CN101130518A - Ionic liquid photobase generator and its preparation method and application - Google Patents
Ionic liquid photobase generator and its preparation method and application Download PDFInfo
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- CN101130518A CN101130518A CNA2007100529621A CN200710052962A CN101130518A CN 101130518 A CN101130518 A CN 101130518A CN A2007100529621 A CNA2007100529621 A CN A2007100529621A CN 200710052962 A CN200710052962 A CN 200710052962A CN 101130518 A CN101130518 A CN 101130518A
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Abstract
本发明公开了一种熔点在－100～200℃范围的离子液体光产碱剂及其制备方法，以及它们作为光引发剂和光产碱剂的用途，其结构通式如式1、式2。
The invention discloses an ionic liquid photobase generator with a melting point in the range of -100 to 200°C, a preparation method thereof, and their use as a photoinitiator and a photobase generator. The general structural formulas are shown in formula 1 and formula 2.
Description
Technical field
The present invention relates to a class fusing point at-100～200 ℃, absorbing wavelength at ionic liquid photo generated base alkaline agent of 150～800nm and preparation method thereof, with and as the purposes of free radical photo-initiation and Photobase generator.
Background technology
Advantages such as radiation curing technology has fast, environmental protection, economy, efficient, multipotency meet various countries, the world today to environmental protection, energy-conservation strict demand, have obtained fast development, be described as " green technology ", be widely used in coating, printing ink, tackiness agent, photoimaging and microelectronic.Radiation curing mainly comprises photocuring (UV-light and visible light) and electrocuring, and present radiation curing material more than 90% is a ultraviolet photocureable material.Ultraviolet light polymerization is meant that under action of ultraviolet light liquid oligopolymer forms the process of solid product through crosslinking polymerization.Photocuring system generally includes light trigger, reactive thinner, and oligopolymer, other auxiliary agent etc., light trigger is the key of photocuring system, and the solidification rate of photocuring system is played a decisive role.
Business-like light trigger comprises radical polymerization and cationoid polymerisation light trigger.The radical polymerization light trigger produces the free radical activity fragment under light action, can cause Raolical polymerizable; Often produce Lewis acid after the photodissociation of cationoid polymerisation light trigger, be called light acid producing agent again, the cationoid polymerisation light trigger produces positively charged ion under thermal effect, causes cationic polymerization.Two photoinitiators are of a great variety, free radical photo-initiation is mainly used in and causes the resin crosslinks polymerization that contains unsaturated link(age), cation light initiator then is mainly used in the crosslinking polymerization of epoxide group ring-opening polymerization and vinyl ether, but two kinds of light triggers all have weak point, fast as free radical photo-initiation at the photocuring reaction medium velocity, cured film is shunk serious, and is subject to oxygen inhibition in air; Cation light initiator speed of response in photocuring reaction is slower, the acidic substance that produce have corrosion to base material, for avoiding these deficiencies, a kind of new light trigger having occurred is Photobase generator, Photobase generator is the compound that can produce alkaline matter under thermal effect, and the alkali that Photobase generator produces through light action then is called light and produces alkali.Early stage Photobase generator produces the quantum yield of alkali and fails to realize commercialization than hanging down always because of light.
The quaternary Photobase generator receives bigger concern in recent years, adds rattan wood Mao Shu (CN1531562A, 2004) and has invented aminimide light alkali propellant and curing thereof; Yang Jianwen (CN1634865A, 2005) has invented the photosensitive quaternary ammonium salt that phenyl ring directly connects tertiary amine, can be used for the dual cure system.Present known quaternary ammonium salt Photobase generator is solid state at normal temperature, and fusing point is higher, has compatibility problem when normal temperature and during the combination of reactive thinner or oligopolymer.
The liquid substance that ionic liquid is made up of positive ion and negative ion because of it has peculiar properties such as low-vapor pressure, fusing point is low, pollution is little, is often made reaction medium, is done ionogen use etc. as catalyzer or in electrochemistry in chemical reaction.Ionic liquid meets the principle of Green Chemistry, thereby is called as green solvent, it is generally acknowledged that its temperature range is at-100～100 ℃.Be called as ionic liquid at room temperature (RTILs) for the ionic liquid of liquid under the room temperature.First ionic liquid is the nitric acid ethyl ammonium, fusing point is 12 ℃, be found in 1914,1992, Wikes leader's research group has synthesized low melting point, anti-hydrolysis, stable strong 1-ethyl-3-methyl imidazolium tetrafluoroborate ionic liquid (mp5.8 ℃), ion liquid subsequently research enlivens gradually, the research institutions such as IFP that the K.Seddon of Britain has set up ionic liquid research centre and BP company and France begin systematically to explore the possibility of RTILs as solvent and catalyzer, and German BASF has at first realized commercialization.Enter 21st century, ion liquid research is advanced by leaps and bounds especially, the ion liquid successfully synthetic of a series of stable performances makes its applied research in catalysis and organic synthesis field very active.Ionic liquid can be divided into four classes by cationic kind: quaternary ammonium alkyl ion [NRxH
4-x]
+, alkyl quaternary phosphine ion [PR
xH
4-x]
+, 1, the pyridinium ion that imidazol ion that the 3-dialkyl group replaces and alkyl replace.Present ion liquid study on the synthesis has arrived the third generation, i.e. functionalized ion liquid.
Although it is more and more to study ion liquid scholar, but most researchs concentrate on ionic liquid as solvent, as aspects such as catalyzer and electrochemistry, the ionic liquid of research mostly is alkyl pyridine or dialkylimidazolium positively charged ion and multiple inorganic or the organic anion composition, and imidazole salts and the pyridinium salt good solidifying agent of epoxide group just, imidazoles and its derivative are because of having consumption few (0.5%-10%), toxicity is little, characteristics such as active height are mainly as epoxy curing agent, the mechanism of its cured epoxy group is that contained tertiary N atom makes epoxy group(ing) generation open loop produce negatively charged ion in the imidazoles, anionic polymerisation takes place, the activation energy that polyreaction is used is 67-80J/mol, belongs to the thermofixation reaction, and curing reaction often need carry out under higher temperature, therefore there are deficiencies such as usage period weak point, if imidazoles is made the quaternary ammonium salt Photobase generator, after optical radiation, imidazoles is discharged, then curing system becomes the photo-thermal curing system, have certain latent period, better workability can be provided.
Summary of the invention
The invention provides a kind of fusing point at-100～200 ℃, absorbing wavelength ionic liquid photo generated base alkaline agent at 150～800nm, with and be applied to photo-cured coating as free radical photo-initiation and Photobase generator, printing ink, tackiness agent, photoresist material, printed circuit board (PCB), optical fiber and organic reaction solvent, catalyzer, extraction agent, lubricant etc.
The general structure of ionic liquid photo generated base alkaline agent of the present invention as the formula (1).Ar is a phenyl in the formula, naphthyl, xenyl, 4-benzoyl benzyl, R
1, R
2, R
3, be respectively H, C
1～C
24Alkyl, alkoxyl group, alkylthio; R
4, R
5, and R
6Be respectively imidazoles, 2,4,5 H or contain the alkyl of 1～4 carbon atom, formula (2) is the structure of pyridine substituted imidazole, X
-Be anionic group, be respectively bromide anion (Br
-), iodide ion (I
-), tetrafluoro boron ion (BF
4 -), hexafluoro phosphonium ion (PF
6 -), isocyanic acid ion (SCN), tetraphenylboron ion [B (C
6H
5)
-], trifluoromethanesulfonic acid ion (CF
3SO
3 -), two trifluoromethanesulfonic acid imines ion [(CF
3SO
2)
2N
-], trifluoroacetic acid ion (CF
3COOO
-) etc.
Ionic liquid photo generated base alkaline agent of the present invention preparation be raw material with the aryl ketones of aryl ketones or replacement, in organic solvent, pass through bromide reagent: the liquid bromine, bromo-succinimide (NBS), or cupric bromide carries out bromo and gets intermediate, then with imidazoles, imdazole derivatives or pyridine, pyridine derivate react bromination quaternary ammonium salt ionic liquid, again with potassiumiodide, sodium tetrafluoroborate, Potassium Hexafluorophosphate, Tetraphenyl sodium borate, isocyanic acid potassium, trifluoromethanesulfonic acid sodium, two trifluoromethane sulfimides, sodium trifluoroacetates etc. carry out anionresin and get ionic liquid photo generated base alkaline agent.
When the present invention prepares the ionic liquid photo generated base alkaline agent method, if aryl ketones in the raw material, the anion structure symmetry is better, gained Photobase generator fusing point is higher when having strong rigidity, if increase flexible group in structure, increase asymmetry, use weak coordinate negatively charged ion, then gained ionic liquid photo generated base alkaline agent fusing point is lower.In the prepared ionic liquid photo generated base alkaline agent, when on the aryl substituting group being arranged, when carbonatoms was between 4～8 on the substituting group carbochain, the fusing point of ionic liquid photo generated base alkaline agent was lower; When positively charged ion was identical, anionic volume was big more, and fusing point is high more.
Ionic liquid photo generated base alkaline agent of the present invention can take place to decompose under 150-800nm UV, visible light rayed to produce free radical, can be used as free radical photo-initiation uses, it is joined in acrylate reactive thinner or the origoester acrylate by a certain amount of, form photocuring system, paint liquid film, under the normal temperature, crosslinking curing film forming fast under the irradiation of low pressure, medium-pressure or high pressure mercury lamp arrived several minutes set time at several seconds.The reactive thinner that is fit to Photobase generator of the present invention has simple function and multi-functional acrylate reactive thinner, comprises simple function group such as isobornyl acrylate (IBOA), Jia Jibingxisuanβ-Qiang Yizhi (HEMA), propenoic acid beta-hydroxy ethyl ester (HEA) etc.; The bifunctional monomer, as 1,6 hexanediyl ester (HDDA), the two propylene glycol double methacrylates (DPGDA) that contract, tripropylene glycol double methacrylate (TPGDA), polyoxyethylene glycol double methacrylate (PEGDA), neopentylglycol diacrylate (NPGDA) etc.; Polyfunctional monomer, as Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), as double pentaerythritol C5 methacrylate, two propylene glycol diacrylates (TPGDA) etc. that contract, esters of acrylic acid (TMPTA) structure.
The radically curing oligopolymer that is suitable for ionic liquid photo generated base alkaline agent of the present invention mainly comprises the polyacrylic ester of unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acroleic acid esterification, silicon Acrylote resin, the fluorine resin of acrylated etc.In radical-cured oligopolymer, esters of acrylic acid has characteristics such as quick solidifying, good film-forming property, but often there are compatibility problem in oligopolymer and light trigger, light trigger for higher melt, the consistency of itself and oligopolymer is relatively poor, the high polarity reactive thinner or the organic solvent hydrotropy in addition that need other, and ionic liquid photo generated base alkaline agent of the present invention, then consistency is preferably arranged when near room temperature, being liquid, solved the compatibility problem of light trigger and reactive thinner or oligopolymer preferably with oligopolymer.
Ionic liquid photo generated base alkaline agent of the present invention connects alkyl imidazole or pyridine under 150～800nm UV, visible light rayed key can rupture, generation has the alkyl imidazole or the pyridine of alkalescence, alkyl imidazole or pyridine can carry out the open loop crosslinking curing to the resin with epoxide group, the Resins, epoxy that is fit to ionic liquid photo generated base alkaline agent of the present invention is the resin that contains two and above epoxy-functional, comprise bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin, Racemic glycidol ether type epoxy etc., as commercially available Epon828, E44 etc., the mechanism of ionic liquid photo generated base alkaline agent cured epoxy resin is that base catalysis is solidified, its using method is that ionic liquid photo generated base alkaline agent cooperates than row by certain with Resins, epoxy, film, rayed produces alkaline matter in advance, the reheat system keeps for some time to certain temperature, makes the alkaline matter heat-curable epoxy resin.Suitable representative epoxy resin structural formula is as follows: bisphenol A type epoxy resin
Phenol aldehyde type epoxy resin
Cycloaliphatic epoxy resin
When ionic liquid photo generated base alkaline agent of the present invention is liquid near normal temperature, refer under the normal pressure its fusing point in the time of-100～100 ℃, characteristics with other common ion liquid, as N-methyl butyl imidazoles fluoroborate (mp ,-82 ℃), Methylimidazole hexafluorophosphate etc., can be used as the material that substitutes volatile organic solvent, have environmental protection, the advantage of low toxicity can be used as organic reaction, electrolytical solvent.
When ionic liquid photo generated base alkaline agent of the present invention is applied to photocuring system as light trigger, need and reactive thinner, oligopolymer and other auxiliary agent compositing formulas, during as esters of acrylic acid system light trigger, mainly illumination is at normal temperatures used, usage quantity is 0.05～10%wt, the fusing point of ionic liquid photo generated base alkaline agent is excellent with ionic liquid at room temperature, the higher Photobase generator of fusing point disperses undesirable in system, and consistency is relatively poor, and it is relatively poor to cause effect, can suitably add solubility promoter, improve consistency, when comparatively high temps, the optional usefulness of ionic liquid light trigger that fusing point is higher.Atmosphere during photocuring can be carried out in air or under the condition of nitrogen gas, in the time of in air, the transformation efficiency of acrylate between 10%～30%, under condition of nitrogen gas between 40～95%.
When ionic liquid photo generated base alkaline agent of the present invention uses as Photobase generator, utilize the base catalysis Resins, epoxy ring-opening polymerization that produces after the optical radiation, method is for to prepare ionic liquid photo generated base alkaline agent and Resins, epoxy in proportion, configuration proportion is 0.1～20%, preferred proportion is 1～5%, paint certain thickness film,, rete is solidified with low pressure, middle pressure, high pressure, ultrahigh pressure mercury lamp or halogen lamp irradiation for some time.In case of necessity can first illumination post-heating, light application time is 1～300s, and being heating and curing temperature is 25～200 ℃, and preferred temperature is 30～160 ℃, and be 1s～4 hour heat-up time, preferred 1～60min.According to the difference of curing system solidification value, should select the ionic liquid photo generated base alkaline agent of fusing point and solidification value coupling for use, can make in the system reactive thinner or resin and ionic liquid that consistency is preferably arranged.
When ionic liquid photo generated base alkaline agent of the present invention uses as ionic liquid, utilize its low-melting characteristics can replace organic solvent commonly used to use, as ethanol, acetone, ethyl acetate, benzene, hexanaphthene, tetracol phenixin etc. are as the solvent of organic reaction, macromolecular polymerization reaction, under the preferred normal temperature to water, the ionic liquid of air-stable.
Ionic liquid photo generated base alkaline agent of the present invention and light-cured components prescription thereof can be used for photo-cured coating, printing ink, tackiness agent, photo-resist, printed circuit board (PCB), coated material and organic solvents such as optical fiber, extraction agent, catalyzer multiple use.
Embodiment
Embodiment one:
Synthesizing of alpha-brominated methyl phenyl ketone claims 20 gram methyl phenyl ketones, is dissolved in the 175ml tetracol phenixin, pours into mechanical stirrer is housed, in the 500ml there-necked flask of reflux condensing tube and dropping funnel; Pipette 10ml liquid bromine with transfer pipet, be dissolved in the 125ml tetracol phenixin, dropwise join in the methyl phenyl ketone solution, stirring at room, the control rate of addition drips off the back and continues reaction 7 hours, pressure reducing and steaming 3/4ths solvents are cooled to 0 ℃, filter, collect solid, use the normal hexane washed twice, recrystallization, it is light green tabular crystal 17.09 grams that vacuum-drying gets product, productive rate 51.5%, 50～51 ℃ of fusing points, synthetic equation is as follows:
Embodiment two:
Synthesizing of N-phenacylidene pyridine bromide, claim 2.0 gram bromoacetophenones to be dissolved in the 60ml tetrahydrofuran (THF), pour in the 150ml round-bottomed flask, slowly drip the ethanol solution that 30ml is dissolved with the 2ml pyridine, stir, drip off the back and continue to stir 2 hours, the adularescent solid is separated out, and filters, solid dehydrated alcohol recrystallization, dry that white needle-like crystals 2.03 restrains productive rate 72.8%, fusing point: 189～191 ℃;
Embodiment three:
Anionresin: N-phenacylidene pyridine tetraphenylboron salt synthetic, claim 0.90 gram N-phenacylidene pyridine bromide to be dissolved in the 50ml distilled water, pour in the 150ml round-bottomed flask, 0.2 the gram sodium tetraphenylborate is dissolved in 30ml distilled water, slowly be added dropwise to N-phenacylidene pyridine bromide solution, stirring at room, produce faint yellow precipitation immediately, dripping off the back continues to stir 2 hours, filter, solid dehydrated alcohol recrystallization, dry that pale yellow powder 1.42 restrains, productive rate 54.1%, fusing point: 195～197 ℃.
Embodiment four:
Synthesizing of 4-benzoyl bromotoluene, claim 20 gram 4-methyldiphenyl ketones, be dissolved in the 230ml carbon tetrachloride solution, pour the 500ml belt stirrer into, in the three-necked flask of reflux condensing tube and dropping funnel, add 150mg Diisopropyl azodicarboxylate (AIBN), stir, add 18 gram bromo-succinimides (NBS) in batches, refluxed 24 hours, filter, remove succinimide, evaporating solvent gets yellow solid, and the mixed solution of usefulness normal hexane and benzene (1: 3, v/v) recrystallization secondary, vacuum-drying, get product 12.14 grams, productive rate 43.28%, fusing point: 96～97 ℃;
Embodiment five:
To synthesizing of butyl phenyl ether ethyl ketone, NaOH5.6g and dehydrated alcohol 70mL are added in the there-necked flask, at 75 ℃ of following backflow 1h, in flask, add parahydroxyacet-ophenone 6.8g, bath temperature is dropped to 55 ℃, add bromination of n-butane 13.7g again, continue reaction 2.5h, oily matter in the flask is told, and dry, productive rate 72.8%.
Embodiment six:
With ionic liquid photo generated base alkaline agent and Viscoat 295 or oligopolymer by 1: 99%wt mixes, and takes by weighing 5 milligrams of mixtures, puts into DSC with aluminum dish, under the high voltage mercury lamp of 300W, shine, nitrogen protection, light intensity is 0.1～100mW/cm
2, to measure its heat release with DSC and change, DSC intensification degree speed is 10 ℃/minute, the acrylic double bond transformation efficiency is greater than 50%.
Embodiment seven:
Ionic liquid photo generated base alkaline agent N-phenacylidene pyridine tetraphenylboron salt is mixed with Epon828, ionic liquid content was 9%wt, and mixture is applied on the silicon chip, with 250W mercury lamp room temperature radiation 1 second～30 minutes, survey infrared spectrogram respectively, ring oxygen groups transformation efficiency is greater than 20%.
Claims (8)
1. an ionic liquid photo generated base alkaline agent is characterized in that its melting range is-100～200 ℃, can produce the compound of free radical and alkaline matter under the thermal effect of 150～800nm, and general structure is suc as formula shown in (1), the formula (2):
Ar is a phenyl in the formula, naphthyl, xenyl, 4-benzoyl benzyl;
R
1, R
2, R
3, be respectively H, C
1～C
24Alkyl, alkoxyl group, alkylthio;
R
4, R
5, and R
6Be respectively imidazoles, 2,4,5 H or contain the alkyl of 1～4 carbon atom;
X
-Be anionic group, be respectively bromide anion, iodide ion, tetrafluoro boron ion, hexafluoro phosphonium ion, isocyanic acid ion, tetraphenylboron ion, trifluoromethanesulfonic acid ion, two trifluoromethanesulfonic acid imines ion, trifluoroacetic acid ion.
2. ionic liquid photo generated base alkaline agent according to claim 1 is characterized in that preparation method one is: alpha-brominated methyl phenyl ketone is dissolved in the certain amount of organic solvent, stirs, under temperature 25-90 ℃, substituted imidazole solution is splashed into, reacted 4 hours, precipitation, filter, crystallization gets the quaternary ammonium salt intermediate, and quaternary ammonium salt intermediate and the described negatively charged ion of claim 1 are carried out replacement(metathesis)reaction in solution, behind the exchange bromide anion, filter, crystallization gets product.
3. ionic liquid photo generated base alkaline agent according to claim 1, it is characterized in that preparation method two is: be raw material with the parahydroxyacet-ophenone, hydroxy ethers is changed into the alkoxy benzene ethyl ketone intermediate that contains C atom 1-24, intermediate is carried out alpha-brominated reaction, again by claim 2 method carry out the quaternary ammonium salt Photobase generator that replaces of alkoxyl group.
4. ionic liquid photo generated base alkaline agent according to claim 1 is characterized in that ionic liquid photo generated base alkaline agent uses in the vinylformic acid system, consumption is at 0.1-10%wt.
5. ionic liquid photo generated base alkaline agent according to claim 1 is characterized in that ionic liquid photo generated base alkaline agent is used to contain the compound of two and above active epoxy group as a kind of Photocurable composition, and consumption is at 1-25%wt.
6. ionic liquid photo generated base alkaline agent according to claim 1 is characterized in that ionic liquid photo generated base alkaline agent is applied to photo-cured coating, printing ink, tackiness agent, photo-resist, printed circuit board (PCB), electronic materials such as optical fiber.
7. ionic liquid photo generated base alkaline agent according to claim 1 is characterized in that ionic liquid photo generated base alkaline agent and other solid photoinitiator are used, as solvent and fill-in light initiator.
8. ionic liquid photo generated base alkaline agent according to claim 1, when it is characterized in that ionic liquid photo generated base alkaline agent uses directly illumination curing get cured article, also can first illumination reheat curing obtain cured article, Heating temperature is between 30～150 ℃.
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| WO2020155744A1 (en) * | 2019-02-02 | 2020-08-06 | 江苏百赛飞生物科技有限公司 | Microcatheter, preparation method therefor, and medical instrument comprising microcatheter |
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