CN117844223A - Preparation method of high-temperature-resistant carbon dioxide-based biodegradable foaming material - Google Patents
Preparation method of high-temperature-resistant carbon dioxide-based biodegradable foaming material Download PDFInfo
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- CN117844223A CN117844223A CN202410030075.8A CN202410030075A CN117844223A CN 117844223 A CN117844223 A CN 117844223A CN 202410030075 A CN202410030075 A CN 202410030075A CN 117844223 A CN117844223 A CN 117844223A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000005187 foaming Methods 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000011324 bead Substances 0.000 claims abstract description 13
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- -1 alum Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 10
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 10
- 239000006261 foam material Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000002194 fatty esters Chemical class 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 235000013399 edible fruits Nutrition 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229920000747 poly(lactic acid) Polymers 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 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 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- XTUSLLYSMVWGPS-UHFFFAOYSA-N carbonic acid;cyclohexene Chemical compound OC(O)=O.C1CCC=CC1 XTUSLLYSMVWGPS-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- ATMABMRDZYWJJU-UHFFFAOYSA-L chromium(2+);2-methylprop-2-enoate;chloride Chemical compound [Cl-].[Cr+2].CC(=C)C([O-])=O ATMABMRDZYWJJU-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A preparation method of a high-temperature-resistant carbon dioxide-based biodegradable foaming material belongs to the technical field of high-molecular foaming materials. The raw materials in parts by weight are: 60-99 parts of PPCHC, 0.5-5 parts of nucleating agent, 0.1-10 parts of filler, 0.1-5 parts of coupling agent and 0.05-0.5 part of foaming agent. Mixing the raw materials, extruding and foaming by adopting a mode of connecting a double-screw extruder and a single-screw extruder in series to form beads, and then further foaming and molding the beads. The foaming material has excellent physical properties, good toughness, strong puncture resistance and soft texture, and can realize better protection when packaging the materials which are easy to collide with fruits and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer foaming materials, and particularly relates to a preparation method of a high-temperature-resistant carbon dioxide-based biodegradable foaming material.
Background
Polystyrene foam (EPS) is a lightweight high molecular polymer. The foaming agent is added into polystyrene resin, and the polystyrene resin is heated to soften and generate gas to form the foamed plastic with a hard closed-cell structure. However, the adhesion between the expanded EPS beads is poor, after the beads are expanded, the expanded plates are easy to threshing when being extruded and beaten, and the expanded plates are difficult to clean due to electrostatic adsorption in the cleaning process. Polystyrene (EPS) is common for the cushioning foam materials of the packaging boxes in the transportation process, and the EPS has high foaming rate and can foam 40-80 times; the softening temperature is above 70 ℃, and the temperature requirement in the container transportation process can be met. However EPS is not biodegradable. The buffering foam material is easy to discard after being used, is not easy to recycle, and causes serious pollution to the environment after being discarded. It is highly desirable to find biodegradable materials that can replace EPS.
The traditional degradable bio-based foaming material is mainly PLA, but because PLA has poor heat resistance and low melt strength, the PLA can deform at 50-55 ℃, and the application field and the application range are greatly limited. The PLA foaming material can not replace EPS, and the application can not be satisfied. As disclosed in chinese patent CN113214618B, a food grade heat resistant PLA foam material is obtained by blending polylactic acid (PLA) and polybutylene adipate with polybutylene terephthalate Polycondensate (PBAT) using a biodegradable cosolvent to obtain a PLA/PBAT alloy; then intercalation treatment is carried out on montmorillonite (MMT) by using polymerized amino acid to obtain organic montmorillonite; finally, PLA/PBAT alloy and organic montmorillonite are mixed and extruded, and foaming is carried out. Although the polymerized amino acid is used as an intercalating agent, the uniform dispersion of MMT in PLA/PBAT alloy is realized, and the melt strength and the heat distortion temperature of PLA are improved, but the heat distortion temperature is only between 50 ℃ and 58 ℃. When the container is transported at sea, the temperature in the container can reach approximately 70 ℃, and obviously, the PLA foaming material can not meet the packaging requirement.
In the Chinese patent CN116444974A of the prior application, PPCHC is used as a modified material of the PPCCP material, and is mixed with PBS to be used as a foaming material, so that the foaming rate is high, and the softening point and the tensile strength of the material are higher. However, the material has high compressive strength and has a problem of excessive hardness when applied in various fields.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a preparation method of the carbon dioxide-based biodegradable foaming material which meets the temperature requirement in the container transportation process.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the high-temperature-resistant carbon dioxide-based biodegradable foaming material is characterized by comprising the following steps of: the high-temperature-resistant carbon dioxide-based biodegradable foaming material is characterized by comprising the following raw materials in parts by weight: 60-99 parts of PPCHC, 0.5-5 parts of nucleating agent, 0.1-10 parts of filler, 0.1-5 parts of coupling agent and 0.05-0.5 part of foaming agent.
The foaming material disclosed by the invention adopts cyclohexene carbonate-propylene carbonate copolymer (PPCHC) as a main material for foaming, the foaming rate of the foaming material can reach 40-80 times, and the thermal deformation temperature reaches 70 ℃. The foaming material has excellent physical properties, good toughness, strong puncture resistance and soft texture, and can realize better protection when packaging the materials which are easy to collide with fruits and the like. In addition, if the foaming material is a plate which is formed by foaming beads, the bonding force among the beads is strong, and the threshing condition is not easy to occur.
Preferably, the raw materials comprise the following components in parts by weight: 70-85 parts of PPCHC, 1.5-2.5 parts of nucleating agent, 0.5-3 parts of filler, 1-2.5 parts of coupling agent and 0.1-0.5 part of foaming agent. Under the preferable composition of parts by weight, the high foaming ratio can be ensured, the light weight is maintained, and the requirements of toughness and soft bullet can be met.
Preferably, the preparation method of PPCHC comprises the following steps: and (3) putting propylene oxide, cyclohexene oxide and a catalyst into a reactor, charging carbon dioxide to enable the reaction pressure to reach 1.0-2.0 MPa, heating to enable the reaction temperature to be kept at 60-80 ℃, performing ring-opening polymerization to generate a glue solution, and washing, devolatilizing and drying the glue solution to obtain a finished product. The PPCHC prepared by the preferred preparation process has excellent foaming effect, and the hardness of the foamed material is smaller.
Specifically, the nucleating agent is one or more of talcum powder, calcium carbonate, silicon dioxide, alum, calcium oxide, magnesium oxide, carbon black and mica. The nucleating agent can meet the basic nucleating requirement of the invention and improve the processing performance.
Preferably, the nucleating agent is acrylic modified titanium dioxide. After titanium dioxide is soaked in an acrylic acid solution in a split manner for a short time (10 s-20 s), the toughening effect of the soft foaming material can be better ensured, and the puncture resistance is improved.
The foaming raw material provided by the invention can adapt to most of the existing foaming processes and foaming agents. Preferably, the foaming agent is carbon dioxide or azodicarbonamide.
Specifically, the filler is one or more of silicon dioxide, heavy calcium carbonate, nano calcium carbonate, light calcium carbonate and zinc oxide. The addition of a proper amount of the filler can keep the uniformity of foaming, thereby ensuring the toughness of the foaming material.
The coupling agent is silane coupling agent, titanate coupling agent and chromium complex coupling agent. The addition of a proper amount of coupling agent can promote the uniform distribution of the filler, the nucleating agent and the like in the material, so that the performance of the foaming material is ensured.
Preferably, the coupling agent is a composite titanate coupling agent, and the composite titanate coupling agent is a coupling agent compounded by a monoalkoxy phosphate type phthalate coupling agent and a monoalkoxy fatty ester phthalate coupling agent. The single alkoxy phthalate ester coupling agent used in PPCHC can better promote the uniform dispersion of the raw materials, and the effect is better when two or more single alkoxy phthalate ester coupling agents are used in a compounding way.
The preparation method of the high-temperature-resistant carbon dioxide-based biodegradable foaming material is characterized in that the raw materials are mixed and then extruded and foamed into beads by adopting a mode of connecting a double-screw extruder and a single-screw extruder in series, and then the beads are further foamed and molded to obtain the high-temperature-resistant carbon dioxide-based biodegradable foaming material. The foaming material is extruded in a mode of connecting double screws and single screws in series, so that uniform mixing of materials can be ensured.
Preferably, in the above production method, the aspect ratio of the twin-screw extruder is 36:1, and the aspect ratio of the single-screw extruder is 30:1. The length-diameter ratio of the double screw and the single screw is adjusted, the front-back extrusion rate is controlled, and a better mixing effect is achieved.
Preferably, in the preparation method, the foaming multiplying power is 40-80 times.
Preferably, the temperature of the twin-screw extruder is set as follows: one region 50-100 ℃, two regions 155-165 ℃, three regions 160-170 ℃ and four regions 170-180 ℃; the temperature of the single screw extruder is set as follows: one region 170-180 ℃, two regions 165-175 ℃, three regions 160-170 ℃ and four regions 160-170 ℃. Through temperature setting, the softening or melting state of the materials in the extruder is adjusted, so that the materials are more uniformly mixed, the chain extender and the cross-linking agent are more fully reacted, and the foaming effect is more ideal.
Carbon dioxide is introduced at the junction of the double-screw extruder and the single-screw extruder. The carbon dioxide gas is used for protecting, so that the residual flammable monomer is prevented from escaping and dangerous.
Compared with the prior art, the high-temperature-resistant carbon dioxide-based biodegradable foaming material and the preparation method have the following beneficial effects: the invention adopts the copolymer (PPCHC) containing cyclohexene carbonate and propylene carbonate as the main material, the PPCHC has high strength and good barrier property, after the modified component is added, the toughness of the whole material is better, after the modified component is used as the main material of the foaming material, the toughness and strength of the foaming material are ideal, and the foaming multiplying power is higher. The PPCHC foaming ratio is high, compared with the blending PBS foaming, the glass transition temperature of the PPCHC is 80-100 ℃, the PPCHC is easy to foam, and the PPCHC is used as a main material, so that the PPCHC foaming effect is better, the degradability is better and the PPCHC foaming agent can resist high temperature. The foaming multiplying power is large, the softening point of the material is high, the stretching deformation is large, and the dimensional stability is good. After the auxiliary agent is used for adjusting the performance, the processing performance of the composition material is better, and the foaming is more uniform.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
The preparation method of the PPCHC comprises the following steps: purging with high-purity carbon dioxide, replacing water and oxygen in a 5L high-pressure reaction kettle, putting 1 part of propylene oxide, 2 parts of cyclohexene oxide and 0.006 part of catalyst into the reaction kettle, and putting the propylene oxide, the cyclohexene oxide and the catalyst into a reactor, wherein the catalyst is a compound catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:2.5; filling carbon dioxide to make the reaction pressure reach 1.5MPa, heating to make the reaction temperature keep at 70 ℃ for reaction for 8 hours, cooling, decompressing, stopping the reaction, dissolving the glue solution with chloroform, precipitating with ethanol, devolatilizing, drying and preparing the pure PPCHC. PPCHC having a molecular weight of 9.5X10 by GPC analysis 4 g/mol。
Raw materials are prepared according to parts by weight: 78 parts of PPCHC, 2.0 parts of acrylic acid modified titanium dioxide, 1.3 parts of nano calcium carbonate, 1.7 parts of monoalkoxy phosphate ester phthalate ester coupling agent and coupling agent compounded by monoalkoxy fatty ester phthalate ester coupling agent according to the mass ratio of 1:1 and 0.3 part of carbon dioxide.
Firstly, extruding and granulating PPCHC at 165 ℃ by using a double-screw extruder, uniformly mixing the PPCHC with other additives, extruding and foaming the mixture by adopting a mode of connecting the double-screw extruder and the single-screw extruder in series to form beads, transferring the beads into a foaming barrel, heating the beads to 135 ℃ for foaming, transferring the foamed materials into a fluidized bed, and curing the foamed materials by using blown hot air at 70 ℃ for 90min to obtain cured materials; and transferring the cured material into a forming plate machine, and heating to 110 ℃ to form the foaming plate. Wherein the length-diameter ratio of the double-screw extruder is 36:1, and the length-diameter ratio of the single-screw extruder is 30:1. The temperature of the twin screw extruder was set to: one region 50-100 ℃, two regions 155-165 ℃, three regions 160-170 ℃ and four regions 170-180 ℃; the temperature of the single screw extruder was set to: one region 170-180 ℃, two regions 165-175 ℃, three regions 160-170 ℃ and four regions 160-170 ℃; the carbon dioxide charge pressure was 2MPa.
Example 2
PPCHC prepared in example 1.
Raw materials are prepared according to parts by weight: 85 parts of PPCHC, 1.5 parts of acrylic acid modified titanium dioxide, 3 parts of light calcium carbonate, 1 part of a coupling agent compounded by 3:1 of a monoalkoxy phosphate ester type phthalate ester coupling agent and 0.3 part of carbon dioxide.
The foaming sheet molding process of example 1.
Example 3
PPCHC prepared in example 1.
Raw materials are prepared according to parts by weight: 70 parts of PPCHC, 2.5 parts of acrylic modified titanium dioxide, 0.5 part of silicon dioxide, 2.5 parts of a coupling agent compounded by 1:3 of monoalkoxy phosphate ester type phthalate ester coupling agent and 0.3 part of carbon dioxide.
A foamed sheet was made using the procedure of example 1.
Example 4
PPCHC prepared in example 1.
Raw materials are prepared according to parts by weight: 78 parts of PPCHC, 2.0 parts of acrylic modified titanium dioxide, 1.3 parts of nano calcium carbonate, 1.7 parts of monoalkoxyphosphate type phthalate coupling agent and 0.3 part of carbon dioxide.
A foamed sheet was made using the procedure of example 1.
Example 5
The preparation method of the PPCHC comprises the following steps: purging with high-purity carbon dioxide, replacing water and oxygen in a 5L high-pressure reaction kettle, and putting 1 part of propylene oxide, 2.5 parts of cyclohexene oxide and 0.008 part of catalyst into the reaction kettle, wherein the catalyst is a compound catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:3; adding propylene oxide, cyclohexene oxide and a catalyst into a reactor, charging carbon dioxide to enable the reaction pressure to reach 3.0MPa, heating to enable the reaction temperature to be kept at 60 ℃ for reaction for 8 hours, cooling, decompressing, stopping the reaction, dissolving a glue solution with chloroform, precipitating with ethanol to separate out, devolatilizing and drying to prepare the pure PPCHC. PPCHC having a molecular weight of 8.6X10 by GPC analysis 4 g/mol。
The raw material mixture ratio and the process of the example 1 prepare the foaming plate.
Example 6
The preparation method of the PPCHC comprises the following steps: purging with high-purity carbon dioxide to displace 5L of high pressureAdding 1 part of propylene oxide, 1.5 parts of cyclohexene oxide and 0.003 part of catalyst into a reaction kettle, wherein the catalyst is a compound catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:2; adding propylene oxide, cyclohexene oxide and a catalyst into a reactor, charging carbon dioxide to enable the reaction pressure to reach 1.0MPa, heating to enable the reaction temperature to be kept at 80 ℃ for reaction for 8 hours, cooling, decompressing, stopping the reaction, dissolving a glue solution with chloroform, precipitating and separating out with ethanol, devolatilizing and drying to prepare the pure PPCHC. PPCHC having a molecular weight of 9.7X10 by GPC analysis 4 g/mol。
The raw material mixture ratio and the process of the example 1 prepare the foaming plate.
Example 7
The preparation method of the PPCHC comprises the following steps: purging with high-purity carbon dioxide, replacing water and oxygen in a 5L high-pressure reaction kettle, and putting 1 part of propylene oxide, 2 parts of cyclohexene oxide and 0.006 part of catalyst into the reaction kettle, wherein the catalyst is a compound catalyst of tetra-n-butyl ammonium halide and triethylboron according to a molar ratio of 1:2.5; adding propylene oxide, cyclohexene oxide and a catalyst into a reactor, charging carbon dioxide to enable the reaction pressure to reach 3.5MPa, heating to enable the reaction temperature to be kept at 50 ℃ for reaction for 8 hours, cooling, decompressing, stopping the reaction, dissolving a glue solution with chloroform, precipitating with ethanol to separate out, devolatilizing and drying to prepare the pure PPCHC. PPCHC has a molecular weight of 1.2X10 by GPC analysis 5 g/mol。
The raw material mixture ratio and the process of the example 1 prepare the foaming plate.
Example 8
PPCHC prepared in example 1.
Raw materials are prepared according to parts by weight: 60 parts of PPCHC, 5 parts of talcum powder, 0.1 part of heavy calcium carbonate, 5 parts of bis- (3-ethoxysilane propyl) -tetrasulfide and 0.5 part of azodicarbonamide.
The process of example 1 was used to make foamed sheet having a twin screw extruder aspect ratio of 33:1 and a single screw extruder aspect ratio of 31:1.
Example 9
PPCHC prepared in example 1.
Raw materials are prepared according to parts by weight: 99 parts of PPCHC, 0.5 part of magnesium oxide, 10 parts of zinc oxide, 0.1 part of chromium chloride methacrylate and 0.05 part of pentane.
The process of example 1 was used to make foamed sheet having a twin screw extruder aspect ratio of 38:1 and a single screw extruder aspect ratio of 28:1.
The results of the performance test of each example are shown in Table 1, wherein the water resistance is the mass loss rate after the sample is immersed in water at 25℃for 12 hours and dried. Dimensional stability was tested according to GB/T8811-2008. Threshing rate refers to the mass loss rate of a 1dm3 cube sample, after a 0.5kg weight is placed on top, after 10m of the sample is pulled on a pine plate with a friction coefficient of 0.2.
| Expansion ratio | Water resistance% | Dimensional stability% | Softening temperature (DEG C) | Threshing rate% | Compressive strength kPa | Shore A hardness | |
| Example 1 | 73 | 0.71 | 0.91 | 71.3 | 2.2 | 33 | 18 |
| Example 2 | 73 | 0.73 | 0.92 | 73.4 | 2.4 | 33 | 18 |
| Example 3 | 74 | 0.75 | 0.91 | 70.1 | 2.3 | 35 | 19 |
| Example 4 | 71 | 0.89 | 1.11 | 66.6 | 2.4 | 36 | 20 |
| Example 5 | 72 | 0.73 | 0.92 | 68.7 | 2.3 | 32 | 17 |
| Example 6 | 72 | 0.76 | 0.93 | 70.1 | 2.1 | 43 | 22 |
| Example 7 | 67 | 0.78 | 1.08 | 66.8 | 2.7 | 56 | 24 |
| Example 8 | 78 | 0.93 | 1.23 | 61.7 | 3.3 | 42 | 20 |
| Example 9 | 41 | 0.99 | 1.34 | 63.4 | 3.4 | 48 | 21 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The high-temperature-resistant carbon dioxide-based biodegradable foaming material is characterized by comprising the following raw materials in parts by weight: 60-99 parts of PPCHC, 0.5-5 parts of nucleating agent, 0.1-10 parts of filler, 0.1-5 parts of coupling agent and 0.05-0.5 part of foaming agent.
2. The high-temperature-resistant carbon dioxide-based biodegradable foaming material according to claim 1, wherein the raw materials comprise the following components in parts by weight: 70-85 parts of PPCHC, 1.5-2.5 parts of nucleating agent, 0.5-3 parts of filler, 1-2.5 parts of coupling agent and 0.1-0.5 part of foaming agent.
3. The high temperature resistant carbon dioxide based biodegradable foam material according to claim 1 or 2, characterized in that PPCHC is prepared by the following method: and (3) putting propylene oxide, cyclohexene oxide and a catalyst into a reactor, charging carbon dioxide to enable the reaction pressure to reach 1.0-2.0 MPa, heating to enable the reaction temperature to be kept at 60-80 ℃, performing ring-opening polymerization to generate a glue solution, and washing, devolatilizing and drying the glue solution to obtain a finished product.
4. The biodegradable foam material according to claim 1 or 2, characterized in that said nucleating agent is one or more of talc, calcium carbonate, silica, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, mica.
5. The high temperature resistant carbon dioxide based biodegradable foam material according to claim 4, wherein said nucleating agent is acrylic modified titanium dioxide.
6. The high temperature resistant carbon dioxide based biodegradable foam material according to claim 1 or 2, wherein the filler is one or more of silica, heavy calcium carbonate, nano calcium carbonate, light calcium carbonate, and zinc oxide.
7. The high-temperature-resistant carbon dioxide-based biodegradable foaming material according to claim 1 or 2, wherein the coupling agent is a composite titanate coupling agent, and the composite titanate coupling agent is a coupling agent formed by compounding a monoalkoxy phosphate type phthalate coupling agent and a monoalkoxy fatty ester type phthalate coupling agent.
8. A method for preparing the high-temperature-resistant carbon dioxide-based biodegradable foam material according to any one of claims 1 to 7, which is characterized in that the raw materials are mixed and extruded and foamed into beads by adopting a mode of connecting a double-screw extruder and a single-screw extruder in series, and then the beads are further foamed and molded.
9. The method for preparing a high temperature resistant carbon dioxide based biodegradable foam according to claim 8, wherein the aspect ratio of the twin screw extruder is 36:1, and the aspect ratio of the single screw extruder is 30:1.
10. The method for preparing the high-temperature-resistant carbon dioxide-based biodegradable foam material according to claim 8, wherein the method comprises the following steps: the foaming multiplying power is 40-80 times.
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