CN113773579A - Precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material and a preparation method thereof, wherein the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material is prepared by melting and blending the following raw materials in parts by weight: 65.4-82.2 parts of polypropylene, 16-25 parts of polyphosphazene coated ammonium polyphosphate, 1-5 parts of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate, 0.1-0.8 part of antioxidant, 0.2-0.8 part of lubricant and 0.5-3 parts of coupling agent. The polypropylene composite material has the advantages of good flame retardant property, precipitation resistance, low odor and excellent antibacterial property, and can be widely applied to the fields of household appliances, automobiles and the like.
Description
Technical Field
The invention relates to a modified polypropylene material and a preparation method thereof, in particular to a precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is one of five general-purpose plastics, because it has excellent mechanical properties, good heat resistance, high chemical stability, excellent electrical insulation and good processability, and is widely used in the fields of household appliances, automobiles, building materials and the like, but because polypropylene has a low oxygen index and is extremely easy to burn, the application of polypropylene is greatly limited, and therefore, if the application range of polypropylene is to be expanded, the polypropylene must be subjected to flame retardant modification.
Among low-smoke halogen-free phosphorus flame retardants, ammonium polyphosphate is the most widely used, and has excellent flame retardant effect due to high phosphorus and nitrogen contents, synergistic flame retardant effect of phosphorus and nitrogen, but also has the disadvantages of high hygroscopicity, easy hydrolysis and large smell, and the toughness of the composite material is greatly reduced due to poor compatibility with matrix resin after the ammonium polyphosphate is added. In some studies, these problems are solved by coating type ii APP, for example, patent No. cn201310742828.x discloses a preparation method of melamine resin coated ammonium polyphosphate with excellent water resistance, and good water resistance is achieved by coating ammonium polyphosphate with ammonium resin, but the ammonium resin used in the preparation method has a strong odor, and the odor of the composite material is increased when the ammonium resin is added into a polymer. For example, patent CN202110177957.3 discloses a halloysite nanotube modified ammonium polyphosphate based flame retardant, a preparation method and an application thereof, wherein a coating layer is halloysite, the improvement of flame retardant performance is limited, the problem of non-uniform dispersion exists, and the appearance of a final product has some defects.
In recent years, with the increasing demand of people for flame-retardant composite materials which are healthy, environment-friendly, green and pollution-free and have excellent performance, biomacromolecules containing phosphorus and nitrogen, such as casein, whey protein, hydrophobic protein, deoxyribonucleic acid, ribonucleic acid and the like, are adopted as flame-retardant synergists, and become a hot point of flame-retardant research. At present, there are related reports, for example, patent CN111454544A discloses a natural protein synergistic flame retardant composite material and a preparation method thereof, which prepares flame retardant PP by compounding natural protein as a synergist with polymer resin and ammonium polyphosphate, but the flame retardant effect is still poor, and ammonium polyphosphate and casein are easy to precipitate, and cannot meet increasingly strict safety requirements. For example, patent CN104151689A discloses a method for preparing a casein-containing halogen-free environment-friendly flame retardant polymer, wherein casein and ammonium polyphosphate are directly compounded to achieve a certain flame retardant effect, but some disadvantages are also brought by the introduction of casein, such as sensitivity to water, film formation, water resistance, poor dry and wet rub resistance, and the like, and the flame retardant property after modification is only V-2, so that adverse effects caused by mechanical properties and the like are not examined, important parameters such as odor, precipitation resistance and the like are not reported, and the method has little guiding significance for downstream practical application.
It can be seen that some flame retardant PP modification methods reported at present mostly adopt a traditional intumescent flame retardant, although a flame retardant effect can be achieved to a certain degree, the flame retardant has the defects of low efficiency, environmental pollution and the like, and the modification methods have the defects that modifiers such as ammonium polyphosphate are easy to be separated out from a modified composite material, the odor is large, and the comprehensive performance of the material is influenced. With the enhancement of awareness of safety and environmental protection, how to realize the flame retardant property and protect the environment becomes a problem which needs to be solved urgently in the current research.
Disclosure of Invention
In order to overcome the defects of the existing flame-retardant polypropylene, the invention provides a precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material and a preparation method thereof. The composite material prepared by the invention has excellent comprehensive performance and wide application prospect in the industries of household appliances, electronic appliances and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material which is prepared by melting and blending the following raw materials in parts by weight:
the polyphosphazene-coated ammonium polyphosphate disclosed by the invention is characterized in that the mass ratio of ammonium polyphosphate to polyphosphazene is 1: 1-5, preferably 1: 1.2-3.5;
the invention relates to casein grafted tetrakis (hydroxymethyl) phosphonium sulfate, wherein the mass ratio of casein to tetrakis (hydroxymethyl) phosphonium sulfate is (1): 1-5, preferably 1: 1.5-3.
The polypropylene is any one or the combination of at least two of homo-polypropylene or co-polypropylene; preferably, the copolymerized polypropylene is a copolymer of propylene and ethylene;
preferably, the polypropylene has a density of 0.89-0.91g/cm3；
Preferably, the polypropylene has a melt index range of 3-100g/10min, more preferably 3-30g/10 min;
more preferably, said homopolypropylene is selected from Shijiazhuang refined T30S, Zhonghai Shell HP 500N; the copolymerized polypropylene is selected from Yanshan petrochemical K8303 and Zhongshatianjin petrochemical EP548 RQ.
The antioxidant is a compound system of hindered phenol antioxidant and phosphite antioxidant;
preferably, the hindered phenolic antioxidant is selected from any one or a combination of at least two of 1010, 1076, 1330 and 3114, and the phosphite antioxidant is selected from 168 and/or 626; more preferably a complex system of the phosphite antioxidant 168 and the hindered phenol antioxidant 1010 with the mass ratio of 1: 1-3.
The lubricant is any one or combination of at least two of magnesium stearate, zinc stearate and calcium stearate, and is preferably magnesium stearate.
The silane coupling agent is any one or a combination of at least two of KH550 silane coupling agent, KH560 silane coupling agent and KH570 silane coupling agent, and preferably KH 550.
The invention also provides a preparation method of the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material, which comprises the following steps: the method comprises the following steps:
1) preparing polyphosphazene coated ammonium polyphosphate;
2) preparing casein grafted tetrakis (hydroxymethyl) phosphonium sulfate;
3) uniformly mixing polypropylene, polyphosphazene-coated ammonium polyphosphate, casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate, an antioxidant, a lubricant and a silane coupling agent, then melting, extruding and granulating to obtain the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material.
The preparation method comprises the following steps of, in step 1), preparing polyphosphazene coated ammonium polyphosphate:
mixing hexachlorocyclotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone with an organic solvent, adding the mixture into an ammonium polyphosphate-absolute ethyl alcohol suspension, adding a catalyst, and reacting to obtain polyphosphazene-coated ammonium polyphosphate.
Preferably, the ammonium polyphosphate is crystal II type ammonium polyphosphate with high polymerization degree, the polymerization degree is more than or equal to 1000, and preferably 1000-5000;
preferably, in the ammonium polyphosphate-absolute ethyl alcohol suspension solution, the mass ratio of ammonium polyphosphate to absolute ethyl alcohol is 1: 2-3;
more preferably, the ammonium polyphosphate-absolute ethyl alcohol suspension is stirred and heated to 70-80 ℃ before addition.
Preferably, the mass ratio of the ammonium polyphosphate to the hexachlorocyclotriphosphazene to the 4, 4' -dihydroxydiphenylsulfone is 1: (1-3.6): (1.5-6), preferably 1: (1.2-3): (2-5).
Preferably, the organic solvent is any one or a combination of at least two of acetone, ethanol, acetonitrile, toluene and tetrahydrofuran, and more preferably ethanol;
more preferably, the mass ratio of the organic solvent to the hexachlorocyclotriphosphazene is (1.5-2.0): 1
Preferably, the catalyst is triethylamine and/or pyridine;
more preferably, the mass ratio of the catalyst to the hexachlorocyclotriphosphazene is (0.02-0.05): 1.
preferably, the hexachlorocyclotriphosphazene and the 4, 4' -dihydroxydiphenylsulfone are mixed with the organic solvent and then added into the ammonium polyphosphate suspension in a continuous feeding mode, wherein the feeding time is 0.5-2.5h, and a dropwise feeding mode is more preferably adopted.
Preferably, the reaction is carried out at a temperature of 40-80 ℃, preferably 40-60 ℃; the time is 10-24h, preferably 12-18 h.
Preferably, after the reaction is finished, the post-treatment processes of centrifugation, washing, drying and the like are all conventional operations in the field, and the invention has no special requirement.
The preparation method comprises the following steps of, in step 2), preparing casein grafted tetrakis (hydroxymethyl) phosphonium sulfate:
adjusting pH value of casein to 9-12 with triethylamine, stirring and heating to 70-80 deg.C to form a solution of casein-triethylamine, adding tetrakis (hydroxymethyl) phosphonium sulfate, reacting at 70-80 deg.C for 8-12h, cooling to 40-60 deg.C, adjusting pH value of the reaction solution to 7-8 with dilute acid to obtain casein grafted tetrakis (hydroxymethyl) phosphonium sulfate.
Preferably, the mass ratio of the casein to the tetrakis (hydroxymethyl) phosphonium sulfate is 1: 1-5, preferably 1: 1.5-3.
Preferably, the dilute acid is dilute nitric acid with a concentration of 30-60 wt%.
Preferably, after the reaction is finished, the post-treatment processes such as filtration, washing, drying and the like are all conventional operations in the field, and the invention has no special requirement.
In the preparation method, step 3), the melting, extruding and granulating are conventional operations in the field, and preferably a parallel twin-screw extruder is adopted;
more preferably, the barrel temperature of the extruder is 120-; the screw rotation speed is 200-500r/min, preferably 300-450 r/min.
Aiming at the defects of the existing halogen-free flame retardant ammonium polyphosphate, the polyphosphazene is firstly adopted to coat and modify the ammonium polyphosphate, so that the problems of easy water absorption and strong smell are effectively solved, and meanwhile, the biomacromolecule casein is introduced and is grafted and modified with tetrakis hydroxymethyl phosphonium sulfate, so that the flame retardant property and the precipitation resistance of the ammonium polyphosphate are further improved. The polyphosphazene-coated ammonium polyphosphate and the casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate act synergistically, so that the flame retardant property is greatly improved, the precipitation resistance and hydrolysis resistance of the product are effectively improved, the problem of large odor is solved, the antibacterial property is excellent, and 99% of antibacterial rate can be realized.
The product prepared by the invention has excellent comprehensive performance, is nontoxic and environment-friendly, accords with the development trend of the current materials, and can be widely applied to the fields of household appliances, electronic appliances and the like.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) according to the invention, polyphosphazene is adopted to coat ammonium polyphosphate, wherein the polyphosphazene contains abundant phosphorus and nitrogen elements, and the modified flame retardant additive with excellent flame retardant property and high thermal stability can be obtained by compounding the polyphosphazene with the ammonium polyphosphate, so that the water resistance and precipitation resistance can be remarkably improved by coating the polyphosphazene on the surface of the ammonium polyphosphate, and the problems of easy water absorption and large smell of the ammonium polyphosphate are effectively solved.
2) The invention adopts casein grafted tetrakis (hydroxymethyl) phosphonium sulfate as a synergist, wherein the casein is a nitrogen-containing natural protein and has the characteristics of no toxicity, environmental protection and reproducibility, and meanwhile, the casein contains a large amount of phosphate groups, which is beneficial to dehydration and carbonization of polymers to form a carbon layer, and the flame retardant property can be greatly improved by compounding with modified ammonium polyphosphate.
3) Tetrakis-hydroxymethyl phosphonium sulfate has reactive methylol groups in its chemical structure, and thus can react with many amines, phenols, etc. to form high polymers. Active groups such as amino, carboxyl and the like exist in a casein peptide chain, and can be grafted on tetrakis hydroxymethyl phosphonium sulfate through the reaction with hydroxyl in the tetrakis hydroxymethyl phosphonium sulfate, so that the precipitation and water resistance of casein can be effectively improved. In addition, the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate also contains active groups, which are more easily combined with substances containing anions in microbial cell walls, and enter cells through the microbial cell walls, so that the genetic factor transformation process is blocked, and the microorganisms cannot be propagated, thereby achieving the antibacterial effect.
Detailed Description
In order to clearly understand the technical content of the present invention, the technical solutions of the present invention are further described by examples, but the scope of the present invention is not limited to the described scope of the examples.
The information on the raw materials used in the first, examples and comparative examples is as follows:
1. homo-polypropylene T30 s: refining Shizhuang, melt means MFR of 3g/10min (230 ℃/2.16kg, ISO1133), density of 0.91g/cm3；
2. Homo-polypropylene HP 500N: mediterranean Shell melt means a MFR of 15g/10min (230 ℃/2.16kg, ISO1133) and a density of 0.91g/cm3；
3. Copolymerized polypropylene K8303: the melt index MFR of the product is 3g/10min (230 ℃/2.16kg, ISO1133), and the density is 0.89g/cm3；
4. Copolypropylene EP548 RQ: the medium sand Tianjin petrochemical melt means that MFR is 18g/10min (230 ℃/2.16kg, ISO1133), and the density is 0.89g/cm3；
5. Casein (casein): beijing Oobo Star Biotechnology Ltd;
6. hexachlorocyclotriphosphazene (SPB-100): tsukamur chemical japan, melting point 112-;
7. 4, 4-dihydroxydiphenyl sulfone: purity 99%, Shanghai Jiachen chemical Co., Ltd;
8. ammonium polyphosphate (form II): degree of polymerization 1000, Yunnan Tianyao chemical Co., Ltd;
9. tetrakis Hydroxymethyl Phosphonium Sulfate (THPS): shanghai Michelin Biochemical technology, Inc.;
10. antioxidant 1010/168: basf (china) ltd;
11. magnesium stearate: li Yang chemical Co., Ltd;
12. silane coupling agent KH 550: nanjing Quanxi chemical Co., Ltd;
the rest are common commercial raw materials unless otherwise specified.
Second, the performance test method of the product of the example and the comparative example is as follows:
1. tensile strength: testing according to method ISO-527 standard;
2. bending strength: testing according to ISO-178 standard;
3. flame retardance: testing according to UL-94 standard, wherein the flame retardant rating is generally defined according to the thickness of the material, and the thickness of 1.6mm is mainly used as the test standard in the invention;
4. precipitation resistance: according to the test of UL746C standard, boiling in hot water of 70 ℃ for 168 hours, testing the flame retardant property;
5. odor grade: testing according to the popular PV3900 standard;
6. antibacterial property: testing according to GB/T31402.
The technical effects of the present invention are illustrated by the following examples and comparative examples:
example 1
1) Preparing polyphosphazene coated ammonium polyphosphate:
taking 50g of ammonium polyphosphate, adding 100g of absolute ethyl alcohol, stirring and heating to 70 ℃ to form ammonium polyphosphate absolute ethyl alcohol suspension; 60g of hexachlorocyclotriphosphazene and 100g of 4, 4' -dihydroxy diphenyl sulfone are mixed with 90g of acetone, then the mixture is dropwise added into an ammonium polyphosphate suspension for 0.5h, 1.2g of triethylamine catalyst is added, and the mixture reacts for 12h at 40 ℃; and centrifuging, washing and drying after the reaction is finished to obtain polyphosphazene-coated ammonium polyphosphate.
2) Preparation of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate:
taking 50g of casein, adjusting the pH value to 9 by using triethylamine, stirring and heating to 70 ℃ to form a solution; and then adding 75g of tetrakis (hydroxymethyl) phosphonium sulfate, reacting at 70 ℃ for 8h, cooling to 40 ℃, adjusting the pH value of the reaction solution to 7 by using 30 wt% dilute nitric acid, filtering, washing and drying to obtain the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate.
3) 78.5g T30s g, 18g polyphosphazene coated ammonium polyphosphate, 2g casein grafted tetramethylolphosphate sulfate, 0.1g antioxidant 1010, 0.1g antioxidant 168, 0.3g magnesium stearate and 1g silane coupling agent KH550 are added into a high-speed mixer together to be mixed for 3min, then the mixture is added into a parallel double-screw extruder to be melted, and then the mixture is extruded and granulated, wherein the temperatures of a first barrel and an eleventh barrel of the extruder are 130 ℃, 170 ℃, 175 ℃, 175 ℃, 180 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 180 ℃ and a screw head are 300r/min, so that the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material is prepared, and the performance test results are shown in Table 1.
Example 2
1) Preparing polyphosphazene coated ammonium polyphosphate:
taking 30g of ammonium polyphosphate, adding 90g of absolute ethyl alcohol, stirring and heating to 80 ℃ to form ammonium polyphosphate-absolute ethyl alcohol suspension; mixing 90g of hexachlorocyclotriphosphazene and 150g of 4, 4' -dihydroxydiphenylsulfone with 180g of acetone, then dropwise adding the mixture into ammonium polyphosphate for 2.5 hours, then adding 4.5g of triethylammonium catalyst, and reacting for 18 hours at 60 ℃; and centrifuging, washing and drying after the reaction is finished to obtain polyphosphazene coated ammonium polyphosphate.
2) Preparation of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate:
taking 60g of casein, adjusting the pH value to 12 by using triethylamine, stirring and heating to 80 ℃ to form a solution; then adding 180g of tetrakis (hydroxymethyl) phosphonium sulfate, reacting at 80 ℃ for 12h, cooling to 60 ℃, adjusting the pH value of the reaction solution to 8 by using 60 wt% dilute nitric acid, filtering, washing and drying to obtain the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate.
3) 72.8g of HP500N, 22g of polyphosphazene coated ammonium polyphosphate, 3g of casein grafted tetramethylolphosphate sulfate, 0.1g of antioxidant 1010, 0.2g of antioxidant 168, 0.4g of magnesium stearate and 1.5g of silane coupling agent KH550 are added into a high-speed mixer together to be mixed for 5min, then the mixture is added into a parallel double-screw extruder to be melted, and then the mixture is extruded and granulated, wherein the temperatures of a first barrel and an eleventh barrel of the extruder are respectively 130 ℃, 170 ℃, 175 ℃, 175 ℃, 180 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 180 ℃, and the head temperature is 180 ℃, and the screw rotating speed is 500r/min, so that the low-odor anti-microbial flame-retardant polypropylene composite material resistant to precipitation is prepared, and the performance test results are shown in Table 1.
Example 3
1) Preparing polyphosphazene coated ammonium polyphosphate:
adding 120g of absolute ethanol solution into 40g of ammonium polyphosphate, stirring and heating to 80 ℃ to form ammonium polyphosphate-absolute ethanol suspension; mixing 80g of hexachlorocyclotriphosphazene and 100g of 4, 4' -dihydroxydiphenylsulfone with 144g of acetone, dropwise adding the mixture into an ammonium polyphosphate suspension for 1 hour, then adding 2.4g of triethylammonium catalyst, and reacting for 12 hours at 50 ℃; and centrifuging, washing and drying after the reaction is finished to obtain polyphosphazene coated ammonium polyphosphate.
2) Preparation of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate:
taking 70g of casein, adjusting the pH value to 10 by using triethylamine, stirring and heating to 75 ℃ to form a solution; and then adding 140g of tetrakis (hydroxymethyl) phosphonium sulfate, reacting at 75 ℃ for 10h, cooling to 50 ℃, adjusting the pH value of the reaction solution to 7 by using 45 wt% dilute nitric acid, filtering, washing and drying to obtain the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate.
3) 71.3g of EP548RQ, 23g of polyphosphazene coated ammonium polyphosphate, 3.5g of casein grafted tetramethylolphosphate sulfate, 0.1g of antioxidant 1010, 0.3g of antioxidant 168, 0.3g of magnesium stearate and 1.5g of silane coupling agent KH550 are added into a high-speed mixer together to be mixed for 5min, then the mixture is added into a parallel double-screw extruder to be melted, and then the mixture is extruded and granulated, wherein the temperatures of a first section of the extruder barrel to an eleventh section of the extruder are respectively 130 ℃, 170 ℃, 175 ℃, 175 ℃, 180 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 180 ℃, 180 ℃ and the screw rotation speed is 500r/min, so that the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material is prepared, and the performance test results are shown in Table 1.
Example 4
1) Preparing polyphosphazene coated ammonium polyphosphate:
taking 60g of ammonium polyphosphate, adding 120g of absolute ethyl alcohol, stirring and heating to 75 ℃ to form ammonium polyphosphate-absolute ethyl alcohol suspension; 150g of hexachlorocyclotriphosphazene and 240g of 4, 4' -dihydroxydiphenylsulfone are mixed with 300g of acetone, then the mixture is dropwise added into an ammonium polyphosphate suspension for 2.0 hours, then 6g of triethylammonium catalyst is added, and the mixture reacts for 18 hours at 70 ℃; and centrifuging, washing and drying after the reaction is finished to obtain polyphosphazene-coated ammonium polyphosphate.
2) Preparation of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate:
taking 70g of casein, adjusting the pH value to 11 by using triethylamine, stirring and heating to 75 ℃ to form a solution; then 175g of tetrakis (hydroxymethyl) phosphonium sulfate is added into the mixture, the mixture is reacted for 10 hours at 75 ℃, then the temperature is reduced to 55 ℃, dilute nitric acid with the concentration of 50 wt% is used for adjusting the pH value of the reaction solution to 8, and the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate is obtained after filtration, washing and drying.
3) 67g K8303 g polyphosphazene-coated ammonium polyphosphate, 25g casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate, 0.2g antioxidant 1010, 0.2g antioxidant 168, 0.6g magnesium stearate and 2.0g silane coupling agent KH550 are added into a high-speed mixer together and mixed for 5min, then added into a parallel double-screw extruder to be melted, and then extruded and granulated, wherein the temperatures of a first barrel and an eleventh barrel of the extruder are 130 ℃, 170 ℃, 175 ℃, 175 ℃, 180 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 180 ℃ and a screw head are 500r/min, so that the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material is prepared, and the performance test results are shown in Table 1.
Comparative example 1
Referring to example 2, step 3), the process is different only in that: 22g of polyphosphazene coated ammonium polyphosphate is replaced by 22g of ammonium polyphosphate, 3g of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate is replaced by 3g of casein, other operation steps and conditions are the same as those in the step 3) of the example 2, and the flame-retardant polypropylene composite material is prepared, wherein performance test results are shown in table 1.
Comparative example 2
Referring to example 2, step 3), the process is different only in that: 22g of polyphosphazene coated ammonium polyphosphate is replaced by 22g of ammonium polyphosphate, other operation steps and conditions are the same as those in the step 3) of the embodiment 2, so that the flame-retardant polypropylene composite material is prepared, and the performance test results are shown in table 1.
Comparative example 3
Referring to example 2, step 3), the process is different only in that: 3g of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate is replaced by 3g of casein, other operation steps and conditions are the same as those in the step 3) of the example 2, so that the flame-retardant polypropylene composite material is prepared, and the performance test results are shown in the table 1.
Comparative example 4
Referring to example 2, step 3), the process is different only in that: 22g of polyphosphazene-coated ammonium polyphosphate is replaced by 11g of ammonium polyphosphate, 11g of polyphosphazene is added, other operation steps and conditions are the same as those in the step 3) of the embodiment 2, the flame-retardant polypropylene composite material is prepared, and performance test results are shown in table 1.
Comparative example 5
Referring to example 2, step 3), the process is different only in that: 22g of polyphosphazene coated ammonium polyphosphate is replaced by 11g of polyphosphazene and 11g of ammonium polyphosphate, 3g of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate is replaced by 1.2g of casein and 1.8g of tetrakis (hydroxymethyl) phosphonium sulfate, other operation steps and conditions are the same as those in the step 3) of the example 2, and the flame-retardant polypropylene composite material is prepared, wherein performance test results are shown in the table 1.
Table 1 results of performance test of examples and comparative examples
As can be seen from the data of examples 1-4 in Table 1, the invention realizes very excellent technical effects by adding polyphosphazene to coat ammonium polyphosphate and casein grafted tetrakis (hydroxymethyl) phosphonium sulfate, wherein example 2 realizes high flame retardance, low odor and 99% strong antibacterial effect on the basis of ensuring excellent mechanical properties, and the following comparative examples are designed to further embody the technical effects of the invention.
In a comparative example 1, polyphosphazene-coated ammonium polyphosphate and casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate in example 2 are replaced by unmodified ammonium polyphosphate and casein, the flame retardance can only reach V-2, the flame retardance is only NR after water boiling, the flame retardance is directly changed into a non-grade state, the odor is large, the antibacterial rate is low, and the actual requirements cannot be met.
In comparative example 2, the polyphosphazene-coated ammonium polyphosphate of example 2 was replaced with a common ammonium polyphosphate, and the rest remained the same. Compared with the embodiment 2, the conventional flame retardant performance and the flame retardant performance after water boiling are both reduced to a certain extent, a sample placed at normal temperature for 48 hours has the flame retardant performance of only 1.6mm V < -1 >, is directly reduced to V < -2 > after water boiling, has the odor grade greatly increased from 3 grades to 4.5 grades, and the result can show that the common ammonium polyphosphate has serious water absorption, poor precipitation resistance and strong odor, and has no influence on bacteria resistance and ammonium polyphosphate.
In comparative example 3, the casein grafted tetrakis (hydroxymethyl) phosphonium sulfate of example 2 was replaced with casein, and the rest remained unchanged. Compared with example 2, the antibacterial effect is greatly reduced, the antibacterial rate is reduced from 99% to 0%, and the result shows that the common casein has no antibacterial effect, in the aspect of flame retardant performance, the flame retardant performance can reach 1.6mm V-0 after being placed for 48 hours at normal temperature, but the flame retardant performance is reduced to V-1 to a certain extent after being boiled in water at 70 ℃ for 168 hours, which is mainly caused by water absorption of the casein, and in addition, aiming at odor, the result shows that the odor is slightly increased compared with example 2, and the result also shows that the modified casein is helpful for reducing the odor.
In comparative example 4, the polyphosphazene coated ammonium polyphosphate of example 2 was replaced with the common ammonium polyphosphate and polyphosphazene, and the balance was kept the same, and we found that 1.6mm V-1 could be achieved with the addition of polyphosphazene for conventional flame retardant performance, but the problem of flame retardant failure after poaching was present. In comparative example 5, compared with example 2, the polyphosphazene-coated ammonium polyphosphate is replaced by the common ammonium polyphosphate and polyphosphazene, and the casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate is replaced by the common casein and tetrakis (hydroxymethyl) phosphonium sulfate, so that the problems of poor flame retardant property, large odor and reduced antibacterial rate exist, and the actual requirements of downstream customers cannot be met.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material is characterized in that,
the material is prepared by melting and blending the following raw materials in parts by weight:
65.4-82.2 parts of polypropylene, preferably 67-78.5 parts;
16-25 parts of polyphosphazene-coated ammonium polyphosphate, preferably 18-25 parts;
1-5 parts of casein grafted tetrakis (hydroxymethyl) phosphonium sulfate, preferably 2-5 parts;
0.1-0.8 part of antioxidant, preferably 0.2-0.4 part;
0.2-0.8 part of lubricant, preferably 0.3-0.6 part;
0.5-3 parts of coupling agent, preferably 1-2 parts.
2. The polypropylene composite material according to claim 1, wherein the polyphosphazene coats ammonium polyphosphate, wherein the mass ratio of the ammonium polyphosphate to the polyphosphazene is 1: 1-5, preferably 1: 1.2-3.5;
the casein is grafted with tetrakis (hydroxymethyl) phosphonium sulfate, wherein the mass ratio of the casein to the tetrakis (hydroxymethyl) phosphonium sulfate is (1): 1-5, preferably 1: 1.5-3.
3. The polypropylene composite according to claim 1 or 2, wherein the polypropylene is any one of homo-polypropylene or co-polypropylene or a combination of at least two of homo-polypropylene and co-polypropylene; preferably, the copolymerized polypropylene is a copolymer of propylene and ethylene;
preferably, the polypropylene has a density of 0.89-0.91g/cm3；
Preferably, the polypropylene has a melt index range of 3-100g/10min, more preferably 3-30g/10 min;
more preferably, said homopolypropylene is selected from Shijiazhuang refined T30S, Zhonghai Shell HP 500N; the copolymerized polypropylene is selected from Yanshan petrochemical K8303 and Zhongshatianjin petrochemical EP548 RQ.
4. The polypropylene composite material according to any one of claims 1 to 3, wherein the antioxidant is a complex system of a hindered phenol antioxidant and a phosphite antioxidant;
preferably, the hindered phenolic antioxidant is selected from any one or a combination of at least two of 1010, 1076, 1330 and 3114, and the phosphite antioxidant is selected from 168 and/or 626; more preferably a complex system of phosphite antioxidant 168 and hindered phenol antioxidant 1010 with the mass ratio of 1: 1-3; and/or
The lubricant is any one or the combination of at least two of magnesium stearate, zinc stearate and calcium stearate, and is preferably magnesium stearate; and/or
The silane coupling agent is any one or a combination of at least two of KH550 silane coupling agent, KH560 silane coupling agent and KH570 silane coupling agent, and preferably KH 550.
5. A method for preparing the anti-precipitation low-odor antibacterial flame-retardant polypropylene composite material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) preparing polyphosphazene coated ammonium polyphosphate;
2) preparing casein grafted tetrakis (hydroxymethyl) phosphonium sulfate;
3) uniformly mixing polypropylene, polyphosphazene-coated ammonium polyphosphate, casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate, an antioxidant, a lubricant and a silane coupling agent, then melting, extruding and granulating to obtain the precipitation-resistant low-odor antibacterial flame-retardant polypropylene composite material.
6. The preparation method according to claim 5, wherein the specific method for preparing polyphosphazene-coated ammonium polyphosphate in the step 1) comprises the following steps:
mixing hexachlorocyclotriphosphazene and 4, 4' -dihydroxy diphenyl sulfone with an organic solvent, adding the mixture into an ammonium polyphosphate-absolute ethyl alcohol suspension, adding a catalyst, and reacting to obtain polyphosphazene-coated ammonium polyphosphate.
7. The preparation method according to claim 6, wherein the ammonium polyphosphate is high polymerization degree crystal II type ammonium polyphosphate, the polymerization degree is not less than 1000, preferably 1000-5000;
preferably, in the ammonium polyphosphate-absolute ethyl alcohol suspension solution, the mass ratio of ammonium polyphosphate to absolute ethyl alcohol is 1: 2-3;
more preferably, the ammonium polyphosphate-anhydrous ethanol suspension is stirred and heated to 70-80 ℃ before feeding;
preferably, the mass ratio of the ammonium polyphosphate to the hexachlorocyclotriphosphazene to the 4, 4' -dihydroxydiphenylsulfone is 1: (1-3.6): (1.5-6), preferably 1: (1.2-3): (2-5);
preferably, the organic solvent is any one or a combination of at least two of acetone, ethanol, acetonitrile, toluene and tetrahydrofuran, and more preferably ethanol;
more preferably, the mass ratio of the organic solvent to the hexachlorocyclotriphosphazene is (1.5-2.0): 1;
preferably, the catalyst is triethylamine and/or pyridine;
more preferably, the mass ratio of the catalyst to the hexachlorocyclotriphosphazene is (0.02-0.05): 1;
preferably, the hexachlorocyclotriphosphazene and the 4, 4' -dihydroxy diphenyl sulfone are mixed with an organic solvent and then are added into the ammonium polyphosphate suspension in a continuous feeding mode, wherein the feeding time is 0.5-2.5h, and a dropwise feeding mode is more preferably adopted;
preferably, the reaction is carried out at a temperature of 40-80 ℃, preferably 40-60 ℃; the time is 10-24h, preferably 12-18 h.
8. The method according to any one of claims 5 to 7, wherein the specific method for preparing the casein-grafted tetrakis (hydroxymethyl) phosphonium sulfate in step 2) comprises the following steps:
adjusting pH value of casein to 9-12 with triethylamine, stirring and heating to 70-80 deg.C to form a solution of casein-triethylamine, adding tetrakis (hydroxymethyl) phosphonium sulfate, reacting at 70-80 deg.C for 8-12h, cooling to 40-60 deg.C, adjusting pH value of the reaction solution to 7-8 with dilute acid to obtain casein grafted tetrakis (hydroxymethyl) phosphonium sulfate.
9. The method according to claim 8, wherein the mass ratio of casein to tetrakis (hydroxymethyl) phosphonium sulfate is 1: 1-5, preferably 1: (1.5-3);
preferably, the dilute acid is dilute nitric acid with a concentration of 30-60 wt%.
10. The method for preparing the compound of any one of claims 5 to 9, wherein in the step 3), a parallel twin-screw extruder is used for melting, extruding and granulating;
preferably, the barrel temperature of the extruder is 120-200 ℃, preferably 140-190 ℃; the screw rotation speed is 200-500r/min, preferably 300-450 r/min.
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