Acrylate functional polymer with photo-initiation active end group and preparation method of polymer

Abstract

The invention relates to an acrylate functional polymer with a photo-initiation active end group and a preparation method of the polymer. The acrylate functional polymer is characterized in that the main chain of the polymer is a polymerized main chain of acrylate polymer; one end or two ends of the main chain is / are connected with the photo-initiation active end group, which is capable of absorbing ultraviolet light and being cracked to generate free radicals, by a polyether chain section with low degree of polymerization. Preferably, the photo-initiation active end group is derived from a photoinitiator 2-hydroxyl-4'-(2- hydroxyethoxy)-2-methyl propiophenone. Compared with the prior art, the acrylate functional polymer is introduced with a cracking type photoinitiator containing an alpha-hydroxyalkyl phenyl ketone structure at two ends or one end of the main chain of the acrylate polymer, so that the photo-initiation active groups of the end group are connected with the main body chain by a soft low-polyether chain end. The acrylate polymer which is connected with the functional polymer can be participated in a photo-curing cross-linked network by virtue of the functional polymer, so that the anti-mobility of the polyacrylate in the cross-linked network is improved, and the adhesion force and the hardness of a photo-curing coating are further improved.

Description

technical field

[0001] The invention relates to a polymer material and a preparation method thereof, in particular to a photocurable material with a photoinitiating active end group and a preparation method thereof. Background technique

[0002] Acrylate polymers, such as polymethacrylate and polyacrylate, are often used in solvent-based coatings and light-curing coatings. As an auxiliary resin, it can adjust the hardness or flexibility of the cured coating, and it can also help on surfaces such as plastic substrates. Improves coating adhesion. The poly(meth)acrylate copolymer obtained with methyl (meth)acrylate as the main monomer is commonly known as "pure acrylic resin", which is widely used in light-curing coatings for plastic substrates. Objectively, it acts as an organic polymer filler, which is helpful for relieving and releasing the curing stress shrinkage, and because of its large molecular weight, it leads to an increase in the adhesion of the light-cured coating ...

Examples

Embodiment 1

[0047] In a 500ml airtight three-neck bottle, add 0.1mol of vacuum-dried photoinitiator Darocur 2959 and sodium hydride mineral oil solution containing 0.15mol of active ingredients in 250ml of pure toluene solvent. Ethylene oxide was reacted at room temperature for 3 hours and the pressure in the reactor did not change. Stop responding. The composition of Darocur 2959 is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0048] The above-mentioned pure toluene can be prepared by using crude toluene to remove water and dry with calcium hydride, and then distill and purify.

[0049] Then the extraction is washed and extracted with dilute sodium chloride brine with a concentration of 5% by weight to remove by-products and impurities, and the solvent is distilled off to obtain a polyether chain modified photoinitiator. The average degree of polymerization of the oligoether chain is 3.3 as determined by proton nuclear magnetic spectrum. The structure of the oligoether is s...

Embodiment 2

[0057] In the airtight three-neck bottle of 500ml volume, in the 250ml toluene solvent that sodium hydride removes water and redistills, add 0.1mol vacuum-dried photoinitiator Darocur 2959 and the sodium hydride mineral oil solution that contains 0.15mol active ingredient, through steel bottle and Pipeline transportation, feed 1.0mol propylene oxide gas, and react at room temperature for 4 hours.

[0058] Then the extraction is washed and extracted with dilute sodium chloride brine with a concentration of 5% by weight to remove by-products and impurities, and the solvent is distilled off to obtain a polyether chain modified photoinitiator. The average degree of polymerization of polyoxypropylene is 8.1 as determined by H NMR spectroscopy, and the schematic diagram of the structure is shown in V. There may be isomerism at the methyl position in the propyleneoxy group.

[0059]

[0060] Take the photoinitiator modified by the polyether chain obtained above, dissolve it in 20...

Embodiment 3

[0066] In a closed three-necked bottle with a volume of 500ml, add 0.1mol of photoinitiator Darocur 2959 and sodium hydride mineral oil solution containing 0.15mol of active ingredients in 250ml of toluene solvent that has been dewatered and redistilled with sodium hydride, and transported through steel cylinders and pipelines. Pass through 0.68mol ethylene oxide, and react at room temperature for 3 hours. Dilute brine was washed and extracted to remove by-products and impurities, and the solvent was distilled off to obtain a photoinitiator modified with polyether chains. The average degree of polymerization of the polyether chains was determined by H NMR spectroscopy to be 5.7, and the structure was shown in VII.

[0067]

[0068] Get all the polyether chain-modified photoinitiators obtained above, dissolve in 200ml toluene, use 2mmol p-toluenesulfonic acid-N,N-dimethylbenzyl quaternary ammonium salt as catalyst, add 0.13mol thioglycolic acid, nitrogen Under protection, th...

technical field

[0001] The invention relates to a polymer material and a preparation method thereof, in particular to a photocurable material with a photoinitiating active end group and a preparation method thereof. Background technique

[0002] Acrylate polymers, such as polymethacrylate and polyacrylate, are often used in solvent-based coatings and light-curing coatings. As an auxiliary resin, it can adjust the hardness or flexibility of the cured coating, and it can also help on surfaces such as plastic substrates. Improves coating adhesion. The poly(meth)acrylate copolymer obtained with methyl (meth)acrylate as the main monomer is commonly known as "pure acrylic resin", which is widely used in light-curing coatings for plastic substrates. Objectively, it acts as an organic polymer filler, which is helpful for relieving and releasing the curing stress shrinkage, and because of its large molecular weight, it leads to an increase in the adhesion of the light-cured coating ...

Examples

Embodiment 1

[0047] In a 500ml airtight three-neck bottle, add 0.1mol of vacuum-dried photoinitiator Darocur 2959 and sodium hydride mineral oil solution containing 0.15mol of active ingredients in 250ml of pure toluene solvent. Ethylene oxide was reacted at room temperature for 3 hours and the pressure in the reactor did not change. Stop responding. The composition of Darocur 2959 is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0048] The above-mentioned pure toluene can be prepared by using crude toluene to remove water and dry with calcium hydride, and then distill and purify.

[0049] Then the extraction is washed and extracted with dilute sodium chloride brine with a concentration of 5% by weight to remove by-products and impurities, and the solvent is distilled off to obtain a polyether chain modified photoinitiator. The average degree of polymerization of the oligoether chain is 3.3 as determined by proton nuclear magnetic spectrum. The structure of the oligoether is s...

Embodiment 2

[0057] In the airtight three-neck bottle of 500ml volume, in the 250ml toluene solvent that sodium hydride removes water and redistills, add 0.1mol vacuum-dried photoinitiator Darocur 2959 and the sodium hydride mineral oil solution that contains 0.15mol active ingredient, through steel bottle and Pipeline transportation, feed 1.0mol propylene oxide gas, and react at room temperature for 4 hours.

[0058] Then the extraction is washed and extracted with dilute sodium chloride brine with a concentration of 5% by weight to remove by-products and impurities, and the solvent is distilled off to obtain a polyether chain modified photoinitiator. The average degree of polymerization of polyoxypropylene is 8.1 as determined by H NMR spectroscopy, and the schematic diagram of the structure is shown in V. There may be isomerism at the methyl position in the propyleneoxy group.

[0059]

[0060] Take the photoinitiator modified by the polyether chain obtained above, dissolve it in 20...

Embodiment 3

[0066] In a closed three-necked bottle with a volume of 500ml, add 0.1mol of photoinitiator Darocur 2959 and sodium hydride mineral oil solution containing 0.15mol of active ingredients in 250ml of toluene solvent that has been dewatered and redistilled with sodium hydride, and transported through steel cylinders and pipelines. Pass through 0.68mol ethylene oxide, and react at room temperature for 3 hours. Dilute brine was washed and extracted to remove by-products and impurities, and the solvent was distilled off to obtain a photoinitiator modified with polyether chains. The average degree of polymerization of the polyether chains was determined by H NMR spectroscopy to be 5.7, and the structure was shown in VII.

[0067]

[0068] Get all the polyether chain-modified photoinitiators obtained above, dissolve in 200ml toluene, use 2mmol p-toluenesulfonic acid-N,N-dimethylbenzyl quaternary ammonium salt as catalyst, add 0.13mol thioglycolic acid, nitrogen Under protection, th...

Images