CN109180961B - Laser response P (AM-co-St) @ Bi2O3Preparation method and application of composite hydrogel - Google Patents

Laser response P (AM-co-St) @ Bi2O3Preparation method and application of composite hydrogel Download PDF

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CN109180961B
CN109180961B CN201810800065.2A CN201810800065A CN109180961B CN 109180961 B CN109180961 B CN 109180961B CN 201810800065 A CN201810800065 A CN 201810800065A CN 109180961 B CN109180961 B CN 109180961B
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曹峥
陈玉园
李丹
张�成
成骏峰
刘春林
吴盾
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Changzhou University
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Abstract

The invention belongs to the field of preparation of polymer hydrogel and laser marking materials, and particularly relates to laser-responsive P (AM-co-St) @ Bi2O3A preparation method and application of the composite hydrogel. The hydrogel is a high polymer material with a three-dimensional network structure and good hydrophilicity. The invention firstly utilizes 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA) to Bi2O3Modifying the surface of the powder, introducing double bonds, modifying the powder by taking acrylamide (AAm) as a main monomer and adding styrene (St) with double bonds to prepare P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. And carrying out laser response test on the prepared hydrogel. P (AM-co-St) @ Bi of this particular laser response2O3The composite hydrogel has important significance for the development of the laser marking fields of permanent marking, product anti-counterfeiting, tracking of important parts and the like.

Description

Laser response P (AM-co-St) @ Bi2O3Preparation method and application of composite hydrogel
Technical Field
The invention belongs to the field of preparation of polymer hydrogel and laser marking materials, and particularly relates to laser-responsive P (AM-co-St) @ Bi2O3A preparation method and application of the composite hydrogel.
Background
The hydrogel is a high polymer material with a three-dimensional network structure and good hydrophilicity. In recent years, polyacrylamide hydrogels have important applications in many fields due to their excellent water absorption properties and tissue equivalence. For example: can be used for removing heavy metal ions in industrial wastewater, simulating and constructing equivalent organism tissues, and being widely applied in daily life. The polyacrylamide hydrogel is further functionalized, and the performance and the application range of the polyacrylamide hydrogel can be improved.
Hydrogel is not much studied in the field of laser marking, and bismuth trioxide (Bi)2O3) Is an inorganic particle with laser response, and can be added into the preparation of hydrogel to synthesize the hydrogel with laser response. Bismuth oxide (Bi)2O3) Is a yellow powder. It has high refractive index and dielectric constant, optically nonlinear and ultra-fast response, and significant photoconductivity and photoluminescence. These unique characteristics make Bi2O3Suitable for a number of applications such as heterogeneous catalysts, sensors, electronics, optical coatings, lasers and glass manufacturing. The comprehensive performance of the hydrogel is also improved while the laser response effect of the hydrogel is researched. Styrene (St) is a commonly used polymer-modified material that can improve the chemical stability of the material.
The patent CN102617837B discloses a PET fast crystallization polyester chip capable of being marked by laser and a preparation method thereof, raw materials of the method contain PET polyester, a laser marking aid and a crystallization nucleating agent, the laser marking aid is selected from at least one of titanium dioxide, Sn/Sb mixed oxide or Sn/Ln mixed oxide, but the preparation process is complicated and is not suitable for large-scale popularization and production. Patent CN101243137B discloses a polyamide resin composition which retains the inherent characteristics of polyamide resin such as moldability, mechanical properties, thermal stability, heat resistance and electrical characteristics, and is excellent in flame retardancy and laser markability, and a resin molded article for laser marking obtained by molding the same, but the cost of this method is not easily controlled and is not environmentally friendly. Therefore, it is necessary to develop a laser responsive material that is easy to handle, low in cost, and environmentally friendly. Laser response type P (AM-co-St) @ Bi2O3The composite hydrogel has the characteristics of ideal laser effect, low cost, simple and convenient operation and environmental protection, and is suitable for permanent magnetThe development of the laser marking field such as long-time marking, product anti-counterfeiting, tracking of important parts and the like has important significance.
Disclosure of Invention
The invention aims to provide P (AM-co-St) @ Bi with simple preparation method, ideal laser response effect and good comprehensive performance2O3A preparation method of composite hydrogel, which aims to solve the problems in the background technology.
The invention firstly utilizes 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA) to Bi2O3Modifying the surface of the powder, introducing double bonds, modifying the powder by taking acrylamide (AAm) as a main monomer and adding styrene (St) with double bonds to prepare P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. Wherein AAm is an environment responsive molecule, Bi2O3Is an inorganic particle with laser response, and St is a common polymer modified material, which can improve the chemical stability of the material.
The invention provides a photoresponse P (AM-co-St) @ Bi2O3The preparation method of the composite hydrogel comprises the following specific processes:
step (1): 40mL of solvent was weighed into a 250mL beaker, and bismuth trioxide (Bi) was added2O3) Stirring uniformly, adding 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA), raising the temperature of an oil bath to 70 ℃, reacting for 2 hours, collecting a product after reaction, placing the product in a vacuum oven for drying at 60 ℃, and grinding after drying to obtain the modified Bi with the double bond at the tail end2O3Particles.
Step (2): acrylamide (AAm) is taken as a main monomer, dissolved in a solvent, added with styrene (St) with double bonds for modification, and then added with modified Bi with double bonds at the tail end in the step (1)2O3Preparing P (AM-co-St) @ Bi by free radical polymerization with addition of accelerator, crosslinking agent and initiator2O3Compounding the hydrogel, purifying the prepared composite hydrogel, changing the purified solution every 8 hours, and purifying for 24 hours. The acrylamide (AAm) monomer has the following structural formula:
Figure BDA0001736883860000031
the structural formula of styrene (St) is as follows:
Figure BDA0001736883860000032
the structural formula of the 3- (methacryloyloxy) propyltrimethoxysilane (TMSPMA) is as follows:
Figure BDA0001736883860000033
the laser response P (AM-co-St) @ Bi2O3The preparation method of the composite hydrogel is characterized by comprising the following steps: TMSPMA and Bi in step (1)2O3The mass ratio of (1): 5.
the laser response P (AM-co-St) @ Bi2O3The preparation method of the composite hydrogel is characterized by comprising the following steps: in the step (2), N, N, N ', N' -Tetramethylethylenediamine (TMEDA) is used as an accelerator; n, N' -Methylene Bisacrylamide (MBA) is taken as a cross-linking agent; potassium persulfate (K)2S2O8) As initiator, added AAm, St, modified Bi2O3、TMEDA、MBA、K2S2O8The mass ratio of (A) to (B) is 50: 1-3: 0-3: 1-2: 1-3, the polymerization temperature is 25 ℃, and the polymerization time is 6-8 h.
In the step (1), the solvent is deionized water; in the step (2), the solvent is N, N-Dimethylformamide (DMF) or deionized water, and the purified solution is deionized water.
In the invention, a semiconductor laser marking machine is adopted to add unmodified Bi2O3P (AM-co-St) hydrogel of (g), P (AM-co-St) @ Bi2O3And respectively carrying out laser response tests on the composite hydrogel, and observing the optimal conditions of the laser response performance of the composite hydrogel. Laser current intensity of 1When the dosage is 6A, the effect is more ideal.
In the present invention, Bi is modified by adding TMSPMA2O3Composite particles and St, the inside of the hydrogel is a porous regular structure, so that the compression performance of the hydrogel is improved, and modified Bi is added2O3The compression property of the composite hydrogel of the particles is that modified Bi is not added2O32-3 times of the P (AM-co-St) hydrogel. Meanwhile, P (AM-co-St) hydrogel and P (AM-co-St) @ Bi2O3The contact angle of the composite hydrogel and water is between 30 degrees and 40 degrees, and the composite hydrogel has good hydrophilicity.
The invention has the beneficial effects that:
the invention synthesizes the laser response P (AM-co-St) @ Bi without complex preparation steps by the method2O3And (3) compounding the hydrogel. Compared with the Bi which is not added with modification2O3The modified Bi is added into the P (AM-co-St) hydrogel2O3The laser marking effect of the composite hydrogel is obviously improved. By adding modified Bi2O3Composite particles and St, the inside of the hydrogel is a porous regular structure, so that the compression performance of the hydrogel is improved, and PS @ Bi is added2O3The compression property of the composite hydrogel of the particles is that modified Bi is not added2O32-3 times of the P (AM-co-St) hydrogel. Meanwhile, P (AM-co-St) hydrogel, P (AM-co-St) @ Bi2O3The contact angle of the composite hydrogel and water is between 30 degrees and 40 degrees, and the composite hydrogel has good hydrophilicity.
The invention utilizes the addition of TMSPMA modified Bi in hydrogel2O3Composite particles of Bi2O3The particles have double bonds at the ends, and then react with St and AAm with double bonds, the double bonds are opened by free radical initiated polymerization, so that the modified Bi2O3The particles, St and AAm can be connected together to form a complex network structure, and the composite hydrogel with ideal laser effect and good comprehensive performance is prepared. Meanwhile, in practical use, the method is an effective method suitable for being directly used for laser marking, has the advantages of simple operation, low cost and high efficiency, andthe development of the laser marking fields such as permanent marking, product anti-counterfeiting, tracking of important parts and the like has important significance.
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FIG. 1 is P (AM-co-St) @ Bi prepared in examples 1-42O3Composite hydrogel pictures (Bi modified from left to right)2O3The mass contents are 0, 1%, 2% and 3%) in sequence.
FIG. 2 is P (AM-co-St) @ Bi prepared in examples 1-42O3Picture after laser marking of composite hydrogel (Bi modified from left to right)2O3The mass contents are 0, 1%, 2% and 3%) in sequence.
FIG. 3 shows examples 1 to 4 using Bi modified differently2O3Stress-strain curve of P (AM-co-St) @ Bi2O3 composite hydrogel in mass content.
FIG. 4 is P (AM-co-St) @ Bi2O3Surface map of composite hydrogel after laser response.
FIG. 5 is P (AM-co-St) @ Bi2O3Hole pattern of composite hydrogel laser response area.
FIG. 6 is P (AM-co-St) @ Bi2O3The structure diagram of the inner part of the hole after the laser response of the composite hydrogel.
Detailed Description
The present invention is further described in detail below with reference to examples, the formulations of which are shown in Table 1.
Table 1 recipe of raw materials added in each example
Figure BDA0001736883860000051
Example 1
Weighing AAm 6g according to the formula in Table 1, dissolving in 15mL DMF, adding 0.15mL TMEDA as accelerator, ultrasonic vibrating for 2min, adding 0.2g St and 0.12g MBA, and finally adding 0.24g K2S2O8And reacting for 6h at 25 ℃ to obtain the P (AM-co-St) hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
And (3) directly carrying out laser response test on the P (AM-co-St) hydrogel by using a semiconductor laser marking machine, and observing the optimal condition of the laser response performance.
Example 2
According to the formulation shown in Table 1, AAm 6g was weighed, dissolved in 15mL of DMF, 0.15mL of TMEDA was added as an accelerator, and 0.06g of modified Bi was added2O3After ultrasonic oscillation for 2min, 0.2g St and 0.12g MBA were added, and finally 0.24g K was added2S2O8Reacting at 25 deg.C for 7h to obtain P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
The modified Bi2O3The preparation method comprises the following steps: 40mL of deionized water was weighed into a 250mL beaker, and 1g of bismuth trioxide (Bi) was added2O3) Stirring uniformly, adding 0.2g of 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA), putting into an oil bath pot, raising the temperature of the oil bath to 70 ℃, and reacting for 2h to obtain the modified Bi with the double bond at the tail end2O3Particles.
Using semiconductor laser marking machine to mark P (AM-co-St) @ Bi2O3The composite hydrogel is directly subjected to a laser response test, and the optimal condition of the laser response performance is observed.
Example 3
Weighing AAm 6g according to the formula in Table 1, dissolving in 15mL deionized water, adding 0.15mL TMEDA as accelerator, adding 0.12g modified Bi2O3After ultrasonic oscillation for 2min, 0.2g St and 0.12g MBA were added, and finally 0.24g K was added2S2O8Reacting at 25 deg.C for 6h to obtain P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
The modified Bi2O3The preparation method comprises the following steps: 40mL of deionized water was weighed into a 250mL beaker, and 1g of bismuth trioxide (Bi) was added2O3) Stirring uniformly, adding 0.2g of 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA), putting into an oil bath pot, raising the temperature of the oil bath to 70 ℃, and reacting for 2h to obtain modified Bi with a double bond at the tail end2O3Particles.
Using semiconductor laser marking machine to mark P (AM-co-St) @ Bi2O3The composite hydrogel is directly subjected to a laser response test, and the optimal condition of the laser response performance is observed.
Example 4
According to the formulation shown in Table 1, AAm 6g was weighed, dissolved in 15mL of DMF, 0.15mL of TMEDA was added as an accelerator, and 0.18g of modified Bi was added2O3After ultrasonic oscillation for 2min, 0.2g St and 0.12g MBA were added, and finally 0.24g K was added2S2O8Reacting at 25 deg.C for 8h to obtain P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
The modified Bi2O3The preparation method comprises the following steps: 40mL of deionized water was weighed into a 250mL beaker, and 1g of bismuth trioxide (Bi) was added2O3) Stirring uniformly, adding 0.2g of 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA), putting into an oil bath pot, raising the temperature of the oil bath to 70 ℃, and reacting for 2h to obtain the modified Bi with the double bond at the tail end2O3Particles.
Using semiconductor laser marking machine to mark P (AM-co-St) @ Bi2O3The composite hydrogel is directly subjected to a laser response test, and the optimal condition of the laser response performance is observed.
Comparative example 1
Weighing AAm 6g, dissolving in 15mL deionized water, adding 0.15mL TMEDA as promoter, adding 0.12g unmodified Bi2O3Ultrasonic vibration for 2min, adding 0.12g of MBA, and adding 0.24g K2S2O8. Reacting for 6h at 25 ℃ to obtain PAM @ Bi2O3And (3) compounding the hydrogel. Then purifying the prepared hydrogel by using deionized water, and replacing one hydrogel at intervals of 8hAnd purifying by deionized water for 24 hours. Using semiconductor laser marking machine to directly make laser response test and observe optimum condition of its laser response property
Comparative example 2
Weighing AAm 6g, dissolving in 15mL DMF, adding 0.15mL TMEDA as promoter, adding 0.12g unmodified Bi2O3After ultrasonic oscillation for 2min, 0.2g St and 0.12g MBA were added, and finally 0.24g K was added2S2O8Reacting at 25 deg.C for 6h to obtain P (AM-co-St) @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours. Using semiconductor laser marking machine to directly make laser response test and observe optimum condition of its laser response property
Comparative example 3
Firstly, Polystyrene (PS) is physically coated with Bi2O3Obtaining PS @ Bi2O3Weighing AAm 6g, dissolving in 15mL DMF, adding 0.15mL TMEDA as promoter, adding 0.12g PS @ Bi2O3Adding 0.12g of MBA after ultrasonic oscillation for 2min, and finally adding 0.24g K2S2O8Reacting for 7 hours at the temperature of 25 ℃ to obtain PAM/PS @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
Comparative example 4
Weighing AAm 6g, dissolving in 15mL DMF, adding 0.15mL TMEDA as promoter, adding 0.2g St, ultrasonic oscillating for 2min, adding 0.24g K2S2O8Reacting at 60 ℃ for 8h to obtain a styrene/polyacrylamide copolymer, and adding 0.12g of unmodified Bi2O30.12g of MBA, reacting for 8h at 25 ℃ to obtain PAM/PS @ Bi2O3And (3) compounding the hydrogel. And then purifying the prepared hydrogel by using deionized water, replacing the deionized water every 8 hours, and purifying for 24 hours.
And (3) directly carrying out laser response test on the prepared composite hydrogel by adopting a semiconductor laser marking machine, and observing the optimal condition of the laser response performance.
P (AM-co-St) hydrogel and P (AM-co-St) @ Bi prepared in examples 1 to 42O3The composite hydrogel was subjected to hydrophilicity measurement to obtain physical parameters as shown in Table 2.
TABLE 2P (AM-co-St) @ Bi2O3Wetting Angle of composite hydrogels
Figure BDA0001736883860000091
P (AM-co-St) hydrogel and P (AM-co-St) @ Bi prepared in examples 1 to 42O3The composite hydrogel and the hydrogels prepared in comparative examples 1 to 4 were subjected to a laser response test, and the obtained results are shown in table 3:
TABLE 3 laser response Effect
Figure BDA0001736883860000092
Table 2 shows the wetting angles of the hydrogels of examples 1 to 4. As can be seen from the table, the modified Bi was added2O3After the composite particles, the hydrophilicity of the hydrogel was slightly decreased due to the modified Bi2O3The composite particle is a hydrophobic particle.
Table 3 shows the laser response effects of examples 1 to 4 and comparative examples 1 to 4. As can be seen from Table 3, in comparative example 1, unmodified Bi was added2O3To obtain PAM @ Bi2O3The composite hydrogel has a common laser effect; in comparative example 2, unmodified Bi was added2O3Preparing P (AM-co-St) @ Bi2O3The composite hydrogel has the same laser effect; in comparative example 3, PS physical coating Bi was prepared2O3Compounding the composite particle and synthesizing PAM/PS @ Bi2O3The composite hydrogel has a common laser effect. In comparative example 4, the styrene/polyacrylamide copolymer was synthesized first and thenIs unmodified Bi2O3The laser effect is general. The reason why the laser effects of comparative examples 1 to 4 are general is that Bi2O3The particles are physically dispersed in the hydrogel, and the uniformity is not good, so that the laser effect is general. In contrast, in examples 1 to 4, 3% of modified Bi was added2O3The composite hydrogel has the most ideal effect on the laser effect, and the modified Bi is not added in the example 12O3The hydrogel is essentially free of laser response because there are no laser-responsive particles in P (AM-co-St). Examples 2, 3 and 4 are laser-responsive, and examples 3 and 4 are better in laser response effect because Bi responsive to laser is added thereto2O3Particles. Addition of modified Bi in comparison with the comparative examples2O3After the particles are formed, the composite hydrogel is synthesized through free radicals, and the composite hydrogel is uniformly dispersed and stable in system, so that the laser response effect is ideal.
FIGS. 4 to 6 show P (AM-co-St) @ Bi of example 42O3And (3) an SEM image of the composite hydrogel, and the surface appearance of the composite hydrogel after laser response is observed. Looking at FIG. 4, the hydrogel surface has many holes after laser response, and the surface protrusions may be PS @ Bi2O3Composite particles; as shown in FIG. 5, the holes in the response region are observed at high magnification, and the network structure of the laser response hydrogel is broken, so that new large holes appear. The reason for this may be that the hydrogel is a three-dimensional network structure, and Bi is present in the laser response process2O3Decomposed to generate black Bi simple substance, and the polystyrene is carbonized to ensure PS @ Bi2O3The composite particles are reduced, the surface structure of the hydrogel is destroyed, and water in the hydrogel is evaporated, so that larger pores are formed. The three-dimensional network structure of the hydrogel is also demonstrated by observing the internal structure of the black pores, which are found to have many small pores inside.

Claims (2)

1. Laser response P (AM-co-St)@Bi2O3The preparation method of the composite hydrogel is characterized by comprising the following steps:
step (1): measuring deionized water solvent in a beaker, adding bismuth trioxide (Bi)2O3) Stirring uniformly, adding 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA), raising the temperature of an oil bath to 70 ℃, reacting for 2 hours, collecting a product after reaction, placing the product in a vacuum oven for drying at 60 ℃, and grinding after drying to obtain modified Bi with a double bond at the tail end2O3Particles; wherein TMSPMA and Bi2O3The mass ratio of (1): 5;
step (2): acrylamide (AAm) as main monomer, dissolving in solvent, adding styrene (St) with double bond, and adding modified Bi with double bond at terminal in step (1)2O3Adding promoter N, N, N ', N ' -tetramethyl ethylenediamine (TMEDA), cross-linking agent N, N ' -Methylene Bisacrylamide (MBA) and initiator potassium persulfate (K)2S2O8) Preparation of P (AM-co-St)@Bi2O3Compounding the hydrogel, and then subjecting the prepared P (AM-co-St)@Bi2O3Purifying the composite hydrogel, changing the purified solution every 8 hours, and purifying for 24 hours;
the solvent in the step (2) is N, N-Dimethylformamide (DMF) or deionized water, and the purified solution is deionized water;
AAm, St, modified Bi described in step (2)2O3、TMEDA、MBA、K2S2O8The mass ratio of (A) to (B) is 50: 1-3: 0-3: 1-2: 1-3, the polymerization temperature is 25 ℃, and the polymerization time is 6-8 h.
2. The laser-responsive P (AM-co-St)@Bi2O3The application of the composite hydrogel in the fields of laser marking, laser anti-counterfeiting and laser tracking is characterized in that: the P (AM-co-St)@Bi2O3The composite hydrogel is directly marked by a semiconductor laser marking machine, and the marking current intensity is 15-20A.
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