CN116574362A - Calcium carbonate filling modified PBAT and preparation method thereof - Google Patents
Calcium carbonate filling modified PBAT and preparation method thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 217
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 102
- 238000011049 filling Methods 0.000 title claims abstract description 40
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 20
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 81
- 238000002156 mixing Methods 0.000 claims description 51
- 239000007822 coupling agent Substances 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 10
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 9
- 239000008116 calcium stearate Substances 0.000 claims description 9
- 235000013539 calcium stearate Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 6
- 238000012986 modification Methods 0.000 abstract description 25
- 230000004048 modification Effects 0.000 abstract description 25
- 238000004132 cross linking Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 description 23
- 239000004033 plastic Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 6
- 239000004626 polylactic acid Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920006238 degradable plastic Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- -1 polybutylene terephthalate-adipate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JJZFJUJKZUIFKN-UHFFFAOYSA-N 1,2-ditert-butyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)C)=C1C(C)(C)C JJZFJUJKZUIFKN-UHFFFAOYSA-N 0.000 description 1
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A calcium carbonate filling modified PBAT and a preparation method thereof relate to the technical field of biodegradable materials. The calcium carbonate filling modified PBAT comprises, in parts by weight: 50-90 parts of PBAT, 10-50 parts of modified calcium carbonate, 1-3 parts of lubricant, 0.1-1 part of opening agent, 0.1-1 part of antioxidant, 1-3 parts of plasticizer, 0.1-1 part of cross-linking agent and 0.05-0.5 part of zinc oxide. The invention uses modified calcium carbonate as filler, improves the compatibility of the calcium carbonate and PBAT, and reduces the cost of raw materials; and the PBAT is subjected to crosslinking modification, so that the mechanical property loss caused by high-filling calcium carbonate is compensated, and the prepared PBAT with the calcium carbonate filling modification has the advantages of low cost and good mechanical property, and can be used for various application occasions.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to a calcium carbonate filling modified PBAT and a preparation method thereof.
Technical Field
Plastic products become an indispensable product in daily life of people and are visible everywhere in production and life. Compared with metal, stone and wood, the plastic product has the advantages of low cost, strong plasticity and the like. The plastic itself exhibits properties such as light weight, excellent chemical stability and electrical insulation, which make the plastic increasingly widely used. However, most plastic materials are not degradable and degrade very slowly in nature. The current common treatment for plastics is incineration and landfill. The incineration process produces harmful gases and carbon dioxide. Land-filled plastics are found in nature for a long period of time, and the resulting microplastic can cause the accumulation of indigestible matter in the human body, causing some of the disorders. The plastic in the environment can also have a serious adverse effect on the environment. The united states of ministry of nine, 1 and 19, 2020 issued "opinion on further enhanced plastic pollution control" suggesting action goals and measures to limit and prohibit the use of non-degradable plastic products in stages (2020, 2022, 2025). Whether the requirements of environmental protection itself or the successive promulgation of policy environments, the development of environmentally friendly biodegradable materials instead of traditional plastics has been a major trend.
The polybutylene terephthalate-adipate (PBAT) can be completely degraded, has the advantages of good film forming performance, convenient film blowing and the like, is widely applied to the fields of disposable packaging films and agricultural films, and is one of the most active degradation materials in the research and market application of degradation plastics. But PBAT has the defects of low tensile strength, poor film opening property and the like, and the prepared film product has higher price, so that the expansion application of the film product as a full-biodegradable material is limited to a certain extent. The modification method of the PBAT mainly comprises filling modification, blending modification, fiber reinforcement modification, chemical modification and the like. The filling modification of the PBAT can reduce the material cost and improve the rigidity, hardness, heat resistance and the like of the material. The calcium carbonate has the advantages of rich sources, low price, high whiteness, no toxicity and the like, and the calcium carbonate is used as a filler and is one of research hotspots for PBAT inorganic filling modification.
The chemical modification method of the PBAT mainly comprises block and graft copolymerization, crosslinking, interpenetrating polymer networks and the like. PBAT is a linear polymer, and is improved in mechanical properties, elasticity, dimensional stability, solvent resistance, thermal stability and the like through moderate crosslinking. The crosslinking modification mainly comprises six methods of a silane crosslinking method, a peroxide crosslinking method, a photo-crosslinking method, a high-energy radiation crosslinking method, an ion crosslinking method and a vulcanization crosslinking method. Chinese patent CN111849132a discloses a high-strength cross-linked PBAT material and preparation method thereof, the raw materials of which comprise the following components in parts by mass: 100 parts of PBAT, 0.01-1 part of initiator, 0.5-2 parts of silane, 0.01-1 part of auxiliary cross-linking agent, 0.01-1 part of catalyst and 0-2 parts of lubricant. The high-strength cross-linked PBAT material and the preparation method thereof adopt silane cross-linked modified PBAT, the compression test strength is 62MPa at most, and the thermal initial decomposition temperature is 383.1 ℃ (see in particular example 5 of the specification). The high-strength cross-linked PBAT material has the composition of more than 90 percent of PBAT and higher cost.
Chinese patent CN114213817A discloses a PBAT/PLA/CaCO 3 The preparation method of the full-biodegradable composite material comprises the following steps: step 1: adding calcium carbonate and a coupling agent into a high-speed mixer, stirring and mixing uniformly, and activating the calcium carbonate; step 2: mixing polybutylene terephthalate-adipate resin and a chain extender, adding the mixture into an internal mixer, and carrying out internal mixing to obtain plasticized PBAT; step 3: adding the plasticized PBAT, activated calcium carbonate and polylactic acid into an internal mixer, and obtaining PBAT/PLA/CaCO through internal mixing 3 And (3) carrying out injection molding on the full-biodegradable composite material by an injection molding machine to obtain a sample. The raw materials comprise the following components in parts by weight: 60-80 parts of poly (butylene adipate-terephthalate), 20-40 parts of calcium carbonate, 5 parts of polylactic acid, 0.1-2 parts of coupling agent and 0.1-2 parts of chain extender. The PBAT/PLA/CaCO 3 Preparation method of full-biodegradable composite material, wherein 25 parts of CaCO 3 The PBAT/PLA/CaCO is prepared by two times of internal refining 3 Fully biodegradable composite material, mechanicsThe performance test strength was 20.25MPa, and the elongation at break was 178% (see example 8 in the specification). The full-biodegradable composite material is produced by twice banburying, and has complex production process and higher cost.
Disclosure of Invention
Aiming at the problem of high cost caused by raw material selection in the prior art, the invention provides the calcium carbonate filling modified PBAT, which takes calcium carbonate as a filler of the PBAT to reduce the raw material cost, and simultaneously carries out peroxide crosslinking modification on the PBAT to compensate the mechanical property loss caused by high-filling calcium carbonate, thereby providing the calcium carbonate filling modified PBAT with low cost and good tensile property.
The invention aims to provide a preparation method of a PBAT (Poly (butylene succinate)) with calcium carbonate filling modification, which realizes the calcium carbonate filling modification of the PBAT and the crosslinking modification of the PBAT by one-time melt extrusion and solves the problems of complex production process and high production cost in the prior art.
In order to achieve the first object, the present invention adopts the following technical scheme:
the calcium carbonate filling modified PBAT is prepared from the following components in parts by weight: 50-90 parts of PBAT, 10-50 parts of modified calcium carbonate, 1-3 parts of lubricant, 0.1-1 part of opening agent, 0.1-1 part of antioxidant, 1-3 parts of plasticizer, 0.1-1 part of cross-linking agent and 0.05-0.5 part of zinc oxide. The invention takes the modified calcium carbonate as the filler, improves the compatibility of the calcium carbonate and the PBAT, and reduces the cost of raw materials; and meanwhile, the PBAT is subjected to crosslinking modification, so that the loss of mechanical properties caused by high-filling calcium carbonate is compensated.
The lubricant is one or a combination of stearic acid and calcium stearate. Calcium carbonate filling and cross-linking modification of PBAT can reduce flowability of composite melt, cause processing difficulties, and even affect product quality. The addition of the lubricant can improve flowability, reduce friction and reduce interfacial adhesion. Stearic acid and calcium stearate lubricants are cheap and easy to obtain, have low toxicity and improve the processability of the composite material to a greater extent.
The opening agent is one or a combination of erucamide and oleamide. Erucamide and oleamide have excellent slipping property and good anti-blocking property, so that the film product of the degradable plastic has good opening property.
The plasticizer is one or a combination of tributyl citrate, glycerol and epoxidized soybean oil. The filling of calcium carbonate and the crosslinking modification of PBAT can reduce the melt index of the degradable plastic, and the addition of the plasticizer can weaken the secondary valence bond between polymer molecules, reduce the crystallinity of polymer molecular chains and increase the plasticity of the degradable plastic.
The cross-linking agent is one or a combination of dicumyl peroxide and di-tert-butyl peroxyisopropyl benzene. The dicumyl peroxide and the di-tert-butyl peroxyisopropyl benzene have low melting point and high boiling point, are easy to melt and mix uniformly in the mixing process, and are not easy to volatilize and lose; meanwhile, under the temperature condition of the calcium carbonate filling modification PBAT, the modified PBAT has higher activity and proper half-life period, and the filling modification and crosslinking modification of the PBAT can be completed through one-time melt extrusion.
The modified calcium carbonate is prepared by mixing calcium carbonate with a coupling agent. Part of the coupling agent is an inorganic-philic group and can act with calcium carbonate; the other part is an organophilic group which can interact with PBAT. The interfacial properties of the PBAT and the calcium carbonate can be improved, the viscosity of the PBAT can be reduced, and the dispersity of the calcium carbonate can be improved to improve the processability.
The calcium carbonate is any one of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate. The calcium carbonate has the advantages of abundant sources, low price, high whiteness and no toxicity, can increase the dimensional stability, rigidity and heat resistance of the material, and reduces the cost.
The coupling agent is one or the combination of aluminate coupling agent, silane coupling agent and titanate coupling agent. The calcium carbonate powder is a hydrophilic inorganic compound, and the surface of the calcium carbonate powder is provided with hydrophilic hydroxyl groups. The hydrophilic and oleophobic properties lead to poor affinity between calcium carbonate and organic high polymer, easy agglomeration, uneven dispersion in PBAT, and poor direct application effect due to interface defect between two materials. The coupling agent can be chemically reacted or physically coated with calcium carbonate to change the surface of the coupling agent from hydrophile to lipophile, thereby achieving the tight combination with PBAT and obviously improving the strength, heat resistance and the like of the material.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a method for preparing a calcium carbonate filling modified PBAT, comprising the following steps in sequence:
1) Mixing the modified calcium carbonate, the lubricant, the opening agent and the zinc oxide in proportion for 3-60 minutes at the temperature of 80-120 ℃ to obtain a first mixture. The opening agents erucamide and oleamide are solid at normal temperature, and are mixed at a temperature higher than the melting point of the opening agents in order to ensure that the opening agents are uniformly mixed with calcium carbonate.
2) And (3) cooling the first mixture, and mixing the cooled first mixture with an antioxidant and a cross-linking agent in proportion for 3-60 minutes at 42-80 ℃ to obtain a second mixture. The crosslinking agents dicumyl peroxide and di-tert-butyl cumene peroxide are solid at normal temperature, and are mixed at a temperature higher than the melting point of the crosslinking agents for ensuring uniform mixing with calcium carbonate; meanwhile, in order to prevent the reaction failure of the antioxidant and other auxiliary agents in the mixing process, a reasonable upper limit of the mixing temperature is required to be controlled.
3) And (3) standing the second mixture at normal temperature for 20-70 hours, and mixing the second mixture with a plasticizer at normal temperature according to a proportion to obtain a third mixture. The second mixture is placed at normal temperature, so that the coupling agent and the crosslinking agent can be promoted to be uniformly dispersed on the surface of the calcium carbonate and migrate into the calcium carbonate particles, and the effects of the calcium carbonate filling modification of the PBAT and the crosslinking modification of the PBAT are better.
4) And mixing the third mixture with PBAT at normal temperature in proportion to obtain a fourth mixture.
5) And transferring the fourth mixture into an extruder, carrying out melt extrusion at 140-200 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
The tensile strength of the calcium carbonate filling modified PBAT is more than or equal to 16MPa, and the elongation at break is more than or equal to 350%.
The invention has the beneficial effects that: the surface modification of the calcium carbonate and the crosslinking modification of the PBAT provide the PBAT with low cost and good tensile property for filling modification of the calcium carbonate, and the problem of high cost caused by raw material selection in the prior art is solved; the calcium carbonate filling modification of the PBAT and the crosslinking modification of the PBAT are realized through one-time melt extrusion, so that the problems of complex production process and high production cost in the prior art are solved.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The invention provides a calcium carbonate filling modified PBAT, which is prepared from the following components in parts by weight: 50-90 parts of PBAT, 10-50 parts of modified calcium carbonate, 1-3 parts of lubricant, 0.1-1 part of opening agent, 0.1-1 part of antioxidant, 1-3 parts of plasticizer, 0.1-1 part of cross-linking agent and 0.05-0.5 part of zinc oxide.
In some embodiments of the invention, the lubricant is one of stearic acid, calcium stearate, or a combination thereof.
In some embodiments of the invention, the opening agent is one of erucamide, oleamide, or a combination thereof.
In some embodiments of the invention, the plasticizer is one of tributyl citrate, glycerol, epoxidized soybean oil, or a combination thereof.
In some embodiments of the invention, the crosslinking agent is one of dicumyl peroxide, di-t-butylperoxyisopropyl benzene, or a combination thereof.
In some embodiments of the invention, the modified calcium carbonate is prepared by mixing calcium carbonate with a coupling agent.
In some embodiments of the invention, the calcium carbonate is any one of heavy calcium carbonate, light calcium carbonate, and nano calcium carbonate.
In some embodiments of the invention, the coupling agent is one of an aluminate coupling agent, a silane coupling agent, a titanate coupling agent, or a combination thereof.
The invention also provides a preparation method of the calcium carbonate filling modified PBAT, which comprises the following steps:
1) Mixing modified calcium carbonate, lubricant, opening agent and zinc oxide for 3-60 minutes at 80-120 ℃ to obtain a first mixture;
2) Cooling the first mixture, and mixing the cooled first mixture with an antioxidant and a cross-linking agent for 3-60 minutes at 42-80 ℃ to obtain a second mixture;
3) Standing the second mixture at normal temperature for at least 20-70 hours, and mixing with a plasticizer at normal temperature to obtain a third mixture;
4) Mixing the third mixture with PBAT at normal temperature to obtain a fourth mixture;
5) And transferring the fourth mixture into an extruder, carrying out melt extrusion at 140-200 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
In some embodiments of the invention, the calcium carbonate fill-modified PBAT has a tensile strength of 16MPa or greater and an elongation at break of 350% or greater.
The calcium carbonate filling modified PBAT has the advantages of low cost, simple production process and good mechanical property, and can be used for various application occasions.
The present invention will be described in further detail with reference to specific examples.
Example 1
Taking 19.5 parts of heavy calcium carbonate and 0.5 part of aluminate coupling agent, heating, stirring and mixing for 20 minutes at 120 ℃ to obtain modified heavy calcium carbonate; adding 1 part of stearic acid, 0.4 part of oleamide and 0.15 part of zinc oxide into the modified heavy calcium carbonate, heating and stirring for 10 minutes at 120 ℃ to obtain a first mixture; cooling the first mixture, adding 0.5 part of antioxidant and 0.6 part of dicumyl peroxide, and stirring and mixing at 42 ℃ for 30 minutes to obtain a second mixture; placing the second mixture at normal temperature for 20 hours, adding 1 part of epoxidized soybean oil, and stirring and mixing for 60 minutes at normal temperature to obtain a third mixture; mixing the third mixture with 80 parts of PBAT at normal temperature for 60 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 200 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
Example 2
29.7 parts of light calcium carbonate, 0.1 part of silane coupling agent and 0.2 part of phthalate coupling agent are taken, heated and stirred for 10 minutes at 80 ℃ to obtain modified light calcium carbonate; adding 1 part of calcium stearate, 1 part of stearic acid, 0.4 part of erucamide and 0.1 part of zinc oxide into the modified light calcium carbonate, heating, stirring and mixing for 15 minutes at 80 ℃ to obtain a first mixture; cooling the first mixture, adding 0.3 part of antioxidant, 0.3 part of dicumyl peroxide and 0.1 part of di-tert-butyl peroxyisopropyl benzene, and stirring and mixing for 30 minutes at 60 ℃ to obtain a second mixture; after the second mixture is placed for 30 hours at normal temperature, 3 parts of epoxidized soybean oil is added, and stirring and mixing are carried out for 90 minutes at normal temperature, so as to obtain a third mixture; mixing the third mixture with 70 parts of PBAT at normal temperature for 30 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 160 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
Example 3
Taking 48.7 parts of nano calcium carbonate, 1 part of aluminate coupling agent, 0.2 part of silane coupling agent and 0.1 part of titanate coupling agent, heating, stirring and mixing for 60 minutes at 93 ℃ to obtain modified nano calcium carbonate; adding 3 parts of calcium stearate, 0.2 part of erucamide, 0.1 part of oleamide and 0.05 part of zinc oxide into the modified nano calcium carbonate, heating, stirring and mixing for 60 minutes at 93 ℃ to obtain a first mixture; cooling the first mixture, adding 0.1 part of antioxidant and 0.1 part of di-tert-butyl peroxy isopropyl benzene, and stirring and mixing at 55 ℃ for 40 minutes to obtain a second mixture; placing the second mixture at normal temperature for 70 hours, adding 1 part of glycerin, 1 part of epoxidized soybean oil and 1 part of tributyl citrate, and stirring and mixing for 60 minutes at normal temperature to obtain a third mixture; mixing the third mixture with 50 parts of PBAT at normal temperature for 60 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 165 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
Example 4
Taking 33.8 parts of heavy calcium carbonate, 1 part of aluminate coupling agent and 0.2 part of titanate coupling agent, and heating, stirring and mixing for 15 minutes at 85 ℃ to obtain modified heavy calcium carbonate; adding 2 parts of stearic acid, 1 part of calcium stearate, 0.1 part of erucamide, 0.1 part of oleamide and 0.1 part of zinc oxide into modified heavy calcium carbonate, heating, stirring and mixing for 10 minutes at 85 ℃ to obtain a first mixture; cooling the first mixture, adding 0.2 part of antioxidant and 0.3 part of di-tert-butyl peroxyisopropyl benzene, and stirring and mixing for 10 minutes at 80 ℃ to obtain a second mixture; placing the second mixture at normal temperature for 40 hours, adding 1 part of glycerol and 1 part of epoxidized soybean oil, and stirring and mixing for 40 minutes at normal temperature to obtain a third mixture; mixing the third mixture with 65 parts of PBAT at normal temperature for 60 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 160 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
Example 5
Taking 24.7 parts of light calcium carbonate, 0.3 part of silane coupling agent, heating, stirring and mixing for 3 minutes at 96 ℃ to obtain modified light calcium carbonate; adding 2 parts of calcium stearate, 0.3 part of oleamide and 0.2 part of zinc oxide into the modified light calcium carbonate, heating, stirring and mixing for 3 minutes at 96 ℃ to obtain a first mixture; cooling the first mixture, adding 0.4 part of antioxidant, 0.3 part of dicumyl peroxide and 0.2 part of di-tert-butyl peroxyisopropyl benzene, and stirring and mixing for 30 minutes at 58 ℃ to obtain a second mixture; placing the second mixture at normal temperature for 45 hours, adding 2 parts of tributyl citrate, and stirring and mixing for 60 minutes at normal temperature to obtain a third mixture; mixing the third mixture with 75 parts of PBAT at normal temperature for 30 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 158 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
Example 6
9.9 parts of nano calcium carbonate and 0.1 part of titanate coupling agent are taken, heated, stirred and mixed for 20 minutes at 85 ℃ to obtain modified nano calcium carbonate; adding 1 part of calcium stearate, 1.0 part of erucamide and 0.5 part of zinc oxide into the modified nano calcium carbonate, heating, stirring and mixing for 10 minutes at 95 ℃ to obtain a first mixture; cooling the first mixture, adding 1 part of antioxidant, 0.6 part of dicumyl peroxide and 0.4 part of di-tert-butyl peroxyisopropyl benzene, and stirring and mixing for 45 minutes at 72 ℃ to obtain a second mixture; placing the second mixture at normal temperature for 48 hours, adding 1 part of glycerol, and stirring and mixing for 60 minutes at normal temperature to obtain a third mixture; mixing the third mixture with 90 parts of PBAT at normal temperature for 80 minutes to obtain a fourth mixture; and transferring the fourth mixture into an extruder, carrying out melt extrusion at 163 ℃ and granulating to obtain the calcium carbonate filling modified PBAT.
Comparative example 1
The preparation process was essentially the same as in example 3, except that the crosslinking agents dicumyl peroxide and zinc oxide were not added and that no PBAT crosslinking occurred during melt extrusion.
Comparative example 2
The preparation process is basically the same as that of example 4, except that no coupling agent is added to modify the ground calcium carbonate; di-tert-butylperoxyisopropyl benzene and zinc oxide were not added and PBAT crosslinking did not occur during melt extrusion.
Comparative example 3
The preparation process was substantially the same as in example 5, except that no coupling agent was added to modify the light calcium carbonate, which was poor in compatibility with PBAT.
The sample bars prepared in the examples and the comparative examples were subjected to mechanical property measurement according to GB/T1040.2-2018 "measurement of Plastic tensile Property", and specific test results are as follows:
| sequence number | Tensile Strength/MPa | Elongation at break/% |
| Example 1 | 19.4 | 415 |
| Example 2 | 19.7 | 408 |
| Example 3 | 18.5 | 393 |
| Example 4 | 17.3 | 377 |
| Example 5 | 20.3 | 426 |
| Example 6 | 24.6 | 483 |
| Comparative example 1 | 14.2 | 336 |
| Comparative example 2 | 9.3 | 212 |
| Comparative example 3 | 12.6 | 238 |
From the above table, it can be seen that: from the data of examples 1-6 and comparative examples 1-3, it can be seen that the tensile strength and elongation at break of the calcium carbonate fill-modified PBAT prepared in examples 1-6 are significantly higher than in the comparative examples, with example 6 being the most preferred example. After modifying calcium carbonate and adding a cross-linking agent, the modified material can effectively reduce the production cost of plastics on the basis of ensuring mechanical properties.
The above description should not be taken as limiting the practice of the invention to these descriptions, but rather as simple deductions or substitutions may be made by those skilled in the art without departing from the spirit of the invention, which is to be considered as falling within the scope of the invention as defined by the appended claims.
Claims (10)
1. The calcium carbonate filling modified PBAT is characterized by comprising the following components in parts by weight: 50-90 parts of PBAT, 10-50 parts of modified calcium carbonate, 1-3 parts of lubricant, 0.1-1 part of opening agent, 0.1-1 part of antioxidant, 1-3 parts of plasticizer, 0.1-1 part of cross-linking agent and 0.05-0.5 part of zinc oxide.
2. The calcium carbonate fill-modified PBAT of claim 1, wherein the lubricant is one of stearic acid, calcium stearate, or a combination thereof.
3. The calcium carbonate fill-modified PBAT of claim 1, wherein the opening agent is one of erucamide, oleamide, or a combination thereof.
4. The calcium carbonate fill-modified PBAT of claim 1, wherein the plasticizer is one of tributyl citrate, glycerol, epoxidized soybean oil, or a combination thereof.
5. The calcium carbonate fill-modified PBAT of claim 1, wherein the cross-linking agent is one of dicumyl peroxide, di-t-butylperoxyisopropyl benzene, or a combination thereof.
6. The modified PBAT of claim 1, wherein the modified calcium carbonate is prepared by mixing calcium carbonate with a coupling agent.
7. The calcium carbonate fill-modified PBAT of claim 6, wherein the calcium carbonate is any one of heavy calcium carbonate, light calcium carbonate, and nano calcium carbonate.
8. The calcium carbonate fill-modified PBAT of claim 6, wherein the coupling agent is one of an aluminate coupling agent, a silane coupling agent, a titanate coupling agent, or a combination thereof.
9. A method for preparing a calcium carbonate filling modified PBAT, which is characterized by comprising the following steps:
1) Mixing modified calcium carbonate, lubricant, opening agent and zinc oxide in proportion for 3-60 minutes at 80-120 ℃ to obtain a first mixture;
2) Cooling the first mixture, and mixing the cooled first mixture with an antioxidant and a cross-linking agent in proportion for 3-60 minutes at 42-80 ℃ to obtain a second mixture;
3) Placing the second mixture at normal temperature for 20-70 hours, and mixing the second mixture with a plasticizer at normal temperature according to a proportion to obtain a third mixture;
4) Mixing the third mixture with PBAT at normal temperature in proportion to obtain a fourth mixture;
5) And transferring the fourth mixture into an extruder, carrying out melt extrusion at 140-200 ℃, and granulating to obtain the calcium carbonate filling modified PBAT.
10. A calcium carbonate filler modified PBAT according to any of claims 1 to 9, characterized in that the tensile strength is not less than 16MPa and the elongation at break is not less than 350%.
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