
1-(4-brombutyl)-2,5-two bromo-4-anisoles (10) synthetic: 500ml two neck bottles in, add 9 (13.0g, 0.05mol) and chloroform 200mL; Stirring is dissolved in 40mL of chloroform with 6.2ml liquid bromine (0.12mol) after solid is dissolved, and dropwise drips in the system and goes, and continues reaction 12 hours, and hydrogen bromide is collected with saturated sodium hydroxide solution.Reaction is removed excessive liquid bromine and is used chloroform extraction with sodium hydroxide solution after finishing.Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain clear crystal 17.6g by column chromatography for separation at last, productive rate 85%.
4-(2,5-two bromo-4-methoxyl group phenoxy groups) butanols acetic ester (11) synthetic: in the two neck bottles of 250ml, add 10 (10g, 0.0254mol), Potassium ethanoate 2.5g (0.0508mol), acetic acid 100ml, a spot of acetic anhydride is made catalyzer, reflux one day.After the reaction, acetic acid is removed in solid part elimination and distillation; The back is with a large amount of water washings and use chloroform extraction.Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain clear crystal 8.32g by column chromatography for separation at last, productive rate 87.4%.
Synthesizing of 4-(2,5-two (9,9-dihexyl-2-(TMS) fluorenes)-4-methoxyl group phenoxy group) butanols (12): synthetic method is with compound 6, and productive rate is 92%.
Synthesizing of 4-(2,5-two (9,9-dihexyl-2-iodo-fluorenes)-4-methoxyl group phenoxy group) butanols (13): synthetic method is with compound 7, and productive rate is 77.5%.
Synthesizing of 4-(2,5-two oligomerizations fluorenes-4-methoxyl group) butanols (14): synthetic method is with compound 6, and productive rate is 50.6%.
Synthesizing of OFB initiator (15): in single neck bottle of 100ml, add 14 (1.236g, 0.5645mmol), trihexylamine 0.157ml (1.1mmol), dibromo-isobutyl acylbromide 0.14ml (1.1mmol), tetrahydrofuran (THF) 30ml, after reaction is spent the night under the room temperature, to beaker, allow trihexylamine vapor away reactant transfer.Product washes with water, and uses chloroform extraction, and organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain yellow solid 1.2g by column chromatography for separation at last, productive rate is 91%.
II. soft chain is monomeric synthetic
CBHOH's (16) is synthetic: in the two neck bottles of 150ml, add 4-hydroxyl-4 '-cyanobiphenyl 5g (25.64mmol), and 6-bromine hexanol 4.6g (25.64mmol), 6g salt of wormwood, 60mlDMF is 60 ℃ in temperature, reacts one day.Reaction finishes after-filtration and removes solid, uses extracted with diethyl ether three times; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain white powder 6.39g by column chromatography for separation at last, productive rate is 84.4%.
CBHMA's (17) is synthetic: in single neck bottle of 150ml, add (16) 6.32g, and 21.6mmol, vinylformic acid 3.5Ml, methylene dichloride 63.2ml, DCC 4.55G, DMAP, 0.7G at room temperature reacted one day.Reaction back dichloromethane extraction; Organic phase is used anhydrous sodium sulfate drying after washing with saturated aqueous common salt.Obtain white crystal 5.83g by column chromatography for separation and recrystallization at last, productive rate is 75%.
III. block polymer is synthetic: in reaction tubes, add cuprous bromide 3.15mg (0.022mmol), macromole evocating agent (15) 0.0515g (0.022mmol), (17) 0.4 (1.1mmol); Orthodichlorobenzene 0.5ml utilizes frozen-thawed circulation deoxygenation, and the temperature with reaction system rises to 60 ℃ then, then adds HEMETA (1,1,4,7,10,70-hexamethyl triethyl four ammoniums), continues reaction 2.5 hours then.Reaction is dissolved in tetrahydrofuran (THF) with reactant, and with neutral alumina elimination mantoquita, with a large amount of methyl alcohol polymkeric substance is settled then after finishing, and with the normal hexane washing for several times, obtains white powder 0.326g, and transformation efficiency is 95%.Obtain the concrete reaction conditions of the different polymkeric substance of molecular weight 18 (P1, P2, P3, P4, P5) respectively and the results are shown in table one.
The sign of block polymer:
Instrument: a Varian Mercury Plus 400 (tetramethylsilane is interior mark)
1H NMR (400MHz) and
13C NMR (100MHz); Tianjin, island UV-3150 spectrophotometer; Tianjin, island RF-5300PC fluorescence spectrophotometer; Tianjin, island IRPrestige-21 infrared spectrophotometer; Agilent 1100GPC (eluent is a tetrahydrofuran (THF), and polystyrene is interior mark); TA-DSC-2910; Olympus BX51 polarizing microscope.
1, Fig. 1 has provided the elution curve of the GPC of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5) and OFB macromole evocating agent; From figure, we are polyreaction generation front and back as can be seen, the variation of elution time, and, polyreaction success and effectively initiation are described in the completely dissolve of the peak at OFB place.The molecular weight of polymkeric substance (P1, P2, P3, P4, P5) increases progressively, and meets us and reacts preceding design, illustrates that the ATRP polymerization process is a kind of very effective controllable polymerization.
2, Fig. 2 has provided the infrared spectra of block polymer OFB-PCBHMA (P1) and oligomer molecule initiator OFB, and as can be seen from the figure, block polymer P1 compares with initiator OFB, is 1607cm in wave number
-1And 2230cm
-1Infrared absorption has appearred in the place, and the stretching vibration of C-H stretching vibration in the biphenyl that their are corresponding respectively in the liquid crystal unit and cyano group absorbs.This result shows, has the block of branched chain type liquid crystal polymer in block polymer.
3, Fig. 3,4 has provided the nucleus magnetic hydrogen spectrum and the carbon spectrum of polymer P 1 and OFB initiator respectively.Consistent with preceding two kinds of characterizing methods is, the spectrogram of P1 and OFB relatively, and in P1 hydrogen spectrum and carbon were composed, we can point out to belong to the characteristic peak of OFB and P1 respectively; Explanation contains OFB and two kinds of blocks of PCBHMA in polymkeric substance.In addition, from analyzing the end group of molecule before and after the polymerization, we can see that displacement in the hydrogen spectrum is that variation has taken place for 1.91 the displacement of hydrogen proton after polymerization; And in carbon 13 spectrums, displacement is respectively 30.8 and 55.8, and (they correspond respectively to end group-C (CH
3)
2Br and-C (CH
3)
2Br) after polymerization, disappear respectively, this statement of facts OFB be connected by polyreaction with the PCBHMA block, be not mixture.We can also obtain another one information from the hydrogen spectrum, and relatively shift value is the integrated value of 7.0ppm and 6.9ppm, can extrapolate the polymerization degree of PCBHMA, thereby obtain the molecular weight (listing in table one) of block polymer.
4, Fig. 5 has provided the DSC curve of polymkeric substance OFB-PCBHMA (P1, P2, P3, P4, P5).A and B provided respectively polymkeric substance heat up with 10 ℃/min and temperature-fall period in thermal behavior.A single peak has all appearred in A and B, corresponding to the clearing point of liquid crystal.The second-order transition temperature and the clearing point of polymkeric substance are listed in the table two respectively.Fig. 6 has provided the relation of changing mutually of liquid crystal and polymericular weight, and as seen from the figure, phase transition temperature increases gradually along with the increase of molecular weight, and greater than 14000 o'clock, phase transition temperature tended towards stability gradually at molecular weight.Fig. 7 has provided the liquid crystal texture of polymkeric substance under polarizing microscope.When the isotropy attitude was lowered the temperature, we had seen the texture of wooden civilian shape at polymkeric substance; We knit attitude with this texture ownership for the smectic phase of liquid crystal.
5, the A of Fig. 8, B have provided ultra-violet absorption spectrum and the fluorescence emission spectrum (excitation wavelength be 297nm) of polymkeric substance in chloroform diluted solution respectively.From figure A, polymkeric substance corresponds respectively to the absorption of PCBHMA and OFB chromophore for the absorption of 297nm and 370nm; In 370nm absorption place, carry out normalization method after,, absorb and strengthen along with molecular weight (content of PCBHMA) increases in the absorption of 297nm; Corresponding with the result of GPC.In figure B, the excitation wavelength of fluorescence is the absorption of 297nm corresponding to PCBHMA; As we can see from the figure, fluorescence all has emission at 370nm and 413mm, correspond respectively to the emission of PCBHMA and OFB, comparing with the homopolymer of PCBHMA, segmented copolymer strengthens the energy transfer that can draw from PCBHMA to OFB chromophore in the fluorescent quenching of 370nm with at 430nm fluorescence, and in dilute solution, the efficient that energy shifts weakens along with the chainpropagation of PCBHMA.Explanation is in dilute solution, and the energy Transfer Mechanism is mainly intramolecular energy and shifts.
6, the A of Fig. 9, B have provided the fluorescence emission spectrum (excitation wavelength be respectively 370nm and 297nm) of polymkeric substance in film respectively.From A, find out among the B that the fluorescence emission spectrum and the spectrum in the dilute solution of film relatively have tangible red shift; B figure shown excitation wavelength be the fluorescence spectrum of 297nm and figure nine (B) relatively, in solid film, the fluorescent emission of 370nm illustrates in film that almost by complete cancellation the efficient that energy shifts is higher.
Table one .ATRP polymeric reaction condition and result
| Polymkeric substance | Time (min) | Monomers/initiator | Monomer/solvent (g/ml) | Transformation efficiency (%) | Molecular weight (theory) | Molecular weight (NMR) | Molecular weight (GPC) | Dispersed (PDI) |
| P1 P2 P3 | 30 60 60 | 10 20 30 | 1/3 1/2 1/2 | 87 86 91 | 5500 8600 12200 | 7800 9200 11400 | 10100 12300 14600 | 1.12 1.18 1.16 |
| P4 P5 | 120 150 | 40 50 | 2/3 2/3 | 91 94 | 15600 19400 | 13600 15800 | 17100 21200 | 1.20 1.16 |
Table two. the DSC data of polymkeric substance
| Polymkeric substance | T g℃ | Phase transition temperature ℃ | |
| Heat up | Cooling | ||
| T s-i | T i-s | ||
| The OFB initiator | 62 | --- | --- |
| P1 P2 P3 P4 P5 | 63 66 66 67 67 | 97.3 105.8 107.6 108.9 110.4 | 90.2 99.6 101.5 102.7 104.0 |
| PCBHMA | 67 | 112.6 | 108.2 |
Claims (3)
1, a kind of soft and hard multi-block polymer is characterized in that having as a structural formula:
Wherein, Ar is an oligomerization benzene, oligo-thiophenes, oligomerization fluorenes, oligomerization benzyne, the support of oligomerization vinylbenzene or the support of oligomerization phenylacetylene, the perhaps multipolymer that is formed by above conjugated polymers monomer;
A, B are simple functional group, or the homopolymer or a plurality of monomeric multipolymer that are polymerized by acrylic acid or the like, methacrylic, vinylcarbazole, caprolactone monomer.
2, polymkeric substance according to claim 1 is characterized in that having following a kind of structure formation:
I.Ar is the oligomerization fluorenes, and A is a methoxyl group, and B is the polymethylmethacrylate that contains the cyanobiphenyl liquid crystal unit; Its structural formula is as follows:
Wherein R is a hexyl; M=2,3,4; N=10,20,30,40;
II.Ar is the oligomerization fluorenes, and A is a methoxyl group, and B is PEG or polycaprolactone; Its structure is as follows:
Wherein R is a hexyl; M=2,3,4; N=10,20,30,40;
III.Ar is the oligomer of being made up of thiophene phenol and fluorenes, and A is a methoxyl group, and B is an Ionomer; Its structure is as follows:
Wherein R is a hexyl; N=10,20,30,40;
IV.Ar is the oligomerization fluorenes, and A, B are the polymethylmethacrylate that contains the cyanobiphenyl liquid crystal unit; Its structural formula is as follows:
Wherein R is a hexyl; M=2,3,4; N=10,20,30,40.
3,, it is characterized in that concrete steps are as follows as the synthetic method of claim 1 or 2 said soft and hard multi-block polymers:
Synthesizing of the multipolymer of I, main chain oligomerization fluorenes or oligomerization thiophene phenol, oligomerization fluorenes and oligomerization benzyne:
(1) protective group: brominated monomer is dissolved in the tetrahydrofuran (THF), adds the n-Butyl Lithium reaction down after 45-90 minute at subzero 78 ℃, adds the trimethyl silane afterreaction 30-120 minute; Separation obtains product through chromatography column;
(2) functional group go the protection: utilize ICl that the blocking group of trimethyl silane is removed, obtaining with I is end capped monomer;
(3) boration reaction: will have monomer to be dissolved in the tetrahydrofuran (THF) with Br or I functional group, add n-Butyl Lithium reaction 45-90 minute down at subzero 78 ℃, add the monomer that obtains having boric acid functional group after the reaction of trimethyl-boron acid esters or triisopropyl boric acid ester is spent the night;
(4) Suzuki metal linked reaction: the monomer that will have boric acid functional group and Br of halogen functional group or I carries out coupling under alkaline condition and under the catalysis of triphenyl phosphorus palladium, obtain corresponding oligomer;
II. the synthetic method of block polymer:
(1) atom transfer radical polymerization method:
To be dissolved in the orthodichlorobenzene by macromole evocating agent and the polymerization single polymerization monomer that oligomer is made, add ligand 1 then, 1,4,7,10,70-hexamethyl triethyl four ammoniums and catalyzer cuprous bromide are 60-90 ℃ in temperature, reaction back 3-10 hour, after the end, reactant is dissolved in tetrahydrofuran (THF), and with neutral alumina elimination mantoquita, with methyl alcohol polymkeric substance is settled then, and wash products therefrom with normal hexane;
(2) ring-opening polymerization method:
With the oligomer of hydroxyl and caprolactone at Sn (Oct)
2Under the catalysis, be to carry out mass polymerization under 120-140 ℃ in temperature, product precipitates in methyl alcohol and washs.
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| CN104693387B (en) * | 2015-04-01 | 2017-03-29 | 中国人民解放军国防科学技术大学 | A kind of synthetic method of carbazole block copolymer |
| CN109321234B (en) * | 2018-10-19 | 2020-04-03 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, preparation method of electroluminescent material and luminescent device |
| CN115895651A (en) * | 2022-11-04 | 2023-04-04 | 汕头大学 | Size-adjustable carbon dot and synthesis method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171130A (en) * | 1994-12-27 | 1998-01-21 | 巴斯福股份公司 | Thermoplastic moulding composition based on graft copolymer and block copolymer |
| CN1177606A (en) * | 1996-09-20 | 1998-04-01 | 中国科学院化学研究所 | Polyester-polyether multi-block copolymer, preparation method and use thereof |
| CN1587300A (en) * | 2004-07-15 | 2005-03-02 | 复旦大学 | Modified soft and hard multiple block conjugate polymer and its preparing method |
| CN1604923A (en) * | 2001-05-29 | 2005-04-06 | 西安大略大学 | Arborescent thermoplastic elastomers and products therefrom |
-
2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171130A (en) * | 1994-12-27 | 1998-01-21 | 巴斯福股份公司 | Thermoplastic moulding composition based on graft copolymer and block copolymer |
| CN1177606A (en) * | 1996-09-20 | 1998-04-01 | 中国科学院化学研究所 | Polyester-polyether multi-block copolymer, preparation method and use thereof |
| CN1604923A (en) * | 2001-05-29 | 2005-04-06 | 西安大略大学 | Arborescent thermoplastic elastomers and products therefrom |
| CN1587300A (en) * | 2004-07-15 | 2005-03-02 | 复旦大学 | Modified soft and hard multiple block conjugate polymer and its preparing method |
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