CN115895017A - Flame-retardant polypropylene foam material and preparation method thereof - Google Patents
Flame-retardant polypropylene foam material and preparation method thereof Download PDFInfo
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- CN115895017A CN115895017A CN202310012129.3A CN202310012129A CN115895017A CN 115895017 A CN115895017 A CN 115895017A CN 202310012129 A CN202310012129 A CN 202310012129A CN 115895017 A CN115895017 A CN 115895017A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 141
- -1 polypropylene Polymers 0.000 title claims abstract description 141
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 141
- 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 82
- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000006261 foam material Substances 0.000 title claims abstract description 30
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 71
- 239000004088 foaming agent Substances 0.000 claims abstract description 63
- 238000002156 mixing Methods 0.000 claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001746 injection moulding Methods 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000006260 foam Substances 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000010452 phosphate Substances 0.000 claims description 23
- 239000002250 absorbent Substances 0.000 claims description 22
- 230000002745 absorbent Effects 0.000 claims description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- 125000003003 spiro group Chemical group 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 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 12
- 238000001816 cooling Methods 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000004156 Azodicarbonamide Substances 0.000 claims description 9
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 9
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 9
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims 2
- 239000007924 injection Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000005187 foaming Methods 0.000 abstract description 2
- 239000002667 nucleating agent Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 230000032683 aging Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000605 extraction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- NEANPRQTNOPNGE-UHFFFAOYSA-N (2,4-dihydroxy-3-methylphenyl)-phenylmethanone Chemical compound CC1=C(O)C=CC(C(=O)C=2C=CC=CC=2)=C1O NEANPRQTNOPNGE-UHFFFAOYSA-N 0.000 description 1
- 241001556567 Acanthamoeba polyphaga mimivirus Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 1
- 235000021268 hot food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of polypropylene foam materials, in particular to a flame-retardant polypropylene foam material and a preparation method thereof. The scheme is that a polypropylene foam material is prepared through low-pressure injection molding waterproof preparation, and polypropylene, zinc oxide and zinc stearate are extruded and granulated to prepare an auxiliary agent master batch; extruding and granulating by utilizing polypropylene and a foaming agent to prepare foaming agent master batches; then extruding and granulating by utilizing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant to prepare foamable polypropylene master batches, and mixing the polypropylene master batches, the foaming agent master batches and the auxiliary agent master batches and then performing injection molding, or performing secondary die sinking injection molding to prepare polypropylene foam; due to the introduction of the graphene oxide and the flame retardant, the product has excellent flame retardant performance, the graphene oxide can play a role of a nucleating agent in the material, uniform foaming is facilitated, the comprehensive mechanical property of the product is also excellent, and the practicability is high.
Description
Technical Field
The invention relates to the technical field of polypropylene foam materials, in particular to a flame-retardant polypropylene foam material and a preparation method thereof.
Background
The polypropylene foam plastic is prepared by taking polypropylene resin as a main body and adding a foaming agent and other additives, has the advantages of good mechanical strength, good tensile strength, high flexibility and elastic friction coefficient, good wear resistance and the like, and is widely used for the buffer packaging of furniture, paneling, high-grade instruments and metal appliances with smooth surfaces; can also be used as heat-insulating package for hot food; it can also be made into cushion material such as liner and lining board.
At present, polypropylene foam plastics have poor flame retardance and poor ultraviolet aging resistance, and cannot meet the requirements of people in practical application, so that the application discloses a flame-retardant polypropylene foam material and a preparation method thereof to prepare the polypropylene foam material with excellent flame retardance and aging resistance.
Disclosure of Invention
The invention aims to provide a flame-retardant polypropylene foam material and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, extruding and granulating to obtain an auxiliary agent master batch;
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the flame retardant is prepared by reacting spiro phosphate diacid chloride, an ultraviolet absorbent containing double bonds and melamine;
mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches;
(2) And (3) uniformly mixing the polypropylene master batch, the foaming agent master batch and the auxiliary agent master batch, and performing injection molding to obtain a finished product.
In an optimized scheme, the preparation steps of the flame retardant are as follows:
s1: mixing 2, 4-dihydroxy benzophenone, N-hydroxymethyl acrylamide and dichloromethane, stirring uniformly at 30-35 ℃, adding a mixed solution of anhydrous aluminum trichloride and dichloromethane, reacting until the system turns to reddish brown, extracting with deionized water, and purifying to obtain an ultraviolet absorbent containing double bonds;
s2: mixing pentaerythritol and phosphorus oxychloride, heating to 80-85 ℃, reacting for 2-3 h, continuously heating to 105-110 ℃, reacting for 20-24h, cooling to room temperature, performing suction filtration washing, and performing vacuum drying to obtain spiro phosphate diacid chloride;
and (2) mixing spiro-phosphate diacid chloride and acetonitrile, stirring uniformly at 25 ℃, adding an ultraviolet absorbent containing double bonds and triethylamine, reacting for 8-10h, adding melamine and triethylamine, heating to 60-65 ℃, reacting for 10-12h, cooling to room temperature, and performing suction filtration and washing to obtain the flame retardant.
In an optimized scheme, in step S2, the molar ratio of pentaerythritol to phosphorus oxychloride is 1: (6 to 6.2); the mol ratio of the spiro phosphate diacid chloride to the double-bond-containing ultraviolet absorbent to the melamine is 1: (1 to 1.1): (1 to 1.2).
According to an optimized scheme, in the step S1, the reaction time is 70 to 75h; the molar ratio of the 2, 4-dihydroxy benzophenone to the N-hydroxymethyl acrylamide is 1: (2 to 2.4).
According to an optimized scheme, in the step (2), the injection molding temperature is 200 to 220 ℃, and the injection molding pressure is 4 to 5MPa.
According to an optimized scheme, in the step (2), the dosage of each component is as follows: 7-8 wt% of foaming agent master batch, 3-5 wt% of auxiliary agent master batch and the balance of polypropylene master batch.
In a more optimized scheme, in the step (1), the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1;
the polypropylene master batch comprises the following components in percentage by weight: 90-100 parts of polypropylene, 10-15 parts of maleic anhydride grafted polypropylene, 4-6 parts of graphene oxide and 10-15 parts of a flame retardant by mass.
According to an optimized scheme, the polypropylene foam material is prepared by the preparation method of the flame-retardant polypropylene foam material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a flame-retardant polypropylene foam material and a preparation method thereof, wherein the scheme is that the polypropylene foam material is prepared by waterproof preparation through low-pressure injection molding, and polypropylene, zinc oxide and zinc stearate are extruded and granulated to prepare an auxiliary agent master batch; extruding and granulating by utilizing polypropylene and a foaming agent to prepare foaming agent master batches; then extruding and granulating by utilizing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant to prepare foamable polypropylene master batches, and mixing the polypropylene master batches, the foaming agent master batches and the auxiliary agent master batches and then performing injection molding, or performing secondary die sinking injection molding to prepare polypropylene foam; due to the introduction of the graphene oxide and the flame retardant, the product has excellent flame retardant performance, the graphene oxide can play a role of a nucleating agent in the material, uniform foaming is facilitated, the comprehensive mechanical property of the product is also excellent, and the practicability is high.
In this scheme, since the flame retardant is applied to the polypropylene foam, in order to ensure compatibility of the flame retardant with polypropylene, the following conditions need to be satisfied when designing the flame retardant: the flame retardant structure contains double bonds capable of being graft-polymerized with polypropylene, so that the flame retardant can be grafted to a polypropylene molecular chain in the preparation process of a product, and the dispersibility of the flame retardant is improved while the compatibility of the flame retardant with polypropylene is ensured; the flame retardant has a proper N and P ratio in the structure, and the excellent flame retardance is realized by the synergistic ratio; meanwhile, when the flame retardant is designed, the requirement of ultraviolet resistance of a polypropylene material is considered, and if the flame retardance and the ultraviolet resistance can be realized by the same component, the process and the cost of the product are greatly reduced;
therefore, based on the above concept, the scheme defines the preparation process of the flame retardant by first reacting 2, 4-dihydroxybenzophenone with N-methylol acrylamide to form a double bond-containing uv absorber (3, 5-diacrylamide methyl-2, 4-dihydroxybenzophenone); and then, pentaerythritol and phosphorus oxychloride are used for reaction to generate intermediate spiro phosphate diacid chloride, and then a P-Cl bond, hydroxyl of the ultraviolet absorbent containing double bonds and amino grafting reaction in melamine are used for obtaining the flame retardant suitable for polypropylene, wherein the dosage of each component needs to be controlled in the process, and the molar ratio of the spiro phosphate diacid chloride to the ultraviolet absorbent containing double bonds to the melamine is 1: (1 to 1.1): (1 to 1.2) "to ensure the smooth preparation of the flame retardant.
Here, it should be noted that: because the 2, 4-dihydroxy benzophenone reacts with the N-hydroxymethyl acrylamide to generate the ultraviolet absorbent containing double bonds, and the ultraviolet absorbent is grafted to the spiro phosphate diacid chloride subsequently, the flame retardant is more easily grafted with a polypropylene molecular chain due to the existence of the double bonds, compared with the conventional method of adding the 2, 4-dihydroxy benzophenone into the polypropylene, the migration resistance is improved, and the ultraviolet aging resistance is also obviously improved.
The invention discloses a flame-retardant polypropylene foam material and a preparation method thereof, the process design is reasonable, the proportion of each component in the scheme is proper, the prepared product not only has excellent flame-retardant property, but also has excellent ultraviolet aging resistance, and meanwhile, due to the existence of graphene oxide, the comprehensive mechanical property of the product is improved, and the practicability is higher.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In this example, polypropylene was obtained from northern Europe chemical industry (BD 950 MO); maleic anhydride grafted polypropylene, with a grafting yield of 1.2%, available from Nippon optical New Material Co., ltd. (GPM 200 CH); graphene oxide was purchased from hexite materials science co ltd, chan zhou (SE 1231); melamine was purchased from Mimi European Chemicals Co., tianjin, china.
Example 1:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, and then extruding and granulating to obtain an auxiliary master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding, wherein the injection molding temperature is 200 ℃, the injection molding pressure is 4MPa, and the injection molding speed is 100mm/s, so that a finished product is obtained.
The preparation steps of the flame retardant are as follows:
s1: 0.1mol of 2, 4-dihydroxy benzophenone, 0.23mol of N-hydroxymethyl acrylamide and 100mL of dichloromethane are mixed, stirred uniformly at 30 ℃, added with 4g of anhydrous aluminum trichloride and 50mL of dichloromethane mixed solution and reacted for 75 hours, at this time, the system is changed into reddish brown, and the ultraviolet absorbent containing double bonds is obtained by extraction and purification with deionized water.
S2: mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 80 ℃, reacting for 3 hours, continuously heating to 105 ℃, reacting for 24 hours, cooling to room temperature, performing suction filtration, washing, and drying in vacuum to obtain the spiro phosphate diacid chloride.
0.1mol of spiro-phosphate diacid chloride is mixed with 500mL of acetonitrile, the mixture is stirred uniformly at 25 ℃, 0.11mol of ultraviolet absorbent containing double bonds and 0.1mol of triethylamine are added for reaction for 8 hours, then 0.12mol of melamine and 0.1mol of triethylamine are added, the mixture is heated to 60 ℃, the reaction is carried out for 12 hours, the mixture is cooled to room temperature, and the mixture is filtered and washed to obtain the flame retardant.
Example 2:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, extruding and granulating to obtain an auxiliary agent master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding at the injection molding temperature of 210 ℃, the injection molding pressure of 5MPa and the injection molding speed of 100mm/s to obtain a finished product.
The preparation steps of the flame retardant are as follows:
s1: 0.1mol of 2, 4-dihydroxy benzophenone, 0.23mol of N-hydroxymethyl acrylamide and 100mL of dichloromethane are mixed, stirred uniformly at 35 ℃, added with 4g of anhydrous aluminum trichloride and 50mL of dichloromethane mixed solution and reacted for 75 hours, at this time, the system is changed into reddish brown, and the ultraviolet absorbent containing double bonds is obtained by extraction and purification with deionized water.
S2: mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 82 ℃, reacting for 2.5 hours, continuously heating to 108 ℃, reacting for 22 hours, cooling to room temperature, performing suction filtration and washing, and performing vacuum drying to obtain the spiro phosphate diacid chloride.
0.1mol of spiro-phosphate diacid chloride is mixed with 500mL of acetonitrile, the mixture is stirred uniformly at 25 ℃, 0.11mol of ultraviolet absorbent containing double bonds and 0.1mol of triethylamine are added for reaction for 9 hours, then 0.12mol of melamine and 0.1mol of triethylamine are added, the mixture is heated to 64 ℃, the reaction is carried out for 11 hours, the mixture is cooled to room temperature, and the mixture is filtered and washed to obtain the flame retardant.
Example 3:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, extruding and granulating to obtain an auxiliary agent master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding, wherein the injection molding temperature is 220 ℃, the injection molding pressure is 5MPa, and the injection molding speed is 100mm/s, so that a finished product is obtained.
The preparation steps of the flame retardant are as follows:
s1: 0.1mol of 2, 4-dihydroxy benzophenone, 0.23mol of N-hydroxymethyl acrylamide and 100mL of dichloromethane are mixed, stirred uniformly at 35 ℃, added with 4g of anhydrous aluminum trichloride and 50mL of dichloromethane mixed solution and reacted for 75 hours, at this time, the system is changed into reddish brown, and the ultraviolet absorbent containing double bonds is obtained by extraction and purification with deionized water.
S2: mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 85 ℃, reacting for 2 hours, continuously heating to 110 ℃, reacting for 20 hours, cooling to room temperature, performing suction filtration, washing and vacuum drying to obtain the spiro phosphate diacid chloride.
Taking 0.1mol of spiro phosphate diacyl chloride and 500mL of acetonitrile, mixing uniformly at 25 ℃, adding 0.11mol of double bond-containing ultraviolet absorbent and 0.1mol of triethylamine, reacting for 10 hours, adding 0.12mol of melamine and 0.1mol of triethylamine, heating to 65 ℃, reacting for 10 hours, cooling to room temperature, carrying out suction filtration and washing to obtain the flame retardant.
Comparative example 1:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, and then extruding and granulating to obtain an auxiliary master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding, the injection molding temperature is 210 ℃, the injection molding pressure is 5MPa, and the injection molding speed is 100mm/s, so that a finished product is obtained.
The preparation steps of the flame retardant are as follows:
mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 82 ℃, reacting for 2.5 hours, continuously heating to 108 ℃, reacting for 22 hours, cooling to room temperature, performing suction filtration and washing, and performing vacuum drying to obtain the spiro phosphate diacid chloride.
0.1mol of spiro-phosphate diacid chloride is mixed with 500mL of acetonitrile, the mixture is stirred uniformly at 25 ℃, 0.11mol of 2, 4-dihydroxy benzophenone and 0.1mol of triethylamine are added for reaction for 9 hours, then 0.12mol of melamine and 0.1mol of triethylamine are added, the mixture is heated to 64 ℃ for reaction for 11 hours, the mixture is cooled to room temperature, and the mixture is filtered and washed to obtain the flame retardant.
Taking example 2 as a control group, in comparative example 1, no double bond is introduced into the ultraviolet absorbent, and the process is not changed in the rest steps.
Comparative example 2:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, extruding and granulating to obtain an auxiliary agent master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding at the injection molding temperature of 210 ℃, the injection molding pressure of 5MPa and the injection molding speed of 100mm/s to obtain a finished product.
The preparation steps of the flame retardant are as follows:
mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 82 ℃, reacting for 2.5 hours, continuously heating to 108 ℃, reacting for 22 hours, cooling to room temperature, performing suction filtration and washing, and performing vacuum drying to obtain the spiro phosphate diacid chloride.
0.1mol of spiro-phosphate diacyl chloride is mixed with 500mL of acetonitrile, the mixture is uniformly stirred at 25 ℃, 0.12mol of melamine and 0.1mol of triethylamine are added, the mixture is heated to 64 ℃, the reaction is carried out for 11h, the mixture is cooled to room temperature, and the mixture is filtered and washed to obtain the flame retardant.
Taking example 2 as a control group, the ultraviolet absorbent containing double bonds is not introduced into the comparative example 2, and the process of the rest steps is not changed.
Comparative example 3:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, extruding and granulating to obtain an auxiliary agent master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding, the injection molding temperature is 210 ℃, the injection molding pressure is 5MPa, and the injection molding speed is 100mm/s, so that a finished product is obtained.
The preparation steps of the flame retardant are as follows:
s1: 0.1mol of 2, 4-dihydroxy benzophenone, 0.23mol of N-hydroxymethyl acrylamide and 100mL of dichloromethane are mixed, stirred uniformly at 35 ℃, added with 4g of anhydrous aluminum trichloride and 50mL of dichloromethane mixed solution and reacted for 75 hours, at this time, the system is changed into reddish brown, and the ultraviolet absorbent containing double bonds is obtained by extraction and purification with deionized water.
S2: mixing 0.2mol of pentaerythritol and 1.22mol of phosphorus oxychloride, heating to 82 ℃, reacting for 2.5 hours, continuously heating to 108 ℃, reacting for 22 hours, cooling to room temperature, performing suction filtration and washing, and performing vacuum drying to obtain the spiro phosphate diacid chloride.
0.1mol of spiro-phosphate diacid chloride is mixed with 500mL of acetonitrile, the mixture is stirred uniformly at 25 ℃, 0.11mol of ultraviolet absorbent containing double bonds and 0.1mol of triethylamine are added, the mixture reacts for 9 hours, the reaction product is cooled to room temperature, and the mixture is filtered and washed to obtain the flame retardant.
With example 2 as a control, no melamine was introduced in comparative example 3, and the remaining steps were unchanged.
Comparative example 4:
a preparation method of a flame-retardant polypropylene foam material comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, and then extruding and granulating to obtain an auxiliary master batch; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary master batch is 8:1:1.
uniformly mixing polypropylene, maleic anhydride grafted polypropylene and graphene oxide, and then extruding and granulating to obtain polypropylene master batches; the polypropylene master batch comprises the following components in percentage by weight: by mass, 90 parts of polypropylene, 10 parts of maleic anhydride grafted polypropylene, 5 parts of graphene oxide and 14 parts of a flame retardant.
Mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches; the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5.
(2) 8.7kg of polypropylene master batch, 0.8kg of foaming agent master batch and 0.5kg of auxiliary agent master batch are uniformly mixed and subjected to injection molding, the injection molding temperature is 210 ℃, the injection molding pressure is 5MPa, and the injection molding speed is 100mm/s, so that a finished product is obtained.
Taking example 2 as a control group, no flame retardant is introduced into comparative example 4, and the process of the rest steps is unchanged.
Detection experiment:
the polypropylene samples prepared in examples 1 to 3 and comparative examples 1 to 4 were tested for tensile strength according to the method disclosed in GB/T6344-2008, the tensile speed was 50mm/min, and the test sample was type 1. The notch impact strength is tested according to GB/T1843-2008, the size of the sample is 80mm multiplied by 10mm multiplied by 4mm, and the notch depth is 1/5 of the thickness of the sample; the limiting oxygen index was measured according to the method disclosed in GB/T2406-1993, with sample sizes of 120mm by 12.7mm by 3.2mm.
And (4) carrying out ultraviolet aging test according to the method disclosed by GB/T16422-2014, wherein the test time is 200h, retesting the notch impact strength of the sample after ultraviolet aging, and calculating the retention rate of the impact strength.
And (4) conclusion: the preparation method is reasonable in process design, the components are properly mixed, the prepared product has excellent flame retardant property and excellent ultraviolet aging resistance, and meanwhile, due to the existence of the graphene oxide, the comprehensive mechanical property of the product is improved, and the practicability is higher.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a flame-retardant polypropylene foam material is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking polypropylene, zinc oxide and zinc stearate, uniformly mixing, and then extruding and granulating to obtain an auxiliary master batch;
uniformly mixing polypropylene, maleic anhydride grafted polypropylene, graphene oxide and a flame retardant, and then extruding and granulating to obtain polypropylene master batches; the flame retardant is prepared by reacting spiro phosphate diacid chloride, an ultraviolet absorbent containing double bonds and melamine;
mixing polypropylene and a foaming agent, and extruding and granulating to obtain foaming agent master batches;
(2) And (3) uniformly mixing the polypropylene master batch, the foaming agent master batch and the auxiliary agent master batch, and performing injection molding to obtain a finished product.
2. The method for preparing a flame retardant polypropylene foam material according to claim 1, wherein: the preparation steps of the flame retardant are as follows:
s1: mixing 2, 4-dihydroxybenzophenone, N-hydroxymethyl acrylamide and dichloromethane, uniformly stirring at 30-35 ℃, adding a mixed solution of anhydrous aluminum trichloride and dichloromethane, reacting until the system turns to reddish brown, extracting with deionized water, and purifying to obtain an ultraviolet absorbent containing double bonds;
s2: mixing pentaerythritol and phosphorus oxychloride, heating to 80-85 ℃, reacting for 2-3 h, continuously heating to 105-110 ℃, reacting for 20-24h, cooling to room temperature, performing suction filtration washing, and performing vacuum drying to obtain spiro phosphate diacid chloride;
and (2) mixing spiro phosphate diacid chloride and acetonitrile, stirring uniformly at 25 ℃, adding an ultraviolet absorbent containing double bonds and triethylamine, reacting for 8 to 10h, adding melamine and triethylamine, heating to 60 to 65 ℃, reacting for 10 to 12h, cooling to room temperature, carrying out suction filtration and washing, and thus obtaining the flame retardant.
3. The method for preparing a flame retardant polypropylene foam material according to claim 2, wherein the method comprises the following steps: in the step S2, the molar ratio of pentaerythritol to phosphorus oxychloride is 1: (6 to 6.2); the mol ratio of the spiro phosphate diacid chloride to the double-bond-containing ultraviolet absorbent to the melamine is 1: (1 to 1.1): (1 to 1.2).
4. The method for preparing a flame retardant polypropylene foam material according to claim 2, wherein the method comprises the following steps: in the step S1, the reaction time is 70 to 75h; the molar ratio of the 2, 4-dihydroxybenzophenone to the N-methylol acrylamide is 1: (2 to 2.4).
5. The method for preparing a flame retardant polypropylene foam material according to claim 1, wherein the method comprises the following steps: in the step (2), the injection temperature is 200 to 220 ℃, and the injection pressure is 4 to 5MPa.
6. The method for preparing a flame retardant polypropylene foam material according to claim 1, wherein the method comprises the following steps: in the step (2), the dosage of each component is as follows: 7-8 wt% of foaming agent master batch, 3-5 wt% of auxiliary agent master batch and the balance of polypropylene master batch.
7. The method for preparing a flame retardant polypropylene foam material according to claim 1, wherein the method comprises the following steps: in the step (1), the foaming agent is azodicarbonamide; the mass ratio of polypropylene to the foaming agent in the foaming agent master batch is 8.5:1.5; the mass ratio of polypropylene, zinc oxide and zinc stearate in the auxiliary agent master batch is 8:1:1;
the polypropylene master batch comprises the following components in percentage by weight: 90-100 parts of polypropylene, 10-15 parts of maleic anhydride grafted polypropylene, 4-6 parts of graphene oxide and 10-15 parts of a flame retardant by mass.
8. The polypropylene foam prepared by the method for preparing the flame-retardant polypropylene foam according to any one of claims 1 to 7.
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