CN1451645A - Acrylate compound, preparing process thereof and its use - Google Patents
Acrylate compound, preparing process thereof and its use Download PDFInfo
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Abstract
An acrylate compound containing photosensitive chalcone groups in its side chain, its preparing process, and its use in preparing acrylate polymer are disclosed. A liquid crystal orientating material containing said polymer is also disclosed.
Description
Technical field
The present invention relates to liquid-crystal display (Liquid Crystal Display, LCD) acrylic ester polymer and the method for making thereof used of both alignment layers.
Background technology
The present flat-panel screens of exploitation on the market, mainly be divided into Field Emission Display (FED, FieldEmission Display), plasma display panel (PDP, Plasma Display) and liquid-crystal display etc., wherein liquid-crystal display has become the market mainstream because have advantages such as low driving voltage, reduce power consumption, long and low radiation of life-span.
In the manufacturing processed of liquid-crystal display, the LCD alignment technology is one of gordian technique of decision liquid-crystal display quality.Because liquid crystal is clipped between two matrix, be difficult to obtain to arrange uniformly.Therefore, usually all will apply the inorganic or organic film of one deck at the inwall of matrix, impel liquid crystal to have stable and initial arrangement uniformly, this have the thin layer of inducing liquid crystal to align effect and be called liquid crystal alignment layer.
The quality of liquid crystal alignment layer directly influences the quality of liquid-crystal display.At present reported the alignment layer material that is used for liquid-crystal display, comprised polystyrene and derivative thereof, polyimide, polyvinyl alcohol, polyester, Resins, epoxy, polyurethane and polysilane etc., but modal then be polyimide (polyimide).These materials can utilize many kinds of methods that liquid crystal aligning is arranged, and carry out little groove facture as film rubbing manipulation (rubbed film), inclination evaporation SiOx embrane method (obliquely evaporated SiOx) with to film.
In many liquid crystal aligning aligning methods, rubbing method is because simple, convenient, become at present on liquid-crystal display is made the method for the most normal use.Generally speaking, be that substrate is pressed onto the Velveting surface of evenly moving, utilize friction to carry out, the method for the round roller friction of also useful bag Velveting.This kind method can produce the observable little groove of electron microscope at substrate surface.On the little flute surfaces of this kind, liquid crystal molecule is parallel or favour on the direction of groove and arrange, and makes liquid crystal aligning.Yet rubbing method has many shortcomings.At first, friction can produce dust, thereby reduces the quality of liquid-crystal display; The second, friction can produce static, destroys thin film transistor etc., makes that the qualification rate of product is not high; The 3rd, friction can only be implemented at planar surface, then can not use rubbing method for curved surface.Therefore, rubbing method can not satisfy demand in the market.
Linear polarization photopolymerization reaction (linearly polarizedphoto-polymerization, liquid crystal aligning technology LPP) are used in existing recently report.This kind technology is the surface with linearly polarized photon irradiated polyethylene alcohol laurate, makes wherein two key groups generations molecule crosslinked and form anisotropic polymeric membrane.Original molecular linkage is regularly arranged at substrate surface, when when polarized ultraviolet shines, causes the generation of anisotropic reactive, and formed polymeric membrane works the effect of aligning to liquid crystal, is called light alignment film (photo-alignment layer).This kind advanced person's liquid crystal aligning aligning method is called liquid crystal light orientation method.
Liquid crystal light orientation method is a kind of contactless surface treatment method, it is applied to the linear polarization light polymerization technique in the manufacturing of liquid-crystal display, not only overcome the above-mentioned shortcoming that rubbing method brings, and make that the manufacturing of display assembly is simple more, convenient, can improve the qualification rate of product, thereby reduce the cost of product.Therefore liquid crystal light orientation method particularly in the manufacturing of large screen display, has good application prospects in high quality lcd, and liquid crystal alignment layer is a critical material of implementing this method.The present inventor finds through broad research, and a kind of acrylic ester polymer that contains phenyl styryl ketone (chalcone) photosensitive group can be used as the material of liquid-crystal display both alignment layers.
Summary of the invention
The side chain that a purpose of the present invention provides a kind of novelty contains acrylic compound of phenyl styryl ketone (chalcone) photosensitive group and preparation method thereof.
Another purpose of the present invention provides a kind of this acrylic compound synthetic acrylic ester polymer and method for making thereof of utilizing.
A further object of the present invention provides a kind of liquid crystal alignment layer material that contains this acrylic ester polymer.
Side chain of the present invention contains the acrylic compound of phenyl styryl ketone group, has suc as formula structure shown in (I):
Wherein, a is that 0 to 10 integer and b are 0 or 1, but when a=0, b=0; And when a ≠ 0, b=1:R is hydrogen atom, halogen, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, cyano group, thiohydroxy, nitro or amido, wherein amido can be through one or two C
1-C
6Alkyl replaces, C
1-C
10Alkyl and C
1-C
10Alkoxyl group can be selected from C through one or more
1-C
10Alkyl, phenyl, do not replace or the halogen, nitro, cyano group or the thiohydroxy that are substituted replace; G is
Or
And R
4Be propenyl or methylpropenyl.Above alleged " alkyl " is meant straight or branched, contains 1 to 10 saturated hydrocarbon chains that carbon atom does not wait, such as but not limited to methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl etc.
Above alleged " alkoxyl group ", stretch alkyl and one of be meant straight or branched, containing 1 to 10 carbon atom stretch the Sauerstoffatom group that alkyl links to each other with this, such as but not limited to methoxyl group, oxyethyl group, propoxy-, butoxy etc.
Above alleged " halogen " is meant fluorine, chlorine, bromine and iodine atom, is preferably fluorine, chlorine and bromine atoms.
The present invention discloses a kind of method of preparation above-mentioned formula (I) acrylic compound in addition, and it comprises the following steps:
(i) with the aromatic aldehyde of formula (II)
Aromatic ketone with formula (III)
Under concentrated alkali solution catalysis, carry out condensation reaction, add an amount of dilute acid soln neutralization again, wherein R
1And R
2Be OH or R, but R
1≠ R
2R is hydrogen atom, halogen, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, cyano group, thiohydroxy, nitro or amido, wherein amido can be through one or two C
1-C
6Alkyl replaces, C
1-C
10Alkyl and C
1-C
10Alkoxyl group can be selected from C through one or more
1-C
10Alkyl, phenyl, do not replace or the group of the halogen, nitro, cyano group or the thiohydroxy that are substituted replaces;
(a) work as R
1=R, R
2Obtain the phenyl styryl ketone phenol throw out of formula (IV) during=OH:
(b) work as R
1=OH, R
2Obtain the phenyl styryl ketone phenol throw out of formula (IV ') during=R:
(ii)
(a) the phenyl styryl ketone phenol with formula (IV) or (IV ') is dissolved in the aprotic polar solvent, with the alkyl acetyl halide compound reaction of formula V,
Obtain the acrylic compound of formula (I),
A=b=0 wherein; R, G and R
4Has foregoing definition, X
1Be halogen; Or
(b) with the phenyl styryl ketone phenol of formula (IV) or (IV '), under the halogenide of weak base and basic metal or alkaline-earth metal existed, the halogenohydrin with formula (VI) reacted earlier,
X
2(CH
2)
aOH (VI)
Obtain the hydroxyalkyl phenyl styryl ketone ether of formula (VII),
Hydroxyalkyl phenyl styryl ketone ether with formula (VII) is dissolved in the aprotic polar solvent again, with the alkyl acetyl halide compound reaction of formula V,
Obtain the acrylic compound of formula (I)
Wherein a is 1 to 10 integer, and b is 1; R, G and R
4Has foregoing definition, X
2Be halogen.
In the method for above-mentioned preparation formula (I) acrylic compound, (i) step mainly is earlier with the aromatic aldehyde of formula (II) and the aromatic ketone of formula (III), under concentrated alkali solution catalysis, carry out condensation reaction, add an amount of dilute acid soln neutralization again, and make the phenyl styryl ketone phenol throw out of formula (IV) or (IV ').Be applicable to the aromatic aldehyde of this formula (II) in this synthetic method, such as but not limited to 4-hydroxy benzaldehyde, phenyl aldehyde, 4-bromobenzaldehyde, 4-cyanobenzaldehyde, 4-methoxybenzaldehyde, 4-ethylbenzene formaldehyde, 4-(N, the N dimethylamine base) phenyl aldehyde or 4-(N, N dimethylamine base) phenyl aldehyde.Be applicable to the aromatic ketone of this formula (III) in this synthetic method, such as but not limited to methyl phenyl ketone, 4-hydroxy acetophenone, 4-bromoacetophenone, 4-cyano-acetophenone, 4-methoxyacetophenone, 4-ethylbenzene ethyl ketone, 4-(N, the N dimethylamine base) methyl phenyl ketone or 4-(N, N dimethylamine base) methyl phenyl ketone.It is noted that, the aromatic ketone of aromatic aldehyde of this formula (II) and formula (III) only wherein one have hydroxyl, that is in above-mentioned substituent definition, R
1And R
2Be OH or R, but R
1≠ R
2
Above alleged " concentrated alkali solution " is meant the solution with highly basic character well known in the art, and for example sodium hydroxide, potassium hydroxide etc. are preferably the solution of potassium hydroxide.
Above alleged " dilute acid soln ", be meant well known in the art have suitable weaker concn, can in and the organic or inorganic acid of basic solution, for example hydrochloric acid, acetic acid, nitric acid etc. are preferably the solution of hydrochloric acid.
In the (ii) in the step of above-mentioned preparation method, be the formula (IV) that step (i) is made or the phenyl styryl ketone phenol of (IV '), be dissolved in the aprotic polar solvent, again with the alkyl acetyl halide compound reaction of formula V, just obtain the acrylic compound of formula (I).
Above alleged " aprotic polar solvent ", be meant and have polarity but the organic solvent of non-activity hydrogen atom, such as but not limited to tetrahydrofuran (THF) (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylacetamide (DMAC), N-methylpyrrole pyridine ketone (NMP) etc.And be applicable to alkyl acetyl halide compound in this step, can be such as but not limited to acrylate chloride or methacrylic chloride.
In (ii) in the step of above-mentioned preparation method, the also formula (IV) that step (i) can be made or the phenyl styryl ketone phenol of (IV '), halogenide in weak base and periodictable IA or IIA family metal exists down, halogenohydrin with formula (VI) reacts earlier, obtain the hydroxyalkyl phenyl styryl ketone ether of formula (VII), after being dissolved in this hydroxyalkyl phenyl styryl ketone ether in the aprotic polar solvent again,, and obtain the acrylic compound of formula (I) with the reaction of the alkyl acetyl halide compound of formula V.
Above alleged " weak base " is meant and uses periodictable IA or the IIA family metallic compound with weak base character in this area always, such as but not limited to salt of wormwood, yellow soda ash.
Above alleged " halogenide " is meant the periodictable IA or the IIA family metallic compound that contain fluorine, chlorine, bromine or iodine, such as but not limited to potassiumiodide.
Above alleged " halogenohydrin " is meant the alcohols that contains fluorine, chlorine, bromine or iodine, for example chloroethanol, trimethylene chlorohydrin, 4-chloro-1-butanols, 5-chloro-1-amylalcohol or 6-chloro-1-hexanol.
In the reaction of above-mentioned formula (IV) phenyl styryl ketone phenol or formula (VII) hydroxyalkyl phenyl styryl ketone ether and formula V alkyl acetyl halide compound, also can further add acid absorber, to improve the effect of reaction.Alleged herein " acid absorber " caught free hydrogen ionic weak base for mending, such as but not limited to triethylamine (TEA), pyridine, N-ethylmorpholine (NEM), xylidine (DMAN) etc.
Above-mentioned obtained side chain contains the acrylic compound of phenyl styryl ketone, can carry out polyreaction after adding light inlet initiator and aprotic polar solvent, obtains the acrylic ester polymer of formula (VIII).
Therefore, the present invention discloses a kind of acrylic ester polymer in addition, and it has formula (VIII) structure:
Wherein:
N is the integer greater than 1;
A is 0 to 10 integer, wherein when a=0, and b=0; When a=1 to 10, b=1;
R and G have foregoing definition; And
R
5Be hydrogen atom or methyl.
Situation on its polyreaction is decided, and the molecular-weight average that this acrylic ester polymer had is about between 500 to 500,000.And the percentage of grafting of this polymkeric substance is 50% to 100%.
The present invention discloses a kind of method for preparing this acrylic ester polymer in addition, and it comprises the following steps:
(i), be dissolved in an amount of aprotic polar solvent with the acrylic compound of formula (I);
After (ii) adding the light initiator, the temperature of rising reaction soln is to carry out polyreaction; And
(iii) reaction soln is poured into a large amount of alcoholic solvents, formed the acrylic ester polymer of formula (VIII).
Above-mentioned steps (ii) in employed " light initiator ", for well known in the art, Ou nitrogen Er Yi Ding Evil (AIBN) for example.Its preferable usage quantity is 0.2～0.5 weight % of reaction soln overall weight.The temperature of reaction soln must be raise in this step, in order to the carrying out of polyreaction, the temperature that the general polymerization reaction is carried out is 50 to 100 ℃, is preferably 60 ℃.
Above-mentioned steps (iii) in employed alcoholic solvent, for known in the art general, be preferably methyl alcohol at the alcohols that carries out polyreaction postprecipitation polymkeric substance.
Above-mentioned prepared acrylic ester polymer can be used in the liquid-crystal display material as liquid crystal alignment layer.This liquid crystal alignment layer material can be incorporated acrylic ester polymer of the present invention in the liquid crystal alignment layer material into by any method as known in the art.For example, acrylic ester polymer of the present invention can be dissolved with aprotic solvent, be deployed into certain density homogeneous solution, by the desk-top even surperficial rotary plating of machine that stir at base material, and shine with polarized ultraviolet (for example wavelength is 365nm), (2+2) cyclization enough takes place in the two bond energys in the contained phenyl styryl ketone photosensitive group of its side chain, makes the polymeric film anisotropy, thereby induces the liquid crystal molecular orientation.This can be applicable to twisted nematic (TN), super-twist nematic (STN), film transistor type (TFT) liquid-crystal display through the layer assembling Liquid crystal module of light orientation, and it has advantages such as giant-screen, on-plane surface, high information content, high resolving power.
Following examples are to be used for that the invention will be further described, and are only non-in order to limit the scope of the invention.Modification that any those skilled in the art can reach easily and change are included within the content and claims of this specification sheets announcement.
Embodiment
Example 1The preparation of acrylate chloride
In being housed, the flask of reflux exchanger adds vinylformic acid (68 milliliters, 1.0 moles) and phosphorus trichloride (29 milliliters, 0.33 mole).Miscellany slowly is heated to little boiling, stops heating.Leave standstill 2 hours with after the reaction mixture layering, isolate supernatant liquid, add cuprous chloride (1.0 gram),, collect the fraction of 30-40 ℃/140mmHg again through underpressure distillation as stopper.
Example 2The preparation of methacrylic chloride
In being housed, the flask of reflux exchanger adds methacrylic acid (83 milliliters, 1.0 moles) and phosphorus trichloride (29 milliliters, 0.33 mole).Miscellany slowly is heated to little boiling.Leave standstill 2 hours with the reaction mixture layering, tell supernatant liquid, add cuprous chloride (1.0 gram) and,, obtain the methacrylic chloride product again through underpressure distillation as stopper.
Example 3(1) 4-hydroxy-benzalacetophenone (4-hydroxyl chalcone) is synthetic
Take by weighing 2.44 gram (0.02 mole) 4-hydroxy benzaldehydes and 2.40 gram (0.02 mole) methyl phenyl ketones, with 5 milliliters of dehydrated alcohols it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, add an amount of dilute hydrochloric acid again and produce precipitation, be the 4-hydroxy-benzalacetophenone.(2) preparation of vinylformic acid (4-hydroxy-benzalacetophenone) ester (MACH)
Taking by weighing 1 gram (0.004464 mole) 4-hydroxy-benzalacetophenone is dissolved in 5 milliliters of tetrahydrofuran (THF)s, after obtaining even orange settled solution, the triethylamine that adds 2 milliliters mixes the back and adds 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides, is reflected at and carries out about 24 hours in the ice-water bath.Reaction precipitates product after finishing in a large amount of deionized waters, obtain vinylformic acid (4-hydroxy-benzalacetophenone) ester after the filtration.(3) polyacrylic acid (4-hydroxy-benzalacetophenone) ester (PMACH) is synthetic
0.527 gram MACH is dissolved in 5 milliliters of tetrahydrofuran solutions, adds 0.2～0.5% Ou nitrogen Er Yi Ding Evil (AIBN) of this MACH then, then be warming up to 60 ℃ of reactions 3 days, obtain brown solutions.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polyacrylic acid (4-hydroxy-benzalacetophenone) ester after the filtration.
Embodiment 4Synthesizing of (1) 4 '-hydroxy-benzalacetophenone (4 '-hydroxyl chalcone)
Take by weighing 2.72 gram (0.02 mole) 4 '-hydroxy acetophenones and 2.12 gram (0.02 mole) phenyl aldehydes, with 5 milliliters ethanol it is dissolved, splash into 5.5 milliliter 50% KOH solution then, the reaction response mixture is scarlet.Reaction finishes, and adds an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral back generation precipitation, and this is 4 '-hydroxy-benzalacetophenone.(2) preparation of vinylformic acid (4 '-hydroxy-benzalacetophenone) ester (MACH ')
Take by weighing 1.0 the gram (0.00446 mole) 4 '-hydroxy-benzalacetophenones be dissolved in obtain settled solution in 5 milliliters of tetrahydrofuran (THF)s after, add 2 milliliters of triethylamines, progressively drip 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides after mixing, be reflected at and carried out in the ice-water bath 24 hours.Reaction precipitates reaction mixture after finishing in a large amount of water, obtain vinylformic acid (4 '-hydroxy-benzalacetophenone) ester after the filtration.(3) polyacrylic acid (4 '-hydroxy-benzalacetophenone) ester (PMACH ') is synthetic
0.527 gram vinylformic acid 4-hydroxy-benzalacetophenone ester is dissolved in 5 milliliters of tetrahydrofuran solutions, obtain uniform orange-yellow solution, 0.2～0.5% Ou nitrogen Er Yi Ding Evil that adds this PMACH ' then is warming up to 60 ℃ of reactions 3 days in nitrogen, obtain brown solutions.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of anhydrous methanols precipitated then, obtain polyacrylic acid (4 '-hydroxy-benzalacetophenone) ester after the filtration.
Embodiment 5(1) 4-hydroxyl-4 '-methyl chalcone (MCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-methyl acetophenone of 2.68 grams (0.02 mole), it is dissolved, splash into 5.5 milliliter 50% KOH solution then with 5 milliliters ethanol.Reaction finishes, and adds an amount of dilute hydrochloric acid reaction mixture is neutralized to a large amount of precipitations of neutral back generation, reaches drying after filtration and obtains 4-hydroxyl-4 '-methyl chalcone.(2) hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether (HEMCH) is synthetic
4-hydroxyl-the 4 '-methyl chalcone that takes by weighing 2 grams (0.008403 mole) is dissolved in 10 milliliters of methyl-sulphoxides (DMSO), adds the salt of wormwood (K of 1 gram then respectively
2CO
3) and 0.1 potassiumiodide (KI) that restrains, be warming up to 60 ℃ and make it be dissolved into homogeneous phase solution.Under agitation add 0.82 gram (0.01008 mole) chloroethanol, finish the back and under oil bath, be warming up to 110 ℃, reacted 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, obtains hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether after producing throw out in the deionized waters in a large number, reaching drying after filtration.(3) preparation of methacrylic acid (hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether) ester (MMAHEMCH) is equipped with
Take by weighing 1.0 gram (0.003546 mole) HEMCH and be dissolved in 5 milliliters of tetrahydrofuran (THF)s, obtain settled solution after, adds 2 milliliters of triethylamines, remix evenly back adding is dissolved with in 5 milliliters of tetrahydrofuran solutions of 2 milliliters of methacrylic chlorides.After treating that methacrylic chloride dropwises, reaction is 24 hours under room temperature.Reaction mixture is precipitated in a large amount of water, reach washing after filtration after, obtain methacrylic acid (hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether) ester.(4) (PMMAHEMCH) synthetic of polymethyl acrylic acid (hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether)
0.50 gram (mole) MMAHEMCH is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains homogeneous solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of this MMAHEMCH then, then be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Then reaction mixture is poured in a large amount of methyl alcohol and precipitated, obtain product polymethyl acrylic acid (hydroxyethyl (4-hydroxyl-4 '-methyl chalcone) ether) after the filtration.
Embodiment 6(1) 4 '-hydroxy-4-methyl phenyl styryl ketone (MCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-tolyl aldehyde of 2.40 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, along with the adding of alkali lye, the color of solution is deepened gradually.After reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to a large amount of precipitations of neutral back generation, obtain 4 '-hydroxy-4-methyl phenyl styryl ketone after filtering.(2) hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether (HEMCH ') is synthetic
The MCH ' that takes by weighing 2.0 grams (0.008403 mole) is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO), divides the salt of wormwood (K that adds 1 gram then
2CO
3) and the potassiumiodide (KI) of 0.1 gram, add 0.82 gram (0.01008 mole) chloroethanol after being warming up to 60 ℃, in oil bath behind the heat temperature raising to 110 ℃, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, obtains hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of methacrylic acid (hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether) ester (MMAHEMCH ') is equipped with
The HEMCH ' that takes by weighing 1.0 grams (0.003546 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, the triethylamine that adds 2 milliliters, progressively drip 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of methacrylic chlorides after mixing, be reflected in the ice-water bath and carry out.After treating that methacrylic chloride dropwises, reacted 24 hours.Reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether) ester after filtering.(4) polymethyl acrylic acid (hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether) ester (PMMAHEMCH ') is synthetic
The MMAHEMCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains homogeneous solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAHEMCH ' then, then be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Pour reaction mixture in a large amount of methyl alcohol generation precipitation, obtain polymethyl acrylic acid (hydroxyethyl (4 '-hydroxy-4-methyl phenyl styryl ketone) ether) ester after filtering.
Embodiment 7(1) 4-hydroxyl-4 '-fluorine phenyl styryl ketone (FCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-fluoro acetophenone of 2.76 grams (0.02 mole), with ethanol it is dissolved, the KOH solution that adds 5.5 milliliter 50% then, reaction finishes, add an amount of dilute hydrochloric acid and reaction mixture is neutralized to neutral back produces precipitation, obtain 4-hydroxyl-4 '-fluorine phenyl styryl ketone after reaching drying after filtration.(2) hydroxypropyl (4-hydroxyl-4 '-fluorine phenyl styryl ketone) ether (HPFCH) is synthetic
The FCH that takes by weighing 2 grams (0.008264 mole) is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO) (DMSO), adds the salt of wormwood (K of 1 gram then respectively
2CO
3) and the potassiumiodide (KI) of 0.1 gram, be warming up to after 60 ℃ the trimethylene chlorohydrin that adds 0.94 gram (0.009917 mole), heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, precipitates in a large amount of deionized waters, obtains hydroxypropyl (4-hydroxyl-4 '-fluorine phenyl styryl ketone) ether after filtering.(3) preparation of vinylformic acid (hydroxypropyl (4-hydroxyl-4 '-fluorine Cha Er) ether) ester (MAHPFCH)
The HPFCH that takes by weighing 1 gram (0.003333 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, adds 2 milliliters of triethylamines, progressively drips 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides after mixing, and is reflected in the ice-water bath and carries out.After treating that acrylate chloride dropwises, room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (hydroxypropyl (4-hydroxyl-4 '-fluorine Cha Er) ether) ester after reaching drying after filtration.(4) polyacrylic acid (hydroxypropyl (4-hydroxyl-4 '-fluorine phenyl styryl ketone) ether) ester (PMAHPFCH) is synthetic
0.50 the MAHPFCH of gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, adds 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAHPFCH then, is warming up to 60 ℃ of reactions 3 days, obtains viscous solution.Pour reaction mixture in a large amount of methyl alcohol generation precipitation, obtain polyacrylic acid (hydroxypropyl (4-hydroxyl-4 '-fluorine phenyl styryl ketone) ether) ester after filtering.
Embodiment 8(1) 4 '-hydroxyl-4-fluorine phenyl styryl ketone (FCH ') synthetic
Take by weighing and get the 4-fluorobenzaldehyde that the 2.72 4 '-hydroxy acetophenones and 2.148 that restrain (0.02 mole) restrain (0.02 mole), with ethanol it is dissolved, splash into 5.5 milliliters of 50%KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, obtain 4 '-hydroxyl-4-fluorine phenyl styryl ketone after reaching drying after filtration.(2) hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether (HPFCH ') is synthetic
Take by weighing 2 gram (0.008264 mole) FCH ' and be dissolved in 10 milliliters of methyl-sulphoxides (DMSO), add the salt of wormwood (K of 1 gram then respectively
2CO
3) and the potassiumiodide (KI) of 0.1 gram, add 0.94 gram (0.009917 mole) trimethylene chlorohydrin after being warming up to 60 ℃, heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and precipitates in a large amount of deionized waters, reaches drying after filtration and obtains hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether.(3) preparation of vinylformic acid (hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether) ester (MAHPFCH ')
Take by weighing 1.0 gram (0.003333 mole) HPFCH ' and be dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, adds 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, be reflected in the ice-water bath and carry out.After treating that acrylate chloride dropwises, room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, reach drying after filtration after, obtain vinylformic acid (hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether) ester.(4) polyacrylic acid (hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether) ester (PMAHPFCH ') is synthetic
0.50 gram (mole) MAHPFCH ' is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAHPFCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Reaction mixture poured in a large amount of methyl alcohol produce precipitation, obtain polyacrylic acid (hydroxypropyl (4 '-hydroxyl-4-fluorine phenyl styryl ketone) ether) ester after reaching drying after filtration.
Embodiment 9(4) 4-hydroxyl-4 '-chloro phenyl styryl ketone (ClCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-chloroacetophenone of 3.07 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliters of 50%KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid the precursor reactant mixture is neutralized to the neutral precipitation that produces, obtain 4-hydroxyl-4 '-chloro phenyl styryl ketone after reaching drying after filtration.(2) hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether (HBClCH) is synthetic
Take by weighing 2.0 gram (0.007737 mole) ClCH and be dissolved in 10 milliliters of methyl-sulphoxides, add the salt of wormwood (K of 1 gram then respectively
2CO
3) and the potassiumiodide (KI) of 0.1 gram, be warming up to after 60 ℃ the 4-chloro-1-butanols that adds 1.01 grams (0.009284 mole), heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and obtains hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of methacrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester (MMAHBClCH) is equipped with
Take by weighing 1.0 gram (0.003016 mole) HBClCH and be dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, adds 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of methacrylic chlorides, be reflected in the ice-water bath and carry out.After treating that methacrylic chloride dropwises, room temperature reaction 24 hours.Reaction finishes, and reaction mixture is precipitated in a large amount of water, obtains methacrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester after reaching drying after filtration.(4) polymethyl acrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester (PMMAHBClCH) is synthetic
The MMAHBClCH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains homogeneous solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAHBClCH then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Reaction mixture poured in a large amount of methyl alcohol produce precipitation, obtain polymethyl acrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester after reaching drying after filtration.
Embodiment 10(1) 4 '-hydroxyl-4-chloro phenyl styryl ketone (ClCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the phenyl aldehyde of 2.81 grams (0.02 mole), it is dissolved, slowly splash into 5.5 milliliters of 50%KOH solution then with ethanol.Reaction finishes, and adds an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, after filtration, obtain 4 '-hydroxyl-4-chloro phenyl styryl ketone after washing and the drying.(2) hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether (HBClCH ') is synthetic
Take by weighing 2 gram (0.007737 mole) ClCH ' and be dissolved in 10 milliliters of anhydrous dimethyl sulfoxides, add the salt of wormwood (K of 1 gram then respectively
2CO
3) and the potassiumiodide (KI) of 0.1 gram, add 1.01 gram (0.009284 mole) 4-chloro-1-butanols after being warming up to 60 ℃, finish back heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and precipitates at a large amount of deionized waters, obtains hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether after reaching drying after filtration.(3) preparation of methacrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester (MMAHBClCH ')
The HBClCH ' that takes by weighing 1.0 grams (0.003016 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, adds 2 milliliters of triethylamines, progressively is added dropwise to 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of methacrylic chlorides after mixing, room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester after reaching drying after filtration.(4) polymethyl acrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester (PMMAHBClCH ') is synthetic
The MMAHBClCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAHBClCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Reaction mixture is precipitated in a large amount of methyl alcohol, obtain polymethyl acrylic acid (hydroxyl butyl (4-hydroxyl-4 '-chloro phenyl styryl ketone) ether) ester after reaching drying after filtration.
Embodiment 11Synthesizing of 4-hydroxyl-4 '-bromo phenyl styryl ketone (BrCH)
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-bromoacetophenone of 3.98 grams (0.02 mole), few ethanol dissolves it with trying one's best, splash into 5.5 milliliters of 50%KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4-hydroxyl-4 '-bromo phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4-hydroxyl-4 '-bromo phenyl styryl ketone) ester (MABrCH)
The BrMCH that take by weighing 1.0 grams (0.003303 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of anhydrous triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, room temperature reaction 24 hours.After reaction finishes, reaction mixture is produced precipitation in a large amount of water, obtain vinylformic acid (4-hydroxyl-4 '-bromo phenyl styryl ketone) ester after reaching drying after filtration.(3) (PMABrCH) synthetic of polyacrylic acid (4-hydroxyl-4 '-bromo phenyl styryl ketone ester)
The MABrCH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains homogeneous solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MABrCH then, be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, obtain polyacrylic acid (4-hydroxyl-4 '-bromo phenyl styryl ketone ester) after reaching drying after filtration.
Embodiment 12(1) 4 '-hydroxyl-4-bromo phenyl styryl ketone (BrCH ') synthetic
Take by weighing 4 '-hydroxy acetophenone and 3.70 gram (0.02 mole) 4-bromobenzaldehydes of 2.72 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4 '-hydroxyl-4-bromo phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4 '-hydroxyl-4-bromo phenyl styryl ketone) ester (MABrCH ')
Take by weighing 1.0 gram (0.003303 mole) BrMCH ' and be dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, add 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides after mixing, be reflected in the ice-water bath and carry out.After treating that acrylate chloride dropwises, room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4 '-hydroxyl-4-bromo phenyl styryl ketone) ester after reaching drying after filtration.(3) polyacrylic acid (4 '-hydroxyl-4-bromo phenyl styryl ketone) ester (PMABrCH ') is synthetic
The MABrCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MABrCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, obtain polyacrylic acid (4 '-hydroxyl-4-bromo phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 13(1) 4-hydroxyl-4 '-cyano group phenyl styryl ketone (CNCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-cyano-acetophenone of 2.90 grams (0.02 mole), adding ethanol dissolves it, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, after filtration, obtain 4-hydroxyl-4 '-cyano group phenyl styryl ketone after washing and the drying.(2) preparation of vinylformic acid (4-hydroxyl-4 '-cyano group phenyl styryl ketone) ester (MACNCH)
The CNMCH that take by weighing 1.0 grams (0.004016 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, in room temperature reaction 24 hours.Reaction precipitates reaction mixture after finishing in a large amount of water, reach drying after filtration and obtain vinylformic acid (4-hydroxyl-4 '-cyano group phenyl styryl ketone) ester.(3) polyacrylic acid 4-hydroxyl-4 '-cyano group phenyl styryl ketone ester (PMACNCH) is synthetic
The MACNCH of 0.50 gram is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MACNCH then, be warming up to 60 ℃ of reactions 3 days, obtain heavy-gravity solution.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polyacrylic acid 4-hydroxyl-4 '-cyano group phenyl styryl ketone ester after reaching drying after filtration.
Embodiment 14(1) 4 '-hydroxyl-4-cyano group phenyl styryl ketone (CNCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-cyanobenzaldehyde of 2.62 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4 '-hydroxyl-4-cyano group phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4 '-hydroxyl-4-cyano group phenyl styryl ketone) ester (MACNCH ')
The CNMCH ' that take by weighing 1.0 grams (0.004016 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, progressively be added dropwise to 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides after mixing after, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4 '-hydroxyl-4-cyano group phenyl styryl ketone) ester after reaching drying after filtration.(3) polyacrylic acid (4 '-hydroxyl-4-cyano group phenyl styryl ketone) ester (PMACNCH ') is synthetic
The MACNCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MACNCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Pour reaction mixture in a large amount of methyl alcohol generation precipitation, obtain polyacrylic acid (4 '-hydroxyl-4-cyano group phenyl styryl ketone) ester after filtering.
Embodiment 15(1) 4-hydroxyl-4 '-nitro phenyl styryl ketone (NOCH) is synthetic
Take by weighing the 4-hydroxyl hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-nitro-acetophenone of 3.30 grams (0.02 mole), with its dissolving of few ethanol of trying one's best, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4-hydroxyl-4 '-nitro phenyl styryl ketone after reaching drying after filtration.(2) hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether (HPNOCH) is synthetic
The NOCH that takes by weighing 2.0 grams (0.007435 mole) is dissolved in 10 milliliters of anhydrous dimethyl sulfoxides, adds the salt of wormwood (K of 1 gram then respectively
2CO
3) and the potassiumiodide (KI) of 0.1 gram, be warming up to 60 ℃ and dropwise add 1.09 gram (0.08922 mole) 5-chloro-1-amylalcohols, heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and obtains hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of hydroxyethyl methacrylate amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether (MMAHPNOCH)
The HPNOCH that take by weighing 1.0 grams (0.002809 mole) were dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, progressively are added dropwise to 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of methacrylic chlorides after mixing, in room temperature reaction 24 hours.Reaction finishes, and reaction mixture is precipitated in a large amount of water, reaches drying after filtration and obtains hydroxyethyl methacrylate amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether.(4) polymethyl acrylic acid hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether (PMMAHPNOCH) is synthetic
The MMAHPNOCH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% the Ou nitrogen Er Yi Ding Evil of MMAHPNOCH then, be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Reaction mixture poured in the methyl alcohol produce precipitation, obtain polymethyl acrylic acid hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether after reaching drying after filtration.
Embodiment 16(1) 4 '-hydroxyl-4-nitro phenyl styryl ketone (NOCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-nitrobenzaldehyde of 3.02 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4 '-hydroxyl-4-nitro phenyl styryl ketone after reaching drying after filtration.(2) hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether (HPNOCH ') is synthetic
The NOCH ' that takes by weighing 2 grams (0.007435 mole) is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO), add the salt of wormwood of 1 gram and the potassiumiodide of 0.1 gram then respectively, be warming up to the 5-chloro-1-amylalcohol that dropwise adds 1.09 grams (0.08922 mole) after 60 ℃, finish back heat temperature raising to 110 ℃ in oil bath, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and obtains hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of methacrylic acid (hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether) ester (MMAHPNOCH ')
The HPNOCH ' that takes by weighing 1.0 grams (0.002809 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, add 2 milliliters of triethylamines, progressively be added dropwise to 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of methacrylic chlorides after mixing, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether) ester after reaching drying after filtration.(4) polymethyl acrylic acid hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether (PMMAHPNOCH ') is synthetic
The MMAHPNOCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAHPNOCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Pour in a large amount of methyl alcohol reaction mixture into precipitation, obtain polymethyl acrylic acid hydroxyl amyl group (4-hydroxyl-4 '-nitro phenyl styryl ketone) ether-ether after reaching drying after filtration.
Embodiment 17(1) 4-hydroxyl-4 '-methoxyl group phenyl styryl ketone (MOCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-methoxyacetophenone of 3.00 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4-hydroxyl-4 '-methoxyl group phenyl styryl ketone after reaching drying after filtration.(2) preparation of methacrylic acid (4-hydroxyl-4 '-methoxyl group phenyl styryl ketone) ester (MMAMOCH) is equipped with
The MOCH that take by weighing 1.0 grams (0.003937 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing dropwise adding be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of methacrylic chlorides, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (4-hydroxyl-4 '-methoxyl group phenyl styryl ketone) ester after reaching drying after filtration.(3) polymethyl acrylic acid (4-hydroxyl-4 '-methoxyl group phenyl styryl ketone) ester (PMMAMOCH) is synthetic
The MMAMOCH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAMOCH then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, obtain polymethyl acrylic acid (4-hydroxyl-4 '-methoxyl group phenyl styryl ketone) ester after reaching vacuum-drying after filtration.
Embodiment 18(1) 4 '-hydroxyl-4-methoxyl group phenyl styryl ketone (MOCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-methoxybenzaldehyde of 2.72 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, obtain 4 '-hydroxyl-4-methoxyl group phenyl styryl ketone after reaching drying after filtration.(2) preparation of methacrylic acid (4 '-hydroxyl-4-methoxyl group phenyl styryl ketone) ester (MMAMOCH ') is equipped with
Take by weighing the MOCH that get 1.0 grams (0.003937 mole) and be dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, progressively be added dropwise to 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of methacrylic chlorides after mixing, room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (4 '-hydroxyl-4-methoxyl group phenyl styryl ketone) ester after reaching drying after filtration.(3) polymethyl acrylic acid (4 '-hydroxyl-4-methoxyl group phenyl styryl ketone) ester (PMMAMOCH ') is synthetic
The MMAMOCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMAMOCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polymethyl acrylic acid (4 '-hydroxyl-4-methoxyl group phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 19(1) 4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone (EOCH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-phenetole ethyl ketone of 3.24 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, obtain 4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone after reaching drying after filtration.(2) hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether (HHEOCH) is synthetic
The MEOCH that takes by weighing 2.0 grams (0.007463 mole) is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO), add the salt of wormwood of 1 gram and the potassiumiodide of 0.1 gram then respectively, be warming up to the 6-chloro-1-hexanol that adds 1.22 grams (0.08955 mole) after 60 ℃, finish in oil bath heat temperature raising to 110 ℃, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and obtains hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of vinylformic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester (MAHHEOCH)
The HHEOCH that take by weighing 1.0 grams (0.002710 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing progressively adding be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester after reaching drying after filtration.(4) polyacrylic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester (PMAHHEOCH) is synthetic
The MAHHEOCH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAHHEOCH then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polyacrylic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester after reaching drying after filtration.
Embodiment 20(1) 4 '-hydroxyl-4-oxyethyl group phenyl styryl ketone (EOCH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-ethoxy-benzaldehyde of 2.72 grams (0.02 mole), it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then with ethanol.Reaction finishes, and adds an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, and obtains 4 '-hydroxyl-4-oxyethyl group phenyl styryl ketone after reaching drying after filtration.(2) hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether (HHEOCH ') is synthetic
The MEOCH that takes by weighing 2.0 grams (0.007463 mole) is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO), add the salt of wormwood of 1 gram and the potassiumiodide of 0.1 gram then respectively, be warming up to the 6-chloro-1-hexanol that adds 1.22 grams (0.08955 mole) after 60 ℃, finish in oil bath heat temperature raising to 110 ℃, isothermal reaction 8 hours.Reaction finishes, and reaction mixture is reduced to room temperature, and obtains hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether after precipitating in the deionized waters in a large number, reaching drying after filtration.(3) preparation of vinylformic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester (MAHHEOCH ')
The HHEOCH ' that takes by weighing 1.0 grams (0.002710 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, adds 2 milliliters of anhydrous triethylamines, progressively drips 5 milliliters of tetrahydrofuran solutions that are dissolved with 2 milliliters of acrylate chlorides, room temperature reaction 24 hours after mixing.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester after reaching drying after filtration.(4) polyacrylic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester (PMAHHEOCH ') is synthetic
The MAHHEOCH ' of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAHHEOCH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polyacrylic acid (hydroxyl hexyl (4-hydroxyl-4 '-oxyethyl group phenyl styryl ketone) ether) ester after reaching drying after filtration.
Embodiment 21(1) 4-hydroxyl-4 '-ethyl phenyl styryl ketone (ECH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-ethylbenzene ethyl ketone of 2.92 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitation that produces, obtain 4-hydroxyl-4 '-ethyl phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4-hydroxyl-4 '-ethyl phenyl styryl ketone) ester (MAECH)
4-hydroxyl-the 4 '-methyl chalcone that takes by weighing 1.0 grams (0.003968 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, add 2 milliliters of triethylamines, progressively drip 5 milliliters of tetrahydrofuran solutions being dissolved with 2 milliliters of acrylate chlorides after mixing, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4-hydroxyl-4 '-ethyl phenyl styryl ketone) ester after reaching vacuum-drying after filtration.(3) polyacrylic acid (4-hydroxyl-4 '-ethyl phenyl styryl ketone) ester (PMAECH) is synthetic
The MAECH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAECH then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Then reaction mixture is poured in a large amount of methyl alcohol and precipitated, obtain polyacrylic acid (4-hydroxyl-4 '-ethyl phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 22(1) 4 '-hydroxyl-4-ethyl phenyl styryl ketone (ECH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-ethylbenzene formaldehyde of 2.40 grams (0.02 mole), with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, obtain 4 '-hydroxyl-4-ethyl phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4 '-hydroxyl-4-ethyl phenyl styryl ketone) ester (MAECH ')
The ECH ' that take by weighing 1.0 grams (0.003968 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of anhydrous triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4 '-hydroxyl-4-ethyl phenyl styryl ketone) ester after reaching drying after filtration.(3) polyacrylic acid (4 '-hydroxyl-4-ethyl phenyl styryl ketone) ester (PMAECH ') is synthetic
The MAECH of 0.50 gram is dissolved in 5 milliliters of tetrahydrofuran (THF)s mutters and obtain uniform solution in the solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MAECH then, be warming up to 60 ℃ of reactions 3 days, obtain viscous solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, obtain polyacrylic acid (4 '-hydroxyl-4-ethyl phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 23(1) 4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone (DMACH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-(N of 3.26 grams (0.02 mole), the N dimethylamine base) methyl phenyl ketone, with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, obtain 4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone after reaching drying after filtration.(2) preparation of vinylformic acid (4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone) ester (MADMACH) is equipped with
The DMACH that take by weighing 1.0 grams (0.003745 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solution room temperature reactions 24 hours of 2 milliliters of acrylate chlorides.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone) ester after reaching vacuum-drying after filtration.(3) polyacrylic acid (4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone) ester (PMADMACH) is synthetic
The MADMACH of 0.50 gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MADMACH then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, reach drying after filtration and obtain polyacrylic acid (4-hydroxyl 4 '-(N, N dimethylamine base) phenyl styryl ketone) ester.
Embodiment 24(1) 4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone (DMACH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-(N of 2.98 grams (0.02 mole), the N dimethylamine base) phenyl aldehyde, few ethanol dissolves it with trying one's best, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, after filtration, obtain 4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone after washing and the drying.(2) preparation of vinylformic acid (4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone) ester (MADMACH ')
The DMACH ' that take by weighing 1.0 grams (0.003745 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of acrylate chlorides, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain vinylformic acid (4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone) ester after reaching drying after filtration.(3) polyacrylic acid (4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone) ester (PMADMACH ') is synthetic
0.50 gram (mole) MADMACH ' is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MADMACH ' then, be warming up to 60 ℃ and reacted 3 days, obtain heavy-gravity solution.Add 10 milliliters of tetrahydrofuran (THF) diluted reaction mixtures, reaction mixture is poured in a large amount of methyl alcohol precipitated then, obtain polyacrylic acid (4 '-hydroxyl-4-(N, N dimethylamine base) phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 25(1) 4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone (DEACH) is synthetic
Take by weighing the 4-hydroxy benzaldehyde of 2.44 grams (0.02 mole) and 4 '-(N of 3.82 grams (0.02 mole), the N dimethylamine base) methyl phenyl ketone, with ethanol it is dissolved, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to the neutral precipitation that produces, after filtration, obtain 4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone after washing and the drying.(2) preparation of methacrylic acid (4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone) ester (MMADEACH)
The DEACH that take by weighing 1.0 grams (0.003390 mole) are dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtain settled solution, add 2 milliliters of triethylamines, after mixing progressively dropping be dissolved with 5 milliliters of tetrahydrofuran solutions of 2 milliliters of methacrylic chlorides, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone) ester after reaching drying after filtration.(3) polymethyl acrylic acid (4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone) ester (PMMADEACH) is synthetic
0.50 the MMADEACH of gram (mole) is dissolved in 5 milliliters of tetrahydrofuran solutions and obtains uniform solution, adds 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMADEACH then, is warming up to 60 ℃ of reactions 3 days, obtains heavy-gravity solution.Reaction mixture poured in a large amount of methyl alcohol precipitate, obtain polymethyl acrylic acid (4-hydroxyl-4 '-(N, N dimethylamine base) phenyl styryl ketone) ester after reaching drying after filtration.
Embodiment 26(1) 4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone (DEACH ') synthetic
Take by weighing the 4 '-hydroxy acetophenone of 2.72 grams (0.02 mole) and the 4-(N of 3.54 grams (0.02 mole), the N dimethylamine base) phenyl aldehyde, few ethanol dissolves it with trying one's best, slowly splash into 5.5 milliliter 50% KOH solution then, reaction finishes, add an amount of dilute hydrochloric acid reaction mixture is neutralized to neutral a large amount of precipitations that produce, after filtration, obtain 4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone after washing and the drying.(2) preparation of methacrylic acid (4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone) ester (MMADEACH ') is equipped with
The DEACH ' that takes by weighing 1.0 grams (0.003390 mole) is dissolved in 5 milliliters of tetrahydrofuran (THF)s and obtains settled solution, add 2 milliliters of triethylamines, progressively drip 5 milliliters of anhydrous tetrahydrofuran solutions being dissolved with 2 milliliters of methacrylic chlorides after mixing, in room temperature reaction 24 hours.After reaction finishes, reaction mixture is precipitated in a large amount of water, obtain methacrylic acid (4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone) ester after reaching drying after filtration.(3) polymethyl acrylic acid (4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone) ester (PMMADEACH ') is synthetic
The MMADEACH ' of 0.50 gram (mole) is dissolved in 5 milliliters of anhydrous tetrahydrofuran solutions and obtains uniform solution, add 0.2～0.5% Ou nitrogen Er Yi Ding Evil of MMADEACH ' then, under nitrogen protection, be warming up to 60 ℃ and reacted 3 days, obtain viscous solution.Reaction mixture poured in 50 milliliters the methyl alcohol and precipitate, obtain polymethyl acrylic acid (4 '-hydroxyl-4-N, N dimethylamine base-phenyl styryl ketone) ester after reaching drying after filtration.
Effect
Use aforesaid method, the polymkeric substance that synthetic various side chains contain the acrylic compound of phenyl styryl ketone group and are used for liquid crystal alignment layer is through infrared spectra (FTIR), nuclear magnetic resonance spectrum (H
1-NMR) analyze DSC to test with heat, the provable product that obtains envisioned configuration, and have higher molecular weight, percentage of grafting is 100%.
With the alignment layer material dissolution with solvents, be made into homogeneous solution, even stir the surperficial rotary plating of machine by desk-top, and shine into capable photo-crosslinking with UV-light (as 365nm) at substrate.
The relatively variation of infrared spectrum before and after the illumination finds that the C=C absorption peak in the infrared spectrum obviously reduces after the illumination, illustrates that position of double bond given birth to photo-crosslinking.Find that illumination post polymerization thing no longer is dissolved in all kinds of SOLVENTS, illustrates that crosslinking reaction has taken place polymkeric substance.The DSC of alignment layer material after the observation illumination, the second-order transition temperature of illumination post polymerization thing has disappeared, and also further specifies polymkeric substance photo-crosslinking has taken place really.
The polymkeric substance that is used for both alignment layers of gained is made into certain density solution, surperficial rotary plating in matrix, it is crosslinked to shine into capable directional light with polarized ultraviolet, make liquid crystal cell, pour into liquid crystal, be placed under the polarizing microscope and observe, find that the visual field is more even, when the rotation liquid crystal cell, can see having tangible light and shade to change in the visual field, illustrate that alignment film makes liquid crystal that directive action has taken place really.
The polymkeric substance that is used for liquid crystal alignment layer through the whole bag of tricks proof synthetic has the molecular structure of anticipation, and finds after tested to realize that really liquid crystal molecule aligns uniformly.
Claims (21)
1. acrylic compound, its structure is suc as formula shown in (I):
Wherein,
A is that 0 to 10 integer and b are 0 or 1, but when a=0, b=0; And when a ≠ 0, b=1;
R is hydrogen atom, halogen, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, cyano group, thiohydroxy, nitro or amido, wherein amido can be through one or two C
1-C
6Alkyl replaces, C
1-C
10Alkyl and C
1-C
10Alkoxyl group can be selected from C through one or more
1-C
10The group of alkyl, phenyl, halogen, nitro, cyano group or thiohydroxy replaces; G is
Or
And R
4Be propenyl or methylpropenyl.
2. compound according to claim 1 is characterized in that described halogen is fluorine atom, chlorine atom and bromine atoms.
3. the method for a preparation formula (I) acrylic compound, it comprises the following steps:
(i) with the aromatic aldehyde of formula (II)
Aromatic ketone with formula (III)
Under concentrated alkali solution catalysis, carry out condensation reaction, add an amount of dilute acid soln neutralization again, wherein R
1And R
2Be OH or R, but R
1≠ R
2R is hydrogen atom, halogen, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, cyano group, thiohydroxy, nitro or amido, wherein amido can be through one or two C
1-C
6Alkyl replaces, C
1-C
10Alkyl and C
1-C
10Alkoxyl group can be selected from C through one or more
1-C
10The group of alkyl, phenyl, halogen, nitro, cyano group or thiohydroxy replaces;
(a) work as R
1=R, R
2Obtain the phenyl styryl ketone phenol throw out of formula (IV) during=OH:
(b) work as R
1=OH, R
2Obtain the phenyl styryl ketone phenol throw out of formula (IV ') during=R:
(ii)
(a) the phenyl styryl ketone phenol with formula (IV) or (IV ') is dissolved in the aprotic polar solvent, with the alkyl acetyl halide compound reaction of formula V,
Obtain the acrylic compound of formula (I)
A=b=0 wherein; R has foregoing definition; G is
Or
R
4Be propenyl or methylpropenyl; And X
1Be halogen; Or (b) with the phenyl styryl ketone phenol of formula (IV) or (IV '), under weak base and alkali metal group or the existence of alkaline earth metal halogenide, the halogenohydrin with formula (VI) reacts earlier,
X
2(CH
2)
aOH (VI) obtains the hydroxyalkyl phenyl styryl ketone ether of formula (VII),
Hydroxyalkyl phenyl styryl ketone ether with formula (VII) is dissolved in the aprotic polar solvent again, with the alkyl acetyl halide compound reaction of formula V
Obtain the acrylic compound of formula (I)
Wherein a is 1 to 10 integer, and b is 1; R, G and R
4Has foregoing definition, X
2Be halogen.
4. method according to claim 3, it is characterized in that this formula (II) compound is 4-hydroxy benzaldehyde, phenyl aldehyde, 4-bromobenzaldehyde, 4-cyanobenzaldehyde, 4-methoxybenzaldehyde, 4-ethylbenzene formaldehyde, 4-(N, the N dimethylamine base) phenyl aldehyde or 4-(N, N dimethylamine base) phenyl aldehyde.
5. method according to claim 3, it is characterized in that this formula (III) compound be methyl phenyl ketone,
4-hydroxy acetophenone, 4-bromoacetophenone, 4-cyano-acetophenone, 4-methoxyacetophenone, 4-ethylbenzene ethyl ketone, 4-(N, N dimethylamine base) methyl phenyl ketone or 4-(N, N dimethylamine base) methyl phenyl ketone.
6. method according to claim 3 is characterized in that this concentrated alkali solution is a potassium hydroxide solution.
7. method according to claim 3 is characterized in that this dilute acid soln is a dilute hydrochloric acid solution.
8. method according to claim 3 is characterized in that this aprotic polar solvent is tetrahydrofuran (THF) (THF), N, dinethylformamide (DMF), methyl-sulphoxide (DMSO), N,N-dimethylacetamide (DMAC) or N-methylpyrrole pyridine ketone (NMP).
9. method according to claim 3 is characterized in that this weak base is salt of wormwood.
10. method according to claim 3 is characterized in that this halogenide is potassiumiodide.
11. method according to claim 3 is characterized in that this alkyl acetyl halide compound is acrylate chloride or methacrylic chloride.
12. method according to claim 3 is characterized in that this halogenohydrin is chloroethanol, trimethylene chlorohydrin, 4-chloro-1-butanols, 5-chloro-1-amylalcohol or 6-chloro-1-hexanol.
12. method according to claim 3 is characterized in that step (ii) further comprises the interpolation acid absorber.
14. method according to claim 13 is characterized in that this acid absorber is triethylamine (TEA), pyridine, N-ethylmorpholine (NEM), xylidine (DMAN).
15. the acrylic ester polymer with formula (VIII),
Wherein: n is the integer greater than 1; A is 0 to 10 integer, wherein when a=0, and b=0; When a=1 to 10, b=1; R is hydrogen atom, halogen, C
1-C
10Alkyl, C
1-C
10Alkoxyl group, cyano group, thiohydroxy, nitro or amido, wherein amido can be through one or two C
1-C
6Alkyl replaces, C
1-C
10Alkyl and C
1-C
10Alkoxyl group can be selected from C through one or more
1-C
10The group of alkyl, phenyl, halogen, nitro, cyano group or thiohydroxy replaces; G is
Or
And R
5Be hydrogen atom or methyl.
16. polymkeric substance according to claim 15 is characterized in that this polymkeric substance has molecular-weight average and is about between 500 to 500,000.
17. polymkeric substance according to claim 15, its percentage of grafting are 50% to 100%.
18. a method for preparing the described formula of claim 15 (VIII) acrylic ester polymer, it comprises the following steps:
(i) with the described formula of claim 1 (I) acrylic compound, be dissolved in an amount of aprotic polar solvent;
After (ii) adding the light initiator, the temperature of rising reaction soln is to carry out polyreaction; And
(iii) reaction soln is poured into a large amount of alcoholic solvents, formed the acrylic ester polymer of formula (VIII).
19. method according to claim 18 is characterized in that the light initiator is Ou nitrogen Er Yi Ding Evil (AIBN).
20. method according to claim 18 is characterized in that alcohol solution is a methyl alcohol.
21. the material of a liquid crystal alignment layer, it comprises the described formula of claim 15 (VIII) acrylic ester polymer.
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| CN100334493C (en) * | 2004-05-28 | 2007-08-29 | 友达光电股份有限公司 | Monomer for stabilizing orientation of polymer and liquid crystal display panel with polymer therefrom |
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| JP2009536655A (en) * | 2006-05-10 | 2009-10-15 | アリゾナ バイオメディカル リサーチ コミッション | Modified chalcone compounds as mitotic inhibitors |
| CN101293880B (en) * | 2007-04-28 | 2010-11-03 | 中国石油天然气集团公司 | Synthesizing method for preparing N-acryloyl morpholine |
| CN101893789A (en) * | 2010-07-07 | 2010-11-24 | 深圳超多维光电子有限公司 | Alignment layer materials, alignment layer manufacturing process and display panel |
| CN101893789B (en) * | 2010-07-07 | 2012-08-29 | 深圳超多维光电子有限公司 | Alignment layer materials, alignment layer manufacturing process and display panel |
| CN107473969A (en) * | 2012-10-05 | 2017-12-15 | 日产化学工业株式会社 | The manufacture method of substrate with the driving liquid crystal orientation film used for liquid crystal display element of horizontal component of electric field |
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| CN109416484B (en) * | 2016-07-04 | 2021-11-09 | 夏普株式会社 | Liquid crystal display device and method for manufacturing liquid crystal display device |
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