CN115960293B - Methyl methacrylate copolymer resistant to stress cracking and preparation method and application thereof - Google Patents
Methyl methacrylate copolymer resistant to stress cracking and preparation method and application thereof Download PDFInfo
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- CN115960293B CN115960293B CN202211580531.3A CN202211580531A CN115960293B CN 115960293 B CN115960293 B CN 115960293B CN 202211580531 A CN202211580531 A CN 202211580531A CN 115960293 B CN115960293 B CN 115960293B
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- methyl methacrylate
- methacrylate copolymer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005336 cracking Methods 0.000 title abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 9
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- 239000000178 monomer Substances 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
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- 238000004519 manufacturing process Methods 0.000 claims description 6
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
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- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- HABNNYNSJFKZFE-UHFFFAOYSA-N 3-Mercapto-2-methylpentanol Chemical compound CCC(S)C(C)CO HABNNYNSJFKZFE-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
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- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010309 melting process Methods 0.000 claims description 2
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
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- 238000002834 transmittance Methods 0.000 description 3
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a stress cracking resistant methyl methacrylate copolymer, a preparation method and application thereof, wherein the methyl methacrylate copolymer is prepared by copolymerizing and devolatilizing the raw materials comprising the following components: 20 to 99.9 parts by mass of methyl methacrylate; 0.1 to 80 parts by mass of a comonomer; 0.01 to 0.5 parts by mass of a chain transfer agent; 0.01-5 parts by mass of a chain extender; wherein the chain transfer agent and the chain extender contain reactive functional groups with each other and the chain extender is added during the devolatilization stage. The methyl methacrylate copolymer provided by the invention has a reduced low molecular weight polymer proportion, so that the stress cracking resistance is effectively improved.
Description
Technical Field
The invention relates to a methyl methacrylate copolymer, in particular to a stress cracking resistant methyl methacrylate copolymer, and a preparation method and application thereof.
Background
The methyl methacrylate copolymer is a polymer obtained by copolymerizing methyl methacrylate serving as a main monomer with other monomers, has many excellent properties such as high light transmittance, good weather resistance, good surface scratch resistance, good dimensional stability and good electrical insulation, and is widely applied to the fields of automobiles, displays, electronic appliances, lighting, billboards and the like.
Because the methyl methacrylate monomer contains ester bonds with strong polarity on the molecular structure, polar substances such as moisture, alcohols, esters and the like easily enter the polymethyl methacrylate to cause the performance defect of the polymer, and particularly, the problem of stress cracking is caused. When the methyl methacrylate polymer is used for extruding a sheet, cracking is easily caused by uneven stress. When the methyl methacrylate polymer is used for, for example, a lamp housing of an automobile tail lamp, cracks may be generated on the surface of the article by the action of a chemical agent such as a detergent for automobile cleaning, a wax remover, etc. In addition, when polymethyl methacrylate is applied to cosmetic packaging or chemical containers, there is also a higher demand for its stress crack resistance.
At present, two methods for improving the chemical resistance of polymethyl methacrylate are mainly adopted, one is to blend and modify a polymer; the other is the introduction of hydrophobic functional groups onto the polymer backbone by copolymerization.
JP2004139839A, JP2004223909a improves the stress crack resistance of resins by copolymerizing styrene with methyl methacrylate. JP1986130330A improves stress cracking resistance of resins by copolymerizing methacrylic acid, glycidyl methacrylate and methyl methacrylate to increase rigidity of a molecular chain. CN102477200B improves the solvent resistance of the resin by introducing a content of 0.02-0.3% of polyfunctional monomer during the polymerization stage.
In the method of copolymerization modification, the introduction of a styrene structure leads to the reduction of yellowing resistance and ageing resistance of the polymer. Methacrylic acid, when involved in copolymerization, causes an increase in the viscosity of the reaction solution and hygroscopicity of the polymer, which is disadvantageous for reaction control and sheet applications. The introduction of polyfunctional monomers can lead to the risk of cross-linking during the polymerization stage, which presents challenges for control of the production process. Therefore, it is of great importance to propose a method for preparing a methyl methacrylate copolymer which can comprehensively solve the above problems.
Disclosure of Invention
In order to solve the above technical problems, the present invention firstly proposes a stress crack resistant methyl methacrylate copolymer. The methyl methacrylate copolymer has a reduced proportion of low molecular weight polymer, so that the stress cracking resistance is effectively improved.
Based on the second aspect of the invention, a preparation method of the methyl methacrylate copolymer with stress cracking resistance is also provided. By introducing a chain extender capable of reacting with hydroxyl mercaptan in the devolatilization stage, the small molecular polymer combined with the chain transfer agent can be further combined to generate macromolecules, so that the problem that the methyl methacrylate copolymer is not resistant to stress cracking is solved.
Based on the third aspect of the invention, the application of the methyl methacrylate copolymer with stress cracking resistance is also provided, especially the application in the fields of cosmetic packaging materials, automobile tail lights and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a stress crack resistant methyl methacrylate copolymer prepared by copolymerizing and devolatilizing raw materials comprising:
20 to 99.9 parts by mass of methyl methacrylate;
0.1 to 80 parts by mass of a comonomer;
0.01 to 0.5 parts by mass of a chain transfer agent;
0.01-5 parts by mass of a chain extender;
wherein the chain transfer agent and the chain extender contain reactive functional groups with each other and the chain extender is added during the devolatilization stage.
As a preferred embodiment, the methyl methacrylate copolymer is produced by copolymerizing and devolatilizing a raw material comprising:
45-99 parts by mass of methyl methacrylate;
1-55 parts by mass of a comonomer;
0.1 to 0.3 parts by mass of a chain transfer agent;
0.1-2 parts by mass of a chain extender.
As a preferred embodiment, the comonomer is selected from alkyl methacrylate, alkyl acrylate or aromatic vinyl monomer, preferably selected from one or more of ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, styrene, a-methylstyrene, more preferably one or more of methyl acrylate, ethyl acrylate, styrene.
In the present invention, the amount of methyl methacrylate is preferably 45 to 99 parts by mass, and the amount of the comonomer is preferably 1 to 55 parts by mass. When the ratio of methyl methacrylate in the copolymer is less than 45 parts by mass, the optical transparency of the prepared copolymer is insufficient; when the ratio of methyl methacrylate monomer in the copolymer is more than 99 parts by mass, the thermal stability and chemical resistance of the prepared copolymer are insufficient.
As a preferred embodiment, the chain transfer agent is a C-chain transfer agent 2 -C 10 Preferably one or more of 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-1-hexanol, 3-mercapto-2-methyl-1-pentanol, preferably 2-mercaptoethanol.
In the methyl methacrylate copolymer provided by the invention, the main function of the chain transfer agent is to adjust the molecular weight of the copolymer. In a preferred embodiment, the weight average molecular weight of the copolymer is from 5 to 20 ten thousand, preferably from 8 to 15 ten thousand. Suitable molecular weights bring about advantageous processability and resistance to chemical changes in the production of the methyl methacrylate copolymers. When the molecular weight of the copolymer is too high, the melt fluidity is poor and the processing is difficult; when the molecular weight of the copolymer is too low, it is difficult to satisfy the requirements in terms of properties.
In order to reduce the proportion of low molecular weight polymer in the copolymer, the invention carries out chain extension reaction by adding a chain extender and a hydroxyl end-capped polymer in a high-temperature extrusion stageTo increase its molecular weight. The chain extender contains reactive functional groups, and as a preferred embodiment, the chain extender has a structure containing at least two epoxy groups or NCO groups, and is preferably selected from epoxy resins having a molecular weight of 300 to 1000, preferably 400 to 800, and carbon atoms C 2 -C 20 Further preferred are polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether. When the molecular weight is too large, the molecular chain movement ability is weak, and the degree of reaction with the low molecular weight polymer is low; when the molecular weight is too small, the molecular weight of the polymer after chain extension is still small, and the effect of improving the stress cracking resistance of the methyl methacrylate copolymer is not obvious.
The amount of the chain extender added to the methyl methacrylate copolymer in the present invention is preferably 0.1 to 2 parts by mass. When the addition amount of the chain extender is too small, the decrease in molecular weight of the low molecular weight polymer in the copolymer is not significant, and when the addition amount is too large, a large amount of the residual chain extender affects the final copolymer application properties.
The invention also provides a preparation method of the stress cracking resistant methyl methacrylate copolymer, which comprises the following steps:
1) Polymerization: mixing methyl methacrylate, a comonomer and a chain transfer agent, continuously adding the mixture into a polymerization reactor, and carrying out polymerization reaction at a temperature of 100-180 ℃ and preferably 130-160 ℃ for 1-6 hours and preferably 2-4 hours until the slurry conversion rate is 50-80%, preferably 55-65%;
2) Devolatilization: and (3) feeding the slurry into a devolatilizer, simultaneously adding a chain extender, devolatilizing the materials in a melting process, and extruding and granulating to obtain the methyl methacrylate copolymer.
As a preferred embodiment, an initiator is further added in the polymerization reaction process in the step 1), so as to further regulate the polymerization reaction rate. The initiator is added in an amount of 10 to 1000ppm, preferably 50 to 300ppm, based on the total mass of methyl methacrylate and comonomer; when the addition amount of the initiator is too low, too much volatile matters in the outlet slurry are unfavorable for devolatilization; when the addition amount of the initiator is too high, the viscosity of the outlet slurry is too high, which is unfavorable for the transportation in the later stage.
Preferably, the initiator is an initiator with a half-life period of 3-30min at the reaction temperature, and when the half-life period is too short, the initiator is decomposed too fast and the initiator efficiency is low; when the half-life period is too long, the initiator is slowly decomposed, and a large amount of initiator remains in the reaction solution, so that a reaction runaway state is likely to occur. Alternative initiators include, but are not limited to, one or more of 1, 1-bis- (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis- (t-butylperoxy) cyclohexane, t-butyl peroxy-3, 5-trimethylhexanoate, 2-bis (t-butylperoxy) butane, t-butylperoxy-2-ethylhexyl carbonate, t-amyl peroxybenzoate, t-butyl peroxybenzoate, dicumyl peroxide, di-t-butyl peroxide.
In the preparation of the methyl methacrylate copolymer of the present invention, a solvent may be optionally added as needed to reduce the viscosity of the materials in the reactor, and the amount of the solvent is 0 to 30%, preferably 10 to 20% of the total mass of all the raw materials in the polymerization system. Alternative solvents include, but are not limited to, one or more of toluene, ethylbenzene, xylene, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, N-dimethylformamide, preferably toluene or ethylbenzene.
The polymerization reactor in step 1) of the present invention may be a fully mixed flow reactor or a plug flow reactor or a combination of both, preferably a fully mixed flow reactor, and more preferably a stirred tank reactor with jacket temperature control. The reactor is provided with a supply port, a discharge port, and a stirring device, and the stirring device preferably has mixing performance throughout the entire reaction zone. Besides jacket temperature control, a flow guide pipe, a coil and the like can be arranged in the reactor, and further temperature control can be performed through heat carrier circulation.
The polymerization temperature is preferably 130 to 160 ℃. When the reaction temperature is too low, the viscosity of the reaction solution is high, which is unfavorable for mass transfer and heat transfer. When the reaction temperature is too high, the proportion of the side-reaction oligomers increases, which is unfavorable for improving the quality of the product.
The polymerization outlet conversion is preferably 55 to 65%. When the outlet conversion rate is too low, the improvement of the production efficiency is not facilitated, and when the outlet conversion rate is too high, the production control is not facilitated due to the large viscosity. In order to control the outlet conversion, the polymerization time is preferably 2 to 4 hours. The polymerization temperature and reactor residence time together determine the outlet conversion.
After the polymerization reaction, the reaction solution was devolatilized by a devolatilizer. The devolatilizer used for preparing the methyl methacrylate copolymer of the present invention may be one or any combination of a vented extruder, a falling-strand devolatilizer, a falling-film devolatilizer, a thin film evaporator, a single-shaft or double-shaft devolatilizer, preferably a falling-strand devolatilizer or a vented extruder or a combination thereof, and more preferably a vented twin-screw extruder. The vented extruder is preferably provided with a rear volatile component outlet, a reaction liquid supply port, a front volatile component outlet, and a polymer outlet arranged from the drive section side to the front end side of the screw. The reaction liquid supplied from the reaction liquid supply port rapidly evaporates the volatile component by releasing heat accumulated as latent heat at the reaction liquid supply port. In order to remove the vapor of the volatile component rapidly from the extruder, it is preferable to provide a rear volatile component outlet on the side opposite to the flow direction of the polymer with respect to the reaction liquid supply port. Further, in order to suppress the generation of carbide and coloring of the product, it is preferable to coat the cylinder inner wall portion, the screw surface, and the like with a metal other than iron such as chromium, titanium, and the like.
In the devolatilizer, in addition to the removal of residual monomers and solvents, reactions between the polymer and the chain extender occur. Therefore, the temperature and residence time of the devolatilized materials in the devolatilizer need to be tightly controlled. As a preferred embodiment, the devolatilization temperature during step 2) is 200-280℃and preferably 220-260 ℃. The devolatilization pressure is below 5KPA, preferably below 3KPA. The residence time is 7-20min, preferably 10-15min. When the devolatilization temperature is too low and the residence time is too short, volatile matters are not easy to be removed sufficiently, and the reaction of the polymer and the chain extender is insufficient; when the devolatilization temperature is too high and the residence time is too long, the polymer is easily colored by heat.
From the viewpoint of economy, it is preferable that the volatile matters such as unreacted monomers are condensed by a condenser and then recycled.
When the above method is used for preparing the methyl methacrylate copolymer with stress crack resistance, auxiliary agents such as a release agent, an ultraviolet absorber, an antioxidant, a colorant, an antistatic agent and the like can be added according to requirements, and the types and the amounts of the additives are all known to those skilled in the art.
The invention also provides an application of the stress crack resistant methyl methacrylate copolymer or the stress crack resistant methyl methacrylate copolymer prepared by the method, especially an application in automobile tail lamps and cosmetic packaging materials. .
According to the invention, a reaction mechanism that the chain transfer agent is finally combined with the micromolecule polymer in the polymerization reaction process is utilized, the chain transfer agent containing hydroxyl functional groups is firstly introduced, a chain extender containing at least two epoxy groups or NCO groups is added in the devolatilization process after the polymerization reaction is finished, and the devolatilization condition is utilized to enable the micromolecule polymerization to continue the chain extension reaction, so that a macromolecule structure is generated, and the stress cracking resistance of the methyl methacrylate copolymer is solved.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The sources of the raw materials involved in the examples and comparative examples are shown in table 1:
table 1, raw material information related to examples
The performance test method according to the following embodiment of the present invention is as follows:
<1> melt index (MFR): the melt index of the methyl methacrylate polymer pellets was measured at 230℃and 3.8KG with reference to the method in ISO 1133.
<2> glass transition temperature measurement (Tg): the glass transition temperature of the methyl methacrylate polymer pellets was tested using the following apparatus and conditions:
temperature programming of a mertler DSC1 thermal analyzer: (1) 25-200 ℃,10K/min; (2) 200 ℃ for 3min; (3) 200-0 ℃ and-10K/min; (4) 0 ℃ for 3min; (5) 0-200 ℃ and 10K/min.
<4> molecular weight test: liquid gel chromatography (GPC) was used, instrument model Water 996, mobile phase Tetrahydrofuran (THF), and parallax refractive detector was used for the detector. Five chromatographic columns, all of which are 7.8X100 mm Column in size; monodisperse PMMA is used as a standard.
<6> light transmittance: sheets of 250mm x 25.4mm x 3mm size were prepared by injection molding (injection molding temperature 240 ℃) and the light transmittance of the sheet at 3mm thickness was tested with reference to the method in ISO 13486.
<7> stress cracking resistance test of copolymer
Sheets of 250mm x 25.4mm x 3mm size (injection temperature 240 ℃) were prepared by injection molding. The obtained sheet was dried in a vacuum dryer for 5 hours, and the following test was performed in a constant temperature and humidity room at 23 ℃ and 50% humidity:
(1) Clamping two ends of the sheet through the fixed base;
(2) Applying a load to the sample to form a deformation of 1% in the sample;
(3) Applying ethanol to the surface of the sheet, and periodically applying ethanol so as to avoid volatilization and disappearance of the ethanol;
(4) Recording the time from the start of ethanol application until a crack appears on the sample;
the stress crack resistance of the article was evaluated by the time at which the crack occurred. The longer the crack occurs, the better the stress crack resistance.
[ example 1 ]
Into the mixing tank were added 95 parts by mass of methyl methacrylate, 5 parts by mass of methyl acrylate, 0.015 part by mass of t-butyl peroxy-3, 5-trimethylhexanoate, and 0.25 part by mass of 2-mercaptoethanol, and the mixture was thoroughly mixed to prepare a reaction solution. And (5) introducing nitrogen and fully removing oxygen.
The reaction liquid after the ingredients is continuously added into a fully mixed flow reaction kettle (effective volume is 30L) at the flow rate of 10KG/h, the temperature in the reactor is controlled to be 135 ℃, the average residence time is 2h, and the outlet conversion rate is 65 percent.
The slurry obtained by the reaction was continuously fed into an exhaust twin screw extruder, 1.5 parts by mass of polyethylene glycol diglycidyl ether (molecular weight 500) was added at the inlet of the extruder, and unreacted monomers and other volatiles were removed under conditions of a pressure of 3KPaA, a temperature of 230℃and a residence time of 12 minutes. And extruding and granulating the devolatilized material to obtain a final product.
[ example 2 ]
85 parts by mass of methyl methacrylate, 15 parts by mass of methyl acrylate, 0.015 part by mass of tert-butyl peroxy-3, 5-trimethylhexanoate and 0.3 part by mass of 2-mercaptoethanol are added into a preparation tank, and the mixture is thoroughly mixed to prepare a reaction solution. And (5) introducing nitrogen and fully removing oxygen.
The reaction solution after the ingredients is continuously added into a fully mixed flow reaction kettle (effective volume is 30L) at the flow rate of 10KG/h, the temperature in the reactor is controlled to 140 ℃, the average residence time is 1.5h, and the outlet conversion rate is 63%.
The slurry obtained by the reaction was continuously fed into an exhaust twin screw extruder, 1.8 parts by mass of polyethylene glycol diglycidyl ether (molecular weight 500) was added at the inlet of the extruder, and unreacted monomers and other volatiles were removed under conditions of a pressure of 3KPaA, a temperature of 235℃and a residence time of 10 minutes. And extruding and granulating the devolatilized material to obtain a final product.
[ example 3 ]
99 parts by mass of methyl methacrylate, 1 part by mass of methyl acrylate, 0.015 part by mass of t-butyl peroxy-3, 5-trimethylhexanoate and 0.2 part by mass of 2-mercaptoethanol were added to the batch tank, and the mixture was thoroughly mixed to prepare a reaction solution. And (5) introducing nitrogen and fully removing oxygen.
The reaction solution after the ingredients is continuously added into a fully mixed flow reaction kettle (effective volume is 30L) at the flow rate of 10KG/h, the temperature in the reactor is controlled to be 130 ℃, the average residence time is 3h, and the outlet conversion rate is 67%.
The slurry obtained by the reaction was continuously fed into an exhaust twin screw extruder, 1.8 parts by mass of polyethylene glycol diglycidyl ether (molecular weight 500) was added at the inlet of the extruder, and unreacted monomers and other volatiles were removed under conditions of a pressure of 3KPaA, a temperature of 220℃and a residence time of 15 minutes. And extruding and granulating the devolatilized material to obtain a final product.
[ example 4 ]
70 parts by mass of methyl methacrylate, 30 parts by mass of styrene, 0.02 part by mass of diisopropyl peroxide and 0.15 part by mass of 3-mercapto-1-propanol are added to a mixing tank, and the mixture is thoroughly mixed to prepare a reaction solution. And (5) introducing nitrogen and fully removing oxygen.
The reaction solution after the ingredients is continuously added into a fully mixed flow reaction kettle (effective volume is 30L) at the flow rate of 10KG/h, the temperature in the reactor is controlled to 145 ℃, the average residence time is 2h, and the outlet conversion rate is 65 percent.
The slurry obtained by the reaction was continuously fed into an exhaust twin screw extruder, 0.8 parts by mass of polypropylene glycol diglycidyl ether (molecular weight 380) was added at the inlet of the extruder, and unreacted monomers and other volatiles were removed under conditions of a pressure of 5KPaA, a temperature of 250℃and a residence time of 7 minutes. And extruding and granulating the devolatilized material to obtain a final product.
[ example 5 ]
50 parts by mass of methyl methacrylate, 50 parts by mass of styrene, 0.025 parts by mass of diisopropyl peroxide and 0.22 parts by mass of 3-mercapto-1-propanol are added to a batch tank, and the mixture is thoroughly mixed to prepare a reaction solution. And (5) introducing nitrogen and fully removing oxygen.
The reaction solution after the ingredients is continuously added into a fully mixed flow reaction kettle (effective volume is 30L) at the flow rate of 10KG/h, the temperature in the reactor is controlled to be 150 ℃, the average residence time is 2h, and the outlet conversion rate is 70%.
The slurry obtained by the reaction was continuously fed into an exhaust twin screw extruder, 1.2 parts by mass of polypropylene glycol diglycidyl ether (molecular weight 380) was added at the inlet of the extruder, and unreacted monomers and other volatiles were removed under conditions of a pressure of 3KPaA, a temperature of 240℃and a residence time of 10 minutes. And extruding and granulating the devolatilized material to obtain a final product.
Comparative example 1
A methyl methacrylate copolymer was produced in substantially the same manner as in example 2 except that 2-mercaptoethanol was replaced with octylmercaptan.
Comparative example 2
A methyl methacrylate copolymer was produced in substantially the same manner as in example 2 except that 2-mercaptoethanol was replaced with t-dodecyl mercaptan.
[ comparative example 3 ]
A methyl methacrylate copolymer was produced in substantially the same manner as in example 2 except that polyethylene glycol diglycidyl ether was not added during devolatilization.
The methyl methacrylate copolymers prepared in each example and comparative example were subjected to the performance test shown in Table 2, and the results were as follows:
TABLE 2 Performance test results
As can be seen from examples 1-5, the methyl methacrylate copolymer prepared by the present invention has excellent stress cracking resistance. As can be seen from the comparison of example 2 with comparative example 1, comparative example 2 and comparative example 3, the mercaptoethanol chain transfer agent is required to be used together with the chain extender of the present invention to effectively improve the stress cracking resistance of the polymer.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (21)
1. A stress crack resistant methyl methacrylate copolymer prepared by copolymerizing and devolatilizing raw materials comprising:
20 to 99.9 parts by mass of methyl methacrylate;
0.1 to 80 parts by mass of a comonomer;
0.01 to 0.5 parts by mass of a chain transfer agent;
0.01-5 parts by mass of a chain extender;
wherein the chain transfer agent and the chain extender contain reactive functional groups with each other and the chain extender is added during the devolatilization stage;
the chain transfer agent has C atoms 2 -C 10 Is a hydroxyl mercaptan of (C).
2. The stress crack resistant methyl methacrylate copolymer according to claim 1, wherein the copolymer is prepared by copolymerization and devolatilization of a feedstock comprising:
45-99 parts by mass of methyl methacrylate;
1-55 parts by mass of a comonomer;
0.1 to 0.3 parts by mass of a chain transfer agent;
0.1-2 parts by mass of a chain extender.
3. The stress crack resistant methyl methacrylate copolymer according to claim 1, wherein the comonomer is selected from alkyl methacrylates, alkyl acrylates or aromatic vinyl monomers.
4. A stress crack resistant methyl methacrylate copolymer according to claim 3, wherein the comonomer is selected from one or more of ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, styrene, a-methylstyrene.
5. The stress crack resistant methyl methacrylate copolymer according to any one of claims 1-4, wherein the chain transfer agent is one or more of 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-1-hexanol, 3-mercapto-2-methyl-1-pentanol.
6. The stress crack resistant methyl methacrylate copolymer of claim 5, wherein the chain extender is a structure comprising at least two epoxy or NCO groups.
7. The stress crack resistant methyl methacrylate copolymer according to claim 6, wherein the chain extender is selected from the group consisting of epoxy resins having a molecular weight of 300 to 1000 and C atoms 2 -C 20 Is a diisocyanate of (a).
8. The stress crack resistant methyl methacrylate copolymer according to claim 7, wherein the chain extender is selected from the group consisting of epoxy resins having a molecular weight of 400 to 800 and C atoms 2 -C 20 Is a diisocyanate of (a).
9. The stress crack resistant methyl methacrylate copolymer according to claim 6, wherein the chain extender is selected from polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.
10. A process for the preparation of a stress crack resistant methyl methacrylate copolymer according to any one of claims 1 to 9, comprising the steps of:
1) Polymerization: mixing methyl methacrylate, a comonomer and a chain transfer agent, continuously adding the mixture into a polymerization reactor, and carrying out polymerization reaction for 1-6h at the temperature of 100-180 ℃ until the slurry conversion rate is 50-80%;
2) Devolatilization: and (3) feeding the slurry into a devolatilizer, simultaneously adding a chain extender, devolatilizing the materials in a melting process, and extruding and granulating to obtain the methyl methacrylate copolymer.
11. The process for preparing a stress crack resistant methyl methacrylate copolymer according to claim 10, wherein in step 1), the polymerization is carried out at a temperature of 130 to 160℃for 2 to 4 hours to a slurry conversion of 55 to 65%.
12. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 10, wherein an initiator is further added in the polymerization reaction process of step 1), and the addition amount of the initiator is 10-1000ppm of the total mass of methyl methacrylate and comonomer.
13. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 12, wherein an initiator is further added during the polymerization reaction in the step 1), and the addition amount of the initiator is 50-300ppm of the total mass of the methyl methacrylate and the comonomer.
14. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 12, wherein the initiator is an initiator having a half life of 3 to 30min at a reaction temperature.
15. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 14, wherein the initiator is one or more of 1, 1-bis- (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis- (t-butylperoxy) cyclohexane, t-butyl peroxy-3, 5-trimethylhexanoate, 2-di (t-butylperoxy) butane, t-butylperoxy-2-ethylhexyl carbonate, t-amyl peroxybenzoate, t-butyl peroxybenzoate, dicumyl peroxide, and di-t-butyl peroxide.
16. The process for preparing a stress crack resistant methyl methacrylate copolymer according to any one of claims 10 to 15, wherein a solvent is further added during the polymerization in step 1), the amount of solvent being 0 to 30% of the total mass of all the raw materials in the polymerization system.
17. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 16, wherein a solvent is added in the polymerization reaction process of step 1), and the amount of the solvent is 10-20% of the total mass of all raw materials in the polymerization system.
18. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 16, wherein the solvent is one or more of toluene, ethylbenzene, xylene, acetone, butanone, ethyl acetate, butyl acetate, tetrahydrofuran, N-dimethylformamide.
19. The process for the preparation of a stress crack resistant methyl methacrylate copolymer according to any one of claims 10 to 15, wherein in step 2) the devolatilization temperature is 200 to 280 ℃ and the devolatilization pressure is lower than 5KPA; the residence time is 7-20min.
20. The method for preparing a stress crack resistant methyl methacrylate copolymer according to claim 19, wherein in the step 2), the devolatilization temperature is 220-260 ℃ and the devolatilization pressure is lower than 3KPA; the residence time is 10-15min.
21. Use of a stress crack resistant methyl methacrylate copolymer according to any one of claims 1 to 9 or a stress crack resistant methyl methacrylate copolymer obtainable by a process according to any one of claims 10 to 20 in automotive tail lights, cosmetic packaging materials.
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| WO2022188268A1 (en) * | 2021-03-12 | 2022-09-15 | 深圳力合博汇光敏材料有限公司 | (meth)acrylic acid polymer containing crosslinkable functional group at terminal position |
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| JPH10152505A (en) * | 1996-09-25 | 1998-06-09 | Mitsubishi Gas Chem Co Inc | Production of styrene-methyl methacrylate-based polymer |
| WO2022188268A1 (en) * | 2021-03-12 | 2022-09-15 | 深圳力合博汇光敏材料有限公司 | (meth)acrylic acid polymer containing crosslinkable functional group at terminal position |
| CN113336882A (en) * | 2021-05-24 | 2021-09-03 | 博立尔化工（扬州）有限公司 | Process for preparing PMMA resin with narrow molecular weight distribution by adopting intermittent bulk polymerization method |
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