CN102391570B - Extrusion foaming polypropylene particles with lower thermal molding temperature and preparation method thereof - Google Patents
Extrusion foaming polypropylene particles with lower thermal molding temperature and preparation method thereof Download PDFInfo
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- CN102391570B CN102391570B CN201110260389XA CN201110260389A CN102391570B CN 102391570 B CN102391570 B CN 102391570B CN 201110260389X A CN201110260389X A CN 201110260389XA CN 201110260389 A CN201110260389 A CN 201110260389A CN 102391570 B CN102391570 B CN 102391570B
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- polypropylene
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- beta nucleater
- foaming
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 109
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 99
- -1 polypropylene Polymers 0.000 title claims abstract description 66
- 238000005187 foaming Methods 0.000 title claims abstract description 49
- 238000001125 extrusion Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000465 moulding Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 title abstract 3
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 12
- 239000011324 bead Substances 0.000 claims description 71
- 239000000463 material Substances 0.000 claims description 29
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims 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 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000010924 continuous production Methods 0.000 abstract description 8
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 10
- 230000004927 fusion Effects 0.000 description 9
- 238000012661 block copolymerization Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003856 thermoforming Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- CNFTYYKCUPPMIJ-UHFFFAOYSA-N 2,3-dicyclohexylbenzene-1,4-dicarboxamide Chemical compound C1CCCCC1C=1C(C(=O)N)=CC=C(C(N)=O)C=1C1CCCCC1 CNFTYYKCUPPMIJ-UHFFFAOYSA-N 0.000 description 1
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 238000012093 association test Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- JILYTPDQRCHWPA-UHFFFAOYSA-L calcium;octanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCCC([O-])=O JILYTPDQRCHWPA-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses extrusion foaming polypropylene particles with lower thermal molding temperature, which comprises the following components in part by weight: 100 parts of polypropylene, 0.02-0.6 part of beta nucleating agent, 0-0.6 part of antioxidant, 0-2 parts of lubricating agent, 0-3 parts of foaming nucleating agent and 0-2 parts of coloring agent, wherein the polypropylene is high-melt-strength polypropylene and co-polypropylene. The invention further discloses a preparation method for the extrusion foaming polypropylene particles. The method is simple to operate, can be applied to continuous production, and is suitable for industrial production.
Description
Technical field
The present invention relates to the high molecular foam material production technical field, be specifically related to a kind of EXTRUSION FOAMED PP bead and preparation method thereof with low hot-forming temperature.
Background technology
Porous plastics has light weight, heat insulation, sound insulation, buffering, specific tenacity height, advantage such as cheap, therefore is used widely in fields such as packing business, industry, agricultural, transportation, war industry, space industry and daily necessities.The conventional foam plastics have polystyrene foamed (PS), polyethylene foamed (PE), expanded polypropylene (PP) and polyurathamc (PU) etc.
Compare with traditional foam PS, foaming PE, foaming PP has the advantage of many uniquenesses: the thermotolerance that (1) is good, foam PS are used down at 80 ℃ usually, and only ability 70-80 ℃ of foaming PE, and 120 ℃ of foaming PP abilities can be at life-time service under the hot environment; (2) excellent mechanical property, the modulus in flexure of PP be much larger than PE, so PP foamy static load ability is better than the PE foam, and PP foamy impact property is better than the PS foam; In addition, foaming PP also has significant thermal insulation, good chemical resistance, good stress cracking resistance.Based on above-mentioned advantage, the PP foam material especially has competitive power in the application of automotive industry and food packaging industry in the application of many industrial circles, can substitute existing P S foam and PE foam, and application prospect is boundless.
At present, the method for preparing polypropylene foam mainly contains extrusion molding, compression molding etc.Wherein, extrusion molding can be produced continuously, but generally can only be used for the production of products such as sheet material, sheet material, is difficult to prepare complex-shaped product.And the mold pressing rule is expanded bead to be put into the mould of specified shape, utilizes steam heating to make then and is welding together the formation goods between the expanded bead.Therefore, compression molding is used for preparing complex-shaped goods widely.In compression molding, it is particularly important that the preparation of expanded bead seems.Expanded bead can prepare with extrusion molding or still formula method.Prepare in the process of foam plastic product in compression molding, the steam that needs to feed certain pressure is welded together the expanded bead surface.The vapor pressure height, equipment cost and energy consumption will sharply rise.In order to reduce production costs, be necessary to reduce the fusion temp of PP expanded bead, (hot-forming temperature).
The method of reduction expanded polypropylene bead hot-forming temperature commonly used mainly contains following two kinds at present:
1. with the blend of random copolymerization PP, block copolymerization PP or they and the linear PP base-material as expanded bead, wherein comonomer can be ethene, 1-butylene, 1-amylene, 1-hexene etc.Can reduce the PP fusing point by copolymerization, thereby reach the purpose that reduces PP expanded bead hot-forming temperature.With Japanese Patent JP 59-91502 is example, and it is base-material with the ethylene-propylene random copolymer, and the therein ethylene weight content is 3.5wt%, and this base-material utilizes the moulding vapor pressure of the expanded bead that still formula foaming obtains can be low to moderate 0.3MPa (134 ℃ of temperature).Chinese patent ZL02803474.0 has adopted the non-cross-linking PP random copolymers of 138～140 ℃ of fusing points as starting material.Because copolymerization has destroyed the molecular structure of PP, make that the heat resisting temperature of foaming product reduces, the mechanical property variation, be unsuitable for preparing high performance polypropylene foaming beads.
2. utilize organo-peroxide to handle the expanded bead surface.The Japan JSP ZL01819174.6 of house journal, ZL 02826640.4, ZL 200410061513.X, ZL 200410063190.8 has described a kind of method of utilizing still formula method to produce polypropylene foaming beads: in this method, coat the organo-peroxide of one deck decomposition temperature between polypropylene fusing point and vicat softening point temperature on the matrix resin surface earlier, and it is decomposed more than 50%, and make the surface produce to a certain degree crosslinked, foam then.Present two melting peaks (cryogenic melting peak heat enthalpy value is less than 86% of high-temperature fusion peak heat enthalpy value) on the DSC curve of gained expanded bead.The homopolymerization PP expanded bead moulding vapor pressure that utilizes this method to obtain can be low to moderate 0.36MPa (140 ℃ of temperature).Adopt organo-peroxide to handle the method on expanded bead surface, meeting residual peroxide and degradation production thereof in foaming product can not be applied to the field that hygienic requirements is arranged with Food Contact; And superoxide and degradation production thereof are influential to the work-ing life of goods; Production technique is comparatively complicated in addition, is difficult to realize in extrusion and foaming process.
Summary of the invention
The invention provides a kind of EXTRUSION FOAMED PP bead with low hot-forming temperature.
The present invention also provides a kind of preparation method with EXTRUSION FOAMED PP bead of low hot-forming temperature, but this method continuous production and environmentally friendly is suitable for suitability for industrialized production.
A kind of EXTRUSION FOAMED PP bead with low hot-forming temperature comprises the polypropylene of 100 weight parts and the beta nucleater of 0.02 weight part-0.6 weight part.
Described polypropylene is selected high melt strength, propylene and Co-polypropylene for use, and described Co-polypropylene comprises atactic copolymerized polypropene or block copolymerization polypropylene etc.
The weight percentage of Co-polypropylene is preferably 10%-60% in described high melt strength, propylene and the Co-polypropylene, more preferably 10%-30%.
Described high melt strength, propylene is selected for use: utilize Gottfert " Rheotens " melt strength tester to measure down at 190 ℃, melt strength values is at the polypropylene of 5cN-50cN.
Described polypropylene all can be selected the commercially available prod for use.
According to the demand of different field, described EXTRUSION FOAMED PP bead further comprises the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part.
Described beta nucleater can be selected the condensed-nuclei aromatics class for use, as quinacridone etc.; Organic carboxyl acid and its esters are as pimelic acid/calcium stearate mixture, calcium suberate etc.; Replace or unsubstituted aromatic amides class, as dicyclohexyl terephthalamide, naphthalene two Cyclohexamides etc.; The rare earth class nucleator; The mineral-type nucleator as in Calucium Silicate powder, the lime carbonate etc. one or more, can be selected the commercially available prod for use.Described beta nucleater consumption is preferably 0.05 weight part-0.6 weight part.
The use of described beta nucleater, the preferred beta nucleater masterbatch that adopts, described beta nucleater masterbatch is made up of the raw material of following part by weight: beta nucleater: polypropylene=1: 2-9 more preferably 1: 9, makes the beta nucleater masterbatch with the mixture extruding pelletization of this ratio.The used preferred high melt strength, propylene of polypropylene in the described beta nucleater masterbatch.
In the preferred antioxidant 1010 of described oxidation inhibitor, the oxidation inhibitor 168 etc. one or both can be selected the commercially available prod for use.Add oxidation inhibitor and can improve polyacrylic heat oxygen aging resistance ability.
The ester compound of long-chain fat family base, in the paraffin one or more are arranged on preferred stearic acid of described lubricant, stearate, the molecular chain, can select the commercially available prod for use.Can select stearic acid and metallic salt thereof for use, as stearic acid, calcium stearate, barium stearate, Magnesium Stearate, Zinic stearas etc.; The ester compound that long-chain fat family base is arranged on the molecular chain is as glyceryl monostearate, Tristearoylglycerol etc.; Amides is as amine hydroxybenzene, stearic amide, ethylene bis stearic acid amide etc.; In the paraffin one or more.Add lubricant and help polyacrylic extrusion moulding.
In described foaming nucleation agent preferably talc powder, Sodium Benzoate, lime carbonate, titanium dioxide, polynite, the silicon-dioxide one or more can be selected the commercially available prod for use.The agent of adding foaming nucleation helps the nucleation of polypropylene abscess.
Described tinting material is selected one or more in pigment dyestuff and the mineral dye for use, can select the commercially available prod for use.Add tinting material and can obtain required color, with dealing with various requirements.
A kind of preparation method with EXTRUSION FOAMED PP bead of low hot-forming temperature comprises step:
Get the polypropylene of 100 weight parts, the beta nucleater of 0.02 weight part-0.6 weight part, the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature.
In order to reach better invention effect, the preparation method of described EXTRUSION FOAMED PP bead preferably includes step: the beta nucleater with polypropylene segment and 0.02 weight part-0.6 weight part mixes and extruding pelletization in advance, makes the beta nucleater masterbatch; Again with beta nucleater masterbatch and remaining polypropylene and the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature;
Wherein, beta nucleater and polyacrylic weight ratio are 1 in the described beta nucleater masterbatch: 2-9, more preferably 1: 9.
Perhaps, the preparation method of described EXTRUSION FOAMED PP bead preferably includes step: the beta nucleater with part high melt strength, propylene and 0.02 weight part-0.6 weight part mixes and extruding pelletization in advance, makes the beta nucleater masterbatch; Again with beta nucleater masterbatch and remaining polypropylene and the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature;
Wherein, the weight ratio of beta nucleater and high melt strength, propylene is 1 in the described beta nucleater masterbatch: 2-9.
With respect to 100 weight part polypropylene, the consumption of described supercritical co or overcritical nitrogen is preferably 4 weight parts-10 weight part.
The foaming density of described expanded polypropylene bead generally can reach 0.025g/cm
3-0.09g/cm
3
Performance test of the present invention:
Foaming density p according to the standard A STM D792-08 of U.S. test materials association test expanded bead
f
Foaming density calculation formula is:
ρ
f＝a/(a+w-b)
A: the aerial quality of foaming sample, w makes the quality of the foaming water-immersed metal cap of sample in water, and b is the quality of foaming sample in water.
The expansion ratio calculation formula:
N: expansion ratio, ρ
P: the density of matrix resin, ρ
f: the density of expanded bead.
Utilize differential scanning calorimeter (DSC) to measure the thermal characteristics of expanded bead.Test condition: take by weighing 5mg left and right sides sample, under the nitrogen protection condition, be warmed up to 200 ℃ from 40 ℃ of conditions with 10 ℃/min.
The present invention has following advantage:
(1) the present invention utilizes extrusion molding to prepare polypropylene foaming beads, the control foaming process conditions, and the expanded bead of the controllable density that can obtain foaming has higher production efficiency.
(2) the resulting polypropylene foaming beads of the present invention has two or more melting peaks.Wherein the melting peak of lesser temps is the melting peak of β crystalline substance, and the melting peak of comparatively high temps is the melting peak of α crystalline substance.The welding of expanded polypropylene bead mainly relies on the fusion of β crystalline substance, can realize at a lower temperature, and in the fusion process of expanded polypropylene bead, part β crystalline substance changes the α crystalline substance into; What the α crystalline substance had then guaranteed the expanded polypropylene bead has higher mechanical strength and a heat-drawn wire.
Description of drawings
The DSC curve of the expanded polypropylene bead that Fig. 1 makes for embodiment 1;
The DSC curve of the expanded polypropylene bead that Fig. 2 makes for Comparative Examples 1;
Embodiment
Below by embodiment the present invention is specifically described, embodiment just is used for the present invention is further specified, but not limiting the scope of the invention.
The preparation of beta nucleater masterbatch: will contain 10 kilograms of beta nucleater (TMB-5, the substituted aroma amides, Shanxi chemical research institute) with 90 kilograms of high melt strength, propylene (RS1684, Basell company, utilize Gottfert " Rheotens " melt strength tester to measure down at 190 ℃, its melt strength values is 5cN) mix and then in twin screw extruder, extrude screw speed 200rpm, 200 ℃ of temperature.Use as the beta nucleater masterbatch after the extruding pelletization drying.The beta nucleater masterbatch that uses among this patent embodiment all for this reason legal system be equipped with.
Embodiment 1:
With 4 kilograms of beta nucleater masterbatch; 66.4 kilogram high melt strength, propylene (RS1684; Basell company); 30 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 3 kilograms; head pressure 17MPa; 160 ℃ of head temperatures, the underwater pelletizer water temperature is controlled at 60 ℃, obtains expansion ratio and be 30 times expanded polypropylene bead.The DSC curve of this expanded polypropylene bead is seen Fig. 1.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.45MPa (148 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is very firm, seamless between the expanded bead.
Embodiment 2:
With 6 kilograms of beta nucleater masterbatch; 44.6 kilogram high melt strength, propylene (RS1684; Basell company); 50 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 2.8 kilograms; head pressure 14MPa; 170 ℃ of head temperatures, the underwater pelletizer water temperature is controlled at 40 ℃, obtains expansion ratio and be 24 times expanded polypropylene bead.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.47MPa (150 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is firm between the expanded bead, and is seamless.
Embodiment 3:
With 4 kilograms of beta nucleater masterbatch; 66.4 kilogram high melt strength, propylene (RS1684; Basell company); 30 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; 1 kilogram of calcium stearate; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 2.8 kilograms; head pressure 15MPa; 150 ℃ of head temperatures; the underwater pelletizer water temperature is controlled at 60 ℃, obtains expansion ratio and be 23 times expanded polypropylene bead.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.45MPa (148 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is firm between the expanded bead, and is seamless.
Embodiment 4:
With 4 kilograms of beta nucleater masterbatch; 66.4 kilogram high melt strength, propylene (RS1684; Basell company); 30 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; 1 kilogram of calcium stearate; 1 kilogram of black masterbatch; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 3 kilograms; head pressure 15MPa; 160 ℃ of head temperatures; the underwater pelletizer water temperature is controlled at 60 ℃, obtains expansion ratio and be 26 times expanded polypropylene bead.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.45MPa (148 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is firm between the expanded bead, and is seamless.
Embodiment 5:
With 4 kilograms of beta nucleater masterbatch; 66.4 kilogram high melt strength, propylene (RS1684; Basell company); 30 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; 1 kilogram of black masterbatch; 1 kilogram of calcium stearate; 500 gram talcum powder; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 3 kilograms; head pressure 17MPa; 160 ℃ of head temperatures; the underwater pelletizer water temperature is controlled at 60 ℃, obtains expansion ratio and be 27 times black expanded polypropylene bead.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.47MPa (150 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is firm between the expanded bead, and is seamless.
Comparative Examples 1: do not add the preparation and the thermoforming thereof of the polypropylene foaming beads of beta nucleater
With 70 kilograms of high melt strength, propylene (RS1684; Basell company); 30 kilograms of block copolymerization polypropylene (K8303; Yanshan Petrochemical company); 0.1 kilogram oxidation inhibitor 168; 0.2 kilogram antioxidant 1010; put into the forcing machine extrusion foaming after mixing; can add materials continuously according to the above-mentioned raw materials ratio; carry out continuous production; the extruded velocity of material is controlled at per hour extrudes 40 kilograms; the injection speed of supercritical co is controlled at per hour injects 3 kilograms; head pressure 17MPa; 160 ℃ of head temperatures, the underwater pelletizer water temperature is controlled at 60 ℃, obtains expansion ratio and be 30 times expanded polypropylene bead.This expanded polypropylene bead DSC curve is seen Fig. 2.
The expanded polypropylene bead that obtains is put into the thermoforming machine moulding, vapor pressure 0.62MPa (160 ℃ of fusion temps), the product surface that obtains is smooth, and bonding is firm between the expanded bead, and is seamless.
Claims (7)
1. the EXTRUSION FOAMED PP bead with low hot-forming temperature comprises the polypropylene of 100 weight parts, the beta nucleater of 0.02 weight part-0.6 weight part, the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part;
Described polypropylene is high melt strength, propylene and Co-polypropylene; Described high melt strength, propylene is meant: utilize Gottfert " Rheotens " melt strength tester to measure down at 190 ℃, melt strength values is at the polypropylene of 5cN-50cN;
The weight percentage of Co-polypropylene is 10%-60% in the described polypropylene;
Described beta nucleater is the substituted aroma amides.
2. the EXTRUSION FOAMED PP bead with low hot-forming temperature according to claim 1 is characterized in that described oxidation inhibitor is one or both in antioxidant 1010, the oxidation inhibitor 168.
3. the EXTRUSION FOAMED PP bead with low hot-forming temperature according to claim 1, it is characterized in that described lubricant is that the ester compound of long-chain fat family base, in the paraffin one or more are arranged on stearic acid, stearate, the molecular chain;
Perhaps, described tinting material is one or more in pigment dyestuff, the mineral dye.
4. the EXTRUSION FOAMED PP bead with low hot-forming temperature according to claim 1 is characterized in that described foaming nucleation agent is one or both in talcum powder, Sodium Benzoate, lime carbonate, titanium dioxide, polynite, the silicon-dioxide.
5. according to each described a kind of preparation method of claim 1-4, comprise step with EXTRUSION FOAMED PP bead of low hot-forming temperature:
Get the polypropylene of 100 weight parts, the beta nucleater of 0.02 weight part-0.6 weight part, the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature.
6. according to each described a kind of preparation method of claim 1-4, comprise step with EXTRUSION FOAMED PP bead of low hot-forming temperature:
Beta nucleater with polypropylene segment and 0.02 weight part-0.6 weight part mixes and extruding pelletization in advance, makes the beta nucleater masterbatch; Again with beta nucleater masterbatch and remaining polypropylene and the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature;
Wherein, beta nucleater and polyacrylic weight ratio are 1:2-9 in the described beta nucleater masterbatch.
7. according to each described a kind of preparation method of claim 1-4, comprise step with EXTRUSION FOAMED PP bead of low hot-forming temperature:
Beta nucleater with part high melt strength, propylene and 0.02 weight part-0.6 weight part mixes and extruding pelletization in advance, makes the beta nucleater masterbatch; Again with beta nucleater masterbatch and remaining polypropylene and the oxidation inhibitor of 0-0.6 weight part, the lubricant of 0-2 weight part, the foaming nucleation agent of 0-3 weight part and the tinting material of 0-2 weight part, mix the back and drop into forcing machine, and in forcing machine, inject supercritical co or overcritical nitrogen, the head pressure of forcing machine is 9MPa-25MPa, head temperature is 140 ℃-170 ℃, per os mould foaming back underwater cutpellet, the water temperature of underwater cutpellet is 40 ℃-70 ℃, makes the EXTRUSION FOAMED PP bead with low hot-forming temperature;
Wherein, the weight ratio of beta nucleater and high melt strength, propylene is 1:2-9 in the described beta nucleater masterbatch.
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| US9562140B2 (en) | 2013-08-16 | 2017-02-07 | Berry Plastics Corporation | Polymeric material for an insulated container |
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| US9957365B2 (en) | 2013-03-13 | 2018-05-01 | Berry Plastics Corporation | Cellular polymeric material |
| US20140262916A1 (en) | 2013-03-14 | 2014-09-18 | Berry Plastics Corporation | Container |
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| EP3127951B2 (en) * | 2015-08-03 | 2025-04-02 | Borealis AG | Polypropylene composition suitable for foamed sheets and articles |
| CN106380624A (en) * | 2016-08-31 | 2017-02-08 | 无锡会通轻质材料股份有限公司 | Easily-molded polypropylene foaming bead and preparation method thereof |
| CA3013585A1 (en) | 2017-08-08 | 2019-02-08 | Berry Global, Inc. | Insulated container |
| CN115895124B (en) * | 2023-01-03 | 2024-08-30 | 中化泉州能源科技有限责任公司 | Antibacterial and antifouling foamed polypropylene material and preparation method thereof |
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| CN101379129A (en) * | 2006-02-06 | 2009-03-04 | 博里利斯技术公司 | Extruded polyolefin for the manufacture of cellular material |
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