CN100441567C - Acrylic ester and methyl acrylic ester kind side chain type luminous polymer and its synthesis - Google Patents
Acrylic ester and methyl acrylic ester kind side chain type luminous polymer and its synthesis Download PDFInfo
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- CN100441567C CN100441567C CNB200510095259XA CN200510095259A CN100441567C CN 100441567 C CN100441567 C CN 100441567C CN B200510095259X A CNB200510095259X A CN B200510095259XA CN 200510095259 A CN200510095259 A CN 200510095259A CN 100441567 C CN100441567 C CN 100441567C
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Abstract
The present invention discloses an acrylate and methylacrylate side chain type luminescent polymer. The present invention is characterized in that biphenyl base groups are contained on the side chain of the polymer. The present invention simultaneously provides a method for synthesizing the polymer and a synthetic monomer in the reaction process. The present invention can utilize an atom transfer free radical polymerization method to synthesize the new side chain type luminescent polymer which is an industrialized product with the advantages of convenient synthesis, controllable molecular weight and molecular weight distribution, mild reaction condition and easy acquirement of catalysts and solvents. The reaction temperature range is wide, and therefore, the reaction can be carried out in room temperature, which is good for industrialization. Simultaneously, the product of the present invention can change the fluorescence performance of mixtures by changing the structure of the side chain.
Description
Technical field
The present invention relates to (methyl) acrylic ester monomer that a class contains biphenyl class group, and pass through atom transition free radical polymerization reaction synthetic side chain type luminous polymer by this monomer; The present invention relates to their synthetic method simultaneously.
Background technology
Luminescence polymer has caused people's extensive concern with its applications well prospect as aspects such as fluorescent material, electroluminescent materials.The electroluminescent device made from organic small molecule material is practicability, product mainly concentrates on the small screen demonstration aspect, built the production line of an organic electroluminescent device as the Philips company of Holland, be mainly used in the demonstration backlight of producing mobile phone and other portable electronics, and based on the luminescent device of organic polymer material in the research of carrying out practicability, market outlook are wide.
Typical case's luminescence polymer is representative to gather styrenic (PPV), and this class material is to study maximum electroluminescent materials at present, and they have following characteristics: have good processing properties, can be made into large area film; Have good electricity, thermostability; Its conjugated polymers electronic structure, glow color can carry out Chemical Regulation in building-up process.By the various electroluminescent polymers that basic luminophore is combined to form, be broadly divided into the main chain conjugated type, conjugated main chain is articulated type, small molecules doped polymer type 4 big classes by isolation-type, side chain.
Organic electroluminescence device is one and relates to multi-disciplinary research fields such as physics, chemistry, material and electronics, the researchdevelopment of having passed through decades has obtained huge achievement, but still exists following problem on the road of practicability in enormous quantities: the luminous efficiency of (1) device is still on the low side; (2) work-ing life of device is too short; (3) impatient the treating of stablizing of device improved; (4) research of luminescence mechanism is not thorough yet.
Therefore, carrying out the design of new organic materials, improve its fluorescence radiation efficient, is to make device practicability, use diversified precondition, also is the main developing direction of organic electroluminescence device from now on.
The luminescence polymer of side chain type is that chromophoric group is connected on the flexible polymkeric substance as side chain, improve the solvability and the processibility of polymkeric substance, serve new advantage to polymer belt: the luminosity of (1) polymkeric substance is by side chain chromophoric group decision, and highdensity chromophoric group side chain can not cause concentration quenching between the molecular chain yet on the polymkeric substance; (2) a lot of physical propertiess of polymkeric substance are relevant with the flexible main chain of polymkeric substance, as the stability under solvability and the metamict.Therefore, seek new side chain type luminous polymer and synthetic method thereof, the development of luminescence polymer is had significance.
Since nineteen ninety-five by since proposition such as Wang Jinshan and having reported atom transition free radical polymerization reaction (ATRP), the ATRP technology has obtained swift and violent development, becomes a kind of synthetic a kind of novel and effective method with polymkeric substance of controlled, narrow molecular weight issue of molecular weight and new structure that is used for.
Atom transfer radical polymerization is one of the most successful active free radical polymerization method.The advantage of radical polymerization of ATRP collection and living polymerization, compare with other living polymerization, its polymerizing condition gentleness, the monomer applicable surface is very extensive, monomer, solvent treatment and technical process are simple, polymerization process is easy to control, and conversion unit is identical with general radical polymerization, and good industrial prospect is arranged.
Though the monomer wide range that ATRP is suitable for, different monomers has very big difference to the conditional request of polyreaction.General oil-soluble monomer, the temperature requirement of polyreaction is higher, needs active higher initiator system to cause, the difficult ATRP reaction that realizes under the low temperature.Selecting active high monomer to realize that the ATRP under the low temperature reacts, is a popular research direction in present this field, also helps realizing the industrialization of ATRP technology.The inventor considers to use the ATRP polymerization technique, to obtain to be suitable for the luminescence polymer synthetic method of suitability for industrialized production.
Summary of the invention
The object of the invention provides a kind of new side chain type luminous polymer, and provides the convenience of synthesizing this polymkeric substance and the method that is suitable for suitability for industrialized production.
For achieving the above object, the technical solution used in the present invention is: a kind of acrylate and methyl acrylic ester side chain type luminous polymer, on the side chain of polymkeric substance, contain biphenyl class group, and the structural formula of polymkeric substance is as follows,
In the formula, R is selected from hydrogen (H), cyano group (CN) or formate (COO
-);
R ' is selected from hydrogen (H) or methyl (CH
3); R " be initiator residue.
The present invention has provided a kind of acrylate and the methyl acrylic ester monomer that is used for synthetic above-mentioned polymkeric substance simultaneously, and its structural formula is as follows:
In the formula, R is selected from hydrogen (H), cyano group (CN) or formate (COO
-);
R ' is selected from hydrogen (H) or methyl (CH
3).
The synthetic method of acrylate of the present invention and methyl acrylic ester side chain type luminous polymer comprises the following steps: successively
(1) 4 '-bromomethylbiphenyl with 4 '-bromomethylbiphenyl or replacement obtains hydrolysate in the hydrolysis under the alkaline condition, and reaction can be expressed as,
In the formula, R
0Be selected from hydrogen (H), cyano group (CN) or ester group (COOR " '), wherein R " ' refer to the fatty alkyl that 5 carbon atoms are following.
(2) (methyl) acrylic ester monomer that contains biphenyl class group is synthesized in the reaction of hydrolysate and (methyl) acrylate chloride, react to be,
In the formula, R ' is hydrogen (H) or methyl (CH
3).
(3) the gained monomer is by the synthetic described side chain type luminous polymer of atom transfer radical polymerization, wherein initiator is selected from alpha-brominated ethyl isobutyrate, 2-cyano group-4 '-bromomethylbiphenyl, 4-(benzoxazole-2-) benzyl chloride or 2-methoxyl group-5-chloromethylbenzene formaldehyde, catalyzer is the title complex of pentamethyl-diethyl triamine and cuprous bromide or cuprous chloride, is reflected in the cyclohexanone solvent to carry out under 10～110 ℃.
Further technical scheme, 4 ' of described replacement-bromomethylbiphenyl is 2-cyano group-4 '-bromomethylbiphenyl or 4 '-bromomethylbiphenyl-2-carboxylicesters.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention has at first obtained to have (methyl) acrylic ester monomer of lighting function group, thereby can utilize atom transfer radical polymerization method to synthesize a kind of new side chain type luminous polymer, and is synthetic easier;
2. can obtain the side chain type luminous polymer involved in the present invention of molecular weight and controllable molecular weight distribution easily by atom transfer radical polymerization;
3. the present invention prepares the atom transition free radical polymerization reaction mild condition of polymkeric substance, and catalyzer and solvent all are the industrialization products that is easy to get, and range of reaction temperature is wide, can at room temperature carry out, and this all helps industrialized carrying out.
4. the fluorescence property of institute of the present invention synthetic side chain type luminous polymer is mainly determined by side chain functionalities, and the influence of end group is very little, can change (comprising the coordination with different metal ions) fluorescence property of mixture by the structure that changes side chain.
5. the solvability of institute of the present invention synthetic side chain type luminous polymer and processing characteristics are soluble in common organic solvent such as tetrahydrofuran (THF), chloroform, pimelinketone etc., and can be prepared into stable film by the spin coating of solution by its flexible main chain decision.
Description of drawings
Accompanying drawing 1 is the embodiment of the invention four causes gained polymethyl acrylic acid-4-(2 '-cyanobiphenyl base) methyl esters (PCBPMMA) at different initiators a fluorescence spectrum.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: synthetic (methyl) vinylformic acid-4-(2 '-cyanobiphenyl base) methyl esters
1.2-the hydrolysis of cyano group-4 '-bromomethylbiphenyl
In 800ml concentration is 0.3～1% diluted alkaline (potassium hydroxide or sodium hydroxide), add 1～3g2-cyano group-4 '-bromomethylbiphenyl reflux, the unreacted raw material of elimination while hot, cooling, separate out crystal, filtration drying gets hydrolysate 2-cyano group-4 '-hydroxymethyl biphenyl.
2. (methyl) vinylformic acid-4-(2 '-cyanobiphenyl base) methyl esters is synthetic
Getting said hydrolyzed product 2-cyano group-4 '-hydroxymethyl biphenyl 4.0g is dissolved in 60～100ml tetrahydrofuran (THF), under ice bath, add 7.0～9.0ml triethylamine, other gets 4.0～6.0ml (methyl) acrylate chloride and is dissolved in the tetrahydrofuran (THF) (both volume ratios are 1: 4), be added drop-wise to again in the above-mentioned solution, ice bath reacted 2～3 hours down, and normal-temperature reaction is 5～10 hours again.Reactant is successively used diluted alkaline, Diluted Acid Washing, gets white solid.Use the dehydrated alcohol recrystallization again, promptly obtain product after the vacuum-drying.
Embodiment two: synthetic (methyl) vinylformic acid-4 '-(2-carboxyl biphenyl base) methyl esters
1.4 the hydrolysis of '-bromomethylbiphenyl-2-carboxylicesters
In the diluted alkaline (potassium hydroxide or sodium hydroxide) of 800ml 0.3～1%, add 2～4 gram 4 '-bromomethylbiphenyl-2-methyl-formiate reflux, the unreacted raw material of elimination while hot, cooling, separate out crystal, filtration drying gets hydrolysate 4 '-hydroxymethyl biphenyl-2-formic acid.
With other 4 '-bromomethylbiphenyl-2-alkyl formate is that raw material also can take place to react accordingly to obtain 4 '-hydroxymethyl biphenyl-2-formic acid.
2. (methyl) vinylformic acid-4 '-(2-carboxyl biphenyl base) methyl esters is synthetic
Getting said hydrolyzed product 4 '-hydroxymethyl biphenyl-2-formic acid 4.2g is dissolved in 60～100ml tetrahydrofuran (THF), under ice bath, add 7.0～9.0ml triethylamine, other gets 4.0～6.0ml (methyl) acrylate chloride and is dissolved in tetrahydrofuran (THF) (both volume ratios are 1: 4), be added drop-wise to again in the above-mentioned solution, ice bath reacted 2～3 hours down, and normal-temperature reaction is 5～10 hours again.Reactant is successively used diluted alkaline, Diluted Acid Washing, gets white solid.Use the dehydrated alcohol recrystallization again, promptly obtain product after the vacuum-drying.
Embodiment three: synthetic (methyl) vinylformic acid-4-(xenyl) methyl esters
1.4-the hydrolysis of bromomethylbiphenyl
In the diluted alkaline (potassium hydroxide or sodium hydroxide) of 800ml 0.3～1%, add 1～3g 4-bromomethylbiphenyl reflux, the unreacted raw material of elimination while hot, crystal is separated out in cooling, and filtration drying gets hydrolysate 4-hydroxymethyl biphenyl.
2. (methyl) vinylformic acid-4-(xenyl) methyl esters is synthetic
Getting said hydrolyzed product 4-hydroxymethyl biphenyl 3.6g is dissolved in 60～100ml tetrahydrofuran (THF), under ice bath, add 7.0～9.0ml triethylamine, other gets 4.0～6.0ml (methyl) acrylate chloride and is dissolved in tetrahydrofuran (THF) (both volume ratios are 1: 4), be added drop-wise to again in the above-mentioned solution, ice bath reacted 2～3 hours down, and normal-temperature reaction is 8～16 hours again.Reactant is successively used diluted alkaline, Diluted Acid Washing, gets white solid.Use the dehydrated alcohol recrystallization again, promptly obtain product after the vacuum-drying.
Embodiment four
With initiator (alpha-brominated ethyl isobutyrate, 2-cyano group-4 '-bromomethylbiphenyl, the benzyl chloride of 4-(benzoxazole-2-), 2-methoxyl group-5-chloromethylbenzene formaldehyde etc., with monomeric mol ratio be 1: 25～1: 500), catalyzer (the title complex of pentamethyl-diethyl triamine and cuprous bromide (or cuprous chloride), the mol ratio of both and initiator is (0.5～1): 1: 1), above-mentioned institute synthetic monomer join the solvent pimelinketone (with the monomer mass ratio be 1: 1～15: 1) in, sealed reaction vessel, vacuum nitrogen filling gas repeatedly, the reaction vessel after the deoxygenation (10～110 ℃) under design temperature carries out polyreaction.To setting-up time (according to polymericular weight, monomer, initiator and the temperature difference of required control, the time can not waited from 0.5～36 hour), take out the dilution of adding tetrahydrofuran (THF), pour into then in the excessive methyl alcohol that is added with 1: 1 hydrochloric acid and precipitate.Isolated polymer dissolution in tetrahydrofuran (THF), is used methanol extraction once more, filter vacuum-drying, the gained solid is product.
Present embodiment causes the fluorescence spectrum of gained polymethyl acrylic acid-4-(2 '-cyanobiphenyl base) methyl esters (PCBPMMA) at different initiators, as shown in Figure 1, and methoxyl group-5-chloromethylbenzene formaldehyde a.2-wherein; B.4-the benzyl chloride of (benzoxazole-2-); C.2-cyano group-4 '-bromomethylbiphenyl; D. alpha-brominated ethyl isobutyrate.
Claims (4)
1. acrylate and methyl acrylic ester monomer is characterized in that its structural formula is as follows:
In the formula, R is selected from cyano group or formate;
R ' is selected from hydrogen or methyl.
2. described acrylate of claim 1 and the monomeric synthetic method of methyl acrylic ester is characterized in that, comprise the following steps: successively
The hydrolysis of 4 '-bromomethylbiphenyl under alkaline condition that (1) will replace obtains hydrolysate;
(2) synthetic (methyl) acrylic ester monomer that contains biphenyl class group of hydrolysate and (methyl) acrylate chloride reaction.
3. synthetic method according to claim 2 is characterized in that: 4 ' of described replacement-bromomethylbiphenyl is 2-cyano group-4 '-bromomethylbiphenyl or 4 '-bromomethylbiphenyl-2-carboxylicesters.
4. the application of the described monomer of claim 1 in acrylic ester synthesizing and methyl acrylic ester side chain type luminous polymer, described monomer is synthesized side chain type luminous polymer by atom transfer radical polymerization, wherein initiator is selected from alpha-brominated ethyl isobutyrate, 2-cyano group-4 '-bromomethylbiphenyl, 4-(benzoxazole-2-) benzyl chloride or 2-methoxyl group-5-chloromethylbenzene formaldehyde, catalyzer is the title complex of pentamethyl-diethyl triamine and cuprous bromide or cuprous chloride, is reflected in the cyclohexanone solvent to carry out under 10～110 ℃.
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| EP3129416B1 (en) * | 2014-04-07 | 2018-06-06 | Dow Global Technologies LLC | Regulation of a controlled radical polymerization of acrylates by light |
| CN104788594B (en) * | 2015-04-16 | 2018-07-24 | 厦门大学 | A kind of preparation method of Amino End Group polymer |
| CN113735772B (en) * | 2021-09-22 | 2024-04-09 | 四川羽玺新材料股份有限公司 | Fluorescent functional monomer, pressure-sensitive adhesive capable of finding coating defects in time and preparation method of pressure-sensitive adhesive |
| CN115466220A (en) * | 2022-08-10 | 2022-12-13 | 盐城工学院 | Bisazo five-membered azole ring monomer with three-order nonlinear optical performance, polymer thereof and preparation method thereof |
| CN115558110B (en) * | 2022-09-14 | 2023-07-21 | 宁夏清研高分子新材料有限公司 | Polymer and preparation method thereof, gel and dielectric material |
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| US5403904A (en) * | 1993-05-27 | 1995-04-04 | Amoco Corporation | Process for preparation of telechelic difunctional unsaturated oligomers or polymers by acyclic olefin metathesis |
| CN1292022A (en) * | 1998-12-28 | 2001-04-18 | 出光兴产株式会社 | Organic electroluminescent device |
| CN1306546A (en) * | 1998-06-19 | 2001-08-01 | 钟渊化学工业株式会社 | Process for producing branched polymer and polymer |
| JP2004258427A (en) * | 2003-02-27 | 2004-09-16 | Hayashi Telempu Co Ltd | Birefringence inducing material, retardation film, method for manufacturing retardation film, and photosensitive polymer |
-
2005
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|---|---|---|---|---|
| US5187248A (en) * | 1989-05-26 | 1993-02-16 | Basf Aktiengesellschaft | Monomers and their use for the production of a laser-optical recording element which can be repeatedly erased and recorded on |
| US5403904A (en) * | 1993-05-27 | 1995-04-04 | Amoco Corporation | Process for preparation of telechelic difunctional unsaturated oligomers or polymers by acyclic olefin metathesis |
| CN1306546A (en) * | 1998-06-19 | 2001-08-01 | 钟渊化学工业株式会社 | Process for producing branched polymer and polymer |
| CN1292022A (en) * | 1998-12-28 | 2001-04-18 | 出光兴产株式会社 | Organic electroluminescent device |
| JP2004258427A (en) * | 2003-02-27 | 2004-09-16 | Hayashi Telempu Co Ltd | Birefringence inducing material, retardation film, method for manufacturing retardation film, and photosensitive polymer |
Non-Patent Citations (4)
| Title |
|---|
| methacrylic esters of aromatic alcohols and glycols. bulatov,m.a. 等.plasticheskie massy. 1975 |
| methacrylic esters of aromatic alcohols and glycols. bulatov,m.a. 等.plasticheskie massy. 1975 * |
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