Polyacrylate macromolecular photoinitiator, synthesis method therefor and use thereof

Abstract

A polyacrylate macromolecular photoinitiator, a synthesis method therefor, and the use thereof. The polyacrylate macromolecular photoinitiator is free of a component having a molecular weight of less than 1000, and can effectively avoid the introduction of a material having a mall molecular weight in the photoinitiator and the odor and migration contamination produced thereby, the general formula thereof being as shown in formula I.

Claims

1. A method for preparing a polyacrylate macromolecular photoinitiator, which is free of a component having a molecular weight of less than 1000, and a general formula thereof being as shown in formula I: ##STR00008## in formula I, PI is a hydrogen abstraction type photoinitiator group; R.sub.1 and R.sub.2 are each H or CH.sub.3; R.sub.3 is C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkyl substituted with hydroxy, C.sub.1-C.sub.3 alkyl terminally substituted with C.sub.5-C.sub.6 cycloalkyl, C.sub.5-C.sub.6 cycloalkyl or H; n.sub.1 is an integer greater than or equal to 1; n.sub.2 is an, integer greater than or equal to 0; a mass percent of the PI group in the polyacrylate macromolecular photoinitiator is 20%-85%, the method comprises: step 1, dissolving a compound of formula III-1, a compound of formula III-2, a molecular weight regulator and a thermal initiator in a solvent to carry out a polymerization reaction to obtain a reaction solution; step 2, after the polymerization reaction is finished, dripping the reaction solution into a post-treatment solvent, standing for liquid separation, separating a lower layer polymer which is prepared in the polymerization reaction and the post-treatment solvent, and removing the post-treatment solvent under reduced pressure to obtain a product, which is the polyacrylate macromolecular photoinitiator; ##STR00009## PI, R.sub.1, R.sub.2, R.sub.3 in formula III-1 and formula III-2 are as defined in formula I.

2. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 1, wherein that the post-treatment solvent is methanol or ethanol.

3. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 1, wherein that the molecular weight regulator is dodecanethiol.

4. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 1, wherein that the thermal initiator is selected from azo-type initiators or organic peroxygen initiators.

5. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 4, wherein that the azo-type initiator is selected from azobisisobutyronitrile and azobisisoheptanenitrile.

6. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 4, wherein that the organic peroxygen initiator is selected from dibenzoyl peroxide, dilauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di(2-ethylhexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.

7. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 1, wherein that the PI group of formula I is selected from benzophenone-type photoinitiator groups, coumarin-type photoinitiator groups or thioxanthone-type photoinitiator groups.

8. The method for preparing the polyacrylate macromolecular photoinitiator as claimed in claim 7, wherein that the PI group of formula I is selected from one or more of formulas II-1 to II-11: ##STR00010## ##STR00011## wherein, R.sub.4, R.sub.5 in formula II-11 are respectively C.sub.1-C.sub.4 alkyl.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Drawings of description forming one part of the application are used for providing further understanding to the disclosure, schematic embodiments of the disclosure and description thereof are used for explaining the disclosure, and are not intended to improperly limit the disclosure. In the drawings:

(2) FIG. 1 shows a GPC molecular weight profile of Embodiment 1 product.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Raw Material Preparation Example 1

Preparation of 4-(2-hydroxyethoxy)benzophenone

(3) Step 1:

(4) Adding 400 g of anhydrous aluminum trichloride, 750 g of dichloroethane into a 2500 ml four-mouth bottle, cooling to 5° C., dropwise adding 250 g of ethylene glycol phenyl ether acetate, reacting for 4 hours, dripping the reaction solution into 1000 ml of water, washing for three times, and desolventizing the organic phase to obtain a product [2-(4-benzoyl)phenoxy]ethanol acetate 350 g.

(5) Step 2:

(6) Adding 350 g of the product [2-(4-benzoyl)phenoxy]ethanol acetate obtained in the previous step and 1000 g of toluene into a 2000 ml four-mouth bottle, dropwise adding 350 g of 20% aqueous sodium hydroxide solution, and after reacting for 4 hours at 50° C., washing with 500 ml of 50° C. water each time for three times, and cooling to −15° C. for crystallization to obtain 4-(2-hydroxyethoxy)benzophenone 250 g.

Raw Material Preparation Example 2

Preparation of 2-(4-benzoyl)phenoxyethoxyethanol

(7) Step 1:

(8) Adding 100 g of 2-(2-phenoxyethoxy) ethanol and 60 g of acetic anhydride into a 250 ml four-mouth bottle, and reacting for 4 hours at 120° C. and then desolventing under reduced pressure to obtain 2-(2-phenoxyethoxy) ethyl acetate 120 g.

(9) Step 2:

(10) Adding 80 g of anhydrous aluminum trichloride and 150 g of dichloroethane into a 500 ml four-mouth bottle, cooling to 5° C., dropwise adding 50 g of the product 2-(2-phenoxyethoxy) ethyl acetate obtained in the previous step, reacting for 4 hours, dripping the reaction solution into 200 ml of water, washing with water for three times, and desolventing the organic phase to obtain a product [2-(4-benzoyl)phenoxyethoxy]ethanol acetate 70 g.

(11) Step 3:

(12) Adding 70 g of the product [2-(4-benzoyl)phenoxyethoxy]ethanol acetate obtained in the previous step and 100 g of isopropanol into a 500 ml four-mouth bottle, dropwise adding 70 g of 20% sodium hydroxide aqueous solution, reacting for 4 hours at room temperature, washing with 100 ml of 20% sodium chloride aqueous solution each time for three times, and carrying out rotary evaporation and desolvation on an organic phase to obtain a product 2-(4-benzoyl)phenoxyethoxyethanol 50 g.

Embodiment 1

(13) Step 1:

(14) Adding 90 g of the product 4-(2-hydroxyethoxy)benzophenone obtained in the raw material preparation example 1, 57 g of acrylic acid, 1.5 g of p-toluenesulfonic acid, 0.045 g of hydroquinone and 150 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxy]ethyl acrylate 112 g.

(15) Step 2:

(16) Adding 100 g of the product [2-(4-benzoyl)phenoxy]ethyl acrylate obtained in the previous step, 100 g of butyl acrylate and 300 g of toluene into an 1 L four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 100 g of toluene, 12 g of azobisisobutyronitrile and 4 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. 200 g of solvent was removed by rotary evaporation under reduced pressure at 70° C. Adding 400 g of ethanol into an 1 L four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 170 g of a yellowish product which is a macromolecular photoinitiator containing an initiator group shown as II-4. GPC test shows that the molecular weight of the initiator is 1000-100000, the content of the initiator group is 42%, and the data are shown in Table 1 and FIG. 1.

Embodiment 2

(17) Step 1:

(18) Adding 90 g of 4-(2-hydroxyethoxy)benzophenone, 57 g of acrylic acid, 1.5 g of p-toluenesulfonic acid, 0.045 g of hydroquinone and 150 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxy]ethyl acrylate 112 g.

(19) Step 2:

(20) Adding 100 g of the product [2-(4-benzoyl)phenoxy]ethyl acrylate obtained in the previous step, 100 g of butyl acrylate and 300 g of toluene into an 1 L four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 100 g of toluene, 24 g of azobisisoheptanenitrile and 10 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. 200 g of solvent was removed by rotary evaporation under reduced pressure at 70° C. Adding 400 g of ethanol into an 1 L four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 142 g of a yellowish product which is a macromolecular photoinitiator containing an initiator group shown as II-4. GPC test shows that the molecular weight of the initiator is 1000-13000, the content of the initiator group is 42%, and the data are shown in Table 1.

Embodiment 3

(21) Step 1:

(22) Adding 90 g of 4-(2-hydroxyethoxy)benzophenone, 57 g of acrylic acid, 1.5 g of p-toluenesulfonic acid, 0.045 g of hydroquinone and 150 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxy]ethyl acrylate 112 g.

(23) Step 2:

(24) Adding 60 g of the product [2-(4-benzoyl)phenoxy]ethyl acrylate obtained in the previous step, 140 g of butyl acrylate and 300 g of toluene into an 1 L four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 100 g of toluene, 24 g of azobisisoheptanenitle and 10 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. 200 g of solvent was removed by rotary evaporation under reduced pressure at 70° C. Adding 400 g of ethanol into an 1 L four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 102 g of a yellowish product, which is a macromolecular photoinitiator containing an initiator group shown as II-4, the content of the initiator group is 24%, and the data are shown in Table 1.

Embodiment 4

(25) Step 1:

(26) Adding 90 g of the product 4-(2-hydroxyethoxy)benzophenone obtained in the previous step, 57 g of acrylic acid, 1.5 g of p-toluenesulfonic acid, 0.045 g of hydroquinone and 150 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxy]ethyl acrylate 112 g.

(27) Step 2:

(28) Adding 180 g of [2-(4-benzoyl)phenoxy]ethyl acrylate, 420 g of butyl acrylate and 300 g of toluene into an 1 L four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 100 g of toluene, 24 g of azobisisoheptanenitrile and 10 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. 200 g of solvent was removed by rotary evaporation under reduced pressure at 70° C. Adding 400 g of ethanol into an 1 L four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 178 g of yellowish product, which is a macromolecular photoinitiator containing an initiator group shown as 1-4, the content of the initiator group is 73%, and the data are shown in Table 1.

Embodiment 5

(29) Step 1:

(30) Adding 20 g of the product 2-(4-benzoylphenoxyethoxy) ethanol obtained in raw material preparation example 2, 15 g of acrylic acid, 0.35 g of p-toluenesulfonic acid, 0.005 g of hydroquinone and 75 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxyethoxy]ethyl acrylate 27 g.

(31) Step 2:

(32) Adding 10 g of the product [2-(4-benzoyl)phenoxyethoxy]ethyl acrylate obtained in the previous step, 10 g of butyl acrylate, 30 g of toluene into a 250 ml four-mouth bottle, replacing gas in the bottle with nitrogen, and dropwise adding a mixed solution of 10 g of toluene, 0.6 g of benzoyl peroxide and 0.2 g of dodecanethiol at 100° C., reacting for 6 hours, heating to 120° C., maintaining for 2 hours, and then cooling to room temperature. Adding 80 g of ethanol into a 250 ml four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 11 g of a yellowish product, which is a macromolecular photoinitiator containing an initiator group shown as formula II-6, the content of the initiator group is 38%, and the data are shown in table 1.

Embodiment 6

(33) Step 1:

(34) Adding 10 g of 2-hydroxythioxanthone, 8 g of acrylic acid, 20 g of toluene, 0.2 g of p-toluenesulfonic acid and 0.005 g of hydroquinone into a 250 ml four-mouth bottle, carrying out reflux dehydration reaction for 12 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain 13 g of yellow oily liquid.

(35) Step 2:

(36) Adding 10 g of the product obtained in the previous step, 10 g of butyl acrylate and 30 g of toluene into a 250 ml four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 10 g of toluene, 0.6 g of azobisisobutyronitrile and 0.2 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. Adding 80 g of methanol into a 250 ml four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 13 g of a yellow product, which is a macromolecular photoinitiator containing an initiator group shown as formula II-8, and the content of the initiator group is 43%, and the data are shown in table 1.

Embodiment 7

(37) Step 1:

(38) Adding 10 g of 4-hydroxybenzophenone, 5 g of acryloyl chloride, 10 g of potassium carbonate, 20 g of DMF into a 250 ml four-mouth bottle, reacting for 4 hours at 80° C. and then desolventing under reduced pressure, dissolving 30 g of ethanol and then crystallizing to obtain 12 g of 4-benzoyl phenyl acrylate as a white solid powder.

(39) Step 2:

(40) Adding 10 g of the product obtained in the previous step, 10 g of butyl acrylate and 30 g of toluene into a 250 ml four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 10 g of toluene, 0.6 g of azobisisobutyronitrile and 0.2 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. Adding 80 g of ethanol into a 250 ml four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 11 g of a yellowish product, which is a macromolecular photoinitiator containing an initiator group shown as formula II-1, the content of the initiator group is 40%, and the data are shown in table 1.

Embodiment 8

(41) Step 1:

(42) Adding 10 g of 2-hydroxythioxanthone, 8 g of acrylic acid, 20 g of toluene, 0.2 g of p-toluenesulfonic acid and 0.005 g of hydroquinone into a 250 ml four-mouth bottle, carrying out reflux dehydration reaction for 12 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain 13 g of yellow oily liquid.

(43) Step 2:

(44) Adding 90 g of the product 4-(2-hydroxyethoxy)benzophenone obtained in the raw material preparation example 1, 57 g of acrylic acid, 1.5 g of p-toluenesulfonic acid, 0.045 g of hydroquinone and 150 g of toluene into a 500 ml four-mouth bottle, carrying out reflux dehydration reaction for 24 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain a yellow oily liquid of [2-(4-benzoyl)phenoxy]ethyl acrylate 112 g.

(45) Step 3:

(46) Adding 5 g of the product obtained in step 1, 5 g of the product obtained in step 2, 10 g of butyl acrylate and 30 g of toluene into a 250 ml four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 10 g of toluene, 0.6 g of azobisisobutyronitrile and 0.2 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. Adding 80 g of methanol into a 250 ml four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 13 g of a yellow product, which is a macromolecular photoinitiator simultaneously containing initiator groups shown as formula II-4 and formula II-8, and the content of the initiator groups is 43%; the data are shown in Table 1.

Embodiment 9

(47) Step 1:

(48) Adding 10 g of 3-[4′-(2″-hydroxyethyl) benzoyl)-5,7-dimethoxycoumarin, 8 g of acrylic acid, 20 g of toluene, 0.2 g of p-toluenesulfonic acid, 0.005 g of hydroquinone into a 250 ml four-mouth bottle, carrying out reflux dehydration reaction for 12 hours, washing with 50 ml of water each time for three times until the pH of an aqueous phase being about 6-7, carrying out decompression desolvation after liquid separation to obtain 12 g of a yellow oily liquid.

(49) Step 2:

(50) Adding 10 g of the product obtained in the previous step, 10 g of butyl acrylate and 30 g of toluene into a 250 ml four-mouth bottle, replacing gas in the bottle with nitrogen, dropwise adding a mixed solution of 10 g of toluene, 0.6 g of azobisisobutyronitrile and 0.2 g of dodecanethiol at 80° C., reacting for 6 hours, heating to 100° C., maintaining for 2 hours, and then cooling to room temperature. Adding 80 g of ethanol into a 250 ml four-mouth bottle, cooling to 10° C., dropping the concentrated reaction solution under stirring, stirring for 30 min, standing for liquid separation, and carrying out vacuum rotary evaporation and desolvation on the lower resin at 80° C. for 1 hour to obtain 18 g of a yellowish product, which is a macromolecular photoinitiator containing an initiator group shown as formula II-11, the content of the initiator group is 43%, and the data are shown in table 1.

(51) TABLE-US-00001 TABLE 1 Molecular weight data measured by GPC method Molecular Weight Distribution Sample Name Test Item Mn Mw Minimum Embodiment 1 molecular 7711.9 15819 >1000 product weight Embodiment 2 molecular 3262.6 5214.7 >1000 product weight Embodiment 3 molecular 5276.8 8365.2 >1000 product weight Embodiment 4 molecular 9535.1 19833 >1000 product weight Embodiment 5 molecular 9022.0 18332 >1000 product weight Embodiment 6 molecular 8532.1 16255 >1000 product weight Embodiment 7 molecular 6522.4 9521.2 >1000 product weight Embodiment 8 molecular 8032.8 15997 >1000 product weight Embodiment 9 molecular 9032.1 16322.1 >1000 product weight

APPLICATION EXAMPLES

Embodiment 9

(52) Application of Polyacrylate Macromolecule

(53) 10 groups of formulations are prepared according to the mass proportion in table 2, 25 μm wire rods are coated on a white cardboard plate, after 4 m/min belt speed curing of a 2000 W high-pressure mercury lamp for one time, 10 groups of F1-F10 sample plates are obtained, and the curing effect is tested by a touch dry method; the odor of the cured surface is artificially sensed. The test results are shown in Table 3, the polyacrylate macromolecular photoinitiator provided by the disclosure has good curing performance and lower odor than commercially available small molecule photoinitiators and macromolecular photo initiators.

(54) TABLE-US-00002 TABLE 2 Photocurable composition formulation table Experimental Photoinitiator Photomer Photomer Formulation Photoinitiator Amount TMP3EOTA 3316 4250 F1 Embodiment 1 0.4 4.6 4.6 0.4 product F2 Embodiment 2 0.4 4.6 4.6 0.4 product F3 Embodiment 3 0.4 4.6 4.6 0.4 product F4 Embodiment 4 0.4 4.6 4.6 0.4 product F5 Embodiment 5 0.4 4.6 4.6 0.4 product F6 Embodiment 6 0.4 4.6 4.6 0.4 product F7 Embodiment 7 0.4 4.6 4.6 0.4 product F8 Embodiment 8 0.4 4.6 4.6 0.4 product F9 Embodiment 9 0.4 4.6 4.6 0.4 product F10 Benzophenone 0.4 4.6 4.6 0.4 F11 Omnipol BP 0.4 4.6 4.6 0.4 * Photomer 3316 is an acrylate resin of IGM, which is a kind of epoxy acrylate resin; Photomer 4250 is a reactive amine of IGM; Omnipol BP is a macromolecular photoinitiator of IGM; TMP3EOTA is ethoxylated trimethylolpropane triacrylate.

(55) TABLE-US-00003 TABLE 3 Application test results of photocurable compositions Experimental Surface Odor Formulation Photoinitiator Curing Effect after Curing F1 Embodiment 1 Good curing Almost odourless product F2 Embodiment 2 Good curing Almost odourless product F3 Embodiment 3 Good curing Almost odourless product F4 Embodiment 4 Good curing Almost odourless product F5 Embodiment 5 Good curing Almost odourless product F6 Embodiment 6 Good curing Almost odourless product F7 Embodiment 7 Good curing Almost odourless product F8 Embodiment 8 Good curing Almost odourless product F9 Embodiment 9 Good curing Almost odourless product F10 Benzophenone Good curing Distinct odour F11 Omnipol BP Good curing Slight odor