Preparation method of UV photolysis glue based on synergistic effect of natural polymer and photoinitiator

Abstract

The invention relates to a preparation method of UV (ultraviolet) photolysis glue based on a synergistic effect of a natural polymer and a photoinitiator. The preparation method comprises the following steps: weighing 20 to 40 parts of urethane acrylate, 18 to 35 parts of cationic curing base resin, 12 to 24 parts of epoxy acrylate, 10 to 18 parts of Rubiq, 10 to 18 parts of biruthenium pyridine, 10 to 18 parts of acrylate o-nitrobenzyl, 3 to 6 parts of a diluent, 2 to 5 parts of a photoinitiator, 1 to 3 parts of a stabilizer, 1 to 2 parts of a leveling agent, 1 to 2 parts of a defoaming agent, 2 to 3 parts of a plasticizer and 1 to 2 parts of a coupling agent. Rubiq, ruthenium-linked pyridine and acrylic ester o-nitrobenzyl are introduced to serve as cross-linking agents, different UV photolysis glue of the cross-linking agents shows selective degradation under irradiation of light with different wavelengths, when the multiple layers of UV photolysis glue are sequentially exposed to red light, green light and blue light, degradation of a specific area can be achieved, response to low-energy light is achieved, and the application range of the UV photolysis glue is widened. The method can be used for synthesizing UV photolysis glue which is rapidly and orthogonally degraded under red, green and blue light, and the UV photolysis glue can be degraded in complex tissues with the depth of 2cm.

Description

Technical Field

[0001] The invention relates to the technical field of photoinitiators, in particular to a UV photodegradation preparation method based on the synergistic effect of natural polymers and photoinitiators. Background Art

[0002] Photoinitiators are compounds that can absorb energy of a certain wavelength in the ultraviolet region (250-420nm) or visible region (400-800nm) to generate free radicals, cations, etc., thereby initiating polymerization, cross-linking and curing of monomers. In the photocuring system, including UV glue, UV coating and UV ink, after receiving or absorbing external energy, chemical changes occur in themselves, decomposing into free radicals or cations, thereby initiating polymerization reactions.

[0003] Initiator molecules have a certain light absorption capacity in the ultraviolet or visible light region. After directly or indirectly absorbing light energy, the initiator molecules transition from the ground state to the excited singlet state, and then to the excited triplet state through intersystem crossing; after the excited singlet or triplet state undergoes unimolecular or bimolecular chemical reactions, active fragments that can initiate monomer polymerization are generated. These active fragments can be free radicals, cations, anions, etc. According to different initiation mechanisms, photoinitiators can be divided into free radical polymerization photoinitiators and cationic photoinitiators, among which free radical polymerization photoinitiators are the most widely used.

[0004] Most UV photosolvents have the ability to degrade under ultraviolet light, but are insufficient for other light degradation. In special environments, they do not have the ability to degrade red light, green light and blue light, which limits their application range. Therefore, a UV photosolvent preparation method based on the synergistic effect of natural polymers and photoinitiators is proposed to solve the above problems. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides a method for preparing UV photosolvents based on the synergistic effect of natural polymers and photoinitiators, which has the advantages of being able to degrade red light, green light and blue light other than ultraviolet light and increasing the application environment, and solves the problem that most UV photosolvents have the ability to degrade ultraviolet light but insufficient ability to degrade other light, and have no ability to degrade red light, green light and blue light in special environments, which limits their application scope.

[0006] To achieve the above object, the present invention provides the following technical solution: a UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators, comprising the following steps:

[0007] Step 1: Raw material preparation

[0008] S1. Weigh 20-40 parts of polyurethane acrylate, 18-35 parts of cationic curing base resin, 12-24 parts of epoxy acrylate, 10-18 parts of Rubiq, 10-18 parts of bis-ruthenium pyridine, 10-18 parts of o-nitrobenzyl acrylate, 3-6 parts of diluent, 2-5 parts of photoinitiator, 1-3 parts of stabilizer, 1-2 parts of leveling agent, 1-2 parts of defoamer, 2-3 parts of plasticizer and 1-2 parts of coupling agent by weight;

[0009] Step 2: Material dispersion

[0010] The weighed polyurethane acrylate, cationic curing base resin, epoxy acrylate, Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate were added into the mixer in sequence, the stirring time was set to 5-10 minutes, the stirring temperature was set to 30-48° C., and the mixture A was obtained after sufficient stirring;

[0011] Step 3: Reaction Mixing

[0012] The mixture A is fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent are poured into the reactor in sequence, the reactor is closed, the reaction time is set to 40-60 min, the reaction temperature is set to 60-80°C, and after the reaction is completed, it is cooled to room temperature to obtain glue solution A;

[0013] Step 4: Filter

[0014] The glue solution A is sent to the filter for filtration 2-3 times, and the filter mesh number is 8000-10000 mesh;

[0015] Step 5: Filling and curing

[0016] The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet radiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 30-50 minutes.

[0017] Preferably, the polyurethane acrylate is prepared by reacting polyisocyanate, polyol and acrylic acid hydroxyl group.

[0018] Preferably, the cationically curable base resin is obtained by cationic copolymerization of various monomers such as olefin, epoxy, ketal, lactone and silicone, and the cationically curable base resin may be one of 3,4-epoxycyclohexylcarboxylic acid-3 and 4-epoxycyclohexyl methyl ester.

[0019] Preferably, the epoxy acrylate may be one of bisphenol A epoxy resin, hexahydrophthalic acid epoxy resin, and aliphatic epoxy resin.

[0020] Preferably, the Rubiq is prepared from a ruthenium compound using a two-step synthesis method and characterized by nuclear magnetic resonance and electrospray ionization mass spectrometry.

[0021] Preferably, the biruthenium pyridine is prepared from a ruthenium compound using a two-step synthesis method.

[0022] Furthermore, the o-nitrobenzyl acrylate is characterized by nuclear magnetic resonance and electrospray ionization mass spectrometry, and the Rubiq, bis-ruthenium pyridine and o-nitrobenzyl acrylate are used as crosslinking agents.

[0023] Preferably, the diluent is an active epoxy resin diluent and one of cyclic ether, cyclic lactone, and vinyl ether monomers, and the photoinitiator is one of aromatic sulfonate, iodine salt, and ferrocenium salt.

[0024] Preferably, the stabilizer is one of hydroquinone, p-methoxyphenol, p-benzoquinone, 2,6-di-tert-butylcresol and phenothiazine, the leveling agent is one of a mixed solvent, silicone, polyacrylate, cellulose acetate butyrate, and nitrocellulose, the defoamer is one of phosphate ester, fatty acid ester and silicone, the plasticizer is one of glycerol, propylene glycol, and dibutyl phthalate, and the coupling agent is one of gamma-methacrylate propyltrimethoxysilane and gamma-aminopropyltriethoxysilane.

[0025] Compared with the prior art, the technical solution of this application has the following beneficial effects:

[0026] 1. The present invention introduces Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate as crosslinking agents. UV photosolvents with different crosslinking agents show selective degradation under different wavelengths of light irradiation. Rubiq-based UV photosolvents degrade rapidly under red light irradiation, biruthenium pyridine-based UV photosolvents degrade under green light irradiation, and o-nitrobenzyl acrylate UV photosolvents degrade sequentially under blue light irradiation. The multilayer UV photosolvent composed of Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate demonstrates spatial control over the dynamic patterning of multi-materials of UV photosolvents. When the multilayer UV photosolvents are exposed to red, green and blue light in sequence, they can achieve degradation in specific areas and respond to low-energy light. They can be used to synthesize UV ​​photosolvents that degrade rapidly and orthogonally under red, green and blue light, and can degrade UV photosolvents in complex tissues with a depth of up to 2 cm.

[0027] 2. The polyurethane acrylate, cationic curing base resin and epoxy acrylate of the present invention are used as monomers to make UV adhesive, which has high surface hardness and good chemical resistance, improves the toughness of the resin, and has flexibility, wear resistance, aging resistance, high tear strength and good weather resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a flow chart of the present invention;

[0029] Figure 2 is a red light photolysis efficiency curve diagram of the present invention;

[0030] Figure 3 This is a green light photolysis efficiency curve diagram of the present invention;

[0031] Figure 4 This is a blue light photolysis efficiency curve of the present invention. DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Embodiment 1

[0034] A UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators comprises the following steps:

[0035] Step 1: Raw material preparation

[0036] S1. Weigh 20-40 parts of polyurethane acrylate, 18-35 parts of cationic curing base resin, 12-24 parts of epoxy acrylate, 10-18 parts of Rubiq, 10-18 parts of bis-ruthenium pyridine, 10-18 parts of o-nitrobenzyl acrylate, 3-6 parts of diluent, 2-5 parts of photoinitiator, 1-3 parts of stabilizer, 1-2 parts of leveling agent, 1-2 parts of defoamer, 2-3 parts of plasticizer and 1-2 parts of coupling agent by weight;

[0037] Step 2: Material dispersion

[0038] The weighed polyurethane acrylate, cationic curing base resin, epoxy acrylate, Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate were added into the mixer in sequence, the stirring time was set to 5-10 minutes, the stirring temperature was set to 30-48° C., and the mixture A was obtained after sufficient stirring;

[0039] Step 3: Reaction Mixing

[0040] The mixture A is fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent are poured into the reactor in sequence, the reactor is closed, the reaction time is set to 40-60 min, the reaction temperature is set to 60-80°C, and after the reaction is completed, it is cooled to room temperature to obtain glue solution A;

[0041] Step 4: Filter

[0042] The glue solution A is sent to the filter for filtration 2-3 times, and the filter mesh number is 8000-10000 mesh;

[0043] Step 5: Filling and curing

[0044] The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet radiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 30-50 minutes.

[0045] Embodiment 1

[0046] A UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators comprises the following steps:

[0047] Step 1: Raw material preparation

[0048] S1. Weigh 20 parts of polyurethane acrylate, 18 parts of cationic curing base resin, 12 parts of epoxy acrylate, 10 parts of Rubiq, 10 parts of bis-ruthenium pyridine, 10 parts of o-nitrobenzyl acrylate, 3 parts of diluent, 2 parts of photoinitiator, 1 part of stabilizer, 1 part of leveling agent, 1 part of defoamer, 2 parts of plasticizer and 1 part of coupling agent by weight;

[0049] Step 2: Material dispersion

[0050] The weighed polyurethane acrylate, cationic curing base resin, epoxy acrylate, Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate were added into the mixer in sequence, the stirring time was set to 5-10 minutes, the stirring temperature was set to 30° C., and the mixture A was obtained after sufficient stirring;

[0051] Step 3: Reaction Mixing

[0052] The mixture A was fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent were poured into the reactor in sequence, and the reactor was closed. The reaction time was set to 40 min and the reaction temperature was set to 60°C. After the reaction was completed, the mixture was cooled to room temperature to obtain glue solution A;

[0053] Step 4: Filter

[0054] The glue solution A is sent into the filter for filtration, and the filtration is performed twice, and the filter mesh number is 8000 mesh;

[0055] Step 5: Filling and curing

[0056] The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet irradiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 30 minutes.

[0057] Embodiment 2

[0058] Embodiment 1

[0059] A UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators comprises the following steps:

[0060] Step 1: Raw material preparation

[0061] S1. Weigh, by weight, 40 parts of polyurethane acrylate, 35 parts of cationic curing base resin, 24 parts of epoxy acrylate, 18 parts of Rubiq, 18 parts of bis-ruthenium pyridine, 18 parts of o-nitrobenzyl acrylate, 6 parts of diluent, 5 parts of photoinitiator, 3 parts of stabilizer, 2 parts of leveling agent, 2 parts of defoamer, 3 parts of plasticizer and 2 parts of coupling agent;

[0062] Step 2: Material dispersion

[0063] The weighed polyurethane acrylate, cationic curing base resin, epoxy acrylate, Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate were added into the mixer in sequence, the stirring time was set to 10 min, the stirring temperature was set to 48° C., and the mixture A was obtained after sufficient stirring;

[0064] Step 3: Reaction Mixing

[0065] The mixture A was fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent were poured into the reactor in sequence, and the reactor was closed. The reaction time was set to 60 min and the reaction temperature was set to 80°C. After the reaction was completed, the mixture was cooled to room temperature to obtain glue solution A;

[0066] Step 4: Filter

[0067] The glue solution A was sent to the filter for filtration for 3 times, and the filter mesh number was 10000 mesh;

[0068] Step 5: Filling and curing

[0069] The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet irradiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 50 minutes.

[0070] Embodiment 3

[0071] Embodiment 1

[0072] A UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators comprises the following steps:

[0073] Step 1: Raw material preparation

[0074] S1. Weigh, by weight, 32 parts of polyurethane acrylate, 26 parts of cationic curing base resin, 13 parts of epoxy acrylate, 4 parts of diluent, 3 parts of photoinitiator, 2 parts of stabilizer, 2 parts of leveling agent, 1 part of defoamer, 2 parts of plasticizer and 1 part of coupling agent;

[0075] Step 2: Material dispersion

[0076] The weighed polyurethane acrylate, cationic curing base resin and epoxy acrylate were added into the mixer in sequence, the stirring time was set to 6 min, the stirring temperature was set to 32° C., and the mixture A was obtained after sufficient stirring;

[0077] Step 3: Reaction Mixing

[0078] The mixture A was fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent were poured into the reactor in sequence, and the reactor was closed. The reaction time was set to 52 min and the reaction temperature was set to 74°C. After the reaction was completed, the mixture was cooled to room temperature to obtain glue solution A.

[0079] Step 4: Filter

[0080] The glue solution A is sent to the filter for filtration 2-3 times, and the filter mesh number is 9850 mesh;

[0081] Step 5: Filling and curing

[0082] The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet irradiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 36 minutes.

[0083] The test results shown in the following table are obtained through the above examples:

[0084]

[0085] It can be seen from the table that in Example 1 and Example 2, the multilayer UV photosolvent composed of Rubiq, biruthenium pyridine and acrylate nitrate demonstrates spatial control over the dynamic patterning of UV photosolvent multi-materials. When the multilayer UV photosolvent is exposed to red, green and blue light in sequence, it can achieve degradation in specific areas and respond to low-energy light. It can be used to synthesize UV ​​photosolvents that degrade rapidly and orthogonally under red, green and blue light, and can enable the UV photosolvent to degrade in complex tissues at a depth of up to 2 cm.

[0086] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0087] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A UV photodisintegrator preparation method based on the synergistic effect of natural polymers and photoinitiators, characterized in that: The steps include: Step 1: Raw material preparation S1. Weigh 20-40 parts of polyurethane acrylate, 18-35 parts of cationic curing base resin, 12-24 parts of epoxy acrylate, 10-18 parts of Rubiq, 10-18 parts of bis-ruthenium pyridine, 10-18 parts of o-nitrobenzyl acrylate, 3-6 parts of diluent, 2-5 parts of photoinitiator, 1-3 parts of stabilizer, 1-2 parts of leveling agent, 1-2 parts of defoamer, 2-3 parts of plasticizer and 1-2 parts of coupling agent by weight; Step 2: Material dispersion The weighed polyurethane acrylate, cationic curing base resin, epoxy acrylate, Rubiq, biruthenium pyridine and o-nitrobenzyl acrylate were added into the mixer in sequence, the stirring time was set to 5-10 minutes, the stirring temperature was set to 30-48° C., and the mixture A was obtained after sufficient stirring; Step 3: Reaction Mixing The mixture A is fed into a reactor, and the weighed diluent, photoinitiator, stabilizer, leveling agent, defoamer, plasticizer and coupling agent are poured into the reactor in sequence, the reactor is closed, the reaction time is set to 40-60 min, the reaction temperature is set to 60-80°C, and after the reaction is completed, it is cooled to room temperature to obtain glue solution A; Step 4: Filter The glue solution A is sent to the filter for filtration 2-3 times, and the filter mesh number is 8000-10000 mesh; Step 5: Filling and curing The filtered glue liquid A is filled into a glass container, and the filled glue liquid A is placed in an ultraviolet radiation device. The photoinitiator reaction is initiated by ultraviolet radiation, so that the glue liquid A is quickly solidified into a colloid. The irradiation time is set to 30-50 minutes.

2. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The polyurethane acrylate is prepared by reacting polyisocyanate, polyol and acrylic acid hydroxyl group.

3. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The cationic curing base resin is obtained by cationic copolymerization of various monomers such as olefin, epoxy, ketal, lactone and silicone. The cationic curing base resin can be one of 3,4-epoxycyclohexylcarboxylic acid-3 and 4-epoxycyclohexyl methyl ester.

4. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The epoxy acrylate may be one of bisphenol A epoxy resin, hexahydrophthalic acid epoxy resin, and aliphatic epoxy resin.

5. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The Rubiq is prepared by a two-step synthesis method using a ruthenium compound and is characterized by nuclear magnetic resonance and electrospray ionization mass spectrometry.

6. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The biruthenium pyridine is prepared by using a ruthenium compound in a two-step synthesis method.

7. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The o-nitrobenzyl acrylate was characterized by nuclear magnetic resonance and electrospray ionization mass spectrometry, and the Rubiq, bis-ruthenium pyridine and o-nitrobenzyl acrylate were used as cross-linking agents.

8. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The diluent is an active epoxy resin diluent and one of cyclic ether, cyclic lactone, and vinyl ether monomers; the photoinitiator is one of aromatic sulfonate, iodine salt, and ferrocenium salt.

9. The method for preparing UV photodisintegrator based on the synergistic effect of natural polymer and photoinitiator according to claim 1, characterized in that: The stabilizer is one of hydroquinone, p-methoxyphenol, p-benzoquinone, 2,6-di-tert-butylcresol and phenothiazine; the leveling agent is one of a mixed solvent, silicone, polyacrylate, cellulose acetate butyrate and nitrocellulose; the defoamer is one of phosphate ester, fatty acid ester and silicone; the plasticizer is one of glycerol, propylene glycol and dibutyl phthalate; and the coupling agent is one of gamma-methacrylate propyltrimethoxysilane and gamma-aminopropyltriethoxysilane.

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