CN118024637A - Preparation process and application of modified polypropylene packaging sheet - Google Patents
Preparation process and application of modified polypropylene packaging sheet Download PDFInfo
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- CN118024637A CN118024637A CN202410449847.1A CN202410449847A CN118024637A CN 118024637 A CN118024637 A CN 118024637A CN 202410449847 A CN202410449847 A CN 202410449847A CN 118024637 A CN118024637 A CN 118024637A
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- -1 polypropylene Polymers 0.000 title claims abstract description 137
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 135
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 46
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 235000013618 yogurt Nutrition 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 9
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000005576 amination reaction Methods 0.000 claims description 12
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000007246 mechanism Effects 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007142 ring opening reaction Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 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 compound 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 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000007337 electrophilic addition reaction Methods 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGDLZZYHWFBVHX-ZPHPHTNESA-N (z)-2-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCC(C(N)=O)CCCCCCCCCC\C=C/CCCCCCCC WGDLZZYHWFBVHX-ZPHPHTNESA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000010471 Markovnikov's rule Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000015140 cultured milk Nutrition 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 235000008924 yoghurt drink Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of yoghurt packaging material research and development, and discloses a preparation process and application of a modified polypropylene packaging sheet, wherein the preparation process comprises the following steps: preparing POSS modified SiO 2 nano particles; the polypropylene resin is modified by the synergistic anti-sticking modification effect of the silicone oil and the POSS modified SiO 2 nano particles, so as to obtain modified polypropylene master batch; the modified polypropylene sheet is prepared by adopting a multilayer coextrusion casting film extrusion method, using modified polypropylene master batches as raw materials of an inner layer and an outer layer, ethylene-vinyl alcohol copolymer resin as raw materials of an intermediate layer and maleic anhydride grafted polypropylene resin as raw materials of a bonding layer. The invention provides a preparation process of a modified polypropylene sheet, and accordingly, a modified polypropylene packaging sheet with excellent anti-sticking performance is prepared, and the modified polypropylene packaging sheet can be applied to eight-cup yoghurt packaging.
Description
Technical Field
The invention relates to the technical field of yoghurt packaging material research and development, in particular to a preparation process and application of a modified polypropylene packaging sheet.
Background
Common packaging forms of yogurt mainly include glass, ceramic packaging, plastic bag and cup and bottle packaging, and a kettles-type packaging and a composite packaging. Among them, plastic cup has become one of the mainstream packaging methods. However, a great problem with yogurt packed in plastic cups is that the residual drinking amount is high, and how to reduce the sticking of yogurt on the solid surface is the focus of the development of the invention.
Polypropylene is a thermoplastic synthetic resin, and can replace styrene as a main material for packaging the eight-cup yoghurt because of the advantages of good chemical stability, good toughness, easy processing and the like. For example, patent publication number CN112706430a discloses a yogurt eight-connected cup made of PP material, a modified PP sheet for manufacturing the yogurt eight-connected cup and a preparation method thereof, polypropylene is used as a main material of the yogurt eight-connected cup instead of polystyrene, so that the cost of packaging materials is greatly reduced, and the use effect of the yogurt eight-connected cup is not obviously different from that of the polystyrene yogurt eight-connected cup.
The present invention refers to the following references: the journal of organosilicon materials discloses the chemical structure and preparation method of vinyl heptaisobutyl POSS in the journal of the fifth period 300-305 of 2011, published by Shoujunping and the like on the synthesis and characterization of monofunctional silsesquioxane.
Disclosure of Invention
The invention provides a preparation process and application of a modified polypropylene packaging sheet, wherein a POSS monomer is utilized to modify SiO 2 nano particles, on one hand, the interfacial compatibility of SiO 2 nano particles and a polypropylene matrix is enhanced, on the other hand, the anti-sticking performance of polypropylene is improved by cooperation with silicone oil, and on the basis, a multilayer coextrusion and tape casting film forming process is adopted to prepare the modified polypropylene sheet, so that the modified polypropylene sheet has excellent anti-sticking performance and mechanical property and can be applied to eight-cup yoghurt packaging.
A preparation process of a modified polypropylene packaging sheet comprises the following steps:
step one: preparing POSS modified SiO 2 nano-particles, wherein the POSS modified SiO 2 nano-particles are single POSS modified SiO 2 nano-particles;
The preparation method of the single POSS modified SiO 2 nano-particle comprises the following steps: firstly synthesizing a monocarboxyl POSS monomer, and then utilizing the monocarboxyl POSS monomer to modify SiO 2 nano particles modified by a silane coupling agent KH560 based on a carboxyl-epoxy ring-opening reaction mechanism;
Step two: modifying the polypropylene resin by the synergistic anti-sticking modification effect of the silicone oil and the POSS modified SiO 2 nano particles prepared in the first step to prepare modified polypropylene master batch;
Step three: the modified polypropylene sheet is prepared by adopting a multilayer coextrusion casting film extrusion method, using modified polypropylene master batches as raw materials of an inner layer and an outer layer, ethylene-vinyl alcohol copolymer resin as raw materials of an intermediate layer and maleic anhydride grafted polypropylene resin as raw materials of a bonding layer.
Preferably, the preparation method of the monocarboxyl POSS monomer comprises the following steps: according to an olefin electrophilic addition reaction mechanism, utilizing strong acid to catalyze the pimelic acid and vinyl heptaisobutyl POSS to generate an addition reaction, so as to generate a monocarboxyl POSS monomer; wherein the ratio of the amounts of the substances of pimelic acid and vinylheptaisobutyl POSS is (1.01-1.09): 1.
Preferably, the strong acid catalyst is one of sulfuric acid, p-toluenesulfonic acid and fluoroboric acid.
Preferably, in the first step, the POSS modified SiO 2 nanoparticles are bridged POSS modified SiO 2 nanoparticles;
The preparation method of the bridged POSS modified SiO 2 nano-particles comprises the following steps: firstly synthesizing an amination bridging POSS monomer, and then utilizing the amination bridging POSS monomer to modify SiO 2 nano particles modified by a silane coupling agent KH560 based on an amino-epoxy ring-opening reaction mechanism.
Preferably, the preparation method of the amination bridging POSS monomer comprises the following steps: generating an amination bridging POSS monomer through esterification reaction of carboxyl functional groups of the monocarboxyl POSS monomer and hydroxyl functional groups of diethanolamine; wherein the mass ratio of the monocarboxyl POSS monomer to the diethanolamine is (2.01-2.05): 1.
Preferably, the preparation method of the modified polypropylene master batch in the second step comprises the following steps: preparing raw materials according to the formula of modified polypropylene master batches, and preparing the modified polypropylene master batches by using a double-screw extruder through the process steps of blending, melting, extruding and granulating;
Wherein, the formula of the modified polypropylene master batch is as follows: 90-95 parts by weight of polypropylene resin, 0.5-5 parts by weight of silicone oil, 0.5-5 parts by weight of POSS modified SiO 2 nano particles, 0.1-0.8 part by weight of talcum powder, 0.05-0.5 part by weight of octadecyl erucamide and 0.05-0.5 part by weight of composite auxiliary agent.
Preferably, the composite auxiliary agent comprises 0.5-3 parts by weight of antioxidant 168, 0.1-5 parts by weight of antioxidant 1010, 0.05-1 parts by weight of antistatic agent AT and 0.05-1.5 parts by weight of ultraviolet resistant agent UV-329.
Preferably, the preparation method of the modified polypropylene sheet in the third step comprises the following steps: firstly setting a film structure of five layers of co-extrusion films, then sequentially putting the raw materials of each layer of film into corresponding hoppers of five screw extruders of a five-layer co-extrusion film casting unit, mixing, merging molten resin at a machine head through a flow divider, and casting and extruding through a die head to obtain the modified polypropylene sheet.
Preferably, the film structure of the five-layer co-extrusion film is an inner layer, a bonding layer, an intermediate layer, a bonding layer and an outer layer;
The mass ratio of the inner layer to the bonding layer to the middle layer to the bonding layer to the outer layer in the five-layer co-extrusion film is (30-50): (1-10): (5-20): (1-10): (30-50).
The invention has the beneficial effects that: according to the invention, through the synergistic effect of the silicone oil and the POSS modified SiO2 nano particles, the modified polypropylene sheet is subjected to modification treatment, so that the prepared modified polypropylene packaging sheet not only has excellent anti-sticking performance, but also has obviously improved mechanical properties, and the barrier property and the hygienic property of the modified polypropylene packaging sheet also meet the requirements of the performance of a yoghurt packaging material.
The modified polypropylene packaging sheet prepared by the invention can be applied to eight-cup yoghurt packaging.
Drawings
FIG. 1 is a chemical structural formula and a hydrogen spectrum of a monocarboxyl POSS monomer;
FIG. 2 is a chemical structural formula and a hydrogen spectrum of an aminated bridged POSS monomer;
FIG. 3 shows the results of performance experiments on polypropylene sheets.
Detailed Description
Example I-1:
the polypropylene sheet PPS-I is prepared by the following steps:
(1) Preparation of polypropylene masterbatch I: according to the formula of the polypropylene master batch I in the table 1, adding the polypropylene resin, silicone oil, talcum powder, octadecyl erucic acid amide and a compound additive into a double-screw extruder, and carrying out blending, melting, extrusion and granulating by the double-screw extruder to prepare the polypropylene master batch I;
Wherein, the technological parameters of the twin-screw extruder are set as follows: the temperature of the 1-3 regions is 130 ℃,150 ℃ and 175 ℃ respectively, and the rotating speed is 30r/min;
(2) The preparation method of the polypropylene sheet PPS-I comprises the following steps:
Step one: the polypropylene sheet PPS-I is provided with five layers of co-extrusion films, and the film structure is as follows:
a first layer: a polypropylene resin layer prepared by taking polypropylene master batch I as a raw material, and 40 parts by weight of a polypropylene resin layer;
a second layer: maleic anhydride grafted polypropylene resin layer, 5 parts by weight;
third layer: an ethylene-vinyl alcohol copolymer resin layer, 10 parts by weight;
fourth layer: maleic anhydride grafted polypropylene resin layer, 5 parts by weight;
Fifth layer: a polypropylene resin layer prepared by taking polypropylene master batch I as a raw material, and 40 parts by weight of a polypropylene resin layer;
Step two, respectively putting the raw materials in the step one into hoppers of five screw extruders of a five-layer co-extrusion film casting unit, mixing by stirring, converging molten resin at a machine head through a flow divider, and casting, extruding, cooling and rolling through a die head to obtain a polypropylene sheet PPS-I with the thickness of 100 mu m;
Wherein, the technological parameters of the screw extruder corresponding to the polypropylene resin layer are set as follows: the temperature of the 1-3 areas is 130 ℃, 150 ℃, 170 ℃, the temperature of the flow channel is 160 ℃ and the rotating speed is 30r/min;
The technological parameters of the screw extruder corresponding to the maleic anhydride grafted polypropylene resin layer are set as follows: the temperature of the 1-3 areas is 115 ℃, 145 ℃, 160 ℃, the temperature of the flow channel is 150 ℃ and the rotating speed is 15r/min;
The technological parameters of the screw extruder corresponding to the ethylene-vinyl alcohol copolymer resin layer are set as follows: the temperature of the 1-3 regions is 180 ℃, 200 ℃, 210 ℃, the temperature of the flow channel is 205 ℃ and the rotating speed is 40r/min.
Example I-2:
The preparation process of the polypropylene sheet PPS-II is as follows:
(1) Preparing polypropylene master batch II: according to the formula of the polypropylene master batch II in the table 1, referring to the preparation steps and the process conditions of the polypropylene master batch I, the polypropylene master batch II is prepared;
(2) Preparation of polypropylene sheet PPS-II: the polypropylene master batch I in example I-1 was replaced with a polypropylene master batch II, and the polypropylene sheet PPS-II was obtained by referring to the preparation steps and process conditions of the polypropylene sheet PPS-I.
Example I-3:
the preparation process of the polypropylene sheet PPS-III is as follows:
(1) Preparing polypropylene master batch III: according to the formula of the polypropylene master batch III in the table 1, referring to the preparation steps and the process conditions of the polypropylene master batch I, the polypropylene master batch III is prepared;
(2) Preparation of polypropylene sheet PPS-III: the polypropylene master batch I in example I-1 was replaced with a polypropylene master batch III, and the polypropylene sheet PPS-III was obtained by referring to the preparation steps and process conditions of the polypropylene sheet PPS-I.
Example I-4:
the preparation process of the polypropylene sheet PPS-IV is as follows:
(1) Preparing polypropylene master batch IV: according to the formula of the polypropylene master batch IV in the table 1, referring to the preparation steps and the process conditions of the polypropylene master batch I, the polypropylene master batch IV is prepared;
(2) Preparing a polypropylene sheet PPS-IV: the polypropylene master batch I in example I-1 was replaced with a polypropylene master batch IV, and the polypropylene sheet PPS-IV was obtained by referring to the preparation steps and process conditions of the polypropylene sheet PPS-I.
Wherein the raw material formulas of the polypropylene master batches used in examples I-1 to I-4 are shown in Table 1;
table 1 Experimental formulation (mass percent) of Polypropylene masterbatch
Note that: the composite auxiliary agent consists of 1 part by weight of antioxidant 168, 1 part by weight of antioxidant 1010, 0.5 part by weight of antistatic agent AT and 0.5 part by weight of ultraviolet resistant agent UV-329;
the specifications and manufacturers of the raw materials used in examples I-1 to I-4 are shown in Table 2;
TABLE 2 Experimental raw materials
| Raw material name | Specification of specification | Manufacturer' s |
| Polypropylene resin | Brand HJ4012 | Shanghai bridge micro chemical technology Co.Ltd |
| Maleic anhydride grafted polypropylene resin | Brand B1 | Keais chemical Co Ltd |
| Ethylene-vinyl alcohol copolymer resin | Brand E105B | Kathy Plastic materials Co., ltd |
| Silicone oil | Viscosity 350cs | Chu eagle New Material Co.Ltd in Shenzhen City |
| Nano silicon dioxide | Goods number S433693 | Shanghai Ala Biochemical technology Co.Ltd |
| Talc powder | Goods number XZD-020 | Dongguan city delun New Material Co., ltd |
| Octadecylerucamide | Purity of 99.0% | Jiangxi Zhi Ling New Material Co., ltd |
| Antioxidant 168 | Purity of 98.0% | Shanghai Rui chemical Co., ltd |
| Antioxidant 1010 | Purity of 98.0% | Shanghai Rui chemical Co., ltd |
| Antistatic agent AT | Model CHEMISTAT 3500 | Shanghai Kaiyin chemical Co., ltd |
| UV-329 as an anti-UV agent | Purity of 99.0% | Shanghai Rui chemical Co., ltd |
Performance test:
1. Anti-sticking performance test: the release properties of the yoghurt were analysed by testing the residual amount of yoghurt on a sample of sheet material, the specific test steps being as follows: fixing a sample with the length of 3cm multiplied by 2cm on a clamping plate with the length of multiplied by the width of 5cm multiplied by 4cm, injecting a drop of yoghourt (Li Yuan fermented milk) to the top end of a film sample by using a syringe with the yoghourt measuring range of 20mL, weighing the initial yoghourt mass, placing a test sample in a mode of forming an angle of 45 degrees with the horizontal plane for simulating the condition of a human body when drinking yoghourt, standing for 20s after the yoghourt flows down, recording the residual yoghourt mass after tilting, and calculating the yoghourt residual quantity to characterize the anti-sticking performance, wherein the method comprises the following steps:
Yoghurt residual (%) = the mass of yoghurt remaining on the sample after tilting/the initial yoghurt mass on the sample;
2. Barrier performance test: the samples were tested for oxygen transmission capacity and water vapor transmission capacity in sequence according to GB/T1038-2000 and GB/T1037-2021, and the specific test steps were as follows: placing a 30cm round sample in a glass dryer with an ambient temperature of 25 ℃ and anhydrous calcium chloride as a drying agent, keeping for 72 hours, and then testing the barrier performance of the sample by using a Y110 type oxygen transmission tester and a W3/060 type water vapor transmission tester respectively;
3. Mechanical property test: the tensile strength of the samples was tested using an Instron 5565 universal tensile tester, the specific test procedure being as follows: a150 mm by 20mm sample was mounted on a tensile tester and tensile testing was performed at a tensile rate of 5mm/min, recording the longitudinal and transverse tensile strength of the sample, as follows:
tensile strength (MPa) =tensile stress/(sample width x sample thickness);
the results of the above experiments are shown in Table 3 below.
TABLE 3 Performance test results of the polypropylene sheets prepared in examples I-1 to I-4
From the results of the performance experiments of the polypropylene sheets in example I, the following facts were found: the polypropylene sheet PPS-IV added with silicone oil and nano silicon dioxide can obviously improve the anti-sticking performance, but the integral mechanical property of the composite sheet is affected, and the possible reasons are as follows: the nano SiO 2 particles have poor dispersibility in a polypropylene matrix and weak interface strength;
Based on the method, modification research is carried out on nano SiO 2 particles, so that the nano SiO 2 can generate a synergistic modification effect with silicone oil, and the technical aim of improving the comprehensive performance of the sheet is fulfilled after the nano SiO 2 is combined with polypropylene;
according to the invention, the following research and development experiments are carried out:
Example II-1:
The preparation process of the modified polypropylene sheet PPS-I is as follows:
(1) The preparation method of the single POSS modified SiO 2 nano-particles comprises the following steps: the SiO 2 nano particles modified by the silane coupling agent KH560 are modified by the monocarboxyl POSS monomer through carboxyl-epoxy ring opening reaction, so as to obtain the monocarboxyl POSS modified SiO 2 nano particles, and the preparation method comprises the following specific steps: 1g of monocarboxyl POSS monomer, 5g of SiO 2 nano particles modified by silane coupling agent KH560 and 50 mL of N, N-dimethylformamide are added into a three-port bottle, 0.5g of tetrabutylammonium chloride is slowly added into the three-port bottle under the action of mechanical stirring, the temperature is raised to 100 ℃ for reaction for 5 hours, and deionized water is used for washing, rotary evaporation and drying to obtain the monocompss modified SiO 2 nano particles;
Wherein, the chemical structure of the monocarboxyl POSS monomer is shown in figure 1, and one preparation process of the monocarboxyl POSS monomer is shown in experimental example I; one preparation process of SiO 2 nano-particles modified by a silane coupling agent KH560 is as in experimental example III;
(2) Preparing modified polypropylene master batch I: replacing the nano silicon dioxide in the embodiment I-4 with single POSS modified SiO 2 nano particles, and preparing the modified polypropylene master batch I by referring to the preparation steps and the process conditions of the polypropylene master batch IV;
(3) Preparation of a modified polypropylene sheet PPS-I: the modified polypropylene master batch I is used for replacing the polypropylene master batch IV in the embodiment I-4, and the modified polypropylene sheet PPS-I is prepared by referring to the preparation steps and the process conditions of the polypropylene sheet PPS-IV.
Example II-2:
the preparation process of the modified polypropylene sheet PPS-II comprises the following steps:
(1) The preparation method of the bridged POSS modified SiO 2 nano-particles comprises the following steps: the preparation method comprises the following steps of modifying SiO 2 nano particles modified by a silane coupling agent KH560 by an amino-epoxy ring-opening reaction, and preparing the bridged POSS modified SiO 2 nano particles by an amino bridged POSS monomer, wherein the specific preparation steps are as follows: adding 1g of amination bridging POSS monomer, 5g of SiO 2 nano particles modified by silane coupling agent KH560 and 50mL of N, N-dimethylformamide into a three-necked flask, heating to 70 ℃, stirring and reacting for 5h, washing with deionized water, rotary evaporating and drying to obtain bridging POSS modified SiO 2 nano particles;
wherein, the chemical structure of the amination bridging POSS monomer is shown in figure 2, and one preparation process of the amination bridging POSS monomer is shown in experimental example II; one preparation process of SiO 2 nano-particles modified by a silane coupling agent KH560 is as in experimental example III;
(2) Preparing modified polypropylene master batch II: replacing the nano silicon dioxide in the embodiment I-4 with the bridged POSS modified SiO 2 nano particles, and preparing a modified polypropylene master batch II by referring to the preparation steps and the process conditions of the polypropylene master batch IV;
(3) Preparing a modified polypropylene sheet PPS-II: the modified polypropylene master batch II is used for replacing the polypropylene master batch IV in the embodiment I-4, and the modified polypropylene sheet PPS-II is prepared by referring to the preparation steps and the process conditions of the polypropylene sheet PPS-IV.
Performance test:
(1) Anti-sticking property, barrier property and mechanical property test: referring to the performance testing steps and methods of examples I-1 through I-4;
(2) Sanitary performance test: the sanitary performance of a sample is tested according to GB/T5009.60-2003 analysis method of sanitary Standard of polyethylene, polystyrene and Polypropylene molded products for food packaging, and the physicochemical index of the experimental result is based on GB/T5009.71-2003 analysis method of sanitary Standard of Polypropylene resin for food packaging;
the results of the above experiments are shown in tables 4-5 below.
TABLE 4 Performance test results of modified Polypropylene sheets prepared in examples II-1 to II-2
TABLE 5 results of Performance experiments on modified Polypropylene sheets prepared in examples II-1 to II-2
From the test data plotted in tables 3 and 4, fig. 3 is obtained, and the following conclusions can be drawn by comprehensively analyzing the above experimental results:
Under the synergistic effect of silicone oil, POSS modified SiO 2 nano particles obtained by modifying SiO 2 nano particles modified by a silane coupling agent KH560 through a POSS monomer obviously improve the mechanical properties of the polypropylene sheet and further improve the anti-sticking property of the polypropylene sheet.
Experimental example I:
The specific synthesis method for synthesizing the monocarboxyl POSS monomer comprises the following steps: based on the regioselective mechanism of olefin electrophilic addition orientation reaction (Markovnikov rule), a strong acid catalyzes the addition reaction of 1.05 molar equivalents of pimelic acid and 1 molar equivalent of vinyl heptaisobutyl POSS to generate a monocarboxyl POSS monomer, and the specific experimental steps are as follows: under the protection of nitrogen, adding 4.2g of vinyl heptaisobutyl POSS, 0.84g of pimelic acid and 40mL of tetrahydrofuran into a three-necked bottle, heating to 30 ℃ for dissolution, then dropwise adding 0.5g of concentrated sulfuric acid into the three-necked bottle, heating to 60 ℃ for stirring reaction for 5 hours, cooling, washing with deionized water, and rotary evaporating to obtain a monocarboxyl POSS monomer, wherein the characterization result of hydrogen spectrum (test condition: 400Hz and CDCl 3) is shown in a figure 1;
Wherein, the strong acid catalyst is selected from one of sulfuric acid, p-toluenesulfonic acid and fluoboric acid; the experimental example preferably uses sulfuric acid as a catalyst.
Experimental example II:
The specific synthesis method for synthesizing the amination bridging POSS monomer comprises the following steps: the carboxyl functional group of 2.03 molar equivalents of monocarboxyl POSS monomer and the hydroxyl functional group of 1 molar equivalent of diethanolamine are subjected to esterification reaction to generate the aminated bridged POSS monomer, and the specific experimental steps are as follows: under the protection of nitrogen, 5.8g of monocarboxyl POSS monomer, 0.3g of diethanolamine and 50mL of tetrahydrofuran are added into a three-necked flask, stirred until the monocarboxyl POSS monomer is completely dissolved, then 0.8g of concentrated sulfuric acid is dripped into the three-necked flask, the temperature is raised to 60 ℃ and stirred for 5 hours, the mixture is cooled, deionized water is used for washing and rotary evaporation, and the amination bridging POSS monomer is obtained, and the characterization result of the hydrogen spectrum (the test condition is 400Hz and CDCl 3) is shown in a graph shown in figure 2.
Experimental example III:
Preparing SiO 2 nano particles modified by a silane coupling agent KH 560: adding 5g of silicon dioxide nano particles, 10mL of deionized water and 40mL of absolute ethyl alcohol into a three-port bottle, stirring and dissolving at normal temperature for 30min, performing ultrasonic dispersion for 30min, then dropwise adding 10mL of KH560 silane coupling agent solution (prepared from 0.5g of KH560 silane coupling agent and 10mL of absolute ethyl alcohol) into the three-port bottle, heating to 60 ℃, stirring and reacting for 2h, performing suction filtration, and performing vacuum drying to obtain SiO 2 nano particles modified by the silane coupling agent KH 560.
Claims (10)
1. The preparation process of the modified polypropylene packaging sheet is characterized by comprising the following steps of:
step one: preparing POSS modified SiO 2 nano-particles, wherein the POSS modified SiO 2 nano-particles are single POSS modified SiO 2 nano-particles;
The preparation method of the single POSS modified SiO 2 nano-particle comprises the following steps: firstly synthesizing a monocarboxyl POSS monomer, and then utilizing the monocarboxyl POSS monomer to modify SiO 2 nano particles modified by a silane coupling agent KH560 based on a carboxyl-epoxy ring-opening reaction mechanism;
Step two: modifying the polypropylene resin by the synergistic anti-sticking modification effect of the silicone oil and the POSS modified SiO 2 nano particles prepared in the first step to prepare modified polypropylene master batch;
Step three: the modified polypropylene sheet is prepared by adopting a multilayer coextrusion casting film extrusion method, using modified polypropylene master batches as raw materials of an inner layer and an outer layer, ethylene-vinyl alcohol copolymer resin as raw materials of an intermediate layer and maleic anhydride grafted polypropylene resin as raw materials of a bonding layer.
2. The process for preparing the modified polypropylene packaging sheet according to claim 1, wherein the preparation method of the monocarboxyl POSS monomer is as follows: according to an olefin electrophilic addition reaction mechanism, utilizing strong acid to catalyze the pimelic acid and vinyl heptaisobutyl POSS to generate an addition reaction, so as to generate a monocarboxyl POSS monomer; wherein the ratio of the amounts of the substances of pimelic acid and vinylheptaisobutyl POSS is (1.01-1.09): 1.
3. The process for producing a modified polypropylene packaging sheet according to claim 2, wherein said strong acid catalyst is one of sulfuric acid, p-toluenesulfonic acid and fluoroboric acid.
4. The process for preparing a modified polypropylene packaging sheet according to claim 1, wherein the POSS modified SiO 2 nanoparticles in the first step are bridged POSS modified SiO 2 nanoparticles;
The preparation method of the bridged POSS modified SiO 2 nano-particles comprises the following steps: firstly synthesizing an amination bridging POSS monomer, and then utilizing the amination bridging POSS monomer to modify SiO 2 nano particles modified by a silane coupling agent KH560 based on an amino-epoxy ring-opening reaction mechanism.
5. The process for preparing a modified polypropylene packaging sheet according to claim 4, wherein the preparation method of the aminated bridged POSS monomer comprises the following steps: generating an amination bridging POSS monomer through esterification reaction of carboxyl functional groups of the monocarboxyl POSS monomer and hydroxyl functional groups of diethanolamine; wherein the mass ratio of the monocarboxyl POSS monomer to the diethanolamine is (2.01-2.05): 1.
6. The process for preparing a modified polypropylene packaging sheet according to claim 1, wherein the preparation method of the modified polypropylene master batch in the second step is as follows: preparing raw materials according to the formula of modified polypropylene master batches, and preparing the modified polypropylene master batches by using a double-screw extruder through the process steps of blending, melting, extruding and granulating;
Wherein, the formula of the modified polypropylene master batch is as follows: 90-95 parts by weight of polypropylene resin, 0.5-5 parts by weight of silicone oil, 0.5-5 parts by weight of POSS modified SiO 2 nano particles, 0.1-0.8 part by weight of talcum powder, 0.05-0.5 part by weight of octadecyl erucamide and 0.05-0.5 part by weight of composite auxiliary agent.
7. The preparation process of the modified polypropylene packaging sheet according to claim 6, wherein the composite additive comprises 0.5-3 parts by weight of antioxidant 168, 0.1-5 parts by weight of antioxidant 1010, 0.05-1 parts by weight of antistatic agent AT and 0.05-1.5 parts by weight of ultraviolet resistant agent UV-329.
8. The process for preparing a modified polypropylene packaging sheet according to claim 1, wherein the preparation method of the modified polypropylene packaging sheet in the step three is as follows: firstly setting a film structure of five layers of co-extrusion films, then sequentially putting the raw materials of each layer of film into corresponding hoppers of five screw extruders of a five-layer co-extrusion film casting unit, mixing, merging molten resin at a machine head through a flow divider, and casting and extruding through a die head to obtain the modified polypropylene sheet.
9. The process for preparing the modified polypropylene packaging sheet according to claim 8, wherein the five-layer co-extrusion film has a film structure of an inner layer, a bonding layer, an intermediate layer, a bonding layer and an outer layer;
The mass ratio of the inner layer to the bonding layer to the middle layer to the bonding layer to the outer layer in the five-layer co-extrusion film is (30-50): (1-10): (5-20): (1-10): (30-50).
10. Use of a modified polypropylene packaging sheet prepared according to any one of claims 1-9 in eight-cup yoghurt packaging.
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