CN102585045B - Macromolecular polymerizable photoinitiator and preparation thereof - Google Patents
Macromolecular polymerizable photoinitiator and preparation thereof Download PDFInfo
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Abstract
The invention discloses a macromolecular polymerizable photoinitiator and a preparation thereof. The method comprises the following steps of: adding 4-hydroxybenzophenone and methanal to a three-necked flask, heating to 95 DEG C, reacting for 2 hours, heating to 150DEG C, leaching under at reduced pressure for 20 minutes, cooling to 105 DEG C, collecting products, pouring products into water, leaching to obtain a macromolecular photoinitiator, dissolving the macromolecular photoinitiator in an organic solvent, dissolving epoxy chloropropane in the solvent under catalysis of boron trifluoride,dropwise adding mixed liquid, reacting at a temperature of 0-5 DEG C, then stirring for 3 hours at a temperature of 70 DEG C, removing epoxy chloropropane and solvent, dissolving residues with a solvent, adding alkali and reacting for 0.5 hour at a temperature of 40 DEG C, removing salt and the solvent, re-dissolving residues with a solvent, washing with water and drying, adding crylic acid, p-hydroxyanisole and tetrabutylammonium bromide, heating for reacting for 6 hours, and then removing the solvent so as to obtain macromolecular polymerizable photoinitiator. The macromolecular polymerizable photoinitiator prepared by the method has the advantages of large molecular weight, weak mobility and good polymerizability.
Description
Technical field
The invention belongs to light sensitive molecule material field, be specifically related to the preparation method that a kind of polymerizable contains the macromolecular photoinitiator of benzophenone.
Background technology
Shine on photosensitive compound by light (UV-light or visible light), make it that a series of optical physics, photochemical reaction take place, generate biologically active fragment, biologically active fragment causes liquid-state oligomers (comprising monomer) polymerization again, and the process that is converted into solid-state macromolecular material is called photopolymerization (claiming photocuring again) liquid coating moment the most at last.Along with the continuous development of science and technology and to the pay attention to day by day of environmental protection, the light polymerization technique fast development, light polymerization technique is repaired and there is the value of practical application in field such as biomaterial in coating, printing ink, tackiness agent, microelectronics, tooth section.
Light trigger is most important in the photopolymerization system, and can it be related to formula system oligopolymer and thinner when rayed and be transformed into solid-state rapidly by liquid state.At present, light trigger mainly is divided into cationic and free radical type two big classes.Cation light initiator mainly contains sulfosalt, salt compounded of iodine.Cationic photoinitiator generally is to utilize the ring-opening polymerization of the protonic acid catalysis epoxy group(ing) that cation light initiator produces under illumination or the cationoid polymerisation of electron rich carbon-carbon double bond (as vinyl ether).The cation photocuring system biggest advantage is the problem that does not have oxygen inhibition, and cure shrinkage is less and bonding strength is stronger in addition.Shortcoming is that curing speed is slower than free radical system, and cost of material is more expensive.Radical photoinitiator is accepted luminous energy and is become excited state from ground state under illumination, further resolve into free radical then.Free radical is combined with the carbon-carbon double bond of monomer, and carries out chain-growth on this basis, makes carbon-carbon double bond generation polymerization.The radical photoinitiator curing system is most widely used system in the photo-cured coating, and advantage is that curing speed is fast, and cost of material is cheap relatively.But problem, the especially latter such as this system existence is shunk greatly, oxygen inhibition usually are the problems that must overcome in the formulating of recipe.Therefore, be necessary the shortcoming of radical photoinitiator is improved, solve its oxygen inhibition and shrink problems such as big.In addition, in the reality prescription, the photodestruciton reaction can take place and produce free small organic molecule in the light trigger of small molecular weight when polymerization, and this point restricts its application on biology, medicine and packaging material for food.So, study the polymerisable light trigger of a kind of macromole self and reduce photolytic product the influence of system is had bright development prospect.
The radical photoinitiator the most widely that the benzophenone photoinitiator is to use, but its uv-absorbing is lower, cause effect relatively poor (R.Liska, Journal of Polymer Science PartA:polymer chemistry, 2002 (40): 1504-1518).People such as F.Sun have studied (Nucl.Instrum.Methods Phys.Rss., Sect B, 2009 (267): 3590-3593) a kind of dynamic performance of siliceous benzophenone derivates light trigger research.Chinese patent CN1850798A (open day: 2006.10.25) disclose a kind of diphenyl ketone photo initiator and preparation method thereof of sulfur-bearing.Chinese patent CN101220106A (open day: 2008.7.16) disclose a kind of siliceous macromolecular photoinitiator, its synthetic method and purposes.Chinese patent CN101077897A (open day: 2007.11.28) disclose super-branching silicon-base macromolecule optical initiator and preparation method thereof.Chinese patent CN1850784A (open day: 2006.10.25) disclose and contain diphenyl ketone photo initiator of phenoxy group and preparation method thereof.
More than these methods have following shortcoming: 1, the molecular weight of initiator is less relatively, and transport property is bigger, is easy to generate free small molecules during photodissociation; 2, do not contain two keys in the molecule, itself is polymerizable not.
Summary of the invention
The object of the invention is to solve the problems of the prior art, from Molecular Structure Design, the two keys in the acrylate are introduced in the resol molecule, provide a kind of molecular weight relatively large, transport property is little, the preparation method of self polymerisable macromolecular photoinitiator.This initiator general structure is as follows:
In the formula, R
1A kind of in hydrogen atom, methyl, methoxyl group, the halogen.
1, a kind of preparation method of polymerisable macromolecular photoinitiator is characterized in that may further comprise the steps:
(1) 4-dihydroxy benaophenonel and excessive formaldehyde solution are joined in the there-necked flask, after mixing, add alkali as a catalyst, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ of reactions then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain containing the macromolecular photoinitiator of benzophenone;
The macromolecular photoinitiator that contains benzophenone that (2) will obtain is dissolved in the organic solvent, under the catalysis of boron trifluoride, epoxy chloropropane is dissolved in the organic solvent, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are reacted 3h down, and mixed solution is removed unreacted epoxy chloropropane and solvent with Rotary Evaporators; Residue slowly adds mineral alkali again with behind the organic solvent dissolution, reacts 0.5h down at 40 ℃, removes by filter salt, revolves the steaming desolventizing; , dewater with Calcium Chloride Powder Anhydrous again after distilling washing the dissolving of residue secondary with organic solvent;
(3) the above-mentioned product that obtains and vinylformic acid are mixed, add catalyzer, add a small amount of MEHQ simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, namely gets the polymerisable light trigger of macromole.
2, method according to claim 1 is characterized in that, the organic solvent described in the step (2) is a kind of in methylene dichloride, trichloromethane, acetone, the ethanol.
3, method according to claim 1 is characterized in that, epoxy chloropropane is dripped in the mixed solution described in the step (2), and wherein the mol ratio of 4-dihydroxy benaophenonel and epoxy chloropropane is 1: 1～2.
4, method according to claim 1 is characterized in that, the mineral alkali described in the step (2) is a kind of in sodium hydroxide, potassium hydroxide, the lithium hydroxide.
5, method according to claim 1 is characterized in that, the catalyzer described in the step (3) is a kind of in Tetrabutyl amonium bromide, tetrabutylammonium chloride, Dodecyl trimethyl ammonium chloride, the tetradecyl trimethyl ammonium chloride.
6, method according to claim 1 is characterized in that, the vinylformic acid described in the step (3) is a kind of in methacrylic acid, methoxy acrylic acid, the 2-chloracrylic acid.
Compared with prior art, the present invention has the following advantages:
1, the preparation method of a kind of macromole polymerizable light trigger provided by the invention has avoided too much reactions steps, and operational condition is simple, and is active high, reduced the cost in the actual mechanical process.
2, the macromole polymerizable light trigger of the present invention's preparation is the 300nm place at wavelength, can absorb UV-light, and trigger monomer carries out polymerization, has improved the initiating activity of light trigger.
3, the macromole polymerizable light trigger of the present invention's preparation, containing two keys in the molecular structure can self-polymerization, has increased molecular weight greatly, has reduced the free small organic molecule that the photodestruciton reaction produces, be applied to biomaterial, the potentiality in food, drug packing material field.
Embodiment
Embodiment 1
Synthesizing of the macromole polymerizable light trigger that hydrogen replaces
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44g sodium hydroxide, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 21.2g methylene dichloride, add the 0.4g boron trifluoride, the 5.6g epoxy chloropropane is dissolved in the 11g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and methylene dichloride with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.83g potassium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g methylene dichloride with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 3.64g vinylformic acid are mixed, add 0.01g MEHQ and 0.05g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is the macromole polymerizable light trigger that hydrogen replaces, and its structure is shown in structural formula 1.
Structural formula 1
Embodiment 2
Synthesizing of methyl substituted macromole polymerizable light trigger
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44g sodium hydroxide, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g methylene dichloride, add the 0.4g boron trifluoride, the 5.6g epoxy chloropropane is dissolved in the 13g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and methylene dichloride with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.83g potassium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g methylene dichloride with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 4.34g methacrylic acid are mixed, add 0.01g MEHQ and 0.05g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is methyl substituted macromole polymerizable light trigger, and its structure is shown in structural formula 2.
Structural formula 2
Embodiment 3
Synthesizing of the macromole polymerizable light trigger that methoxyl group replaces
10g4-dihydroxy benaophenonel and 4.6g formaldehyde solution are joined in the there-necked flask, add 0.5g sodium hydroxide, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 21g methylene dichloride, add the 0.4g boron trifluoride, the 5.6g epoxy chloropropane is dissolved in the 15g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and methylene dichloride with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.83g potassium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g methylene dichloride with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 5.15g methoxy acrylic acid are mixed, add 0.01g MEHQ and 0.05g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is the macromole polymerizable light trigger that methoxyl group replaces, and its structure is shown in structural formula 3.
Structural formula 3
Embodiment 4
Synthesizing of the macromole polymerizable light trigger that chlorine replaces
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44g sodium hydroxide, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g methylene dichloride, add the 0.4g boron trifluoride, the 5.6g epoxy chloropropane is dissolved in the 15g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and methylene dichloride with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.83g potassium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g methylene dichloride with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 5.4g Lv Daibingxisuan are mixed, add 0.01g MEHQ and 0.05g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is the macromole polymerizable light trigger that chlorine replaces, and its structure is shown in structural formula 4.
Structural formula 4
Embodiment 5
Synthesizing of the polymerisable macromolecule photoinitiator that hydrogen replaces
11.5g4-dihydroxy benaophenonel and 5.22g formaldehyde solution are joined in the there-necked flask, add 0.5g sodium hydroxide, heated and stirred to 98 ℃, reaction 2h; Be warming up to 145 ℃ then, carry out decompress filter reaction 20min, be cooled to 104 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 25g methylene dichloride, add the 0.4g boron trifluoride, the 6.44g epoxy chloropropane is dissolved in the 13g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and methylene dichloride with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.32g sodium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g methylene dichloride with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 4.18g vinylformic acid are mixed, add 0.01g MEHQ and 0.06g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is the macromole polymerizable light trigger that hydrogen replaces, and its structure is shown in structural formula 5.
Structural formula 5
Embodiment 6
Synthesizing of the macromole polymerizable light trigger that hydrogen replaces
11.5g4-dihydroxy benaophenonel and 5.22g formaldehyde solution are joined in the there-necked flask, add 0.5g sodium hydroxide, heated and stirred to 98 ℃, reaction 2h; Be warming up to 145 ℃ then, carry out decompress filter reaction 20min, be cooled to 104 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 25g trichloromethane, add the 0.4g boron trifluoride, the 6.44g epoxy chloropropane is dissolved in the 13g trichloromethane, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and trichloromethane with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2.32g sodium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g trichloromethane with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 4.18g vinylformic acid are mixed, add 0.01g MEHQ and 0.06g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is the macromole polymerizable light trigger that hydrogen replaces, and its structure is shown in structural formula 6.
Structural formula 6
Embodiment 7
Synthesizing of methyl substituted macromole polymerizable light trigger
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44g sodium hydroxide, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g trichloromethane, add the 0.35g boron trifluoride, the 5.6g epoxy chloropropane is dissolved in the 13g trichloromethane, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are stirred 3h down, and mixed solution is removed unreacted epoxy chloropropane and trichloromethane with Rotary Evaporators; With 40g ethanol residue is dissolved, slowly add 2g sodium hydroxide, react 0.5h down at 40 ℃, remove by filter salt, revolve to steam and remove ethanol; With the 40g trichloromethane with residue secondary dissolving, use the 40g distilled water wash again after, use the Calcium Chloride Powder Anhydrous drying, remove by filter calcium chloride.The above-mentioned product that obtains and 4.34g methacrylic acid are mixed, add 0.01g MEHQ and 0.05g Tetrabutyl amonium bromide simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, the yellow solid that obtains is methyl substituted macromole polymerizable light trigger, and its structure is shown in structural formula 7.
Structural formula 7
Claims (7)
1. macromole polymerizable light trigger, general structure is as follows:
In the formula, R
1A kind of in hydrogen atom, methyl, methoxyl group, the halogen.
2. the preparation method of a polymerisable macromolecular photoinitiator is characterized in that may further comprise the steps:
(1) 4-dihydroxy benaophenonel and excessive formaldehyde solution are joined in the there-necked flask, after mixing, add alkali as a catalyst, heated and stirred to 95 ℃, reaction 2h; Be warming up to 150 ℃ of reactions then, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured in the water precipitated, behind suction filtration, obtain containing the macromolecular photoinitiator of benzophenone;
The macromolecular photoinitiator that contains benzophenone that (2) will obtain is dissolved in the organic solvent, under the catalysis of boron trifluoride, epoxy chloropropane is dissolved in the organic solvent, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, 70 ℃ are reacted 3h down, and mixed solution is removed unreacted epoxy chloropropane and solvent with Rotary Evaporators; Residue slowly adds mineral alkali again with behind the organic solvent dissolution, reacts 0.5h down at 40 ℃, removes by filter salt, revolves the steaming desolventizing; , dewater with Calcium Chloride Powder Anhydrous again after distilling washing the dissolving of residue secondary with organic solvent;
(3) the above-mentioned product that obtains and vinylformic acid are mixed, add catalyzer, add a small amount of MEHQ simultaneously, reacting by heating 6h, reaction finishes the back desolventizing, namely gets the polymerisable light trigger of macromole.
3. method according to claim 2 is characterized in that, the organic solvent described in the step (2) is a kind of in methylene dichloride, trichloromethane, acetone, the ethanol.
4. method according to claim 2 is characterized in that, epoxy chloropropane is dripped in the mixed solution described in the step (2), and wherein the mol ratio of 4-dihydroxy benaophenonel and epoxy chloropropane is 1:1～2.
5. method according to claim 2 is characterized in that, the mineral alkali described in the step (2) is a kind of in sodium hydroxide, potassium hydroxide, the lithium hydroxide.
6. method according to claim 2 is characterized in that, the catalyzer described in the step (3) is a kind of in Tetrabutyl amonium bromide, tetrabutylammonium chloride, Dodecyl trimethyl ammonium chloride, the tetradecyl trimethyl ammonium chloride.
7. method according to claim 2 is characterized in that, the vinylformic acid described in the step (3) is substitutable for a kind of in methacrylic acid, methoxy acrylic acid, the 2-chloracrylic acid.
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| CN103048883B (en) * | 2012-12-05 | 2014-08-13 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing polymerizable photoinitiator |
| CN103232343A (en) * | 2013-04-08 | 2013-08-07 | 北京化工大学常州先进材料研究院 | Hydroxyl-comprising low-volume-shrinkage nonylphenyl acrylate monomer and preparation method thereof |
| CN103804165A (en) * | 2014-03-05 | 2014-05-21 | 南通惠康国际企业有限公司 | Method for preparing light stabilizer methylene bi(2,3,4-trihydroxybenzophenone) |
| ES2882573T3 (en) | 2015-03-20 | 2021-12-02 | Henkel IP & Holding GmbH | UV Curable Hot Melt Pressure Sensitive Adhesives |
| CN104844736B (en) * | 2015-04-30 | 2016-03-30 | 上海交通大学 | Fluoridize hydrogen-abstraction Polymeric photoinitiators, preparation method and application thereof |
| JP2017149794A (en) * | 2016-02-22 | 2017-08-31 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealant and liquid crystal display panel |
| CN109653523A (en) * | 2017-10-12 | 2019-04-19 | 蒲连影 | A kind of civil buildings exterior wall crack repairing method |
| CN109734635A (en) * | 2018-12-28 | 2019-05-10 | 天津久日新材料股份有限公司 | A kind of method and application of the photoinitiator introducing light-cured resin and monomer |
| CN109988262B (en) * | 2019-04-03 | 2020-07-14 | 北京化工大学 | Polymeric macromolecular photoinitiator and preparation method thereof |
| CN109988268B (en) * | 2019-04-03 | 2020-08-04 | 北京化工大学 | Copolymerization macromolecular photoinitiator and preparation method thereof |
| CN112796000B (en) * | 2021-01-20 | 2021-11-19 | 东华大学 | High-gel-content high-crystallinity aliphatic polyester and preparation method thereof |
| CN115073638B (en) * | 2022-08-04 | 2024-03-08 | 盐城工学院 | C 36 -D-Br 2 Macromolecular initiator, polymethyl acrylate, preparation method and application |
| CN115572229A (en) * | 2022-11-10 | 2023-01-06 | 江苏三木化工股份有限公司 | Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone |
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