CN115960416A - Low-shrinkage, low-warpage and high-oxygen-index antibacterial polypropylene composite material and preparation method thereof - Google Patents
Low-shrinkage, low-warpage and high-oxygen-index antibacterial polypropylene composite material and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 82
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 72
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 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 claims abstract description 66
- 239000003063 flame retardant Substances 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 44
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 36
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical class [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 239000010456 wollastonite Substances 0.000 claims abstract description 28
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 239000002557 mineral fiber Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 18
- 239000010445 mica Substances 0.000 claims abstract description 14
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 18
- 229920000388 Polyphosphate Polymers 0.000 claims description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 18
- 239000001205 polyphosphate Substances 0.000 claims description 18
- 235000011176 polyphosphates Nutrition 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 claims description 16
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 16
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 16
- 239000004599 antimicrobial Substances 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007580 dry-mixing Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000945 filler Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 229920005606 polypropylene copolymer Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 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 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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Abstract
The invention discloses a low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material and a preparation method thereof, wherein the polypropylene composite material comprises 60-80% by weight of polypropylene; 5 to 20 percent of wollastonite mineral fiber; 5 to 15 percent of modified synthetic mica powder; 2 to 5 percent of phosphorus-nitrogen flame retardant; 1 to 5 percent of flame retardant synergist; 0.3 to 0.8 percent of antibacterial agent; 0.5 to 2 percent of lubricant; 0.2-0.8% of antioxidant, wherein the wollastonite mineral fiber is fibrous wollastonite with a high length-diameter ratio of 12-18: 1, the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder by using a silane coupling agent. The polypropylene composite material has the advantages of low cost, low shrinkage, difficult warping, high oxygen index, long-acting antibacterial effect and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an antibacterial polypropylene composite material with low shrinkage, low warpage and high oxygen index and a preparation method thereof.
Background
Polypropylene materials, as a crystalline thermoplastic material, are widely used in various fields due to their excellent overall properties. However, in the processes of injection molding, storage and use of polypropylene products, due to the crystallization characteristics of polypropylene, some shrinkage behaviors often occur, so that the products generate buckling deformation, and the phenomena of internal stress and unstable product size are generated locally, thereby greatly limiting the application of polypropylene in the field of products with higher requirements on dimensional accuracy and flatness. On the other hand, the polypropylene material is easy to burn because the limiting oxygen index is as low as 17-18 percent, and in order to solve the two defects, filling flame-retardant modification is often carried out in the industry.
In the current industry, when the flame retardant grade of the modified polypropylene needs to reach UL 94V 0 grade, the proportion of the added flame retardant is large, and the cost is too high, so that in many product designs with flame retardant requirements, the UL 94V2 grade is usually used for evaluation and application according to the actual use requirements of the products. At present, a V2-grade polypropylene filling modification method mainly comprises two modes of bromine-antimony synergistic filling flame-retardant modification and free radical-initiated dripping flame-retardant filling modification.
For the bromine-antimony synergistic flame-retardant filling modification, the application range is smaller and smaller due to the increasingly strict environmental protection requirement and cost problem. The free radical initiated dripping flame-retardant filling modification method is widely applied in the industry because the flame retardant is added in a small proportion, the addition amount is generally 1-3%, the flame-retardant efficiency is high, and harmful substances released in the combustion process are few. However, in the process of improving the shrinkage deformation warpage of polypropylene, the addition of the mineral filler can greatly reduce the flame retardant efficiency of a free radical initiated dripping flame retardant system, and even cause the flame retardant failure of the flame retardant system when the selection of the type of the filler is not appropriate or the addition amount of the filler reaches a certain amount.
Disclosure of Invention
In order to overcome the defects and problems in the prior art, the invention aims to provide a polypropylene composite material which has the advantages of low cost, low shrinkage, difficult warping, high oxygen index, long-acting antibacterial effect and the like.
The second purpose of the present invention is to provide a preparation method of the polypropylene composite material.
In order to achieve the purpose, the invention provides an antibacterial polypropylene composite material with low shrinkage, low warpage and high oxygen index, which comprises the following components in percentage by weight:
wherein the wollastonite mineral fiber is fibrous wollastonite with a high length-diameter ratio of 12-18: 1, the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder by using a silane coupling agent.
Compared with the prior art, the antibacterial polypropylene composite material with low shrinkage, low warpage and high oxygen index adopts the wollastonite mineral fiber with a fibrous structure with a high length-diameter ratio, greatly limits the crystallization shrinkage of the polypropylene matrix resin, simultaneously compensates the shrinkage difference of products in different directions caused by the orientation problem of the wollastonite mineral fiber by matching with the lamellar structure of the modified synthetic mica, and ensures that the composite material has the characteristics of low shrinkage and low warpage simultaneously under the synergistic effect of the wollastonite mineral fiber and the modified synthetic mica. Meanwhile, a phosphorus-nitrogen flame retardant and a flame-retardant synergist are introduced, so that the flame retardance of the composite material is improved, the flame retardant and the mineral filler in the material are subjected to dispersion lubrication by virtue of a lubricant, and the influence on the rapid dropping process of the molten PP when a high-proportion filler is added is greatly reduced, so that the high oxygen index is obtained. The polypropylene composite material has excellent flame retardant property, and has a permanent broad-spectrum antibacterial effect, so that the polypropylene composite material can be widely applied to the fields of electronic appliances, smart homes and the like.
Illustratively, the content of the polypropylene may be, but is not limited to, 60%, 65%, 70%, 75%, 80% by weight, and the polypropylene as the matrix resin may be a co-polypropylene, but is not limited thereto. Further, the melt flow rate of the polypropylene is 25 to 65g/10min under the test conditions of 230 ℃ and 2.16 kg.
By way of example, the wollastonite mineral fiber may be used in an amount, but not limited to, 5%, 10%, 15%, 20% by weight. Further, the wollastonite mineral fiber has an average particle diameter of 30 to 50 μm.
Illustratively, the modified synthetic mica powder may be used in an amount of, but not limited to, 5%, 10%, 15%, 20% by weight, preferably, the modified synthetic mica powder has an average particle size of 10 μm or less.
As an example, the amount of the phosphorus nitrogen flame retardant may be, but is not limited to, 2%, 3%, 4%, 5% by weight. In some embodiments, the phosphorus-nitrogen flame retardant is a mixture of aluminum hypophosphite, melamine hydrobromide, and paraquat, and preferably, the phosphorus-nitrogen flame retardant comprises the following components in a mass ratio of 83.
As an example, the flame retardant synergist may be used in an amount of, but not limited to, 1%, 2%, 3%, 4%, 5% by weight. In some embodiments, the flame retardant synergist is at least one of melamine polyphosphate and melamine cyanurate. More preferably, the flame-retardant synergist is melamine polyphosphate, and in the system, the flame-retardant efficiency can be improved by adding the melamine polyphosphate, so that the oxygen index of the material is improved.
Illustratively, the antimicrobial agent may be used in an amount of, but not limited to, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% by weight. The antibacterial performance of the composite material is improved by adding a proper antibacterial agent. In some embodiments, the antimicrobial agent is an inorganic antimicrobial agent, such as a nanosilver antimicrobial agent.
By way of example, the lubricant may be used in amounts of, but not limited to, 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 2% by weight. The lubricant is used for performing dispersion lubrication on the flame retardant and the mineral filler in the material, so that the influence on the rapid dropping process of the molten PP when the high-proportion filler is added is greatly reduced, and the high oxygen index is obtained. In some embodiments, the lubricant is at least one of fatty acid ester wax, calcium stearate, ethylene bis stearamide. Further, the lubricant is preferably fatty acid ester wax, and the inventor finds that in the system disclosed by the invention, the fatty acid ester wax has a very strong dispersion lubrication effect on the flame retardant and the filler in the bulk material, so that the influence on the rapid dripping process of molten PP (polypropylene) when a high-proportion filler is added is greatly reduced, and the material has a high oxygen index.
Illustratively, the antioxidant may be used in an amount of, but not limited to, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% by weight. Further, the antioxidant is selected from at least one of hydroxylamine antioxidants or phenolic antioxidants. Specifically, the hydroxylamine antioxidant may be, but is not limited to, antioxidant Revonox420; the phenolic antioxidant can be, but is not limited to, antioxidant 1010, antioxidant 168.
Correspondingly, the invention also provides a preparation method of the low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material, which comprises the following steps:
(1) Placing polypropylene, wollastonite mineral fiber, modified synthetic mica powder, phosphorus-nitrogen flame retardant, flame-retardant synergist, antibacterial agent, lubricant and antioxidant into a mixer for dry mixing to obtain a semi-finished product;
(2) And (3) putting the semi-finished product into a double-screw extruder for melting and mixing, and extruding and granulating.
Further, the temperature of each section of the extruder is as follows in sequence: the first section is 185-195 deg.c and the rest sections are 200-220 deg.c.
Detailed Description
The technical solutions in the embodiments of the present invention are 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.
Some of the raw materials in the material formulations of the examples and comparative examples are as follows:
the polypropylene is copolymerized polypropylene PPB-MN50-G provided by the Branch of the China petrochemical company Limited;
wollastonite mineral fiber: AH-0023 (Oster science and technology Co., ltd., jiangxi);
artificially synthesizing mica powder: YF1250 (new sanbao materials);
calcium carbonate powder: XL2500 (Guangdong Cheng Langbai Stone industries, inc.);
talc powder: talc 803 (jiaquan new materials, inc);
phosphorus nitrogen flame retardant: m-116 aluminum hypophosphite, M-108MHB melamine hydrobromide, DMDPB paraquat (Kyonan Meileper scientific development Co., ltd.);
flame retardant synergist: melamine polyphosphate (zhongshan Kang Nuode new materials, ltd); melamine cyanurate (Zhejiang Xursen non-halogen smoke free flame retardant Co., ltd.);
antibacterial agents: RHA-TZ (Shanghai Runshe nanometer materials science and technology Co., ltd.);
antioxidant: irganox 1010 (BASF); the trade mark is as follows; revonox420 (Shanghai uncut Act industries, ltd.).
Example 1
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
76.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
5wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation method of the polypropylene composite material comprises the following steps:
(1) Placing the PPB-MN50-G, the phosphorus-nitrogen flame retardant, the melamine polyphosphate, the modified synthetic mica powder, the wollastonite mineral fiber AH-0023, the fatty acid ester wax and the antioxidant in a mixer, and dry-mixing for 4min at the rotating speed of 800rpm to obtain a semi-finished product;
(2) Adding the semi-finished product into a double-screw extruder for melting and mixing, and extruding and granulating to obtain the polypropylene composite material, wherein the temperature of each section of the extruder is as follows in sequence: the first section is 185-195 ℃, and the rest sections are 200-220 ℃; the residence time of the whole extrusion process is 3min, and the pressure is 25MPa.
Example 2
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
71.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
10wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Example 3
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
66.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
15wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation process is the same as in example 1 and is not further described here.
Practice ofExample 4
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
61.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
20wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation process is the same as in example 1 and is not further described here.
Example 5
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
66.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
20wt% of modified synthetic mica powder;
5wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Example 6
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
66.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine cyanurate;
10wt% of modified synthetic mica powder;
15wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Example 7
A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material comprises the following components in percentage by weight:
66.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
15wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% ethylene bis stearamide;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Comparative example 1
A polypropylene composite comprising, in weight percent:
66.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
25wt% calcium carbonate XL2500;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation process is the same as in example 1 and is not further described here.
Comparative example 2
A polypropylene composite comprising, in weight percent:
66.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
25wt% talc 803;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Comparative example 3
A polypropylene composite comprising, in weight percent:
66.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
25wt% of modified synthetic mica powder;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation process is the same as in example 1 and is not further described here.
Comparative example 4
A polypropylene composite comprising, in weight percent:
66.5wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
25wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation process is the same as in example 1 and is not further described here.
Comparative example 5
A polypropylene composite comprising, in weight percent:
69.5wt% of polypropylene copolymer PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
10wt% of modified synthetic mica powder;
15wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% fatty acid ester wax;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
Comparative example 6
A polypropylene composite comprising, in weight percent:
67wt% of copolymerized polypropylene PPB-MN50-G;
4wt% of a phosphorus nitrogen flame retardant;
3wt% melamine polyphosphate;
10wt% of modified synthetic mica powder;
15wt% wollastonite mineral fiber AH-0023;
0.5wt% of an inorganic antibacterial agent RHA-TZ;
0.5wt% hydroxylamine antioxidant Revonox420;
wherein:
the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder YF1250 by using a silane coupling agent;
the phosphorus-nitrogen flame retardant comprises 83 parts by weight of aluminum hypophosphite, 8.5 parts by weight of melamine hydrobromide and 8.5 parts by weight of paraquat.
The preparation is the same as in example 1 and is not described further here.
The polypropylene composites prepared in examples 1 to 7 and comparative examples 1 to 5 were subjected to performance tests, and the results are shown in table 1 below.
Wherein: and (3) carrying out appearance observation and evaluation on the deformation condition after cooling for 48 hours by preparing 200mm/2mm square plates through injection molding under the same conditions.
TABLE 1 test results
As can be seen from the data in Table 1, the polypropylene composites prepared in examples 1 to 6 have the characteristics of low shrinkage, low deformation, high oxygen index, long-lasting antibacterial effect, and the like. The wollastonite mineral fiber with the fibrous structure and the high length-diameter ratio selected by the invention can obviously reduce the shrinkage rate of the polypropylene matrix resin, and can greatly improve the problem of warping deformation of the material by matching with the lamellar structure of the modified synthetic mica.
Comparative example 3 contains no wollastonite mineral fiber, has a high shrinkage ratio, a large deformation, and a poor flame retardance.
Comparative example 4 contains no modified synthetic mica and has a low oxygen index.
As can be seen from the comparison between example 3 and comparative example 5, the addition of melamine polyphosphate in the system can improve the flame retardant efficiency, thereby improving the oxygen index of the material.
As can be seen from a comparison of example 3 and comparative example 6, the absence of lubricant reduces the oxygen index of the material.
Compared with ethylene bis-stearamide, the fatty acid ester wax has a strong dispersion and lubrication effect on the flame retardant and the filler in the bulk material, so that the influence on the rapid dripping process of molten PP (propene polymer) is greatly reduced when a high proportion of the filler is added, and the material has a high oxygen index.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (8)
1. A low-shrinkage, low-warpage and high-oxygen index antibacterial polypropylene composite material is characterized by comprising the following components in percentage by weight:
wherein the wollastonite mineral fiber is fibrous wollastonite with a high length-diameter ratio of 12-18: 1, the modified synthetic mica powder is prepared by modifying the surface of artificially synthesized mica powder by using a silane coupling agent.
2. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite material according to claim 1, wherein said phosphorus-nitrogen flame retardant comprises aluminum hypophosphite, melamine hydrobromide, paraquat in a mass ratio of 83.5.
3. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite of claim 1, wherein the polypropylene is a co-polypropylene having a melt flow rate of 25-65 g/10min.
4. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite of claim 1, wherein the flame retardant synergist is at least one of melamine polyphosphate and melamine cyanurate.
5. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite of claim 1, said antimicrobial agent being an inorganic antimicrobial agent.
6. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite of claim 1, said lubricant being at least one of fatty acid ester wax, calcium stearate, ethylene bis stearamide.
7. The low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite of claim 1, said antioxidant being selected from at least one of a hydroxylamine based antioxidant or a phenolic antioxidant.
8. A method of making a low shrinkage, low warpage, high oxygen index antimicrobial polypropylene composite as claimed in any one of claims 1 to 7, comprising the steps of:
(1) Placing polypropylene, wollastonite mineral fiber, modified synthetic mica powder, a phosphorus-nitrogen flame retardant, a flame-retardant synergist, an antibacterial agent, a lubricant and an antioxidant into a mixer for dry mixing to obtain a semi-finished product;
(2) And (3) putting the semi-finished product into a double-screw extruder for melting and mixing, and extruding and granulating.
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