CN114752034B - Self-repairing polyurethane acrylic ester photosensitive resin and preparation method thereof - Google Patents
Self-repairing polyurethane acrylic ester photosensitive resin and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/506—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses a self-repairing polyurethane acrylate photosensitive resin and a preparation method thereof. The invention introduces reversible quadruple hydrogen bonds, and the synthesized polyurethane-based resin has good viscoelasticity shape memory effect at room temperature, realizes effective self-perception of damaged parts when the material is damaged, realizes self-repair without external intervention, and has better ultraviolet aging resistance and yellowing resistance.
Description
Technical Field
The invention belongs to the field of photosensitive resin, and particularly relates to photo-thermal dual-cured self-repairing polyurethane acrylate photosensitive resin and a preparation method thereof.
Background
The photosensitive resin is a high-performance resin mainly composed of an oligomer, a reactive diluent and a photoinitiator, and has important application value in different fields of coating, adhesive, printing ink, microelectronics, dental composite materials, 3D printing and the like due to the excellent performance and unique use conditions. The photosensitive resin is cured by using ultraviolet light to initiate the liquid material with chemical activity to quickly crosslink and polymerize into a solid material, and the curing speed is high, the energy utilization rate is high, the organic Volatile (VOC) is less, and the environment is friendly.
The resin product is inevitably damaged and cracked after long-term use in an external complex environment, if the resin product cannot be timely and accurately repaired, the defects not only can lead to failure of the product and even catastrophic consequences, so that the preparation of the resin material with the self-repairing function can avoid further development of damage, and is an effective way for solving the problems. Self-healing materials refer to materials that recover performance by releasing a healing agent or self-molecule to move/react when stimulated under certain conditions to repair the damaged area. At present, in the reported self-repairing resin, repairing is carried out by adding a repairing agent, and the repairing process is fast, effective and spontaneous, but the repairing times are limited; while the repeated repair can be realized theoretically by constructing a material which is repaired by dynamic reversible covalent bonds and non-covalent bonds or by utilizing a shape memory effect, the method mostly needs to realize self-repair under the condition of manual intervention (heating, manual contact and the like), and the generation of a plurality of micro-damages is not easy to perceive, so that the material cannot be repaired in time in the initial stage of material failure.
Polyurethane acrylate is an important type of photosensitive resin, but the existing photosensitive resin system has the following problems: on the one hand, because the ultraviolet curing system is initiated by ultraviolet light, the ultraviolet curing system is mainly used for two-dimensional thin surfaces and light-colored coatings, and in the occasions of complex three-dimensional surfaces, thicker systems, colored coatings and the like, the filler can not reach the inside of a base material due to the fact that a non-illumination area or ultraviolet light can not penetrate, and the photosensitive resin can not be completely cured, so that the repairing process is greatly limited, and the effect is not ideal; on the other hand, for the intrinsic photosensitive resin with the self-repairing function, the intrinsic photosensitive resin can only repair microcracks, or the repairing process needs manual intervention, such as heating or manual contact, so that the repairing efficiency is low, the repairing process is troublesome, and the waste of manpower and material resources is caused.
Disclosure of Invention
Aiming at the defects, the invention prepares the self-repairing polyurethane acrylate photosensitive resin and the preparation method thereof, which have important significance for widening the application range of the photosensitive resin.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows.
A process for preparing the photosensitive resin of self-repairing polyurethane acrylate includes such steps as reaction of polytetrahydrofuran diol and isophorone diisocyanate to obtain prepolymer, reaction with allopyrimidinone to obtain prepolymer, introducing hydroxyethyl methacrylate to obtain the double-bond blocked polyurethane acrylate polymerizing solution, adding photo-initiator and thermal initiator, and photo-thermal dual-solidifying.
The method specifically comprises the following steps of:
preheating 5-10 parts of polytetrahydrofuran glycol for 1-3 hours at 100-120 ℃ under the protection of nitrogen, reducing the temperature to 70-90 ℃, sequentially adding 5-15 parts of dried dimethylformamide, 5-15 parts of isophorone diisocyanate and 0.2-0.4 part of dibutyl tin dilaurate, and mechanically stirring for 3-5 hours under the protection of nitrogen; heating to 80-100 ℃, adding 3-5 parts of allopyrimidinone, and mechanically stirring for 4-8 hours under the protection of nitrogen to obtain an-NCO end-capped prepolymer;
step two, after the temperature is reduced to 40-60 ℃, adding 10-20 parts of hydroxyethyl methacrylate, and mechanically stirring for 3-5 hours under the protection of nitrogen to obtain double-bond blocked polyurethane acrylate prepolymer;
and thirdly, placing the solution obtained in the second step in a vacuum chamber for 12-18h, evaporating the solvent, and adding 0.1-0.3 part of photoinitiator and 0.1-0.2 part of thermal initiator to obtain the self-repairing polyurethane acrylate photosensitive resin.
In the first step, isophorone diisocyanate and dimethylformamide are placed in a 4A molecular sieve in advance and dried for 24-36 hours.
In the third step, the photoinitiator is a photoinitiator TPO.
In the third step, the thermal initiator is an initiator BPO.
The self-repairing polyurethane acrylate photosensitive resin prepared by the preparation method is prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, polytetrahydrofuran glycol is used as a soft segment, isophorone diisocyanate is used as a hard segment, a reversible quadruple hydrogen bond (UPY) in ureidopyrimidinone is used as a dynamic reversible chain extender, hydroxyethyl methacrylate is introduced to obtain a double-bond-terminated polyurethane acrylate polymerization solution, the synthesized polyurethane resin has a good viscoelastic shape memory effect at room temperature, and can promote the shape recovery of damaged parts, so that the crack surface is spatially similar, and the self-repair of larger-size damage at room temperature is facilitated; the introduction of the reversible quadruple hydrogen bond (UPY) strengthens the hydrogen bond action in the polyurethane-based resin system, on one hand, the dynamic reversible characteristic and the high bonding strength of the polyurethane-based resin system enable the damaged part which is close in space to be further repaired in chemical scale, the mechanical property to be effectively recovered, the mechanical property of the repaired matrix is guaranteed, on the other hand, the UPY is added to enable isocyanate and a chain extender to be gathered in a hard segment phase through the interaction of the strong hydrogen bond, so that the microphase separation structure of a curing system becomes more obvious, and the polyurethane-based resin system is very beneficial to realizing the shape memory effect on the matrix. In the damage repair process, the material efficiently stores and releases conformational entropy energy by using the viscoelastic shape memory effect under the room temperature condition, so that the material can effectively self-sense the damaged part when damaged, and then self-repair is realized. The invention successfully prepares the resin material which can realize autonomous and repeated self-repairing of the crack with larger size without external intervention by combining the shape memory effect with the intrinsic self-repairing.
(2) The synthetic polyurethane acrylate resin disclosed by the invention selects the IPDI as an isocyanate reaction monomer, and the IPDI has stable reaction, two isocyanate groups have different reactivity which is about ten times different, so that the preparation of various prepolymers is facilitated, and the aliphatic isocyanate does not contain unsaturated bonds which are sensitive to ultraviolet rays and are easy to cause yellowing of the polymer, so that the polyurethane resin prepared from the aliphatic isocyanate has better ultraviolet ageing resistance and yellowing resistance.
(3) The product prepared by the invention can realize autonomous and repeated self-repairing of the large-size crack under the room temperature condition without external intervention, thereby saving manpower and material resources and improving repairing efficiency.
(4) In order to make up the defects in the prior art, the invention uses a dual curing system, and the system combines ultraviolet curing with other curing modes so as to realize the purpose of completely curing the matrix.
(5) The hydroxy-containing hydroxyethyl methacrylate provides active double bonds required by photosensitive resin, and residual hydroxy groups in the resin can provide good substrate wettability, so that the adhesion of the cured resin to a substrate is improved.
Drawings
FIG. 1 is a TGA curve of the product of example 1;
FIG. 2 is a stress-strain curve of the product of example 1;
FIG. 3 is a schematic diagram of the shape recovery process of the product of example 1;
FIG. 4 is a graph of a scratch repair process for a pre-scored example 1 product at room temperature;
FIG. 5 is a graph showing the effect of recovering 3 hours at room temperature after cutting the drawn sample bar.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention include, but are not limited to, the scope of the following examples.
Example 1
(1) Placing isophorone diisocyanate (IPDI) and Dimethylformamide (DMA) in a 4A molecular sieve, and drying for 36h;
(2) 8g of polytetrahydrofuran diol (PTMEG) are placed in a 250ml four-necked flask and preheated at 110℃for 3h under nitrogen protection; the temperature is reduced to 80 ℃, 5g of dried DMA, 5g of IPDI and 0.2g of dibutyl tin dilaurate are added into a four-mouth bottle in sequence, and the mixture is mechanically stirred for 3 hours under the protection of nitrogen; heating to 100 ℃, adding 3g of allopyrimidinone (UPy), and mechanically stirring for 4 hours under the protection of nitrogen to obtain the-NCO end capped prepolymer
(3) When the temperature is reduced to 40 ℃, 10g of hydroxyethyl methacrylate is added, and the mixture is mechanically stirred for 3 hours under the protection of nitrogen to obtain double-bond blocked polyurethane acrylate prepolymer;
(4) the resulting solution was placed in a vacuum chamber for 12 hours, the solvent was evaporated, and 0.2g of photoinitiator (TPO) and 0.1g of thermal initiator (BPO) were added to obtain a photo-thermal dual curable urethane acrylate resin.
FIG. 1 is a TGA curve of the product of example 1, as shown, the thermal decomposition curve is composed of two parts. The first decomposition platform corresponds to the decomposition of the soft segment phase of the product at 254-362 ℃; the second decomposition platform corresponds to the decomposition of the hard segment phase of the product, and at the temperature of 362-430 ℃, the TGA curve shows that the microphase separation inside the prepared resin is obvious in two-phase structure, and the resin has good thermal stability.
FIG. 2 is a graph of stress-strain curve of the product of example 1, showing that the breaking strength of the product reaches 3MPa and the breaking elongation exceeds 400%.
Fig. 3 is a schematic diagram of the shape recovery process of the product of example 1, wherein the product of example 1 with a well-shaped shape is fixed at a low temperature, and can be recovered to the original shape basically about 5min at room temperature.
FIG. 4 shows the scratch repair process at room temperature for the pre-scratched example 1 product, with scratches of about 50 μm substantially healed at room temperature for 1h macroscopic cracks and substantially repaired for 3h scratches.
FIG. 5 is a graph showing the effect of recovering the mechanical properties of a drawn spline at room temperature for 3 hours after cutting, wherein the mechanical properties are effectively recovered, and the marked parts in the graph are broken instead of the healed surfaces in the drawing process.
Example 2
(1) Placing isophorone diisocyanate (IPDI) and Dimethylformamide (DMA) in a 4A molecular sieve, and drying for 24 hours;
(2) 6g of polytetrahydrofuran diol (PTMEG) are placed in a 250ml four-necked flask and preheated at 100℃for 3h under the protection of nitrogen; the temperature is reduced to 80 ℃, 10g of dried DMA, 10g of IPDI and 0.2g of dibutyl tin dilaurate are added into a four-mouth bottle in sequence, and the mixture is mechanically stirred for 5 hours under the protection of nitrogen; heating to 100 ℃, adding 3g of allopyrimidinone (UPy), and mechanically stirring for 8 hours under the protection of nitrogen to obtain a prepolymer with-NCO end capping;
(3) after the temperature is reduced to 40 ℃, adding 15g of hydroxyethyl methacrylate, and mechanically stirring for 3 hours under the protection of nitrogen to obtain a double-bond blocked polyurethane acrylate prepolymer;
(4) the resulting solution was placed in a vacuum chamber for 12 hours, the solvent was evaporated, and 0.3g of photoinitiator (TPO) and 0.1g of thermal initiator (BPO) were added to obtain a photo-thermal dual curable urethane acrylate resin.
Example 3
(1) Placing isophorone diisocyanate (IPDI) and Dimethylformamide (DMA) in a 4A molecular sieve, and drying for 36h;
(2) 5g of polytetrahydrofuran diol (PTMEG) are placed in a 250ml four-necked flask and preheated at 120℃for 2h under nitrogen protection; the temperature is reduced to 70 ℃, 15g of dried DMA, 15g of IPDI and 0.4g of dibutyl tin dilaurate are added into a four-mouth bottle in sequence, and the mixture is mechanically stirred for 3 hours under the protection of nitrogen; heating to 80 ℃, adding 4g of allopyrimidinone (UPy), and mechanically stirring for 6 hours under the protection of nitrogen to obtain a prepolymer with-NCO end-capped;
(3) when the temperature is reduced to 60 ℃, 10g of hydroxyethyl methacrylate is added, and the mixture is mechanically stirred for 5 hours under the protection of nitrogen to obtain double-bond blocked polyurethane acrylate prepolymer;
(4) the resulting solution was placed in a vacuum chamber for 15 hours, the solvent was evaporated, and 0.1g of photoinitiator (TPO) and 0.2g of thermal initiator (BPO) were added to obtain a photo-thermal dual curable urethane acrylate resin.
Example 4
(1) Placing isophorone diisocyanate (IPDI) and Dimethylformamide (DMA) in a 4A molecular sieve, and drying for 30h;
(2) 5g of polytetrahydrofuran diol (PTMEG) are placed in a 250ml four-necked flask and preheated at 110℃for 2h under nitrogen protection; the temperature is reduced to 90 ℃, 10g of dried DMA, 10g of IPDI and 0.3g of dibutyl tin dilaurate are added into a four-mouth bottle in sequence, and the mixture is mechanically stirred for 4 hours under the protection of nitrogen; heating to 90 ℃, adding 5g of allopyrimidinone (UPy), and mechanically stirring for 4 hours under the protection of nitrogen to obtain a prepolymer with-NCO end-capped;
(3) after the temperature is reduced to 50 ℃, 13g of hydroxyethyl methacrylate is added, and the mixture is mechanically stirred for 4 hours under the protection of nitrogen to obtain double-bond blocked polyurethane acrylate prepolymer;
(4) the resulting solution was placed in a vacuum chamber for 18 hours, the solvent was evaporated, and 0.2g of photoinitiator (TPO) and 0.2g of thermal initiator (BPO) were added to obtain a photo-thermal dual curable urethane acrylate resin.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A preparation method of self-repairing polyurethane acrylate photosensitive resin is characterized by comprising the following steps: the preparation method comprises the following steps of firstly reacting polytetrahydrofuran glycol and isophorone diisocyanate to generate prepolymer, then reacting with allophycocyanin to generate prepolymer with-NCO end-capped, introducing hydroxyethyl methacrylate to obtain polyurethane acrylic ester polymerization solution with double-bond end-capped, adding photoinitiator and thermal initiator, and preparing self-repairing polyurethane acrylic ester photosensitive resin through photo-thermal dual curing;
the method specifically comprises the following steps of:
preheating 5-10 parts of polytetrahydrofuran glycol for 1-3 hours at 100-120 ℃ under the protection of nitrogen, reducing the temperature to 70-90 ℃, sequentially adding 5-15 parts of dried dimethylformamide, 5-15 parts of isophorone diisocyanate and 0.2-0.4 part of dibutyl tin dilaurate, and mechanically stirring for 3-5 hours under the protection of nitrogen; heating to 80-100 ℃, adding 3-5 parts of allopyrimidinone, and mechanically stirring for 4-8 hours under the protection of nitrogen to obtain an-NCO end-capped prepolymer;
step two, when the temperature is reduced to 40-60 ℃, 10-20 parts of hydroxyethyl methacrylate is added, and the mixture is mechanically stirred for 3-5 hours under the protection of nitrogen
Obtaining a double-bond-terminated polyurethane acrylate prepolymer;
and thirdly, placing the solution obtained in the second step in a vacuum chamber for 12-18h, evaporating the solvent, and adding 0.1-0.3 part of photoinitiator and 0.1-0.2 part of thermal initiator to obtain the self-repairing polyurethane acrylate photosensitive resin.
2. The method for preparing the self-repairing polyurethane acrylate photosensitive resin according to claim 1, which is characterized in that: in the first step, isophorone diisocyanate and dimethylformamide are placed in a 4A molecular sieve in advance and dried for 24-36 hours.
3. The method for preparing the self-repairing polyurethane acrylate photosensitive resin according to claim 2, which is characterized in that: in the third step, the photoinitiator is a photoinitiator TPO.
4. The method for preparing the self-repairing polyurethane acrylate photosensitive resin according to claim 3, which is characterized in that: in the third step, the thermal initiator is an initiator BPO.
5. A self-healing urethane acrylate photosensitive resin prepared by the preparation method of claim 1.
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| CN116606587A (en) * | 2023-06-27 | 2023-08-18 | 江苏必奥生物材料科技有限公司 | Biological-based coating material with adjustable photo-curing rate |
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| CN107383332B (en) * | 2017-08-22 | 2020-07-03 | 广东电网有限责任公司电力科学研究院 | Polyurethane polymer and preparation method and application thereof |
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| CN106700024A (en) * | 2015-11-15 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of UV-curable polyurethane acrylate self-repair resin |
| CN108456290A (en) * | 2017-12-28 | 2018-08-28 | 滁州金桥德克新材料有限公司 | A kind of dual cure polyurethane acrylate resin and preparation method thereof |
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