CN116731301B - Bio-based scratch-resistant plastic suction tray and preparation method thereof - Google Patents
Bio-based scratch-resistant plastic suction tray and preparation method thereof Download PDFInfo
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- CN116731301B CN116731301B CN202310786133.5A CN202310786133A CN116731301B CN 116731301 B CN116731301 B CN 116731301B CN 202310786133 A CN202310786133 A CN 202310786133A CN 116731301 B CN116731301 B CN 116731301B
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- 239000004033 plastic Substances 0.000 title claims abstract description 28
- 229920003023 plastic Polymers 0.000 title claims abstract description 28
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 35
- 229960002479 isosorbide Drugs 0.000 claims abstract description 35
- 239000003094 microcapsule Substances 0.000 claims abstract description 30
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004417 polycarbonate Substances 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 20
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- -1 isocyanate modified silica Chemical class 0.000 claims description 19
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000006065 biodegradation reaction Methods 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GUNLIKIXAWIAGM-UHFFFAOYSA-N NC(=N)N.OCC(O)CO Chemical compound NC(=N)N.OCC(O)CO GUNLIKIXAWIAGM-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000941 anti-staphylcoccal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008782 xin-kang Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a bio-based scratch-resistant plastic suction tray and a preparation method thereof; in order to reduce environmental burden, the invention uses biological isosorbide as raw material, reacts with dimethyl carbonate to prepare polycarbonate material, and simultaneously uses nano titanium dioxide as core to synthesize modified microcapsule, and introduces isosorbide and 1- (diaminomethylene) guanidine on the surface of the modified microcapsule, thereby enhancing compatibility with polycarbonate, simultaneously utilizing antibacterial property of the modified microcapsule, avoiding biodegradation during use, prolonging service life, and avoiding strength reduction caused by biodegradation problem during use, and causing safety risk.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a bio-based scratch-resistant plastic suction tray and a preparation method thereof.
Background
Plastic pallets are economical and practical containers for transporting and storing articles, have the advantages of light weight and convenient use, but are limited by the self-performance of the plastic pallets, which are inferior to metal pallets in terms of wear resistance, and are easily scratched, and the plastic pallets are mostly made of petroleum or other non-renewable materials, which means that they are not decomposed or degraded in natural environment, and cause a large environmental burden after being discarded, so that it is necessary to prepare an environment-friendly bio-based plastic pallet to meet market demands in view of the above drawbacks.
Disclosure of Invention
The invention aims to provide a bio-based scratch-resistant plastic suction tray and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, preparing a modified microcapsule;
s11, dispersing nano titanium dioxide into absolute ethyl alcohol, performing ultrasonic dispersion for 30-45min, dropwise adding tetraethoxysilane, dropwise adding ammonia water, adjusting the pH value to 10-11, performing light-proof reaction for 4-8h, performing centrifugal separation, washing precipitate with absolute ethyl alcohol for 3-5 times, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing nano titanium dioxide coated with silicon dioxide into DMAc under nitrogen atmosphere, preparing titanium dioxide suspension after ultrasonic dispersion for 1-2h, dripping into isophorone diisocyanate, heating to 70-90 ℃ after dripping is finished, reacting for 4-8h, centrifugally separating, washing for 2-5 times by using DMAc, and drying to constant weight to obtain isocyanate modified silicon dioxide;
s13, under the nitrogen atmosphere, dissolving 1,3, 5-triaminobenzene in butyl acetate, treating to constant temperature by using an ice water bath, adding triethylamine, uniformly mixing, dropwise adding isosorbide, heating to 35-45 ℃, stirring and reacting for 4-8 hours, and removing a solvent by rotary evaporation to obtain isosorbide grafted 1,3, 5-triaminobenzene;
s14, dissolving isosorbide grafted 1,3, 5-triaminobenzene in butyl acetate, adding isocyanate group modified silicon dioxide, heating to 45-55 ℃, stirring for reaction for 8-12 hours, centrifuging, drying to constant weight, and obtaining amino-terminated modified nano silicon dioxide;
s15, dispersing 1, 6-hexanediol diglycidyl ether in DMF, carrying out ice water bath treatment to constant temperature, adding 1- (diaminomethylene) guanidine, heating to 40-60 ℃, reacting for 2-4h, adding amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80-90 ℃, reacting for 8-12h, centrifuging, separating, and vacuum drying to constant weight to obtain modified microcapsules;
s2, mixing the modified microcapsule with isosorbide in a nitrogen atmosphere, stirring and dispersing for 0.5-1h, adding dimethyl carbonate and di-n-butyliden tin oxide, heating to 130-150 ℃, reacting for 4-8h, vacuumizing to the reaction air pressure of 0.5-1KPa, reacting for 0.5-1h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing the bio-based polycarbonate, the glass fiber and the antioxidant, heating to 240-270 ℃, mixing for 45-60min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, and performing plastic suction molding to obtain the tray.
Further, in step S11, the mass ratio of the nano titanium dioxide to the tetraethyl orthosilicate is 10: (2-5).
Further, in step S12, the mass ratio of the silica coated nano titanium dioxide to isophorone diisocyanate is 10: (1-3).
Further, in step S13, the mass ratio of the 1,3, 5-triaminobenzene, triethylamine and isosorbide is 1: (0.03-0.05): (1-1.3).
Further, in the step S14, the mass ratio of the isosorbide grafted 1,3, 5-triaminobenzene to the cyanate ester modified silica is (1-3): 10.
further, in the step S15, the mass ratio of the 1- (diaminomethylene) guanidine, the 1, 6-hexanediol diglycidyl ether and the amino-terminated modified nano-silica is 1: (1.5-2.3): (10-15).
Further, in the step S2, the mass ratio of the modified microcapsule, the isosorbide, the dimethyl carbonate and the di-n-butylidenenoxide is (1-2): (2.5-4): (11-18): (0.3-0.8).
Further, in the step S3, the mass ratio of the bio-based polycarbonate to the glass fiber to the antioxidant is (50-80): (20-40): (0.1-0.5).
Further, in step S4, the plastic sucking temperature is 235-245 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. in order to reduce environmental burden, the invention uses biological isosorbide as a raw material, and the biological isosorbide reacts with the methyl carbonate to prepare the polycarbonate material, so that the polycarbonate material has better degradability compared with petroleum-based plastics, has small environmental burden and reduces the dependence on non-renewable resources such as petroleum and the like;
2. in order to enhance the wear resistance of the plastic tray prepared by the invention, the nano titanium dioxide is used as a core, the modified microcapsule is synthesized, the surface of the titanium dioxide is coated with a layer of silicon dioxide, and then isocyanate is used for treatment on the surface of the titanium dioxide, so that the surface of the titanium dioxide is grafted with isocyanate groups, the reactivity is improved, and the grafting rate of subsequent reactions is increased; on the basis, the invention uses 1,3, 5-triaminobenzene as a grafting core, reacts with isosorbide, and ensures that the 1,3, 5-triaminobenzene still has enough free amino groups for further reaction by controlling reaction conditions; and isosorbide introduced on the surface of the microcapsule can still react with dimethyl carbonate, so that the compatibility and crosslinking property of the microcapsule and polycarbonate are further enhanced, and the strength and wear resistance of the microcapsule are further improved.
3. The plastic tray prepared by the invention is a bio-based plastic tray, can be biodegraded in natural environment, and is prevented from being biodegraded in the use process to influence the strength, so that the invention also introduces 1- (diaminomethylene) guanidine in the process of preparing the modified microcapsule, the 1, 6-hexanediol diglycidyl ether with epoxy groups reacts with the guanidine-glycerol ether, the reaction condition and the addition amount are controlled, the guanidine-glycerol ether compound with free epoxy groups is prepared, the ring opening of amino groups to epoxy groups is utilized, the guanidine-glycerol ether compound is grafted on the surface of the microcapsule, and the antibacterial property is utilized, so that the biodegradation in the use process is avoided, and the service life is prolonged.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the embodiment and the comparative example, the used nano titanium dioxide is XFI02 type nano titanium dioxide provided by Jiangsu Xianfeng nano material technology Co., ltd; ethyl orthosilicate is provided by Anhui Jin Yueguan new materials technology Co., ltd; 1,3, 5-Triaminobenzene is supplied by Shanghai Ala Biochemical technologies Co., ltd; dimethyl carbonate is supplied by ala Ding Shiji limited; isosorbide is supplied by the chemical technology company limited of eastern, hubei; 1, 6-hexanediol diglycidyl ether is available from the biological sciences Co., ltd. In Wuhan Ji Xinyi; 1- (diaminomethylene) guanidine is supplied by Hubei Xinkang pharmaceutical chemical Co., ltd; glass fibers are provided by Hebei's Sikang mineral products Co., ltd., and have an average diameter of 1.02 μm and a fiber length of 3-19mm; the antioxidant is antioxidant 1010;
example 1.
A preparation method of a bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, preparing a modified microcapsule;
s11, dispersing 10 parts of nano titanium dioxide into 200 parts of absolute ethyl alcohol according to parts by weight, performing ultrasonic dispersion for 30min, then dropwise adding 2 parts of tetraethoxysilane, then dropwise adding ammonia water, adjusting the pH to 10, performing light-shielding reaction for 4h, performing centrifugal separation, washing precipitate 3 times by using the absolute ethyl alcohol, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing 10 parts of silicon dioxide coated nano titanium dioxide into DMAc under nitrogen atmosphere, preparing titanium dioxide suspension after ultrasonic dispersion for 1h, dripping into 1 part of isophorone diisocyanate, heating to 70 ℃ after dripping is finished, reacting for 4h, centrifugally separating, washing for 2 times by using DMAc, and drying to constant weight to obtain isocyanate modified silicon dioxide;
s13, under the nitrogen atmosphere, 1 part of 1,3, 5-triaminobenzene is dissolved in butyl acetate, the solution is treated by ice water bath until the temperature is constant, 0.03 part of triethylamine is added, after the solution is uniformly mixed, 1 part of isosorbide is dropwise added, the temperature is raised to 35 ℃, after stirring reaction is carried out for 4 hours, the solvent is removed by rotary evaporation, and the isosorbide grafted 1,3, 5-triaminobenzene is obtained;
s14, 1 part of isosorbide grafted 1,3, 5-triaminobenzene is dissolved in butyl acetate, 10 parts of isocyanate group modified silicon dioxide is added, the temperature is raised to 45 ℃, after stirring reaction is carried out for 8 hours, centrifugal separation is carried out, and after the mixture is dried to constant weight, the amino-terminated modified nano silicon dioxide is obtained;
s15, dispersing 1.5 parts of 1, 6-hexanediol diglycidyl ether in DMF, carrying out ice water bath treatment to constant temperature, adding 1 part of 1- (diaminomethylene) guanidine, heating to 40 ℃, reacting for 2 hours, adding 10 parts of amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80 ℃, reacting for 8 hours, centrifuging, separating, and carrying out vacuum drying to constant weight to obtain a modified microcapsule;
s2, mixing 1 part of modified microcapsule with 2.5 parts of isosorbide under nitrogen atmosphere, stirring and dispersing for 0.5h, adding 11 parts of dimethyl carbonate and 0.3 part of di-n-butylidene tin oxide, heating to 130 ℃, reacting for 4h, vacuumizing to the reaction air pressure of 0.5KPa, reacting for 0.5h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing 50 parts of bio-based polycarbonate, 20 parts of glass fiber and 0.1 part of antioxidant according to parts by weight, heating to 240 ℃, mixing for 45min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, heating to 235 ℃, and performing plastic suction molding to obtain the tray.
Example 2.
Compared with example 1, this example increases the addition amount of 1, 6-hexanediol diglycidyl ether in step S15;
a preparation method of a bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, preparing a modified microcapsule;
s11, dispersing 10 parts of nano titanium dioxide into 200 parts of absolute ethyl alcohol according to parts by weight, performing ultrasonic dispersion for 30min, then dropwise adding 2 parts of tetraethoxysilane, then dropwise adding ammonia water, adjusting the pH to 10, performing light-shielding reaction for 4h, performing centrifugal separation, washing precipitate 3 times by using the absolute ethyl alcohol, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing 10 parts of silicon dioxide coated nano titanium dioxide into DMAc under nitrogen atmosphere, preparing titanium dioxide suspension after ultrasonic dispersion for 1h, dripping into 1 part of isophorone diisocyanate, heating to 70 ℃ after dripping is finished, reacting for 4h, centrifugally separating, washing for 2 times by using DMAc, and drying to constant weight to obtain isocyanate modified silicon dioxide;
s13, under the nitrogen atmosphere, 1 part of 1,3, 5-triaminobenzene is dissolved in butyl acetate, the solution is treated by ice water bath until the temperature is constant, 0.03 part of triethylamine is added, after the solution is uniformly mixed, 1 part of isosorbide is dropwise added, the temperature is raised to 35 ℃, after stirring reaction is carried out for 4 hours, the solvent is removed by rotary evaporation, and the isosorbide grafted 1,3, 5-triaminobenzene is obtained;
s14, 1 part of isosorbide grafted 1,3, 5-triaminobenzene is dissolved in butyl acetate, 10 parts of isocyanate group modified silicon dioxide is added, the temperature is raised to 45 ℃, after stirring reaction is carried out for 8 hours, centrifugal separation is carried out, and after the mixture is dried to constant weight, the amino-terminated modified nano silicon dioxide is obtained;
s15, dispersing 2.3 parts of 1, 6-hexanediol diglycidyl ether in DMF, carrying out ice water bath treatment to constant temperature, adding 1 part of 1- (diaminomethylene) guanidine, heating to 40 ℃, reacting for 2 hours, adding 10 parts of amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80 ℃, reacting for 8 hours, centrifuging, separating, and carrying out vacuum drying to constant weight to obtain a modified microcapsule;
s2, mixing 1 part of modified microcapsule with 2.5 parts of isosorbide under nitrogen atmosphere, stirring and dispersing for 0.5h, adding 11 parts of dimethyl carbonate and 0.3 part of di-n-butylidene tin oxide, heating to 130 ℃, reacting for 4h, vacuumizing to the reaction air pressure of 0.5KPa, reacting for 0.5h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing 50 parts of bio-based polycarbonate, 20 parts of glass fiber and 0.1 part of antioxidant according to parts by weight, heating to 240 ℃, mixing for 45min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, heating to 235 ℃, and performing plastic suction molding to obtain the tray.
Example 3.
Compared with example 1, this example increases the addition amount of the modified microcapsules in step S2;
a preparation method of a bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, preparing a modified microcapsule;
s11, dispersing 10 parts of nano titanium dioxide into 200 parts of absolute ethyl alcohol according to parts by weight, performing ultrasonic dispersion for 30min, then dropwise adding 2 parts of tetraethoxysilane, then dropwise adding ammonia water, adjusting the pH to 10, performing light-shielding reaction for 4h, performing centrifugal separation, washing precipitate 3 times by using the absolute ethyl alcohol, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing 10 parts of silicon dioxide coated nano titanium dioxide into DMAc under nitrogen atmosphere, preparing titanium dioxide suspension after ultrasonic dispersion for 1h, dripping into 1 part of isophorone diisocyanate, heating to 70 ℃ after dripping is finished, reacting for 4h, centrifugally separating, washing for 2 times by using DMAc, and drying to constant weight to obtain isocyanate modified silicon dioxide;
s13, under the nitrogen atmosphere, 1 part of 1,3, 5-triaminobenzene is dissolved in butyl acetate, the solution is treated by ice water bath until the temperature is constant, 0.03 part of triethylamine is added, after the solution is uniformly mixed, 1 part of isosorbide is dropwise added, the temperature is raised to 35 ℃, after stirring reaction is carried out for 4 hours, the solvent is removed by rotary evaporation, and the isosorbide grafted 1,3, 5-triaminobenzene is obtained;
s14, 1 part of isosorbide grafted 1,3, 5-triaminobenzene is dissolved in butyl acetate, 10 parts of isocyanate group modified silicon dioxide is added, the temperature is raised to 45 ℃, after stirring reaction is carried out for 8 hours, centrifugal separation is carried out, and after the mixture is dried to constant weight, the amino-terminated modified nano silicon dioxide is obtained;
s15, dispersing 1.5 parts of 1, 6-hexanediol diglycidyl ether in DMF (dimethyl formamide) for ice water bath treatment to constant temperature, adding 1 part of 1- (diaminomethylene) guanidine, heating to 40 ℃, reacting for 2 hours, adding 10 parts of amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80 ℃, reacting for 8 hours, centrifuging, separating, and vacuum drying to constant weight to obtain modified microcapsules;
s2, mixing 2 parts of modified microcapsules with 2.5 parts of isosorbide in a nitrogen atmosphere, stirring and dispersing for 0.5h, adding 11 parts of dimethyl carbonate and 0.3 part of di-n-butylidene tin oxide, heating to 130 ℃, reacting for 4h, vacuumizing to the reaction air pressure of 0.5KPa, reacting for 0.5h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing 50 parts of bio-based polycarbonate, 20 parts of glass fiber and 0.1 part of antioxidant according to parts by weight, heating to 240 ℃, mixing for 45min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, heating to 235 ℃, and performing plastic suction molding to obtain the tray.
Example 4.
A preparation method of a bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, preparing a modified microcapsule;
s11, dispersing 10 parts of nano titanium dioxide into 200 parts of absolute ethyl alcohol according to parts by weight, performing ultrasonic dispersion for 30min, then dropwise adding 5 parts of tetraethoxysilane, then dropwise adding ammonia water, adjusting the pH to 10, performing light-shielding reaction for 4h, performing centrifugal separation, washing precipitate 3 times by using the absolute ethyl alcohol, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing 10 parts of silicon dioxide coated nano titanium dioxide into DMAc under nitrogen atmosphere, preparing titanium dioxide suspension after ultrasonic dispersion for 1h, dripping into 3 parts of isophorone diisocyanate, heating to 70 ℃ after dripping is finished, reacting for 4h, centrifugally separating, washing for 2 times by using DMAc, and drying to constant weight to obtain isocyanate modified silicon dioxide;
s13, under the nitrogen atmosphere, 1 part of 1,3, 5-triaminobenzene is dissolved in butyl acetate, the mixture is treated by ice water bath until the temperature is constant, 0.05 part of triethylamine is added, after the mixture is uniformly mixed, 1.3 parts of isosorbide is added dropwise, the temperature is raised to 35 ℃, after stirring reaction is carried out for 4 hours, the solvent is removed by rotary evaporation, and the isosorbide grafted 1,3, 5-triaminobenzene is obtained;
s14, 3 parts of isosorbide grafted 1,3, 5-triaminobenzene is dissolved in butyl acetate, 10 parts of isocyanate group modified silicon dioxide is added, the temperature is raised to 45 ℃, after stirring reaction is carried out for 8 hours, centrifugal separation is carried out, and after the constant weight is obtained, the amino-terminated modified nano silicon dioxide is obtained;
s15, dispersing 2.3 parts of 1, 6-hexanediol diglycidyl ether in DMF (dimethyl formamide) for ice water bath treatment to constant temperature, adding 1 part of 1- (diaminomethylene) guanidine, heating to 40 ℃, reacting for 2 hours, adding 15 parts of amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80 ℃, reacting for 8 hours, centrifuging, separating, and vacuum drying to constant weight to obtain modified microcapsules;
s2, mixing 2 parts of modified microcapsules with 4 parts of isosorbide in a nitrogen atmosphere, stirring and dispersing for 0.5h, adding 18 parts of dimethyl carbonate and 0.8 part of di-n-butylidene tin oxide, heating to 130 ℃, reacting for 4h, vacuumizing to the reaction air pressure of 0.5KPa, reacting for 0.5h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing 80 parts of bio-based polycarbonate, 40 parts of glass fiber and 0.5 part of antioxidant according to parts by weight, heating to 270 ℃, mixing for 45min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, heating to 245 ℃, and performing plastic suction molding to obtain the tray.
Comparative example 1.
The comparative example did not prepare modified microcapsules, using only nano titania equivalent replacement;
a preparation method of a bio-based scratch-resistant plastic suction tray comprises the following steps:
s1, mixing 1 part of nano titanium dioxide with 2.5 parts of isosorbide in a nitrogen atmosphere, stirring and dispersing for 0.5h, adding 11 parts of dimethyl carbonate and 0.3 part of di-n-butylidene tin oxide, heating to 130 ℃, reacting for 4h, vacuumizing to the reaction air pressure of 0.5KPa, reacting for 0.5h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s2, mixing 50 parts of bio-based polycarbonate, 20 parts of glass fiber and 0.1 part of antioxidant according to parts by weight, heating to 240-270 ℃, mixing for 45-60min, and extruding and granulating to obtain bio-based tray master batch;
s4, extruding the bio-based tray master batch to prepare a sheet, heating to 235 ℃, and performing plastic suction molding to obtain the tray.
And (3) detection: samples prepared in examples 1-4 and comparative example 1 were prepared as 80 x 10 x 4mm specimens according to ISO-179, and tested for flexural strength at 2mm/min; detecting the wear resistance according to DIN abrasion test; the anti-Staphylococcus aureus properties of examples 1-4 and comparative example 1 were tested according to the film method in GB/T21551.2; the detection results are shown in the following table:
finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. The preparation method of the bio-based scratch-resistant plastic suction tray is characterized by comprising the following steps of:
s1, preparing a modified microcapsule;
s11, dispersing 10 parts by mass of nano titanium dioxide into absolute ethyl alcohol, performing ultrasonic dispersion for 30-45min, dropwise adding 2-5 parts by mass of tetraethoxysilane, dropwise adding ammonia water, adjusting the pH to 10-11, performing light-proof reaction for 4-8h, performing centrifugal separation, washing precipitate 3-5 times by using absolute ethyl alcohol, and drying to constant weight to obtain the nano titanium dioxide coated with silicon dioxide;
s12, dispersing 10 parts by mass of silica coated nano titanium dioxide into DMAc under a nitrogen atmosphere, preparing a titanium dioxide suspension after ultrasonic dispersion for 1-2 hours, dripping into 1-3 parts by mass of isophorone diisocyanate, heating to 70-90 ℃ after dripping is finished, reacting for 4-8 hours, centrifugally separating, washing for 2-5 times by using DMAc, and drying to constant weight to obtain isocyanate modified silica;
s13, under the nitrogen atmosphere, 1 part by mass of 1,3, 5-triaminobenzene is dissolved in butyl acetate, the solution is treated to be constant temperature by ice water bath, 0.03 to 0.05 part by mass of triethylamine is added, after uniform mixing, 1 to 1.3 parts by mass of isosorbide is added dropwise, the temperature is raised to 35 to 45 ℃, after stirring reaction is carried out for 4 to 8 hours, the solvent is removed by rotary evaporation, and the isosorbide grafted 1,3, 5-triaminobenzene is obtained;
s14, 1-3 parts by mass of isosorbide grafted 1,3, 5-triaminobenzene is dissolved in butyl acetate, 10 parts by mass of isocyanate group modified silicon dioxide is added, the temperature is raised to 45-55 ℃, stirring reaction is carried out for 8-12 hours, centrifugal separation is carried out, and after drying is carried out to constant weight, the amino-terminated modified nano silicon dioxide is obtained;
s15, dispersing 1.5-2.3 parts by mass of 1, 6-hexanediol diglycidyl ether in DMF, carrying out ice water bath treatment to constant temperature, adding 1 part by mass of 1- (diaminomethylene) guanidine, heating to 40-60 ℃, reacting for 2-4 hours, adding 10-15 parts by mass of amino-terminated modified nano silicon dioxide prepared in the step S14, heating to 80-90 ℃, reacting for 8-12 hours, centrifuging, separating, and carrying out vacuum drying to constant weight to obtain modified microcapsules;
s2, mixing 1-2 parts by mass of modified microcapsules with 2.5-4 parts by mass of isosorbide in a nitrogen atmosphere, stirring and dispersing for 0.5-1h, adding 11-18 parts by mass of dimethyl carbonate and 0.3-0.8 part by mass of di-n-butylidene tin oxide, heating to 130-150 ℃, reacting for 4-8h, vacuumizing to the reaction air pressure of 0.5-1KPa, reacting for 0.5-1h, stopping heating, washing with absolute ethyl alcohol, and vacuum drying to constant weight to obtain the bio-based polycarbonate;
s3, mixing 50-80 parts by mass of bio-based polycarbonate, 20-40 parts by mass of glass fiber and 0.1-0.5 part by mass of antioxidant, heating to 240-270 ℃, mixing for 45-60min, and extruding and granulating to obtain bio-based tray master batch;
s5, extruding the bio-based tray master batch to prepare a sheet, and performing suction molding at 235-245 ℃ to obtain the tray.
2. A biobased scratch resistant plastic tray prepared according to the method of claim 1.
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