CN111171446B - Composite high-oxygen-index flame-retardant polypropylene master batch and preparation method thereof - Google Patents
Composite high-oxygen-index flame-retardant polypropylene master batch and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite high-oxygen-index flame-retardant polypropylene master batch and a preparation method thereof, wherein the polypropylene master batch comprises the following components in parts by weight: 60-75 parts of polypropylene PP, 15-20 parts of ammonium polyphosphate, 5-8 parts of pentaerythritol, 1-3 parts of aluminum hypophosphite, 0.3-0.7 part of antioxidant, 0.3-1 part of lubricant and 0.1-0.3 part of silane coupling agent; according to the method, the ammonium polyphosphate is modified, the vinyl silicone oil is used as a base, the hydrogen-containing silicone oil cross-linking agent and the platinum-based catalyst are used together, and the ammonium polyphosphate dispersion liquid and the nano alumina powder are doped to prepare the ammonium polyphosphate grafted with the liquid silica gel, so that the ammonium polyphosphate has excellent hydrophobicity; the liquid silica gel is a nonpolar molecule, and a nonpolar chain segment exists in the modified molecule, so that the compatibility with polypropylene is improved; in addition, the ammonium polyphosphate is grafted with nano alumina on a molecular chain, and the nano alumina and the liquid silica gel form a synergistic effect, so that the decomposition temperature of the ammonium polyphosphate is obviously improved, the master batch is effectively prevented from generating a large amount of white smoke in the combustion process, and the master batch has excellent smoke suppression property.
Description
Technical Field
The invention relates to the technical field of flame-retardant master batches, in particular to a composite high-oxygen-index flame-retardant polypropylene master batch and a preparation method thereof.
Background
The polypropylene has wide application due to the characteristics of rich raw material source, low price, simple production process, excellent comprehensive mechanical property and the like. However, polypropylene is extremely easy to burn, the limited oxygen index is only 17 to 18%, the char formation rate is extremely low, the burning rate is high, the released heat is large, and a large amount of molten drops are accompanied, so that the application range is greatly limited, and the addition of a flame retardant into polypropylene is a research hotspot in recent years.
Ammonium polyphosphate is a novel halogen-free intumescent flame retardant, has low toxicity and excellent flame retardant property, is widely applied to the fields of flame retardant research of polymers such as flame retardant polypropylene and the like, fire-retardant coatings and building exterior wall heat insulation materials in recent years, and can also be used for producing a dry powder extinguishing agent to extinguish large areas of coal fields, forests and the like.
The Chinese patent with the application publication number of CN103087414A in the existing patent discloses a composite intumescent flame retardant general-purpose polypropylene and a preparation method thereof, and the required characteristic substances and the parts by weight thereof are as follows: 100 parts of general polypropylene, 5 to 10 parts of composite intumescent flame retardant (ammonium polyphosphate, 5 to 10 parts of pentaerythritol, 1 to 5 parts of melamine, 1 to 6 parts of acidified 4A molecular sieve), 1 to 2 parts of antioxidant and 0 to 6 parts of flame retardant synergist; the composite flame retardant is adopted, and has a good flame retardant effect when being applied to polypropylene.
However, ammonium polyphosphate has a molecular chain of an ammonium salt structure with a high polymerization degree, and has the disadvantages of low decomposition temperature, poor water resistance and the like, and in addition, when the ammonium polyphosphate is mixed with polyolefin materials, the compatibility is poor when the ammonium polyphosphate is applied to polymers because the structure polarity of the ammonium polyphosphate is strong, and most of the polyolefin materials are nonpolar polymers.
Disclosure of Invention
Aiming at the defects in the prior art, one of the purposes of the invention is to provide a composite high-oxygen-index flame-retardant polypropylene master batch, ammonium polyphosphate is modified in a composite intumescent flame retardant, and the defects of poor water resistance, white smoke emission and poor compatibility with polypropylene of the ammonium polyphosphate are obviously improved.
The above object of the present invention is achieved by the following technical solutions:
the composite high-oxygen-index flame-retardant polypropylene master batch comprises the following components in parts by weight: 60-75 parts of polypropylene PP, 15-20 parts of ammonium polyphosphate, 5-8 parts of pentaerythritol, 1-3 parts of aluminum hypophosphite, 0.3-0.7 part of antioxidant, 0.3-1 part of lubricant and 0.1-0.3 part of silane coupling agent; the ammonium polyphosphate is modified by adopting the following method: (1) Dispersing ammonium polyphosphate in absolute ethyl alcohol to obtain an ammonium polyphosphate dispersion liquid, wherein the weight ratio of the ammonium polyphosphate to the absolute ethyl alcohol is 1 (2-3); (2) Dripping ethyl acetate into vinyl silicone oil, then pouring ammonium polyphosphate dispersion liquid, and stirring at the temperature of 60-80 ℃, wherein the weight ratio of the vinyl silicone oil to the ethyl acetate to the ammonium polyphosphate dispersion liquid is (5) - (3-4); (3) Under the action of negative pressure pumping, adding nano alumina powder and continuously stirring; (4) Adding a hydrogen-containing silicone oil cross-linking agent and a platinum catalyst under the stirring action, and reacting for 3 to 5min; (5) Heating to 90-110 ℃, continuously adding the maleic anhydride grafting compatilizer, and reacting for 45-60min.
By adopting the technical scheme, the ammonium polyphosphate is modified, the vinyl silicone oil is used as a base, the hydrogen-containing silicone oil cross-linking agent and the platinum-based catalyst are used together, and the ammonium polyphosphate dispersion liquid and the nano alumina powder are doped to prepare the ammonium polyphosphate grafted with the liquid silica gel, so that the ammonium polyphosphate has excellent hydrophobicity; the liquid silica gel is a nonpolar molecule, and after ammonium polyphosphate is modified, a nonpolar chain segment exists in the molecule, so that the compatibility with polypropylene is improved; in addition, the nano alumina has the advantages of porosity, high dispersibility, high activity, low surface energy and high temperature resistance, the nano alumina is grafted on the ammonium polyphosphate molecular chain, and the nano alumina and the liquid silica gel form a synergistic effect, so that the decomposition temperature of the ammonium polyphosphate is obviously improved, the master batch is effectively prevented from generating a large amount of white smoke in the combustion process, and the master batch has excellent smoke suppression performance.
The present invention in a preferred example may be further configured to: the polypropylene is isotactic polypropylene.
By adopting the technical scheme, the isotactic polypropylene has better mechanical strength, rigidity and environmental stress cracking resistance; the heat resistance is good, the melting point is high, and isotactic polypropylene is preferably used in the present application.
The invention in a preferred example may be further configured to: the antioxidant is selected from a mixture of an antioxidant 1010 and a copper bisulfate antioxidant, which are compounded in a weight ratio of 1.
By adopting the technical scheme, the antioxidant 1010 is a multi-element hindered phenol type antioxidant, has good compatibility with most polymers, can be widely applied to PE, PP, PS, ABS resin and synthetic rubber, and can effectively prevent discoloration caused by light and heat; the copper bisulphate antioxidant has better thermal stability, and the compounded antioxidant is beneficial to keeping the polypropylene master batch white and reducing the amount of white smoke generated in the combustion process of the polypropylene master batch.
The invention in a preferred example may be further configured to: the preparation process of the copper bisulfate antioxidant is as follows: mixing a copper sulfate solution and ethylenediamine according to a molar ratio of 1.
By adopting the technical scheme, the copper bisulfate antioxidant contains NH groups, and the ammonium polyphosphate molecular chain contains NH groups, so that the compatibility of the antioxidant and ammonium polyphosphate can be improved; the antioxidant 1010 is suitable for polypropylene master batches, and after the copper bisulphate antioxidant is mixed with the antioxidant 1010, the compatibility of ammonium polyphosphate and polypropylene is improved.
The present invention in a preferred example may be further configured to: the nano alumina powder is pretreated by the following steps: preparing an expanded graphite dispersion liquid in advance, mixing the nano aluminum oxide and the expanded graphite dispersion liquid by a ratio of 4.
By adopting the technical scheme, the expanded graphite is a loose and porous vermicular substance obtained by carrying out intercalation treatment and high-temperature expansion on high-quality natural crystalline flake graphite by using strong acid and strong oxidant, has the characteristics of high temperature resistance, corrosion resistance and easy adsorption, and can be adsorbed among the layers of the expanded graphite by dispersing the nano alumina in the expanded graphite dispersion liquid to form nuclear crystals to grow, so that the lattice energy is increased, and the release of white smoke is inhibited.
The present invention in a preferred example may be further configured to: the lubricant is a compound of zinc stearate and silicone powder with the weight ratio of 1.
By adopting the technical scheme, the silicone powder has excellent reaction activity, smaller friction coefficient and excellent flame retardance, and the compounding of the silicone powder and the zinc stearate is beneficial to improving the processing easiness of the polypropylene master batch and also improving the flame retardance of the polypropylene master batch.
The present invention in a preferred example may be further configured to: the silane coupling agent is KH-550 or KH-570.
By adopting the technical scheme, the KH-550 or KH-570 silane coupling agent is adopted, so that the wettability and the dispersibility of each component in the polypropylene PP are improved, and the processability of the polypropylene master batch is improved.
The second aim of the invention is realized by the following technical scheme:
a preparation method of a composite high-oxygen-index flame-retardant polypropylene master batch comprises the following steps:
(1) Preparing modified ammonium polyphosphate;
(2) Preparing materials: weighing 60 to 75 parts of polypropylene PP, 15 to 20 parts of ammonium polyphosphate, 5 to 8 parts of pentaerythritol, 1 to 3 parts of aluminum hypophosphite, 0.3 to 0.7 part of antioxidant, 0.3 to 1 part of lubricant and 0.1 to 0.3 part of silane coupling agent according to parts by weight;
(3) Mixing ammonium polyphosphate, pentaerythritol, aluminum hypophosphite, an antioxidant, a lubricant and a silane coupling agent in a high-speed mixer, mixing for 5-10min at the rotating speed of 480-520r/min, and then mixing for 1-3min at the rotating speed of 1400-1600r/min to obtain mixed powder;
(4) Adding the mixed powder and polypropylene PP into an extruder, extruding at 165-175 ℃, and air-cooling and granulating.
By adopting the technical scheme, the method for preparing the polypropylene master batch is simple in process and convenient and fast to form; air cooling is adopted, and water cooling is not adopted, so that the stable product quality is ensured.
In summary, the invention includes at least one of the following beneficial technical effects:
1. excellent water resistance: according to the method, the ammonium polyphosphate is modified, so that the defect of high hygroscopicity of the ammonium polyphosphate is overcome, and the prepared sample has excellent water resistance after being boiled by hot water;
2. the sample added with the modified ammonium polyphosphate has increased tensile strength and elongation at break and enhanced mechanical properties, which shows that the compatibility of the ammonium polyphosphate and polypropylene is improved;
3. after the ammonium polyphosphate is modified, the flame retardance and smoke suppression of the master batch can be improved; after the copper bisulfate antioxidant and the antioxidant 1010 are compounded, the antioxidant effect is achieved, and the smoke suppression performance of the master batch can be improved; after the silicone powder and the zinc stearate are compounded, the flame retardance of the master batch can be improved while the lubricity is improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
The antioxidant is formed by compounding an antioxidant 1010 and a copper bisulfate antioxidant in a weight ratio of 1.
The copper bisulfate antioxidant is prepared by the following method:
(1) Adding 25 parts by weight of copper sulfate pentahydrate into 150 parts by weight of distilled water to be fully dissolved;
(2) Slowly adding 12 parts by weight of ethylenediamine into the copper sulfate solution, and stirring for 30min;
(3) Drying in air at 115 ℃, and grinding to obtain powder of 1-10 μm.
Preparation of raw materials example one:
ammonium polyphosphate is modified by adopting the following method:
(1) Dispersing 10 parts by weight of ammonium polyphosphate in 20 parts by weight of absolute ethyl alcohol to obtain ammonium polyphosphate dispersion liquid;
(2) Dripping 10 parts by weight of ethyl acetate into 50 parts by weight of vinyl silicone oil, and then pouring 30 parts by weight of ammonium polyphosphate dispersion liquid to stir at the temperature of 70 ℃;
(3) Under the stirring action, adding 15 parts by weight of nano alumina powder;
(4) Under the action of negative pressure pumping, adding 1.5 parts by weight of hydrogen-containing silicone oil cross-linking agent and 1 part by weight of platinum catalyst, and reacting for 3min;
(5) Heating to 120 ℃, continuously adding 3 parts by weight of maleic anhydride grafted compatilizer, and reacting for 60min.
Preparation example two of raw materials:
ammonium polyphosphate is modified by adopting the following method:
(1) Dispersing 10 parts by weight of ammonium polyphosphate in 25 parts by weight of absolute ethyl alcohol to obtain ammonium polyphosphate dispersion liquid;
(2) Dripping 10 parts by weight of ethyl acetate into 50 parts by weight of vinyl silicone oil, and pouring 35 parts by weight of ammonium polyphosphate dispersion liquid into the vinyl silicone oil to stir at the temperature of 70 ℃;
(3) Under the stirring action, 18 parts by weight of nano alumina powder is added;
(4) Under the action of negative pressure pumping, adding 2 parts by weight of hydrogen-containing silicone oil cross-linking agent and 1.5 parts by weight of platinum catalyst, and reacting for 4min;
(5) Heating to 120 ℃, continuously adding 4 parts by weight of maleic anhydride grafted compatilizer, and reacting for 60min.
Preparation example three of raw materials:
ammonium polyphosphate is modified by adopting the following method:
(1) Dispersing 10 parts by weight of ammonium polyphosphate in 30 parts by weight of absolute ethyl alcohol to obtain ammonium polyphosphate dispersion liquid;
(2) Dripping 10 parts by weight of ethyl acetate into 50 parts by weight of vinyl silicone oil, and pouring 40 parts by weight of ammonium polyphosphate dispersion liquid into the vinyl silicone oil to stir at the temperature of 70 ℃;
(3) Under the stirring action, 20 parts by weight of nano alumina powder is added;
(4) Adding 2.5 parts by weight of hydrogen-containing silicone oil cross-linking agent and 2 parts by weight of platinum catalyst under the action of negative pressure pumping, and reacting for 3 to 5min;
(5) Heating to 120 ℃, continuously adding 5 parts by weight of maleic anhydride grafted compatilizer, and reacting for 60min.
Preparation of the starting material example four:
the ammonium polyphosphate is different from the second raw material preparation example in that the nano alumina powder is pretreated by the following steps: (1) Dispersing 10 parts by weight of expanded graphite in 10 parts by weight of n-butanol to form an expanded graphite dispersion; (2) Dispersing 80 parts by weight of nano alumina in 20 parts by weight of expanded graphite dispersion liquid; and (3) drying and grinding into powder under the condition of negative pressure pumping.
The first embodiment is as follows:
a composite high-oxygen-index flame-retardant polypropylene master batch is prepared by the following method:
(1) Preparing materials: weighing 60 parts of polypropylene PP, 15 parts of ammonium polyphosphate prepared in the first raw material preparation example, 5 parts of pentaerythritol, 1 part of aluminum hypophosphite, 1010.15 parts of antioxidant, 0.15 part of copper disulfide antioxidant, 0.15 part of zinc stearate, 0.15 part of silicone powder and 0.1 part of KH-550;
(2) Mixing ammonium polyphosphate, pentaerythritol, aluminum hypophosphite, an antioxidant 1010, a copper disulfide antioxidant, zinc stearate, silicone powder and KH-550 in a high-speed mixer, mixing for 10min at the rotating speed of 500r/min, and then mixing for 2min at the rotating speed of 1500r/min to obtain mixed powder;
(3) Adding the mixed powder and polypropylene PP into an extruder, extruding at 170 ℃, and air-cooling and granulating.
The second embodiment:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the first embodiment in that ammonium polyphosphate is prepared by adopting the second raw material preparation embodiment.
Example three:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the first embodiment in that ammonium polyphosphate is prepared by adopting a third raw material preparation example.
Example four:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in that ammonium polyphosphate is prepared by adopting the fourth raw material preparation example.
Example five:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in component content: weighing 65 parts of polypropylene PP, 17 parts of ammonium polyphosphate, 6 parts of pentaerythritol, 1.5 parts of aluminum hypophosphite, 1010.2 parts of antioxidant, 0.2 part of copper bisulfate antioxidant, 0.25 part of zinc stearate, 0.25 part of silicone powder and 0.15 part of KH-550.
Example six:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in component content: 68 parts of polypropylene PP, 18 parts of ammonium polyphosphate, 7 parts of pentaerythritol, 2 parts of aluminum hypophosphite, 1010.25 parts of antioxidant, 0.25 part of copper disulfide antioxidant, 0.35 part of zinc stearate, 0.35 part of silicone powder and 0.2 part of KH-550.
Example seven:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in component content: 72 parts of polypropylene PP, 19 parts of ammonium polyphosphate, 8 parts of pentaerythritol, 2.5 parts of aluminum hypophosphite, 1010.3 parts of antioxidant, 0.3 part of copper disulfide antioxidant, 0.4 part of zinc stearate, 0.4 part of silicone powder and 0.25 part of KH-550 are weighed.
Example eight:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in component content: 75 parts of polypropylene PP, 20 parts of ammonium polyphosphate, 8 parts of pentaerythritol, 3 parts of aluminum hypophosphite, 1010.35 parts of antioxidant, 0.35 part of copper disulfide antioxidant, 0.5 part of zinc stearate, 0.5 part of silicone powder and 0.3 part of KH-550 are weighed.
Comparative example one:
an example 5 disclosed in a composite intumescent flame retardant general purpose polypropylene disclosed in a Chinese patent with the application publication number CN103087414A in the prior patent is taken as a first comparative example.
Comparative example two:
the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in that unmodified ammonium polyphosphate is adopted.
Comparative example three:
the difference between the composite high-oxygen-index flame-retardant polypropylene master batch and the second embodiment is that the antioxidant is 1010.
Comparative example four: the composite high-oxygen-index flame-retardant polypropylene master batch is different from the second embodiment in that zinc stearate is selected as a lubricant.
And (3) performance detection:
(1) Hydrophobicity of raw materials: flattening the powder on a glass substrate respectively aiming at the ammonium polyphosphate prepared in the first raw material preparation example to the fourth raw material preparation example and the unmodified ammonium polyphosphate, dripping 5 mu L of deionized water on the powder, and testing a contact angle by using a contact angle measuring instrument;
(2) Water resistance: selecting master batches of the first embodiment to the fourth embodiment and the second comparative embodiment, preparing sample strips by using an injection molding machine, and weighing the sample strips as m 0 Then, the sample is put into distilled water of 70 ℃ and boiled for 168 hours, the sample is taken out, dried and cooled, possible residual exudates on the surface are wiped off, and the weight is recorded as m 1 According to the formula (m) 0 -m 1 ）/ m 0 * Calculating the mass loss rate of the sample by 100 percent;
(3) Tensile strength and elongation at break: the samples of each example and the comparative example are measured according to the GB/T1040.2-2006 standard;
(4) Oxygen index: oxygen index measurement is carried out on samples of examples and comparative examples by using a JF-3 type oxygen index instrument;
(5) Vertical combustion: the samples of the examples and the comparative examples were tested using a CZF-3 horizontal vertical combustion tester;
(6) Smoke density: and testing each sample by using a smoke density testing box according to the GB/T8323.1-2008 standard.
The results of the hydrophobicity measurements are shown in the following table:
| sample(s) | Contact angle (°) |
| Raw Material preparation example 1 | 148 |
| Preparation of starting Material example II | 150 |
| Preparation of starting Material example III | 149 |
| Preparation of starting Material example four | 148 |
| Unmodified ammonium polyphosphate | 0 |
According to the table, the ammonium polyphosphate is modified, so that the contact angle of the ammonium polyphosphate is obviously increased after modification, and the hydrophobic property of the ammonium polyphosphate is improved.
The results of the water resistance measurements are shown in the following table:
| sample(s) | Mass loss rate (%) |
| Example one | 0 |
| Example two | 0 |
| EXAMPLE III | 0 |
| Example four | 0 |
| Comparative example No. two | 15 |
According to the table, the modified ammonium polyphosphate adopted in the application has excellent hydrophobicity and waterproofness, and after the sample of the embodiment is placed in hot water for cooking, the sample still has good hydrophobicity and waterproofness, while precipitates exist on the surface of the sample of the unmodified ammonium polyphosphate, and the sample of the unmodified ammonium polyphosphate has poor waterproofness.
The results of the tensile strength and elongation at break measurements are shown in the following table:
| sample (I) | Tensile strength (Mpa) | Elongation at Break (%) |
| Example one | 34.25 | 120 |
| Example two | 34.36 | 125 |
| EXAMPLE III | 34.18 | 122 |
| Example four | 35.52 | 132 |
| EXAMPLE five | 36.36 | 126 |
| EXAMPLE six | 36.95 | 128 |
| EXAMPLE seven | 38.23 | 132 |
| Example eight | 37.45 | 130 |
| Comparative example No. two | 26.72 | 78 |
The above table shows that, when the master batch of the embodiment is used for preparing samples, the tensile strength of the samples is more than 34Mpa, and the elongation at break is more than 120%, so that the modified ammonium polyphosphate has good compatibility with polypropylene, and the tensile strength and the elongation at break of the samples are obviously improved; according to the comparative example II, the unmodified ammonium polyphosphate is added into the polypropylene, so that the compatibility of the ammonium polyphosphate and the polypropylene is poor, and the tensile strength and the elongation at break of the sample are reduced.
The results of the oxygen index, vertical burn and smoke density measurements are shown in the following table:
| sample (I) | Oxygen index | Vertical combustion class | Density of smoke |
| Example two | 36 | V 0 Stage | 22 |
| Example four | 40 | V 0 Stage | 18 |
| EXAMPLE five | 37 | V 0 Stage(s) | 20 |
| EXAMPLE six | 38 | V 0 Stage | 20 |
| EXAMPLE seven | 38.5 | V 0 Stage | 18 |
| Example eight | 36.5 | V 0 Stage | 19 |
| Comparative example 1 | 28 | V 0 Stage | 28 |
| Comparative example No. two | 26.5 | V 1 Stage | 32 |
| Comparative example No. three | 30 | V 0 Stage | 22 |
| Comparative example No. four | 28 | V 0 Stage | 25 |
The above table shows that the samples in the examples have excellent flame retardant properties compared with the samples in the first and second comparative examples, and the heat resistance and flame retardant properties of the master batch are remarkably improved after the ammonium polyphosphate is modified; compared with the comparative example II, the oxygen index of the sample added with the modified ammonium polyphosphate is obviously improved, and the vertical combustion grade reaches V 0 The oxygen index of the second comparative example is obviously reduced, the vertical combustion grade is reduced, and the flame retardant property of the sample master batch is reduced; according to the sample in the embodiment and the third comparative example, the flame retardant property of the sample is improved by compounding the copper bisulfate antioxidant and the antioxidant 1010; according toThe second embodiment and the fourth embodiment show that after the nano-alumina is dispersed in the expanded graphite dispersion liquid, the smoke suppression performance of the sample is obviously improved; according to the second embodiment and the fourth embodiment, the compound of the silicone powder and the zinc stearate is helpful for further improving the smoke suppression performance of the sample.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (4)
1. The composite high-oxygen-index flame-retardant polypropylene master batch is characterized by comprising the following components in parts by weight: 60 to 75 parts of polypropylene PP, 15 to 20 parts of ammonium polyphosphate, 5 to 8 parts of pentaerythritol, 1 to 3 parts of aluminum hypophosphite, 0.3 to 0.7 part of antioxidant, 0.3 to 1 part of lubricant and 0.1 to 0.3 part of silane coupling agent; the ammonium polyphosphate is modified by adopting the following method: (1) Dispersing ammonium polyphosphate in absolute ethyl alcohol to obtain an ammonium polyphosphate dispersion liquid, wherein the weight ratio of the ammonium polyphosphate to the absolute ethyl alcohol is (1) - (2) - (3); (2) Dripping ethyl acetate into vinyl silicone oil, then pouring ammonium polyphosphate dispersion liquid, and stirring at the temperature of 60-80 ℃, wherein the weight ratio of the vinyl silicone oil to the ethyl acetate to the ammonium polyphosphate dispersion liquid is (5) - (3-4); (3) adding nano-alumina powder under the stirring action; (4) Adding a hydrogen-containing silicone oil cross-linking agent and a platinum catalyst under the action of negative pressure pumping, and reacting for 3 to 5min; (5) Heating to 110 to 130 ℃, continuously adding the maleic anhydride grafting compatilizer, and reacting for 45 to 60min;
the antioxidant is a mixture of an antioxidant 1010 and a copper bisulfate antioxidant which are compounded in a weight ratio of 1; the preparation process of the copper bisulfate antioxidant is as follows: mixing a copper sulfate solution and ethylenediamine according to a molar ratio of 1 to 2, drying at 110 to 120 ℃, and grinding into micron-sized powder;
the nano alumina powder is pretreated by the following steps: preparing an expanded graphite dispersion liquid in advance, mixing nano aluminum oxide and the expanded graphite dispersion liquid by a ratio of 4;
the lubricant is a compound of zinc stearate and silicone powder with the weight ratio of 1.
2. The composite high oxygen index flame retardant polypropylene masterbatch according to claim 1, wherein: the polypropylene is isotactic polypropylene.
3. The composite high oxygen index flame retardant polypropylene masterbatch of claim 1, wherein: the silane coupling agent is KH-550 or KH-570.
4. The preparation method of the composite high-oxygen-index flame-retardant polypropylene master batch as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Preparing modified ammonium polyphosphate;
(2) Preparing materials: weighing 60 to 75 parts of polypropylene PP, 15 to 20 parts of ammonium polyphosphate, 5 to 8 parts of pentaerythritol, 1 to 3 parts of aluminum hypophosphite, 0.3 to 0.7 part of antioxidant, 0.3 to 1 part of lubricant and 0.1 to 0.3 part of silane coupling agent according to parts by weight;
(3) Mixing ammonium polyphosphate, pentaerythritol, aluminum hypophosphite, an antioxidant, a lubricant and a silane coupling agent in a high-speed mixer, mixing for 5-10min at the rotating speed of 480-520r/min, and then mixing for 1-3min at the rotating speed of 1400-1600r/min to obtain mixed powder;
(4) Adding the mixed powder and polypropylene PP into an extruder, extruding at 165-175 ℃, and air-cooling and granulating.
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