CN1887913A - High molecular diphenylketone photoinitiator and its prepn - Google Patents
High molecular diphenylketone photoinitiator and its prepn Download PDFInfo
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Abstract
The present invention discloses one kind of high molecular weight diphenylketone photoinitiator and its preparation process. The high molecular weight diphenylketone photoinitiator is prepared through the first reaction of diphenylmethane-4, 4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 2,4-toluene diisocyanate and hydroxyl group-containing diphenylketone photoinitiator, and the subsequent reaction of the reaction product and polyester polyol or polyether polyol with molecular weight 500-5000 at 50-80 deg.c through stirring. The high molecular weight diphenylketone photoinitiator has photosensitivity similar to that of available small molecular weight one but relatively great molecular weight, so that it has less surface migration in curing paint, less toxicity, less smell and less yellowing, is especially suitable for use in food packing, and may find its wide application in photocuring field.
Description
Technical field: the present invention relates to a kind of light trigger and preparation method thereof, particularly high molecular benzophenone photoinitiator and preparation method thereof.
Background technology: photopolymerization is to utilize light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.Therefore photopolymerization is the advanced manufacturing technology of a kind of being described as " green technology ".
Light trigger (photoinitiator) is the key components of photocuring system, and can it be related to formula system oligopolymer and thinner when rayed and be transformed into solid-state rapidly by liquid state.Its basic role characteristics are: initiator molecule has certain extinction ability at ultraviolet region (250-400nm) or visible region (400-800nm), after directly or indirectly absorbing luminous energy, initiator molecule is scurried between being and is jumped to excited triplet state from the ground state transition to the excited singlet; After excited singlet or triplet state experience unit molecule or bimolecular chemical action, generation can trigger monomer polymeric biologically active fragment, and these biologically active fragments can be free radical, positively charged ion, negatively charged ion or ion free radical etc.Wherein be most widely used with the radical polymerization light trigger that produces the free radical activity fragment.According to the mechanism of action difference of free radical photo-initiation generation living radical, it can be divided into crack type photoinitiator, also claims the first type light trigger; Hydrogen-capture-type light initiator claims the second type light trigger again.The ideal light trigger requires to have the following advantages: (1) cheapness is synthetic simple; (2) light trigger and photodestruciton product thereof should be nonpoisonous and tasteless; (3) good stability is convenient to long-time storage; (4) absorption spectrum of light trigger must be complementary with the emission band of radiating light source, and has higher optical extinction coefficient; (5) adjourn to excited singlet because most of photoinitiator molecules absorb the luminous energy last transitions, between being, scurry the excited triplet state that jumps, therefore, initiator be between scurry the efficient that jumps and want high; (6) higher efficiency of initiation.
Benzophenone is a kind of widely used hydrogen-capture-type light initiator because its surface cure is good, solubility property is good, cheap and obtain easily.But its molecular weight is low, easily distillation, smell is strong, and the fragment that produces after the photolysis also can cause offensive odour, and remains in the material after the curing easily and move to material surface gradually, smell and toxicity occur, restricted its application at aspects such as food and drug packages.
If the small molecules diphenyl ketone photo initiator is made macromolecular cpd or polymerizable structure, the problem that then above-mentioned drawback is especially moved can be overcome.The macromolecular photoinitiator relative molecular mass is often higher, becomes the thickness liquid state more, and is better with the compatibility of resin system; Secondly, generally contain a plurality of initiators unit on the molecular chain, can form a plurality of free radicals simultaneously on a macromole during photoirradiation, local number of free radical can be very high.The high local concentrations effect can effectively tackle oxygen inhibition, helps quickening photopolymerization, but the probability of the mutual coupling termination of living radical also can increase in the macromole, by the design molecular structure, can reduce the intramolecularly free radical coupling.The photochemistry behavior of macromolecular photoinitiator and the mechanism of action and small molecules parent do not have the difference of essence, may be on amount difference to some extent.
Summary of the invention: the invention provides a kind of high molecular benzophenone photoinitiator and preparation method thereof, the gained compound has than high molecular weight, better with the compatibility of resin system, can replace benzophenone to use, and its preparation cost is low, easy and simple to handle, the yield height of product as light trigger.
The high molecular benzophenone photoinitiator of the present invention's preparation, its chemical structure is shown below:
Wherein, R and R` are selected from hydrogen, alkyl, alkoxyl group, R respectively alone
1Be ditan-4,4`-vulcabond (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 2,4-tolylene diisocyanate (TDI) is removed the residue after two isocyanic ester (NCO) functional group, and its structure is as follows successively:
-CH
2-CH
2-CH
2-CH
2-CH
2-CH
2-
R
2Be the residue of molecular weight after the polyester polyol of 500-5000 or polyether glycol are removed hydroxy functional group (OH).
The method of high molecular benzophenone photoinitiator preparation of the present invention is as follows:
(a) the benzophenone photoinitiator with 1 part of (molfraction) hydroxyl at room temperature is dissolved in the organic solvent, then with 1 part of (molfraction) ditan-4,4`-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or 2,4 toluene diisocyanate at room temperature are dissolved in 5-10 part organic solvent.In the presence of 30-60 ℃, catalyzer dibutyl tin laurate, the solution of the benzophenone photoinitiator of hydroxyl is added to ditan-4,4`-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or 2, in the solution of 4-tolylene diisocyanate, stirring reaction 2-6 hour reaction mixture;
The benzophenone photoinitiator of described hydroxyl be as shown in the formula compound:
In the formula, R and R` are selected from hydrogen, alkyl, alkoxyl group respectively alone;
(b) will at room temperature be dissolved in the organic solvent at polyester polyol or the polyether glycol of 500-5000 above the molecular weight of 0.5 part (molfraction), in the presence of 50-80 ℃, catalyzer dibutyl tin laurate, join in the reaction mixture in (a) stirring reaction 2-5 hour; Reaction is used saturated sodium bicarbonate solution and deionized water wash reaction solution respectively after finishing; Add anhydrous sodium sulfate drying then, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.
The entire reaction equation that the present invention prepares high molecular benzophenone photoinitiator can be expressed as:
Organic solvent used in the present invention comprises: ethyl acetate, butanone, chloroform.
High molecular benzophenone photoinitiator preparation cost of the present invention is low, easy and simple to handle, the yield height of product, and its photosensitive activity is suitable with existing small molecules light trigger.And, because its relative molecular mass is higher, be the thickness liquid state, better with the compatibility of resin system; Secondly, contain a plurality of initiators unit on the molecular chain, can form a plurality of free radicals simultaneously on a macromole during photoirradiation, local number of free radical can be very high, and the high local concentrations effect can effectively tackle oxygen inhibition, helps quickening photopolymerization; The photolysis debris relative molecular mass of this photoinitiator is also higher, thus its in solidified coating seldom to the migration on surface, avoided causing the problem of toxicity, smell and xanthochromia aggravation, be particularly suitable on health, the packaging material for food.
Embodiment:
Following embodiment describes the present invention in detail, but does not limit the scope of the invention.
Embodiment 1:
(a) 0.1mol (19.8g) 4-dihydroxy benaophenonel at room temperature is dissolved in the 100ml ethyl acetate, then 0.1mol (17.6g) 2,4 toluene diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml ethyl acetate.Under 60 ℃, the drips of solution of 4-dihydroxy benaophenonel is added in the solution of 2,4 toluene diisocyanate stirring reaction 3 hours by the speed of per second 0.8mL;
(b) 0.052mol (31.2g) Polyethylene Glycol-600 (PEG600) at room temperature is dissolved in the 150ml ethyl acetate, under 80 ℃, joins in the reaction mixture in (a), stirring reaction 3 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished, and obtains product.
Embodiment 2:
(a) 0.1mol (22.8g) 2-hydroxyl-4-methoxy benzophenone at room temperature is dissolved in the 100ml ethyl acetate, then 0.1mol (22.2g) isophorone diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml ethyl acetate.Under 60 ℃, the drips of solution of 2-hydroxyl-4-methoxy benzophenone is added in the solution of isophorone diisocyanate stirring reaction 3 hours by the speed of per second 0.8mL;
(b) 0.052mol (41.6g) polyoxyethylene glycol 800 (PEG800) at room temperature are dissolved in the 150ml ethyl acetate, under 80 ℃, join in the reaction mixture in (a) stirring reaction 3 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product identifies that through infrared spectra to the transformation of amino peak N-H (3305cm-1) and the disappearance of isocyanate peak NCO (2272cm-1), proved response is finished, and obtains product by monitoring hydroxyl peak O-H (3450cm-1).
Embodiment 3:
(a) 0.1mol (22.8g) 2-hydroxyl-4-methoxy benzophenone at room temperature is dissolved in the 100ml butanone, with 0.1mol (22.6g) ditan-4,4`-vulcabond and 2ml dibutyl tin laurate at room temperature are dissolved in the 100ml butanone then.Under 60 ℃, by the speed of per second 0.8mL the drips of solution of 2-hydroxyl-4-methoxy benzophenone is added to ditan-4, in the solution of 4`-vulcabond, stirring reaction 3 hours;
(b) 0.052mol (52g) polyester glycol OxyesterT 1136 (molecular weight is 1000) at room temperature is dissolved in the 200ml butanone, under 80 ℃, joins in the reaction mixture in (a) stirring reaction 3 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product identifies that through infrared spectra to the transformation of amino peak N-H (3305cm-1) and the disappearance of isocyanate peak NCO (2272cm-1), proved response is finished, and obtains product by monitoring hydroxyl peak O-H (3450cm-1).
Embodiment 4:
(a) 0.1mol (19.8g) 4-dihydroxy benaophenonel at room temperature is dissolved in the 100ml ethyl acetate, then 0.1mol (17.6g) 2,4 toluene diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml ethyl acetate.Under 50 ℃, the drips of solution of 4-dihydroxy benaophenonel is added in the solution of 2,4 toluene diisocyanate stirring reaction 4 hours by the speed of per second 0.8mL;
(b) 0.052mol (41.6g) polyoxyethylene glycol 800 (PEG800) at room temperature are dissolved in the 150ml ethyl acetate, under 50 ℃, join in the reaction mixture in (a) stirring reaction 5 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished, and obtains product.
Embodiment 5:
(a) 0.1mol (19.8g) 4-dihydroxy benaophenonel at room temperature is dissolved in the 100ml chloroform, then 0.1mol (17.6g) 2,4 toluene diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml chloroform.Under 30 ℃, the drips of solution of 4-dihydroxy benaophenonel is added in the solution of 2,4 toluene diisocyanate stirring reaction 6 hours by the speed of per second 0.8mL;
(b) 0.052mol (52.0g) cetomacrogol 1000 (PEG800) at room temperature is dissolved in the 150ml chloroform, under 50 ℃, joins in the reaction mixture in (a), stirring reaction 6 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product is identified through infrared spectra, by monitoring hydroxyl peak O-H (3450cm
-1) to amino peak N-H (3305cm
-1) transformation and isocyanate peak NCO (2272cm
-1) disappearance, proved response is finished, and obtains product.
Embodiment 6:
(a) 0.1mol (22.8g) 2-hydroxyl-4-methoxy benzophenone at room temperature is dissolved in the 100ml ethyl acetate, then 0.1mol (22.2g) isophorone diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml ethyl acetate.Under 60 ℃, the speed that is no more than 0.8mL by per second is added in the solution of isophorone diisocyanate stirring reaction 3 hours with the drips of solution of 2-hydroxyl-4-methoxy benzophenone;
(b) 0.052mol (31.2g) Polyethylene Glycol-600 (PEG600) at room temperature is dissolved in the 150ml ethyl acetate, under 70 ℃, joins in the reaction mixture in (a), stirring reaction 4 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product identifies that through infrared spectra to the transformation of amino peak N-H (3305cm-1) and the disappearance of isocyanate peak NCO (2272cm-1), proved response is finished, and obtains product by monitoring hydroxyl peak O-H (3450cm-1).
Embodiment 7:
(a) 0.1mol (19.8g) 4-dihydroxy benaophenonel at room temperature is dissolved in the 100ml ethyl acetate, with 0.1mol (22.6g) ditan-4,4`-vulcabond and 2ml dibutyl tin laurate at room temperature are dissolved in the 100ml ethyl acetate then.Under 60 ℃, by the speed of per second 0.8mL the drips of solution of 2-hydroxyl-4-methoxy benzophenone is added to ditan-4, in the solution of 4`-vulcabond, stirring reaction 3 hours;
(b) 0.052mol (52g) polyester glycol Oxyester T 1136 (molecular weight is 1000) at room temperature are dissolved in the 200ml ethyl acetate, under 80 ℃, join in the reaction mixture in (a) stirring reaction 3 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product identifies that through infrared spectra to the transformation of amino peak N-H (3305cm-1) and the disappearance of isocyanate peak NCO (2272cm-1), proved response is finished, and obtains product by monitoring hydroxyl peak O-H (3450cm-1).
Embodiment 8:
(a) 0.1mol (22.8g) 2-hydroxyl-4-methoxy benzophenone at room temperature is dissolved in the 100ml ethyl acetate, then 0.1mol (16.8g) hexamethylene diisocyanate and 2ml dibutyl tin laurate at room temperature is dissolved in the 100ml ethyl acetate.Under 60 ℃, the drips of solution of 2-hydroxyl-4-methoxy benzophenone is added in the solution of hexamethylene diisocyanate stirring reaction 3 hours by the speed of per second 0.8mL;
(b) 0.052mol (41.6g) polyoxyethylene glycol 800 (PEG800) at room temperature are dissolved in the 150ml ethyl acetate, under 80 ℃, join in the reaction mixture in (a) stirring reaction 3 hours.Reaction is used 150ml saturated sodium bicarbonate solution and deionized water wash reaction solution 2 times respectively after finishing.Added anhydrous sodium sulfate drying then 20 hours, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.Product identifies that through infrared spectra to the transformation of amino peak N-H (3305cm-1) and the disappearance of isocyanate peak NCO (2272cm-1), proved response is finished, and obtains product by monitoring hydroxyl peak O-H (3450cm-1).
Claims (3)
1. high molecular benzophenone photoinitiator is characterized in that the chemical structure of this high molecular benzophenone photoinitiator is shown below:
Wherein, R and R` are selected from hydrogen, alkyl, alkoxyl group, R respectively alone
1Be ditan-4,4`-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or 2,4 toluene diisocyanate are removed two residues behind the isocyanate functional group, R
2Be the residue of molecular weight after the polyester polyol of 500-5000 or polyether glycol are removed hydroxy functional group.
2. the preparation method of the described high molecular benzophenone photoinitiator of claim 1 is characterized in that:
(a) the benzophenone photoinitiator with 1 molfraction hydroxyl at room temperature is dissolved in the organic solvent, at room temperature is dissolved in 1 molfraction vulcabond in the organic solvent then; In the presence of 30-60 ℃, catalyzer dibutyl tin laurate, the solution of the benzophenone photoinitiator of hydroxyl is added in the solution of vulcabond, stirring reaction 2-6 hour reaction mixture; Described vulcabond is a ditan-4,4`-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or 2,4 toluene diisocyanate;
The benzophenone photoinitiator of described hydroxyl be as shown in the formula compound:
In the formula, R and R` are selected from hydrogen, alkyl, alkoxyl group respectively alone;
(b) will at room temperature be dissolved in the organic solvent at polyester polyol or the polyether glycol of 500-5000 above the molecular weight of 0.5 molfraction, in the presence of 50-80 ℃, catalyzer dibutyl tin laurate, join in the reaction mixture in (a) stirring reaction 2-5 hour; Reaction is used saturated sodium bicarbonate solution and deionized water wash reaction solution respectively after finishing; Add anhydrous sodium sulfate drying then, filter out solid matter after, on Rotary Evaporators, remove organic solvent, obtain high molecular benzophenone photoinitiator.
3. the preparation method of high molecular benzophenone photoinitiator according to claim 2 is characterized in that employed organic solvent is ethyl acetate, butanone or chloroform.
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| CN116478370A (en) * | 2023-06-15 | 2023-07-25 | 中国农业科学院农业环境与可持续发展研究所 | Ultraviolet absorbent and preparation method and application thereof |
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