CN112390905A - Methyl methacrylate polymer and preparation method and application thereof - Google Patents
Methyl methacrylate polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of high molecular materials, and discloses a methyl methacrylate polymer and a preparation method thereof. The methyl methacrylate polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is a structural unit with a structure shown in a formula (3);
Description
Technical Field
The invention relates to the technical field of preparation of high molecular materials, in particular to a methyl methacrylate polymer and a preparation method and application thereof.
Background
Polymethyl methacrylate (PMMA), commonly known as organic glass, is a thermoplastic material with excellent performance, and has excellent optical performance, mechanical performance and weather resistance. Relative density of 1.19-1.22, light transmittance>92 percent, the refractive index is 1.49, the tensile strength is 60-80MPa, the impact strength is 12-25kJ/m, and the tensile strength is 8-20 times higher than that of inorganic glass; the stretching orientation is realized, and the impact strength is improved by 1.5 times; the paint has excellent ultraviolet resistance and atmospheric aging resistance; glass transition temperature (T)g)90-110 deg.C, decomposition temperature>250℃。
In addition, PMMA is a very beautiful material, has good processing performance, and is widely applied to the fields of aviation, construction, agriculture, optical instruments, liquid crystal light guide plates and the like. The common production methods comprise bulk polymerization, suspension polymerization and solution polymerization, and the product forms obtained by different production methods are different from the application fields. With the increase of the demand of high-end products at home and abroad, the high-performance PMMA material synthesized by adopting the bulk polymerization method is more and more concerned.
The PMMA product produced by the mass polymerization of Methyl Methacrylate (MMA) is pure and has high transparency; the continuous production is convenient, the utilization rate of equipment is high, and the problem of sewage treatment is avoided; the colloid post-treatment has low energy consumption, and only a small amount of unreacted monomers need to be recycled. In a polymerization kettle with a powerful stirrer and a pneumatic control device, the PMMA slurry after prepolymerization can be directly cast in a mould for secondary polymerization to produce products such as plates, bars, pipes and the like; or removing unreacted monomers (devolatilization for short) at high temperature by a screw, and then extruding and granulating to obtain the PMMA molding compound product.
Because PMMA has excellent solubility in the monomer, the system is uniform and transparent, homogeneous free radical polymerization is adopted, and a polymer product with high relative molecular weight and narrow distribution can be prepared by a bulk polymerization method. But because the bulk polymerization system does not contain other solvents, the viscosity of the system is increased rapidly in the middle and later stages of polymerization, so that the mass transfer and the heat transfer are relatively difficult, the heat generated by polymerization is difficult to remove, and the gel phenomenon is easy to occur due to local overheating, so that the operation difficulty is increased and the comprehensive performance of the product is reduced.
Disclosure of Invention
The invention aims to overcome the problems of heat resistance and over-narrow actual use temperature range of polymethyl methacrylate in the prior art, and provides a methyl methacrylate polymer, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a methyl methacrylate polymer, wherein the polymer comprises a structural unit a, a structural unit B and a structural unit C, the structural unit a is a structural unit having a structure represented by formula (1), the structural unit B is a structural unit having a structure represented by formula (2), and the structural unit C is a structural unit having a structure represented by formula (3);
wherein n is an integer of 40-50, and m is an integer of 1-8.
Preferably, the content of the structural unit A is 88 to 98 wt%, the content of the structural unit B is 0.2 to 2 wt%, and the content of the structural unit C is 1 to 10 wt%, based on the total weight of the polymer.
More preferably, the content of the structural unit A is 89 to 94% by weight, the content of the structural unit B is 0.5 to 1% by weight, and the content of the structural unit C is 5 to 10% by weight, based on the total weight of the polymer.
Preferably, the polymer has a glass transition temperature greater than 120 ℃ and a light transmission greater than 92%.
The second aspect of the present invention provides a method for preparing a methyl methacrylate polymer, comprising the steps of:
(1) mixing methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a mixture I;
(2) mixing a chain transfer agent, an accelerator and the mixture I to obtain a stable solution;
(3) in a nitrogen atmosphere, uniformly mixing an initiator with the solution, and carrying out a polymerization reaction to obtain a polymer colloid;
(4) transferring the polymer colloid to an extruder for extrusion reaction, and then granulating, cooling and drying to obtain the methyl methacrylate polymer;
the functional monomer X has a structure shown in a formula (4),
the functional monomer Y has a structure shown in a formula (5),
wherein n is an integer of 40-50; m is an integer of 1 to 8.
Preferably, in the step (1), the amount of the methyl methacrylate is 88 to 98 wt%, the amount of the functional monomer X is 0.2 to 2 wt%, and the amount of the functional monomer Y is 1 to 10 wt%, based on 100 wt% of the total of the methyl methacrylate and the functional monomer.
Preferably, the amount of the methyl methacrylate is 89-94 wt%, the amount of the functional monomer X is 0.5-1 wt%, and the amount of the functional monomer Y is 5-10 wt%, based on 100% by mass of the total of the methyl methacrylate and the functional monomer.
Preferably, in the step (2), the chain transfer agent is at least one of dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and tert-butyl mercaptan; the accelerator is at least one of guanyl thiourea, 4-methyl thiosemicarbazide and dithiobiuret.
Preferably, the chain transfer agent is used in an amount of 0.05 to 1 wt% and the accelerator is used in an amount of 0.05 to 0.5 wt%, based on the total weight of the methyl methacrylate and the functional monomer.
Preferably, in the step (3), the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxypivalate, and di-tert-butyl peroxide.
Preferably, the initiator is used in an amount of 0.05 to 0.8 wt% based on the total weight of the methyl methacrylate and the functional monomer.
Preferably, in step (3), the polymerization conditions include: the reaction temperature is 90-130 ℃, and the reaction time is 20-60 min.
Preferably, in the step (4), the front section temperature of the extruder is 180-; the extrusion reaction time is 1-2 h.
The third aspect of the invention provides a methyl methacrylate polymer prepared by the preparation method, wherein the glass transition temperature of the polymer is more than 120 ℃, and the light transmittance is more than 92%.
In a fourth aspect, the present invention provides a use of the methyl methacrylate polymer of the present invention.
Through the technical scheme, the polymethyl methacrylate and the preparation method and application thereof provided by the invention have the following beneficial effects:
the functional monomer X and the functional monomer Y are introduced into the macromolecular structure of the polymethyl methacrylate, and the polymerization promoter is added into a polymerization system, so that the polymerization activity of the two functional monomers can be improved, the rigidity and the random copolymerization degree of a polymer molecular chain can be improved, and the heat resistance and the impact resistance of a polymer product are further improved under the condition of ensuring high light transmittance of the polymethyl methacrylate. In addition, in the polymer macromolecular chain, the introduction of the functional monomer X structural unit enables the copolymer macromolecular chains to generate a micro-crosslinking structure, so that the interaction force among the copolymer molecular chains is enhanced, the polymer has higher glass transition temperature, the upper limit service temperature of the polymethyl methacrylate product is further widened, and the high-temperature-resistant polymethyl methacrylate is more suitable for the fields of aviation, optical instruments, liquid crystal light guide plates and the like which need to bear higher temperature.
More importantly, the invention can also adjust the distribution of the copolymer structural units and the sequence structure thereof according to the requirements of special engineering plastics so as to meet the requirements of different markets.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a methyl methacrylate polymer, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is a structural unit with a structure shown in a formula (3);
wherein n is an integer of 40-50, and m is an integer of 1-8.
In the invention, the methyl methacrylate and the specific functional monomer are copolymerized in a copolymerization mode, so that the methyl methacrylate polymer not only has excellent light transmittance, but also has excellent impact resistance. Meanwhile, the methyl methacrylate has high glass transition temperature, which shows that the methyl methacrylate provided by the invention has excellent heat resistance.
According to the invention, the polymer comprises a structural unit A, a structural unit B and a structural unit C, wherein the introduction of the structural units B and C enables micro-crosslinking structures to occur between polymer high molecular chains of the polymer high molecular chains, so that the interaction force between the copolymer molecular chains is enhanced, the polymer has higher glass transition temperature, and the upper limit use temperature of a polymethyl methacrylate product is further widened.
In order to provide excellent heat resistance and impact resistance, the inventor researches the content of each structural unit in the polymer, and finds that when the content of the structural unit A is 88-98 wt%, the content of the structural unit B is 0.2-2 wt% and the content of the structural unit C is 1-10 wt% based on the total weight of the polymer, the polymer of the invention not only has excellent light transmittance, but also has excellent heat resistance and impact resistance, and the polymer shows high glass transition temperature, thereby greatly widening the upper use temperature of the polymethyl methacrylate product.
Further, when the content of the structural unit a is 89 to 94% by weight, the content of the structural unit B is 0.5 to 1% by weight, and the content of the structural unit C is 5 to 10% by weight, based on the total weight of the polymer, the properties of the polymethylmethacrylate are more excellent.
According to the invention, the glass transition temperature of the polymer is greater than 120 ℃ and the light transmittance is greater than 92%.
In the invention, the number average molecular weight of the provided polymer is 8-10.5 ten thousand, and the molecular weight distribution is 1.5-1.7, and the inventor finds that the comprehensive performance of the polymer is more excellent at the moment.
In the invention, gel permeation chromatography is adopted to measure the molecular weight and molecular weight distribution of the polymer; testing of the glass transition temperature T of polymers using differential scanning calorimetryg(ii) a Measuring the light transmittance of the polymer according to the national standard GB/T2410; the polymer impact strength was tested according to ISO 179.
The second aspect of the present invention provides a method for preparing a methyl methacrylate polymer, comprising the steps of:
(1) mixing methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a mixture I;
(2) mixing a chain transfer agent, an accelerator and the mixture I to obtain a stable solution;
(3) in a nitrogen atmosphere, uniformly mixing an initiator with the solution, and carrying out a polymerization reaction to obtain a polymer colloid;
(4) transferring the polymer colloid to an extruder for extrusion reaction, and then granulating, cooling and drying to obtain the methyl methacrylate polymer;
the functional monomer X has a structure shown in a formula (4),
the functional monomer Y has a structure shown in a formula (5),
wherein n is an integer of 40-50; m is an integer of 1 to 8.
In the invention, the methyl methacrylate and the specific functional monomer are copolymerized in a copolymerization mode, so that the methyl methacrylate polymer not only has excellent light transmittance, but also has excellent heat resistance and impact resistance.
In the invention, the polymer is prepared by copolymerizing methyl methacrylate and functional monomers X and Y. Specifically, the introduction of the functional monomers X and Y leads the polymer macromolecular chains to generate a micro-crosslinking structure, thereby enhancing the interaction force among the copolymer molecular chains, leading the polymer to have higher glass transition temperature, improving the heat resistance and the shock resistance of the methyl methacrylate, and widening the upper limit service temperature of the methyl methacrylate product.
According to the invention, in the step (1), the amount of the methyl methacrylate is 88-98 wt%, the amount of the functional monomer X is 0.2-2 wt%, and the amount of the functional monomer Y is 1-10 wt%, based on 100% of the total mass percentage of the methyl methacrylate and the functional monomer.
In the present invention, in order to further improve the heat resistance and glass transition temperature of the methyl methacrylate polymer without affecting the light transmittance of the methyl methacrylate polymer, the inventors have studied the amounts of methyl methacrylate, functional monomer X and functional monomer Y used in the preparation of the polymer, and have found that when the amounts of methyl methacrylate, functional monomer X and functional monomer Y used satisfy the above ranges, the prepared methyl methacrylate polymer has not only excellent light transmittance but also excellent heat resistance and impact resistance.
Furthermore, when the total mass percent of the methyl methacrylate and the functional monomer is 100%, the amount of the methyl methacrylate is 89-94 wt%, the amount of the functional monomer X is 0.5-1 wt%, and the amount of the functional monomer Y is 5-10 wt%, the prepared methyl methacrylate polymer has more excellent performance.
In the invention, the methyl methacrylate is purified methyl methacrylate, and concretely, the methyl methacrylate is purified by reduced pressure distillation.
According to the invention, in the step (2), the chain transfer agent is at least one of dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and tert-butyl mercaptan; the accelerator is at least one of guanyl thiourea, 4-methyl thiosemicarbazide and dithiobiuret.
In the invention, the accelerant is added into the polymerization system, so that the polymerization activity of the functional monomer X and the functional monomer Y is obviously improved, the rigidity and the random copolymerization degree of the molecular weight of the polymer can be improved, and the heat resistance and the impact resistance of the methyl methacrylate polymer are further improved.
According to the present invention, the chain transfer agent is used in an amount of 0.05 to 1 wt% and the accelerator is used in an amount of 0.05 to 0.5 wt%, based on the total weight of methyl methacrylate and functional monomer.
According to the present invention, in the step (3), the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxypivalate, and di-tert-butyl peroxide.
According to the invention, the initiator is used in an amount of 0.05 to 0.8% by weight, based on the total weight of methyl methacrylate and functional monomer.
According to the present invention, in the step (3), the polymerization conditions include: the reaction temperature is 90-130 ℃, and the reaction time is 20-60 min.
In the present invention, in the step (3), in order to prevent the influence of air present in the polymerization system on the polymerization reaction, nitrogen gas is previously introduced into the polymerization system to discharge the air and the like present in the system.
According to the invention, in the step (4), the front section temperature of the extruder is 180-; the extrusion reaction time is 1-2 h.
In the present invention, the extruder used for the extrusion reaction is a screw devolatilization extruder.
The third aspect of the invention provides a methyl methacrylate polymer prepared by the preparation method, wherein the glass transition temperature of the polymer is more than 120 ℃, and the light transmittance is more than 92%.
In a fourth aspect, the present invention provides a use of the methyl methacrylate polymer of the present invention.
The present invention will be described in detail below by way of examples. In the following examples, the molecular weight and molecular weight distribution of the polymer were measured by gel permeation chromatography (PL-GPC 20); the glass transition temperature T of the polymers was measured by differential scanning calorimetry (DSC8500)g(ii) a Measuring the light transmittance of the polymer according to the national standard GB/T2410; the polymer impact strength was tested according to ISO 179.
The following examples and comparative examples used the starting materials:
methylmethacrylate was purchased from west longa science, inc;
the structural formula of the functional monomer X1 is shown in formula 4, wherein n is 40, and the functional monomer is purchased from Shanghai Allantin Biotech Co., Ltd;
the structural formula of the functional monomer X2 is shown in formula 4, wherein n is 50, and the functional monomer is purchased from Shanghai Allantin Biotechnology Co., Ltd;
the structural formula of the functional monomer X3 is shown in formula 4, wherein n is 45, and the functional monomer is purchased from Shanghai Allantin Biotechnology Co., Ltd;
the structural formula of the functional monomer Y1 is shown in formula 5, wherein m is 1, and the functional monomer is purchased from Shanghai Allantin Biotech Co., Ltd;
the structural formula of the functional monomer Y2 is shown in formula 5, wherein m is 2, and the functional monomer is purchased from Shanghai Allantin Biotech Co., Ltd;
the structural formula of the functional monomer Y3 is shown in formula 5, wherein m is 8, and the functional monomer is purchased from Shanghai Allantin Biotechnology Co., Ltd;
the structural formula of the functional monomer Y4 is shown in formula 5, wherein m is 4, and the functional monomer is purchased from Shanghai Allantin Biotechnology Co., Ltd;
all other raw materials are commercially available.
Example 1
1. Weighing 88g (mass content: 88%) of purified methyl methacrylate, adding the methyl methacrylate into a polymerization kettle, adding 2.0g (mass content: 2%) of functional monomer X1 and 10g (mass content: 10%) of functional monomer Y1 into the polymerization kettle, and fully stirring to completely dissolve the methyl methacrylate;
2. adding 0.1g of tert-dodecyl mercaptan and 0.2g of guanyl thiourea into a polymerization kettle, and stirring to dissolve the mixture to form a stable solution;
3. blowing nitrogen into the polymerization kettle for 30 minutes, adding 0.2g of dibenzoyl peroxide, continuously blowing the nitrogen to uniformly mix the dibenzoyl peroxide and the dibenzoyl peroxide, heating the polymerization kettle to 120 ℃, and reacting for 25 minutes;
4. extruding polymer colloid in a polymerization kettle from the bottom of the kettle, and conveying the polymer colloid to a screw devolatilization extruder, wherein the temperature of the front section of the extruder is 180 ℃, the temperature of the middle section of the extruder is 220 ℃, and the temperature of the tail end of the extruder is 240 ℃; the reaction time of the colloid in the extruder was 1.5 hours;
5. and starting a cutting machine head at the front section of the extruder to carry out granulation, cooling and drying to obtain the methyl methacrylate polymer. The results of the performance tests on the methyl methacrylate polymer are shown in Table 1.
Example 2
1. Weighing 90g (mass content is 90%) of purified methyl methacrylate, adding the methyl methacrylate into a polymerization kettle, adding 0.5g (mass content is 0.5%) of functional monomer X2 and 9.5g (mass content is 9.5%) of functional monomer Y2 into the polymerization kettle, and fully stirring to completely dissolve the methyl methacrylate;
2. adding 0.25g of dodecyl mercaptan and 0.3g of 4-methyl thiosemicarbazide into a polymerization kettle, and stirring to dissolve the dodecyl mercaptan and the 4-methyl thiosemicarbazide to obtain a stable solution;
3. blowing nitrogen into the polymerization kettle for 30 minutes, adding 0.2g of dibenzoyl peroxide, continuously blowing the nitrogen to uniformly mix the dibenzoyl peroxide and the dibenzoyl peroxide, heating the polymerization kettle to 110 ℃, and reacting for 30 minutes;
4. extruding polymer colloid in a polymerization kettle from the bottom of the kettle, and conveying the polymer colloid to a screw devolatilization extruder, wherein the temperature of the front section of the extruder is 190 ℃, the temperature of the middle section of the extruder is 210 ℃, and the temperature of the tail end of the extruder is 250 ℃; the reaction time of the colloid in the extruder was 2.0 hours;
5. and starting a cutting machine head at the front section of the extruder to carry out granulation, cooling and drying to obtain the methyl methacrylate polymer. The results of the performance tests on the methyl methacrylate polymer are shown in Table 1.
Example 3
1. Weighing 98g (mass content 98%) of purified methyl methacrylate, adding the methyl methacrylate into a polymerization kettle, adding 0.2g (mass content 0.2%) of functional monomer X3 and 1.8g (mass content 1.8%) of functional monomer Y3 into the polymerization kettle, and fully stirring to completely dissolve the methyl methacrylate;
2. adding 0.5g of dodecyl mercaptan and 0.5g of dithiobiuret into a polymerization kettle, and stirring for dissolving to obtain a stable solution;
3. after blowing nitrogen into the polymerization kettle for 30 minutes, adding 0.5g of azobisisobutyronitrile, continuously blowing nitrogen to uniformly mix the azodiisobutyronitrile and the azoisobutyronitrile, heating the polymerization kettle to 130 ℃, and reacting for 20 minutes;
4. extruding polymer colloid in a polymerization kettle from the bottom of the kettle, and conveying the polymer colloid to a screw devolatilization extruder, wherein the temperature of the front section of the extruder is 210 ℃, the temperature of the middle section of the extruder is 240 ℃, and the temperature of the tail end of the extruder is 260 ℃; the reaction time of the colloid in the extruder was 1.0 hour;
5. and starting a cutting machine head at the front section of the extruder to carry out granulation, cooling and drying to obtain the methyl methacrylate polymer. The results of the performance tests on the methyl methacrylate polymer are shown in Table 1.
Example 4
1. Weighing 92g (mass content 92%) of purified methyl methacrylate, adding the methyl methacrylate into a polymerization kettle, adding 0.3g (mass content 0.3%) of functional monomer X2 and 7.7g (mass content 7.7%) of functional monomer Y4 into the polymerization kettle, and fully stirring to completely dissolve the methyl methacrylate;
2. adding 0.4g of dodecyl mercaptan and 0.35g of 4-methyl thiosemicarbazide into a polymerization kettle, and stirring to dissolve the dodecyl mercaptan and the 4-methyl thiosemicarbazide to form a stable solution;
3. blowing nitrogen into the polymerization kettle for 30 minutes, adding 0.25g of dibenzoyl peroxide, continuously blowing the nitrogen to uniformly mix the dibenzoyl peroxide and the dibenzoyl peroxide, heating the polymerization kettle to 115 ℃, and reacting for 25 minutes;
4. extruding polymer colloid in a polymerization kettle from the bottom of the kettle, and conveying the polymer colloid to a screw devolatilization extruder, wherein the temperature of the front section of the extruder is 190 ℃, the temperature of the middle section of the extruder is 220 ℃, and the temperature of the tail end of the extruder is 240 ℃; the reaction time of the colloid in the extruder was 1.5 hours;
5. and starting a cutting machine head at the front section of the extruder to carry out granulation, cooling and drying to obtain the methyl methacrylate polymer. The results of the performance tests on the methyl methacrylate polymer are shown in Table 1.
Example 5
A methyl methacrylate polymer was prepared according to the method of example 4, except that: the functional monomer X2 was used in an amount of 7.5 wt%, and the functional monomer Y4 was used in an amount of 0.5 wt%. The results of the performance test of the methyl methacrylate polymer are shown in Table 1.
Comparative example 1
A methyl methacrylate polymer was prepared according to the method of example 1, except that: does not contain the functional monomer X. The results of the performance test of the methyl methacrylate polymer are shown in Table 1.
Comparative example 2
A methyl methacrylate polymer was prepared according to the method of example 1, except that: does not contain a functional monomer Y. The results of the performance test of the methyl methacrylate polymer are shown in Table 1.
Comparative example 3
A methyl methacrylate polymer was prepared according to the method of example 2, except that: no accelerator was added. The results of the performance test of the methyl methacrylate polymer are shown in Table 1.
Comparative example 4
A methyl methacrylate polymer was prepared according to the method of example 3, except that: ethylene glycol dimethacrylate is used to replace the functional monomer X, and methyl acrylate is used to replace the functional monomer Y. The results of the performance test of the methyl methacrylate polymer are shown in Table 1.
TABLE 1
As can be seen from the results of table 1, the methyl methacrylate polymers provided in examples 1 to 5 of the present invention not only have excellent light transmittance, but also have significantly increased glass transition temperature, and the produced methyl methacrylate has high glass transition temperature, indicating that the methyl methacrylate polymers have improved heat resistance and higher upper use temperature of the methyl methacrylate polymers.
Meanwhile, the methyl methacrylate polymers provided in examples 1 to 5 have excellent impact resistance.
Furthermore, in the methyl methacrylate polymer, the respective contents of the structural unit A, the structural unit B and the structural unit C satisfy the requirements that the methyl methacrylate provided by the examples 1 to 4 defined by the invention has higher heat resistance and impact strength and more excellent comprehensive performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A methyl methacrylate polymer, wherein the polymer comprises a structural unit A, a structural unit B and a structural unit C, the structural unit A is a structural unit with a structure shown in a formula (1), the structural unit B is a structural unit with a structure shown in a formula (2), and the structural unit C is a structural unit with a structure shown in a formula (3);
wherein n is an integer of 40-50, and m is an integer of 1-8.
2. The methyl methacrylate polymer according to claim 1, wherein the content of the structural unit a is 88 to 98% by weight, the content of the structural unit B is 0.2 to 2% by weight, and the content of the structural unit C is 1 to 10% by weight, based on the total weight of the polymer;
preferably, the content of the structural unit A is 89 to 94 wt%, the content of the structural unit B is 0.5 to 1 wt%, and the content of the structural unit C is 5 to 10 wt%, based on the total weight of the polymer.
3. The methyl methacrylate polymer of claim 1 or 2, wherein the polymer has a glass transition temperature greater than 120 ℃ and a light transmittance greater than 92%.
4. A method for preparing a methyl methacrylate polymer, comprising the steps of:
(1) mixing methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a mixture I;
(2) mixing a chain transfer agent, an accelerator and the mixture I to obtain a stable solution;
(3) in a nitrogen atmosphere, uniformly mixing an initiator with the solution, and carrying out a polymerization reaction to obtain a polymer colloid;
(4) transferring the polymer colloid to an extruder for extrusion reaction, and then granulating, cooling and drying to obtain the methyl methacrylate polymer;
the functional monomer X has a structure shown in a formula (4),
the functional monomer Y has a structure shown in a formula (5),
wherein n is an integer of 40-50; m is an integer of 1 to 8.
5. The production method according to claim 4, wherein in the step (1), the amount of the methyl methacrylate is 88 to 98 wt%, the amount of the functional monomer X is 0.2 to 2 wt%, and the amount of the functional monomer Y is 1 to 10 wt%, based on 100% by mass of the total of the methyl methacrylate and the functional monomer;
preferably, the amount of the methyl methacrylate is 89-94 wt%, the amount of the functional monomer X is 0.5-1 wt%, and the amount of the functional monomer Y is 5-10 wt%, based on 100% by mass of the total of the methyl methacrylate and the functional monomer.
6. The production method according to claim 4 or 5, wherein, in the step (2), the chain transfer agent is at least one of dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and tert-butyl mercaptan; the accelerant is at least one of guanyl thiourea, 4-methyl thiosemicarbazide and dithiobiuret;
preferably, the chain transfer agent is used in an amount of 0.05 to 1 wt% and the accelerator is used in an amount of 0.05 to 0.5 wt%, based on the total weight of the methyl methacrylate and the functional monomer.
7. The production method according to any one of claims 4 to 6, wherein in the step (3), the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxypivalate, and di-tert-butyl peroxide;
preferably, the initiator is used in an amount of 0.05 to 0.8 wt% based on the total weight of methyl methacrylate and functional monomer;
preferably, the polymerization conditions include: the reaction temperature is 90-130 ℃, and the reaction time is 20-60 min.
8. The preparation method according to any one of claims 4-7, wherein in the step (4), the temperature of the front section of the extruder is 180-210 ℃, the temperature of the middle section is 200-240 ℃, and the temperature of the end section is 230-260 ℃; the extrusion reaction time is 1-2 h.
9. A methyl methacrylate polymer produced by the production method according to any one of claims 4 to 8, wherein the polymer has a glass transition temperature of more than 120 ℃ and a light transmittance of more than 92%.
10. Use of a methacrylic polymer according to any of claims 1 to 3 and 9.
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| CN201910745669.6A CN112390905B (en) | 2019-08-13 | 2019-08-13 | Methyl methacrylate polymer and preparation method and application thereof |
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