CN117720577A - Novel high-molecular bisacylphosphine oxide and preparation method and application thereof - Google Patents
Novel high-molecular bisacylphosphine oxide and preparation method and application thereof Download PDFInfo
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- CN117720577A CN117720577A CN202311711347.2A CN202311711347A CN117720577A CN 117720577 A CN117720577 A CN 117720577A CN 202311711347 A CN202311711347 A CN 202311711347A CN 117720577 A CN117720577 A CN 117720577A
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- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
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- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a novel polymer bisacylphosphine oxide, which has the following structural general formula:
Description
Technical Field
The invention belongs to the field of photo-curing new materials, relates to a radiation-curing new material, and in particular relates to a novel polymer bisacylphosphine oxide, a preparation method and application thereof.
Background
In the field of Ultraviolet (UV) radiation curing new materials, photoinitiators (Photo-initiators) are key materials that absorb the energy of UV radiation sources to generate active substances such as free radicals, cations or anions to initiate polymerization of ethylenically unsaturated double bonds or epoxy compounds, vinyl ethers, lactones, acetals, cyclic ethers and the like.
Among them, "acylphosphine oxides and bisacylphosphine oxides" are excellent LED photoinitiators, and are widely used in applications such as paint, printing ink or electronic materials. Such photoinitiators are very effective for UV-A band light absorption, and even absorb light in the visible (vis) region, with concomitant photobleaching, with unique cure properties that other photoinitiators cannot match. The currently reported oxidized bisacylphosphines such as TPO, BAPO, TPO-L, etc., are mostly monofunctional photoinitiators, i.e., have one photoactive oxidized bisacylphosphine structural unit per molecule.
However, diphenyl- (2, 4, 6-Trimethylbenzoyl) Phosphorus Oxide (TPO) in the community rolling action draft (CoRAP) of 2020-2022 published by ECHA at 10/23 of 2019 is naturally listed in what is commonly known as the reproductive toxicity class 1B in CMR (English full: substances classified as carcinogenic, mutagenic, or toxic for reproduction, chinese full: carcinogenic, mutagenic or reproductive toxicity class). The use of photoinitiators, which are included in CMR 1B, is greatly limited and can be disabled in a number of products, particularly those related to food and in intimate contact with the human body. If this change in categorization becomes realistic, it means that TPOs will be disabled or restricted in many applications. It can be seen in the ECHA report that the property of TPO that is now of interest is "suspected reproductive toxicity (Suspected to be Toxic to Reproduction)", which in CLP is classified as reproductive toxicity 2. The class of substances toxic to reproduction in CLP is also 1. And 1 is again divided into 1A and 1B.1A refers to "known reproductive toxicity to humans (Known human reproductive toxicant)", based on evidence of a large number of humans. And 1B refers to "putative reproductive toxicity to humans (Presumed human reproductive toxicant)", which is evidence based on a number of animal experiments. For class 2, i.e. suspected to be reproductive toxic, based on evidence obtained in an existing human or laboratory animal, possibly aided by other information, the adverse effects on sexual function and fertility, or development are demonstrated, but the evidence is insufficient to convincingly rank the substance in class 1, and the substance is ranked as reproductive toxic class 2. This suggests that TPO is now classified as reproductive toxicity 2, which has been categorized based on actual data. It is also likely that TPO is classified as a reproductive toxicity 1B class as more experimental data is supplemented.
Photoinitiators which have now been listed by the european union ECHA as CMR reproductive toxicity 1B, include: morpholino Ding Bentong (CAS: 119313-12-1) (alias 369); 2-ethylhexyl 4- (dimethylamino) benzoate (CAS: 21245-02-3) (EHA for short); ethyl 4- (dimethylamino) benzoate (CAS: 10287-53-3) (abbreviated EDB); 4-phenylbenzophenone (CAS: 2128-93-0) (PBZ for short); 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (CAS: 71868-10-5) (alias 907). The use of photoinitiators, which are included in CMR 1B, is greatly limited and can be disabled in a number of products, particularly those related to food and in intimate contact with the human body.
With the increasing human interest in environmental and health, photoinitiators are also being iteratively updated. And with the continuous popularization and development of UV-LEDs, the demand for environment-friendly and low-toxicity photoinitiators is always very strong. Many studies are therefore developing new photoinitiators to meet this growing new demand for photoinitiators. The upcoming disablement of TPO will inject new power for this development effort.
Disclosure of Invention
The invention aims to solve the technical problems of providing an environment-friendly and nontoxic novel high-molecular bisacylphosphine oxide, a preparation method and application thereof, and the invention utilizes cheap and easily available industrial raw materials as a break to prepare the high-molecular bisacylphosphine oxide, and uses the compound as a photoinitiator in radiation curing, so that the problems of high toxicity and volatile micromolecular toxic pollutants generated after radiation curing of the existing photoinitiator compound can be effectively avoided.
The invention adopts the following technical scheme to solve the technical problems:
the novel high polymer bisacylphosphine oxide has a structural general formula shown in a formula (I):
wherein R is selected from one or more of a compound comprising at least one unsaturated c=c double bond, a compound comprising at least one multi-membered epoxy, a compound comprising at least one multi-membered isocyanate;
the value range of n is more than or equal to 1, and the total number of unsaturated functionalities of three compounds, namely C=C double bond, epoxy and isocyanate in the R group is less than or equal to.
As one of the preferred modes of the present invention, regarding the specific selection of the R group, one or more of the following structures are selected:
as one of preferable modes of the present invention, the specific value of n is as follows:
if the number of unsaturated functionalities in the R group structure is 4, the value range of n in the general formula (I) is 1-4, and the result obtained by the corresponding general formula (I) is that "one single chemical substance with the value of n being 1, 2, 3 and 4, or 2-4 mixtures of 1, 2, 3 and 4" are taken;
if the number of unsaturated functionalities in the R group structure is 6, the value range of n in the general formula (I) is 1-6, and the result obtained by the corresponding general formula (I) is "one single chemical substance with the value of n being 1, 2, 3, 4, 5 and 6, or 2-6 mixtures of 1, 2, 3, 4, 5 and 6".
Specifically, if the R group structure isThe unsaturation degree of the molecule which can be added by BAPH is 3, and then n can be 1, 2 and 3, and the result corresponding to the general formula (I) is one or a mixed system of several of the following compounds:
if the R group structure isThen n can take the values of 1, 2, 3 and 4, corresponding to the general formula (I)
The result is a mixed system of one or more of the following compounds:
as one of the preferable modes of the invention, the polymer bisacylphosphine oxide is prepared by reacting bisacylphosphine hydride BAPH with R group compound to obtain corresponding polymer bisacylphosphine compound BAP, and then oxidizing;
wherein, the structural formula of the group of the bisacylphosphine hydride BAPH is as follows:
the structural formula of the group of the bisacylphosphine compound BAP is as follows:
and, when the R group is a compound comprising at least one unsaturated c=c double bond, the first reaction is a michael-co-addition reaction;
when the R group is a compound comprising at least one multi-membered epoxy, the first reaction is an epoxy ring opening reaction;
when the R group is a compound comprising at least one polyisocyanate, the first reaction is an isocyanate addition reaction.
The preparation method of the novel polymer bisacylphosphine oxide comprises the steps of preparing PNa3 by using metal sodium and red phosphorus, carrying out substitution on two equivalents of H proton donors, then reacting with two equivalents of 2,4, 6-trimethylbenzoyl chloride, and neutralizing by using one equivalent of H proton donors to obtain a BAPH structure; then, adding or ring-opening reacting the compound with BAPH structure and R group compound to obtain corresponding polymer bisacylphosphine compound BAP; finally, preparing the polymer bisacylphosphine oxide required by the target through oxidation; the reaction process is as follows:
the application of the novel polymer bisacylphosphine oxide as a photoinitiator.
A light radiation curable hybrid system comprising a photoinitiator and at least one ethylenically unsaturated photopolymerizable compound; the photoinitiator adopts the novel high polymer bisacylphosphine oxide.
As a preferred embodiment of the present invention, the polymeric bisacylphosphine oxide is used as a photoinitiator in an amount of 0.01 to 20 parts, preferably 0.5 to 10 parts, per 100 parts by weight of the total amount of the ethylenically unsaturated photopolymerizable compounds. For example, the photoinitiator is used in an amount of 0.8, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 parts, etc. (mass ratio).
As one of the preferred modes of the present invention, the ethylenically unsaturated photopolymerizable compound is a monomer compound, an oligomer, or an ethylenically unsaturated photopolymerizable compound containing at least two c=c double bonds; among them, the monomer compound and the oligomer are preferably a compound having one carbon-carbon double bond, and more preferably an acrylate compound or a methacrylate compound; as regards the ethylenically unsaturated photopolymerizable compounds of at least two c=c double bonds, preference is given to alkyl diols, acrylic or methacrylic esters of polyols or unsaturated polyesters of polyester polyols, polyether polyols, epoxy polyols, acrylic esters of polyurethane polyols, vinyl ethers and unsaturated dicarboxylic acid polyols.
As one of the preferred modes of the invention, the radiation-curable mixture system further comprises functional additives or/and coagents, UV absorbers or/and light stabilizers which enhance the weatherability of the coating ink, and suitable aqueous dispersions or water-soluble products of the above components.
Wherein the functional additives or/and coagents include, but are not limited to, inhibitors, leveling agents, defoamers, anti-sagging agents, thickeners, tackifiers, dispersants, solubilizers, diluents, antistatic agents, water or organic solvents, antimicrobial agents, flame retardants, reactive amine co-initiators, inorganic or organic fillers (e.g., carbonates, sulfates, titanium dioxide, etc.), and/or organic, inorganic colorants (e.g., pigments or dyes, etc.).
The light radiation curing mixed system is applied to the fields of wood furniture paint, plastic product paint, printing packaging ink, ink-jet printing, electronic consumer products, automotive vehicle interior and exterior trim, pipeline section bar, industrial floor paint, building curtain wall paint, 3D printing additive manufacturing and ship/container body industrial paint.
As one of the preferred modes of the present invention, when the photo-radiation curable mixture system is used specifically for photo-curing radiation resist ink, photoresist and the like, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, preferably a carboxyl group-containing resin.
Compared with the prior art, the invention has the advantages that:
(1) The high polymer bisacylphosphine oxide disclosed by the invention is low in toxicity, does not generate any volatile toxic small-molecule organic compound when being applied as a photoinitiator, and is an environment-friendly, nontoxic and efficient photoinitiator; meanwhile, the invention also obviously improves the comprehensive properties of the bisacylphosphine oxide photoinitiator, such as smell, mobility, solubility, activity, yellowing resistance and the like, and improves the market competitiveness while solving the problems of toxicity and pollution of the photoinitiator;
(2) The high polymer bisacylphosphine oxide takes bulk chemicals such as metallic sodium, red phosphorus and the like as initial raw materials, has low price and is easy to obtain, and the performance of the compound shown in the formula (I) can be adjusted through a multi-unsaturated system or a multi-epoxy ring-opening system of Michael addition, so that the cost advantage of the product is further improved.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples. Meanwhile, the reagent products and the experimental method used in the invention are not specifically described, are all conventional reagents or methods in the field, and are not described in detail.
Example 1: preparation of bisacylphosphine hydride BAPH (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; 83 kg of concentrated hydrochloric acid is slowly added dropwise at room temperature, sodium chloride is removed by filtration, and the solvent is removed by distillation under reduced pressure to obtain the required bisacylphosphine hydride BAPH.
1 H NMR(300MHz,CDCl3),δ:7.25(4H,s),2.52(12H，s),2.55(6H,s)。
Example 2: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly dropwise adding 83 kg of concentrated hydrochloric acid at room temperature; after stirring for half an hour, 115 kg of trimethylolpropane trimethacrylate is dripped into the reaction kettle, sodium chloride is removed by filtration after 3 hours of reaction, and the solvent is removed by reduced pressure distillation; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; and continuing to react for 2 hours after the dripping is finished, collecting an organic phase, and decompressing to remove the solvent to obtain 440 kg of a final product, wherein the yield is 92%.
HRMS analysis: molecular weight 1440.60 is 93%; molecular weight 1112.48 is 6%; the molecular weight 770.34 was 1%.
Wherein, the molecular weight 1440.60 is the target main product of the embodiment, namely high molecular bisacylphosphine oxide; molecular weight 1112.48 is an effective product and has the formula shown in formula A; molecular weight 770.34 is also an effective product and has the formula shown in formula B below.
In the industrial application scene, the proportion of the target product and other two effective products can be adjusted by adjusting the addition amount and the dropping speed of the trimethylolpropane trimethacrylate so as to adjust the photocuring performance of the application end.
Example 3: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly adding 83 kg of concentrated hydrochloric acid dropwise at room temperature, stirring for half an hour, adding 150 kg of tripropylene glycol diacrylate dropwise to the reaction kettle, reacting for 3 hours, filtering to remove sodium chloride, and distilling under reduced pressure to remove solvent; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; and continuing to react for 2 hours after the dripping is finished, collecting an organic phase, and decompressing to remove the solvent to obtain 472 kg of a final product, wherein the yield is 96%.
HRMS analysis: molecular weight 984.43 is 95%; the molecular weight 642.30 was 5%.
Wherein, the molecular weight 984.43 is the target main product of the embodiment, namely high molecular bisacylphosphine oxide; molecular weight 642.30 is an effective product of the formula A 1 As shown.
Molecular formula A 1 ：
In the industrial application scene, the proportion of the target product and other effective products can be adjusted by adjusting the addition amount and the dropping speed of tripropylene glycol diacrylate so as to adjust the photo-curing performance of the application end.
Example 4: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly dropwise adding 83 kg of concentrated hydrochloric acid at room temperature; after stirring for half an hour, 87 kg of glycerol triglycidyl ether is dropwise added into the reaction kettle, sodium chloride is removed by filtration after 3 hours of reaction, and the solvent is removed by reduced pressure distillation; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; after the dripping is finished, the reaction is continued for 2 hours, the organic phase is collected, the solvent is removed under reduced pressure, 394 kg of final product is obtained, and the yield is 92%.
HRMS analysis: molecular weight 1286.54 is 82%; molecular weight 944.40 accounts for 15%; the molecular weight 602.26 was 2%.
Wherein, the molecular weight 1286.54 is the target main product of the embodiment, namely high molecular bisacylphosphine oxide; molecular weight 944.40 is an effective product of the formula A 1 Shown; molecular weight 602.26 is also an effective product, and has the formula A 2 As shown.
In the industrial application scene, the proportion of the target product and other two effective products can be adjusted by adjusting the addition amount and the dropping speed of the glycerol triglycidyl ether so as to adjust the photocuring performance of the application end.
Example 5: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly adding 83 kg of concentrated hydrochloric acid dropwise at room temperature, stirring for half an hour, adding 101 kg of trimethylolpropane triglycidyl ether dropwise to the reaction kettle, reacting for 3 hours, filtering to remove sodium chloride, and distilling under reduced pressure to remove the solvent; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; after the dripping is finished, the reaction is continued for 2 hours, the organic phase is collected, and the solvent is removed under reduced pressure to obtain 412 kg of final product with the yield of 93 percent.
HRMS analysis: molecular weight 1328.59 by 81%; molecular weight 986.45 accounts for 15%; the molecular weight 644.31 was 2%.
Wherein, the molecular weight 1328.59 is the target main product of the embodiment, namely high molecular bisacylphosphine oxide; molecular weights 986.45 and 644.31 are also useful products and have the formula A 1 、A 2 As shown.
In the industrial application scene, the proportion of the target product and other two effective products can be adjusted by adjusting the addition amount and the dropping speed of the trimethylolpropane triglycidyl ether so as to adjust the photocuring performance of the application end.
Example 6: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly dropwise adding 83 kg of concentrated hydrochloric acid at room temperature; after stirring for half an hour, 84 kg of hexamethylene diisocyanate is added dropwise into the reaction kettle, sodium chloride is removed by filtration after 3 hours of reaction, and the solvent is removed by reduced pressure distillation; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; and continuing to react for 2 hours after the dripping is finished, collecting an organic phase, and decompressing to remove the solvent to obtain 363 kg of a final product, wherein the yield is 98%.
1 H NMR(300MHz,CDCl3),7.15(4H,s),3.18(4H,t),2.31(24H，s)，2.13(12H，s)，1.50(4H，m)，1.38(2H，m)。
Example 7: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 31 kg of red phosphorus and 200 liters of solvent are added into a reaction kettle, and stirring and cooling are started; cutting 69 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and keeping stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 370 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly dropwise adding 83 kg of concentrated hydrochloric acid at room temperature; after stirring for half an hour, 125 kg of hexamethylene diisocyanate is added into the reaction kettle in batches, sodium chloride is removed by filtration after 3 hours of reaction, and the solvent is removed by reduced pressure distillation; dissolving the intermediate product in 300 liters of toluene, cooling and stirring, and slowly dropwise adding 345 kg of 30% hydrogen peroxide; after the dripping is finished, the reaction is continued for 2 hours, the organic phase is collected, and the solvent is removed under reduced pressure to obtain 399 kg of final product, and the yield is 97%.
1 H NMR(300MHz,CDCl3),7.53(2H,d),7.12(2H,d),3.86(2H,s),2.32(24H，s)，2.13(12H，s)。
Example 8: preparation of the other ten kinds of high molecular bisacylphosphine oxides:
based on the methods for the preparation and synthesis of the compounds of examples 1 to 4 above, another ten polymer bisacylphosphine oxides were prepared in this example. Specific target compounds and their corresponding data are shown in table 1 below, wherein "compound of example 8-1" refers to the first compound prepared in this example 8, "compound of example 8-2" refers to the second compound prepared in this example 8, and so on.
Table 1 ten compound displays of example 8 and corresponding preparation data information
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Example 9: preparation of a polymeric bisacylphosphine oxide (structural formula:
under the protection of nitrogen, 3.1 kg of red phosphorus and 20 liters of solvent are put into a glass kettle, and stirring and cooling are started; cutting 6.9 kg of sodium metal into blocks, putting the blocks into a reaction kettle at one time, heating to a molten state of sodium metal, and starting and maintaining stirring; reacting for 4 hours, cooling, adding two equivalent proton sources (alcohols, protonic acid, water and the like are selected, preferably protonic acid), stirring for 10 minutes, then dropwise adding 37 kg of 2,4, 6-trimethyl benzoyl chloride into a reaction kettle for 2 hours, and keeping the kettle temperature below 30 ℃; after the dripping is finished, stirring is continued for 4 hours; slowly dripping 8.3 kg of concentrated hydrochloric acid at room temperature; after stirring for half an hour, 18 kg of intermediate A is added into a reaction kettle, sodium chloride is filtered and removed after 3 hours of reaction, and the solvent is removed by reduced pressure distillation; dissolving the intermediate product in 30 liters of toluene, cooling and stirring, and slowly dropwise adding 35 kg of 30% hydrogen peroxide; and continuing to react for 2 hours after the dripping is finished, collecting an organic phase, and decompressing to remove the solvent to obtain 45 kg of a final product, wherein the yield is 92%.
Wherein intermediate a preparation is derived from a conventional photoinitiator 1173 process:
1 H NMR(300MHz,CDCl3),8.03(2H,m),7.68(1H,t),7.52(2H,m),7.21(4H，s)，2.50(12H,s),2.32(6H，s)，1.45(6H，s)。
example 10: preparation of the other three high molecular bisacylphosphine oxides:
based on the above-described synthetic method for the preparation of the compound of example 9, another three polymer bisacylphosphine oxides were prepared in this example. Specific target compounds and their corresponding data are shown in Table 2 below, wherein "compound of example 10-1" refers to the first compound prepared in this example 10, "compound of example 10-2" refers to the second compound prepared in this example 10, and "compound of example 10-3" refers to the third compound prepared in this example 10.
Table 2 three compounds of example 10 are shown and correspond to the preparation data information
Example 11: evaluation of Performance
In this example, by preparing an example photo-curing composition, various application properties of the photoinitiator shown in the structural formula (I) of the present invention were evaluated, including storage curing property test, odor, solubility, and the like.
Wherein R is selected from one or more of a compound comprising at least one unsaturated c=c double bond, a compound comprising at least one multi-membered epoxy, a compound comprising at least one multi-membered isocyanate;
the value range of n is more than or equal to 1, and the total number of unsaturated functionalities of three compounds, namely C=C double bond, epoxy and isocyanate in the R group is less than or equal to.
1. Curing Performance test of photo-curable composition
The macromolecular phosphoryl photoinitiator has excellent photocuring capability in a colored system in a radiation curing system, is particularly suitable for photocuring colored paint or colored ink, has photo bleaching performance, and is widely applied in a white or yellowing-resistant photocuring system, so that the photoinitiator is applied to the colored ink system and varnish (gloss oil) to simultaneously carry out curing performance test:
1.1 preparation of color paste
TABLE 3 color paste composition
| Component (A) | Black color | White color | Yellow colour |
| Pigment component | Carbon black | Titanium white powder | Benzidine yellow |
| Pigment content (%) | 10 | 10 | 10 |
| HDDA(％) | 30 | 30 | 30 |
| TMPTA(％) | 57 | 57 | 57 |
| EFKA-4310(％) | 3 | 3 | 3 |
After the components are uniformly mixed, grinding the mixture to the particle size of less than 1 mu m by using a vertical hydraulic frequency conversion bead mill, and filtering the mixture to obtain color paste.
1.2 preparation of photo-curing test ink
The ink composition is shown in Table 4 below.
TABLE 4 ink Components
The photoinitiators in the above ink compositions are photoinitiators of the present invention or commercially available TPOs and 819. Because the solubility of TPO and 819 is relatively poor, 5-10% butanone solvent can be properly added into the formula to assist in complete dissolution; in the ink composition, each component is in parts by mass.
The addition amount of the photoinitiator in the photo-curing composition system is the addition amount of the known formula experience, and the addition amount in different composition systems needs to be adjusted according to the overall performance activity of the composition system and the requirement of the composition system, and can be determined according to actual requirements. For example, the amount of the macromolecular phosphoryl type photoinitiator defined by the general formula (I) used varies from 0.01 to 20 parts per 100 parts by weight of the total ethylenically unsaturated-containing substance.
1.3 curing Rate
The above composition was coated on white cardboard using a 40 μm bar coater to compare the properties of photoinitiators TPO, 819, TPO-L and the compounds of the invention as photoinitiators. The coated sample was mounted on a conveyor belt and transported under a medium pressure mercury lamp with an energy of 80mw/cm 2 . The lamp passing belt speed of the fully cured samples was determined with the nail repeated embossing scratch producing no marks as a fully cured standard.
1.4 odor rating
The photocurable composition was completely cured according to the above-mentioned curing method and curing speed. The residual odor test uses 5 persons to evaluate the odor grades independently, and uses the odor grade evaluation of more than or equal to 3 persons as a standard.
The criteria for evaluation are numerically indicated as follows:
class a: no smell was felt;
b level: very slight smell;
c level: a slight smell;
d stage: a noticeable smell;
e level: a strong odor;
grade F: very strong smell
3. Adhesion test
Adhesion was tested using the hundred-cell method with reference to GB/T9286-1998 test standard and evaluated on a scale of 0-5.
The evaluation results are shown in tables 5 to 8 below.
TABLE 5 Black ink curing test results
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TABLE 6 white ink curing test results
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TABLE 7 yellow ink curing test results
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TABLE 8 varnish (gloss oil) cure test results
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From the results of the above table, it can be seen that:
the photocuring composition containing the novel macromolecular phosphoryl photoinitiator shown in the general formula (I) has good photoinitiation activity, better deep curing performance in a colored system and varnish (gloss oil), and better mechanical property after film formation. The photoinitiating activity was significantly higher than that of the commercially available photoinitiators TPO, TPO-L,819, slightly lower than 819 for TPO-L and TPO, and in particular, the "compounds of examples 8-10" were slightly inferior in yellowing resistance after curing.
The yellowing resistance of the novel macromolecular phosphoryl photoinitiator shown in the general formula (I) is higher than that of TPO-L and 819, and the novel macromolecular phosphoryl photoinitiator has obvious competitive advantage and is equivalent to TPO;
the novel macromolecular phosphoryl photoinitiator shown in the general formula (I) also has low odor, migration resistance, low toxicity and environmental friendliness due to the macromolecular characteristics;
the novel macromolecular phosphoryl photoinitiator shown in the general formula (I) is in a liquid state, so that the novel macromolecular phosphoryl photoinitiator can be mutually dissolved with a photocuring system in any ratio, the solubility problem of the traditional photoinitiator can be effectively improved, the use of a micromolecular active diluent is reduced, and the environmental protection performance of the photocuring system is further improved;
as can be seen from the description, under the requirement of fixed activity, the photoinitiator shown in the general formula (I) has high photosensitivity and lower addition amount, can effectively reduce cost, has excellent environment-friendly performance of yellowing resistance, low odor and low migration, and has good promotion effect on popularization and application of colored ink and varnish (gloss oil) systems in the photocuring field.
4. Solubility and dissolution rate test
Solubility test the solubility of the photoinitiators according to the invention and of the commercial photoinitiators Irgacure 907, irgacure369, APi 307 were tested against the more widely known reactive diluents HDDA (1, 6-hexanediol diacrylate) in the art and acetone as solvents, and the maximum weight of 100g of solvent in solution at 25℃was used as evaluation criterion. The dissolution rate was measured at 50℃at a stirring speed of 120 rpm for a period of time required for complete dissolution of the test photoinitiator at a mass ratio of 5% to HDDA (1, 6-hexanediol diacrylate) and the results are shown in Table 9 below.
TABLE 9 solubility and dissolution Rate test results
As can be seen from Table 9, the solubility of the novel macromolecular phosphoryl photoinitiator of the invention is competitive with that of the commercial phosphoryl photoinitiators TPO and 819; compared with TPO-L, the use of small molecule reactive diluents and solvents can be greatly reduced; the solubility of the example 9 series was slightly poorer.
In summary, compared with the prior art, the novel macromolecular phosphoryl photoinitiator shown in the general formula (I) has better application performance, and can greatly improve the performance of the prior art photo-curing product or develop new application in the field.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The novel high polymer bisacylphosphine oxide is characterized in that the structural general formula is shown as the formula (I):
wherein R is selected from one or more of a compound comprising at least one unsaturated c=c double bond, a compound comprising at least one multi-membered epoxy, a compound comprising at least one multi-membered isocyanate;
the value range of n is more than or equal to 1, and the total number of unsaturated functionalities of three compounds, namely C=C double bond, epoxy and isocyanate in the R group is less than or equal to.
2. The novel polymeric bisacylphosphine oxide according to claim 1 wherein, with respect to the specific choice of R groups, one or more of the following structures are selected:
3. the novel polymeric bisacylphosphine oxide according to claim 1, wherein, with respect to the specific value of n:
if the number of unsaturated functionalities in the R group structure is 4, the value range of n in the general formula (I) is 1-4, and the result obtained by the corresponding general formula (I) is that "one single chemical substance with the value of n being 1, 2, 3 and 4, or 2-4 mixtures of 1, 2, 3 and 4" are taken;
if the number of unsaturated functionalities in the R group structure is 6, the value range of n in the general formula (I) is 1-6, and the result obtained by the corresponding general formula (I) is "one single chemical substance with the value of n being 1, 2, 3, 4, 5 and 6, or 2-6 mixtures of 1, 2, 3, 4, 5 and 6".
4. The novel polymer bisacylphosphine oxide according to any one of claims 1 to 3, wherein the polymer bisacylphosphine oxide is prepared by reacting bisacylphosphine hydride BAPH with R group compound to obtain corresponding polymer bisacylphosphine BAP, and then oxidizing;
wherein, the structural formula of the group of the bisacylphosphine hydride BAPH is as follows:
the structural formula of the group of the bisacylphosphine compound BAP is as follows:
and, when the R group is a compound comprising at least one unsaturated c=c double bond, the first reaction is a michael-co-addition reaction;
when the R group is a compound comprising at least one multi-membered epoxy, the first reaction is an epoxy ring opening reaction;
when the R group is a compound comprising at least one polyisocyanate, the first reaction is an isocyanate addition reaction.
5. A process for preparing novel polymer bisacylphosphine oxides according to any one of claims 1 to 4, wherein PNa is prepared from sodium metal and red phosphorus 3 After replacement of two equivalents of H proton donor, the reaction is carried out with two equivalents of 2,4, 6-trimethyl benzoyl chloride, and after neutralization of one equivalent of H proton donor, the BAPH structure is prepared; then, adding or ring-opening reacting the compound with BAPH structure and R group compound to obtain corresponding polymer bisacylphosphine compound BAP; finally, preparing the polymer bisacylphosphine oxide required by the target through oxidation; the reaction process is as follows:
6. use of a novel polymeric bisacylphosphine oxide according to any one of claims 1 to 4 as photoinitiator.
7. A radiation curable hybrid system comprising a photoinitiator and at least one ethylenically unsaturated photopolymerizable compound; the photoinitiator adopts the novel high polymer bisacylphosphine oxide as claimed in any one of claims 1 to 4.
8. The radiation-curable mixture system according to claim 7, wherein the polymeric bisacylphosphine oxide is used as a photoinitiator in an amount of 0.01 to 20 parts per 100 parts by weight of the total amount of the ethylenically unsaturated photopolymerizable compounds.
9. The radiation curable mixture system according to claim 7, wherein the ethylenically unsaturated photopolymerizable compound is a monomeric compound, an oligomer or an ethylenically unsaturated photopolymerizable compound comprising at least two c=c double bonds.
10. Use of a photo-radiation curable mixture system according to any one of claims 7 to 9 in the fields of wood furniture paints, plastic product coatings, printing packaging inks, inkjet printing, electronic consumer goods, automotive interior and exterior trim, pipe profiles, industrial floor paints, building curtain wall paints, 3D printing additive manufacturing, marine/container body industrial paints.
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