CN114479383A - Flame-retardant PET (polyethylene terephthalate) foam material with good melt strength and preparation method thereof - Google Patents
Flame-retardant PET (polyethylene terephthalate) foam material with good melt strength and preparation method thereof Download PDFInfo
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- CN114479383A CN114479383A CN202210212276.0A CN202210212276A CN114479383A CN 114479383 A CN114479383 A CN 114479383A CN 202210212276 A CN202210212276 A CN 202210212276A CN 114479383 A CN114479383 A CN 114479383A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- 239000006261 foam material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 title abstract description 150
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 150
- 238000005187 foaming Methods 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 40
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- 238000007605 air drying Methods 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 25
- 239000003963 antioxidant agent Substances 0.000 claims description 24
- 230000003078 antioxidant effect Effects 0.000 claims description 24
- 239000003822 epoxy resin Substances 0.000 claims description 20
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- 239000012745 toughening agent Substances 0.000 claims description 19
- 239000004970 Chain extender Substances 0.000 claims description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 230000002411 adverse Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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Images
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
- 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
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
The invention discloses a flame-retardant PET (polyethylene terephthalate) foam material with good melt strength and a preparation method thereof, and the material is prepared by supercritical CO2The prepared PET foam material has the advantages of small pore size and good uniformity of the pores of the flame-retardant PET foam material with good melt strength, and lays a foundation for wide popularization and application of the PET foam material. The preparation method of the flame-retardant PET foaming material with good melt strength provided by the invention comprises the following steps of firstly, carrying out melt extrusion granulation on the raw material components by using a double-screw extruder to prepare the PET master batch with good melt strength, namely, the melt strength and the stability of PET resin are improved by in-situ chain extension and melting-up, and the later-stage situation that the PET master batch is subjected to supercritical N is effectively avoided2The phenomenon of foam collapse occurs in the foaming process; in addition, N2Low solubility in PET foaming system, good distribution uniformity, and remarkably improvedThe cell uniformity of the PET foaming material; the raw material cost is low, the preparation process is simple, the requirement on equipment is low, pollutants are hardly generated in the foaming process, and the requirements of environmental protection are met.
Description
Technical Field
The invention relates to the technical field of polyester foaming, in particular to a flame-retardant PET (polyethylene terephthalate) foaming material with good melt strength and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is one of five engineering plastics, commonly called polyester resin, and is the most widely applied variety in thermoplastic polyester. PET has the comprehensive properties of chemical reagent resistance, friction resistance, impact resistance, high temperature resistance, excellent electrical insulation and the like, and is widely applied to the fields of electronic appliances, automobile parts, synthetic fibers, films, engineering plastics and the like at present. However, the limited oxygen index of PET is only about 21%, which belongs to flammable fiber, and this is consistent with the weak point that greatly limits its application range, so flame retardant modification of PET becomes a problem to be solved in its application field.
In recent years, with the demand for weight reduction of electric vehicles and new energy materials, it is very promising to research how to foam PET materials. The PET foaming material has ideal dimensional stability, good gas barrier property, excellent wear resistance and surface barrier property, and the thermal stability of the PET foaming material is far superior to polystyrene foam, polyvinyl chloride foam and the like, so the foaming application of the PET foaming material has great research value.
Compared with chemical foaming and other physical foaming methods, the supercritical fluid foaming has the advantages of economy, environmental protection, high cost performance and the like, and the microcellular foam prepared by the supercritical fluid has large pore density, small pore diameter and high bubble nucleation speed. Wherein, CO2Has a critical temperature of 31.1 ℃ and a critical pressure of 7.37MPa, compared with N having a critical temperature of-147 DEG C2Supercritical CO2The processing conditions for preparing the foaming material are lower, but supercritical N is adopted2The pore size of the prepared foaming material is smaller, so that the supercritical CO2Processing conditions and supercritical N for the preparation of foamed materials2The processing conditions for preparing the foamed material have advantages and disadvantages.
The Chinese patent with the patent number ZL 201410231325.0 discloses a PET foaming product and a preparation method thereof, which mainly adopts a solid phase polycondensation mode to carry out chain extension on waste PET bottle flakes, and then adopts supercritical CO2Foaming to prepare a foamed product; the invention discloses a modified PET (polyethylene terephthalate) foaming material and a forming method thereof, which are Chinese invention patent with the patent number of ZL 201810756657.9. At present, supercritical N is used2Reports on the preparation of PET foamed materials by foaming are rare.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a flame-retardant PET (polyethylene terephthalate) foam material with good melt strength and a preparation method thereof, compared with supercritical CO2The prepared PET foam material has the advantages of small pore diameter and good uniformity of the pores of the flame-retardant PET foam material with good melt strength, and lays a foundation for wide popularization and application of the PET foam material. The preparation method of the flame-retardant PET foaming material with good melt strength provided by the invention comprises the following steps of firstly, carrying out melt extrusion granulation on the raw material components by using a double-screw extruder to prepare the PET master batch with good melt strength, namely, the melt strength and the stability of PET resin are improved by in-situ chain extension and melting-up, and the later-stage situation that the PET master batch is subjected to supercritical N is effectively avoided2The phenomenon of foam collapse occurs in the foaming process; in addition, N2The solubility in a PET foaming system is low, the distribution uniformity is good, and the bubble uniformity of the PET foaming material is obviously improved; the raw material cost is low, the preparation process is simple, the requirement on equipment is low, pollutants are hardly generated in the foaming process, and the requirements of environmental protection are met.
In order to achieve the purpose, one of the purposes of the invention is to provide a preparation method of a flame-retardant PET (polyethylene terephthalate) foam material with good melt strength, which comprises the following raw materials, by weight, 100 parts of PET resin, 10-15 parts of a toughening agent, 10-20 parts of an isocyanate chain extender, 10-20 parts of epoxy resin, 0.1-0.5 part of an antioxidant, 10-15 parts of a flame retardant and 1-5 parts of a flame-retardant synergist;
the preparation method of the flame-retardant PET foam material with good melt strength comprises the following steps:
step 1: placing the PET resin in a forced air drying oven, carrying out forced air drying for 12-24 h at the temperature of 100-120 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4-6 h at the temperature of 100-120 ℃;
step 2: according to the weight ratio of claim 1, adding the dried PET resin, toughening agent, isocyanate chain extender, epoxy resin, antioxidant, flame retardant and flame retardant synergist in the step S1 into a double-screw extruder, and performing melt extrusion granulation to obtain PET master batch with good melt strength, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch with good melt strength prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12-24 h at the temperature of 100-120 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4-6 h at the temperature of 100-120 ℃;
step S4: subjecting the PET master batch with good melt strength dried in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 160-180 MPa, the gas injection delay is 2-3.2 s, and the gas injection time is 1-2 s; the injection pressure is about 30-35 MPa, the injection time is about 3-4 s, and the pressure maintaining time is about 2-3 s; the cooling time is about 40-50 s, and the oil temperature is set to be 50-60 ℃.
The preferable technical scheme is that the PET resin is sliced PET resin, and the initial intrinsic viscosity is 0.800-0.815 dL/g. More preferably, commercially available CR-8816, CR-8828, CR-8839 and CR-8863 are used.
In a preferred technical scheme, the toughening agent is graft modified polyolefin resin or copolymer of olefin substances.
Further preferably, the substrate of the graft-modified polyolefin resin is one of Polyethylene (PE), polypropylene (PP) or a copolymer (POE) of ethylene and octene, and the graft of the graft-modified polyolefin resin is one of Maleic Anhydride (MAH) and Glycidyl Methacrylate (GMA), such as PE-g-MAH, PP-g-MAH and POE-g-GMA; the copolymer of the olefin substance is a polymer consisting of methacrylic acid, styrene and organic silicon, or is a terpolymer of methyl methacrylate, butadiene and styrene. The toughening agent mainly aims to improve the crystallization behavior of the PET foaming material, refine crystal grains and crystallinity to improve the toughness of the PET foaming material and improve the cell strength of the PET foaming material. The graft-modified polyolefin resin is specifically preferably commercially available as 9905B, 3401, AX 8900; the olefin copolymer is preferably S-2001, S-2030, EMA 1125A, EBA 35BA40, EMA 1HP771, which are commercially available.
The preferable technical scheme is that the percentage content of-NCO groups in the isocyanate chain extender is 21.5-22.1%. the-NCO group in the isocyanate chain extender is capable of reacting with the terminal carboxyl group in the PET resin, and specifically, commercially available PM-200, M20S, 44V20L, MR200, 5005 and the like are preferable.
Preferably, the epoxy resin is glycidyl ester epoxy resin. The epoxy resin is used as a chain extension synergist and can promote the chain extension reaction of isocyanate chain extenders and PET resin. The glycidyl ester epoxy resin has high reactivity, easy processing, multiple functional groups and high crosslinking density, has small influence on raw materials of the PET foam material in the chain extension reaction process, has high crosslinking density, and can improve the heat resistance of the foam material. More specifically, commercially available Dowfax9N, HEXION EPON 1031, EPON 1031-A-70 and the like are preferable.
The preferable technical proposal is that the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 164, antioxidant DNP, antioxidant DLTP and antioxidant TNP. The antioxidant effectively prevents the problems of thermal oxygen degradation and the like in the process of processing and forming the PET master batches, can effectively delay or inhibit the process of oxidizing the PET master batches, and avoids bringing adverse effects to the subsequent foaming process.
In a preferred technical scheme, the flame retardant is an organic aluminum hypophosphite flame retardant. More preferably, it is commercially available
OP 1248、
OP 1240, Exolit OP950, etc.
In a preferred technical scheme, the flame retardant synergist is a nitrogen compound or a phosphorus compound. More specifically, commercially available Melapur 200-70, Melapur 200FF, SP-6072B, SP-6075J, SPB-100, KR-480 and the like are preferable.
The invention also aims to provide the flame-retardant PET foam material with good melt strength, which is prepared by adopting the preparation method.
The invention has the advantages and beneficial effects that:
1. the invention provides a preparation method of a flame-retardant PET (polyethylene terephthalate) foaming material with good melt strength, which comprises the following steps of firstly, carrying out melt extrusion granulation on raw material components by a double-screw extruder to prepare PET master batches with good melt strength, namely, the melt strength and the stability of PET resin are improved by in-situ chain extension and melting-up, and the later-stage situation that the PET master batches are subjected to supercritical N (nitrogen) melting is effectively avoided2The phenomenon of foam collapse occurs in the foaming process; in addition, N2The PET foaming material has low solubility in a PET foaming system and good distribution uniformity, and obviously improves the uniformity of foam holes of the PET foaming material.
2. The invention provides a preparation method of a flame-retardant PET (polyethylene terephthalate) foaming material with good melt strength, which has the advantages of low raw material cost, simple preparation process and low equipment requirement, almost no pollutant is generated in the foaming process, and the preparation method meets the requirement of environmental protection.
3. The invention provides a flame-retardant PET (polyethylene terephthalate) foam material with good melt strength, which is relatively to supercritical CO2The prepared PET foam material has smaller pore diameter and good uniformity, and lays a foundation for the wide popularization and application of the PET foam material.
Drawings
FIG. 1 is an electron microscope scanning image of the flame-retardant PET foamed material with good melt strength prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The flame-retardant PET foam material with good melt strength comprises the following raw materials, by weight, 100 parts of CR-8816(PET resin), 10 parts of S-2001 (toughening agent), 10 parts of PM-200 (isocyanate chain extender), 10 parts of Dowfax9N (epoxy resin), 10100.1 parts of antioxidant, and,
OP 1248 (flame retardant) 10 parts and Melapur 200-70 (flame retardant synergist) 1 part;
the preparation method of the flame-retardant PET foam material with good melt strength comprises the following steps:
step 1: putting PET resin in a forced air drying oven, carrying out forced air drying for 12h at the temperature of 100 ℃, then putting the PET resin in a vacuum drying oven, and carrying out vacuum drying for 4h at the temperature of 100 ℃;
step 2: adding the dried PET resin, the toughening agent, the isocyanate chain extender, the epoxy resin, the antioxidant, the flame retardant and the flame retardant synergist in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches with good melt strength, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch with good melt strength prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12 hours at the temperature of 100 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4 hours at the temperature of 100 ℃;
step S4: subjecting the PET master batch with good melt strength dried in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 160MPa, the gas injection delay is 2s, and the gas injection time is 1 s; the injection pressure is about 30MPa, the injection time is about 3s, and the pressure maintaining time is about 2 s; the cooling time was about 40s and the oil temperature was set at 50 ℃.
The electron microscope scanning image of the prepared flame-retardant PET foaming material with good melt strength is shown in figure 1, figure 1 shows,
example 1 the flame retardant PET foam material with good melt strength prepared by the method of the present invention has uniform and fine cells inside.
Example 2
The flame-retardant PET foam material with good melt strength comprises, by weight, 100 parts of CR-8828(PET resin), 15 parts of S-2030 (toughening agent), 10 parts of M20S (isocyanate chain extender), 15 parts of HEXION EPON 1031 (epoxy resin), 0.2 part of antioxidant 1076/antioxidant 164 (the weight ratio of the two is 1: 1),
OP 1240 (flame retardant) 15 parts and Melapur 200 (flame retardant synergist) 3 parts;
the preparation method of the flame-retardant PET foam material with good melt strength comprises the following steps:
step 1: putting the PET resin into a forced air drying oven, carrying out forced air drying at the temperature of 110 ℃ for 18h, then putting the PET resin into a vacuum drying oven, and carrying out vacuum drying at the temperature of 110 ℃ for 5 h;
step 2: adding the dried PET resin, the toughening agent, the isocyanate chain extender, the epoxy resin, the antioxidant, the flame retardant and the flame retardant synergist in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches with good melt strength, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch with good melt strength prepared in the step S2 in a forced air drying oven, carrying out forced air drying at the temperature of 110 ℃ for 13h, then placing in a vacuum drying oven, and carrying out vacuum drying at the temperature of 110 ℃ for 5 h;
step S4: subjecting the PET master batch with good melt strength dried in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 170MPa, the gas injection delay is 3s, and the gas injection time is 2 s; the injection pressure is about 35MPa, the injection time is about 4s, and the pressure maintaining time is about 3 s; the cooling time was about 45s and the oil temperature was set to 55 ℃.
Example 3
The flame-retardant PET foam material with good melt strength comprises the following raw materials, by weight, 100 parts of CR-8839(PET resin), 15 parts of 9905B (toughening agent), 10 parts of MR200 (isocyanate chain extender), 20 parts of EPON 1031-A-70 (epoxy resin), 0.5 part of antioxidant DNP, 15 parts of Exolit OP950 (flame retardant) and 5 parts of Melapur 200FF (flame retardant synergist);
the preparation method of the flame-retardant PET foam material with good melt strength comprises the following steps:
step 1: putting PET resin in a forced air drying oven, carrying out forced air drying at the temperature of 120 ℃ for 24 hours, then putting the PET resin in a vacuum drying oven, and carrying out vacuum drying at the temperature of 120 ℃ for 6 hours;
step 2: adding the dried PET resin, the toughening agent, the isocyanate chain extender, the epoxy resin, the antioxidant, the flame retardant and the flame retardant synergist in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches with good melt strength, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch with good melt strength prepared in the step S2 into a forced air drying oven, carrying out forced air drying for 14h at the temperature of 120 ℃, then placing into a vacuum drying oven, and carrying out vacuum drying for 6h at the temperature of 120 ℃;
step S4: subjecting the PET master batch with good melt strength dried in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 180MPa, the gas injection delay is 2.2s, and the gas injection time is 2 s; the injection pressure is about 35MPa, the injection time is about 4s, and the pressure maintaining time is about 3 s; the cooling time was about 50s and the oil temperature was set at 60 ℃.
Comparative example 1
The PET foam material comprises, by weight, 100 parts of CR-8816(PET resin), 10 parts of S-2001 (toughening agent), 10100.1 parts of antioxidant, and,
OP 1248 (flame retardant) 10 parts and Melapur 200-70 (flame retardant synergist) 1 part;
the preparation method of the PET foaming material comprises the following steps:
step 1: putting PET resin in a forced air drying oven, carrying out forced air drying for 12h at the temperature of 100 ℃, then putting the PET resin in a vacuum drying oven, and carrying out vacuum drying for 4h at the temperature of 100 ℃;
step 2: adding the dried PET resin, the toughening agent, the antioxidant, the flame retardant and the flame retardant synergist in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and 3, step 3: placing the PET master batch prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12 hours at the temperature of 100 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4 hours at the temperature of 100 ℃;
step S4: subjecting the dried PET master batch obtained in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 160MPa, the gas injection delay is 2s, and the gas injection time is 1 s; the injection pressure is about 30MPa, the injection time is about 3s, and the pressure maintaining time is about 2 s; the cooling time was about 40s and the oil temperature was set at 50 ℃.
Comparative example 2
The PET foam material comprises the following raw materials, by weight, 100 parts of CR-8816(PET resin), 10 parts of S-2001 (toughening agent), 10 parts of PM-200 (isocyanate chain extender), 10 parts of Dowfax9N (epoxy resin) and 10100.1 parts of antioxidant;
the preparation method of the PET foaming material comprises the following steps:
step 1: putting PET resin in a forced air drying oven, carrying out forced air drying for 12h at the temperature of 100 ℃, then putting the PET resin in a vacuum drying oven, and carrying out vacuum drying for 4h at the temperature of 100 ℃;
step 2: adding the dried PET resin, the toughening agent, the isocyanate chain extender, the epoxy resin and the antioxidant in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host machine frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12 hours at the temperature of 100 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4 hours at the temperature of 100 ℃;
step S4: subjecting the dried PET master batch obtained in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps:supercritical N2The gas injection pressure is 160MPa, the gas injection delay is 2s, and the gas injection time is 1 s; the injection pressure is about 30MPa, the injection time is about 3s, and the pressure maintaining time is about 2 s; the cooling time was about 40s and the oil temperature was set at 50 ℃.
Comparative example 3
The PET foam material comprises, by weight, 100 parts of CR-8816(PET resin), 10 parts of S-2001 (toughening agent), 10 parts of PM-200 (isocyanate chain extender), 10 parts of Dowfax9N (epoxy resin), 10100.1 parts of antioxidant, and,
OP 1248 (flame retardant) 10 parts and Melapur 200-70 (flame retardant synergist) 1 part;
the preparation method of the PET foaming material comprises the following steps:
step 1: putting PET resin in a forced air drying oven, carrying out forced air drying for 12h at the temperature of 100 ℃, then putting the PET resin in a vacuum drying oven, and carrying out vacuum drying for 4h at the temperature of 100 ℃;
step 2: adding the dried PET resin, the toughening agent, the isocyanate chain extender, the epoxy resin, the antioxidant, the flame retardant and the flame retardant synergist in the step S1 into a double-screw extruder according to the weight ratio, and carrying out melt extrusion granulation to obtain PET master batches, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12 hours at the temperature of 100 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4 hours at the temperature of 100 ℃;
step S4: subjecting the PET master batch dried in the step S3 to supercritical CO2Preparing PET foaming material by a foaming process, wherein supercritical CO is adopted2The foaming process comprises the following specific steps: supercritical CO2The gas injection pressure is 160MPa, the gas injection delay is 2s, and the gas injection time is 1 s; the injection pressure is about 30MPa, the injection time is about 3s, and the pressure maintaining time is 2s is about; the cooling time was about 40s and the oil temperature was set at 50 ℃.
The flame-retardant PET foam materials with good melt strength prepared in the examples 1-3 and the PET foam materials prepared in the comparative examples 1-3 are respectively subjected to performance tests of intrinsic viscosity, foaming ratio, limiting oxygen index and UL-94, and the specific operations are as follows:
testing intrinsic viscosity: taking 0.3g of a PET foaming material sample, dissolving the PET foaming material sample by adopting a mixed solvent of phenol and 1,1, 2-trichloroethane (the mass ratio of the phenol to the 1,1, 2-trichloroethane is 2: 3), and continuously preserving heat for 2 hours in an oil bath environment at the temperature of 100 ℃; after the solution is cooled to room temperature, filtering the solution by using a Buchner funnel, and fixing the volume of the filtrate in a 50ml volumetric flask; and measuring and calculating intrinsic viscosity and viscosity-average molecular weight by using a spherical Ubbelohde viscometer (0.8-0.9mm) in a constant temperature environment of 25 ℃.
Testing of foaming ratio: the foaming ratio was obtained by comparing the densities of the unfoamed PET sample plate and the PET foamed sample plate.
Limit oxygen index test: the tests were carried out in accordance with ISO 4589-1984, plastics, determination of their flammability by means of the oxygen index.
UL-94 test: the test was carried out according to GB 4609-84 "test methods for Plastic Combustion Properties horizontal and vertical methods".
TABLE 1 data of the performance test of the flame retardant PET foams with good melt strength prepared in examples 1 to 3 and the PET foams prepared in comparative examples 1 to 3
The experimental data show that: the intrinsic viscosity, the foaming ratio, the limiting oxygen index and UL-94 of the flame-retardant PET foam material with good melt strength prepared by the method in the embodiments 1-3 are obviously superior to those of the PET foam material prepared in the comparative examples 1-3, and the purpose of the invention is achieved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant PET foam material with good melt strength is characterized in that the flame-retardant PET foam material with good melt strength comprises the following raw materials, by weight, 100 parts of PET resin, 10-15 parts of a toughening agent, 10-20 parts of an isocyanate chain extender, 10-20 parts of epoxy resin, 0.1-0.5 part of an antioxidant, 10-15 parts of a flame retardant and 1-5 parts of a flame-retardant synergist;
the preparation method of the flame-retardant PET foam material with good melt strength comprises the following steps:
step 1: placing the PET resin in a forced air drying oven, carrying out forced air drying for 12-24 h at the temperature of 100-120 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4-6 h at the temperature of 100-120 ℃;
step 2: according to the weight ratio of claim 1, adding the dried PET resin, toughening agent, isocyanate chain extender, epoxy resin, antioxidant, flame retardant and flame retardant synergist in the step S1 into a double-screw extruder, and performing melt extrusion granulation to obtain PET master batch with good melt strength, wherein the temperature of each section in the double-screw extruder is 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃, 265 ℃ and 260 ℃, the host frequency is 7.5Hz, and the feeding frequency is 4.5 HZ;
and step 3: placing the PET master batch with good melt strength prepared in the step S2 in a forced air drying oven, carrying out forced air drying for 12-24 h at the temperature of 100-120 ℃, then placing in a vacuum drying oven, and carrying out vacuum drying for 4-6 h at the temperature of 100-120 ℃;
step S4: subjecting the PET master batch with good melt strength dried in the step S3 to supercritical N2Preparing PET foaming material by foaming process, wherein the supercritical N is2The foaming process comprises the following specific steps: supercritical N2The gas injection pressure is 160-180 MPa, the gas injection delay is 2-3.2 s, and the gas injection time is 1-2 s; the injection pressure is about 30-35 MPa, the injection time is about 3-4 s, and the pressure maintaining time is about 2-3 s; the cooling time is about 40-50 s, and the oil temperature is set to be 50-60 ℃.
2. The flame retardant PET foam material with good melt strength as claimed in claim 1, wherein the PET resin is a sliced PET resin and has an initial intrinsic viscosity of 0.800-0.815 dL/g.
3. The flame-retardant PET foam material with good melt strength as claimed in claim 1, wherein the toughening agent is a graft-modified polyolefin resin or a copolymer of olefins.
4. The flame-retardant PET foam material with good melt strength as claimed in claim 3, wherein the substrate of the graft-modified polyolefin resin is one of Polyethylene (PE), polypropylene (PP) or a copolymer of ethylene and octene (POE), and the graft of the graft-modified polyolefin resin is one of Maleic Anhydride (MAH) and Glycidyl Methacrylate (GMA); the copolymer of the olefin substance is a polymer consisting of methacrylic acid, styrene and organic silicon, or is a terpolymer of methyl methacrylate, butadiene and styrene.
5. The flame-retardant PET foaming material with good melt strength as claimed in claim 1, wherein the isocyanate chain extender has a percentage content of-NCO groups of 21.5-22.1%.
6. The flame-retardant PET foam material having good melt strength according to claim 1, wherein the epoxy resin is a glycidyl ester epoxy resin.
7. The flame-retardant PET foam material with good melt strength as claimed in claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 164, antioxidant DNP, antioxidant DLTP and antioxidant TNP.
8. The flame-retardant PET foam material with good melt strength as claimed in claim 1, wherein the flame retardant is an organic aluminum hypophosphite flame retardant.
9. The flame-retardant PET foam material with good melt strength as claimed in claim 1, wherein the flame-retardant synergist is a nitrogen compound or a phosphorus compound.
10. The flame-retardant PET foam material with good melt strength is characterized by being prepared by the preparation method of any one of claims 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959928A (en) * | 2022-06-07 | 2022-08-30 | 兴惠化纤集团有限公司 | Production process of double-color sea-island composite stretch yarn |
| CN115466492A (en) * | 2022-10-24 | 2022-12-13 | 北京化工大学 | Flame-retardant polyester foam material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959928A (en) * | 2022-06-07 | 2022-08-30 | 兴惠化纤集团有限公司 | Production process of double-color sea-island composite stretch yarn |
| CN115466492A (en) * | 2022-10-24 | 2022-12-13 | 北京化工大学 | Flame-retardant polyester foam material and preparation method thereof |
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