CN112831126A - High-molecular film material resistant to cooking and preparation method thereof - Google Patents
High-molecular film material resistant to cooking and preparation method thereof Download PDFInfo
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- CN112831126A CN112831126A CN202110154409.9A CN202110154409A CN112831126A CN 112831126 A CN112831126 A CN 112831126A CN 202110154409 A CN202110154409 A CN 202110154409A CN 112831126 A CN112831126 A CN 112831126A
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- glass fiber
- hollow glass
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002120 nanofilm Substances 0.000 title description 3
- 238000010411 cooking Methods 0.000 title description 2
- 239000003365 glass fiber Substances 0.000 claims abstract description 56
- -1 polypropylene Polymers 0.000 claims abstract description 44
- 239000002667 nucleating agent Substances 0.000 claims abstract description 43
- 239000004743 Polypropylene Substances 0.000 claims abstract description 31
- 229920001155 polypropylene Polymers 0.000 claims abstract description 31
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 15
- 229920006254 polymer film Polymers 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 239000004611 light stabiliser Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 21
- 239000000600 sorbitol Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
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- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims 6
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
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- 239000008103 glucose Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 238000005937 allylation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 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
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- IQUCNXSZNHPPML-UHFFFAOYSA-N 2-chloro-n-[(4-chlorophenyl)-phenylmethyl]acetamide Chemical compound C=1C=C(Cl)C=CC=1C(NC(=O)CCl)C1=CC=CC=C1 IQUCNXSZNHPPML-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polypropylene composite materials, and discloses a boiling-resistant high polymer film material and a preparation method thereof, wherein the film material comprises the following components in parts by weight: 40-80 parts of polypropylene, 20-40 parts of modified hollow glass fiber, 1-5 parts of compatilizer, 0.2-1 part of lubricant, 0.2-1 part of heat stabilizer and 0.2-1 part of light stabilizer; the modified hollow glass fiber is a hollow glass fiber with a surface loaded with a nucleating agent and a coupling agent, and the mass ratio of the hollow glass fiber to the nucleating agent to the coupling agent is 20-40: 0.4-0.8: 0.4 to 0.8. The film material has high strength, heat resistance and transparency.
Description
Technical Field
The invention relates to the technical field of polypropylene composite materials, in particular to a boiling-resistant high-molecular film material and a preparation method thereof.
Background
Polypropylene (PP) is a semi-crystalline thermoplastic plastic, has the advantages of white color, no odor, no toxicity, low cost, easy processing and the like, and can be widely used in the food fields of food packaging, tableware and the like. However, polypropylene belongs to semi-crystalline resin, and the application of polypropylene is greatly limited due to the defects of slow crystallization speed, large spherulite size, low strength, poor heat resistance, low transparency and the like. At present, the nucleating agent is generally added to effectively shorten the polypropylene forming period, refine polypropylene grains and increase crystallinity, and the glass fiber is combined to be used as a reinforcing filler to effectively improve the strength and heat resistance of polypropylene, so that the physical properties of the polypropylene are improved.
For example, chinese patent CN201210574617.5 discloses a hydrolysis-resistant glass fiber reinforced polypropylene composite material for an automobile water bottle and a preparation process thereof, wherein the hydrolysis-resistant glass fiber reinforced polypropylene composite material comprises the following components in parts by weight: 48-86 wt% of polypropylene; 2-6 wt% of metallocene polypropylene elastomer; 0-2 wt% of a heat stabilizer; 0-2 wt% of an auxiliary agent; 0-2 wt% of a nucleating agent; 2-10 wt% of a compatilizer; 10-30 wt% of chopped glass fiber. The composite material has good strength and heat resistance, but has general transparency.
At present, a polypropylene composite material with high strength, good heat resistance and high transparency is not developed to meet the requirements of the food field.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and on one hand, provides a boiling-resistant polymer film material which has the characteristics of high strength, good heat resistance and high transparency; on the other hand, the preparation method of the steaming-resistant polymer film material is provided.
The purpose of the invention is realized by the following technical scheme:
on one hand, the invention provides a boiling-resistant polymer film material which comprises the following components in parts by weight: 40-80 parts of polypropylene, 20-40 parts of modified hollow glass fiber, 1-5 parts of compatilizer, 0.2-1 part of lubricant, 0.2-1 part of heat stabilizer and 0.2-1 part of light stabilizer;
the modified hollow glass fiber is a hollow glass fiber with a surface loaded with a nucleating agent and a coupling agent, and the mass ratio of the hollow glass fiber to the nucleating agent to the coupling agent is 20-40: 0.4-0.8: 0.4 to 0.8.
In one embodiment, the hollow glass fiber has a diameter of 20 to 30 μm. For example, the hollow glass fiber has a diameter of 20 microns, 22 microns, 24 microns, 26 microns, 28 microns, or 30 microns.
In one embodiment, the nucleating agent is a sorbitol-based nucleating agent. For example, the nucleating agent may be selected from DBS nucleating agents, MDBS nucleating agents, DMDBS nucleating agents, Millad NX8000 nucleating agents, 1,3-2, 4-bis (p-methylbenzylidene) -1-allyl sorbitol, and the like.
In one embodiment, the coupling agent is a silane coupling agent. For example, the coupling agent may be selected from the group consisting of KH550 coupling agent, KH560 coupling agent, KH570 coupling agent, KH792 coupling agent, DL602 coupling agent, and the like.
In one embodiment, the compatibilizer is a polar monomer graft polymer, the matrix of the polar monomer graft polymer is at least one of polyethylene, polypropylene, a copolymer of styrene and butadiene, a polyethylene-polystyrene-polypropylene terpolymer, an ethylene-propylene-butadiene terpolymer, an ethylene-acrylate copolymer, and an ethylene-acrylate-glycidyl methacrylate copolymer, and the polar monomer of the polar monomer graft polymer is at least one of maleic anhydride and its analogs, and acrylic acid and its ester derivatives. For example, the compatibilizer is maleic anhydride grafted polypropylene.
In one embodiment, the lubricant comprises at least one of low molecular esters, metal soaps, complex esters of stearic acid, and amides. For example, the lubricant is pentaerythritol stearate, triglycerol monostearate sorbitan monostearate, glyceryl monostearate, magnesium stearate, calcium stearate, and the like.
In one embodiment, the heat stabilizer comprises at least one of an amine heat stabilizer, a hindered phenol heat stabilizer, a phosphite heat stabilizer, a calixarene heat stabilizer, and a thioester heat stabilizer.
In one embodiment, the light stabilizer comprises at least one of phenyl ortho-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, resorcinol monobenzoate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, and 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorobenzotriazole.
On the other hand, the invention provides a preparation method of the steaming-resistant polymer film material, which comprises the following steps:
and S111, heating and uniformly mixing the hollow glass fiber, the nucleating agent and the coupling agent, and drying to obtain the modified hollow glass fiber.
In step S111, the hollow glass fiber has an axially thin tubular cavity therein, so that the nucleating agent and the coupling agent are distributed inside and outside the hollow glass fiber, the coupling agent increases the interface bonding force between the hollow glass fiber and the nucleating agent, so that the nucleating agent can be uniformly and firmly distributed inside and outside the hollow glass fiber, and the bonding force is further improved by drying, so that the hollow glass fiber with the inner and outer surfaces uniformly and firmly loaded with the nucleating agent and the coupling agent can be obtained.
And S112, adding the modified hollow glass fiber, the compatilizer, the lubricant, the heat stabilizer and the light stabilizer into the polypropylene, uniformly mixing, and then carrying out melt mixing and granulation to obtain the composite material.
In step S112, the modified hollow glass fiber has an axial cavity structure therein, and a nucleating agent and a coupling agent loaded on the inner and outer surfaces, so that the polypropylene unit cell uniformly grows along the inner and outer surfaces of the modified hollow glass fiber, the glass fiber is more uniformly distributed in the polypropylene, and the glass fiber and the polypropylene have higher bonding strength, so that the composite material has higher strength, transparency and heat resistance.
In one embodiment, the heating temperature in step S111 is 60 to 80 ℃, the drying temperature in step S111 is 100 to 120 ℃, and the temperature for melt-kneading in step S112 is 200 to 250 ℃.
In the prior art, Milliken company patent reports a synthesis method and a route of Millad NX8000 of a new-generation polypropylene nucleating agent, namely, in the process of metal catalytic allylation reaction, a raw material glucose allylation reaction needs to be carried out under the protection of nitrogen introduced at the reflux temperature of a solvent, and after the reaction, the white powdery solid can be obtained by repeatedly carrying out treatments such as decolorization and filtration by using activated carbon. The method has the advantages of complex operation steps, difficult control of the reaction process and low melting point of the prepared final product, namely 245 ℃. This is mainly due to the high temperature reaction conditions that lead to various side reactions. Therefore, in order to improve the production efficiency of the sorbitol nucleating agent, reduce the production cost and improve the thermal stability of the sorbitol nucleating agent, a novel sorbitol nucleating agent and a preparation method thereof need to be developed.
In one embodiment, referring to fig. 1, the method for preparing the boiling-resistant polymer film material further includes a method for preparing 1,3-2, 4-bis (p-methylbenzylidene) -1-allyl sorbitol, which includes the following steps:
s121, preparing an aqueous HBr alcohol solution with the concentration of 0.3-0.7 mol/L, placing 2-4 parts by mass of glucose, 1.5-2.5 parts by mass of allyl bromide, 1.5-2.5 parts by mass of metal powder and 40-60 parts by mass of the aqueous HBr alcohol solution in a reaction kettle, and stirring and reacting at room temperature for 40-60 hours to obtain a mixed solution; dropwise adding 3-7 mol/L NaOH aqueous solution into the mixed solution to neutralize until the pH value is 6-8, and generating a large amount of white precipitate in the dropwise adding process to obtain suspension; suction-filtering the suspension to remove the precipitate to obtain a filtrate; and removing the solvent from the filtrate through rotary evaporation to obtain milky white solid 1-allyl sorbitol.
In the reaction of step S121, glucose and allyl bromide are used as reactants, Sn powder is used as a catalyst, and HBr alcohol aqueous solution is used as a reaction solvent, and the intermediate product 1-allyl sorbitol is catalytically synthesized at room temperature.
For example, the metal powder is at least one of M parts by mass powder, Al powder, Zn powder, Fe powder, In powder, Sn powder, and Cu powder. The metal powder is preferably In or Sn because In and Sn exhibit a good catalytic activity for the reaction under the same conditions of solvent, temperature, time, and the like.
For example, the alcohol-water HBr solution contains 8-12% by volume of ethanol.
S122, placing 2.7-4.7 parts by mass of the milky white solid, 3-5 parts by mass of p-tolualdehyde, 0.15-0.35 part by mass of p-toluenesulfonic acid, 8-12 parts by mass of cyclohexane and 15-20 parts by mass of methanol in a reaction kettle, carrying out water division reaction (namely aldol condensation reaction) at 62 ℃ until no water is generated, neutralizing with 0.8-1.2 mol/L NaOH aqueous solution until the pH value is 8-9, and distilling to remove the solvent to obtain a pre-precipitate; washing the pre-precipitate with boiling water and boiling cyclohexane, filtering and drying to obtain the target product 1,3-2, 4-bis (p-methylbenzylidene) -1-allyl sorbitol as white solid.
In the reaction of step S122, 1-allyl sorbitol, p-tolualdehyde and p-toluenesulfonic acid are used as reactants, cyclohexane is used as a solvent, methanol is used as an accelerator, and a new generation of sorbitol nucleating agent 1,3-2, 4-bis (p-methylbenzylidene) -1-allyl sorbitol is synthesized by aldol condensation reaction at room temperature.
The target product is subjected to structure identification and thermal stability investigation through Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance hydrogen spectroscopy (H NMR), nuclear magnetic resonance carbon spectroscopy (' C NMR), thermogravimetry-differential scanning calorimetry (T part-DSC) and a melting point determination means, and a test result shows that the melting point of the target product is 275-278 ℃, and the purity of the target product can reach more than 97%, which shows that the target product has higher thermal stability and purity; the method has the advantages of simple operation steps, mild reaction temperature conditions, capability of avoiding the problem of multiple side reactions under high-temperature reaction conditions, easiness in reaction process control, high production efficiency and low production cost, and is suitable for large-scale popularization and application.
Compared with the prior art, the invention has at least the following advantages:
(1) the hollow glass fiber is prepared by utilizing the hollow glass fiber, the nucleating agent and the coupling agent are distributed inside and outside the hollow glass fiber through the thin tubular cavity arranged inside the hollow glass fiber in the axial direction, the coupling agent increases the interface bonding force between the hollow glass fiber and the nucleating agent, the nucleating agent can be uniformly and firmly distributed inside and outside the hollow glass fiber, the bonding force of the hollow glass fiber and the nucleating agent is further improved through drying, and the hollow glass fiber with the inner surface and the outer surface uniformly and firmly loaded with the nucleating agent and the coupling agent can be obtained.
(2) According to the invention, the hollow glass fiber with the surface loaded with the nucleating agent and the coupling agent is used as the reinforcing filler, and the modified hollow glass fiber is internally provided with the axial cavity structure, the nucleating agent and the coupling agent loaded on the inner surface and the outer surface, so that polypropylene unit cells can uniformly grow along the inner surface and the outer surface of the modified hollow glass fiber, the glass fiber can be more uniformly distributed in the polypropylene, the glass fiber and the polypropylene can be promoted to have higher bonding strength, and the composite material has higher strength, transparency and heat resistance.
(3) The invention also provides a new sorbitol nucleating agent which has higher thermal stability and purity, and can obviously improve the heat resistance and the transparency of the composite material under the synergistic effect with other components in the formula.
(4) The invention also provides a preparation method of the new sorbitol nucleating agent, and the 1,3-2, 4-di (p-methylbenzylidene) -1-allyl sorbitol prepared by the method has higher thermal stability and purity; the method has the advantages of simple operation steps, mild reaction temperature condition, capability of avoiding the problem of multiple side reactions under the high-temperature reaction condition, easiness in control of the reaction process, high production efficiency, low production cost and suitability for popularization and use in large quantities.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scheme showing the synthesis of 1,3-2, 4-bis (p-methylbenzylidene) -1-allylsorbitol according to an embodiment of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, preferred embodiments of the invention are given below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The steam-resistant polymer film materials of examples 1 to 4 included the components shown in table 1 in parts by mass.
TABLE 1 EXAMPLES 1-4 component tables
In the above table, the compound heat stabilizer is prepared from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenol) phosphite ester according to the mass ratio of 1: 1 is prepared by compounding. The compound light stabilizer is prepared from 2-hydroxy-4-methoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole and resorcinol monobenzoate ester according to the mass ratio of 1: 1: 1 is prepared by compounding.
S111, weighing the components according to the data in the table, putting the hollow glass fiber, the nucleating agent and the coupling agent into a high-speed mixer, heating to 60-80 ℃, uniformly mixing, and drying at 100-120 ℃ to obtain the modified hollow glass fiber.
S112, adding the polypropylene, the compatilizer, the lubricant, the heat stabilizer and the light stabilizer into a stirrer to be uniformly mixed to obtain a mixture; and adding the mixture from a main feeding port of a double-screw extruder, adding the modified hollow glass fiber from a side feeding port, and carrying out melting, mixing and granulation to obtain the composite material. Wherein the rotating speed of the screw is 400-500 r/min, and the temperature of each zone of the extruder is 200-250 ℃.
The novel sorbitol nucleating agent in the embodiment 4 is 1,3-2, 4-bis (p-methylbenzylidene) -1-allyl sorbitol, and the synthesis method comprises the following steps:
(1) preparing aqueous HBr alcohol solution with the concentration of 0.5mol/L, wherein the volume percent of ethanol is 10 percent; placing 3 parts of glucose, 2.02 parts of allyl bromide, 1.98 parts of Sn powder and 50 parts of 0.5mo/L aqueous HBr alcohol in a reaction kettle, and stirring at room temperature for 48 hours to obtain a mixed solution; dropwise adding 5mol/L NaOH aqueous solution into the mixed solution to neutralize until the pH value is 7, wherein a large amount of white precipitate is generated in the dropwise adding process to obtain suspension; suction-filtering the suspension to remove the precipitate to obtain a filtrate; removing the solvent from the filtrate through rotary evaporation to obtain milky white solid 1-allyl sorbitol;
(2) putting 3.7 parts of milky white solid, 4.0 parts of p-methylbenzaldehyde, 0.25 part of p-toluenesulfonic acid, 10 parts of cyclohexane and 18.6 parts of methanol into a reaction kettle, carrying out water division reaction at 62 ℃ until no water is generated, neutralizing with 1mol/L NaOH aqueous solution until the pH value is 8-9, and distilling to remove the solvent to obtain a pre-precipitate; washing the pre-precipitate with boiling water and boiling cyclohexane, filtering and drying to obtain white solid 1,3-2, 4-di (p-methylbenzylidene) -1-allyl sorbitol.
Comparative example 1:
adding 60 parts of polypropylene, 3 parts of compatilizer, 0.6 part of lubricant, 0.6 part of nucleating agent, 0.6 part of heat stabilizer and 0.6 part of light stabilizer into a stirrer, and uniformly mixing to obtain a mixture; and adding the mixture from a main feeding port of a double-screw extruder, adding 30 parts of common glass fiber from a side feeding port, and carrying out melt mixing and granulation to obtain the composite material. Wherein the rotating speed of the screw is 400-500 r/min, and the temperature of each zone of the extruder is 200-250 ℃.
Comparative example 2:
the same as in example 3, except that the hollow glass fiber was replaced with a common glass fiber.
Comparative example 3:
the same as in example 3, except that the mass ratio of the hollow glass fiber, the nucleating agent and the coupling agent was changed to 30: 1: 0.2.
the composite materials of examples 1 to 4 and comparative examples 1 to 3 were prepared into standard samples by an injection molding machine, and a plurality of physical property tests were performed according to the industry standards, and the average value was taken, and the test results are shown in table 2.
TABLE 2 Performance test results of the steam resistant polymeric film materials
The test results of examples 1 and 2 are similar to those of example 3 and are not repeated. As can be seen from Table 1, the samples prepared by the present invention have high strength, heat resistance and transparency. Compared with example 3, example 4 adopts a novel sorbitol nucleating agent, so that the heat resistance and the transparency of the sample are obviously improved. Compared with the embodiment 3, the components or the proportion of the common glass fiber or the modified hollow glass fiber are adopted in the comparative examples 1 to 3, so that the strength and the heat resistance of the sample are greatly reduced. This indicates that the superior physical properties of the composite material of the present invention are produced by the synergy between the specific components and the specific proportions.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The boiling-resistant high polymer film material is characterized by comprising the following components in parts by weight: 40-80 parts of polypropylene, 20-40 parts of modified hollow glass fiber, 1-5 parts of compatilizer, 0.2-1 part of lubricant, 0.2-1 part of heat stabilizer and 0.2-1 part of light stabilizer;
the modified hollow glass fiber is a hollow glass fiber with a surface loaded with a nucleating agent and a coupling agent, and the mass ratio of the hollow glass fiber to the nucleating agent to the coupling agent is 20-40: 0.4-0.8: 0.4 to 0.8.
2. The steam-resistant polymer film material of claim 1, wherein the diameter of the hollow glass fiber is 20-30 μm.
3. The boiling-resistant polymeric film material of claim 1, wherein the nucleating agent is a sorbitol nucleating agent.
4. The retort-resistant polymeric film material of claim 1, wherein the coupling agent is a silane coupling agent.
5. The retort-resistant polymeric film material of claim 1, wherein the compatibilizer is a polar monomer graft polymer, the matrix of the polar monomer graft polymer is at least one of polyethylene, polypropylene, a copolymer of styrene and butadiene, a polyethylene-polystyrene-polypropylene terpolymer, an ethylene-propylene-butadiene terpolymer, an ethylene-acrylate copolymer, and an ethylene-acrylate-glycidyl methacrylate copolymer, and the polar monomer of the polar monomer graft polymer is at least one of maleic anhydride and its analogs and acrylic acid and its ester derivatives.
6. The retort-resistant polymeric film material of claim 1, wherein the lubricant comprises at least one of low molecular esters, metal soaps, complex esters of stearic acid, and amides.
7. The retort-resistant polymeric film material of claim 1, wherein the thermal stabilizer comprises at least one of an amine thermal stabilizer, a hindered phenol thermal stabilizer, a phosphite thermal stabilizer, a calixarene thermal stabilizer, and a thioester thermal stabilizer.
8. The retort-resistant polymer film material of claim 1, wherein the light stabilizer comprises at least one of phenyl ortho-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, resorcinol monobenzoate, 2- (2-hydroxy-5-methylphenyl) benzotriazole, and 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-phenyl) -5-chlorobenzotriazole.
9. The preparation method of the steaming-resistant polymer film material according to any one of claims 1 to 8, characterized by comprising the following steps:
heating and uniformly mixing the hollow glass fiber, the nucleating agent and the coupling agent, and drying to obtain the modified hollow glass fiber;
and adding the modified hollow glass fiber, the compatilizer, the lubricant, the heat stabilizer and the light stabilizer into the polypropylene, uniformly mixing, and then carrying out melt mixing and granulation to obtain the composite material.
10. The method for preparing the steam-resistant polymer film material according to claim 9, wherein the heating temperature is 60-80 ℃, the drying temperature is 100-120 ℃, and the temperature for melt-kneading is 200-250 ℃.
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| CN111019315A (en) * | 2019-12-24 | 2020-04-17 | 上海中镭新材料科技有限公司 | Glass fiber reinforced PC material and preparation method and application thereof |
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| CN108623901A (en) * | 2017-03-26 | 2018-10-09 | 合肥杰事杰新材料股份有限公司 | A kind of high strength glass fiber reinforced polypropylene compound material and preparation method thereof |
| CN111019315A (en) * | 2019-12-24 | 2020-04-17 | 上海中镭新材料科技有限公司 | Glass fiber reinforced PC material and preparation method and application thereof |
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