Photocurable hydrogel composition, photocurable hydrogel composite material and preparation method

Abstract

The present invention belongs to the field of 3D printing, and specifically relates to a photocurable hydrogel composition, a photocurable hydrogel composite material and a preparation method. The photocurable hydrogel composition of the present invention includes water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant; in the photocurable hydrogel composition, the content of water is 47.5-48.5wt%, the content of the water-soluble compound containing a carbon-carbon double bond is 43.7-46.6wt%, the content of the photoinitiator is 1.9-3.9wt%, the content of the dispersant is 0.3-0.7wt%, and the content of the titanium dioxide is 2.7-6.3wt%. The photocurable hydrogel composite material prepared by the present invention has excellent mechanical properties and high formaldehyde removal efficiency.

Description

Technical Field

[0001] The present invention belongs to the field of 3D printing, and in particular relates to a photocurable hydrogel composition, a photocurable hydrogel composite material and a preparation method thereof. Background Art

[0002] Indoor air pollution has become one of the five most harmful environmental factors to public health. In interior decoration and furniture manufacturing, the commonly used artificial boards contain a large amount of organic pollutants such as formaldehyde. Formaldehyde is a common harmful substance. The presence of formaldehyde exceeding a certain concentration will have a strong irritating effect on human skin and mucous membranes, and can cause selective damage to the retina. Long-term exposure to formaldehyde will cause symptoms of mental weakness such as memory loss and drowsiness, and can even cause mutations in genetic material and damage chromosomes. Therefore, the removal of formaldehyde pollution is an urgent problem that environmental workers need to solve.

[0003] In recent years, domestic and foreign methods for controlling indoor organic pollutants have mainly adopted methods such as ozone purification, activated carbon filters, molecular complexation technology, and catalytic conversion. However, most indoor air treatment technologies are not ideal for formaldehyde control, and have problems such as low efficiency, high cost, and inconvenience in use.

[0004] Ozone purification technology uses oxidation properties to remove organic pollutants, but it cannot completely oxidize them and there is a problem of secondary pollution. Activated carbon filters can adsorb organic matter, but the effect on formaldehyde removal is limited. Molecular complexation technology passes toxic gases into water, causing pollutants in the gas to react with complexing agents in the water, prompting molecules to complex and dissolve in water to achieve the purpose of air purification, but it is difficult to apply to indoor formaldehyde removal. Catalytic conversion technology can convert organic pollutants into inorganic substances. The oxidation reaction is relatively thorough and fast, and it is harmless to the human body. Nano-TiO 2 Photocatalysts have attracted the attention of many scientific researchers due to their high catalytic activity, good stability, strong oxidation ability, low cost and non-toxicity. Their application research in indoor formaldehyde pollution control is very active. Specifically, TiO 2 Photocatalysts can generate active free radicals under the excitation of ultraviolet light to decompose formaldehyde in the environment; however, the current 2 Photocatalysts are mostly sprayed in the form of coatings or films or attached to the surface of carriers such as metals, ceramics or glass fiber filters. The contact area with formaldehyde is limited, and the formaldehyde removal efficiency is low.

[0005] Therefore, it is urgent to develop a kind of efficient formaldehyde removal material. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a photocurable hydrogel composition, a photocurable hydrogel composite material and a preparation method. The photocurable hydrogel composite material of the present invention uses water, a water-soluble compound containing a carbon-carbon double bond, titanium dioxide, an initiator and a dispersant as raw materials, and uses a 3D printing photocuring molding method to manufacture a primary porous structure of the hydrogel, and then forms a secondary porous structure by baking the water in the gel, so that the titanium dioxide in the composite material is fully exposed, the contact area between formaldehyde and titanium dioxide is increased, and the formaldehyde removal efficiency is high.

[0007] Specifically, the present invention provides a photocurable hydrogel composition, which includes water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant; in the photocurable hydrogel composition, the content of water is 47.5-48.5wt%, the content of the water-soluble compound containing a carbon-carbon double bond is 43.7-46.6wt%, the content of the photoinitiator is 1.9-3.9wt%, the content of the dispersant is 0.3-0.7wt%, and the content of the titanium dioxide is 2.7-6.3wt%.

[0008] In one or more embodiments, the water-soluble compound containing a carbon-carbon double bond is selected from one or more of acrylate monomers, acrylate oligomers, and acrylamide monomers.

[0009] In one or more embodiments, the photoinitiator is diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0010] In one or more embodiments, the dispersant is selected from one or more of LeAd300, LeAd340, and LeAd348N.

[0011] In one or more embodiments, the acrylic acid ester monomer is an acrylic acid ester monomer containing a hydroxyl group and / or a carboxyl group.

[0012] In one or more embodiments, the acrylate oligomer is polyethylene glycol diacrylate and / or a water-soluble acrylate resin.

[0013] In one or more embodiments, the acrylamide-based monomer includes 4-acryloylmorpholine.

[0014] In one or more embodiments, the acrylate monomer containing a hydroxyl group and / or a carboxyl group is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

[0015] In one or more embodiments, the titanium dioxide content is 2.7-4.5 wt %.

[0016] In one or more embodiments, the titanium dioxide is spherical in shape.

[0017] In one or more embodiments, the titanium dioxide has a particle size of 10-300 nm.

[0018] The present invention provides a method for preparing the photocurable hydrogel composition of the present invention, the method comprising: uniformly mixing water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant in a batch mixing or direct mixing manner to obtain the photocurable hydrogel composition.

[0019] In one or more embodiments, the batch mixing method includes: firstly mixing water, a photoinitiator and a water-soluble compound containing a carbon-carbon double bond uniformly to obtain a hydrogel matrix, and then mixing the hydrogel matrix with titanium dioxide and a dispersant uniformly to obtain a photocurable hydrogel composition.

[0020] In one or more embodiments, the direct mixing method includes: mixing water, a photoinitiator, a water-soluble compound containing a carbon-carbon double bond, titanium dioxide and a dispersant uniformly at the same time to obtain a photocurable hydrogel composition.

[0021] The present invention provides a method for preparing a photocurable hydrogel composite material, the method comprising the following steps:

[0022] (1) using 3D modeling software to design a printing model of a photocurable hydrogel composite material, importing the file of the printing model into a photocurable printer, and performing photocurable printing on the photocurable hydrogel composition of the present invention in the photocurable printer to obtain a preliminarily cured printed sample;

[0023] (2) Cleaning and baking the preliminarily cured printed sample to obtain a dry printed sample;

[0024] (3) The dried printed sample is post-cured to obtain a photocurable hydrogel composite material.

[0025] In one or more embodiments, in step (1), the photocurable hydrogel composition is subjected to a degassing treatment before being added to the photocurable printer.

[0026] In one or more embodiments, in step (1), during photocuring printing, the light intensity is 32000-38000 μW / cm 2 .

[0027] In one or more embodiments, in step (1), during photocuring printing, the exposure time is 5000-6500 ms.

[0028] In one or more embodiments, in step (2), the baking time is 2-3 hours.

[0029] In one or more embodiments, in step (2), the baking temperature is 40-100°C.

[0030] In one or more embodiments, in step (3), during the post-curing treatment, the light intensity is 100-150 μW / cm 2 .

[0031] In one or more embodiments, in step (3), during the post-curing treatment, the exposure time is 20-25 minutes.

[0032] The invention provides a light-cured hydrogel composite material prepared by the method of the invention.

[0033] Compared with the prior art, the present invention has the following beneficial effects: 3D printing is simple and convenient, and the photocurable hydrogel composite material can form a complex primary porous structure through 3D printing, thereby increasing the specific surface area of ​​the printed sample; by baking the water in the hydrogel to form a secondary porous structure, the exposure area of ​​the photocatalyst is increased, and the interaction between light and air and TiO is improved. 2 The contact area of ​​the photocatalyst improves the efficiency of formaldehyde removal and has broad application prospects in indoor pollution control. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the photocurable hydrogel composite material printed in Example 1 of the present invention. DETAILED DESCRIPTION

[0035] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0036] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0037] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0038] In this document, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible sub-ranges and individual values ​​within the range (including integers and fractions).

[0039] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0040] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0041] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0042] The invention provides a photocurable hydrogel composition. The photocurable hydrogel composition may include water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant.

[0043] The content of water in the photocurable hydrogel composition of the present invention can be 47.5-48.5wt%, the content of the water-soluble compound containing carbon-carbon double bonds can be 43.7-46.6wt%, the content of the photoinitiator can be 1.9-3.9wt%, the content of the dispersant can be 0.3-0.7wt%, and the content of titanium dioxide can be 2.7-6.3wt%. In the present invention, the content of each component in the photocurable hydrogel composition is controlled within the above range, which is conducive to the printing and molding of the photocurable hydrogel composite material, is conducive to improving the formaldehyde removal efficiency of titanium dioxide, is conducive to reducing the amount of titanium dioxide used, and reduces costs.

[0044] In the present invention, the content of titanium dioxide can be preferably 2.7-4.5wt%. For example, controlling the titanium dioxide content within the above-mentioned preferred range is beneficial to the printing and molding of photocurable hydrogel composite materials, to improving the formaldehyde removal efficiency of titanium dioxide, to reducing the amount of titanium dioxide used, and to reducing costs.

[0045] In the present invention, the shape of titanium dioxide can be spherical. In the present invention, the particle size of titanium dioxide can be 10-300nm, preferably 50-100nm, and more preferably 50nm. In the present invention, controlling the particle size of titanium dioxide within the above preferred range is conducive to the printing and molding of the photocurable hydrogel composite material.

[0046] In the present invention, the water-soluble compound containing a carbon-carbon double bond may be one or more selected from acrylate monomers, acrylate oligomers and acrylamide monomers. The acrylate monomer may be an acrylate monomer containing a hydroxyl group and / or a carboxyl group; preferably, the acrylate monomer containing a hydroxyl group and / or a carboxyl group may be one or more selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate and hydroxypropyl methacrylate; the acrylate oligomer may be polyethylene glycol diacrylate (PEGDA) and / or water-soluble acrylate resin GENOMER 7311, and in some embodiments, the polyethylene glycol diacrylate is selected from one or more of polyethylene glycol (100) diacrylate, polyethylene glycol (600) diacrylate and polyethylene glycol (800) diacrylate; the acrylamide monomer may include 4-acryloylmorpholine (ACMO). In the present invention, the water-soluble compound containing carbon-carbon double bonds used contains polar groups such as hydroxyl, carboxyl and amino groups, which can form hydrogen bonds with water to increase its solubility in water, thereby increasing the water content of the hydrogel matrix.

[0047] In the present invention, the photoinitiator may be diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0048] In the present invention, the dispersant may be one or more selected from LeAd300, LeAd340 and LeAd348N. The dispersant of the present invention is a block polymer copolymer containing titanium dioxide affinity groups.

[0049] The invention provides a method for preparing a photocurable hydrogel composition, comprising: uniformly mixing water, a water-soluble compound containing a carbon-carbon double bond, an initiator, titanium dioxide and a dispersant in a batch mixing or direct mixing manner to obtain the photocurable hydrogel composition.

[0050] In the present invention, the batch mixing method includes: firstly mixing water, a photoinitiator and a water-soluble compound containing a carbon-carbon double bond uniformly to obtain a hydrogel matrix, and then mixing the hydrogel matrix with titanium dioxide and a dispersant uniformly to obtain a photocurable hydrogel composition.

[0051] In the present invention, the direct mixing method includes: uniformly mixing water, a photoinitiator, a water-soluble compound containing a carbon-carbon double bond, titanium dioxide and a dispersant at the same time to obtain a photocurable hydrogel composition.

[0052] The present invention provides a method for preparing a photocurable hydrogel composite material, the method comprising the following steps:

[0053] (1) Designing a printing model of a photocurable hydrogel composite material using 3D modeling software, importing the printing model file into a photocurable printer, and performing photocurable printing on the photocurable hydrogel composition in the photocurable printer to obtain a preliminarily cured printed sample;

[0054] (2) Cleaning and baking the preliminarily cured printed sample to obtain a dry printed sample;

[0055] (3) The dried printed sample is post-cured to obtain a photocurable hydrogel composite material.

[0056] In the present invention, the sample is prepared by 3D printing and photocuring, which can form a complex primary three-dimensional porous structure. After removing the water in the composite hydrogel through the aforementioned drying step, the specific surface area of ​​the sample can be further increased. 2 Compared with the film or coating prepared by traditional coating method, it has a larger contact area with formaldehyde and improves the formaldehyde removal efficiency.

[0057] In step (1), before adding the photocurable hydrogel composition to the photocurable printer, the photocurable hydrogel composition may be subjected to a degassing treatment.

[0058] In step (1), during light-curing printing, the light intensity can be 32000-38000 μW / cm 2 , for example 32000μW / cm 2 、34000μW / cm 2 、36000μW / cm 2 、38000μW / cm 2 .

[0059] In step (1), during light-curing printing, the exposure time may be 5000-6500 ms, for example, 5000 ms, 5500 ms, 6000 ms, 6500 ms.

[0060] In step (2), the baking time can be 2-3 hours, for example, 2 hours, 2.5 hours, or 3 hours.

[0061] In step (2), the baking temperature can be 40-100°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C.

[0062] In step (3), during the post-curing treatment, the light intensity can be 100-150 μW / cm 2 , for example 100 μW / cm 2 、110μW / cm 2 , 120μW / cm 2 、130μW / cm 2 , 140μW / cm 2 、150μW / cm 2 .

[0063] In step (3), during the post-curing treatment, the exposure time is 20-25 minutes, for example, 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, and 25 minutes.

[0064] The invention provides a light-cured hydrogel composite material prepared by the method of the invention.

[0065] The present invention will be described below in the form of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise stated, conventional methods, reagents and materials in the art. The raw material compounds in the examples can all be purchased through commercial routes.

[0066] In the embodiments of the present invention, the polyethylene glycol diacrylate used is of the grades of PEG100DA, PEG600DA and PEG800DA, purchased from YOUNGING.

[0067] In the embodiments of the present invention, the water-soluble acrylic resin used is GENOMER 7311, purchased from RAHN.

[0068] In the embodiments of the present invention, the dispersants used are LeAd300, LeAd340, and LeAd348N, which are purchased from Guangdong Wenli Materials Technology Co., Ltd.

[0069] Example 1

[0070] (1) Deionized water, PEG600DA, ACMO and TPO were added into a container in a mass ratio of 50:16:32:2, and stirred at 30°C and 2000 rpm for 1 h to mix evenly to obtain a hydrogel matrix;

[0071] (2) TiO 2 (50nm) and a mixture of LeAd300 (LeAd300 and TiO 2The mass ratio of TiO2 to the hydrogel matrix is ​​1:9) and the mass ratio of TiO2 to the hydrogel matrix is ​​3:97. The mixture is stirred at 25°C and 1000 rpm for 1 hour to make the mixture uniform. The photocurable hydrogel composition is obtained. 2 The dosage is 2.7wt%;

[0072] (3) performing vacuum degassing treatment on the photocurable hydrogel composition to remove bubbles in the photocurable hydrogel composition and then filling it into a medicine tank of a photocurable printer;

[0073] (4) Using 3D modeling software to design a printing model of a photocurable composite hydrogel composite material, the printing model is a three-dimensional lattice structure with a maximum pore size of 100 μm and a size of 10 mm × 10 mm × 10 mm; the printing model is imported into a photocurable printer, and the photocurable hydrogel composition in the photocurable printer is directly printed to obtain a preliminarily cured printed sample; the printing parameters are: light intensity 34000 μW / cm 2 , exposure time 6000ms, layer thickness 10μm, vibration mode 100X;

[0074] (5) The preliminarily cured printed sample was placed in alcohol for ultrasonic cleaning for 3 minutes to rinse the remaining uncured raw materials, and then dried in a centrifuge for 20 minutes; the dried printed sample was placed in an oven and baked at 80°C for 2 hours to obtain a dry printed sample;

[0075] (6) Place the dried printed sample in a UV curing oven at a light intensity of 100 μW / cm 2 The resulting film was cured for 20 min to obtain a light-cured hydrogel composite material.

[0076] Example 2

[0077] This example prepares a photocurable hydrogel composite material according to the method of Example 1, except that the TiO 2 (50nm) and a mixture of LeAd300 (LeAd300 and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​5:95. 2 The dosage is 4.5wt%.

[0078] Example 3

[0079] This example prepares a photocurable hydrogel composite material according to the method of Example 1, except that the TiO 2 (50nm) and a mixture of LeAd300 (LeAd300 and TiO 2The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​7:93. 2 The dosage is 6.3wt%.

[0080] Comparative Example 1

[0081] In this comparative example, the photocurable hydrogel composite material was prepared according to the method of Example 1, except that TiO was not added in step (2) of this comparative example. 2 and dispersant LeAd300, i.e., TiO 2 The dosage is 0wt%.

[0082] Comparative Example 2

[0083] This comparative example prepares a photocurable hydrogel composite material according to the method of Example 1, except that the TiO 2 (50nm) and a mixture of LeAd300 (LeAd300 and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​1:99. 2 The dosage is 0.9wt%.

[0084] Example 4

[0085] (1) Deionized water, ACMO, HEMA and TPO were added into a container in a mass ratio of 50:18:28:4, and stirred at 30°C and 2500 rpm for 1 h to mix evenly to obtain a hydrogel matrix;

[0086] (2) TiO 2 (50nm) and a mixture of LeAd340 (LeAd340 and TiO 2 The mass ratio of TiO2 to the hydrogel matrix is ​​1:9) and the mass ratio of TiO2 to the hydrogel matrix is ​​3:97. The mixture is stirred at 25°C and 1500 rpm for 1 hour to make the mixture uniform. The photocurable hydrogel composition is obtained. 2 The dosage is 2.7wt%;

[0087] (3) performing vacuum degassing treatment on the photocurable hydrogel composition to remove bubbles in the photocurable hydrogel composition and then filling it into a medicine tank of a photocurable printer;

[0088] (4) Using 3D modeling software to design a printing model of a photocurable composite hydrogel composite material, the printing model is a three-dimensional lattice structure with a maximum pore size of 100 μm and a size of 10 mm × 10 mm × 10 mm; the printing model is imported into a photocurable printer, and the photocurable hydrogel composition in the photocurable printer is directly printed to obtain a preliminarily cured printed sample; the printing parameters are: light intensity 36000 μW / cm 2 , exposure time 6000ms, layer thickness 10μm, vibration mode 100X;

[0089] (5) The preliminarily cured printed sample was placed in alcohol for ultrasonic cleaning for 3 minutes to rinse the remaining uncured raw materials, and then dried in a centrifuge for 20 minutes; the dried printed sample was placed in an oven and baked at 80°C for 2 hours to obtain a dry printed sample;

[0090] (6) Place the dried printed sample in a UV curing oven at a light intensity of 150 μW / cm 2 The resulting film was cured for 20 min to obtain a light-cured hydrogel composite material.

[0091] Example 5

[0092] This example prepares a light-curable hydrogel composite material according to the method of Example 4, except that in step (2) of this example, TiO 2 (50nm) and a mixture of LeAd340 (LeAd340 and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​5:95. 2 The dosage is 4.5wt%.

[0093] Example 6

[0094] This example prepares a light-curable hydrogel composite material according to the method of Example 4, except that in step (2) of this example, TiO 2 (50nm) and a mixture of LeAd340 (LeAd340 and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​7:93. 2 The dosage is 6.3wt%.

[0095] Comparative Example 3

[0096] In this comparative example, the photocurable hydrogel composite material was prepared according to the method of Example 4, except that TiO was not added in step (2) of this comparative example. 2 and dispersant LeAd340, i.e., TiO 2 The dosage is 0wt%.

[0097] Comparative Example 4

[0098] This comparative example prepares a photocurable hydrogel composite material according to the method of Example 4, except that in step (2) of this comparative example, TiO 2 (50nm) and a mixture of LeAd340 (LeAd340 and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​1:99. 2 The dosage is 0.9wt%.

[0099] Example 7

[0100] (1) Deionized water, PEG800DA, GENOMER 7311 and BAPO were added into a container in a mass ratio of 50:25:23:2, and stirred at 40°C and 3000 rpm for 1 h to mix evenly to obtain a hydrogel matrix;

[0101] (2) TiO 2 (50nm) and a mixture of LeAd348N (LeAd348 and TiO 2 The mass ratio of TiO2 to the hydrogel matrix is ​​1:9) and the mass ratio of TiO2 to the hydrogel matrix is ​​3:97. The mixture is stirred at 35°C and 2500 rpm for 1 hour to make the mixture uniform. The photocurable hydrogel composition is obtained. 2 The dosage is 2.7wt%;

[0102] (3) performing vacuum degassing treatment on the photocurable hydrogel composition to remove bubbles in the photocurable hydrogel composition and then filling it into a medicine tank of a photocurable printer;

[0103] (4) Using 3D modeling software to design a printing model of a photocurable composite hydrogel composite material, the printing model is a three-dimensional lattice structure with a maximum pore size of 100 μm and a size of 10 mm × 10 mm × 10 mm; the printing model is imported into a photocurable printer, and the photocurable hydrogel composition in the photocurable printer is directly printed to obtain a preliminarily cured printed sample; the printing parameters are: light intensity 36000 μW / cm 2 , exposure time 6500ms, layer thickness 10μm, vibration mode 100X;

[0104] (5) The preliminarily cured printed sample was placed in alcohol for ultrasonic cleaning for 3 minutes to rinse the remaining uncured raw materials, and then dried in a centrifuge for 20 minutes; the dried printed sample was placed in an oven and baked at 80°C for 2 hours to obtain a dry printed sample;

[0105] (6) Place the dried printed sample in a UV curing oven at a light intensity of 150 μW / cm 2 The film was cured for 25 min to obtain a light-cured hydrogel composite material.

[0106] Example 8

[0107] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 7, except that in step (2) of this embodiment, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​5:95. 2 The dosage is 4.5wt%.

[0108] Example 9

[0109] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 7, except that in step (2) of this embodiment, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​7:93. 2 The dosage is 6.3wt%.

[0110] Comparative Example 5

[0111] This comparative example prepares a photocurable hydrogel composite material according to the method of Example 7, except that TiO is not added in step (2) of this comparative example. 2 and dispersant LeAd348N, i.e., TiO 2 The dosage is 0wt%.

[0112] Comparative Example 6

[0113] This comparative example prepares a photocurable hydrogel composite material according to the method of Example 7, except that in step (2) of this comparative example, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​1:99. 2 The dosage is 0.9wt%.

[0114] Example 10

[0115] (1) Deionized water, PEG100DA, GENOMER 7311, TPO and BAPO were added into a container in a mass ratio of 50:15:33:2:2, and stirred at 40°C and 3000 rpm for 1 h to mix evenly to obtain a hydrogel matrix;

[0116] (2) TiO 2 (50nm) and a mixture of LeAd348N (LeAd348 and TiO 2 The mass ratio of TiO2 to the hydrogel matrix is ​​1:9) and the mass ratio of TiO2 to the hydrogel matrix is ​​3:97. The mixture is stirred at 35°C and 2500 rpm for 1 hour to make the mixture uniform. The photocurable hydrogel composition is obtained. 2 The dosage is 2.7wt%;

[0117] (3) performing vacuum degassing treatment on the photocurable hydrogel composition to remove bubbles in the photocurable hydrogel composition and then filling it into a medicine tank of a photocurable printer;

[0118] (4) Using 3D modeling software to design a printing model of a photocurable composite hydrogel composite material, the printing model is a three-dimensional lattice structure with a maximum pore size of 100 μm and a size of 10 mm × 10 mm × 10 mm; the printing model is imported into a photocurable printer, and the photocurable hydrogel composition in the photocurable printer is directly printed to obtain a preliminarily cured printed sample; the printing parameters are: light intensity 36000 μW / cm 2 , exposure time 6500ms, layer thickness 10μm, vibration mode 100X;

[0119] (5) The preliminarily cured printed sample was placed in alcohol for ultrasonic cleaning for 3 minutes to rinse the remaining uncured raw materials, and then dried in a centrifuge for 20 minutes; the dried printed sample was placed in an oven and baked at 80°C for 2 hours to obtain a dry printed sample;

[0120] (6) Place the dried printed sample in a UV curing oven at a light intensity of 150 μW / cm 2 The film was cured for 25 min to obtain a light-cured hydrogel composite material.

[0121] Embodiment 11

[0122] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 10, except that in step (2) of this embodiment, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​5:95. 2 The dosage is 4.5wt%.

[0123] Example 12

[0124] This example prepares a light-curable hydrogel composite material according to the method of Example 10, except that in step (2) of this example, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​7:93. 2 The dosage is 6.3wt%.

[0125] Comparative Example 7

[0126] In this comparative example, the photocurable hydrogel composite material was prepared according to the method of Example 10, except that TiO was not added in step (2) of this comparative example. 2 and dispersant LeAd348N, i.e., TiO 2 The dosage is 0wt%.

[0127] Comparative Example 8

[0128] This comparative example prepares a photocurable hydrogel composite material according to the method of Example 10, except that in step (2) of this comparative example, TiO 2 (50nm) and a mixture of LeAd348N (LeAd348N and TiO 2 The mass ratio of TiO in the photocurable hydrogel composition is 1:9) and the mass ratio of the hydrogel matrix is ​​1:99. 2 The dosage is 0.9wt%.

[0129] Example 13

[0130] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 1, except that in step (2) of this embodiment, TiO 2 The particle size is 10nm.

[0131] Embodiment 14

[0132] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 1, except that in step (2) of this embodiment, TiO 2 The particle size is 100nm.

[0133] Embodiment 15

[0134] This embodiment prepares a light-curable hydrogel composite material according to the method of embodiment 1, except that in step (2) of this embodiment, TiO 2 The particle size is 300nm.

[0135] Comparative Example 9

[0136] In this embodiment, the photocurable hydrogel composite material is prepared according to the method of embodiment 1, except that no dispersant is added in step (2) of this embodiment.

[0137] Comparative Example 10

[0138] In this example, the photocurable hydrogel composite material was prepared according to the method of Example 1, except that in this example, PEG600DA and ACMO in step (1) of Example 1 were replaced with epoxy resin (UVR6110) of equal mass.

[0139] Comparative Example 11

[0140] This embodiment prepares the photocurable hydrogel composite material according to the method of embodiment 1, except that the sample initially cured in step (4) of this embodiment is formed by pouring the same mass of the hydrogel composite material into a glass dish and heating it under a light intensity of 34000 μW / cm 2 , and cured for 6000ms under ultraviolet light with a wavelength of 405nm to obtain a preliminarily cured hydrogel sheet.

[0141] Test Example 1

[0142] Compression strength test: According to GB / T 1041-2008, a universal electronic testing machine was used to perform a compression strength test on the photocurable hydrogel composite materials prepared in Examples 1-15 and Comparative Examples 1-10. The test results are shown in Table 1.

[0143] Test Example 2

[0144] Formaldehyde degradation performance test: Formaldehyde gas is output by heating the formaldehyde aqueous solution in a water bath and sent into the reactor. When the formaldehyde concentration reaches 1mg / m 3 The aeration was stopped and the reactor was irradiated with a 405 nm ultraviolet lamp to an initial formaldehyde concentration of 1 mg / m 3 The formaldehyde degradation experiment was started. At 0 min, the materials of Examples 1-15 and Comparative Examples 1-11 were placed in the reactor. The real-time formaldehyde concentration in the reactor was tested using a formaldehyde meter. The real-time formaldehyde concentration was recorded every 5 min and the real-time formaldehyde concentration was recorded for the last time at 30 min. The formaldehyde residual rate = real-time formaldehyde concentration / initial formaldehyde concentration. The test results of the formaldehyde degradation performance are shown in Table 2.

[0145] Table 1: Compressive strength of photocurable hydrogel composites prepared in Examples 1-15 and Comparative Examples 1-10

[0146]

[0147] Table 2: Formaldehyde degradation performance of materials prepared in Examples 1-15 and Comparative Examples 1-11

[0148]

[0149] It can be seen from Table 1 and Table 2 that compared with the TiO 2 The light-cured hydrogel composite material prepared by the embodiment 1, embodiment 2 and embodiment 3 has TiO 2 The prepared photocurable hydrogel composites have higher compressive strength and better formaldehyde degradation performance, which indicates that the TiO 2 By adjusting the content within the protection scope of the present invention, a material with better mechanical properties and more efficient formaldehyde removal can be obtained.

[0150] It can be seen from Tables 1 and 2 that, compared with the photocurable hydrogel composite material prepared by the photosensitive resin in Comparative Example 10, the photocurable hydrogel composite material prepared by the photosensitive resin in Example 1 has higher compressive strength and more excellent formaldehyde degradation performance, which shows that using the photosensitive resin of the present invention as a raw material, a material with better mechanical properties and more efficient formaldehyde removal can be obtained.

[0151] It can be seen from Table 2 that compared with the hydrogel sheet prepared by ordinary photocuring in Comparative Example 11, the photocurable hydrogel composite material prepared by 3D photocuring printing in Example 1 has better formaldehyde removal performance, which indicates that the photocurable hydrogel composite material prepared by the 3D photocuring printing method of the present invention is more efficient in removing formaldehyde.

[0152] In summary, the present invention simultaneously uses a specific TiO 2 The light-curable hydrogel composition with a specific photosensitive resin and 3D light-curing printing can produce a material with excellent mechanical properties and high formaldehyde removal efficiency. 2 There is a synergistic effect between the content, the choice of photosensitive resin and 3D light-curing printing, and none of them can be missing.

Claims

1. A method for preparing a photocurable hydrogel composite material, characterized in that: The method comprises the following steps: (1) Designing a printing model of a photocurable hydrogel composite material using 3D modeling software, importing the printing model file into a photocurable printer, and performing photocurable printing on the photocurable hydrogel composition in the photocurable printer to obtain a preliminarily cured printed sample; (2) Cleaning and baking the preliminarily cured printed sample to obtain a dry printed sample; (3) performing post-curing treatment on the dried printed sample to obtain a light-cured hydrogel composite material; The photocurable hydrogel composition comprises water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant; in the photocurable hydrogel composition, the content of water is 47.5-48.5wt%, the content of the water-soluble compound containing a carbon-carbon double bond is 43.7-46.6wt%, the content of the photoinitiator is 1.9-3.9wt%, the content of the dispersant is 0.3-0.7wt%, and the content of the titanium dioxide is 2.7-6.3wt%; The water-soluble compound containing carbon-carbon double bonds is selected from one or more of acrylate monomers, acrylate oligomers and acrylamide monomers.

2. The method according to claim 1, characterized in that The photoinitiator is diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide and / or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and / or The dispersant is selected from one or more of LeAd300, LeAd340 and LeAd348N.

3. The method according to claim 2, characterized in that The photocurable hydrogel composition has one or more of the following characteristics: The acrylic acid ester monomer is an acrylic acid ester monomer containing a hydroxyl group and / or a carboxyl group; The acrylic ester oligomer is a water-soluble acrylic ester resin; The acrylamide monomer includes 4-acryloylmorpholine.

4. The method according to claim 3, characterized in that The hydroxyl and / or carboxyl-containing acrylic acid ester monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; and / or The water-soluble acrylate resin is polyethylene glycol diacrylate.

5. The method according to claim 1, characterized in that The photocurable hydrogel composition has one or more of the following characteristics: The content of titanium dioxide is 2.7-4.5wt%; The titanium dioxide is spherical in shape; The particle size of the titanium dioxide is 10-300 nm.

6. The method according to claim 1, characterized in that The method further comprises: uniformly mixing water, a water-soluble compound containing a carbon-carbon double bond, a photoinitiator, titanium dioxide and a dispersant in a batch mixing or direct mixing manner to obtain a light-curable hydrogel composition.

7. The method according to claim 6, characterized in that The batch mixing method includes: firstly mixing water, a photoinitiator and a water-soluble compound containing a carbon-carbon double bond uniformly to obtain a hydrogel matrix, and then mixing the hydrogel matrix with titanium dioxide and a dispersant uniformly to obtain a photocurable hydrogel composition; or The direct mixing method includes: uniformly mixing water, a photoinitiator, a water-soluble compound containing a carbon-carbon double bond, titanium dioxide and a dispersant at the same time to obtain a photocurable hydrogel composition.

8. The method according to claim 1, characterized in that The method has one or more of the following features: In step (1), before adding the photocurable hydrogel composition to the photocurable printer, the photocurable hydrogel composition is subjected to a degassing treatment; In step (1), during light-curing printing, the light intensity is 32000-38000 μW / cm 2 ; In step (1), during light-curing printing, the exposure time is 5000-6500ms; In step (2), the baking time is 2-3 hours; In step (2), the baking temperature is 40-100°C; In step (3), during the post-curing treatment, the light intensity is 100-150 μW / cm 2 ; In step (3), during the post-curing treatment, the exposure time is 20-25 minutes.

9. A photocurable hydrogel composite material prepared by the method according to any one of claims 1 to 8.

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