A method for preparing a (meth)acrylate glycidyl ester polymer

Abstract

This invention relates to a method for preparing a glycidyl methacrylate polymer, comprising the following steps: S1: under the action of a first initiator, a first monomer is subjected to a bulk polymerization reaction at a first temperature to obtain a first polymerization system; S2: a second monomer and a second initiator are added to the first polymerization system, and a bulk polymerization reaction is carried out at a second temperature to obtain a second polymerization system; and S3: a third monomer and a third initiator are added to the second polymerization system, and a bulk polymerization reaction is carried out at a third temperature. The method for preparing a glycidyl methacrylate polymer according to one embodiment of this invention, by using gradient heating and batch addition of monomers for bulk polymerization, can improve the monomer conversion rate and reaction yield.

Description

Technical Field

[0001] This invention relates to (meth)acrylate polymers, and more particularly to a method for preparing a (meth)acrylate glycidyl ester polymer with a high conversion rate. Background Technology

[0002] (Meth)acrylate polymers (especially homopolymers and copolymers of glycidyl methacrylate) are a class of functional polymers with wide applications in various fields due to their unique chemical structure and properties. For example, these polymers can be used in functional coating materials, adhesives, biomedical materials, fiber and textile processing, electronic and photoresists, environmental protection and separation materials, and many other fields.

[0003] However, existing methods for preparing glycidyl methacrylate polymers suffer from low conversion rates and low purity, and cannot achieve efficient preparation of glycidyl methacrylate polymers. Summary of the Invention

[0004] To overcome at least one of the defects of the prior art, in a first aspect, one embodiment of the present invention provides a method for preparing a glycidyl acrylate polymer, comprising the following steps:

[0005] S1: Under the action of the first initiator, the first monomer undergoes a bulk polymerization reaction at the first temperature to obtain the first polymerization system; S2: A second monomer and a second initiator are added to the first polymerization system, and a bulk polymerization reaction is carried out at a second temperature to obtain a second polymerization system; and S3: Add a third monomer and a third initiator to the second polymerization system and carry out a bulk polymerization reaction at a third temperature; Wherein, the first monomer, the second monomer, and the third monomer each independently include glycidyl (meth)acrylate; the first temperature is 40–90°C, the second temperature is 60–130°C, and the third temperature is 90–170°C.

[0006] The present invention discloses a method for preparing glycidyl methacrylate polymers by using gradient heating and batch addition of monomers for bulk polymerization, which can improve monomer conversion and reaction yield. Attached Figure Description

[0007] The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of the invention. Wherein: Figure 1a The above is the 1H NMR spectrum of the glycidyl methacrylate homopolymer prepared in Example 1. Figure 1b This is a GPC test report image of the glycidyl methacrylate homopolymer obtained in Example 1; Figure 2a The 1H NMR spectrum of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 2; Figure 2b This is a GPC test report image of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 2; Figure 3a The 1H NMR spectrum of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 3; Figure 3b The image shows the GPC test report of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 3; Figure 4a The 1H NMR spectrum of the (glycidyl methacrylate-r-butyl methacrylate) copolymer prepared in Example 4; Figure 4b This is a GPC test report image of the (glycidyl methacrylate-r-butyl methacrylate) copolymer prepared in Example 4; Figure 5a The hydrogen nuclear magnetic resonance spectrum of the (glycidyl methacrylate-r-butyl acrylate) copolymer prepared in Example 5; Figure 5b The image shows the GPC test report of the (glycidyl methacrylate-r-butyl acrylate) copolymer prepared in Example 5; Figure 6a The 1H NMR spectrum of the (glycidyl methacrylate-r-tert-butyl acrylate) copolymer prepared in Example 6; Figure 6b The image shows the GPC test report of the (glycidyl methacrylate-r-tert-butyl acrylate) copolymer prepared in Example 6; Figure 7a The photon NMR spectrum of the glycidyl methacrylate homopolymer prepared in Comparative Example 1 is shown below. Figure 7b The image shows the GPC test report of the glycidyl methacrylate homopolymer prepared in Comparative Example 1. Figure 8a The photon NMR spectrum of the glycidyl methacrylate homopolymer prepared in Comparative Example 2 is shown below. Figure 8b The image shows the GPC test report of the glycidyl methacrylate homopolymer prepared in Comparative Example 2. Figure 9aThe photon NMR spectrum of the glycidyl methacrylate homopolymer prepared in Comparative Example 3 is shown below. Figure 9b The image shows the GPC test report of the glycidyl methacrylate homopolymer prepared in Comparative Example 3. Figure 10a The photon NMR spectrum of the glycidyl methacrylate homopolymer prepared in Comparative Example 4 is shown below. Figure 10b The image shows the GPC test report of the glycidyl methacrylate homopolymer prepared in Comparative Example 4. Figure 11a The photon NMR spectrum of the glycidyl methacrylate homopolymer prepared in Comparative Example 5 is shown in the 1H NMR spectrum. Figure 11b The image shows the GPC test report of the glycidyl methacrylate homopolymer prepared in Comparative Example 5. Detailed Implementation

[0008] Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the description herein is for illustrative purposes only and not intended to limit the present invention.

[0009] One embodiment of the present invention provides a method for preparing a glycidyl acrylate polymer, comprising the following steps: S1: Under the action of the first initiator, the first monomer undergoes a bulk polymerization reaction at the first temperature to obtain the first polymerization system; S2: A second monomer and a second initiator are added to the first polymerization system, and a bulk polymerization reaction is carried out at a second temperature to obtain the second polymerization system; and S3: Add a third monomer and a third initiator to the second polymerization system and carry out a bulk polymerization reaction at a third temperature; The first monomer, the second monomer, and the third monomer each independently include glycidyl (meth)acrylate; the first temperature is 40–90°C, the second temperature is 60–130°C, and the third temperature is 90–170°C.

[0010] In one embodiment, the first temperature can be 40 to 90°C, for example 50°C, 55°C, 60°C, 63°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 85°C, 87°C, or 88°C.

[0011] In one embodiment, a chain transfer agent is also added to the reaction system in step S1.

[0012] In one embodiment, the chain transfer agent includes one, two or more of the following: n-octylthiol, tert-octylthiol, n-dodecylthiol, tert-dodecylthiol, mercaptoethanol, and isooctyl 3-mercaptopropionate.

[0013] In one embodiment, the molar content of the chain transfer agent can be 0.05 to 20%, for example, 0.1%, 0.2%, 0.5%, 1%, 5%, 10% or 15%, based on the sum of the molar numbers of the first monomer, the second monomer and the third monomer.

[0014] In one embodiment, the second temperature can be 60 to 130°C, for example 70°C, 80°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, 100°C, 105°C, 107°C, 109°C, 110°C, 113°C, 115°C, 117°C, 120°C, or 125°C.

[0015] In one embodiment, the third temperature can be 90–170°C, for example 93°C, 95°C, 97°C, 100°C, 105°C, 108°C, 110°C, 113°C, 115°C, 118°C, 120°C, 125°C, 127°C, 130°C, 135°C, 140°C, 145°C, 155°C, 158°C, 160°C, 163°C, 165°C, or 167°C.

[0016] In one implementation, the second temperature is greater than (or higher than) the first temperature.

[0017] In one implementation, the third temperature is the same as the second temperature, or the third temperature is greater than (or higher than) the second temperature.

[0018] In one embodiment, glycidyl methacrylate comprises glycidyl methacrylate and / or glycidyl acrylate.

[0019] In one embodiment, the (meth)acrylate glycidyl ester polymer is a homopolymer, that is, the first monomer, the second monomer, and the third monomer are each independently glycidyl acrylate or glycidyl methacrylate.

[0020] In one embodiment, the (meth)acrylate glycidyl ester polymer is a copolymer, such as a random copolymer. It can be a copolymer of glycidyl acrylate and glycidyl methacrylate, or a copolymer of glycidyl methacrylate and other (meth)acrylates. That is, the first monomer, the second monomer, and the third monomer each independently include glycidyl methacrylate (glycidyl methacrylate and / or glycidyl acrylate), and one or more of other (meth)acrylates.

[0021] In one embodiment, the structural formula of the other (meth)acrylate is: CH2=CR1-COOR2; wherein R1 is selected from hydrogen or methyl; and R2 is selected from methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, dodecyl (or lauryl), octadecyl (or stearyl), dimethylaminoethyl, ethyl acetoacetate (CH3(C=O)CH2COOCH2CH2-), benzyl, cyclohexyl or hydroxyethyl.

[0022] In one embodiment, other (meth)acrylates include one, two, or more of the following: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, dimethylaminoethyl methacrylate, ethyl acetoacetate, benzyl methacrylate, cyclohexyl methacrylate, and hydroxyethyl methacrylate.

[0023] In one embodiment, the monomers used to prepare the (meth)acrylate glycidyl ester polymers include a first monomer, a second monomer, and a third monomer. The monomers used to prepare the (meth)acrylate glycidyl ester polymers include glycidyl esters of (meth)acrylate and other (meth)acrylates, wherein the mass ratio of glycidyl esters of (meth)acrylate to other (meth)acrylates is 0.1 to 100:1, for example, 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, or 90:1.

[0024] In one embodiment, the (meth)acrylate glycidyl ester polymer is a copolymer of glycidyl methacrylate and other (meth)acrylates, with the following structural formula:

[0025] R1 is selected from hydrogen or methyl; R2 is selected from methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, dodecyl (lauryl), octadecyl (stearyl), dimethylaminoethyl, ethyl acetoacetate, benzyl, cyclohexyl or hydroxyethyl; m and n are each independently selected from 1 to 500.

[0026] It should be noted that the above structural formula is only a schematic representation of the structure and number of the two structural units of the copolymer.

[0027] In one implementation, m+n is greater than 2.

[0028] In one implementation, m or n can be 1, 2, 5, 10, 20, 50, 100, 150, 200, 250, 300, 350, 400 or 450.

[0029] In one embodiment, the weight-average molecular weight of the (meth)acrylate glycidyl ester polymer can be from 1 to 1000 kg / mol, for example 10 kg / mol, 12 kg / mol, 13 kg / mol, 15 kg / mol, 20 kg / mol, 30 kg / mol, 31 kg / mol, 32 kg / mol, 35 kg / mol, 50 kg / mol, 100 kg / mol, 120 kg / mol, 122 kg / mol, 123 kg / mol, 150 kg / mol, 200 kg / mol, 220 kg / mol, 223 kg / mol, 224 kg / mol. / mol, 230kg / mol, 238kg / mol, 240kg / mol, 250kg / mol, 252kg / mol, 253kg / mol, 300kg / mol, 400kg / mol, 450kg / mol, 455kg / mol, 456kg / m ol, 460kg / mol, 500kg / mol, 517kg / mol, 518kg / mol, 700kg / mol, 716kg / mol, 717kg / mol, 720kg / mol, 721kg / mol, 722kg / mol, 730kg / mol.

[0030] In one embodiment, the molecular weight distribution (PDI) of the (meth)acrylate polymer can be 1.5 to 5, more specifically 1.5 to 2.4, for example 1.7, 1.75, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.7, 2.77, 2.8, 2.9, 2.93, 3.0.

[0031] In one implementation, the first monomer, the second monomer, and the third monomer may be of the same or different types.

[0032] In one embodiment, the first monomer includes glycidyl methacrylate and other (meth)acrylates, the second monomer includes glycidyl methacrylate, and the third monomer includes glycidyl methacrylate.

[0033] In one embodiment, based on the sum of the masses of the first monomer, the second monomer, and the third monomer, the mass content of the first monomer is 40-99.8%, the mass content of the second monomer is 0.1-30%, and the mass content of the third monomer is 0.1-30%.

[0034] In one embodiment, the mass content of the first monomer can be 40-99.8%, for example, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 89%, 90%, 91%, 93%, 95% or 98%, based on the sum of the masses of the first monomer, the second monomer and the third monomer.

[0035] In one embodiment, the mass content of the second monomer can be 0.1% to 30%, based on the sum of the masses of the first monomer, the second monomer, and the third monomer, for example, 0.5%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 2%, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 15%, 18%, 20%, 22%, 25%, or 28%.

[0036] In one embodiment, the mass content of the third monomer can be 0.1% to 30%, based on the sum of the masses of the first monomer, the second monomer, and the third monomer, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 2%, 5%, 8%, 9%, 10%, 11%, 12%, 15%, 18%, 20%, 22%, 25%, or 28%.

[0037] In one embodiment, based on the mass of the first monomer, the mass content of the first initiator can be 0.01 to 0.5%, more specifically 0.01 to 0.1%, for example 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.2%, 0.3%, or 0.4%.

[0038] In one embodiment, the mass content of the second initiator can be 0.1 to 1.0%, more specifically 0.1 to 0.5%, for example 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, based on the mass of the second monomer.

[0039] In one embodiment, the mass content of the third initiator can be 0.1% to 1.0%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, based on the mass of the third monomer.

[0040] In one embodiment, the first initiator, the second initiator, and the third initiator are each independently selected from one, two, or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobis(cyclohexane-1-nitrile), benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide.

[0041] In one embodiment, the content of the sum of the molar numbers of the first monomer, the second monomer, and the third monomer is 0.05 to 5%, for example, 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or 4%.

[0042] In one embodiment, the reaction time of step S1 can be 0.5 to 24 hours, for example 35 min, 40 min, 50 min, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 15 hours, 16 hours, 18 hours, 20 hours or 22 hours.

[0043] In one embodiment, the reaction time of step S2 can be 1 to 12 hours, for example 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours or 10 hours.

[0044] In one embodiment, the reaction time of step S3 can be 1 to 10 hours, for example 2.5 hours, 3 hours, 3.5 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or 9 hours.

[0045] In one embodiment, the gauge pressure of the polymerization reaction in steps S1, S2, and S3 can be 0 to 0.3 MPa.

[0046] In one embodiment, the polymerization reactions in steps S1, S2, and S3 are all carried out in an inert gas atmosphere, such as nitrogen.

[0047] In one embodiment, glycidyl methacrylate and / or other (meth)acrylates may be purified before participating in the polymerization reaction.

[0048] In one embodiment, the second monomer and the second initiator of step S2, and the third monomer and the third initiator of step S3, can be added to their respective systems by dropwise addition.

[0049] One embodiment of the present invention provides a glycidyl methacrylate polymer, which is prepared by the method described above. Furthermore, the glycidyl methacrylate polymer is applicable to functional coating materials, adhesives, biomedical materials, fiber and textile processing, electronic and photoresists, environmental protection and separation materials, and other fields.

[0050] This invention discloses a method for preparing glycidyl methacrylate polymers, which improves monomer conversion and product purity by gradient heating and batch-adding monomers to the system for bulk polymerization. Furthermore, the monomer conversion rate can be increased to over 99%.

[0051] This invention discloses a method for preparing glycidyl methacrylate polymers, which yields high output, high monomer conversion, and high product purity. Furthermore, this method offers advantages such as simple operation, no need for catalysts or solvents, and no byproduct generation during the reaction process, making it highly suitable for industrial production.

[0052] The method for preparing (meth)acrylate glycidyl ester polymers according to one embodiment of the present invention can simplify the reaction operation steps (no post-processing required), reduce the introduction of by-products and impurities, and improve the purity and conversion rate of the reaction product, for example, the purity can reach 99% and the conversion rate can reach 100%.

[0053] The preparation method of glycidyl methacrylate polymer according to one embodiment of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. The test methods involved in each embodiment and comparative example are as follows.

[0054] Test methods 1. Nuclear magnetic resonance (NMR) test The products were detected using an Agilent Technologies 1260 Infinity II liquid nuclear magnetic resonance spectrometer. 1 ¹H NMR spectra, with deuterated DMSO and deuterated MeOH as solvents, and tetramethylsilane (TMS) as an internal standard.

[0055] 2. Molecular weight test The number-average molecular weight, weight-average molecular weight, and PDI of the products were determined using a Varian 400 M gel permeation chromatograph.

[0056] Example 1 S1: Mix 1300g of glycidyl methacrylate monomer and 36.318g of tert-dodecyl mercaptan in a reaction apparatus to obtain a mixture. Heat the mixture to 87°C, start mechanical stirring and maintain a speed of 200 rpm, while keeping the reaction system under nitrogen gas.

[0057] Take 100g of glycidyl methacrylate monomer and 1.123g of dicumyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 1 hour.

[0058] S2: Immediately after the addition is complete, heat the above reaction system to 107°C, take 144g of glycidyl methacrylate monomer and 0.403g of di-tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 30 minutes, and then react for 4 hours.

[0059] S3: Then, heat the above reaction system to 127°C, take 10g of glycidyl methacrylate monomer, 0.05g of dicumyl peroxide and 0.03g of di-tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 5 minutes, and then react for 2 hours to complete the reaction.

[0060] The structural formula of the obtained glycidyl methacrylate homopolymer is as follows:

[0061] The reaction yield of the glycidyl methacrylate homopolymer prepared in Example 1 was measured to be 99.4%. The glycidyl methacrylate homopolymer was subjected to relevant detections using the aforementioned method, with the proton NMR spectrum shown below. Figure 1a See GPC test report Figure 1b The weight-average molecular weight of the glycidyl methacrylate homopolymer was measured to be approximately 122,716 g / mol, and the PDI was 2.00.

[0062] in, Figure 1a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 1a The absence of residual peaks in the 5.5–6.5 shift indicates that the conversion rate of the reaction is 100%. Figure 1b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0063] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.4%.

[0064] Example 2 S1: Mix 400g glycidyl methacrylate monomer, 500g methyl methacrylate monomer, 1.22g tert-dodecyl mercaptan, and 8.95g mercaptoethanol in a reaction apparatus to obtain a homogeneous mixture. Heat the mixture to 75°C, start mechanical stirring and maintain a speed of 200 rpm, while simultaneously purging the reaction system with nitrogen gas.

[0065] Take 100g of glycidyl methacrylate monomer and 0.53g of dicumyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 30 minutes.

[0066] S2: Immediately after the addition is complete, heat the above reaction system to 95°C, take 100g of glycidyl methacrylate monomer and 0.31g of tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the mixed solution is homogeneous, add it dropwise to the above reaction system over 30 minutes, and then react for 5 hours.

[0067] S3: Mix 10g of glycidyl methacrylate monomer, 0.03g of dicumyl peroxide, and 0.02g of tert-butyl peroxide to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 5 minutes, and then react for 2 hours to complete the reaction.

[0068] The structural formula of the obtained (glycidyl methacrylate-r-methyl methacrylate) copolymer is as follows:

[0069] The reaction yield of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 2 was measured to be 99.2%. The (glycidyl methacrylate-r-methyl methacrylate) copolymer was subjected to relevant tests using the aforementioned methods, and the 1H NMR spectrum is shown below. Figure 2a See GPC test report Figure 2b The weight-average molecular weight of the (glycidyl methacrylate-r-methyl methacrylate) copolymer was measured to be approximately 238,466 g / mol, and the PDI was 1.92.

[0070] in, Figure 2a The peaks at shifts of 0.5–4.5 in the graph can prove that the synthesized polymer is poly(glycidyl methacrylate-r-methyl methacrylate). Figure 2a There is a very small peak (which can be ignored) in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 99%. Figure 2b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0071] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.2%.

[0072] Example 3 S1: Mix 300g of glycidyl methacrylate monomer, 450g of methyl methacrylate monomer, 1.02g of tert-dodecyl mercaptan, and 8.15g of mercaptoethanol in a reaction apparatus to obtain a homogeneous mixture. Heat the mixture to 75°C, start mechanical stirring and maintain a speed of 200 rpm, while simultaneously purging the reaction system with nitrogen gas.

[0073] Take 100g of methyl methacrylate monomer and 0.51g of dicumyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 30 minutes.

[0074] S2: Immediately after the addition is complete, heat the above reaction system to 95°C, take 100g of methyl methacrylate monomer and 0.31g of tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the mixed solution is homogeneous, add it dropwise to the above reaction system within 1 hour, and then react for another 5 hours.

[0075] S3: Mix 10g of methyl methacrylate monomer, 0.03g of dicumyl peroxide and 0.02g of tert-butyl peroxide to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 5 minutes, and then react for 2 hours to complete the reaction.

[0076] The structural formula of the obtained (glycidyl methacrylate-r-methyl methacrylate) copolymer is as follows:

[0077] The reaction yield of the (glycidyl methacrylate-r-methyl methacrylate) copolymer prepared in Example 3 was measured to be 99.2%. The (glycidyl methacrylate-r-methyl methacrylate) copolymer was subjected to relevant tests using the aforementioned methods, and the 1H NMR spectrum is shown below. Figure 3a See GPC test report Figure 3b The weight-average molecular weight of the (glycidyl methacrylate-r-methyl methacrylate) copolymer was measured to be approximately 252,435 g / mol, and the PDI was 2.20.

[0078] in, Figure 3a The peaks at shifts of 0.5–4.5 in the graph can prove that the synthesized polymer is poly(glycidyl methacrylate-r-methyl methacrylate). Figure 3aThere is a very small peak (which can be ignored) in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 99%. Figure 3b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0079] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.2%.

[0080] Example 4 S1: Mix 600g of glycidyl methacrylate monomer, 300g of butyl methacrylate monomer, 0.35g of tert-dodecyl mercaptan, and 4.72g of mercaptoethanol in a reaction apparatus to obtain a homogeneous mixture. Heat the mixture to 65°C, start mechanical stirring and maintain a speed of 200 rpm, while simultaneously purging the reaction system with nitrogen gas.

[0081] Take 100g of glycidyl methacrylate monomer and 0.33g of dicumyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 30 minutes.

[0082] S2: Immediately after the addition is complete, heat the above reaction system to 115°C, take 100g of glycidyl methacrylate monomer and 0.31g of tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 30 minutes, and then react for 1 hour.

[0083] S3: Then, heat the above reaction system to 165℃, take 10g of glycidyl methacrylate monomer, 0.01g of dicumyl peroxide and 0.01g of tert-butyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is uniform, add it dropwise to the above reaction system within 5min, and then react for 2 hours to complete the reaction.

[0084] The structural formula of the obtained (glycidyl methacrylate-r-butyl methacrylate) copolymer is as follows:

[0085] The reaction yield of the (glycidyl methacrylate-r-butyl methacrylate) copolymer prepared in Example 4 was measured to be 99.2%. The (glycidyl methacrylate-r-butyl methacrylate) copolymer was subjected to relevant tests using the aforementioned methods, and the 1H NMR spectrum is shown below. Figure 4a See GPC test report Figure 4b The weight-average molecular weight of the (glycidyl methacrylate-r-butyl methacrylate) copolymer was measured to be approximately 517,808 g / mol, and the PDI was 2.05.

[0086] in, Figure 4a The peaks at shifts of 0.5–4.5 in the graph can prove that the synthesized polymer is a copolymer of glycidyl methacrylate and γ-butyl methacrylate. Figure 4a There is a very small peak (which can be ignored) in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 99%. Figure 4b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0087] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.2%.

[0088] Example 5 S1: Mix 600g of glycidyl methacrylate monomer, 300g of butyl acrylate monomer, 0.78g of tert-dodecyl mercaptan, and 2.27g of mercaptoethanol in a reaction apparatus to obtain a homogeneous mixture. Heat the mixture to 70°C, start mechanical stirring and maintain a speed of 200 rpm, while simultaneously purging the reaction system with nitrogen gas.

[0089] Take 100g of glycidyl methacrylate monomer and 0.23g of dicumyl peroxide and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 30 minutes.

[0090] S2: Immediately after the addition is complete, heat the above reaction system to 90°C, take 100g of glycidyl methacrylate monomer and 0.13g of dimethyl azobisisobutyrate and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 30 minutes, and then react for 4 hours.

[0091] S3: Then, heat the above reaction system to 110℃, take 10g of glycidyl methacrylate monomer, 0.03g of dicumyl peroxide and 0.03g of dimethyl azobisisobutyrate and mix them to obtain a monomer / initiator solution; after the solution is uniform, add it dropwise to the above reaction system within 5min, and then react for 2 hours to complete the reaction.

[0092] The structural formula of the obtained (glycidyl methacrylate-r-butyl acrylate) copolymer is as follows:

[0093] The reaction yield of the (glycidyl methacrylate-r-butyl acrylate) copolymer prepared in Example 5 was measured to be 99.4%. The (glycidyl methacrylate-r-butyl acrylate) copolymer was subjected to relevant tests using the aforementioned methods, and the 1H NMR spectrum is shown below. Figure 5a See GPC test report Figure 5b The weight-average molecular weight of the (glycidyl methacrylate-r-butyl acrylate) copolymer was measured to be approximately 716,381 g / mol, and the PDI was 2.35.

[0094] in, Figure 5a The peaks at shifts of 0.5–4.5 in the graph can prove that the synthesized polymer is a copolymer of glycidyl methacrylate and butyl acrylate. Figure 5a The absence of residual peaks in the 5.5–6.5 shift indicates that the conversion rate of the reaction is 100%. Figure 5b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0095] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.4%.

[0096] Example 6 S1: Take 400g of glycidyl methacrylate monomer, 500g of tert-butyl acrylate monomer, and 6.78g of tert-dodecyl mercaptan and mix them evenly in a reaction apparatus to obtain a mixture. Heat the mixture to 70℃, start mechanical stirring and maintain a speed of 200rpm, while keeping the reaction system under nitrogen gas.

[0097] Take 100g of glycidyl methacrylate monomer and 0.27g of dimethyl azobisisobutyrate and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over a period of 30 minutes.

[0098] S2: Immediately after the addition is complete, heat the above reaction system to 110°C, take 100g of glycidyl methacrylate monomer and 0.31g of azobisisobutyronitrile and mix them to obtain a monomer / initiator solution; after the solution is homogeneous, add it dropwise to the above reaction system over 30 minutes, and then react for 1 hour.

[0099] S3: Then, heat the above reaction system to 160℃, take 10g of glycidyl methacrylate monomer, 0.01g of dimethyl azobisisobutyrate, 0.01g of azobisisobutyronitrile and mix them to obtain monomer / initiator solution; after the solution is uniform, add it dropwise to the above reaction system in 5min, and then react for 2 hours to complete the reaction.

[0100] The structural formula of the obtained (glycidyl methacrylate-r-tert-butyl acrylate) copolymer is as follows:

[0101] The reaction yield of the (glycidyl methacrylate-r-tert-butyl acrylate) copolymer prepared in Example 6 was measured to be 99.4%. The (glycidyl methacrylate-r-tert-butyl acrylate) copolymer was subjected to relevant tests using the aforementioned methods, and the 1H NMR spectrum is shown below. Figure 6a See GPC test report Figure 6b The weight-average molecular weight of the (glycidyl methacrylate-r-tert-butyl acrylate) copolymer was measured to be approximately 31685 g / mol, and the PDI was 1.83.

[0102] in, Figure 6a The peaks at shifts of 0.5 to 4.5 in the graph can prove that the synthesized polymer is a copolymer of glycidyl methacrylate and tert-butyl acrylate. Figure 6a The absence of residual peaks in the 5.5–6.5 shift indicates that the conversion rate of the reaction is 100%. Figure 6b The presence of a single, complete peak indicates that there are no residual monomers in the reaction, suggesting that the conversion rate of the reaction is close to 100%.

[0103] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 99.4%.

[0104] Comparative Example 1 This example uses solution polymerization to prepare glycidyl methacrylate homopolymer, and the specific process is as follows: S1: Add 1000g of glycidyl methacrylate monomer, 25.22g of tert-dodecyl mercaptan, and 2200ml of ethyl acetate to a 5L reactor and mix thoroughly. Then heat the mixture to 65℃, stir and maintain a speed of 200rpm, and keep the reaction system under nitrogen gas.

[0105] S2: Mix 100g of ethyl acetate and 1.95g of dicumyl peroxide to obtain an initiator solution; after the solution is homogeneous, add it to a constant pressure dropping funnel; add the initiator solution dropwise to the reaction system of step (1) over a period of 1 hour through the constant pressure dropping funnel, and then react for another 12 hours to complete the reaction.

[0106] The yield of the homopolymer of glycidyl methacrylate in Comparative Example 1 was measured to be 76.1%, and the 1H NMR spectrum is shown in [reference needed]. Figure 7a See GPC test report Figure 7b The weight-average molecular weight of the glycidyl methacrylate homopolymer was approximately 76,508, and the PDI was 2.29, as determined by gel permeation chromatography.

[0107] in, Figure 7a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 7a There are two distinct residual peaks in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 76.5%. Figure 7b The presence of only one complete single peak indicates that most of the monomers in the reaction have been converted.

[0108] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 76.1%.

[0109] Comparative Example 2 This example uses suspension polymerization to prepare glycidyl methacrylate homopolymer, and the specific process is as follows: (1) Prepare the aqueous system solution in a 5L reactor. Add 20g of dispersant polyvinyl alcohol 1799 type, 1g of carboxymethyl cellulose, 1g of additives and regulators sodium carbonate and sodium bicarbonate, 0.5g of acidic substance phosphoric acid, and 3g of electrolyte salts sodium nitrate, 1g of sodium sulfate and 0.5g of sodium chloride.

[0110] (2) Stir the above system at 200 rpm and keep nitrogen gas flowing through it.

[0111] (3) Prepare the oil phase in a single-necked bottle: Take 1000g of glycidyl methacrylate monomer, 25.22g of tert-dodecyl mercaptan, and 7.01g of dicumyl peroxide and mix them evenly.

[0112] (4) Add the above oil phase mixture to the aqueous phase system solution and heat it to 60°C.

[0113] (5) The reaction is completed after 18 hours.

[0114] (6) The reaction system is post-processed to remove additives, purify and dry.

[0115] The yield of the preparation of glycidyl methacrylate homopolymer in Comparative Example 2 was 90.1%, and the 1H NMR spectrum is shown in [reference needed]. Figure 8a See GPC test report Figure 8b The weight-average molecular weight of the glycidyl methacrylate homopolymer was approximately 32,794, and the PDI was 1.89, as determined by gel permeation chromatography.

[0116] in, Figure 8a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 8a There are two distinct residual peaks in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 93%. Figure 8b The presence of only one complete single peak indicates that most of the monomers in the reaction have been converted.

[0117] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 90.1%.

[0118] Comparative Example 3 S1: Take 900g of glycidyl methacrylate monomer and 25.22g of tert-dodecyl mercaptan and mix them evenly in a reaction apparatus to obtain a mixture. Heat the mixture to 127℃, start mechanical stirring and maintain a speed of 200rpm, while keeping the reaction system under nitrogen gas.

[0119] S2: Mix 100g of glycidyl methacrylate monomer and 0.78g of dicumyl peroxide to obtain a monomer / initiator solution; S3: Mix 100g of glycidyl methacrylate monomer and 0.28g of di-tert-butyl peroxide to obtain a monomer / initiator solution; S4: Mix 10g of glycidyl methacrylate monomer, 0.05g of dicumyl peroxide, and 0.03g of di-tert-butyl peroxide to obtain a monomer / initiator solution; S51: After the monomer / initiator solutions are homogeneous, add them all at once to the above reaction system within 30 minutes. The reaction is completed in 4 hours.

[0120] The structural formula of the obtained glycidyl methacrylate homopolymer is as follows:

[0121] The reaction yield for preparing the glycidyl methacrylate homopolymer in Comparative Example 3 was measured to be 93.7%. The glycidyl methacrylate homopolymer was subjected to relevant detections using the aforementioned method, with the proton NMR spectrum shown below. Figure 9a See GPC test report Figure 9b The weight-average molecular weight of the glycidyl methacrylate homopolymer was approximately 451,320, and the PDI was 3.23.

[0122] in, Figure 9a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 9a There are two distinct residual peaks in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 94%. Figure 9b The presence of only one complete single peak indicates that most of the monomers in the reaction have been converted.

[0123] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 93.7%.

[0124] Comparative Example 4 S1: Mix 900g of glycidyl methacrylate monomer and 25.22g of tert-dodecyl mercaptan in a reaction apparatus to obtain a mixture. Heat the mixture to 87°C, start mechanical stirring and maintain a speed of 200 rpm, while keeping the reaction system under nitrogen gas.

[0125] S2: Mix 100g of glycidyl methacrylate monomer and 0.78g of dicumyl peroxide to obtain a monomer / initiator solution; S3: Mix 100g of glycidyl methacrylate monomer and 0.28g of di-tert-butyl peroxide to obtain a monomer / initiator solution; S4: Mix 10g of glycidyl methacrylate monomer, 0.05g of dicumyl peroxide, and 0.03g of di-tert-butyl peroxide to obtain a monomer / initiator solution; S51: After the monomer / initiator solutions are homogeneous, add them all at once to the above reaction system within 30 minutes. The reaction is completed in 4 hours.

[0126] The structural formula of the obtained glycidyl methacrylate homopolymer is as follows:

[0127] The reaction yield for preparing the glycidyl methacrylate homopolymer in Comparative Example 4 was 91.1%. The glycidyl methacrylate homopolymer was subjected to relevant detections using the aforementioned method, with the proton NMR spectrum shown below. Figure 10a See GPC test report Figure 10b The weight-average molecular weight of the glycidyl methacrylate homopolymer was approximately 8413, and the PDI was 2.50.

[0128] in, Figure 10a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 10a There are two distinct residual peaks in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 91.5%. Figure 10b The presence of only one complete single peak indicates that most of the monomers in the reaction have been converted.

[0129] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 91.1%.

[0130] Comparative Example 5 S1: Take 1000g of glycidyl methacrylate monomer, 25.22g of tert-dodecyl mercaptan, 0.78g of dicumyl peroxide and 0.28g of di-tert-butyl peroxide and mix them evenly in the reaction equipment to obtain a mixture.

[0131] S2: Heat the mixture to 127°C, start mechanical stirring and maintain a speed of 200 rpm, while keeping the reaction system under nitrogen gas. The reaction is completed in 14 hours.

[0132] The structural formula of the obtained glycidyl methacrylate homopolymer is as follows:

[0133] The reaction yield for preparing the glycidyl methacrylate homopolymer in Comparative Example 5 was measured to be 89.9%. The glycidyl methacrylate homopolymer was subjected to relevant detections using the aforementioned method, with the proton NMR spectrum shown below. Figure 11a See GPC test report Figure 11b The weight-average molecular weight of the glycidyl methacrylate homopolymer was approximately 7389, and the PDI was 1.16.

[0134] in, Figure 11a The peaks at shifts of 0.5–4.5 in the image can prove that the synthesized polymer is a homopolymer of glycidyl methacrylate. Figure 11a There are two distinct residual peaks in the 5.5-6.5 shift, and the conversion rate of the reaction is calculated to be 91.5%. Figure 11b The presence of only one complete single peak indicates that most of the monomers in the reaction have been converted.

[0135] The reaction yield = (total reaction product - total loss from sample testing) / total reaction feed = 89.9%.

[0136] In Example 1 of this invention, bulk polymerization is employed, and by segmented heating and segmented addition of monomers and initiators, the product achieves good purity and polymer reaction yield, while also effectively preventing explosive polymerization.

[0137] Comparative Example 1 prepared glycidyl methacrylate homopolymer by solution polymerization. The results showed that the polymer yield was very low and it was impossible to make polymers with large molecular weights. Furthermore, the molecular weight control was unstable and the molecular weight could not be accurately replicated.

[0138] Comparative Example 2 used a suspension polymerization method, which required the polymer product to be purified to remove most of the additives from the water used in the experiment. The post-processing steps were very complicated and increased the experimental cost. Furthermore, the residue of a small amount of the aqueous additives that could not be removed resulted in low purity of the polymer product.

[0139] Although Comparative Example 3 also used bulk polymerization, the reaction temperature was always set at a high temperature, which led to explosive polymerization and caused the polymer product to exhibit cross-linking, insoluble or even insoluble phenomena.

[0140] Although Comparative Example 4 also used bulk polymerization, the monomers and initiators were added all at once at a relatively low temperature, which led to incomplete polymerization and resulted in lower polymer molecular weight and monomer conversion rate.

[0141] Although Comparative Example 5 also used bulk polymerization, the monomers and initiators were added all at once at a relatively high temperature, which led to rapid growth and breakage of the polymer chains, resulting in lower molecular weight of the polymer and lower monomer conversion rate.

[0142] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0143] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. A method for preparing a glycidyl methacrylate polymer, comprising the following steps: S1: Under the action of the first initiator, the first monomer undergoes a bulk polymerization reaction at the first temperature to obtain the first polymerization system; S2: A second monomer and a second initiator are added to the first polymerization system, and a bulk polymerization reaction is carried out at a second temperature to obtain a second polymerization system; and S3: Add a third monomer and a third initiator to the second polymerization system and carry out a bulk polymerization reaction at a third temperature; in, The first monomer, the second monomer, and the third monomer each independently comprise glycidyl (meth)acrylate; the first temperature is 40–90°C, the second temperature is 60–130°C, and the third temperature is 90–170°C.

2. The preparation method according to claim 1, wherein, The first monomer, the second monomer, and the third monomer each independently comprise glycidyl (meth)acrylate, and one or more other (meth)acrylates; The structural formula of the other (meth)acrylate is: CH2=CR1-COOR2; wherein R1 is selected from hydrogen or methyl; and R2 is selected from methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, dodecyl, octadecyl, dimethylaminoethyl, ethyl acetoacetate, benzyl, cyclohexyl or hydroxyethyl.

3. The preparation method according to claim 1, wherein, The (meth)acrylate glycidyl ester polymer is a homopolymer or copolymer; and / or, The second temperature is greater than the first temperature; and / or, The third temperature is greater than or equal to the second temperature.

4. The preparation method according to claim 1, wherein, Based on the sum of the masses of the first monomer, the second monomer, and the third monomer, the mass content of the first monomer is 40-99.8%, the mass content of the second monomer is 0.1-30%, and the mass content of the third monomer is 0.1-30%.

5. The preparation method according to claim 1, wherein, Based on the mass of the first monomer, the mass content of the first initiator is 0.01 to 0.5%; based on the mass of the second monomer, the mass content of the second initiator is 0.1 to 1.0%; based on the mass of the third monomer, the mass content of the third initiator is 0.1 to 1.0%.

6. The preparation method according to claim 1, wherein, The first initiator, the second initiator, and the third initiator are each independently selected from one, two, or more of the following: azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobis(cyclohexane-1-nitrile), benzoyl peroxide, dicumyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide.

7. The preparation method according to claim 1, wherein, The reaction time for step S1 is 0.5 to 12 hours; and / or, The reaction time for step S2 is 1–12 hours; and / or, The reaction time for step S3 is 1 to 10 hours.

8. The preparation method according to claim 1, wherein, A chain transfer agent is also added to the reaction system in step S1.

9. The preparation method according to claim 8, wherein, The chain transfer agent includes one, two or more of the following: n-octylthiol, tert-octylthiol, n-dodecylthiol, tert-dodecylthiol, mercaptoethanol, and isooctyl 3-mercaptopropionate.

10. The preparation method according to claim 8, wherein, Based on the sum of the molar numbers of the first monomer, the second monomer, and the third monomer, the molar content of the chain transfer agent is 0.05 to 20%.

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