CN101117369A - Inorganic network structure based modified non-linear optical polymer and preparation method thereof - Google Patents
Inorganic network structure based modified non-linear optical polymer and preparation method thereof Download PDFInfo
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- CN101117369A CN101117369A CNA2007100092130A CN200710009213A CN101117369A CN 101117369 A CN101117369 A CN 101117369A CN A2007100092130 A CNA2007100092130 A CN A2007100092130A CN 200710009213 A CN200710009213 A CN 200710009213A CN 101117369 A CN101117369 A CN 101117369A
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Abstract
The invention provides a reshaping nonlinear optics polymer based on the inorganic network structure and the preparation method relates to an organic and inorganic complex function polymers, and has superior second order nonlinear optics performance, superior heat stability and excellent processability, and includes organic and inorganic complex stroma and hydroxylorganic chromophore, when the invention is prepared, the mixed solution A of the double-linked carbon organosilane and the methyl methacrylate and the initiator are added into a reactor, and are heated, after being reacted by back flow, the mixed solution is put into a container, the copolymer B of the methyl methacrylate and the organic siloxane is obtained. The copolymer B, the inorganic glass precursor, the dehydrated alcohol and tetrahydrofuran are loaded into a reaction bottle, the HCl solution is added, to make the reaction mixture hydrolyze, the organic chromophore is added, after being dissolved, the organic/inorganic collosol containing the organic chromophore is obtained by filtration, the solvent is heated to volatilize, then the reshaping nonlinear optics polymer based inorganic network structure is obtained.
Description
Technical field
The present invention relates to a kind of organic/inorganic complex function macromolecular material, particularly a kind of non-linear optical polymer based on the inorganic network structure modification and preparation method thereof.
Background technology
(Nonlinear Optic NLO) is the response of research material under high light (laser) effect and the science of the nonlinear relationship that field intensity presents to nonlinear optics.The optical effect relevant with field intensity is called non-linear optical effect.Nowadays, the development of information technology (IT) is noticeable, and laser and Fibre Optical Communication Technology are the emerging communication technologys that replaces microelectronics and integrated circuit technique, utilize electric light and opto-electronic conversion and all-optical network can improve communication efficiency greatly.Integrated photosystem comprises important devices such as waveguide, photoswitch and photoconverter, all must use nonlinear optical material in these devices.Promoted the extensive development of microelectronics and unicircuit as the progress of semiconductor material, the raising of NLO material property also is the push agent of optical communication era development.Initial NLO material subsequently, it is found that some organism also has non-linear optical effect (benzopyrene etc.) based on inorganic materials (Lithium niobium trioxide etc.); Since 20th century the mid-80s, the research develop rapidly of the exploitation of polymkeric substance nonlinear optical material and device thereof.This be since organic and polymer materials have inorganic materials incomparable advantage, as: the structure of polymkeric substance is various, makes people carry out molecular designing according to the performance requriements of concrete device; The electro-optic response speed of polymkeric substance can reach nanosecond (10
-9S) even femtosecond (10
-15S) level has improved communication efficiency greatly; The transmission loss of polymkeric substance is less; The processing characteristics of polymkeric substance is superior, can be made into various difform devices or the like (Marder S.R., Kippelen B., JenA.K.Y.et al.Nature[J], 1997,388:845-851).
Polymethylmethacrylate (PMMA) produces the organic substrate material of (SHG) as optical second harmonic commonly used, have preparation simple, good with the non-linear organic chromophore molecule of object consistency, do not have advantages such as interaction with non-linear organic chromophore molecule generally speaking, people have carried out extensive studies (Burland K.D to this class Subjective and Objective doping type optical nonlinearity, Miller R.D, Walsh C.A.Chem.Rev.[J], 1994,94 (1): 31-75).But because this class material ubiquity is than lower glass transition temperatures, therefore the fast shortcoming of its relaxation has limited its application in optics simultaneously.In order to improve the thermal stability of PMMA type nonlinear optical material, people carry out various new trials, and as grafting epoxide group on main chain, open loop is crosslinked then, obtain cross-linking type PMMA structure (Wang Yao, Fu Na, Chuan Xiao-hong, et al.Chem.J.ChineseUniversities[J], 2004,25:565-569), but all there is severe reaction conditions in these methods, productive rate is low and shortcoming such as cost height, are unfavorable for practicability.Sol-gel (sol-gel) technology provides a kind of method (HayJ.N. of synthetic organic/inorganic composite material, Raval H.M., Chem.Mater.[J], 2001,13:3396-3340), this synthetic method preparation does not simply need exacting terms, the material that makes has concurrently organic and advantage inorganic materials, as on the basis that keeps good characteristics such as organic macromolecule filming, the transparency and flexibility, therefore the advantages such as high thermal stability, scuff resistance, solvent resistance, high rigidity that have inorganic materials again have utmost point using value widely.
Summary of the invention
The object of the present invention is to provide a kind of non-linear optical polymer based on the inorganic network structure modification with bigger second-order nonlinear optical property, higher thermostability and good processing characteristics.
Another object of the present invention is to provide a kind of preparation method of the non-linear optical polymer based on the inorganic network structure modification.
Technical scheme of the present invention is to be organic chromophore with the hydroxyl dyestuff with non-linear optical active, the carbon-carbon double bonds organosilane is a coupling agent, methyl methacrylate and organosilane or titanate ester are raw material, go out non-linear optical polymer by the inorganic network structure modification by mass polymerization and original position sol-gel technology preparing.In this base polymer, unorganic glass inflexible three-dimensional net structure has suppressed the organism segment and has relaxed with the activity performance of temperature rising and the orientation of nlo molecule, has improved the thermostability of nonlinear optical material greatly.The polymkeric substance of this method preparation has characteristics such as second order nonlinear coefficient height, Heat stability is good, film forming properties be good, helps practicability.
Non-linear optical polymer based on the inorganic network structure modification of the present invention comprises organic/inorganic composite interstitial substance and the hydroxyl organic chromophore two portions with network structure, and its chemical structure is respectively:
The organic/inorganic composite interstitial substance
Organic chromophore
Wherein X is Si or Ti; R is the alkyl of H or 1～9 carbon; A for do not exist or-C
nH
2n-or-NR-C
nH
2n-; B is-CN-NO
2,-CF
3,-SO
2R ,-R ,-CH=CH
2,-N=N-CN ,-CH=N-N=CH-NO
2,-CH=N-SO
2R or the like; N is 0～9 integer, and x, y are natural number.
The preparation method of the non-linear optical polymer based on the inorganic network structure modification of the present invention is as follows:
1) under nitrogen protection; the mixed solution A that in reactor, adds carbon-carbon double bonds organosilane and methyl methacrylate; in molar ratio; carbon-carbon double bonds organosilane: methyl methacrylate=1: (5～10); add the initiator Diisopropyl azodicarboxylate again; by mass percentage; the add-on of initiator Diisopropyl azodicarboxylate is 1%～2% of a mixed solution A; under stirring condition, be heated to 50～80 ℃; pour container into behind back flow reaction 0.5～3h; be incubated 8h at least in 50～80 ℃ again, obtain transparent methyl methacrylate and organo-siloxane copolymer B.
2) with the copolymer B for preparing in the step 1), the unorganic glass presoma, dehydrated alcohol and tetrahydrofuran (THF) be 1-x in molar ratio: x: 0.5: 8～12, x=0.2～0.5 wherein, the amount of copolymer B is calculated with the amount of monomer whose, pack in the reaction flask, stir, add HCl solution, it is 4: 1 that the add-on of HCl solution makes the mol ratio of water and unorganic glass presoma, continue to stir and make the reaction mixture hydrolysis, add organic chromophore again, by mass percentage, the add-on of organic chromophore is 5%～15% of copolymer B, and the stirring and dissolving after-filtration is removed insoluble impurity, obtains containing the hybrid colloidal sol of organic chromophore, sealing, leave standstill, after the ageing, the solvent heated volatile is promptly obtained non-linear optical polymer based on the inorganic network structure modification.
Unorganic glass can adopt SiO
2, the unorganic glass presoma should be tetraethoxy mutually.Unorganic glass also can adopt SiO
2/ TiO
2Binary composite inorganic glass, unorganic glass presoma should be positive four butyl esters of metatitanic acid mutually, or tetraethoxy and positive four butyl esters of metatitanic acid.
In step 2) in, the concentration of HCl solution is preferably 0.1～0.5mol/L.The hybrid colloidal sol that obtains containing organic chromophore through sealing, leave standstill after the aged time be preferably 3～7 days.
Described organic chromophore contains terminal hydroxy group, and easy and doping matrix forms stronger hydrogen bond action, helps improving consistency, improves doping content and thermostability.
Advantage of the present invention and beneficial effect are:
(1) the present invention uses the non-linear optical polymer based on the inorganic network structure modification of IN-SITU SOL-GEL preparation, utilizes unorganic glass inflexible network structure, has improved the resistance toheat of nonlinear optical material greatly.
(2) preparation method of the non-linear optical polymer based on the inorganic network structure modification of the present invention is simple, does not need harsh reaction conditions, and cost is low, and film forming properties is good, more helps practicability.
(3) non-linear optical polymer based on the inorganic network structure modification of the present invention's preparation has good thermostability and higher second order nonlinear coefficient.
Embodiment
Embodiment 1
(1) under nitrogen protection; the mol ratio that adds 10ml in the exsiccant three-necked bottle is 1: 5 gamma-methyl allyl acyloxypropyl trimethoxysilane and a methyl methacrylate mixing solutions; adding quality again is the initiator Diisopropyl azodicarboxylate of mixing solutions 1%; heating in water bath to 80 ℃ under the condition of magnetic agitation; pour container into behind the reflux 0.5; in 50 ℃ of insulation 24h, obtain the transparent methyl methacrylate and the copolymer of gamma-methyl allyl acyloxypropyl trimethoxysilane again.
(2) get above-mentioned copolymer, tetraethoxy, water, dehydrated alcohol and tetrahydrofuran (THF) were according to 0.7: 0.3: 0.5: 12 mol ratio is respectively charged in the three-necked bottle, magnetic agitation is dissolved polymkeric substance fully, the HCl solution that dropwise adds 0.5mol/L then while stirring, it is 4: 1 that add-on makes the mol ratio of water and tetraethoxy, continue to stir and make the reaction mixture hydrolysis, adding quality again is the organic chromophore Red-1 200 (DR1) of copolymer 5%, fully remove insoluble impurity with the syringe filter of 0.22 μ m after the stirring and dissolving, obtain red transparent hybrid colloidal sol; Seal, leave standstill, ageing is after 3 days, the solvent heated volatile is promptly obtained based on SiO
2The non-linear optical polymer of inorganic network structure modification.
The molecular formula of organic chromophore DR1 is as follows:
PMMA/SiO
2The synthetic route of composite interstitial substance is as follows:
Embodiment 2
(1) under nitrogen protection; the ratio that adds the 10ml amount of substance in strict exsiccant three-necked bottle is 1: 10 acryloyl-oxy propyl trimethoxy silicane and a methyl methacrylate mixing solutions; adding quality again is the initiator Diisopropyl azodicarboxylate of mixing solutions 2%; heating in water bath to 50 ℃ under the condition of magnetic agitation; pour container into behind the reflux 3h; in 80 ℃ of insulation 8h, obtain the copolymer of transparent methyl methacrylate and acryloyl-oxy propyl trimethoxy silicane again.
(2) get above-mentioned copolymer, tetraethoxy, positive four butyl esters of metatitanic acid, dehydrated alcohol and tetrahydrofuran (THF) were according to 0.8: 0.1: 0.1: 0.5: 8 mol ratio is respectively charged in the three-necked bottle of packing into, magnetic agitation is dissolved polymkeric substance fully, the HCl solution that dropwise adds 0.1mol/L then while stirring, add-on makes water and tetraethoxy, the mol ratio of the positive four butyl ester sums of metatitanic acid is 4: 1, continue to stir and make the reaction mixture hydrolysis, the organic chromophore that adds quality again and be copolymer 15% is to nitro-azo phenol (NHA), fully remove insoluble impurity with the syringe filter of 0.22 μ m after the stirring and dissolving, obtain red transparent hybrid collosol; Seal, leave standstill, ageing is after 7 days, the solvent heated volatile is promptly obtained based on SiO
2/ TiO
2The non-linear optical polymer of binary inorganic network structure modification.
Organic chromophore NHA molecular formula is as follows:
PMMA/SiO
2-TiO
2The synthetic route of composite interstitial substance is as follows:
Embodiment 3
(1) under nitrogen protection; the ratio that adds the 10ml amount of substance in strict exsiccant three-necked bottle is 1: 6 gamma-methyl allyl acyloxypropyl triethoxyl silane and a methyl methacrylate mixing solutions; adding quality again is the initiator Diisopropyl azodicarboxylate of mixing solutions 1.5%; heating in water bath to 65 ℃ under the condition of magnetic agitation; pour container into behind the reflux 2h; in 70 ℃ of insulation 16h, obtain the copolymer of transparent methyl methacrylate and gamma-methyl allyl acyloxypropyl triethoxyl silane again.
(2) get above-mentioned copolymer, positive four butyl esters of metatitanic acid, dehydrated alcohol and tetrahydrofuran (THF) were according to 0.5: 0.5: 0.5: 10 mol ratio is respectively charged in the three-necked bottle of packing into, magnetic agitation is dissolved polymkeric substance fully, the HCl solution that dropwise adds 0.15mol/L then while stirring, it is 4: 1 that add-on makes water and the positive four butyl ester mol ratios of metatitanic acid, continue to stir and make the reaction mixture hydrolysis, adding quality again is the organic chromophore Red-1 200 9 (DR19) of copolymer 10%, fully remove insoluble impurity with the syringe filter of 0.22 μ m after the stirring and dissolving, obtain red transparent hybrid collosol; Seal, leave standstill, ageing is after 6 days, the solvent heated volatile is promptly obtained based on SiO
2/ TiO
2The non-linear optical polymer of binary inorganic network structure modification.
The molecular formula of organic chromophore DR19 is as follows:
PMMA/SiO
2-TiO
2The synthetic route of composite interstitial substance is as follows:
Embodiment 4
(1) under nitrogen protection; the ratio that adds the 10ml amount of substance in strict exsiccant three-necked bottle is 1: 8 acryloyl-oxy propyl-triethoxysilicane and a methyl methacrylate mixing solutions; adding quality again is the initiator Diisopropyl azodicarboxylate of mixing solutions 1.2%; heating in water bath to 75 ℃ under the condition of magnetic agitation; pour container into behind the reflux 1h; in 60 ℃ of insulation 20h, obtain the copolymer of transparent methyl methacrylate and acryloyl-oxy propyl-triethoxysilicane again.
(2) get above-mentioned copolymer, tetraethoxy, dehydrated alcohol and tetrahydrofuran (THF) were according to 0.6: 0.4: 0.5: 9 mol ratio is respectively charged in the three-necked bottle of packing into, magnetic agitation is dissolved polymkeric substance fully, the HCl solution that dropwise adds 0.35mol/L then while stirring, it is 4: 1 that add-on makes water and tetraethoxy mol ratio, continue to stir and make the reaction mixture hydrolysis, adding quality again is the organic chromophore Red-1 200 (DR1) of copolymer 12%, fully remove insoluble impurity with the syringe filter of 0.22 μ m after the stirring and dissolving, obtain red transparent hybrid collosol; Seal, leave standstill, ageing is after 5 days, the solvent heated volatile is promptly obtained based on SiO
2The non-linear optical polymer of inorganic network structure modification.
The molecular formula of organic chromophore DR1 is shown in embodiment 1.
PMMA/SiO
2The synthetic route of composite interstitial substance is as follows:
Claims (6)
1. based on the non-linear optical polymer of inorganic network structure modification, it is characterized in that comprising organic/inorganic composite interstitial substance and hydroxyl organic chromophore two portions with network structure, its chemical structure is respectively:
The organic/inorganic composite interstitial substance
Organic chromophore
Wherein X is Si or Ti; R is the alkyl of H or 1～9 carbon; A for do not exist or-C
nH
2n-or-NR-C
nH
2n-; B is-CN-NO
2,-CF
3,-SO
2R ,-R ,-CH=CH
2,-N=N-CN ,-CH=N-N=CH-NO
2,-CH=N-SO
2R or the like; N is 0～9 integer, and x, y are natural number.
2. the preparation method of the non-linear optical polymer based on the inorganic network structure modification as claimed in claim 1 is characterized in that its step is as follows:
1) under nitrogen protection, the mixed solution A that in reactor, adds carbon-carbon double bonds organosilane and methyl methacrylate, in molar ratio, carbon-carbon double bonds organosilane: methyl methacrylate=1: 5～10, add the initiator Diisopropyl azodicarboxylate again, by mass percentage, the add-on of initiator Diisopropyl azodicarboxylate is 1%～2% of a mixed solution A, under stirring condition, be heated to 50～80 ℃, pour container into behind back flow reaction 0.5～3h, be incubated 8h at least in 50～80 ℃ again, obtain transparent methyl methacrylate and organo-siloxane copolymer B;
2) with the copolymer B for preparing in the step 1), the unorganic glass presoma, dehydrated alcohol and tetrahydrofuran (THF) be 1-x in molar ratio: x: 0.5: 8～12, x=0.2～0.5 wherein, the amount of copolymer B is calculated with the amount of monomer whose, pack in the reaction flask, stir, add HCl solution, it is 4: 1 that the add-on of HCl solution makes the mol ratio of water and unorganic glass presoma, continue to stir and make the reaction mixture hydrolysis, add organic chromophore again, by mass percentage, the add-on of organic chromophore is 5%～15% of copolymer B, and the stirring and dissolving after-filtration is removed insoluble impurity, obtains containing the hybrid colloidal sol of organic chromophore, sealing, leave standstill, after the ageing, the solvent heated volatile is promptly obtained non-linear optical polymer based on the inorganic network structure modification.
3. the preparation method of the non-linear optical polymer based on the inorganic network structure modification as claimed in claim 2 is characterized in that unorganic glass is SiO
2, the unorganic glass presoma should be tetraethoxy mutually.
4. the preparation method of the non-linear optical polymer based on the inorganic network structure modification as claimed in claim 2 is characterized in that unorganic glass is SiO
2/ TiO
2Binary composite inorganic glass, unorganic glass presoma should be positive four butyl esters of metatitanic acid mutually, or tetraethoxy and positive four butyl esters of metatitanic acid.
5. the preparation method of the non-linear optical polymer based on the inorganic network structure modification as claimed in claim 2, the concentration that it is characterized in that HCl solution is 0.1～0.5mol/L.
6. the preparation method of the non-linear optical polymer based on the inorganic network structure modification as claimed in claim 2 is characterized in that the aged time is 3～7 days.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641954A (en) * | 2013-11-04 | 2014-03-19 | 西南石油大学 | Polyacrylate organic-inorganic hybrid polymer and preparation method thereof |
| CN104744896A (en) * | 2013-12-30 | 2015-07-01 | 中国科学院理化技术研究所 | Double-chromophore composite system and synthesis method and application thereof |
| US12019352B2 (en) | 2019-09-24 | 2024-06-25 | Samsung Electronics Co., Ltd. | Composition, electro-optic material, and method for preparing electro-optic material |
-
2007
- 2007-07-13 CN CN2007100092130A patent/CN101117369B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641954A (en) * | 2013-11-04 | 2014-03-19 | 西南石油大学 | Polyacrylate organic-inorganic hybrid polymer and preparation method thereof |
| CN104744896A (en) * | 2013-12-30 | 2015-07-01 | 中国科学院理化技术研究所 | Double-chromophore composite system and synthesis method and application thereof |
| US12019352B2 (en) | 2019-09-24 | 2024-06-25 | Samsung Electronics Co., Ltd. | Composition, electro-optic material, and method for preparing electro-optic material |
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|---|---|
| CN101117369B (en) | 2010-07-07 |
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