A method for preparing and using itaconic acid-based polymeric materials

Abstract

The application relates to the technical field of materials, and discloses a preparation method and application of itaconic acid-based polymer material.The itaconic acid-based polymer material is prepared through free radical polymerization reaction of itaconic acid, methyl acrylate and other acrylate monomers in cooperation with a macromolecular crosslinking agent under the action of an initiator.The macromolecular crosslinking agent is a macromolecular polymer alternately connected by adamantane and phenyl sulfone.The existence of the rigid heterocycle can greatly increase the stability of the acrylate resin molecular chain, so that the acrylate resin molecular chain can remain stable under high-temperature conditions.In addition, after being crosslinked by the macromolecular crosslinking agent, the crosslinking density of the acrylate resin molecular chain is greatly increased, and the linear structure is converted into a three-dimensional network structure, so that the bonding performance and high-temperature stability of the material can be effectively improved.In addition, the macromolecular crosslinking agent structure further contains a large number of ether bonds and active hydroxyl substituents generated through ring-opening reaction, so that the bonding performance of the material can be further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a preparation method and application of itaconic acid-based polymer material. BACKGROUND

[0002] Acrylic resin is a kind of high molecular compound, which is polymerized by acrylic acid, methacrylic acid and its derivatives. Acrylic resin has excellent film forming property, transparency and adhesion, which makes it widely used in many fields, especially in the field of adhesives. Compared with other types of adhesives, acrylic resin adhesive has higher saturation, better oxidation resistance and is not easy to yellow under long-term sunlight irradiation. In addition, acrylic resin has low glass transition temperature, which makes it have good flexibility and viscosity, and is suitable for various printing materials. Therefore, acrylic resin plays an important role in pressure-sensitive adhesive, structural adhesive, hot melt adhesive and other products, and occupies an important position.

[0003] However, with the progress of science and technology and the continuous development of adhesive technology, the application of acrylic resin in the field of adhesives will be more extensive and in-depth. Therefore, the research and development of acrylic resin will pay more attention to its high performance and multifunctionalization. Among them, the enhancement of bonding performance is the most important. In addition, it is found that the high temperature resistance of acrylic resin adhesive is also general in the long-term application process. The use in long-term high temperature environment may cause aging and falling off, which also affects the continuous application of acrylic resin adhesive.

[0004] Since acrylic resin is prepared by free radical polymerization of acrylic ester monomer, the adhesion and high temperature resistance of acrylic resin can be further improved by improving the synthesis method and adding functional monomers, thereby widening its application field. Based on this, the present application provides an itaconic acid-based polymer material, which has good bonding performance and other comprehensive performance and can be directly used as an adhesive. SUMMARY

[0005] (I) Technical problems to be solved

[0006] In view of the shortcomings of the prior art, the present application provides a preparation method and application of itaconic acid-based polymer material.

[0007] (II) Technical solutions

[0008] A preparation method of itaconic acid-based polymer material, the itaconic acid-based polymer material is made of raw materials including the following weight fractions:

[0009] Itaconic acid 15-25 parts;

[0010] Methyl acrylate 20-30 parts;

[0011] Isocetyl acrylate 3-5 parts;

[0012] Butyl methacrylate 1-2 parts;

[0013] Macromolecular crosslinking agent 2-3.5 parts;

[0014] Initiator 0.1-0.3 parts;

[0015] Organic solvent 20-35 parts;

[0016] The preparation method comprises the following steps:

[0017] Firstly, each raw material is weighed and prepared;

[0018] Secondly, itaconic acid, methyl acrylate, isooctyl acrylate and butyl methacrylate are added to the organic solvent, stirring is started, and after uniform mixing, the temperature is increased to 75-78 DEG C, then the initiator is added to the formed mixed solution, after the addition is completed, the temperature is kept for 1-2 hours to form a prepolymer;

[0019] Thirdly, the macromolecular crosslinking agent is added to the prepolymer, then the temperature is further increased to 80-83 DEG C, after the temperature is kept for 8-16 hours, the heating is stopped, the temperature is lowered, and the product is discharged, thereby obtaining the itaconic acid-based polymer material.

[0020] As a further scheme of the present application, the preparation method of the macromolecular crosslinking agent is as follows:

[0021] The adamantyl linker and toluene solvent are sequentially added to a reaction kettle filled with nitrogen, after the addition is completed, stirring is started, the stirring speed is controlled to be 100-200 r / min, the mechanical stirring is uniform, then the chain extender is added to the reaction kettle, after the addition is completed, the temperature is gradually increased to 70-80 DEG C, the phase transfer catalyst is added to the reaction kettle, after the temperature is kept for 6-9 hours, the nitrogen is removed, the solvent is evaporated and removed, the heating is stopped, the temperature is lowered, and the product is discharged, thereby obtaining the macromolecular crosslinking agent.

[0022] As a further scheme of the present application, the adamantyl linker is 4,6-bis(1-adamantyl)-1,3-diglycidyl ether phenyl.

[0023] As a further scheme of the present application, the chain extender is 4,4'-sulfonyl bis[2-(2-propenyl)] phenol.

[0024] As a further scheme of the present application, the molar ratio of the adamantyl linker and the chain extender is 1.1-1.2:1.

[0025] As a further scheme of the present application, the phase transfer catalyst is boron trifluoride etherate complex.

[0026] As a further aspect of the present invention, the mass of the phase transfer catalyst added is 2-3% of the total mass of the adamantyl linker and the chain extender.

[0027] In the above technical solution, the adamantyl linkage structure contains terminal epoxy groups, which can undergo ring-opening reaction with the phenolic hydroxyl groups in the chain extender structure under the action of a phase transfer catalyst. Since the chain extender structure contains two equivalent phenolic hydroxyl substituents, the two can undergo continuous ring-opening polymerization to form a polymer macromolecular chain with alternating structures. Since the reactant structure contains unsaturated alkenyl functional groups, the product structure of the ring-opening polymerization will contain a large number of polymerizable unsaturated alkenyl functional groups, which can act as crosslinking agents, i.e., macromolecular crosslinking agents, in the process of free radical polymerization of acrylate monomers.

[0028] As a further aspect of the present invention, the initiator is benzoyl peroxide or dicumyl peroxide.

[0029] As a further aspect of the present invention, the organic solvent is ethyl acetate or butyl acetate.

[0030] An application of an itaconic acid-based polymer material: The itaconic acid-based polymer material prepared by the above-described method is applied to the field of adhesives.

[0031] (iii) Beneficial technical effects

[0032] This invention designs the molecular chain structure of acrylic resin. First, it uniquely designs and synthesizes a macromolecular crosslinking agent. This macromolecular crosslinking agent is a macromolecular polymer with alternating links of adamantane and sulfone. The presence of these rigid heterocycles significantly increases the stability of the acrylic resin molecular chain, enabling it to remain stable under high-temperature conditions. Furthermore, after crosslinking with the macromolecular crosslinking agent, the crosslinking density of the acrylic resin molecular chain increases significantly, transforming it from a linear structure to a three-dimensional network structure. This results in higher cohesive strength, improving the material's adhesion performance, and also greatly hinders the movement of the acrylate molecular chains, indirectly enhancing the material's high-temperature stability. In addition, the macromolecular crosslinking agent structure contains numerous ether bonds and active hydroxyl substituents generated by the ring-opening reaction. Simultaneously, the selected itaconic acid structure contains two equivalents of active carboxyl substituents. These groups can generate more hydrogen bond sites with the substrate, thereby further improving the material's adhesion performance. Attached Figure Description

[0033] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is the FT-IR image of a macromolecular crosslinking agent. Detailed Implementation

[0035] To facilitate understanding of the present invention, a more complete description will be provided below. Preferred embodiments of the invention are given below. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0036] Preparation Example 1

[0037] Preparation of macromolecular crosslinking agents:

[0038] 0.2 g of 4,6-bis(1-adamantyl)-1,3-diglycidyl ether benzene and toluene solvent were added sequentially to a nitrogen-filled reactor. After the addition was complete, stirring was started and the stirring speed was controlled at 200 r / min. After mechanical mixing, 0.12 g of 4,4'-sulfonylbis[2-(2-propenyl)]phenol was added to the reactor. After the addition was complete, the temperature was gradually increased to 75℃, and 0.008 g of boron trifluoride diethyl ether complex was added to the reactor. After stirring at this temperature for 8 hours, the nitrogen gas was removed, the solvent was evaporated and removed, heating was stopped, and the material was cooled and discharged to obtain the macromolecular crosslinking agent.

[0039] Figure 1 The image shows the Fourier Transform Infrared (FT-IR) spectrum of the macromolecular crosslinking agent, with 3401 cm⁻¹ as an example. -1 The characteristic absorption peak appearing at 3098 cm⁻¹ is the characteristic absorption peak of the hydroxyl group produced by the ring-opening addition reaction. -1 and 3087cm -1 The characteristic absorption peak appearing at 3031 cm⁻¹ is a characteristic absorption peak of hydrocarbons in the benzene ring skeleton. -1 The characteristic absorption peak appearing at 1060 cm⁻¹ is the characteristic absorption peak of hydrocarbons on an unsaturated carbon-carbon double bond. -1 The characteristic absorption peak appearing at this point is the characteristic absorption peak of the ether bond generated by the ring-opening reaction. Example 1

[0040] An itaconic acid-based polymer material is made from raw materials comprising the following parts by weight:

[0041] 15 parts of itaconic acid;

[0042] 20 parts methyl acrylate;

[0043] 3 parts of isooctyl acrylate;

[0044] 1 part butyl methacrylate;

[0045] Two parts of macromolecular crosslinking agent;

[0046] Benzoyl peroxide 0.1 parts;

[0047] 20 parts of ethyl acetate;

[0048] The preparation method of the itaconic acid-based polymer material includes the following steps:

[0049] Step 1: Weigh and prepare all the raw materials according to their weight proportions;

[0050] Step 2: Add itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to ethyl acetate, start stirring, mix evenly, raise the temperature to 75°C, then add benzoyl peroxide to the mixture, and keep it at the temperature for 2 hours to form a prepolymer.

[0051] The third step is to add the macromolecular crosslinking agent to the prepolymer, then raise the temperature to 80°C, keep it at that temperature for 16 hours, stop heating, cool down and discharge the material to obtain the itaconic acid-based polymer material.

[0052] The macromolecular crosslinking agent used is the macromolecular crosslinking agent prepared in Preparation Example 1, and the same applies below. Example 2

[0053] An itaconic acid-based polymer material is made from raw materials comprising the following parts by weight:

[0054] Itaconic acid 20 parts;

[0055] 25 parts methyl acrylate;

[0056] 4 parts of isooctyl acrylate;

[0057] 1.5 parts of butyl methacrylate;

[0058] 3 parts macromolecular crosslinking agent;

[0059] 0.2 parts of dicumyl peroxide;

[0060] 30 parts of butyl acetate;

[0061] The preparation method of the itaconic acid-based polymer material includes the following steps:

[0062] Step 1: Weigh and prepare all the raw materials according to their weight proportions;

[0063] Step 2: Add itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to butyl acetate, start stirring, mix evenly, raise the temperature to 76°C, then add dicumyl peroxide to the mixture, and keep it at the temperature for 2 hours to form a prepolymer.

[0064] The third step is to add the macromolecular crosslinking agent to the prepolymer, then raise the temperature to 82°C, keep it at that temperature for 12 hours, stop heating, cool down and discharge the material to obtain the itaconic acid-based polymer material. Example 3

[0065] An itaconic acid-based polymer material is made from raw materials comprising the following parts by weight:

[0066] Itaconic acid 25 parts;

[0067] 30 parts methyl acrylate;

[0068] 5 parts of isooctyl acrylate;

[0069] 2 parts butyl methacrylate;

[0070] 3.5 parts of macromolecular crosslinking agent;

[0071] 0.3 parts of dicumyl peroxide;

[0072] 35 parts of butyl acetate;

[0073] The preparation method of the itaconic acid-based polymer material includes the following steps:

[0074] Step 1: Weigh and prepare all the raw materials according to their weight proportions;

[0075] Step 2: Add itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to butyl acetate, start stirring, mix evenly, raise the temperature to 78°C, then add dicumyl peroxide to the mixture, and keep it at the temperature for 1 hour to form a prepolymer.

[0076] The third step is to add the macromolecular crosslinking agent to the prepolymer, then raise the temperature to 83°C, keep it at that temperature for 8 hours, stop heating, cool down and discharge the material to obtain the itaconic acid-based polymer material.

[0077] Comparative Example 1

[0078] An itaconic acid-based polymer material is made from raw materials comprising the following parts by weight:

[0079] Itaconic acid 20 parts;

[0080] 25 parts methyl acrylate;

[0081] 4 parts of isooctyl acrylate;

[0082] 1.5 parts of butyl methacrylate;

[0083] 3 parts of 4,4'-sulfonylbis[2-(2-propenyl)]phenol;

[0084] 0.2 parts of dicumyl peroxide;

[0085] 30 parts of butyl acetate;

[0086] The preparation method of the itaconic acid-based polymer material includes the following steps:

[0087] Step 1: Weigh and prepare all the raw materials according to their weight proportions;

[0088] Step 2: Add itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to butyl acetate, start stirring, mix evenly, raise the temperature to 76°C, then add dicumyl peroxide to the mixture, and keep it at the temperature for 2 hours to form a prepolymer.

[0089] The third step involves adding 4,4'-sulfonylbis[2-(2-propenyl)]phenol to the prepolymer, then raising the temperature to 82°C and holding it at that temperature for 12 hours. After that, heating is stopped, the material is cooled and discharged to obtain itaconic acid-based polymer material.

[0090] Comparative Example 2

[0091] An itaconic acid-based polymer material is made from raw materials comprising the following parts by weight:

[0092] Itaconic acid 20 parts;

[0093] 25 parts methyl acrylate;

[0094] 4 parts of isooctyl acrylate;

[0095] 1.5 parts of butyl methacrylate;

[0096] 0.2 parts of dicumyl peroxide;

[0097] 30 parts of butyl acetate;

[0098] The preparation method of the itaconic acid-based polymer material includes the following steps:

[0099] Step 1: Weigh and prepare all the raw materials according to their weight proportions;

[0100] The second step involves adding itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to butyl acetate, stirring, and mixing thoroughly. The temperature is then raised to 76°C, and dicumyl peroxide is added to the resulting mixture. After the addition is complete, the mixture is kept at this temperature for 2 hours. The temperature is then further raised to 82°C and kept at this temperature for 12 hours. After heating is stopped, the mixture is cooled and discharged to obtain the itaconic acid-based polymer material.

[0101] Test case

[0102] The polymer material used in the examples and comparative examples was uniformly coated onto the surface of a PET substrate, with the coating amount controlled at 10 g / m². 2 After the hike was completed, the sample was placed in a 100℃ oven for 30 minutes to cure. Then, a release film was applied to the coated surface, and the sample was cured at 60℃ for 12 hours. The sample was then removed and tested. The test results are recorded in the table below:

[0103] Table 1 - Test Results

[0104]

[0105] Note: The test method refers to standard GB / T 2791-1995. First, the samples are subjected to routine tests to obtain initial values. After the test is completed, the samples of the same batch are placed in an oven at 150℃ for 24 hours for heat treatment and then tested to obtain heat treatment values. By comparing the decrease in peel strength before and after heat treatment, the high temperature resistance of the samples is judged. Generally speaking, the smaller the decrease, the stronger the high temperature resistance, and vice versa.

[0106] Analysis of the test results shows that the polymer material prepared by crosslinking the acrylate monomer with the macromolecular crosslinking agent prepared in Preparation Example 1 exhibits significantly better bonding performance and high temperature resistance than the polymer material prepared without the addition of the macromolecular crosslinking agent.

[0107] When the macromolecular crosslinking agent is replaced with 4,4'-sulfonylbis[2-(2-propenyl)]phenol, the resulting acrylic resin molecular chain does not contain adamantane heterocyclic structure, and the crosslinking density is also relatively low. Therefore, the bonding performance and high temperature resistance are significantly reduced.

[0108] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0109] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an itaconic acid-based polymer material, characterized in that, The itaconic acid-based polymer material is made from raw materials comprising the following parts by weight: Itaconic acid 15-25 parts; 20-30 parts of methyl acrylate; 3-5 parts of isooctyl acrylate; 1-2 parts of butyl methacrylate; 2-3.5 parts of macromolecular crosslinking agent; Initiator 0.1-0.3 parts; 20-35 parts organic solvent; The preparation method includes the following steps: Step 1: Weigh and prepare all the raw materials according to their weight proportions; Step 2: Add itaconic acid, methyl acrylate, isooctyl acrylate, and butyl methacrylate to an organic solvent, start stirring, and mix evenly. Then raise the temperature to 75-78℃, add the initiator to the mixture, and keep it at the temperature for 1-2 hours to form a prepolymer. The third step is to add the macromolecular crosslinking agent to the prepolymer, then raise the temperature to 80-83℃, keep it at that temperature for 8-16 hours, stop heating, cool down and discharge the material to obtain the itaconic acid-based polymer material. The preparation method of the macromolecular crosslinking agent is as follows: Add the adamantyl linker and toluene solvent sequentially to a nitrogen-filled reactor. After the addition is complete, start stirring and control the stirring rate at 100-200 r / min. After mechanically mixing, add the chain extender to the reactor. After the addition is complete, gradually raise the temperature to 70-80℃ and add the boron trifluoride diethyl ether complex to the reactor. Keep the mixture warm and stir for 6-9 hours, then remove the nitrogen, evaporate and remove the solvent, stop heating, cool down and discharge the material to obtain the macromolecular crosslinking agent. The adamantyl linker is 4,6-bis(1-adamantyl)-1,3-diglycidyl etherbenzene; The chain extender is 4,4'-sulfonylbis[2-(2-propenyl)]phenol.

2. The method for preparing an itaconic acid-based polymer material according to claim 1, characterized in that, The molar ratio of the adamantyl linker to the chain extender is 1.1-1.2:

1.

3. The method for preparing an itaconic acid-based polymer material according to claim 1, characterized in that, The mass of the boron trifluoride diethyl ether complex added is 2-3% of the total mass of the adamantyl linker and chain extender.

4. The method for preparing an itaconic acid-based polymer material according to claim 1, characterized in that, The initiator is benzoyl peroxide or dicumyl peroxide.

5. The method for preparing an itaconic acid-based polymer material according to claim 1, characterized in that, The organic solvent is ethyl acetate or butyl acetate.

6. An application of an itaconic acid-based polymer material, characterized in that, The itaconic acid-based polymer material prepared by the method described in any one of claims 1-5 can be applied to the field of adhesives.

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