CN115746517B - Open silica master batch and preparation method and application thereof - Google Patents
Open silica master batch and preparation method and application thereof Download PDFInfo
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- CN115746517B CN115746517B CN202211651869.3A CN202211651869A CN115746517B CN 115746517 B CN115746517 B CN 115746517B CN 202211651869 A CN202211651869 A CN 202211651869A CN 115746517 B CN115746517 B CN 115746517B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 68
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 229920001896 polybutyrate Polymers 0.000 claims abstract 14
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract 3
- 239000007822 coupling agent Substances 0.000 claims description 19
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- -1 polybutylene adipate-butylene terephthalate Polymers 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229940037312 stearamide Drugs 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 239000012567 medical material Substances 0.000 claims description 2
- 239000012170 montan wax Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000010096 film blowing Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 44
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 36
- 229910021485 fumed silica Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XRKBQVGBWJWJJJ-UHFFFAOYSA-N 2-aminooctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(N)C(O)=O XRKBQVGBWJWJJJ-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 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
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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides an open silicon dioxide master batch, a preparation method and application thereof, wherein the raw materials of the open silicon dioxide master batch comprise carrier resin and silicon dioxide in specific parts, and the silicon dioxide comprises fumed nano silicon dioxide and/or precipitation method silicon dioxide; the polyhydroxy structure contained on the surface of the specific type of silicon dioxide is utilized to match with the open-ended silicon dioxide master batch made of the carrier resin, so that the problem that PBAT and PPC are difficult to open in the blend film blowing application process is solved, the synergistic compatibilization effect is achieved, the compatibility of the PBAT and PPC materials is improved, and the obtained PBAT/PPC film has excellent processing stability and openness.
Description
Technical Field
The invention belongs to the technical field of silica master batches, and particularly relates to an open silica master batch, and a preparation method and application thereof.
Background
The PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and butanediol terephthalate, has good ductility and elongation at break, thus having good film forming property and being widely applied in the packaging field and the agricultural field.
The propylene oxide and carbon dioxide based copolymer (PPC) is a widely studied carbon dioxide based degradable plastic, and the PPC material has the characteristics of excellent normal temperature flexibility, biocompatibility, transparency, barrier property and the like, has huge potential application in the fields of packaging, medical treatment, agricultural film mulching film and the like, and has wide market development prospect under the targets of carbon peak, carbon neutralization and strategy.
The PBAT/PPC blend material is widely applied to film products at present and has the advantages of good flexibility, controllable barrier property and the like. CN113174124a discloses a PPC and PBAT composite material and a preparation method thereof. The composite material provided by the invention comprises the following raw materials in parts by weight: PPC, PBAT, polymer modifier, inorganic nanofiller and inorganic nanofiller modifier; the polymer modifier is one or more of polymaleic anhydride, succinic anhydride, glyceryl monostearate, acetylated monoglyceride and propylene glycol polyether; the inorganic nano filler modifier is one or more of cetyl trimethyl ammonium bromide, gamma-glycidyl ether oxypropyl trimethoxy silane, amino octadecanoic acid and 3-amino propyl triethoxy silane. The composite material provided by the invention has good mechanical property and crystallization property, lays a good foundation for further expanding the application field of the polypropylene carbonate and poly (adipic acid)/butylene terephthalate composite material, and has very broad market prospect. However, because the PPC has few molecular chain end groups, few compatibilization reaction active points and poor blending compatibility with PBAT, the blending material is distributed in a sea-island shape, and when the addition amount of the PPC is more than 30%, the blending extrusion processing is unstable, the melt fracture and the bamboo joint phenomenon can occur, and in addition, the problem of difficult adhesion and opening can be easily generated after the PBAT/PPC is blown after being blended.
Therefore, it is desirable to develop an open silica master batch which can not only improve the compatibility of PBAT and PPC, but also solve the problem of difficult opening in the process of PBAT/PPC blending film blowing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an open silica master batch, a preparation method and application thereof, wherein the open silica master batch not only can effectively improve the compatibility of a PBAT and PPC blend, but also can solve the problem that the PBAT and PPC blend is difficult to open in the film blowing application process.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an open silica master batch, which comprises the following raw materials in parts by weight:
70 to 85 parts by weight of carrier resin
10 To 25 parts by weight of silicon dioxide
The silica includes fumed silica and/or precipitated silica.
The open silica master batch provided by the invention comprises a combination of carrier resin and silica, and the silica comprises gas phase nano silica and/or precipitation method silica, and the polyhydroxy structure on the surface of the specific type of silica is utilized to help promote the surface reaction activity of a matrix phase and a disperse phase, so that the compatibility of PBAT and PPC is promoted when the open silica master batch is applied to preparing a PBAT/PPC composite material, and meanwhile, the problem that a PBAT and PPC blend is difficult to open in the film blowing application process can be solved, so that the PBAT/PPC film prepared by taking the open silica master batch provided by the invention as one of raw materials has excellent mechanical property, and also has excellent processing stability and openness.
Wherein the carrier resin may be 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, or the like.
The silica may be 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, or the like.
Preferably, the fumed silica has a particle size of 10 to 20nm, for example 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, or the like.
Preferably, the fumed silica comprises hydrophobic fumed silica and/or hydrophilic fumed silica.
Preferably, the particle size of the precipitated silica is 10 to 40 μm, for example 15 μm, 20 μm, 25 μm, 30 μm or 35 μm, etc.
Preferably, the precipitated fumed silica comprises hydrophobic precipitated fumed silica and/or hydrophilic precipitated silica.
Preferably, the carrier resin comprises a biodegradable resin.
Preferably, the biodegradable resin includes any one or a combination of at least two of polylactic acid (PLA), polybutylene adipate-terephthalate (PBAT), polybutylene succinate (PBS), or polypropylene carbonate (PPC).
Preferably, the raw materials of the open silica master batch further comprise a coupling agent and/or a lubricant.
Preferably, the content of the coupling agent in the raw material of the open silica master batch is 0 to 2 parts by weight and not equal to 0, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, or the like.
Preferably, the coupling agent comprises any one or a combination of at least two of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent or a borate coupling agent.
Preferably, the content of the lubricant in the raw material of the open silica master batch is 0 to 2 parts by weight and not equal to 0, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, or the like.
Preferably, the lubricant comprises any one or a combination of at least two of vinyl bis-stearamide, polyethylene wax, oxidized polyethylene wax, montan wax, erucamide, oleamide, stearic acid, calcium stearate or magnesium stearate.
In a second aspect, the present invention provides a method for preparing the open silica masterbatch according to the first aspect, the method comprising: extruding and granulating the carrier resin, the silicon dioxide, the optional coupling agent and the optional lubricant to obtain the open silicon dioxide master batch.
Preferably, the extrusion granulation is performed in a twin screw extruder.
Preferably, the temperature of the extrusion granulation is 140 to 170 ℃, for example 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, or the like.
Preferably, the twin screw extruder is rotated at a speed of 150 to 300rpm, for example 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, or the like.
Preferably, the preparation method specifically comprises the following steps: and (3) blanking the carrier resin from a main feeding port of a double-screw extruder, uniformly stirring and mixing silicon dioxide, an optional coupling agent and an optional lubricant, blanking from a side feeding port of the double-screw extruder, extruding at the temperature of 140-170 ℃ of the extruder at the host rotation speed of 150-300 rpm of the double-screw extruder, and performing air-cooled granulation to obtain the open silicon dioxide master batch.
In a third aspect, the present invention provides a PBAT/PPC film, wherein the PBAT/PPC film is prepared from a starting material comprising a combination of the open silica master batch, PBAT and PPC as described in the first aspect.
Preferably, the PBAT/PPC film comprises the following raw materials in parts by weight:
60 to 80 parts by weight of PBAT
10 To 30 parts by weight of PPC
7-9 Parts by weight of open silica master batch.
Wherein, the PBAT may be 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, or the like.
The PPC may be 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, or the like.
The open silica masterbatch may be 7.2 parts by weight, 7.4 parts by weight, 7.6 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.4 parts by weight, 8.6 parts by weight, 8.8 parts by weight, or the like.
Preferably, the preparation raw materials of the PBAT/PPC film further comprise a processing aid.
In a fourth aspect, the invention provides the use of a PBAT/PPC film according to the third aspect in packaging material, medical material or agricultural film.
Compared with the prior art, the invention has the following beneficial effects:
(1) The carrier resin selected in the open silica master batch provided by the invention can effectively improve the distribution of silica in a matrix phase or a disperse phase, and the surfaces of the selected gas phase nano silica and/or precipitation method silica contain polyhydroxy structures, so that the surface reaction active points of the matrix phase or the disperse phase can be improved, and the compatibility of PBAT/PPC two phases is improved.
(2) The preparation method of the open silica master batch provided by the invention is simple to operate, is environment-friendly and is beneficial to industrial production.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw material information related to the detailed description is as follows:
PBAT: is from Zhejiang Huafeng environmental protection materials limited company, with the brand of HF101 and the melt index of 3-5 g/10min;
PPC: from Zhejiang Huafeng environmental protection materials limited company, the melt index is 1-5 g/10min;
coupling agent: titanate coupling agent TCA, available from Nanjing Netherlands New Material technologies Co., ltd;
and (3) a lubricant: vinyl bis-stearamide, available from american dragon sand;
hydrophobic fumed silica: average particle size of 16nm, purchased from win-win, germany;
hydrophilic fumed silica: average particle size of 12nm, purchased from win-win, germany;
hydrophobic precipitated silica: the average particle size is 6 μm, purchased from Shanghai West Union chemical industry;
Hydrophilic precipitated silica: the average particle size is 4.5 μm, purchased from Shanghai West Union chemical industry;
Antioxidant 1010 and antioxidant 168 (weight part ratio 1:1), purchased from neoxiu chemistry;
Epoxy chain extender: epoxy chain extender 4400, available from BASF.
Examples 1 to 12
The components of the raw materials of the open silica master batch are shown in table 1, and the dosage unit of each component is weight part;
TABLE 1
The preparation method of the open silica master batch provided in examples 1 to 12 comprises: and (3) blanking the carrier resin from a main feeding port of the double-screw extruder, uniformly stirring and mixing silicon dioxide, a coupling agent and a lubricant, blanking from a side feeding port of the double-screw extruder, extruding at the speed of a main machine of the double-screw extruder of 200rpm and the temperature of the extruder of 150 ℃, and performing air-cooled granulation to obtain the open silicon dioxide master batch.
Comparative example 1
A master batch differing from example 1 only in that the amount of PBAT added was 95 parts by weight, and hydrophobic fumed silica was not added, and other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A masterbatch which was different from example 5 only in that the amount of PPC added was 95 parts by weight, and hydrophobic fumed silica was not added, and other components, amounts and preparation methods were the same as in example 5.
Application examples 1 to 12
The PBCT/PPC film has the raw materials with the components shown in Table 2, wherein the open silica master batches provided in examples 1-12 are added in application examples 1-12, and the dosage unit of each component is "parts by weight";
TABLE 2
The preparation method of the PBAT/PPC film provided in application examples 1-12 comprises the following steps: and uniformly mixing the open silica master batch, the PBAT, the PPC, the antioxidant, the vinyl bis-stearamide and the epoxy chain extender, extruding by a double-screw extruder, wherein the extruding temperature is 160 ℃, cooling and granulating by air cooling, and performing film blowing molding by a film blowing machine within the temperature range of 135 ℃ in a main control temperature zone, wherein the film thickness is 30 mu m, so that the PBAT/PPC film is obtained.
Comparative application examples 1 to 2
The PBAT/PPC film was different from application example 1 only in that the open silica master batch provided in example 1 was replaced with the open silica master batch obtained in comparative examples 1 to 2, respectively, and other components, amounts and preparation methods were the same as application example 1.
Performance test:
(1) Tensile strength and elongation at break: testing on a universal testing machine according to a testing method provided by a standard GB/1040.2-2006, wherein the stretching speed is 500mm/min;
(2) Openness: after two PBAT/PPC films are overlapped, the two PBAT/PPC films are rubbed by fingers, the two PBAT/PPC films are very easy to rub off, namely "good", the two PBAT/PPC films are relatively easy to rub off, namely "medium", and the two PBAT/PPC films are difficult to rub off, namely "bad";
(3) Processing stability: and observing whether the material strips are uniform or not in the double-screw extrusion process, and whether intermittent phenomena such as bamboo joint shape and the like exist or not to cause discontinuous production.
PBCT/PPC films provided in application examples 1 to 12 and comparative application examples 1 to 2 were tested according to the above test methods, and the test results are shown in Table 3:
TABLE 3 Table 3
As can be seen from the data in table 3:
the PBCT/PPC films provided in application examples 1 to 12 were excellent in the opening property and the processing stability, and were high in tensile strength (longitudinal tensile strength: 35 to 42 MPa), and high in elongation at break (longitudinal elongation at break: 372 to 462%).
As can be seen from the data of comparative application example 1 and comparative application example 1, application example 5 and comparative application example 5, the PBCT/PPC film obtained without adding the open silica masterbatch is inferior in mechanical properties, openness and processing stability.
It can also be seen from a comparison of the data of application example 1 and application examples 11 and 12 that the addition of the lubricant and coupling agent also helps to improve the mechanical properties of PBCT/PPC film.
The applicant states that the present invention is illustrated by the above examples as well as a method for preparing the same and its use, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (9)
1. The PBAT/PPC film is characterized by comprising the following raw materials in parts by weight:
60 to 80 parts by weight of PBAT
10 To 30 parts by weight of PPC
7-9 Parts by weight of open silica master batch;
The raw materials of the open silica master batch comprise the following components in parts by weight:
70 to 85 parts by weight of carrier resin
16 To 25 parts by weight of silicon dioxide
0 To 2 parts by weight of coupling agent and not equal to 0
0 To 2 parts by weight of lubricant and not equal to 0;
the silicon dioxide is hydrophilic gas phase nano silicon dioxide and/or hydrophilic precipitation method silicon dioxide;
the grain diameter of the gas phase nano silicon dioxide is 10-20 nm;
the particle size of the silicon dioxide by the precipitation method is 10-40 mu m;
the carrier resin is polybutylene adipate-butylene terephthalate;
The open silica master batch is prepared by the following method, and the method comprises the following steps:
Extruding carrier resin, silicon dioxide, a coupling agent and a lubricant, granulating after air-cooling granulating, and obtaining the open silicon dioxide master batch.
2. The PBAT/PPC film according to claim 1, wherein said coupling agent comprises any one or a combination of at least two of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent or a borate coupling agent.
3. The PBAT/PPC film according to claim 1, wherein said lubricant comprises any one or a combination of at least two of vinyl bis-stearamide, polyethylene wax, oxidized polyethylene wax, montan wax, erucamide, oleamide, stearic acid, calcium stearate or magnesium stearate.
4. The PBAT/PPC film according to claim 1, wherein said extruding and said granulating are performed in a twin screw extruder.
5. The PBAT/PPC film according to claim 1, wherein said extrusion and said pelletization are at a temperature of 140 to 170 ℃.
6. The PBAT/PPC film according to claim 4, wherein said twin screw extruder is rotated at 150 to 300rpm.
7. The PBAT/PPC film according to claim 6, wherein said open silica master batch preparation method comprises: and (3) blanking the carrier resin from a main feeding port of the double-screw extruder, uniformly stirring and mixing silicon dioxide, a coupling agent and a lubricant, blanking from a side feeding port of the double-screw extruder, extruding at the temperature of 140-170 ℃ under the condition that the rotation speed of a main machine of the double-screw extruder is 150-300 rpm, and performing air-cooled granulation to obtain the open silicon dioxide master batch.
8. The PBAT/PPC film according to claim 1, wherein said PBAT/PPC film is made from a raw material further comprising a processing aid.
9. Use of a PBAT/PPC film as claimed in any one of claims 1 to 8 in packaging material, medical material or agricultural film.
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| CN103756270A (en) * | 2013-12-31 | 2014-04-30 | 山东农业大学 | Full biodegrade mulch master batch as well as preparation method and application thereof |
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