CN115160746A - Polyethylene terephthalate foam material and preparation method and application thereof - Google Patents
Polyethylene terephthalate foam material and preparation method and application thereof Download PDFInfo
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- CN115160746A CN115160746A CN202211066346.2A CN202211066346A CN115160746A CN 115160746 A CN115160746 A CN 115160746A CN 202211066346 A CN202211066346 A CN 202211066346A CN 115160746 A CN115160746 A CN 115160746A
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- polyethylene terephthalate
- foam material
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- terephthalate foam
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 54
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 54
- -1 Polyethylene terephthalate Polymers 0.000 title claims abstract description 52
- 239000006261 foam material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 49
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 239000010806 kitchen waste Substances 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 11
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- IZHVBANLECCAGF-UHFFFAOYSA-N 2-hydroxy-3-(octadecanoyloxy)propyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCCCCCCCCCCC IZHVBANLECCAGF-UHFFFAOYSA-N 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 229940074045 glyceryl distearate Drugs 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012768 molten material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000006260 foam Substances 0.000 abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 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 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940075529 glyceryl stearate Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- UQDVHJGNIFVBLG-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O UQDVHJGNIFVBLG-UHFFFAOYSA-N 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
Abstract
The invention discloses a polyethylene glycol terephthalate foam material, and a preparation method and application thereof, and belongs to the technical field of new materials. The polyethylene terephthalate foam material is prepared by physical extrusion foaming, and comprises the following components in parts by weight: 50 to 80 parts; polyethylene elastomer: 15 to 38 portions of; chain extender: 1 to 3 parts; hydrophilic auxiliary agent: 3 to 5 parts; nucleating agent: 0.3 to 1.5 portions; and (3) foam promoter: 0.5 to 2 parts; antioxidant: 0.2 to 0.5 portion. The polyethylene terephthalate foam material provided by the invention has the hardness of Shore C85-95 ℃, is not broken after being continuously stirred for 3-6 months, has the hydrophilic speed of less than 1.5s, can meet the use requirement of a biological carrier in kitchen waste treatment, plays a role in grinding kitchen waste, prolongs the service life of the biological carrier, and reduces the use cost.
Description
Technical Field
The invention relates to the technical field of new materials, and particularly relates to a polyethylene terephthalate foam material, and a preparation method and application thereof.
Background
With the development of society, huge quantities of kitchen waste can be generated every day, and how to rapidly degrade the kitchen waste and return the kitchen waste to the natural circulation is a worldwide problem. The kitchen waste is fermented and then converted into the organic fertilizer by utilizing the efficient microbial flora existing in the nature, and the method is a green and environment-friendly technical route. In the fermentation process, the biological strains are required to be inoculated on a carrier firstly, so that the biological strains are propagated to a certain amount, and then the biological strains are contacted with the kitchen waste to realize fermentation and conversion. In order to improve the propagation efficiency of the biological strains used therein, a lightweight, porous and wear-resistant bacteria-carrying foam is required to create water and oxygen conditions for living and propagation of biological bacteria, and to be able to grind the kitchen waste, thereby improving the efficiency of decomposition and fermentation.
The existing bacteria-carried thallus foam mainly adopts a PP foam material, has the problems of low hardness and poor wear resistance, is difficult to realize effective grinding of kitchen waste, is easy to wear in the using process, has short service life and high use cost, and is difficult to meet the use requirements.
The PET foam mainly comprises Polyethylene terephthalate (Polyethylene terephthalate), has good mechanical strength and high temperature resistance after foaming, can be recycled, and has good environmental protection performance.
How to modify PET foam to have the advantages of high hardness and wear resistance so as to meet the use requirements of the foam carrying bacteria is the research direction of the technicians in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of low hardness and poor wear resistance of the existing bacteria carrier foaming material, and provides the polyethylene terephthalate foaming material which has higher hardness and good wear resistance and can meet the use requirement of the biological carrier for treating the kitchen waste.
In order to solve the technical problems, the invention adopts the following technical scheme:
a polyethylene glycol terephthalate foaming material is prepared by physical extrusion foaming, and comprises the following components in parts by weight,
polyethylene terephthalate: 50 to 80 parts;
polyethylene elastomer: 15 to 38 portions of;
chain extender: 1 to 3 parts;
hydrophilic auxiliary agent: 3 to 5 parts;
nucleating agent: 0.3 to 1.5 portions;
and (3) foam promoter: 0.5 to 2 parts;
antioxidant: 0.2 to 0.5 part;
wherein the IV value of the polyethylene terephthalate is 0.6 to 0.8dL/g;
the polyethylene elastomer is a high-density polyethylene elastomer, and the density of the polyethylene elastomer is 0.8 to 0.97g/cm 3 。
The common IV value in the market is 0.6 to 0.8dL/g, wherein the fiber grade is 0.6 to 0.7, and the bottle grade is 0.7 to 0.8. The content of the additive is less than 0.6, and the additive is a recycling grade and has no thickening and utilizing value. If the IV value is higher than 0.8, the thickening reaction is more likely to occur, but it is necessary to customize the product, which is expensive. Therefore, the cost can be saved by selecting the polyethylene terephthalate with the IV value of 0.6 to 0.8dL/g.
Preferably, the polyethylene terephthalate is a constant-emissivity semi-dull PET resin, a Huarun polyester WB-8816 or a Sichuan east material 8401.
Preferably, the polyethylene elastomer is mesopetrochemical FMA016, dow 8130, sabic C1070D, or mitsui DF110.
Preferably, the chain extender is pyromellitic anhydride PMDA or bisoxazoline PBO. Thus, polyfunctional acid anhydride such as PMDA reacts with terminal hydroxyl of PET, or polyfunctional epoxy such as PBO reacts with terminal carboxyl of PET, so that the molecular weight of PET is increased, the molecular weight distribution is enlarged, a micro-crosslinking structure is formed, the melt strength of PET is improved, and foaming is realized.
Preferably, the hydrophilic auxiliary agent is PP-g-MAH, and the grafting ratio of the MAH is more than 1%. The MAH with the grafting rate of more than 1% can provide more anhydride groups to participate in the grafting reaction of PET terminal hydroxyl groups and the reaction of glyceryl stearate.
Preferably, the nucleating agent is 1000 to 3000 meshes of talcum powder.
Preferably, the foaming promoter is glyceryl monostearate or a mixture of glyceryl monostearate and glyceryl distearate in a mass ratio of 90. The glycerol stearate of the industrial products is classified according to different esterification degrees, and the industrial products generally comprise monoester: the diester is between 60 and 90. Used in extrusion foaming, the higher the monoester content the better, the highest commercial grade at present being 90.
Preferably, the antioxidant is prepared by mixing an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 40 or 50.
The second purpose of the invention is to provide a preparation method of the polyethylene terephthalate foaming material.
A preparation method of polyethylene terephthalate foam material comprises the following steps,
s1, putting the polyethylene terephthalate, the polyethylene elastomer, the chain extender, the hydrophilic assistant, the nucleating agent, the foaming assistant and the antioxidant which are subjected to vacuum drying into a high-speed mixer, and mixing for 10 to 15 minutes to obtain a mixture;
s2, melting and plasticizing the mixture by using a double-screw extruder, and simultaneously injecting supercritical fluid CO 2 Blending and then continuously extruding, and carrying out pressure relief and foaming on the molten material through a neck ring die to obtain the polyethylene terephthalate foaming material.
Wherein, in the step S1, the vacuum drying is carried out in a vacuum oven at the temperature of 60 to 100 ℃ for 3 to 6 hours; the rotating speed of the high-speed mixer is 200 to 300rpm.
In step S2, twin-screw extrusionThe temperature of the machine is controlled to be 240-260 ℃, the temperature of the neck mold is controlled to be 250-265 ℃, and CO is injected at the speed of 15-25 g/min by a booster pump 2 And the pressure of the neck ring die is 2 to 4MPa.
The invention also aims to provide the application of the polyethylene glycol terephthalate foam material in a biological carrier in kitchen waste treatment.
Compared with the prior art, the invention has the following advantages:
1. according to the polyethylene terephthalate foam material provided by the invention, the high-density polyethylene elastomer is added, so that on one hand, the toughness of the material can be improved, and the foam is endowed with strong and tough performance, so that the wear-resisting property of the material is improved, and the material is not easy to break in grinding and stirring; on the other hand, the addition of the high-density polyethylene elastomer increases the free volume of the polyethylene terephthalate, further improves the melt strength of the polyethylene terephthalate, prevents the combination of foam holes in the foaming process, realizes continuous extrusion foaming and simultaneously improves the hardness of the polyethylene terephthalate foaming material. And then adding a small amount of chain extender pyromellitic anhydride PMDA or bisoxazoline PBO, and utilizing the reaction of anhydride with functionality of pyromellitic anhydride PMDA and terminal hydroxyl of the polyethylene glycol terephthalate or the reaction of epoxy with functionality of bisoxazoline PBO and terminal carboxyl of the polyethylene glycol terephthalate to increase the molecular weight of the polyethylene glycol terephthalate, enlarge the molecular weight distribution and form a micro-crosslinking structure, thereby improving the melt strength of the polyethylene glycol terephthalate and realizing the high hardness and the wear resistance of the material. By adding PP-g-MAH with the grafting rate of more than 1% and glyceryl stearate, an intramolecular hydrophilic grafting structure is formed, and the hydrophilicity of the foam material is improved. Therefore, the polyethylene terephthalate foaming material provided by the invention has higher hardness and wear resistance.
2. The polyethylene terephthalate foam material provided by the invention has the hardness of Shore C85-95 ℃, is stirred for 20 days in a forward and reverse rotation mode at a speed of 20rpm, has the breakage rate of only 1 to 1.6%, can meet the use requirement of a biological carrier in kitchen waste treatment, has high hardness, can play a role in grinding kitchen waste, prolongs the service life of the biological carrier, and reduces the use cost.
3. The preparation method provided by the invention is simple in process production, easy in process flow control and suitable for industrial production.
Detailed Description
Example 1
A polyethylene terephthalate foam material comprises 80kg of constant-density petrochemical semi-dull PET resin (IV value is 0.6 dL/g) and medium-density petrochemical FMA016 (density is 0.965 g/cm) 3 ) 15kg of a chain extender PMDA (analytically pure, yufeng glass instruments Co., ltd., changsha, manufacturer) 1kg, a hydrophilic additive PP-g-MAH (DuPont P613) 3kg, a nucleating agent 3000-mesh talcum powder (Asfeng powder raw materials Co., ltd., ma, quanzhou) 0.3kg, a foaming aid (glyceryl monostearate: glycerin distearate proportion 90, 0.5kg of hangzhou chun food additives ltd, T90), an antioxidant (antioxidant 1010: antioxidant 168 ratio 50, basf, irganox 1010FF and Irgafos 168) 0.2kg.
The preparation method comprises the following steps of,
s1, drying the components at 80 ℃ for 2 hours, and mixing for 15 minutes by using a high-speed mixer with the rotating speed of 200rpm to obtain a uniformly mixed mixture.
S2, melting and plasticizing the mixture by using a double-screw extruder, and simultaneously injecting supercritical fluid CO 2 Blending and then continuously extruding. Wherein the temperature of the double-screw extruder is controlled to be 240 to 260 ℃, the temperature of the neck mold is controlled to be 250 to 265 ℃, a trace amount of carbon dioxide foaming agent is added through a booster pump, the dosage is 15 to 25g/min, the pressure relief pressure of the neck mold is 2 to 4MPa (because the process temperature is gradually transited in the preparation process, the gas injection amount and the neck mold pressure are fluctuation values, the same is applied below). And (3) releasing pressure and foaming the material through an oral mold to obtain a foaming material strip, namely the polyethylene terephthalate foaming material. Cutting the foaming strip at a constant speed by a granulator to obtain hexagonal porous foaming particles with the diameter of 1.2-1.5 cm.
Through measurement, the aperture of a cell of the foaming material prepared in the embodiment is 150 to 350 micrometers, the foaming multiplying power is 1.5 times, and the Shore C hardness is 95 degrees. The low speed stirring experiment was carried out, and the breakage rate was as shown in Table 1, while stirring was carried out at a speed of 20rpm for 20 days in a counter-rotating manner.
Example 2
A polyethylene terephthalate foam material comprises 50kg of Huarun polyester WB-8816 (IV value 0.8 dL/g) and 50kg of Sabic C1070D (density 0.868 g/cm) 3 ) 38kg of chain extender PBO (trademark 2,2' - (1, 3-phenylene) -bisoxazoline, hao (Dalian) chemical research and design institute Co., ltd.) in a factory is 3kg; 5kg of hydrophilic additive PP-g-MAH (Dupont P613); 1000-mesh talc powder (Asaheng powder materials Co., ltd., quanzhou, no. 818-F1) as a nucleating agent 1.5kg, 2kg of a foam booster (glyceryl monostearate: glyceryl distearate ratio 90.
The preparation method comprises the following steps of,
s1, drying the components at 80 ℃ for 4 hours, and mixing for 15 minutes by using a high-speed mixer with the rotating speed of 200rpm to obtain a uniformly mixed mixture.
S2, melting and plasticizing the mixture by using a double-screw extruder, and simultaneously injecting supercritical fluid CO 2 Blending and then continuously extruding. Wherein the temperature of the double-screw extruder is controlled to be 240-260 ℃, the temperature of the neck mold is controlled to be 250-265 ℃, a booster pump is used for adding a trace amount of carbon dioxide foaming agent, the dosage is 15-25g/min, and the pressure relief pressure of the neck mold is 2-4 MPa. And (3) releasing pressure and foaming the material through an oral mold to obtain a foaming material strip, namely the polyethylene terephthalate foaming material. Cutting the foaming strip at a constant speed by a granulator to prepare hexagonal porous foaming particles with the diameter of 1.2 to 1.5 cm.
Through measurement, the foam material prepared in the embodiment has the cell diameter of 200 to 400 mu m, the foaming multiplying power of 2 times and the Shore C hardness of 85 degrees. The low speed stirring experiment was carried out, and the breakage rate was as shown in Table 1, while stirring was carried out at a speed of 20rpm for 20 days in a counter-rotating manner.
Comparative example 1
The difference from example 1 is that comparative example 1 is based on the formulation of example 1, except that high density polyethylene elastomer component is removed and replaced with PET resin, including euthanized semi-dull PET resin (IV value 0.6 dL/g) 95kg, chain extender PMDA (analytical grade, afficho glass instruments ltd., changsha) 1kg, hydrophilic aid PP-g-MAH (dupont P613) 3kg, nucleating agent 3000 mesh talc (asahi feng powder raw materials ltd., no. 1250A) 0.3kg, foaming agent aid (glycerin monostearate: distearate ratio 90, hangzhou chun food additives ltd., T90) 0.5kg, antioxidant (antioxidant 1010: antioxidant 168 ratio 50, basff, irganox 1010FF and irfos 168) 0.2kg.
The preparation method comprises the following steps:
after the respective components were sufficiently dried in vacuum, they were mixed by a high-speed mixer for 10 to 15 minutes. And extruding and foaming the mixed material through a double-screw extruder, controlling the temperature of a screw of the extruder to be 240-260 ℃, controlling the temperature of an extrusion die to be 250-265 ℃, adding a trace amount of carbon dioxide foaming agent through a booster pump, wherein the dosage is 15-25 g/min, the pressure relief pressure of the die is 2-4 MPa, and releasing pressure and foaming the material through an oral die to obtain the foaming material strip. Cutting the foaming strip at a constant speed by a granulator to prepare hexagonal porous foaming particles with the diameter of 1.5-2.0 cm.
According to detection, the pore diameter of the foam prepared in the comparative example 1 is 350 to 500 mu m, the foaming multiplying power is 5 times, and the Shore C hardness is 75 degrees. The low speed stirring experiment was carried out, and the breakage rate was as shown in Table 1, while stirring was carried out at a speed of 20rpm for 20 days in a counter-rotating manner.
Comparative example 2
The difference from example 2 is that comparative example 2 also removed the high density polyethylene based elastomer component and replaced with PET resin based on the formulation of example 2, including hua run polyester WB-8816 (IV value 0.8 dL/g) 88kg, chain extender PBO (brand 2,2' - (1, 3-phenylene) -bisoxazoline, hao (Dalian) chemical research design institute Co., ltd. In the factory) 3kg, hydrophilic aid PP-g-MAH (DuPont P613) 5kg, nucleating agent 1000 mesh talc (Asaho powder raw materials Co., ltd., brand 818-F1) 1.5kg, foam booster (glyceryl monostearate: glyceryl distearate ratio 90, hangzhou Fuchun food additives Co., ltd., T90) 2kg, antioxidant (antioxidant 1010: antioxidant 168 ratio 50, basff, irganox 1010 and Irgas 168) 0.5kg.
The preparation method comprises the following steps:
the components were thoroughly dried in vacuo and then mixed by a high-speed mixer for 15 minutes. And extruding and foaming the mixed material by a double-screw extruder, controlling the temperature of a screw of the extruder to be 240-260 ℃, controlling the temperature of an extrusion opening die to be 250-265 ℃, adding a trace amount of carbon dioxide foaming agent by a booster pump, wherein the dosage is 15-25 g/min, the pressure relief pressure of the opening die is 2-4 MPa, and releasing pressure and foaming the material through the opening die to obtain the foaming material strip. Cutting the foaming strip at a constant speed by a granulator to prepare hexagonal porous foaming particles with the diameter of 2.0-2.5 cm.
Detection shows that the pore diameter of the foam material prepared in comparative example 1 is 100 to 200 mu m, the foaming multiplying power is 6 times, and the Shore C hardness is 70 degrees. The low speed stirring experiment was carried out, and the breakage rate of the mixture was shown in Table 1, while stirring was carried out at a speed of 20rpm for 20 days in a counter-rotating manner.
TABLE 1 Table of Performance data of the foams prepared in examples 1 to 2 and comparative examples
Therefore, after the polyethylene terephthalate foaming material prepared by the invention is modified by a high-density polyethylene elastomer, the hardness is obviously improved to reach Shore hardness C85 to 95 ℃, and the wear rate is 1 to 1.6 percent in 20 days. The use requirement of the biological carrier in the kitchen waste treatment can be met, the high hardness of the biological carrier can play a role in grinding the kitchen waste, the service life of the biological carrier is prolonged, and the use cost is reduced.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The polyethylene terephthalate foam material is characterized by being prepared by physical extrusion foaming, and the components of the polyethylene terephthalate foam material in parts by weight comprise,
polyethylene terephthalate: 50 to 80 parts;
polyethylene elastomer: 15 to 38 portions of;
chain extender: 1 to 3 parts;
hydrophilic auxiliary agent: 3 to 5 parts;
nucleating agent: 0.3 to 1.5 parts;
and (3) foaming aid: 0.5 to 2 parts;
antioxidant: 0.2 to 0.5 part;
wherein the IV value of the polyethylene terephthalate is 0.6 to 0.8dL/g;
the polyethylene elastomer is a high-density polyethylene elastomer, and the density of the polyethylene elastomer is 0.8 to 0.97g/cm 3 。
2. The polyethylene terephthalate foam material as recited in claim 1, wherein the chain extender is pyromellitic anhydride or bisoxazoline.
3. The polyethylene terephthalate foam material as recited in claim 1, wherein the hydrophilic auxiliary agent is PP-g-MAH, and a grafting ratio of the MAH is 1% or more.
4. The polyethylene terephthalate foam material as claimed in claim 1, wherein the nucleating agent is 1000 to 3000 mesh talc.
5. The polyethylene terephthalate foam material as claimed in claim 1, wherein the foaming promoter is glyceryl monostearate or a mixture of glyceryl monostearate and glyceryl distearate at a mass ratio of 90.
6. The polyethylene terephthalate foam material as claimed in claim 1, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 40 or 50.
7. A preparation method of a polyethylene terephthalate foam material is characterized by comprising the following steps,
s1, putting the polyethylene terephthalate, the polyethylene elastomer, the chain extender, the hydrophilic assistant, the nucleating agent, the foaming assistant and the antioxidant which are subjected to vacuum drying into a high-speed mixer, and mixing for 10 to 15 minutes to obtain a mixture;
s2, melting and plasticizing the mixture by using a double-screw extruder, and simultaneously injecting supercritical fluid CO 2 Continuously extruding after blending, and decompressing and foaming the molten material through a die to obtain the polyethylene terephthalate foam material as claimed in claim 1.
8. The method for producing a polyethylene terephthalate foam material according to claim 7, wherein in step S1, the vacuum drying is performed in a vacuum oven at 60 to 100 ℃ for 3 to 6 hours; the rotating speed of the high-speed mixer is 200 to 300rpm.
9. The method for preparing the polyethylene terephthalate foam material according to claim 7, wherein in the step S2, the temperature of the twin-screw extruder is controlled to be 240 to 260 ℃, the temperature of the die is controlled to be 250 to 265 ℃, and CO is injected at a rate of 15 to 25g/min by a booster pump 2 And the pressure of the neck ring die is 2 to 4MPa.
10. Use of the polyethylene terephthalate foam material according to claim 1 as a bio-carrier in the treatment of kitchen waste.
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| CN101870803A (en) * | 2009-04-24 | 2010-10-27 | 上海金发科技发展有限公司 | Toughened polyethylene glycol terephthalate and preparation method thereof |
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| CN113563630A (en) * | 2021-08-11 | 2021-10-29 | 江苏中科聚合新材料产业技术研究院有限公司 | Preparation method and application of durable hydrophilic polypropylene foaming particles |
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| CN101870803A (en) * | 2009-04-24 | 2010-10-27 | 上海金发科技发展有限公司 | Toughened polyethylene glycol terephthalate and preparation method thereof |
| US20110274554A1 (en) * | 2010-05-07 | 2011-11-10 | Armacell Enterprise Gmbh | Ductile expanded polyesters having high impact resistance |
| CN111269539A (en) * | 2020-04-15 | 2020-06-12 | 南京越升挤出机械有限公司 | Chain extender master batch for PET extrusion foaming, and preparation method and application thereof |
| CN113563630A (en) * | 2021-08-11 | 2021-10-29 | 江苏中科聚合新材料产业技术研究院有限公司 | Preparation method and application of durable hydrophilic polypropylene foaming particles |
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