CN103435515B - Modification pentaerythritol acrylate of the low volumetric shrinkage of a kind of low viscosity high reaction activity and preparation method thereof - Google Patents
Modification pentaerythritol acrylate of the low volumetric shrinkage of a kind of low viscosity high reaction activity and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses modification pentaerythritol acrylate of the low volumetric shrinkage of a kind of low viscosity high reaction activity and preparation method thereof.The structural formula of the modification pentaerythritol acrylate of the low volumetric shrinkage of low viscosity high reaction activity is:
Description
Technical field
The present invention relates to modification pentaerythritol acrylate of the low volumetric shrinkage of a kind of low viscosity high reaction activity and preparation method thereof.
Background technology
Photocuring technology has fast setting, energy-and time-economizing, the release of low solvent, solidification value is low, equipment volume is little, invest the advantages such as low, its Application Areas has now developed into multiple field of industrial productions such as decorative plastic, metal parts application, medicine equipment, electronic component, information recording carrier, photosensitive printing, plastic material and optical fiber from initial wood finishing, and it mainly occurs with forms such as UV coating, UV ink, UV tackiness agent.
Ultraviolet photocureable material is made up of UV-Curable Prepolymer (oligopolymer), activity diluting monomer, light trigger and all kinds of interpolation auxiliary agent (color stuffing, defoamer etc.).Performed polymer is the base resin of UV curing system, in whole system, occupy larger proportion.Reactive thinner is used to dilute performed polymer, makes resin system reach the viscosity of expectation.Performed polymer generally accounts for more than 90% of whole curing system quality together with activity diluting monomer, and wherein activity diluting monomer accounts for 40-60%.They are to the performance of whole system, as hardness, sticking power, snappiness, weather resistance, wear resistance, tensile strength, shock-resistance and ageing-resistant performance etc. play decisive role.
The photocuring reactive thinner of excellent performance needs low viscosity, high reaction activity, low volumetric shrinkage (improving base material sticking power), low mobility, the characteristics such as hypotoxicity, traditional single reactive thinner can not meet above-mentioned performance simultaneously, meet high reaction activity, low mobility, hypotoxicity, just can not meet low viscosity and low volumetric shrinkage, great majority need to select the reactive thinner of two kinds or more of different Guan Nengdu to arrange in pairs or groups, to obtain the photocuring formula for a product of excellent combination property.The Photocurable oligomers of excellent performance then needs low viscosity, high photo-curing rate, low volumetric shrinkage and comprises with excellent physical and mechanical property: the wettability etc. of hardness, snappiness, wear resistance, tensile strength, shock-resistance, sticking power, chemical-resistant, color inhibition, gloss, pigment.Although traditional oligopolymer has low volumetric shrinkage, low mobility, hypotoxicity, is difficult to meet low viscosity and hyperergy simultaneously, and when performances such as the hardness of satisfied excellence, scratch-proofness and resistances, is difficult to meet shock resistance simultaneously.
Traditional multi-functional acrylate's reactive monomer, although it is fast to have photo-curing rate, cross-linking density is large, coating or hardness of film high, resistance is excellent, high boiling point, the advantages such as low volatilization, but it is corresponding enbrittles large, and viscosity is high, and dilution properties is poor, volumetric shrinkage is large, poor adhesive force, curing efficiency is low, the shortcomings such as coating or film shock resistance difference.Traditional origoester acrylate or its composition such as Epocryl show many shortcomings when applying for UV hardenable coatings, the coating that gained UV-solidifies or film tend to fragility instead of flexibility, and to the application needed for major part, enough binding propertys are lacked to the ground of coating.Those skilled in the art can evaluate binding property and the flexibility of coating according to shock test, such as, after shock test coating not leafing show at least there is minimum acceptable bonding; If the experiment after coating or film Impact Test demonstrates seldom (or not having) visible crack, this coating or film are considered as at least having minimum acceptable flexibility by those skilled in the art.In addition, traditional acrylate resin, particularly epoxy acrylic resin, have the viscosity more than 4Pa.s.When higher viscosity makes this resinoid be applied in UV-hardenable coatings, the relatively little lower molecular weight reactive thinner of viscosity must be added to reduce the viscosity of coating composition to being no more than the viscosity of 4Pa.s and the room-temperature applications viscosity preferably more than 2.5Pa.s, although the low dilution effect of lower molecular weight reactive thinner viscosity is good, but there is low-steam pressure, toxicity and pungency mostly, still can remain in the product after illumination terminates, detrimentally affect is produced to environment and HUMAN HEALTH, and cost is high, complicated operation, the volatile migration of products obtained therefrom, loss are greatly.
Common pentaerythritol acrylate, there is viscosity large, dilution property is poor, cured film is hard and crisp, higher volumetric shrinkage affects sticking power, shock resistance poor (flexible poor), the shortcomings such as snappiness is poor, to product snappiness, there is very large defect the aspects such as the adsorptive power of flexibility and product application base material or viscosity.Design and develop novel chemically-reactive and there is high reactive behavior, lower viscosity, the low migration of high molecular, the monomer of low volumetric shrinkage and the excellent combination property such as adjustable flexibility and flexibility and oligomer resin to expanding the Application Areas of photo-curing material and to prepare high performance photo-curing material significant.
Summary of the invention
The object of this invention is to provide modification pentaerythritol acrylate of the low volumetric shrinkage of a kind of low viscosity high reaction activity and preparation method thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A modification pentaerythritol acrylate for the low volumetric shrinkage of low viscosity high reaction activity, its structural formula is:
Wherein, R
1and R
2be respectively hydrogen or methyl; R
3and R
4be respectively general formula I I, general formula III, general formula I V or general formula V, but R
3, R
4can not be general formula I I simultaneously;
Wherein, m, n, k, l are respectively the integer between 0 to 10; R
5, R
6, R
7, R
10, R
12be respectively hydrogen or methyl; R
8, R
9, R
11, R
13be respectively hydrogen, the alkyl of optional C1-C10, the optional cycloalkyl replaced by the alkyl of C0-C10 or the optional benzyl replaced by the alkyl of C0-C10; R
14for the alkyl of hydrogen, optional C1-C10, the optional cycloalkyl replaced by the alkyl of C0-C10, the optional benzyl replaced by the alkyl of C0-C10 or the optional ketone group replaced containing the alkyl that can form the C1-C10 of amido linkage with N.
The modification pentaerythritol acrylate of the low volumetric shrinkage of above-mentioned low viscosity high reaction activity has high reactive behavior, low viscosity, the low migration of high molecular, low volumetric shrinkage, excellent sticking power and adjustable flexibility and flexibility.
The modification pentaerythritol acrylate of the low volumetric shrinkage of above-mentioned low viscosity high reaction activity, preferably, R
1and R
2be hydrogen or simultaneously for methyl simultaneously; R
3and R
4it is general formula III or simultaneously for general formula I V or simultaneously for general formula V simultaneously; R
5, R
6, R
7, R
10, R
12be hydrogen or methyl respectively simultaneously.Such modification pentaerythritol acrylate of the low volumetric shrinkage of low viscosity high reaction activity that can make has lower viscosity with better flexible and flexible.
The preparation method of the modification pentaerythritol acrylate of the low volumetric shrinkage of above-mentioned low viscosity high reaction activity, comprises the following steps that order connects:
A, be the methylcarbonate of (200-600): 100:1, tetramethylolmethane and the first catalyzer by mol ratio, after back flow reaction 7-24h, distill out methyl alcohol and unnecessary methylcarbonate that reaction produces, obtain material A;
B, by material A with at least be with the primary amine of a hydroxyl or the amine substance of secondary amine back flow reaction 1-6h in the first solvent, obtain material B, wherein, the mole dosage of amine substance is 1-3 times of tetramethylolmethane mole number;
C, acrylate chloride or methacrylic chloride are slowly instilled in material B, after dropwising, under room temperature, react 1-3 hour, after purification and get final product, wherein, the mole dosage of acrylate chloride or methacrylic chloride be the 4-10 of tetramethylolmethane mole number doubly;
In steps A, the first catalyzer is Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO) or DMAP (DMAP);
In step B, the first solvent is the alkane of benzene, toluene, hexanaphthene or C6-C10.
In step B, the preferred benzene of the first solvent, toluene, hexanaphthene or normal heptane, more preferably hexanaphthene.Reaction efficiency can be ensured further like this, and not affect the quality of products obtained therefrom.In step C, the mole dosage of acrylate chloride or methacrylic chloride is preferably the 6-10 of tetramethylolmethane mole number doubly.
Applicant finds after deliberation: the material A of steps A gained is ring-type 1, the tetramethylolmethane of 3 propylene carbonate types, and the reflux temperature in steps A is 70-120 DEG C; The material B of step B gained is the polyvalent alcohol of band tertiary amine and hydroxyl, and the reflux temperature in step B is 60-120 DEG C; Preferably, reflux temperature is 60-80 DEG C, and the reaction times is 2-4h.
The speed slowly dripped in above-mentioned steps C is preferably 30-60 drips/minute, room temperature refers to that temperature is 20-30 DEG C.
Above-mentioned preparation method is simple and easy to control, and products obtained therefrom purity is high, performance good.
Preferably, in steps A, the mol ratio of methylcarbonate, tetramethylolmethane and the first catalyzer is (300-500): 100:1, reflux temperature is 70-100 DEG C, return time is 10-15h, and catalyzer is Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane (DABCO).
Above-mentioned steps C also can be: by vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate and material B in the second solvent, under the effect of the second catalyzer and stopper, 70-110 DEG C, reaction 7-13h, after purification and get final product, wherein, the mole dosage of vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate is 4-10 times of tetramethylolmethane mole number.With the product that this kind of method obtains, there is lower viscosity and the reactive behavior of Geng Gao, low volumetric shrinkage, excellent sticking power and better flexible and flexible.
Preferably, in above-mentioned steps C, the mole dosage of vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate is 6-10 times of tetramethylolmethane mole number, reaction times preferred 8-16h.
In step B, the primary amine of a hydroxyl or the amine substance of secondary amine is at least with to be preferably uncle's amine substance of the band monohydroxy-alcohol of C2-C15 or the secondary amine substance of dibasic alcohol; Be more preferably the secondary amine substance of the dibasic alcohol of C2-C8, more preferably ethylene glycol amine, propylene glycol amine.Like this, the material obtained has better flexible and flexible.
Above-mentioned second solvent is preferably the mixture of one or more any proportionings in benzene,toluene,xylene, trieline, trichloromethane, methylene dichloride, ethyl acetate, ethylene glycol Potassium ethanoate, N, N-Dicyclohexylcarbodiimide, hexanaphthene, normal hexane, normal heptane or Skellysolve A.Be more preferably, benzene, toluene, hexanaphthene, normal hexane, normal heptane, Skellysolve A, more preferably hexanaphthene.
Above-mentioned solvent can ensure carrying out smoothly of reaction, and does not affect the quality of product, easily removes simultaneously.
The consumption of above-mentioned second solvent be preferably vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate and material B quality and 40-60%.So both ensure that carrying out smoothly of reaction, again save raw material, convenient reaction simultaneously terminates the removal of rear solvent.
Above-mentioned stopper is preferably para benzoquinone, adjacent benzoquinones, toluhydroquinone, Resorcinol, 2-Tert. Butyl Hydroquinone, 2,5-di-tert-butyl hydroquinone, MEHQ, thiodiphenylamine, the acid of Ursol D, dimethylamino diethylamino copper, copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl piperidine oxide compound, 4-hydroxyl-2,2, the mixture of one or more any proportionings in 6,6-tetramethyl piperidine-1-oxyradical; The mole dosage of stopper is the 0.5-5 ‰ of tetramethylolmethane mole number.Above-mentioned stopper further ensures the quality of products obtained therefrom.The mixture of one or more any proportionings in stopper further preferably 2,5 di tert butyl hydroquinone, MEHQ, copper dibutyldithiocarbamate or 2,2,6,6-tetramethyl piperidine oxide compound.
Preferably, when acrylic or methacrylic acid is reacted with material B, second catalyzer is the mixture of one or more any proportionings in sulfuric acid, phosphoric acid, Mono Chloro Acetic Acid, methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid, ethyl phenenyl azochlorosulfonate acid, p-methyl benzenesulfonic acid or solid acid catalyst, and the second catalyst quality consumption is the 2%-8% of vinylformic acid or methacrylic acid quality; When methyl acrylate or methyl methacrylate and material B react, the second catalyzer is dibutyltin dilaurate, stannous octoate, two acetic acid dibutyl esters, NaOH, KOH, NaOCH
3, triethylamine, trolamine, triethylenediamine, solid base catalyst, phosphoric acid, one or more any proportionings in Mono Chloro Acetic Acid and sulfuric acid, sulfonic acid, methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid or solid acid catalyst mixture, the second catalyst quality consumption is the 2%-8% of methyl acrylate or methyl methacrylate quality.The kind of above-mentioned catalyzer and consumption improve the efficiency of reaction effectively.
Further preferably, when acrylic or methacrylic acid is reacted with material B, the second catalyzer is sulfuric acid, methylsulphonic acid or p-methyl benzenesulfonic acid; When methyl acrylate or methyl methacrylate and material B react, the second catalyzer is dibutyltin dilaurate, two acetic acid dibutyl esters, triethylamine, triethylenediamine, methylsulphonic acid or Phenylsulfonic acid.
Step C purifies and comprises filtration, pickling, alkali cleaning, washing and distillation removal residual solvent; During alkali cleaning alkali used be sodium carbonate, the alkaline solution that configures of the mixture of one or more any proportionings in sodium bicarbonate, salt of wormwood, sodium hydroxide or potassium hydroxide.The above-mentioned alkali number that adds is 1-2 times that reacts remaining sour molar weight.
The not specified technology of the present invention is prior art.
The functionality of the modification pentaerythritol acrylate of the low volumetric shrinkage of low viscosity high reaction activity of the present invention is 4-6, viscosity is 40-70mPa.s, molecular weight is 750-2500, there is very high reactive behavior, lower viscosity, the low migration of high molecular, high curing efficiency, low volumetric shrinkage, excellent sticking power and adjustable flexibility and flexibility, prepared coating shock-resistance is good, strong adhesion.Higher functionality makes it have a lot of reactive behavior higher than pentaerythritol acrylate and traditional acrylate; Applicant finds after deliberation, by introducing tertiary amine groups to tetramethylolmethane modification, acrylate with tertiary amine group can be used as aided initiating, with the hydrogen-abstraction free radical photo-initiations such as benzophenone with the use of, photo-curing rate can be improved, the impact of oxygen inhibition can be reduced, be conducive to the surface cure improving photo-curing material, improve Light-Curing Efficiency; Owing to introducing a large amount of side chains to the modification of tetramethylolmethane, make this acrylate not only have higher molecular weight, and there is low volumetric shrinkage and lower viscosity.Preparation method of the present invention is simple and easy to control, and products obtained therefrom purity is high, performance good.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In embodiment, " room temperature " and " envrionment temperature " is 25 DEG C.Yield: the actual quality product generated and the per-cent generating quality according to tetramethylolmethane theory.In example, the mensuration of acid number is with reference to HB/FG02-2009, and the mensuration of colourity is with reference to GB9282, and the mensuration of stopper is with reference to GB/T17530.5-1998, and the mensuration of viscosity is with reference to GB/T5561-1994.The mensuration of volumetric shrinkage: liquid, solid density before and after surely solidifying with specific gravity flask side, make reference with water, photocuring volumetric shrinkage formula is:
In formula: η
vfor photocuring volumetric shrinkage; ρ s: for solidifying the relative density of caudacoria; ρ
l: be the relative density of solidification forward slip value liquid material.Photo-curing rate adopts real-time infrared spectroscopy to measure, and utilize carbon-carbon double bond to react front and back, the Strength Changes of the charateristic avsorption band of=C-H characterizes its curing speed:
DC(％)＝(A
0-A
t)/A
0×100
In formula: DC is acrylic double bond transformation efficiency at any time, A
0it is the peak area before illumination; A
tbe the peak area of any time after illumination, photo-curing rate is tried to achieve by double bond conversion rate time differential.
In order to better understand the present invention, following present the reaction equation being prepared modification tetramethylolmethane polyvalent alcohol by tetramethylolmethane:
In Fig. 1, m, n are the integer of 0-10; X is hydrogen, one in the alkyl of optional C1-C10, the optional cycloalkyl replaced by the alkyl of C0-C10, the optional benzyl replaced by the alkyl of C0-C10; Y is hydrogen, one in the alkyl of optional C1-C10, the optional cycloalkyl replaced by the alkyl of C0-C10, the optional benzyl replaced by the alkyl of C0-C10 and the optional ketone group replaced containing the alkyl that can form the C1-C10 of amido linkage with N; A, B, C are respectively the primary, secondary amine modifying process of different band hydroxyl, and a is acrylate chloride or methacrylic chloride; B is vinylformic acid or methacrylic acid; C is methyl acrylate or methyl methacrylate.
Embodiment 1
Ring-type 1 is prepared, 3 propylene carbonate type modification tetramethylolmethanes by tetramethylolmethane and methylcarbonate:
By (68g, 0.5mol) tetramethylolmethane, (180g, 2mol) methylcarbonate and (0.56g, 5mmol) 1, 4-diazabicylo [2.2.2] octane DABCO adds and is equipped with in the 2000ml reaction flask of electric stirring and water-cooled reflux condenser, flask is placed in the sand-bath in electric mantle, the temperature regulator being connected to the thermopair immersed in sand-bath is used to control sand-bath temperature, solution mass in flask is made to be 80 DEG C, by stirring, in flask, the solid ingredient of solution mass is dissolved into colourless transparent solution, temperature of reaction is made to maintain 80 DEG C of Keep agitation 14h, in reaction process, reaction product methyl alcohol is constantly distilled, react complete excessive methylcarbonate and be distilled out reaction flask, resultant product is weighed about has 92.1g, many parts of experiments are simultaneously done under above-mentioned reaction equal conditions, a copy of it products therefrom carries out ethanol and the purification processes such as water precipitation, recrystallization, with silica-gel plate point sample to reaction process and at the end of product solution carry out a plate analysis, adopt silica gel column chromatography to be separated (normal hexane: ethyl acetate=5:2), all the other products therefroms do not process further as next step raw material, to purify after product carry out FTIR infrared and
1h-NMR nmr analysis, has stronger absorption peak to show, containing C=O key stretching vibration peak, have C=O key to generate after showing substance reaction 1760 in product FTIR infrared spectrum,
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference, 1HNMR (300MHz, CDCl3) ppm:4.08 (s, 8H), and analytical results display product is the structural formula I in reaction equation.
Embodiment 2
By ring-type 1, the 3 propylene carbonate type modification tetramethylolmethane of embodiment 1 gained and the modification tetramethylolmethane polyvalent alcohol of diethanolamine Reactive Synthesis band tertiary amine:
By before in embodiment 1 flask, reaction product is cooled to room temperature, add (105g, 1mol) diethanolamine and 600ml hexanaphthene, under electric stirring effect, in flask, solution mass is slowly warming up to 70 DEG C, temperature of reaction maintains 70 DEG C of Keep agitation 3h, and reaction terminates, and is cooled to room temperature; Many parts of experiments are simultaneously done under above-mentioned reaction equal conditions, a copy of it products therefrom carries out ethanol and the purification processes such as water precipitation, recrystallization, adopt silica gel column chromatography to be separated (normal hexane: ethyl acetate=4:1), all the other products therefroms do not process further as next step raw material; To purify after product carry out FTIR infrared and
1h-NMR nmr analysis, has stronger absorption peak to show containing C=O key stretching vibration peak 1680 in product FTIR infrared spectrum, show material react after C=O key be subjected to displacement,
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:4.0 (s, 4H, C-CH
2-O-C=O), 3.79 (t, 8H, CH
2-CH
2-OH), 3.45 (d, 4H, C-CH
2-OH), 3.15 (t, 8H, N-CH
2), 2.0 (6H ,-OH), analytical results display product is that (wherein X, Y are hydrogen for structural formula J in reaction equation; M, n are 1).
Embodiment 3
Ring-type 1,3 propylene carbonate type modification tetramethylolmethane and the tertiary-amine modified tetramethylolmethane polyvalent alcohol of diisopropanolamine (DIPA) Reactive Synthesis band by embodiment 1 gained:
By before in embodiment 1 flask, reaction product is cooled to room temperature, add (133g, 1mol) diisopropanolamine (DIPA) and 600ml hexanaphthene, under electric stirring effect, in flask, solution mass is slowly warming up to 75 DEG C, temperature of reaction maintains 75 DEG C of Keep agitation 3h, and reaction terminates, and is cooled to room temperature.
Embodiment 4
Ring-type 1,3 propylene carbonate type modification tetramethylolmethane and the tertiary-amine modified tetramethylolmethane polyvalent alcohol of two octanol amine Reactive Synthesis bands by embodiment 1 gained:
By before in embodiment 1 flask, reaction product is cooled to room temperature, add (273g, 1mol) two octanol amine and 600ml hexanaphthene, under electric stirring effect, in flask, solution mass is slowly warming up to 70 DEG C, temperature of reaction maintains 70 DEG C of Keep agitation 3h, and reaction terminates, and is cooled to room temperature.
Embodiment 5
Ring-type 1,3 propylene carbonate type modification tetramethylolmethane and the tertiary-amine modified tetramethylolmethane polyvalent alcohol of thanomin Reactive Synthesis band by embodiment 1 gained:
In embodiment 1 by before in flask, reaction product is cooled to room temperature, add (61g, 1mol) thanomin and 600ml hexanaphthene, under electric stirring effect, in flask, solution mass is slowly warming up to 70 DEG C, temperature of reaction maintains 70 DEG C of Keep agitation 3h, reaction terminates, be cooled to room temperature, many parts of experiments are simultaneously done under above-mentioned reaction equal conditions, a copy of it products therefrom carries out ethanol and water precipitation, the purification processes such as recrystallization, silica gel column chromatography is adopted to be separated (normal hexane: ethyl acetate=8:1), all the other products therefroms do not process further as next step raw material, to purify after product carry out FTIR infrared and
1h-NMR nmr analysis, has stronger absorption peak to show containing C=O key stretching vibration peak 1680 in product FTIR infrared spectrum, show material react after C=O key be subjected to displacement,
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:8.0 (2H, NH), 4.0 (s, 4H, C-CH
2-O-C=O), 3.79 (t, 4H, CH
2-CH
2-OH), 3.45 (d, 4H, C-CH
2-OH), 3.15 (t, 4H, N-CH
2), 2.0 (4H ,-OH), analytical results display product is that (wherein X is hydrogen to K in Fig. 1, m is 1).
Embodiment 6
Ring-type 1,3 propylene carbonate type modification tetramethylolmethane and the tertiary-amine modified tetramethylolmethane polyvalent alcohol of N-ethanol based formamide anamorphic zone by embodiment 1 gained:
By before in embodiment 1 flask, reaction product is cooled to room temperature, add (89g, 1mol) N-ethanol based methane amide and 600ml hexanaphthene, under electric stirring effect, in flask, solution mass is slowly warming up to 70 DEG C, taking-up sample carry out silica-gel plate point plate and to reaction process and at the end of before product solution carries out a plate analysis, temperature of reaction maintains 70 DEG C of Keep agitation 3h, room temperature is cooled to after reaction terminates, many parts of experiments are simultaneously done under above-mentioned reaction equal conditions, a copy of it products therefrom carries out ethanol and water precipitation, the purification processes such as recrystallization, silica gel column chromatography is adopted to be separated (normal hexane: ethyl acetate=6:1), all the other products therefroms do not process further as next step raw material, to purify after product carry out FTIR infrared and
1h-NMR nmr analysis, has stronger absorption peak to show containing C=O key stretching vibration peak 1680 in product FTIR infrared spectrum, show material react after C=O key be subjected to displacement,
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:4.0 (s, 4H, C-CH
2-O-C=O), 3.79 (t, 4H, CH
2-CH
2-OH), 3.67 (t, 4H, N-CH
2), 3.45 (d, 4H, C-CH
2-OH), 2.4 (s, 6H, CH3-C=O), 2.0 (4H ,-OH), analytical results display product is that (wherein X is hydrogen to L in Fig. 1, Y is methyl ketone group CH3-C=O-, m is 1).
Embodiment 7
Obtained modification pentaerythritol acrylate is reacted by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 2 gained and acrylate chloride:
By when in embodiment 2 flask, reaction product is cooled to room temperature, add (333g, 3.3mol) triethylamine, remove the electric mantle of heating, with an ice-water bath cooling temperature to 0 DEG C, make the reaction that will occur milder, application of sample constant pressure funnel is adopted slowly to drip (297g afterwards, in the flask of band electric stirring that 3.3mol) acrylate chloride cools to ice bath, after acrylate chloride is dropwised, remove ice-water bath, progressively flask temperature is warming up to room temperature, reaction mixture at room temperature maintains 2h, after reaction terminates, reaction mixture removes solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling is carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.2g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary cyclohexane solution, products therefrom is weighed as 291.7g, theoretical yield is about 80.8%.Product test index is as follows: acidity 0.19mgKOH/g, stopper 321.27 (MEHQ, ppm), colourity 60 ((APHA) platinum-cobalt method), viscosity 63.6mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:6.43 (d, 6H, C=CH
2), 6.05 (t, 6H, CH=C), 5.8 (d, 6H, C=CH
2), 4.41 (t, 8H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.24 (t, 8H, N-CH
2) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) Spectrum Analysis show that (be equivalent to R1 and R2 in general formula I is hydrogen to modification tetramethylolmethane six acrylate that product structure formula is the such as band tertiary amine shown in following general formula VI, R3 and R4 is general formula III; In general formula III, m and n is 1, R6, R7, R8, R9 is hydrogen).
Embodiment 8
Obtained modification pentaerythritol acrylate is reacted by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 2 gained and vinylformic acid:
By when in embodiment 2 flask, reaction product is cooled to room temperature, add (238g, 3.3mol) vinylformic acid, (0.248g, 2mmol) MEHQ, (34.4g, 0.2mol) tosic acid, (6.02g, 70mmol) inferior sodium phosphate, (0.34g, 2mmol) Copper dichloride dihydrate, 350ml cyclohexane solution, the water that a water trap produces for separating of esterification is increased below circulating condensing return line on flask, 10 minutes are stirred with 100r/min, in reaction soln, air is passed into by three mouthfuls of reaction flasks bottleneck, open wide above circulating condensing return line, control the temperature to 83 DEG C of the thermopair in sand-bath, temperature of reaction maintains 83 DEG C of Keep agitation 12h, reaction terminates, and be cooled to room temperature, in reaction process, isolate the generation water 59.2g that hexanaphthene condensing reflux is taken out of, gained reactant is removed solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling is carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.4g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary cyclohexane solution, and products therefrom is weighed as 287g, and theoretical yield is about 79.5%.Product test index is as follows: acidity 0.33mgKOH/g, stopper 641.51 (MEHQ, ppm), colourity 90 ((APHA) platinum-cobalt method), viscosity 65.2mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:6.43 (d, 6H, C=CH
2), 6.05 (t, 6H, CH=C), 5.8 (d, 6H, C=CH
2), 4.41 (t, 8H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.24 (t, 8H, N-CH
2) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) Spectrum Analysis draws modification tetramethylolmethane six acrylate that product structure formula is the band tertiary amine as described in example 7 above shown in general formula VI.
Embodiment 9
Obtained modification pentaerythritol acrylate is reacted by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 2 gained and methyl acrylate:
By when in embodiment 2 flask, reaction product is cooled to room temperature, add (284g, 3.3mol) methyl acrylate, (0.248g, 2mmol) MEHQ, (31.3g, 50mmol) dibutyltin dilaurate, (6.02g, 70mmol) inferior sodium phosphate, (0.157g, 1mmol) 2,2,6,6-tetramethyl piperidine oxide compound, 400ml cyclohexane solution, above-mentioned solution adds after in the 2000ml reaction flask that electric stirring and water-cooled reflux condenser are housed, and is placed on by flask in the sand-bath in electric mantle, the temperature regulator being connected to the thermopair immersed in sand-bath is used to control sand-bath temperature, solution mass is to 70 DEG C to use sand-bath to stir in lower heating flask, and by stirring, in flask, the solid ingredient of solution mass is dissolved into colourless transparent solution, temperature of reaction maintains 70 DEG C of Keep agitation 7h, after back flow reaction terminates, change reaction unit into water distilling apparatus, continue to stir, the azeotrope of methyl alcohol and unreacted methyl acrylate is completely distilled out under the temperature of reaction of 70 DEG C, room temperature is cooled to after reaction terminates, reaction mixture removes solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling is carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.4g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary cyclohexane solution, products therefrom is weighed as 286g, theoretical yield is about 79.2%.Acidity 0.36mgKOH/g, stopper 642.26 (MEHQ, ppm), colourity 90 ((APHA) platinum-cobalt method), viscosity 64.7mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:6.43 (d, 6H, C=CH
2), 6.05 (t, 6H, CH=C), 5.8 (d, 6H, C=CH
2), 4.41 (t, 8H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.24 (t, 8H, N-CH
2) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) Spectrum Analysis draws modification tetramethylolmethane six acrylate that product structure formula is the band tertiary amine as described in example 7 above shown in general formula VI.
Embodiment 10
Modification tetramethylolmethane methacrylic ester is obtained by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 2 gained and methacrylic acid-respons:
By when in embodiment 2 flask, reaction product is cooled to room temperature, add (284g, 3.3mol) methacrylic acid, (0.248g, 2mmol) MEHQ, (34.4g, 0.2mol) tosic acid, (6.02g, 70mmol) inferior sodium phosphate, (0.34g, 2mmol) Copper dichloride dihydrate, 350ml cyclohexane solution, the water that a water trap produces for separating of esterification is increased below circulating condensing return line on flask, 10 minutes are stirred with 100r/min, in reaction soln, air is passed into by three mouthfuls of reaction flasks bottleneck, open wide above circulating condensing return line, control the temperature to 83 DEG C of the thermopair in sand-bath, temperature of reaction maintains 83 DEG C of Keep agitation 13h, reaction terminates, and be cooled to room temperature, in reaction process, isolate the generation water 78.2g that hexanaphthene condensing reflux is taken out of, gained reaction product is removed solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling is carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.4g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary cyclohexane solution, products therefrom is weighed as 317g, theoretical yield is about 78.7%.Acidity 0.29mgKOH/g, stopper 638.97 (MEHQ, ppm), colourity 90 ((APHA) platinum-cobalt method), viscosity 62.7mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:6.15 (s, 6H, C=CH
2), 5.58 (s, 6H, C=CH
2), 4.41 (t, 8H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.24 (t, 8H, N-CH
2), 1.93 (s, 18H, C-CH
3) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) (be equivalent to R1, R2 in general formula I is methyl to the structural formula of the Spectrum Analysis products obtained therefrom modification tetramethylolmethane hexamethacrylate that is the such as band tertiary amine shown in following general formula VII, R3 and R4 is general formula III; In general formula III, m and n is 1, R6 and R7 is methyl, R8 and R9 is hydrogen).
Embodiment 11
Obtained modification pentaerythritol acrylate is reacted by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 5 gained and vinylformic acid:
By when in embodiment 5 flask, reaction product is cooled to room temperature, add (158g, 2.2mol) vinylformic acid, (0.444g, 2mmol) 2, 5-di-tert-butyl hydroquinone, (19.2g, 0.2mol) methylsulphonic acid, (6.02g, 70mmol) inferior sodium phosphate, (0.34g, 2mmol) Copper dichloride dihydrate, 350ml toluene solution, the water that a water trap produces for separating of esterification is increased below circulating condensing return line on flask, 10 minutes are stirred with 100r/min, in reaction soln, air is passed into by three mouthfuls of reaction flasks bottleneck, open wide above circulating condensing return line, control the temperature to 110 DEG C of the thermopair in sand-bath, temperature of reaction maintains 110 DEG C of Keep agitation 12h, reaction terminates, be cooled to room temperature, in reaction process, isolate the generation water 59.4g that toluene condensing reflux is taken out of, gained reaction mixture being removed solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling being carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.2g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary toluene solution, and products therefrom is weighed as 241g, and theoretical yield is about 76%.Product test index is as follows: acidity 0.33mgKOH/g, stopper 421.13 (MEHQ, ppm), colourity 100 ((APHA) platinum-cobalt method), viscosity 52.7mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:8.0 (2H, NH), 6.43 (d, 4H, C=CH
2), 6.05 (t, 4H, CH=C), 5.8 (d, 4H, C=CH
2), 4.41 (t, 4H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.24 (m, 4H, N-CH
2) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) structural formula of Spectrum Analysis products obtained therefrom (is equivalent to R in general formula I for the such as modification tetramethylol methane tetraacrylate shown in following general formula VIII
1and R
2for hydrogen, R
3and R
4for general formula I V; In general formula I V, k is 1, R10 and R11 is hydrogen).
Embodiment 12
Obtained modification pentaerythritol acrylate is reacted by the modification tetramethylolmethane polyvalent alcohol of the band tertiary amine of embodiment 6 gained and methyl acrylate:
By when in embodiment 6 flask, reaction product is cooled to room temperature, add (189g, 2.2mol) methyl acrylate, (0.444g, 2mmol) 2, 5-di-tert-butyl hydroquinone, (7.84g, 70mmol) triethylenediamine, (6.02g, 70mmol) inferior sodium phosphate, (0.157g, 1mmol) 2, 2, 6, 6-tetramethyl piperidine oxide compound, 400ml toluene solution, above-mentioned solution adds after in the 2000ml reaction flask that electric stirring and water-cooled reflux condenser are housed, flask is placed in the sand-bath in electric mantle, the temperature regulator being connected to the thermopair immersed in sand-bath is used to control sand-bath temperature, in use sand-bath stirring lower heating flask, solution mass is to 110 DEG C, by stirring, in flask, the solid ingredient of solution mass is dissolved into colourless transparent solution, temperature of reaction maintains 110 DEG C of Keep agitation 7h, after back flow reaction terminates, change reaction unit into water distilling apparatus, continue to stir, the azeotrope of methyl alcohol and unreacted methyl acrylate is completely distilled out under the temperature of reaction of 110 DEG C, room temperature is cooled to after reaction terminates, reaction mixture removes solid by filtering, with the hydrochloric acid of the 1M concentration of 300ml, pickling is carried out to product, after pickling terminates, wash with 300ml saturated sodium bicarbonate solution, finally use 300ml distilled water wash 3 times, after washing, 0.4g MEHQ is added in product solution, underpressure distillation removes a small amount of water and unnecessary toluene solution, products therefrom is weighed as 256g, theoretical yield is about 74.2%.Acidity 0.35mgKOH/g, stopper 637.16 (MEHQ, ppm), colourity 100 ((APHA) platinum-cobalt method), viscosity 56.4mPa.s25 DEG C, after products obtained therefrom carries out ethanol and water precipitation recrystallization, adopt silica gel column chromatography be separated (normal hexane: ethyl acetate=5:2), final product carry out FTIR infrared and
1h-NMR nmr analysis, stronger absorption peak is had to show containing C=O key stretching vibration peak 1670 in product FTIR infrared spectrum, 3080 is the stretching vibration peak of-C=C-H key, 1820,995 and 915 be-CH=CH-H plane outside wave flexural vibration peak, show that propylene key is connected on modification tetramethylolmethane polyol molecule by esterification
1h-NMR adopts the test of BrukerAV300NMR nuclear magnetic resonance analyser, and TMS is interior mark reference,
1hNMR (300MHz, CDCl
3) ppm:8.1 (2H, N-CH), 6.43 (d, 4H, O=C-C=CH
2), 6.05 (t, 4H, CH=C), 5.8 (d, 4H, H-C=CH
2), 4.41 (t, 4H, C-CH
2-O), 4.07 (s, 4H, C-CH
2-O-C=O-C), 4.0 (s, 4H, C-CH
2-O-C=O-N), 3.76 (t, 4H, N-CH
2) .FTIR and hydrogen nuclear magnetic resonance (
1hNMR) Spectrum Analysis obtains the modification tetramethylol methane tetraacrylate that the structural formula of products obtained therefrom is the band tertiary amine such as shown in following general formula I X (being equivalent to R1 and R2 in general formula I is hydrogen, R3 and R4 is general formula V; In general formula V, l is 1, R12 and R13 is hydrogen, and R14 is aldehyde radical).
The performance evaluation table of table 1 embodiment 7-12 products obtained therefrom
Application Example 1
Respectively by the product 33 parts of embodiment 7-12 gained and urethane acrylate (Qing Te company EB264): 68 parts, initiator 1173/184:1.5 part, flow agent Eterslip0.1 part, defoamer: BYK-0520.03 part, coupling agent KH570:1.0 part, prepare coating with reference to prior art, described number is mass fraction, and to the test of gained coating property, the shock-resistant mensuration of paint film is with reference to GB1732-1979; Paint film adhesion measures with reference to GB1720-1979; Hardness of paint film measures with reference to GB6739-1986.
Comparative example: tetramethylol methane tetraacrylate 33 parts and urethane acrylate (Qing Te company EB264): 68 parts, initiator 1173/184:1.5 part, flow agent Eterslip0.1 part, defoamer: BYK-0520.03 part, coupling agent KH570:1.0 part, prepare coating with reference to prior art, described number is mass fraction, and the application performance of gained coating is in table 2.
The application performance of table 2 embodiment 7-12
| Embodiment | Hardness | Shock-resistance | Sticking power |
| Embodiment 7 | 2H | Be greater than 50kg.cm | Zero level |
| Embodiment 8 | 2H | Be greater than 50kg.cm | Zero level |
| Embodiment 9 | 2H | Be greater than 50kg.cm | Zero level |
| Embodiment 10 | 2H | Be greater than 50kg.cm | Zero level |
| Embodiment 11 | 2H | Be greater than 50kg.cm | One-level |
| Embodiment 12 | 2H | Be greater than 50kg.cm | One-level |
| Comparative example | 4H | Be less than 20kg.cm | Be greater than level Four severe detachment |
Claims (10)
1. a modification pentaerythritol acrylate, is characterized in that: its structural formula is:
General formula I
Wherein, R1 and R2 is respectively hydrogen or methyl; R3 and R4 is respectively general formula I I, general formula III, general formula I V or general formula V,
General formula I I
General formula III
General formula I V
General formula V
Wherein, m, n, k, l are respectively the integer of 0 to 10; R5, R6, R7, R10, R12 are respectively hydrogen or methyl; R8, R9, R11, R13 are hydrogen; R14 is H or CHO;
Condition is R3, R4 can not be general formula I I simultaneously; When R3 or R4 is general formula I I, another in R3 or R4 is not general formula I V; And R3, R4 can not be general formula III simultaneously.
2. modification pentaerythritol acrylate as claimed in claim 1, is characterized in that: R1 and R2 is hydrogen simultaneously or is methyl simultaneously; R5, R6, R7, R10, R12 are hydrogen or methyl respectively simultaneously; R3 and R4 is general formula I V simultaneously or is general formula V simultaneously.
3. the preparation method of the modification pentaerythritol acrylate described in claim 1 or 2, is characterized in that: comprise the following steps that order connects:
A, be the methylcarbonate of (200-600): 100:1, tetramethylolmethane and the first catalyzer by mol ratio, after back flow reaction 7-24h, distill out methyl alcohol and unnecessary methylcarbonate that reaction produces, obtain material A;
B, by material A with at least be with the primary amine of a hydroxyl or the amine substance of secondary amine back flow reaction 1-6h in the first solvent, obtain material B, wherein, the mole dosage of amine substance is 1-3 times of tetramethylolmethane mole number;
C, acrylate chloride or methacrylic chloride are slowly instilled in material B, after dropwising, under room temperature, react 1-3 hour, after purification and get final product, wherein, the mole dosage of acrylate chloride or methacrylic chloride be the 4-10 of tetramethylolmethane mole number doubly;
In steps A, the first catalyzer is Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane or DMAP;
In step B, the first solvent is the alkane of benzene, toluene, hexanaphthene or C6-C10.
4. method as claimed in claim 3, it is characterized in that: step C is: by vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate and material B in the second solvent, under the effect of the second catalyzer and stopper, 70-110 DEG C, reaction 7-13h, after purification and get final product, wherein, the mole dosage of vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate is 4-10 times of tetramethylolmethane mole number.
5. method as claimed in claim 3, is characterized in that: in step B, is at least with the primary amine of a hydroxyl or the amine substance of secondary amine to be uncle's amine substance of the band monohydroxy-alcohol of C2-C15 or the secondary amine substance of dibasic alcohol.
6. method as claimed in claim 3, it is characterized in that: the second solvent is the mixture of one or more any proportionings in benzene,toluene,xylene, trieline, trichloromethane, methylene dichloride, ethyl acetate, ethylene glycol Potassium ethanoate, N, N-Dicyclohexylcarbodiimide, hexanaphthene, normal hexane, normal heptane or Skellysolve A.
7. method as claimed in claim 6, is characterized in that: the consumption of the second solvent be vinylformic acid, methacrylic acid, methyl acrylate or methyl methacrylate and material B quality and 40-60%.
8. method as claimed in claim 4, it is characterized in that: stopper is para benzoquinone, adjacent benzoquinones, toluhydroquinone, Resorcinol, 2-Tert. Butyl Hydroquinone, 2,5-di-tert-butyl hydroquinone, MEHQ, thiodiphenylamine, the acid of Ursol D, dimethylamino diethylamino copper, copper dibutyldithiocarbamate, 2,2,6,6-tetramethyl piperidine oxide compound, 4-hydroxyl-2, the mixture of one or more any proportionings in 2,6,6-tetramethyl piperidine-1-oxyradical; The mole dosage of stopper is the 0.5-5 ‰ of tetramethylolmethane mole number.
9. method as claimed in claim 4, it is characterized in that: when acrylic or methacrylic acid is reacted with material B, second catalyzer is the mixture of one or more any proportionings in sulfuric acid, phosphoric acid, Mono Chloro Acetic Acid, methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid, ethyl phenenyl azochlorosulfonate acid, p-methyl benzenesulfonic acid or solid acid catalyst, and the second catalyst quality consumption is the 2%-8% of vinylformic acid or methacrylic acid quality; When methyl acrylate or methyl methacrylate and material B react, second catalyzer is the mixture of one or more any proportionings in dibutyltin dilaurate, stannous octoate, two acetic acid dibutyl esters, NaOH, KOH, NaOCH3, triethylamine, trolamine, triethylenediamine, solid base catalyst, phosphoric acid, Mono Chloro Acetic Acid and sulfuric acid, sulfonic acid, methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid or solid acid catalyst, and the second catalyst quality consumption is the 2%-8% of methyl acrylate or methyl methacrylate quality.
10. method as claimed in claim 4, is characterized in that: purified by step C and comprise filtration, pickling, alkali cleaning, washing and distillation removal residual solvent; During alkali cleaning alkali used be sodium carbonate, the alkaline solution that configures of the mixture of one or more any proportionings in sodium bicarbonate, salt of wormwood, sodium hydroxide or potassium hydroxide.
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| EP1449650A2 (en) * | 2003-02-21 | 2004-08-25 | Fuji Photo Film Co., Ltd. | Photosensitive composition and planographic printing plate precursor using the same |
| JP2007076297A (en) * | 2005-09-16 | 2007-03-29 | Jsr Corp | Laminate for surface coating of optical article |
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