CN111333475A - Preparation method of hydrophilic photoinitiator powder and hydrophilic photoinitiator powder - Google Patents
Preparation method of hydrophilic photoinitiator powder and hydrophilic photoinitiator powder Download PDFInfo
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- CN111333475A CN111333475A CN202010080263.3A CN202010080263A CN111333475A CN 111333475 A CN111333475 A CN 111333475A CN 202010080263 A CN202010080263 A CN 202010080263A CN 111333475 A CN111333475 A CN 111333475A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000011737 fluorine Substances 0.000 claims abstract description 90
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 90
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000000126 substance Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 48
- 238000011049 filling Methods 0.000 claims description 30
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- 230000003068 static effect Effects 0.000 claims description 13
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- -1 photoinitiator 784 Chemical compound 0.000 claims description 6
- 229910000792 Monel Inorganic materials 0.000 claims description 5
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004698 Polyethylene Substances 0.000 claims description 3
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- 229960002130 benzoin Drugs 0.000 claims description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 10
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- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 3
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- C07—ORGANIC CHEMISTRY
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
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- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
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Abstract
The invention provides a preparation method of hydrophilic photoinitiator powder and the hydrophilic photoinitiator powder. The method specifically comprises the following steps: adding photoinitiator powder into a vacuum reactor, and carrying out first vacuumizing treatment and heat treatment; wherein, the vacuum reactor is thermally treated to the reaction temperature to obtain the vacuum reactor to be reacted; introducing gas containing fluorine simple substance into a vacuum reactor to be reacted, adjusting the temperature in the vacuum reactor to the reaction temperature for reaction to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain hydrophilic photoinitiator powder. The preparation method of the invention obviously improves the hydrophilic performance of the photoinitiator by introducing fluorine-carbon bonds.
Description
Technical Field
The invention belongs to the technical field of initiator preparation, and particularly relates to a preparation method of hydrophilic photoinitiator powder and the hydrophilic photoinitiator powder.
Background
In modern manufacturing, the status of the coating industry is becoming more important and there is data indicating that in developed industrial countries the yield of coatings is about 10% of the total value of the chemical industry. From military to civilian use, protection of coatings or imparting special properties is required. The most common coating varieties currently on the market include: the solvent-based coating, the photocureable coating, the powder coating, the water-based coating and the like have increasingly strict requirements on environmental protection, the quantity of the solvent-based coating is sharply reduced, and the consumption of the water-based coating and the photocureable coating with the environmental protection characteristic is rapidly expanded.
The photocureable coating is an energy-saving and environment-friendly coating, and has the advantages of extremely low or even zero VOC emission, energy saving (the energy consumption is only 10-20 percent of that of powder coating), high curing speed (0.1-10 seconds), low curing temperature, high production efficiency, low production cost and the like. The curing principle of the photocuring coating is that a photoinitiator absorbs ultraviolet light to generate free radicals, so that the oligomer photosensitive resin and the reactive diluent molecule are initiated to generate chain polymerization reaction to be cured.
The light-cured coating comprises an oil system and a water system, wherein the light-cured coating of the oil system also has the problem of solvent volatilization. The water-based system coating has the advantages of environmental friendliness, good fluidity, easiness in viscosity adjustment, no need of an active diluent, no VOC (volatile organic compound) and toxicity, low irritation and the like.
For photocurable coatings, photoinitiators are the most critical components, which play a decisive role in the photocuring speed. A photoinitiator is a substance that absorbs radiation energy and initiates a chemical reaction, thereby producing a reactive intermediate with the ability to initiate polymerization. Photoinitiators can be classified into ultraviolet light and visible light initiators due to different absorption of radiation energy; the active intermediate can be divided into free radical type and cationic photoinitiator; in the radical photoinitiators, the action mechanisms are different and can be divided into cracking photoinitiators and hydrogen abstraction photoinitiators.
The following factors are considered for the selection of the photoinitiator:
1. the absorption spectrum of the photoinitiator is matched with the emission spectrum of the light source;
2. the photoinitiation efficiency is high;
3. good compatibility in the oligomer resin and the reactive diluent;
4. the smell is small, the toxicity is low;
5. no migration and no volatilization.
Photoinitiators used in aqueous UV coatings are classified into two classes, dispersive and water soluble. The dispersive photoinitiator is oil-soluble, can be dispersed into a water-based system by virtue of an emulsifier and a monomer, has the problem of compatibility, and has great influence on the film forming performance and the initiation performance of the coating. To overcome this problem, studies have been made to introduce an anionic group, a cationic group or a hydrophilic group into the structure of an oil-soluble photoinitiator, and a water-soluble photoinitiator is developed, but such a result often results in failure or reduced efficiency of the photoinitiator.
Therefore, the hydrophilic performance of the photoinitiator with improved dispersibility has important significance on the premise of not reducing the efficiency of the photoinitiator.
Disclosure of Invention
The invention aims to provide a preparation method of hydrophilic photoinitiator powder, which comprises the steps of regulating reaction conditions and time, reacting fluorine simple substance with the photoinitiator powder, and randomly substituting a part of elements on the surface of the photoinitiator powder to form a carbon-fluorine bond, so that the modified photoinitiator powder has higher surface activity; further, compared with the conventional modification process, the preparation method provided by the invention has the advantages that the obtained hydrophilic photoinitiator powder has a good modification effect and long duration, and even reaches permanent aging.
The invention also aims to provide hydrophilic photoinitiator powder which is obtained by the preparation method and has higher surface performance and can be rapidly and uniformly dispersed in a water-based system.
In order to achieve the above object, the technical scheme of the present invention is a method for preparing hydrophilic photoinitiator powder, comprising the following steps:
adding photoinitiator powder into a vacuum reactor, and carrying out first vacuumizing treatment and heat treatment; wherein, the vacuum reactor is thermally treated to the reaction temperature to obtain the vacuum reactor to be reacted;
and (2) introducing gas containing the fluorine simple substance into a vacuum reactor to be reacted, adjusting the temperature in the vacuum reactor to the reaction temperature for reaction to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain hydrophilic photoinitiator powder.
According to the method of the present invention, preferably, in the step (1), the photoinitiator powder is one selected from 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, the photoinitiator 500, benzoin diethyl ether, the photoinitiator 784, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, the photoinitiator 1700, the photoinitiator 1800, the photoinitiator 1850, and the photoinitiator 2959.
According to the method provided by the invention, preferably, in the step (1), the pressure in the vacuum reactor to be reacted is-0.1-0 Mpa, and the reaction temperature is-40-120 ℃.
According to the method of the present invention, preferably, in the step (2), the gas containing elemental fluorine is selected from elemental fluorine, or a mixed gas of elemental fluorine and an inert gas; wherein the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the photoinitiator powder is 1: 50-1000.
According to the method of the present invention, preferably, in the step (2), the reaction is carried out at a reaction temperature for 1min to 5 hr.
According to the method of the invention, preferably, in the step (2), the vacuum reactor after the reaction is subjected to a second vacuumizing treatment before being opened, and the gas extracted during the second vacuumizing treatment absorbs a small amount of HF and residual elemental fluorine contained in the gas through an adsorbent.
According to the method of the present invention, preferably, in the step (1), the vacuum reactor is a static vacuum reactor made of monel material, the photoinitiator powder is placed on a gas permeable tray, and the tray is made of metal or polyethylene; or in the step (1), the vacuum reactor is a vibrating vacuum reactor.
According to the method provided by the invention, preferably, in the step (1), the first vacuumizing treatment comprises filling inert gas, and vacuumizing until the pressure is-0.1-0 Mpa; repeating the steps for 1-5 times.
According to the method provided by the invention, preferably, in the step (2), the second vacuumizing treatment comprises filling inert gas, and vacuumizing to-0.1-0 Mpa; repeating the steps for 1-5 times.
In another aspect, the present invention provides a hydrophilic photoinitiator powder, the hydrophilic photoinitiator powder prepared according to the above method.
The invention has the beneficial effects that:
by adjusting the reaction conditions and time, the preparation method uses the fluorine simple substance to react with the photoinitiator powder, and randomly substitutes a part of elements on the surface of the photoinitiator powder to form a carbon-fluorine bond, and the applicant speculates that the carbon-fluorine bond is an irregular carbon-fluorine bond, so that the obtained hydrophilic photoinitiator powder has higher surface activity; further, compared with the conventional modification process, the preparation method provided by the invention has the advantages that the obtained hydrophilic photoinitiator powder has a good modification effect and long duration, and even reaches permanent aging.
Drawings
FIG. 1 is a graph comparing the results of the dispersion property test on the photoinitiator powder (FIG. 1, left) not treated by the preparation method of the present invention and the hydrophilic photoinitiator powder (FIG. 1, right) treated by the preparation method of the present invention.
FIG. 2 is a schematic diagram showing that no infiltration of the dyne liquid and the powder occurs during the surface energy test by the dyne liquid dropping method of the present invention.
FIG. 3 is a schematic diagram showing the immersion of the dyne liquid and the powder in the surface energy test by the dyne liquid dropping method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
The pressure in the present invention refers to the relative pressure.
The preparation method of the oil-water amphiphilic powder comprises the following steps: (1) a preparation step of a vacuum reactor to be reacted; (2) and (3) a vacuum reactor reaction step.
< preparation step of vacuum reactor to be reacted >
Adding photoinitiator powder into a vacuum reactor, and carrying out first vacuumizing and heat treatment; wherein, the vacuum reactor is thermally treated to the reaction temperature, and the vacuum reactor to be reacted is obtained through the steps.
In the invention, the photoinitiator can be selected from any solid photoinitiator powder; preferably, the photoinitiator powder is selected from one of 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (photoinitiator 369), photoinitiator 500, benzoin diethyl ether (photoinitiator 651), photoinitiator 784, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (photoinitiator 907), photoinitiator 1700, photoinitiator 1800, photoinitiator 1850 and photoinitiator 2959; more preferably, the photoinitiator powder is one selected from 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (photoinitiator 369), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819) and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-one (photoinitiator 907). By adopting the photoinitiator powder, the photoinitiator powder can be better modified, and particularly the surface energy rising range is larger.
In the invention, the grain diameter of the photoinitiator powder is 0.01 mu m-1 mm; preferably, the particle size of the photoinitiator powder is 0.1-500 μm; more preferably, the particle size of the photoinitiator powder is 20 to 200. mu.m.
In the invention, after the vacuum reactor to be reacted is subjected to primary vacuum pumping treatment and heat treatment, the pressure in the vacuum reactor to be reacted is-0.1-0 Mpa; preferably, the pressure in the vacuum reactor to be reacted is between-0.1 and-0.05 MPa; more preferably, the pressure in the vacuum reactor to be reacted is between-0.1 and-0.08 MPa. Carrying out heat treatment on the vacuum reactor to be reacted to the reaction temperature of-80-150 ℃; preferably, the reaction temperature is-60 ℃ to 80 ℃; more preferably, the reaction temperature is from-40 ℃ to 60 ℃. The reaction of the fluorine simple substance and the photoinitiator is a violent exothermic reaction, and the lower reaction temperature can avoid the phenomenon that the photoinitiator is melted by the exothermic reaction to influence the quality of the product. According to one embodiment of the present invention, the pressure in the vacuum reactor to be reacted is-0.1 to-0.08 MPa, and the reaction temperature is-20 to 40 ℃. By adopting the pressure range, gas impurities in the vacuum reactor, including oxygen, existing moisture and the like, can be removed better, particularly, the moisture is removed completely, the moisture reacts violently with the fluorine simple substance and releases heat, and irritant oxygen fluoride is generated. The reaction equation of water and fluorine and the reaction equation of oxygen and fluorine are shown in the following formulas (1) and (2):
2F2+2H2O＝2HF+O2(1)
O2+F2＝OF2(2)
because the reaction of the fluorine simple substance and the photoinitiator powder is an exothermic reaction, the reaction of the fluorine simple substance and the photoinitiator powder can be promoted by adopting the reaction temperature range, the reaction speed can be controlled to control the exothermic speed, and the generation of a symmetrical carbon-fluorine bond structure can be prevented by controlling the reaction speed.
In one embodiment of the present invention, the vacuum reactor is a static vacuum reactor made of monel material, and the photoinitiator powder is placed on a gas permeable tray made of metal or polyethylene. The Monel vacuum reactor has better tolerance to fluorine simple substances, and other materials can be selected and need to be passivated to prevent the adsorption and release of potential impurities to reaction gas in the reaction process. The breathable tray can enable the fluorine simple substance to be contacted with the photoinitiator powder of each layer more uniformly, so that the fluorine simple substance can react with the photoinitiator powder more uniformly and fully. In another embodiment of the present invention, the vacuum reactor is a rotary or vibrating vacuum reactor of monel material. The vacuum reactor can be used for realizing more uniform reaction of powder by stirring, throwing and other modes of the powder.
In the invention, the first vacuum-pumping treatment comprises filling inert gas at-0.05-0.1 Mpa, and pumping vacuum to-0.1-0 Mpa; repeating the above steps 0-5 times, preferably repeating the above steps 1-4 times, more preferably 2-3 times. According to an embodiment of the present invention, the first vacuuming process comprises filling inert gas to a relative pressure of 0Mpa, vacuuming to-0.095 Mpa, and repeating the above steps 2 times. The inert gas is preferably one or a mixture of two of nitrogen and argon.
< vacuum reactor reaction step >
The invention leads the gas containing the fluorine simple substance into the vacuum reactor to be reacted, and the reaction is carried out at the reaction temperature to obtain the reacted vacuum reactor, and the reacted vacuum reactor is opened to obtain the hydrophilic photoinitiator powder. During the reaction process of the vacuum reactor, the fluorine simple substance exists in the form of fluorine ions.
In the invention, the gas containing the elemental fluorine is selected from elemental fluorine or a mixed gas of the elemental fluorine and an inert gas, preferably a mixed gas of the elemental fluorine and the inert gas, more preferably a mixed gas of the elemental fluorine and nitrogen, and a mixed gas of the elemental fluorine and argon. In one embodiment of the present invention, the concentration of the elemental fluorine in the mixed gas of the elemental fluorine and the inert gas is 1 vol% to 99 vol%, preferably 1 vol% to 50 vol%; more preferably 1 vol% -20 vol%, and the reaction rate is controlled by controlling the proportion of the fluorine simple substance and the inert gas, so that the phenomenon that the reaction is too fast or too slow, the reaction time is too long, and the reaction is too fast, so that the local part is easy to generate excessive reaction, the excessive fluorine simple substance is consumed, and the other parts are insufficient in reaction, and the overall performance of the modified powder is seriously influenced is prevented.
In the invention, the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the photoinitiator powder is 1: 50-1000, preferably 1: 80-500, and more preferably 1: 100-300. Experiments prove that the polarity of the photoinitiator powder can be better improved on the premise that the content of fluorine in the photoinitiator powder is higher by adopting the mass ratio. The applicant speculates that the use of the above mass ratio avoids the occurrence of symmetric carbon-fluorine bonds, i.e. increases the surface energy of the photoinitiator powder.
In the present invention, the vacuum reactor to be reacted is reacted at a reaction temperature for 1min to 5hr, preferably, for 10min to 4hr, more preferably, for 10min to 3 hr; by adopting the reaction time, the appearance of symmetrical carbon-fluorine bonds can be avoided on the premise of ensuring higher fluorine content in the photoinitiator powder, namely the surface energy of the photoinitiator powder is increased. Experiments prove that the performance of the photoinitiator powder obtained after the elemental fluorine and the photoinitiator powder react for 10min according to the mass ratio is well improved, the performance is basically stable after the reaction lasts for 5hr, and the surface energy of the photoinitiator powder begins to decrease along with the continuous lapse of the reaction time. Applicants speculated that after 5hr of reaction time, as the reaction continued, symmetric carbon-fluorine bonds began to appear and randomly occurring carbon-fluorine bonds began to decrease.
In the invention, the vacuum reactor after reaction is subjected to secondary vacuum treatment before being opened, and the gas extracted during the secondary vacuum treatment absorbs a small amount of HF and residual fluorine contained in the gas through the adsorbent. Preferably, the adsorbent is selected from water, calcium carbonate particles, activated carbon particles; more preferably, the adsorbent is selected from calcium carbonate particles.
The second vacuumizing treatment comprises the steps of filling inert gas until the pressure is-0.05-0.1 Mpa, and vacuumizing until the pressure is-0.1-0 Mpa; repeating the steps for 1-5 times. Preferably, the above steps are repeated 1 to 4 times, more preferably 2 to 3 times. According to one embodiment of the present invention, the second evacuation process comprises filling inert gas at 0.1MPa, evacuating to-0.1 MPa, and repeating the above steps for 2 times. The inert gas is preferably one or a mixture of two of nitrogen and argon.
As an optional step, opening the reacted vacuum reactor to obtain photoinitiator powder, and performing heating post-treatment, wherein the heating post-treatment step comprises heating the photoinitiator powder to 20-100 ℃, heating for 10-120min, and removing hydrogen fluoride attached to the surface of the photoinitiator powder; preferably, the photoinitiator powder is heated to 50-100 ℃ for 30-40 min. Some hydrogen fluoride remains in the reacted photoinitiator powder, the hydrogen fluoride is acidic, the use of the subsequent powder can be affected, and the residual hydrogen fluoride in the powder can be removed by adopting the heating mode, wherein the hydrogen fluoride is harmful to human bodies.
< photoinitiator powder >
The photoinitiator powder is prepared by the preparation method, and details are not repeated here. The photoinitiator powder prepared by the preparation method is added with fluorine element in a random mode, breaks through the convention of symmetrical appearance of fluorine-containing structures, greatly increases the polarity of the photoinitiator powder, and thus obviously improves the compatibility of the photoinitiator and a water-based system.
Introduction to test methods
And (3) testing the dispersion performance:
1. the transparent bottle is filled with 1/2-2/3 of water, and a small amount of photoinitiator powder is poured into the transparent bottle (the small amount of photoinitiator powder is 1/2 which is smaller than the volume of the solvent in the transparent bottle, so that the state of the photoinitiator powder in the water can be observed conveniently);
2. screwing the bottle cap and shaking for 10 s;
3. the photoinitiator powder in the solvent is carefully observed, and if no agglomeration phenomenon exists, the modification effect is good.
Example 1: preparation of the photoinitiator 184
Chemical name: 1-hydroxycyclohexyl phenyl methanones
The chemical formula is as follows: c13H16O2
Appearance: white crystals; purity: 99.0 wt%; melting point: 44-48 ℃; absorption wavelength: 244,280,330 nm; the chemical formula is shown as the following formula:
vacuum reactor volume and type: 400L static vacuum reactor with gas-filled pipeline and vacuum-pumping pipeline
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
The preparation steps are as follows:
step 1, spreading 1000g of photoinitiator powder in a tray;
step 2, placing the tray in a static vacuum reactor;
step 3, cooling the temperature of the vacuum reactor to-20 ℃ and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, balancing the temperature of the vacuum reactor at the reaction temperature of-20 ℃, and standing for 1 hour;
step 8, carrying out vacuum pumping treatment on the vacuum reactor to ensure that the pressure in the vacuum reactor reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.085 mpa (the mass of the introduced fluorine simple substance is 7.23g by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 138;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at-20 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 35 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining hydrophilic photoinitiator powder.
The photoinitiator powder (left figure) which is not processed by the preparation method of the invention and the hydrophilic photoinitiator powder (right figure) which is processed by the preparation method of the invention respectively pass the dispersion performance test, and the test result is shown in the following figure 1. Therefore, the dispersibility of the photoinitiator powder treated by the preparation method of the invention in water is obviously improved. The introduction of fluorine element is proved to increase the surface energy of the photoinitiator powder, thereby improving the hydrophilicity.
Example 2: preparation of the photoinitiator 184
Chemical name: 1-hydroxycyclohexyl phenyl methanones
The chemical formula is as follows: c13H16O2
Appearance: white crystals; purity: 99.0 wt%; melting point: 44-48 ℃; absorption wavelength: 244,280,330 nm; the chemical formula is shown as the following formula:
vacuum reactor volume and type: 400L static vacuum reactor with gas-filled pipeline and vacuum-pumping pipeline
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
The preparation steps are as follows:
step 1, spreading 800g of photoinitiator powder in a tray, and spreading a layer of breathable filter cloth on the upper surface of the spread powder to avoid the powder from being blown away by gas;
step 2, placing the tray in a static vacuum reactor;
step 3, cooling the vacuum reactor to-20 ℃ and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, continuously balancing the temperature of the reactor at the reaction temperature of-20 ℃, and standing for 1 hour;
step 8, carrying out vacuum pumping treatment on the vacuum reactor to ensure that the pressure in the vacuum reactor reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.085 mpa (the mass of the introduced fluorine simple substance is 7.23g by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 110;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at-20 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 35 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining hydrophilic photoinitiator powder.
The photoinitiator powder (fig. 1, left) which is not processed by the preparation method of the invention and the hydrophilic photoinitiator powder (fig. 1, right) which is processed by the preparation method of the invention respectively pass the dispersion performance test, and the test result is shown in the following fig. 1. Therefore, the dispersibility of the photoinitiator powder treated by the preparation method of the invention in water is obviously improved. The introduction of fluorine element is proved to increase the surface energy of the photoinitiator powder, thereby improving the hydrophilicity.
The photoinitiator powder which is not processed by the preparation method and the hydrophilic photoinitiator powder which is processed by the preparation method are respectively subjected to surface energy test by a dyne liquid dropping method detection surface energy test.
Example 2: preparation of photoinitiator 369
Chemical name: 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl) butanone
The chemical formula is as follows: c23H30N2O2
Appearance: a light yellow powder; purity: 99.0 wt%; melting point: 110-119 ℃; absorption wavelength: 232nm, 323 nm; the chemical formula is shown as the following formula:
vacuum reactor volume and type: 400L static vacuum reactor with gas-filled pipeline and vacuum-pumping pipeline
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
The preparation steps are as follows:
step 1, paving 2000g of photoinitiator powder in a tray, and paving a layer of breathable filter cloth on the upper surface of the paved powder in order to prevent the powder from being blown away by gas;
step 2, placing the tray in a static vacuum reactor;
step 3, heating the temperature of the vacuum reactor to 40 ℃ and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, balancing the temperature of the powder at 40 ℃ through heat treatment, and standing for 1 hour;
step 8, carrying out vacuum pumping treatment on the vacuum reactor to ensure that the pressure in the vacuum reactor reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.075 mpa (the mass of the introduced fluorine simple substance is 11.7g by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 171;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at 40 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying oven at 70 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining hydrophilic photoinitiator powder.
The photoinitiator powder not treated by the preparation method of the present invention and the hydrophilic photoinitiator powder treated by the preparation method of the present invention were respectively subjected to a dispersion property test, and the test results were the same as those of example 1. Therefore, the dispersibility of the photoinitiator powder treated by the preparation method of the invention in water is obviously improved. The introduction of fluorine element is proved to increase the surface energy of the photoinitiator powder, thereby improving the hydrophilicity.
The photoinitiator powder which is not processed by the preparation method and the hydrophilic photoinitiator powder which is processed by the preparation method are respectively tested by a dyne liquid dropping method to test the surface energy.
Example 3: preparation of photoinitiator 907
Chemical name: 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone
The chemical formula is as follows: c15H21NO2S
Appearance: white powder crystals; the content is as follows: 99.0 percent; melting point: 73-76 ℃; absorption wavelength: 231nm,307 nm; the chemical formula is shown as the following formula:
vacuum reactor volume and type: 20L static vacuum reactor with gas-filled pipe and vacuum-pumping pipe
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
The preparation steps are as follows:
step 1, paving 2000g of photoinitiator powder in a tray, and paving a layer of breathable filter cloth on the upper surface of the paved powder in order to prevent the powder from being blown away by gas;
step 2, placing the tray in a static vacuum reactor;
step 3, cooling the temperature of the vacuum reactor to 10 ℃ and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, balancing the temperature of the powder at the reaction temperature of 10 ℃ through heat treatment, and standing for 1 hour;
step 8, carrying out vacuum pumping treatment on the vacuum reactor to ensure that the pressure in the vacuum reactor reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.07 mpa (the mass of the introduced fluorine simple substance is 19.4g calculated by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 103;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at 10 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 60 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining hydrophilic photoinitiator powder.
The dispersion performance test shows that the dispersibility of the photoinitiator powder treated by the preparation method of the invention in water is obviously improved. The introduction of fluorine element is proved to increase the surface energy of the photoinitiator powder, thereby improving the hydrophilicity.
Example 4: preparation of photoinitiators 819
Chemical name: phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide
The chemical formula is as follows: c26H27O3P
Appearance: light yellow powder; purity: 99.0 wt%; melting point: 131 ℃ and 135 ℃; absorption wavelength: 360,405 nm; the chemical formula is shown as the following formula:
vacuum reactor volume and type: 400L static vacuum reactor with gas-filled pipeline and vacuum-pumping pipeline
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
The preparation steps are as follows:
step 1, paving 2000g of photoinitiator powder in a tray, and paving a layer of breathable filter cloth on the upper surface of the paved powder in order to prevent the powder from being blown away by gas;
step 2, placing the tray in a static vacuum reactor;
step 3, heating the temperature of the vacuum reactor to 60 ℃ by using a jacket and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, balancing the temperature of the powder at a reaction temperature of 60 ℃ through heat treatment, and standing for 1 hour;
step 8, carrying out vacuum pumping treatment on the vacuum reactor to ensure that the pressure in the vacuum reactor reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.07 mpa (the mass of the introduced fluorine simple substance is 13.7g calculated by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 146;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at 60 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 80 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining hydrophilic photoinitiator powder.
The dispersion performance test shows that the dispersibility of the photoinitiator powder treated by the preparation method of the invention in water is obviously improved. The introduction of fluorine element is proved to increase the surface energy of the photoinitiator powder, thereby improving the hydrophilicity.
Comparative example 1:
the difference from example 1 is: in step 9, the charged fluorine-nitrogen mixture gas is a fluorine-nitrogen mixture gas containing 20 vol% of fluorine to-0.055 Mpa (the mass of the introduced fluorine simple substance is 28.9g calculated by the following calculation method), that is, the mass ratio of the fluorine simple substance to the powder is about 1: 35.
Comparative example 2:
the difference from example 1 is: in step 10, it was allowed to stand for 6 hours (while maintaining the temperature of the vacuum reactor at-20 ℃ C.) to allow the reaction to proceed sufficiently.
As can be seen from the dispersion property test of the photoinitiator powders prepared in comparative examples 1 and 2, the dispersion effect of comparative examples 1 and 2 is not as good as that of example 1. Thus, it is proved that the preparation method of the invention introduces fluorine element to increase the hydrophilicity of the photoinitiator powder.
According to the above analysis, by adjusting the mass ratio of the fluorine simple substance to the photoinitiator powder, the reaction conditions and other influencing elements, the applicant speculates that the preparation method of the present invention introduces the fluorine element to the surface of the photoinitiator powder in a random manner, so as to improve the surface energy and the hydrophilicity of the photoinitiator powder; and the introduction of fluorine improves the lipophilicity, so the powder prepared by the preparation method has oil-water amphiphilicity.
In the present invention, the molar extinction coefficient of the light emitted from the high-pressure mercury lamp was used to detect the photoinitiation activity of the photoinitiator powder, and experiments showed that the molar extinction coefficients of the photoinitiator powder prepared in examples 1 to 4 were not changed before and after the hydrophilic treatment of the present invention, indicating that the hydrophilic treatment of the present invention did not affect the activity of the photoinitiator.
Note: mass m of fluorine used in the present inventionfThe calculation method is as follows:
mf＝(p2-p1)*VM/R/(T+273)*F*106
wherein p is1(Mpa) the pressure in the reactor before filling the fluorine/inert gas mixture;
p2(Mpa): pressure in the reactor after filling the fluorine/inert gas mixture;
f (vol%): the fluorine content in the fluorine/inert gas mixed gas;
V(m3): a reactor volume;
m is the molar mass of the fluorine simple substance is 38 g/mol;
r is gas constant 8.314;
t (. degree. C.) is the reaction temperature.
Claims (10)
1. A preparation method of hydrophilic photoinitiator powder is characterized by comprising the following steps:
adding photoinitiator powder into a vacuum reactor, and carrying out first vacuumizing treatment and heat treatment; wherein, the vacuum reactor is thermally treated to the reaction temperature to obtain the vacuum reactor to be reacted;
and (2) introducing gas containing the fluorine simple substance into a vacuum reactor to be reacted, adjusting the temperature in the vacuum reactor to the reaction temperature for reaction to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain hydrophilic photoinitiator powder.
2. The method according to claim 1, wherein in the step (1), the photoinitiator powder is selected from one of 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, photoinitiator 500, benzoin diethyl ether, photoinitiator 784, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, photoinitiator 1700, photoinitiator 1800, photoinitiator 1850, and photoinitiator 2959.
3. The method according to claim 1, wherein in the step (1), the pressure in the vacuum reactor to be reacted is-0.1-0 MPa, and the reaction temperature is-40-150 ℃.
4. The method according to claim 1, wherein in the step (2), the gas containing elemental fluorine is selected from elemental fluorine, or a mixed gas of elemental fluorine and an inert gas; wherein the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the photoinitiator powder is 1: 50-1000.
5. The method according to claim 1, wherein in the step (2), the reaction is carried out at a reaction temperature for 1min to 5 hr.
6. The method according to claim 1, wherein in the step (2), the vacuum reactor after the reaction is subjected to a second vacuumizing treatment before being opened, and the gas extracted in the second vacuumizing treatment absorbs a small amount of HF and residual elemental fluorine contained in the gas through an adsorbent.
7. The method according to any one of claims 1 to 6, wherein in the step (1), the vacuum reactor is a Monel static vacuum reactor, the photoinitiator powder is placed on a gas-permeable tray, and the tray is made of a material selected from metal or polyethylene; or
In the step (1), the vacuum reactor is a vibration vacuum reactor.
8. The method according to any one of claims 1 to 6, wherein in the step (1), the first vacuum treatment comprises filling inert gas, and vacuumizing to a pressure of-0.1 to 0 MPa; repeating the steps for 1-5 times.
9. The method according to any one of claims 1 to 6, wherein in the step (2), the second vacuuming treatment comprises filling inert gas, and vacuumizing to-0.1 to 0 MPa; repeating the steps for 1-5 times.
10. A hydrophilic photoinitiator powder prepared by the method according to claims 1 to 9.
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| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
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| CN101798748A (en) * | 2010-02-10 | 2010-08-11 | 成都百塑高分子科技有限公司 | Aramid III fiber with fluorine-containing surface and preparation method thereof |
| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
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