CN114456328A - Preparation method of methyl methacrylate polymer, methyl methacrylate polymer and application thereof - Google Patents
Preparation method of methyl methacrylate polymer, methyl methacrylate polymer and application thereof Download PDFInfo
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- CN114456328A CN114456328A CN202011131320.2A CN202011131320A CN114456328A CN 114456328 A CN114456328 A CN 114456328A CN 202011131320 A CN202011131320 A CN 202011131320A CN 114456328 A CN114456328 A CN 114456328A
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- methyl methacrylate
- methacrylate polymer
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- polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 90
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 15
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl mercaptan Chemical compound 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000012567 medical material Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012773 agricultural material Substances 0.000 claims description 3
- JIRRNZWTWJGJCT-UHFFFAOYSA-N carbamothioylthiourea Chemical compound NC(=S)NC(N)=S JIRRNZWTWJGJCT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OKGXJRGLYVRVNE-UHFFFAOYSA-N diaminomethylidenethiourea Chemical compound NC(N)=NC(N)=S OKGXJRGLYVRVNE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- PTVZQOAHCSKAAS-UHFFFAOYSA-N 4-methyl-3-thiosemicarbazide Chemical compound CNC(=S)NN PTVZQOAHCSKAAS-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 17
- 239000004926 polymethyl methacrylate Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011825 aerospace material Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of high polymer material preparation, and discloses a preparation method of a methyl methacrylate polymer, the methyl methacrylate polymer and application thereof, wherein the method comprises the following steps: under an inert atmosphere, in the presence of an initiator, an accelerator and a chain transfer agent, carrying out bulk polymerization on reaction monomers comprising methyl methacrylate, a monomer X with a structure of a formula (1) and a monomer Y with a structure of a formula (2) to obtain a methyl methacrylate polymer; wherein n is 40-50, m is 1-4;
Description
Technical Field
The invention relates to the technical field of high polymer material preparation, in particular to a preparation method of a methyl methacrylate polymer, the methyl methacrylate polymer 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. The common production methods include bulk polymerization, suspension polymerization and solution polymerization, and the product forms obtained by different production processes are different from the application fields. The product has light weight, high light transmittance, high tensile strength and impact strength which are 8-20 times higher than those 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, and can keep no yellowing for more than 10 years without adding any antioxidant; the glass transition temperature (Tg) is 90-110 ℃, and the decomposition temperature is more than 250 ℃. In addition, PMMA is a very beautiful material, has good processing performance, and is widely applied to the fields of aviation, building, agriculture and the like. Meanwhile, along with popularization and application in the fields of liquid crystal light guide plates, optical materials, high-end medical materials and the like, the demand on optical PMMA products is greatly increased, and the optical PMMA products are wider in the market. The optical-grade product has the characteristics of pure product, uniform molecular weight, low volatile component, high transparency, good heat resistance and the like, and the optical-grade PMMA material synthesized by adopting the bulk polymerization process is more and more concerned with the increase of the demand of high-end products at home and abroad.
The PMMA material is produced by adopting a bulk polymerization process, so that the industrial continuous production is facilitated, the equipment utilization rate 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, PMMA slurry after prepolymerization can be directly cast in a die, and is molded after secondary polymerization to produce products such as plates, bars, pipes and the like; or after high-temperature devolatilization by a screw, extruding, cutting and granulating to obtain the PMMA molding compound product.
Because PMMA has excellent solubility in the monomer, the polymerization system is uniform and transparent, and is homogeneous free radical polymerization, and a polymer product with high relative molecular weight and narrow distribution can be prepared by a bulk polymerization process. However, when the monomer conversion rate is more than 20% in a bulk polymerization system, the viscosity of the polymerization system is rapidly increased, which causes very difficult mass and heat transfer, difficult removal of heat generated by polymerization, and easy occurrence of local overheating and gel phenomenon, even implosion, resulting in increased operation difficulty and reduced comprehensive performance of products.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a methyl methacrylate polymer, a preparation method and application thereof.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a methyl methacrylate polymer, the method comprising the steps of:
under the atmosphere of inert gas and in the presence of an initiator, an accelerator and a chain transfer agent, carrying out bulk polymerization on reaction monomers comprising methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a methyl methacrylate polymer;
wherein the functional monomer X has a structure shown in a formula (1), wherein n is an integer of 40-50,
the functional monomer Y has a structure shown in a formula (2), wherein m is an integer of 1-4;
wherein, based on the total weight of the reaction monomers, the dosage of the methyl methacrylate is 84-99 wt%, the dosage of the functional monomer X is 0.5-3 wt%, and the dosage of the functional monomer Y is 0.5-15 wt%.
In a second aspect, the present invention provides a methyl methacrylate polymer prepared by the preparation method as described above.
In a third aspect, the present invention provides a methyl methacrylate polymer comprising a structural unit a, a structural unit B and a structural unit C, wherein the structural unit a has a structure represented by formula (3), the structural unit B has a structure represented by formula (4), and the structural unit C has a structure represented by formula (5); wherein, based on the total weight of the polymer, the content of the structural unit A is 84-99 wt%, the content of the structural unit B is 0.5-3 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein n is an integer of 40-50, and m is an integer of 1-4.
In a fourth aspect, the present invention provides the use of a methyl methacrylate polymer as described above in an aerospace material, a building material, an agricultural material, a liquid crystal material, an optical material or a medical material.
Through the technical scheme of the invention, the following beneficial effects can be achieved:
1. according to the invention, the functional monomer X, the functional monomer Y and the accelerant are introduced, and the methyl methacrylate polymer is prepared by adopting a bulk polymerization system, so that the polymerization reaction is stable, the mass transfer and heat transfer are improved, and the heat generated by polymerization can be easily removed, so that the phenomena of gelation and even implosion caused by local overheating are not easy to occur.
2. 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 the polymerization system, so that the polymerization activity of free radicals of the two functional monomers can be improved, and the randomness of the polymer can be improved, namely the heat resistance of the polymer product is further improved under the condition of ensuring high light transmittance of the polymethyl methacrylate.
3. In a polymer macromolecular chain, the introduction of a large side group Y structural unit can further improve the rigidity and the temperature resistance of the polymer, reduce the water absorption of the polymer, enable the polymer to have higher thermal decomposition temperature and further widen the upper limit use temperature of a polymethyl methacrylate product.
4. The process of the present invention can produce polymer products having relatively high molecular weight and narrow distributions.
5. 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.
In a first aspect, the present invention provides a process for preparing a methyl methacrylate polymer, the process comprising the steps of:
under the atmosphere of inert gas and in the presence of an initiator, an accelerator and a chain transfer agent, carrying out bulk polymerization on reaction monomers comprising methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a methyl methacrylate polymer;
wherein the functional monomer X has a structure shown in a formula (1), wherein n is an integer of 40-50,
the functional monomer Y has a structure shown in a formula (2), wherein m is an integer of 1-4;
wherein, based on the total weight of the reaction monomers, the dosage of the methyl methacrylate is 84-99 wt%, the dosage of the functional monomer X is 0.5-3 wt%, and the dosage of the functional monomer Y is 0.5-15 wt%.
According to the present invention, the amount of the methyl methacrylate used may be any value between 84 and 99 wt% and a range of values obtained by combining any of these values, based on the total weight of the reaction monomers, for example, the amount of the methyl methacrylate used may be 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%; preferably 86 to 93% by weight, more preferably 86 to 89% by weight.
The methyl methacrylate, which preferably has a purity of at least 99.8% by weight, is commercially available or may be purified after commercial use by methods known in the art, for example, by distillation under reduced pressure.
According to the present invention, the functional monomer X may be used in an amount of any value between 0.5 and 3 wt% based on the total weight of the reaction monomers and in a range of any value in combination between these values, for example, the functional monomer X may be used in an amount of 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%; preferably 1 to 2% by weight, and may be, for example, 1% by weight, 1.2% by weight, 1.4% by weight, 1.6% by weight, 1.8% by weight, or 2% by weight.
According to the invention, in the functional monomer X, the structure is shown as the formula (1), n is any integer between 40 and 50, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50, preferably 40 to 45.
According to the invention, the reactive monomers X are commercially available.
According to the present invention, the functional monomer Y may be used in an amount of any number between 0.5 and 15 wt% and in a range of any combination of these values, based on the total weight of the reaction monomers, for example, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; preferably 6 to 12 wt%, more preferably 10 to 12 wt%.
According to the invention, in the functional monomer Y, the structure is shown as formula (2), m is any integer between 1 and 4, for example, can be 1, 2, 3 and 4, preferably 2 to 3.
According to the present invention, the reactive monomer Y may be commercially available.
According to the present invention, the inert gas may be any gas which does not participate in the polymerization reaction of the present invention, and for example, it may be nitrogen, argon, helium or the like, and preferably nitrogen.
According to the present invention, the initiator may be a conventional initiator for initiating polymerization of monomers, and for example, may include, but is not limited to, at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxypivalate, and di-tert-butyl peroxide, preferably dibenzoyl peroxide and/or azobisisobutyronitrile, more preferably dibenzoyl peroxide.
Preferably, the initiator is used in an amount of 0.05 to 0.8 wt.%, for example, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.45 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, based on the total mass of the reactive monomers.
According to the invention, the introduction of the accelerator effectively improves the activity of free radical polymerization of the monomers, the light transmittance of the obtained methyl methacrylate and the heat resistance of the product, and preferably, the accelerator is a thiourea accelerator, preferably at least one of guanyl thiourea, 4-methyl thiosemicarbazide and dithiobiuret, and more preferably, the guanyl thiourea and/or the dithiobiuret.
Preferably, the promoter is used in an amount of 0.05 to 0.5 wt.%, for example, 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, based on the total mass of the reaction monomers.
According to the invention, the chain transfer agent may be a conventional agent for chain transfer, preferably an alkyl mercaptan type chain transfer agent, preferably an alkyl mercaptan of C4-C12, for example, an alkyl mercaptan of C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, preferably at least one of n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and t-butyl mercaptan.
Preferably, the chain transfer agent is used in an amount of 0.05 to 1 wt%, and may be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, based on the total mass of the reaction monomers.
According to the present invention, the conditions of the polymerization reaction may be selected within a wide range as long as the polymerization reaction between the monomers and the formation of the methyl methacrylate polymer can be caused. Preferably, in order to further improve the performance of the obtained methyl methacrylate polymer, the polymerization reaction temperature is 90-130 ℃, for example, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, preferably 90-125 ℃, and the reaction time is 20-60min, for example, 20min, 30min, 40min, 50min, 60 min.
According to a preferred embodiment of the present invention, a method for preparing a methyl methacrylate polymer comprises:
(1) mixing and dissolving methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a reaction monomer solution;
(2) adding a chain transfer agent and an accelerator into the reaction monomer solution to obtain a reaction solution;
(3) and adding an initiator into the reaction solution under the inert gas atmosphere to carry out bulk polymerization reaction, thereby obtaining the methyl methacrylate polymer.
According to the present invention, preferably, in the step (3), before the initiator is added, the inert gas is introduced into the reaction system for a period of time, for example, 20 to 40min, then the initiator is added, and then the inert gas is continuously introduced, and after the reaction system is uniform, the system is controlled to the polymerization reaction condition to start the reaction.
According to the present invention, preferably, the method further comprises: and (3) sequentially extruding, granulating, cooling and drying the methyl methacrylate polymer obtained by the reaction.
Preferably, the extrusion comprises a front section, a middle section and a tail section, wherein the extrusion temperature of the front section is 180-.
In a second aspect, the present invention provides a methyl methacrylate polymer prepared by the preparation method as described above.
In a third aspect, the present invention provides a methyl methacrylate polymer comprising a structural unit a, a structural unit B and a structural unit C, wherein the structural unit a has a structure represented by formula (3), the structural unit B has a structure represented by formula (4), and the structural unit C has a structure represented by formula (5); wherein, based on the total weight of the polymer, the content of the structural unit A is 84-99 wt%, the content of the structural unit B is 0.5-3 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein n n is an integer of 40-50, and m is an integer of 1-4.
According to the present invention, the content of the structural unit a may be any value between 84 and 99 wt% and a range of values obtained by combining any of these values, based on the total weight of the polymer, for example, the content of the structural unit a may be 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%; preferably 86 to 93% by weight, more preferably 86 to 89% by weight.
According to the present invention, the content of the structural unit B may be any value between 0.5 and 3 wt% and any range of values obtained by combining any of these values, based on the total weight of the polymer, for example, the content of the structural unit B may be 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%; preferably 1 to 2% by weight, and may be, for example, 1% by weight, 1.2% by weight, 1.4% by weight, 1.6% by weight, 1.8% by weight, or 2% by weight.
According to the invention, in the structural unit B, shown as the formula (4), n is any integer between 40 and 50, for example, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50, preferably 40 to 45.
According to the present invention, the content of the structural unit C may be any value between 0.5 and 15 wt% and any range of values obtained by combining any of these values, based on the total weight of the polymer, for example, the structural unit C may be used in an amount of 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; preferably 6 to 12 wt%, more preferably 10 to 12 wt%.
According to the invention, in the structural unit C, as shown in formula (5), m is any integer between 1 and 4, for example, 1, 2, 3, 4, preferably 2 to 3.
In the present invention, the content of each structural unit in the polymer can be measured by a method conventional in the art, such as infrared spectroscopy, nuclear magnetism, and the like.
According to the present invention, it is preferable that the number average molecular weight Mn of the methyl methacrylate polymer is 10 to 12 ten thousand. The number average molecular weight can be measured by a gel permeation chromatography (PL-GPC20) method.
According to the invention, it is preferred that the impact strength of the methyl methacrylate polymer is greater than 21KJ/m2. Wherein the impact strength can be tested according to ISO 179-1-2010.
According to the present invention, it is preferred that the glass transition temperature of the methyl methacrylate polymer is greater than 120 ℃. Wherein the glass transition temperature can be measured by differential scanning calorimetry (DSC 8500).
According to the present invention, it is preferable that the water absorption rate of the methyl methacrylate polymer is less than 0.3%. Wherein the water absorption can be determined according to the water absorption of ISO 62-2008 plastics.
According to the present invention, it is preferable that the light transmittance of the methyl methacrylate polymer is more than 92%. Wherein, the light transmittance can be measured according to the national standard GB/T2410.
In a fourth aspect, the present invention provides the use of a methyl methacrylate polymer as described above in an aerospace material, a building material, an agricultural material, a liquid crystal material, an optical material or a medical material.
The present invention will be described in detail below by way of examples. In the following examples, the number average molecular weight of the polymer was measured by gel permeation chromatography (PL-GPC 20); the glass transition temperature Tg of the polymer was tested with a differential scanning calorimeter (DSC 8500); water absorption of the test sample according to ISO 62-2008 plastic water absorption; measuring the light transmittance of the polymer according to the national standard GB/T2410; the polymer was tested for impact strength according to ISO 179-1-2010.
The methyl methacrylate was purified by distillation under reduced pressure and had a purity of 99.8% by weight.
Examples 1 to 4
Examples 1 to 4 are for illustrating the methyl methacrylate polymer and the preparation method thereof provided by the present invention
1. According to table 1, the purified methyl methacrylate was weighed and added to a polymerization kettle, and then functional monomer X and functional monomer Y were added to the polymerization kettle and sufficiently stirred to be completely dissolved.
2. Adding chain transfer agent and accelerator into a polymerization kettle, stirring and dissolving to obtain a stable solution.
3. And blowing nitrogen into the polymerization kettle for 30 minutes, adding an initiator, continuously blowing the nitrogen to uniformly mix the initiator and the nitrogen, and heating the polymerization kettle to the polymerization reaction temperature to perform bulk polymerization.
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 front section temperature, the middle section temperature and the tail section temperature of the extruder are shown in table 1; the reaction time of the gel in the extruder is shown in table 1.
5. According to the calculated and determined material charging amount and the raw material allowance, the content of the structural unit A provided by the methyl methacrylate, the content of the structural unit B provided by the functional monomer X and the content of the structural unit C provided by the functional monomer Y are basically consistent with the charging amount by taking the total weight of the obtained methyl methacrylate polymer as a reference.
6. The cutting head at the front end of the extruder is started to carry out granulation, cooling and drying to obtain the polymethyl methacrylate molding compound, and the performance test results are shown in Table 2.
TABLE 1
Note: in example 1, functional monomer X was purchased from Profenox technologies, Inc.; functional monomer Y was purchased from Beijing YinoKay science and technology Ltd;
in example 2, functional monomer X was purchased from carbofuran technologies ltd; functional monomer Y was purchased from Beijing YinoKay science and technology Ltd;
in example 3, functional monomer X was purchased from carbofuran technologies ltd; functional monomer Y was purchased from Beijing YinoKay science and technology Ltd;
in example 4, functional monomer X was purchased from Profenox technologies, Inc.; functional monomer Y was purchased from Onky technologies, Inc. of Beijing.
Example 5
This example illustrates the methyl methacrylate polymer and the preparation method thereof according to the present invention
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 1, except that t-dodecyl mercaptan was replaced with the same amount of 3-mercaptohexyl α -methacrylate.
Example 6
This example illustrates the methyl methacrylate polymer and the preparation method thereof according to the present invention
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 1, except that the initiator dibenzoyl peroxide was replaced with a persulfate oxidizer and a sulfite reducer as the oxidation-reduction system initiator.
Comparative example 1
Comparative example to illustrate a reference methyl methacrylate Polymer and method of making the same
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 1 except that the functional monomer X was not used.
Comparative example 2
Comparative example to illustrate a reference methyl methacrylate Polymer and method of making the same
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 1 except that the functional monomer Y was not used.
Comparative example 3
Comparative example to illustrate a reference methyl methacrylate Polymer and method of making the same
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 1, except that no accelerator was used.
Comparative example 4
Comparative example to illustrate a reference methyl methacrylate Polymer and method of making the same
The preparation of a methyl methacrylate polymer was carried out in the same manner as in example 6 except that the functional monomer Y was not used.
TABLE 2
As can be seen from the results of table 2:
1. comparing example 1 with comparative examples 1-3, it can be seen that the invention introduces functional monomer X, functional monomer Y and accelerator, and adopts bulk polymerization system to prepare methyl methacrylate polymer, the molecular weight distribution of polymer is narrowed, which shows that the reaction is stable, the mass and heat transfer is improved, and the heat generated by polymerization can be easily removed, so that local overheating and gel, even implosion, are not easy to occur.
2. Comparing example 1 with comparative examples 1-3, it can be seen that functional monomer X and functional monomer Y are introduced into the macromolecular structure of polymethyl methacrylate, and polymerization accelerator is added into the polymerization system, so that the heat resistance and impact strength of the polymer product are further improved under the condition of ensuring high light transmittance of polymethyl methacrylate.
3. Compared with the comparative example 2, the introduction of the large side group Y structural unit in the macromolecular chain of the polymer can further improve the rigidity and the temperature resistance of the polymer, reduce the water absorption of the polymer, enable the polymer to have higher thermal decomposition temperature and further widen the upper limit use temperature of the polymethyl methacrylate product.
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 (13)
1. A method for preparing a methyl methacrylate polymer, comprising the steps of:
under the atmosphere of inert gas and in the presence of an initiator, an accelerator and a chain transfer agent, carrying out bulk polymerization on reaction monomers comprising methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a methyl methacrylate polymer;
wherein the functional monomer X has a structure shown in a formula (1), wherein n is an integer of 40-50,
the functional monomer Y has a structure shown in a formula (2), wherein m is an integer of 1-4;
wherein, based on the total weight of the reaction monomers, the dosage of the methyl methacrylate is 84-99 wt%, the dosage of the functional monomer X is 0.5-3 wt%, and the dosage of the functional monomer Y is 0.5-15 wt%.
2. The preparation method according to claim 1, wherein the methyl methacrylate is used in an amount of 86 to 93 wt%, the functional monomer X is used in an amount of 1 to 2 wt%, and the functional monomer Y is used in an amount of 6 to 12 wt%, based on the total weight of the reaction monomers.
3. The production method according to claim 1 or 2, wherein n is an integer of 40 to 45; and/or
m is 2 or 3.
4. The production method according to any one of claims 1 to 3, wherein the conditions of the polymerization reaction include: the temperature is 90-130 deg.C, preferably 90-125 deg.C, and the time is 20-60 min.
5. The production method according to any one of claims 1 to 4, wherein the chain transfer agent is an alkyl mercaptan, preferably an alkyl mercaptan of C4 to C12, more preferably at least one of n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and t-butyl mercaptan; further preferably, the chain transfer agent is used in an amount of 0.05 to 1% by weight, based on the total mass of the reaction monomers; and/or
The accelerant is thiourea, preferably at least one of guanyl thiourea, 4-methyl thiosemicarbazide and dithiobiuret, and more preferably, the accelerant is used in an amount of 0.05-0.5 wt% based on the total mass of the reaction monomers; and/or
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, and more preferably, the initiator is used in an amount of 0.05-0.8 wt% based on the total mass of the reaction monomers.
6. The production method according to any one of claims 1 to 5, wherein the method further comprises:
(1) mixing and dissolving methyl methacrylate, a functional monomer X and a functional monomer Y to obtain a reaction monomer solution;
(2) adding a chain transfer agent and an accelerator into the reaction monomer solution to obtain a reaction solution;
(3) and adding an initiator into the reaction solution under the inert gas atmosphere to carry out bulk polymerization reaction, thereby obtaining the methyl methacrylate polymer.
7. The production method according to any one of claims 1 to 6, wherein the method further comprises: sequentially extruding, granulating, cooling and drying the methyl methacrylate polymer obtained by the reaction;
preferably, the extrusion comprises a front section, a middle section and a rear section, wherein the extrusion temperature of the front section is 180-.
8. A methyl methacrylate polymer produced by the production method according to any one of claims 1 to 7.
9. A methyl methacrylate polymer is characterized by comprising a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A has a structure shown in a formula (3), the structural unit B has a structure shown in a formula (4), and the structural unit C has a structure shown in a formula (5); wherein, based on the total weight of the polymer, the content of the structural unit A is 84-99 wt%, the content of the structural unit B is 0.5-3 wt%, and the content of the structural unit C is 0.5-15 wt%;
wherein n is an integer of 40-50, and m is an integer of 1-4.
10. The methyl methacrylate polymer according to claim 9, wherein the content of the structural unit a is 86 to 93% by weight, the content of the structural unit B is 1 to 2% by weight, and the content of the structural unit C is 6 to 12% by weight, based on the total weight of the polymer.
11. The methyl methacrylate polymer according to claim 9 or 10, wherein n is an integer of 40 to 45 and m is 2 or 3.
12. The methyl methacrylate polymer according to any one of claims 9 to 11, wherein the number average molecular weight Mn of the methyl methacrylate polymer is from 10 to 12 ten thousand; and/or
The impact strength of the methyl methacrylate polymer is more than 21KJ/m2(ii) a And/or
The glass transition temperature of the methyl methacrylate polymer is greater than 120 ℃; and/or
The water absorption of the methyl methacrylate polymer is less than 0.3%; and/or
The light transmittance of the methyl methacrylate polymer is greater than 92%.
13. Use of the methyl methacrylate polymer as claimed in any one of claims 8 to 12 in aeronautical materials, construction materials, agricultural materials, liquid crystal materials, optical materials or medical materials.
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