阅读说明：本技术 单分子膨胀型阻燃剂mppr及mppr/poss复合协效无卤阻燃聚丙烯复合材料 (Single-molecule intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material ) 是由 陈英红 张铭丹 王琪 华正坤 于 2021-07-26 设计创作，主要内容包括：本发明提供一种单分子膨胀型阻燃剂MPPR及MPPR/POSS复合协效无卤阻燃聚丙烯复合材料,具体而言,为单分子膨胀型阻燃剂MPPR及其制备方法,包括单分子膨胀型阻燃剂MPPR的MPPR阻燃聚丙烯复合材料及其制备方法、以及MPPR/POSS复合协效无卤阻燃聚丙烯复合材料及其制备方法。其中所述单分子膨胀型阻燃剂MPPR,其原料组分包括植酸、多元醇、三聚氰胺,且植酸、多元醇、三聚氰胺摩尔比为1：(2.4～2.6)：(1.9～2.1),其制备方法是植酸先与多元醇搅拌反应后再加入三聚氰胺进行反应。制备所得阻燃聚丙烯复合材料阻燃效率高,力学强度高,可满足阻燃PP在高强度高模量应用场合的要求。(The invention provides a monomolecular intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material, in particular to a monomolecular intumescent flame retardant MPPR and a preparation method thereof, and the MPPR flame retardant polypropylene composite material comprise the monomolecular intumescent flame retardant MPPR and the preparation method thereof, and the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material and the preparation method thereof. The raw material components of the monomolecular intumescent flame retardant MPPR comprise phytic acid, polyhydric alcohol and melamine, and the molar ratio of the phytic acid to the polyhydric alcohol to the melamine is 1: (2.4-2.6): (1.9-2.1), the preparation method comprises the steps of stirring phytic acid and polyhydric alcohol for reaction, and then adding melamine for reaction. The prepared flame-retardant polypropylene composite material has high flame-retardant efficiency and high mechanical strength, and can meet the requirements of flame-retardant PP on high-strength and high-modulus application occasions.)

1. The MPPR is characterized in that raw material components comprise phytic acid, polyhydric alcohol and melamine, and the molar ratio of the phytic acid to the polyhydric alcohol to the melamine is 1: (2.4-2.6): (1.9-2.1),

wherein the polyhydric alcohol is at least one of pentaerythritol, dipentaerythritol and tripentaerythritol.

2. A method for preparing an MPPR as set forth in claim 1, characterized in that it comprises the following steps:

(1) preparing phytic acid into phytic acid solution;

(2) adding polyalcohol into the phytic acid solution obtained in the step (1), and stirring and reacting for at least 1h at the temperature of 95-100 ℃; adding melamine, and continuously stirring and reacting for at least 0.5h at the temperature of 95-100 ℃ to obtain a mixed solution;

(3) cooling the mixed solution obtained in the step (2), and drying to constant weight to obtain the MPPR (monomolecular intumescent flame retardant);

wherein, the mole ratio of the phytic acid, the polyalcohol and the melamine used in the preparation method is 1: (2.4-2.6): (1.9-2.1), wherein the polyhydric alcohol is at least one of pentaerythritol, dipentaerythritol and tripentaerythritol.

3. The method of claim 2, wherein: the phytic acid in the step (1) is prepared into a phytic acid solution, and the phytic acid is prepared into the phytic acid solution according to the molar concentration ratio of 0.125-0.25 mol/L.

4. The method of claim 2, wherein: and (2) adding the polyalcohol into the phytic acid solution obtained in the step (1), and stirring and reacting for at least 1h at the temperature of 95-100 ℃, wherein the stirring and reacting are carried out under a closed condition or a condensing reflux condition.

5. The method of claim 2, wherein: the preparation method is characterized in that the molar ratio of phytic acid to pentaerythritol to melamine is 1: 2.5: 2.

6. an MPPR flame retardant polypropylene composite material comprising the monomolecular intumescent flame retardant MPPR as the claim 1 is characterized by mainly comprising the following components in parts by weight:

75-80 parts of polypropylene,

20-25 parts of a monomolecular intumescent flame retardant MPPR;

wherein the total weight part of the polypropylene and the monomolecular intumescent flame retardant MPPR is 100 parts.

7. The MPPR flame-retardant polypropylene composite material according to claim 6, mainly comprising the following components in parts by weight:

75 parts of polypropylene, namely polypropylene,

25 parts of a monomolecular intumescent flame retardant MPPR.

8. A preparation method of the MPPR flame retardant polypropylene composite material as set forth in claim 6, characterized by mainly comprising the steps of:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR and polypropylene to obtain a mixture, adding the mixture into a torque rheometer for melt blending, carrying out banburying treatment for 5-10 min, and collecting the obtained banburying mixture; wherein the screw rotating speed of the torque rheometer is 40-50 rpm;

secondly, carrying out hot press molding treatment on the banburying mixture obtained in the step one through a flat vulcanizing machine to obtain the MPPR flame-retardant polypropylene composite material; wherein the hot pressing temperature of the plate vulcanizing machine is 190-200 ℃;

the preparation method comprises the following steps of (1) preparing polypropylene and a monomolecular intumescent flame retardant MPPR according to the following weight parts:

75-80 parts of polypropylene,

20-25 parts of a monomolecular intumescent flame retardant MPPR;

wherein the total weight part of the polypropylene and the monomolecular intumescent flame retardant MPPR is 100 parts.

9. An MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material containing the monomolecular intumescent flame retardant MPPR as claimed in claim 1 is characterized by mainly comprising the following components in parts by weight:

78 parts of polypropylene, namely polypropylene, and (C),

20-21 parts of a monomolecular intumescent flame retardant MPPR,

1-2 parts of octavinyl oligomeric silsesquioxane;

wherein the total weight parts of the polypropylene, the single-molecule intumescent flame retardant MPPR and the octavinyl oligomeric silsesquioxane are 100 parts.

10. The preparation method of the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material as set forth in claim 9, characterized in that the preparation method mainly comprises the following steps:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR, polypropylene and octavinyl oligomeric silsesquioxane to obtain a mixture, adding the mixture into an internal mixer, carrying out internal mixing treatment for 5-10 min, and collecting the obtained internal mixing mixture; wherein the banburying treatment temperature is 180-200 ℃, and the screw rotating speed is 40-50 rpm;

cooling the obtained banburying mixture, crushing and granulating to obtain the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material;

the preparation method comprises the following steps of preparing a monomolecular intumescent flame retardant MPPR, polypropylene and octavinyl oligomeric silsesquioxane, wherein the monomolecular intumescent flame retardant MPPR, the polypropylene and the octavinyl oligomeric silsesquioxane are prepared from the following components in parts by weight:

78 parts of polypropylene, namely polypropylene, and (C),

20-21 parts of a monomolecular intumescent flame retardant MPPR,

1-2 parts of octavinyl oligomeric silsesquioxane;

wherein the total weight parts of the polypropylene, the single-molecule intumescent flame retardant MPPR and the octavinyl oligomeric silsesquioxane are 100 parts.

Technical Field

The invention belongs to the technical field of monomolecular intumescent flame retardants, and relates to a monomolecular intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material, in particular to a monomolecular intumescent flame retardant MPPR and a preparation method thereof, and an MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material and a preparation method thereof.

Background

The polypropylene has excellent comprehensive performance and wide application, but the full-hydrocarbon chain structure of the polypropylene ensures that the PP is extremely easy to burn, and generates a large amount of flaming molten drops during burning, releases a large amount of heat, is extremely easy to spread flame to cause fire, harms the life and property safety of people, and seriously limits the application of the polypropylene in certain fields needing high flame retardance. Therefore, in order to widen the application range of polypropylene, the development of a novel flame retardant PP composite material is urgent. According to the development and environmental protection requirements of the existing flame retardant for polypropylene, the halogen flame retardant can release a large amount of toxic smog and gas during combustion, which seriously harms human health and environmental protection safety, and the application of the halogen flame retardant is gradually limited, so the development of the green and environmental-friendly halogen-free flame retardant is a research hotspot and development direction of polypropylene flame retardance.

The Intumescent Flame Retardant (IFR) is considered to be one of the most promising halogen-free flame retardants due to the advantages of low toxicity, low smoke, high flame retardant efficiency and the like. The IFR which is researched more traditionally is mainly mixed intumescent flame retardant, such as the simplest mixed IFR system which is formed by compounding ammonium polyphosphate (APP), Pentaerythritol (PER) and Melamine (ME) according to a certain proportion. However, the traditional IFR system has poor thermal stability, APP and PER are easy to absorb moisture and separate out, and the PER is easy to migrate to the surface of a matrix in the processing and using processes, so that the flame retardant property, the mechanical property and the service performance of PP are seriously deteriorated. Therefore, there is a need to develop and construct new intumescent flame retardant systems suitable for PP flame retardancy.

Phytic Acid (PA), also known as inositol hexaphosphoric acid, molecular formula C₆H₁₈O₂₄P₆Mainly in plant seeds, roots and stems, is environmentally friendly and has high phosphorus content (up to 28 wt%). At present, phytic acid has been preparedThe literature for polymer flame retardation reports, but the research on applying the flame retardant to the synthesis of halogen-free flame retardant, especially intumescent flame retardant, suitable for polypropylene (PP) is still less, and the flame retardation efficiency is generally poor, for example, the oxygen index of the flame retardant PP can only be increased to 25.5% when phytic acid and piperazine are synthesized into phytate.

In order to overcome the disadvantages of the mixed intumescent flame retardant in the prior art, researchers have synthesized a monomolecular intumescent flame retardant with a trinity of an acid source, a carbon source and a gas source, and used the monomolecular intumescent flame retardant for flame retardance of polymers.

The invention of Chinese authorization 'a preparation method of phosphorus-nitrogen-carbon polymerization type intumescent flame retardant and application thereof' (authorization publication number CN106519239B) discloses a preparation method of phosphorus-nitrogen-carbon polymerization type intumescent flame retardant with a nano sheet structure, which is characterized in that: taking phytic acid, melamine and a solvent, wherein the mass ratio of the phytic acid to the melamine is 1: 3-1: 15, and the dosage of the solvent is 20-50 ml for every 0.01mol of melamine; adding melamine into a reaction vessel provided with a thermometer and a stirrer, adding a solvent under stirring, adding phytic acid at the temperature of 20-40 ℃, and reacting for 20-50 minutes under stirring to obtain a reaction solution; and pouring the reaction solution into a reaction kettle, reacting at 70-120 ℃ for 24-56 h, cooling, performing suction filtration, washing the solid with ethanol, washing with water until the pH value is 7, and drying to obtain the catalyst.

In the granted patent, phytic acid is used as an acid source and a carbon source, and melamine is used as an air source to prepare an intumescent flame retardant which is abbreviated as PAMA, and application example 4 in the specification discloses that when the PAMA is added in an amount of 25 wt%, the oxygen index of flame-retardant polypropylene (PP) reaches 29.6%, and the vertical combustion performance UL-94 reaches the V-0 grade.

However, in this patent, phytic acid is used as both an acid source and a carbon source, and a flame-retardant comonomer is composed of melamine at a large addition ratio (1:3 to 1: 15). Wherein, the specific chemical structural formula of the phytic acid is as follows:

it is evident that phytic acid, which has a relatively low carbon content (10.9 wt%, carbon content of pentaerythritol, a common carbon source, is 44.1 wt%), is not favorable for char formation when used as a char source, and melamine in intumescent flame retardants is generally not a suitable char source due to its low carbon content.

It is important to point out that the carbon source in the intumescent flame retardant is the basis for forming the condensed phase porous carbon layer. When the polymer is burnt, the acid source part mainly has the main function of decomposing to generate inorganic acid (usually phosphoric acid or metaphosphoric acid), the catalytic carbon source (charring agent) is subjected to dehydration reaction to form a condensed phase carbon layer, meanwhile, the metaphosphoric acid can promote the dehydration and carbonization of the polymer and enhance the flame retardant effect of the condensed phase, so that on one hand, the phosphorus content in the acid source has great influence on the flame retardant effect of the intumescent flame retardant, on the other hand, the carbon source also has higher carbon content to form a dehydrated carbon layer to cover the surface of the flame retardant material during the burning, and the transmission of the matrix, external heat and oxygen is effectively isolated, thereby reducing the flammability of the material.

Therefore, although the technical scheme of the granted patent still has better flame retardant performance under the laboratory test condition, based on theoretical analysis of the components of the flame retardant, the total carbon content of the PAMA is low, when the matrix material is ignited, the carbonization speed of the PAMA is slow, the carbon layer can be jacked or blown by the non-combustible gas generated by the decomposition of the gas source, an effective expanded carbon layer structure can not be formed to isolate the contact of the matrix and external hot oxygen, the PAMA is difficult to self-extinguish when large-area ignition occurs, and an ideal flame retardant effect cannot be obtained.

However, if the carbon-containing material is prepared by further compounding and using a component (such as pentaerythritol) serving as a carbon source on the basis of the technical content of the patent, as described in the background art of the granted patent: … … in practical application, it is often necessary to use a mixture of carbon source materials (such as pentaerythritol) to obtain good effect, and at the same time, it is necessary to add a high amount of carbon source materials. "again, according to the prior art, the ratio of the ammonium polyphosphate, melamine and pentaerythritol in the traditional monomolecular intumescent flame retardant is generally 2: 1:1, so that the addition of pentaerythritol with higher addition amount is really needed on the basis of the technical content of the patent, but the flame retardant performance is greatly influenced by the reduction of the phosphorus content caused by the low addition amount of the phytic acid.

Meanwhile, the acid source, the gas source and the carbon source system of the phytic acid, the melamine and the pentaerythritol are three-component systems, and the melamine and the pentaerythritol are polyfunctional compounds, so that a plurality of groups can form chemical bonds with six phosphate groups in the phytic acid, and the optimal reaction synthesis ratio cannot be determined through the chemical structures of the groups. Therefore, in order to improve the comprehensive flame retardant performance of the intumescent flame retardant using phytic acid as an acid source, a further exploration and research on an acid source, a gas source and a carbon source three-component system are necessary.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a monomolecular intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material, in particular to a monomolecular intumescent flame retardant MPPR and a preparation method thereof, the MPPR flame retardant polypropylene composite material comprising the monomolecular intumescent flame retardant MPPR and the preparation method thereof, and the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material and the preparation method thereof. The prepared flame-retardant polypropylene composite material has high flame-retardant efficiency and high mechanical strength, and can meet the requirements of flame-retardant PP on high-strength and high-modulus application occasions.

In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.

The single-molecule intumescent flame retardant MPPR comprises the following raw material components of phytic acid, polyhydric alcohol and melamine, wherein the molar ratio of the phytic acid to the polyhydric alcohol to the melamine is 1: (2.4-2.6): (1.9-2.1),

wherein the polyhydric alcohol is at least one of pentaerythritol, dipentaerythritol and tripentaerythritol.

The preparation method of the single-molecule intumescent flame retardant MPPR comprises the following steps:

(1) preparing phytic acid into phytic acid solution;

(2) adding polyalcohol into the phytic acid solution obtained in the step (1), and stirring and reacting for at least 1h at the temperature of 95-100 ℃; adding melamine, and continuously stirring and reacting for at least 0.5h at the temperature of 95-100 ℃ to obtain a mixed solution;

(3) and (3) cooling the mixed solution obtained in the step (2), and drying to constant weight to obtain the single-molecule intumescent flame retardant MPPR.

Wherein, the mole ratio of the phytic acid, the polyalcohol and the melamine used in the preparation method is 1: (2.4-2.6): (1.9-2.1), wherein the polyhydric alcohol is at least one of pentaerythritol, dipentaerythritol and tripentaerythritol.

Generally speaking, the phytic acid is a liquid which is easy to dissolve in water, so that the phytic acid in the step (1) is prepared into a phytic acid solution, and an appropriate volume of deionized water is selected according to the addition amount of the phytic acid to dissolve the phytic acid to prepare the phytic acid solution, so that the subsequent complete reaction with the polyhydric alcohol and the melamine in an aqueous solution environment is facilitated. In order to better illustrate the invention and provide an alternative technical scheme, the phytic acid in the step (1) is prepared into the phytic acid solution, and the phytic acid is prepared into the phytic acid solution according to the molar concentration ratio of 0.125-0.25 mol/L.

Wherein, in the step (2), the polyalcohol is added into the phytic acid solution obtained in the step (1), and the mixture is stirred and reacted for at least 1h at the temperature of 95-100 ℃, and the stirring and the reaction can be carried out under the condition of closed condition or condensation reflux usually, so that the incomplete reaction caused by the increase of the solution concentration of the reaction system due to evaporation at the temperature is prevented.

Adding the polyalcohol into the phytic acid solution obtained in the step (1) in the step (2), and stirring and reacting for at least 1h in a closed system at the temperature of 95-100 ℃, wherein the stirring and reacting time is an empirical summary under laboratory conditions. Generally speaking, under the condition of laboratory, when the addition amount of the phytic acid is not more than 1mol, the polyalcohol is added, and the mixture is stirred and reacted for 1-2 hours in a closed system at the temperature of 95-100 ℃. In the actual industrial production, a person skilled in the art can select a proper stirring reaction time according to the actual situation and the industrial amplification effect so as to achieve the sufficient reaction of the phytic acid and the polyol.

And (3) adding melamine in the step (2), and continuously stirring and reacting for at least 0.5h in an open system at the temperature of 95-100 ℃, wherein the stirring and reacting time is an empirical summary under laboratory conditions. Generally speaking, under the condition of laboratory, when the addition amount of the phytic acid is not more than 1mol, the polyalcohol is added, and the mixture is stirred and reacted for 0.5 to 1 hour in a closed system at the temperature of 95 to 100 ℃. In the actual industrial production, a person skilled in the art can select a proper stirring reaction time according to the actual situation and the industrial amplification effect so as to achieve the sufficient salt-forming reaction of the melamine.

The polyhydric alcohol is at least one of pentaerythritol, dipentaerythritol and tripentaerythritol, and is pentaerythritol in order to unify experimental design and test standards, and the preferable polyhydric alcohol is pentaerythritol, and the following test and analysis results are all technical schemes adopting pentaerythritol.

Generally speaking, the mixed solution prepared in the step (2) is a yellow clear transparent solution, and the monomolecular intumescent flame retardant MPPR prepared in the step (3) is a white massive solid under the condition that other components or auxiliary agents are not added.

Generally, the mixed solution obtained in step (2) is cooled in step (3) and then dried to constant weight, and usually, a standing cooling manner can be selected, and a person skilled in the art can also cool the mixed solution according to the prior art or a conventional industrial cooling technology; wherein the drying can be carried out by a forced air drier, for example, a forced air drier with a hot air temperature of 90 ℃ is placed in the forced air drier to dry the product to constant weight, and the skilled person can also carry out the drying according to the prior art or the conventional industrial drying technology.

The synthesis principle of the preparation method of the single-molecule intumescent flame retardant MPPR is as follows:

the Phytic Acid (PA) contains six phosphate groups, and the P-OH structure of the Phytic Acid (PA) can be matched with-CH in Pentaerythritol (PER) when the Phytic Acid (PA) is heated₂the-OH groups form intermolecular hydrogen bonds in aqueous solution to form a PA … PER hydrogen bond compound, the obtained PA … PER hydrogen bond compound intermediate can react with Melamine (ME) in a salt forming way under the heating condition to prepare a target product, namely the nitrogen-phosphorus intumescent flame retardant MPPR with the monomolecular structure characteristic, and the specific reaction process and mechanism can be shown in the attached figure 1 of the specification.

It is worth to be noted that, in the invention, the molar ratio of the phytic acid, the polyol and the melamine which are respectively used as an acid source, a carbon source and a gas source is 1: (2.4-2.6): (1.9-2.1) is obtained by the inventor of the invention through experimental comparison and based on experimental facts, and the thermal weight loss analysis of the obtained monomolecular intumescent flame retardant MPPR shows good thermal stability under the mixture ratio, and meets the requirements of PP flame retardant modification and molding processing. Under the proportion, the single-molecule intumescent flame retardant MPPR has the optimal phosphorus content and carbon content, and has excellent comprehensive flame retardant property.

Note that, in the present invention, the mole ratio of phytic acid, polyhydric alcohol and melamine used is defined as 1: (2.4-2.6): (1.9-2.1) is a main protection range, and is mainly based on the optimal proportioning provided by the inventor of the invention after a large amount of experiments and research comparison, the proportioning range claimed by the invention is expanded on the optimal proportioning by a proper protection range, so that the expanded proportioning range is ensured to be the same as the optimal proportioning in technical principle, and the technical effects are nearly the same.

In order to better illustrate the invention and provide an optimal technical scheme, the monomolecular intumescent flame retardant MPPR comprises the following raw material components of phytic acid, pentaerythritol and melamine, wherein the molar ratio of the phytic acid to the pentaerythritol to the melamine is 1: 2.5: 2.

the MPPR flame-retardant polypropylene composite material is prepared by mixing the single-molecule intumescent flame retardant MPPR and polypropylene, and mainly comprises the following components in parts by weight:

75-80 parts of polypropylene,

20-25 parts of a monomolecular intumescent flame retardant MPPR;

wherein the total weight part of the polypropylene and the monomolecular intumescent flame retardant MPPR is 100 parts.

Typically, the polypropylene selection may be a commercially conventional polypropylene feedstock.

Generally speaking, a person skilled in the art can select an appropriate blending processing and forming manner according to the actual requirement and the prior art according to the mixture ratio of the MPPR flame-retardant polypropylene composite material, for example, a preparation process method suitable for blending and forming a polypropylene/filler system, which is described in the prior art, such as twin-screw extrusion forming, hot press forming, vulcanization forming, and the like, so as to prepare the MPPR flame-retardant polypropylene composite material.

In order to better illustrate the present invention and provide a preferred technical solution, the preparation method of the MPPR flame retardant polypropylene composite material mainly comprises the following steps:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR and polypropylene to obtain a mixture, adding the mixture into a torque rheometer for melt blending, carrying out banburying treatment for 5-10 min, and collecting the obtained banburying mixture; wherein the screw rotating speed of the torque rheometer is 40-50 rpm;

secondly, carrying out hot press molding treatment on the banburying mixture obtained in the step one through a flat vulcanizing machine to obtain the MPPR flame-retardant polypropylene composite material; wherein the hot pressing temperature of the plate vulcanizing machine is 190-200 ℃.

The preparation method comprises the following steps of (1) preparing polypropylene and a monomolecular intumescent flame retardant MPPR according to the following weight parts:

75-80 parts of polypropylene,

20-25 parts of a monomolecular intumescent flame retardant MPPR;

wherein the total weight part of the polypropylene and the monomolecular intumescent flame retardant MPPR is 100 parts.

The MPPR flame-retardant polypropylene composite material prepared according to the preferable technical scheme has the vertical burning performance not less than UL 94V-2 grade, the limited oxygen index of 26.3-28.7 percent and the improvement of at least 46.1 percent compared with pure PP.

Meanwhile, the MPPR flame-retardant polypropylene composite material can be directly observed by naked eyes, and an expanded carbon layer is generated after the MPPR flame-retardant polypropylene composite material is used as a flame-retardant sample strip and is ignited, wherein an acid source (PA) in the MPPR is partially decomposed by heating to generate inorganic acid (metaphosphoric acid), the inorganic acid catalyzes a carbon source (PER) to partially generate carbon reaction, and meanwhile, a gas source is partially decomposed to generate non-combustible gas (NH)₃、N₂Etc.) to cause the carbon layer to expand. The generated expanded carbon layer can effectively isolate the transmission of PP matrix and external heat and oxygen, and prevent the further combustion of the bottom matrix, thereby realizing the purpose of flame retardance.

Further, in order to ensure that the comprehensive flame retardant performance of the MPPR flame retardant polypropylene composite material is better, the polypropylene and the monomolecular intumescent flame retardant MPPR are in the following proportion in parts by weight:

75 parts of polypropylene, namely polypropylene,

25 parts of a monomolecular intumescent flame retardant MPPR.

The MPPR flame-retardant polypropylene composite material prepared according to the preferable technical scheme has the vertical burning performance of UL 94V-0 grade and the limiting oxygen index of 28.7 percent.

However, through further tests, the mechanical properties of the PP material are reduced to different degrees after the polypropylene is added with the monomolecular intumescent flame retardant MPPR, wherein the mechanical property loss of a flame-retardant sample bar (25MPPR75PP) is the largest, and the tensile strength and the notch impact strength of the polypropylene are respectively reduced to 27.4MPa and 2.42kJ/m². The tensile strength of the pure PP is 32.0MPa, and the notch impact strength is 3.15kJ/m²。

Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic nano hybrid material with a cage-shaped rigid structure, and the particle size of the POSS is usually between 1 nm and 3 nm. The prior research shows that the POSS has excellent thermal stability and is successfully used for preparing flame-retardant high polymer materials. POSS having the formula (RSiO)_1.5) n, wherein R is an organic group such as vinyl, amino, phenyl, and the like. Through adopting methods such as grafting, crosslinking, melt blending, copolymerization and the like, POSS molecules and structures can be introduced into various thermoplastic or thermosetting polymers, so that the mechanical property, the thermal stability and the flame retardant property of the POSS are improved. Under high temperature conditions, POSS can be oxidized to Silica (SiO)₂) And the carbon layer is transferred to the surface of the substrate, so that the formed carbon layer is prevented from being thermally oxidized and combustible gas is prevented from being released, the thermal stability and the flame retardant property of the material are improved, and the flame retardant effect of the material is exerted. Octavinyl silsesquioxane (OV-POSS) is one type of POSS, the R group of which is an octavinyl group.

In the prior art, it is generally considered that the addition amount of octavinyl silsesquioxane (OV-POSS) is not excessive, and when the addition amount exceeds 22 wt%, the POSS nanoparticles are obviously agglomerated, and the agglomerated POSS particles cannot be well dispersed in the polypropylene matrix. Octavinyl silsesquioxane (OV-POSS) is formulated with flame retardants based on prior literature descriptions and is typically added in amounts that follow the principle of equal mass substitution (i.e., 1 wt% POSS replaces 1 wt% flame retardant).

The inventor of the invention finds that the introduction of the octavinyl silsesquioxane (OV-POSS) into the technical scheme provided by the invention is beneficial to improving the dispersibility and the interfacial compatibility of the MPPR flame retardant particles in the PP matrix and uniformly dispersing the flame retardant particles in the PP matrix resin. As shown in the attached figure 10, when POSS particles are mixed with MPPR flame retardant particles, a plurality of POSS nano particles are coated on the surfaces of the MPPR flame retardant particles, so that the surface modification of the MPPR flame retardant particles can be realized, and the compatibility and the dispersity of the MPPR and the PP matrix resin are improved. In summary, POSS nanoparticles function as compatibilizers primarily by: on one hand, the POSS nano particles have good compatibility with a PP matrix; on the other hand, the POSS nano-particle has large specific surface area, the electrostatic adsorption effect caused by the nano-size effect is easily adsorbed on the surface of the flame retardant particle, and meanwhile, the oxygen atom in the POSS nano-particle structure and the hydrogen atom of the amino group in the MPPR can generate hydrogen bond interaction. Through the above analysis, it can be reasonably considered that the introduced POSS nanoparticles actually function as small molecule compatibilizers in the system. Therefore, the compatibility between the MPPR particles of the POSS-coated monomolecular intumescent flame retardant and the PP matrix is obviously improved, and the dispersity of the MPPR particles of the POSS-coated monomolecular intumescent flame retardant in the PP matrix is also improved, so that the flame retardant property and the mechanical property of the PP/MPPR/POSS flame retardant composite material are improved.

Based on the discovery, the flame-retardant polypropylene composite material is further explored and optimized, and the invention further provides an MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material which mainly comprises the following components in parts by weight:

78 parts of polypropylene, namely polypropylene, and (C),

20-21 parts of a monomolecular intumescent flame retardant MPPR,

1-2 parts of octavinyl oligomeric silsesquioxane;

wherein the total weight parts of the polypropylene, the single-molecule intumescent flame retardant MPPR and the octavinyl oligomeric silsesquioxane are 100 parts.

Generally speaking, a person skilled in the art can select a suitable blending processing and forming manner according to the actual requirement and the prior art according to the mixture ratio of the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material, for example, a suitable polypropylene/filler system blending forming preparation process means recorded in the prior art, such as twin-screw extrusion forming, hot press forming, vulcanization forming, and the like, so as to prepare the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material.

In order to better illustrate the invention and provide a preferable technical scheme, the preparation method of the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material mainly comprises the following steps:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR, polypropylene and octavinyl oligomeric silsesquioxane to obtain a mixture, adding the mixture into an internal mixer, carrying out internal mixing treatment for 5-10 min, and collecting the obtained internal mixing mixture; wherein the banburying treatment temperature is 180-200 ℃, and the screw rotating speed is 40-50 rpm;

and secondly, cooling the banburying mixture obtained in the step I, crushing and granulating to obtain the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material.

The method comprises the following steps of mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR, polypropylene and octavinyl oligomeric silsesquioxane uniformly to obtain a mixture, and optionally blowing and drying the mixture and the mixture at a constant temperature of 80-90 ℃ to constant weight before adding the mixture into an internal mixer.

The inventor of the invention finds that the addition amount of the monomolecular intumescent flame retardant MPPR can be reduced by 4-5 wt% by selecting and adding 1-2 wt% of the octavinyl oligomeric silsesquioxane through actual comparison experiments, the flame retardant has the optimal flame retardant comprehensive performance, and the char forming capability of a PP/MPPR flame retardant system condensed phase can be obviously improved.

However, it is important to point out that the continuous increase of the substituted amount (more than 2 wt%) of POSS (polyhedral oligomeric silsesquioxane) serving as a synergistic flame retardant reduces the carbon residue rate of the system, thereby deteriorating the flame retardant performance of the material. This is mainly due to the following two reasons: on one hand, the char forming capability of POSS is poorer than that of MPPR, and the increase of POSS content means that the MPPR content of the main flame retardant playing the main flame retardant role is correspondingly reduced, so that the flame retardant performance of the material is influenced by the relative reduction of MPPR, and the carbon residue rate of the flame retardant material is reduced; on the other hand, more POSS nano-particles are added and are easy to agglomerate, so that the dispersion of the MPPR (maximum power point regulator) as the main flame retardant in matrix resin and the carbonization reaction of the POSS participating in the PP macromolecular chain are influenced, and the carbonization capability and the carbon residue rate of the flame-retardant PP composite material are reduced. Meanwhile, the mechanical performance of the system is reduced by reducing the substitution amount (less than 1 wt%) of POSS (polyhedral oligomeric silsesquioxane) serving as the synergistic flame retardant, and the reason is also that the MPPR (modified Polypropylene) serving as the flame retardant has poor interface compatibility with a PP matrix.

Tests prove that the prepared MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material has the vertical combustion performance reaching UL 94V-0 grade, the limited oxygen index reaching 27.6 percent, the tensile strength reaching 32.3Mpa, and the notch impact strength reaching 2.92kJ/m². It is obvious that under the premise of not obvious difference of flame retardant property, the addition amount of the flame retardant is less, and the mechanical property is closer to that of pure PP.

In general, in addition to the components, the present invention may be added with other processing aids known in the art, such as pigments, antioxidants, and the like. However, it is a prerequisite that these processing aids do not adversely affect the achievement of the objects of the present invention and the achievement of the advantageous effects of the present invention.

The technical scheme of the invention has the following beneficial effects:

the invention provides a monomolecular intumescent flame retardant MPPR, which is mixed with polypropylene to prepare an MPPR flame-retardant polypropylene composite material, and the vertical burning, the limited oxygen index and the cone calorimetry test result show that the flame-retardant property of the polypropylene is obviously improved by adding the monomolecular intumescent flame retardant MPPR. In addition, by limiting the preparation method of the MPPR, the time required by preparation is greatly shortened through the reaction mechanism, and the time required by industrial preparation is greatly reduced compared with the existing preparation process of the MPPR.

And secondly, the comprehensive flame retardant property of the MPPR flame retardant polypropylene composite material is proved by adopting thermogravimetric analysis and SEM analysis of a condensed phase carbon layer. The result shows that the MPPR has the flame retardant function of both gas phase and condensed phase. For gas-phase flame retardance, MPPR is heated and decomposed to generate non-combustible gas, so that the concentration of the combustible gas is diluted, and the combustion of the material is inhibited. For condensed phase flame retardance, the MPPR acid source catalyzes part of carbon sources to generate carbon reaction and promote the carbonization of a polymer matrix through phosphoric acid generated by thermal decomposition, and meanwhile, gas generated by thermal decomposition enables the carbon layer to expand to form an expanded carbon layer, so that the transfer of external hot oxygen is isolated, the further combustion of the bottom matrix is prevented, and the flame retardant effect is realized.

The invention also provides a technical scheme of synergistic flame retardance of POSS to MPPR. Vertical burning test, LOI test and cone calorimetry test data show that the flame retardant property of the MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material is obviously improved, and the POSS has an obvious synergistic flame retardant effect on the MPPR.

And (IV) SEM, FTIR and Raman analysis of the carbon residue show that the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material has better comprehensive flame-retardant effect. In the combustion process of the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material, MPPR is heated and decomposed to release non-combustible gas and generate an expanded carbon layer, and POSS is heated and decomposed to generate nano SiO₂The particles cover the surface of the carbon layer, so that a more stable silicon-containing carbonized layer is formed and thermal oxygen transfer is isolated. On the other hand, the POSS particles also participate in the carbonization reaction of the PP macromolecular chains in the material combustion process, so that the macromolecular chain structure of the PP matrix is more retained in the residual carbon condensed phase, the residual carbon rate and the condensed phase carbon layer quality of the flame-retardant polypropylene composite material are improved, and the purpose of obviously improving the flame-retardant phase is realized.

The preparation method of the MPPR/POSS/glass fiber composite synergistic halogen-free flame-retardant polypropylene composite material provided by the invention has the advantages of simple process, short flow and no three-waste pollution in the production process, and can provide a new method and a new technology for preparing the expanded flame-retardant PP composite material with excellent comprehensive performance.

Drawings

FIG. 1 is a schematic diagram of a specific reaction process and a mechanism of the preparation method of the single-molecule intumescent flame retardant MPPR.

FIG. 2 is a diagram of the infrared spectrum analysis of the MPPR of the unimolecular intumescent flame retardant prepared in Synthesis example 1 of the invention. As can be seen, in the infrared spectrum of PA, the characteristic absorption peaks corresponding to PA are 3410cm respectively^-1(P-OH)，1061cm^-1(P ═ O) and 859cm^-1(P-O in P-O-C); in the PER spectrum, 3326cm^-1Is a C-OH characteristic absorption peak. Compared with PA and PER, the-OH absorption peak of the intermediate PA … PER hydrogen bond complex is 3332cm^-1In between. the-OH absorption peak of PA … PER shifts to a lower wavenumber than PA, and a red shift occurs. The reason for this change is that the addition of PER breaks the intermolecular hydrogen bonds between PA and PA, while a new intermolecular hydrogen bond PA … PER is formed between PA and PER, the new intermolecular hydrogen bond interaction force being stronger than the PA's own hydrogen bond interaction. In addition, the P-O absorption peak of intermediate PA … PER is from 859cm^-1Move to 872cm in the direction of high wave number^-1This is due to the reduced interaction between P and O under hydrogen bonding. Compared with an intermediate PA … PER, a series of new characteristic absorption peaks appear in the infrared spectrum of the MPPR. Wherein, the characteristic absorption peak is 1673cm^-1、1499cm^-1And 1403cm^-1Triazine ring derived from ME, 3364cm^-1is-NH₂3143cm for the absorption of stretching vibration^-1Is NH⁺1174cm of^-1Then corresponds to PO^2-The characteristic absorption indicates that the PA and the ME have undergone salt forming reaction in aqueous solution to generate functional groups of-PO-HN + ≦ and the second functional group is obtained. The infrared analysis results prove that the related reactions occur in the figure, and also prove that the MPPR (maximum power point tracking) of the monomolecular intumescent flame retardant is successfully synthesized.

FIG. 3 is a graph showing TG and DTG curves of the MPPR prepared in Synthesis example 1 of the present invention. As can be seen, MPPR has only one main decomposition peak, the initial thermal decomposition temperature is 238 ℃, the maximum thermal decomposition rate is about 0.28%/DEG C, and the processing temperature of PP is generally 180-220 ℃. In addition, the carbon residue rate of the MPPR at 700 ℃ is as high as 41.9 percent, and the high carbon residue rate is also beneficial to efficiently playing the flame retardant role of the flame retardant. Therefore, the MPPR prepared has good thermal stability and can meet the requirements of PP flame-retardant modification and molding processing.

FIG. 4 is photographs of samples prepared in application examples 1 to 3 according to the present invention and in application example 1 in a vertical burning test, in which (a) is a sample prepared in application example 1, (b) is a sample prepared in application example 3, (c) is a sample prepared in application example 2, and (d) is a sample prepared in application example 1. It can be seen that the PP/MPPR (82/18, w/w) sample has poor flame retardant properties, burns all the way to the fixture after ignition, cannot self-extinguish, and therefore cannot pass the vertical burn rating test; after 20 wt% MPPR is added, the composite material can extinguish combustion flame only by taking away partial heat through molten drop dripping after the second ignition, so that the grade of UL 94V-2 (3.2mm) can be achieved only; when 22 wt% of MPPR is added, no molten drop is generated when the PP flame retardant material is combusted, but the sum of the two ignition self-extinguishing times exceeds 10s, and the grade of UL 94V-1 can be achieved according to the UL94 standard; after the flame retardant content is further increased to 25 wt%, the PP/MPPR composite material can reach UL 94V-0 grade, and the flame retardant property is obviously improved. Meanwhile, it can be seen that all PP/MPPR flame-retardant sample strips generate an expanded carbon layer after being ignited, namely, an acid source (PA) part in the MPPR is heated and decomposed to generate inorganic acid (metaphosphoric acid), the inorganic acid catalyzes a carbon source (PER) part to generate a carbon reaction, and meanwhile, a gas source part is decomposed to generate non-flammable gas (NH)₃、N₂Etc.) to cause the carbon layer to expand. The generated expanded carbon layer can effectively isolate the transmission of PP matrix and external heat and oxygen, and prevent the further combustion of the bottom matrix, thereby realizing the purpose of flame retardance.

FIG. 5 is a graph showing the results of cone calorimetry tests on samples prepared in application example 1 of the present invention. It can be seen from (a) and (b) that the ignition time of pure PP is 40s, which is shorter after ignitionA large amount of heat is released within 40-300 s, and the PHRR value and the THR value of the heat release reach 1463kW/m respectively²And 155MJ/m². The ignition time of the sample prepared in application example 1 (25MPPR75PP) was advanced to 26s compared to the pure PP, due to the fact that the flame retardant promoted the advanced degradation of the PP. In addition, the PHRR value of the flame-retardant PP material is reduced to 189kW/m²THR is reduced to 139MJ/m²The addition of the flame retardant MPPR obviously reduces the HRR and THR of the PP composite material, and proves that the flame retardant can obviously improve the flame retardant property of PP. From (c) and (d), it can be seen that the SPR and TSP curves of the sample (25MPPR75PP) prepared in application example 1 are significantly decreased relative to the pure PP, and the smoke release rate and the total smoke release amount are respectively decreased from 0.155m of the pure PP sample²S and 20.3m²Down to 0.038m²S and 16.4m²This indicates that MPPR addition has an inhibitory effect on smoke release.

FIG. 6 is a graph of mass loss versus time for samples prepared in application example 1 of the present invention. Obviously, after the MPPR is added, the average mass loss rate of the flame-retardant PP composite material is reduced, and the carbon residue rate of the flame-retardant PP composite material after a cone calorimetry test is up to 25.1%, which shows that the MPPR has the function of promoting carbon formation.

FIG. 7 is a digital photograph of carbon residue after a cone calorimeter test of a sample (b) prepared in application example 1 and pure PP (a) according to the present invention. As can be seen, pure PP has no residue after combustion, but the sample prepared in application example 1 still has a great deal of carbon residue after combustion and the formed carbon layer has higher expansion degree, which indicates that MPPR

The gas phase flame retardant effect is exerted by releasing inert gas in the combustion process.

FIG. 8 is a Scanning Electron Microscope (SEM) image of samples prepared in application example 1, application example 3 and application comparative example 1 of the present invention, wherein (a), (b) are samples of application comparative example 1, (c), (d) are samples of application example 3, and (e), (f) are samples of application example 1. From the SEM images, it can be seen that the carbon layer densification and degree of expansion gradually increase with increasing MPPR content of the flame retardant. When the addition amount of the MPPR is increased to 25 wt%, a carbon layer formed after combustion is continuous and compact, and the quality of the carbon layer is greatly improved. Generally, the carbon layer can affect the flame retardant property of the material by its barrier effect against external oxygen and combustible gas generated by decomposition of the matrix resin. Therefore, the carbon layer formed in the combustion process of the PP/MPPR flame retardant material can better play the condensed phase flame retardant role. Therefore, the MPPR can play the flame retardant role of gas phase and condensed phase simultaneously in the combustion process, and has obvious effect of improving the flame retardant property of the PP material.

FIG. 9 shows C of carbon residue formed at 500 ℃ in a sample prepared in application example 1 of the present invention_1sAnd P_2pXPS spectra of (a). The XPS test results confirmed that some products with stable chemical structures were formed during combustion. In the C1s spectrum, the peak at 284.7eV is assigned to a C-C or C ═ C bond, while the spectral peaks near 285.7eV and 288.6eV are assigned to C-O (and/or C-N) and C ═ O bonds, respectively, in the degradation products of flame retardant PP materials. P_2pTwo different energy spectrum peaks appear in the spectrum, wherein the energy spectrum peak near 134.8eV is attributed to an O ═ P-O-C group, and the energy spectrum peak near 134.1eV is attributed to pyrophosphate and/or polyphosphate, so that the P element in the flame retardant participates in a condensed phase carbonization reaction in the degradation process of the PP/MPPR composite material.

FIG. 10 is a Scanning Electron Microscope (SEM) image of brittle sections of samples prepared according to application example 4, application comparative example 2 and application comparative example 3 of the present invention. It can be seen that the samples (a and b) of comparative example 2 have smooth brittle fracture surfaces and do not have defects such as holes, because the POSS particles have small sizes and are well compatible with the matrix, but it is also noted that the POSS nanoparticles are significantly agglomerated due to the excessive POSS addition (22 wt%), and the agglomerated POSS particles cannot be well dispersed in the polypropylene matrix. The samples (c and d) of comparative example 3 were applied, and had rough brittle fracture surfaces, and had significant agglomerated flame retardant particles and large pores (formed by separation of the flame retardant particles from the PP matrix at brittle fracture), indicating that the compatibility and dispersibility of the flame retardant particles in the PP matrix were poor; application example 4 samples (e and f) were relatively flat in cross section, less flame retardant particles were exposed on the surface of the samples, and the hole diameters caused by defects were significantly reduced. This is because the presence of POSS particles is beneficial for improving the dispersibility and interfacial compatibility of MPPR flame retardant particles in the PP matrix, allowing the flame retardant particles to be uniformly dispersed in the PP matrix resin.

FIG. 11 is a graph showing cone calorimetry results of samples prepared in application example 4 and application comparative example 3 of the present invention and pure PP (PP 0). From (a), pure PP (PP0) burns rapidly and intensely, and the Heat Release Rate (HRR) curve shows a strong single peak, which indicates that PP releases a large amount of heat in a short time (30-350 s). The Peak HRR (PHRR) of the pure PP (PP0) reaches 1025kW/m². The PHRR value of the sample (PP2) using comparative example 3 was greatly reduced to 315kW/m when 22 wt% MPPR filler was added². The PHRR value of application example 4 sample (PP3) was further reduced to 252kW/m²Time to reach PHRR (t)_-PHRR) Delaying to 200 s. Meanwhile, the HRR of the PP3 is continuously reduced after 200s, which indicates that the condensed-phase carbon formation reaction in the corresponding PP/MPPR/POSS system is continuously carried out and the quality of the formed condensed-phase carbon layer is continuously improved. Therefore, when a small amount of MPPR flame retardant is replaced by POSS particles, the flame retardant property of the material is not reduced, and the flame retardant property of the material is obviously improved.

FIG. 12 is a graph of mass loss versus time for samples prepared according to application example 4 of the present invention, using comparative example 3, and pure PP (PP 0). It is clear that the quality of pure PP decreases rapidly with time, leaving almost no carbon residue. After the MPPR or MPPR/POSS composite flame retardant is added into the PP, the mass reduction rate of the flame-retardant PP composite material in the combustion process is obviously inhibited, and the mass retention rate of the residual carbon is obviously increased. In addition, by comparing the mass loss curves of PP2 and PP3, the carbon residue mass of the latter at different times is found to be significantly higher than that of the former, and the final carbon residue rates of PP2 and PP3 are 10.8% and 18.0%, respectively. Obviously, the MPPR/POSS synergistic flame retardant system is superior to the MPPR flame retardant which is used alone in the aspects of promoting the formation of a carbon layer and reducing the heat release rate, and can better slow down the combustion of a PP matrix material.

Fig. 13 is a Scanning Electron Microscope (SEM) image of a flame retardant PP material carbon layer after a cone calorimetry test of samples prepared in application example 4 and application comparative example 3 of the present invention. It can be seen that the carbon layer of PP2 samples (a and b) has a higher degree of expansion, but has more pores, and can not effectively isolate the matrix resin from the external hot oxygen during combustion. On the contrary, the applicationThe carbon layer quality of sample 4(PP3) was significantly improved (c and d), forming a continuous dense carbon layer. In addition, if the SEM photograph (d) of the carbon layer of the flame retardant sample PP3 is carefully observed, it is found that the surface of the carbon layer after burning of the sample is obviously covered with many fine white particles. In order to determine the composition of these white particulate matters, the PP2 and PP3 carbon layers were analyzed by EDS in comparison, and as a result, it can be seen that the carbon residue of the PP2 sample is composed of three elements C, O and P, and the surface of the carbon residue of the PP3 sample also contains Si element. Therefore, it is reasonable to consider that the white particulate matter covering the surface of the PP3 carbon layer is SiO formed by the decomposition of POSS introduced in the sample₂Particles. These SiO₂The particles can effectively enhance the strength of the carbon layer and prevent the carbon layer from being oxidized and degraded, thereby preventing the transfer of combustible gas and heat in the combustion process and showing the excellent synergistic flame-retardant effect of POSS.

Detailed Description

The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.

The following synthetic examples, application examples and application comparative examples adopt experimental raw materials and reagents:

polypropylene (PP): t30s, Mao Ming division of China petrochemical company Limited;

phytic Acid (PA): aladdin Biotechnology Ltd;

melamine (ME): industrial purity, 99.8% purity, Chengdu Yulong chemical Co., Ltd;

pentaerythritol (PER): purity 98.0%, Tianjin City Guang & lt & gt Fine chemical research institute;

dipentaerythritol (DPER): 95.0% purity, Anhui gold grain industries, Ltd;

tripentaerythritol (TPER): purity 95.0%, wuhan fuxin distance science and technology limited;

deionized water: is sold on the market;

octavinyl oligomeric silsesquioxanes (OV-POSS): zhengzhou alpha chemical Co., Ltd;

chopped Glass Fiber (GF): 508A, megalite group, Inc.;

maleic anhydride grafted polypropylene (MAPP): grafting rate is 1.2%, and Kangjin new material of Dongguan city, Guangdong province

Science and technology limited;

antioxidant 1010: purity 99%, Kangjin New Material science and technology Co., Ltd, Dongguan city.

The following synthesis examples, application examples and main experimental equipment adopted in the application comparative examples are as follows:

electric heating constant temperature air blast drying cabinet: DHG-9245 type A, Shanghai-constant technology Instrument Co., Ltd;

torque rheometer: model RM-200C, Haerbin Hacept electric technology, Inc.;

a plate vulcanization press: model YJ63, gumeri zui chuanghong manufacturing ltd;

a double-screw extruder: TSSJ-25, enhanced tools Equipment, Midlin-blue Chenguang chemical research institute;

fourier transform infrared spectrometer (FT-IR): nicilet model 6700, Saimer Feishell science;

limiting oxygen index tester: model JF-3, south kyo jiangning analytical instruments ltd;

vertical (horizontal) combustion integrated tester: model LZB-3WB, Kite instruments Inc. of Dongguan;

CONE Calorimeter (CONE): FTT0007 type, FTT corporation, uk;

micro Combustion Calorimeter (MCC): FAA type, uk combustion testing technology corporation;

x-ray photoelectron spectrometer (XPS): AXIS Supra, Kratos, UK;

pendulum impact tester: PIT-501J model, Shenzhen Wan testing verification equipment Limited;

notch type sampling machine: 4302Instron model, Shenzhen, New Miss materials detection Limited;

universal testing machine: instron 5967, inte & ltd & gt;

scanning Electron Microscope (SEM): XSAM type 800, FEI USA;

thermogravimetric analyzer (TGA): model Q50, TA corporation, usa;

differential Scanning Calorimeter (DSC): model Q20, TA corporation, usa;

a Raman spectrum analyzer: RA802, Renishaw corporation, uk;

melt flow rate tester: model ZRZ1442, meits industrial systems (china) ltd.

The following synthesis examples, application examples and test and characterization methods adopted by the application comparative examples are as follows:

fourier transform infrared spectroscopy (FT-IR) analysis: preparing a sample by a KBr tabletting method, and using a Nicolet 20SXB infrared FT-IR spectrometer at 400-4000 cm^-1And scanning and recording a Fourier infrared spectrogram.

Thermogravimetric (TGA) analysis: thermogravimetric analysis (TGA) was carried out on a sample at a temperature range of 50 to 700 ℃ at a temperature rise rate of 10 ℃/min under a nitrogen or air atmosphere using a Q50 type thermogravimetric analyzer (TA Corp., USA), with a gas flow rate of 50mL/min and a sample mass of about 5 mg.

Differential Scanning Calorimetry (DSC) analysis: DSC curves of the samples were recorded using a differential scanning calorimeter model Q-20 (TA Co., USA). The sample mass was about 7mg and was measured between 0 and 200 ℃ at a heating rate of 10 ℃/min under a nitrogen flow of 50 mL/min.

Micro Combustion Calorimetry (MCC) test: about 4-5 mg of the sample was taken and the heat release of the sample was measured on a FAA type micro combustion calorimeter (British Combustion test technology) at a heating rate of 1 ℃/s under a nitrogen atmosphere of 80mL/min, wherein the test temperature range was 80 ℃ to 750 ℃.

Limiting Oxygen Index (LOI) test: the LOI test was carried out on an oxygen index tester model JF-3 according to ASTM D2863-97, with sample sizes of 100mm by 6.5mm by 3.0 mm.

Vertical burning UL94 test: the vertical burn performance test was performed on a vertical (horizontal) burn integrated tester according to ASTM D3801 test standards, with sample dimensions of 127mm by 12.7mm by 3.2 mm.

Synthesis example 1

The preparation method of the single-molecule intumescent flame retardant MPPR comprises the following steps:

(1) preparing phytic acid solution by 0.05mol of phytic acid and 200ml of deionized water;

(2) adding pentaerythritol into the phytic acid solution obtained in the step (1), and stirring and reacting for 1h at the temperature of 95-100 ℃; adding melamine, and continuously stirring and reacting for 0.5h at the temperature of 95-100 ℃ to obtain a yellow clear and transparent mixed solution;

(3) and (3) cooling the mixed solution obtained in the step (2), and drying to constant weight to obtain the white blocky monomolecular intumescent flame retardant MPPR.

Wherein, the mol ratio of the phytic acid, the pentaerythritol and the melamine used in the preparation method is 1: 2.5: 2.

synthesis example 2

The preparation method of the single-molecule intumescent flame retardant MPPR comprises the following steps:

(1) preparing phytic acid solution by 0.1mol of phytic acid and 600ml of deionized water;

(2) adding dipentaerythritol into the phytic acid solution obtained in the step (1), and stirring and reacting for 1.5 hours at the temperature of 95-100 ℃; adding melamine, and continuously stirring and reacting for 1h at the temperature of 95-100 ℃ to obtain a yellow clear and transparent mixed solution;

(3) and (3) cooling the mixed solution obtained in the step (2), and drying to constant weight to obtain the white blocky monomolecular intumescent flame retardant MPPR.

Wherein, the mol ratio of the phytic acid, the dipentaerythritol and the melamine used in the preparation method is 1: 2.4: 2.1.

synthesis example 3

The preparation method of the single-molecule intumescent flame retardant MPPR comprises the following steps:

(1) preparing phytic acid solution by 0.15mol of phytic acid and 1000ml of deionized water;

(2) adding tripentaerythritol into the phytic acid solution obtained in the step (1), and stirring and reacting for 2 hours at the temperature of 95-100 ℃; adding melamine, and continuously stirring and reacting for 1h at the temperature of 95-100 ℃ to obtain a yellow clear and transparent mixed solution;

(3) and (3) cooling the mixed solution obtained in the step (2), and drying to constant weight to obtain the white blocky monomolecular intumescent flame retardant MPPR.

Wherein, the mol ratio of the phytic acid, the tripentaerythritol and the melamine used in the preparation method is 1: 2.6: 1.9.

application examples 1 to 3 and application comparative example 1

The application examples 1-3 and the application comparative example 1 are a preparation method of MPPR flame-retardant polypropylene composite material by mixing the single-molecule intumescent flame retardant MPPR prepared in the synthesis example 1 and polypropylene, and mainly comprise the following steps:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR and polypropylene to obtain a mixture, adding the mixture into a torque rheometer for melt blending, carrying out banburying treatment for 5-10 min, and collecting the obtained banburying mixture; wherein the screw rotating speed of the torque rheometer is 40-50 rpm;

secondly, carrying out hot press molding treatment on the banburying mixture obtained in the step one through a flat vulcanizing machine to obtain the MPPR flame-retardant polypropylene composite material; wherein the hot pressing temperature of the plate vulcanizing machine is 190 ℃.

In the preparation method, the polypropylene and the monomolecular intumescent flame retardant MPPR are calculated according to the following weight parts, wherein the application examples 1-3 and the application comparative example 1 are as follows:

	polypropylene	Single-molecule intumescent flame retardant MPPR
			Application example 1	75	25
Application example 2	78	22
			Application example 3	80	20
Application comparative example 1	82	18

The results of the vertical burning UL94 test and the limiting oxygen index test of the application examples 1-3, the application comparative example 1 and the pure PP are shown in the following table:

the cone calorimetry test was performed on the above application example 1 with pure PP, and the results are shown in the following table:

the EHC values given in the table above reflect the extent of combustion of volatile gases in the gas phase. It can be seen that the EHC value of pure PP was 39.5MJ/kg, whereas the EHC value of the sample prepared in application example 1 was reduced to 33.8 MJ/kg. Obviously, the addition of the flame retardant MPPR significantly reduces the EHC and HRR values of the PP material, indicating that the added MPPR plays a flame retardant role mainly in the gas phase and the condensed phase during the combustion process. In one aspect, MPPR decomposition produces non-combustible gases (e.g., CO)₂And NH₃) The concentration of combustible gas generated by PP degradation is diluted, thereby reducing the combustion of materials to a certain extentDegree of the disease. On the other hand, the inorganic acid generated by the decomposition of the acid source in the MPPR catalyzes the dehydration reaction of the carbon source and forms a char layer, thereby isolating the hot oxygen and preventing further combustion of the PP matrix.

Thermogravimetric analysis is carried out on the application examples 1-3, the application comparative example 1 and pure PP respectively under a nitrogen atmosphere and an air atmosphere, and the results are as follows:

it is obvious that in N₂Initial decomposition temperature (T) of pure PP under an atmosphere_onset) At 407.1 ℃ and T_maxThe value (temperature corresponding to the maximum decomposition rate) was 447.9 ℃ and the carbon residue rate after degradation was 0. After the flame retardant MPPR is added, the initial decomposition temperature of all flame retardant PP samples is lower than that of pure PP, which may be caused by the decomposition of the added flame retardant MPPR on one hand, and the MPPR which is added on the other hand promotes the early decomposition of PP (240-410 ℃). Thereafter, as the degradation proceeds, the degradation rate of the PP/MPPR composite material is lower than that of the pure polypropylene material after 410 ℃, because the MPPR promotes the formation of the expanded carbon layer of the PP/MPPR composite system in the early decomposition stage, and inhibits the degradation of the PP matrix, and therefore, the thermal stability of the flame retardant polypropylene is gradually higher than that of the pure PP. In the final decomposition stage, the maximum decomposition rate of the PP/MPPR flame retardant material corresponds to a temperature value and the carbon residue rate at 700 ℃ which are both higher than those of pure PP, wherein the T of the PP/MPPR (75/25, w/w) composite material is_maxThe value of 457.7 ℃ and the final char yield is as high as 11.4%, which shows the best thermal stability in all flame retardant materials. This is because the MPPR improves the thermal stability of the carbon residue formed at high temperature of the PP flame retardant sample, which is advantageous for improving the flame retardant property thereof.

Under the air atmosphere, the thermal degradation behavior of PP and PP/MPPR flame-retardant samples is obviously changed. T of pure PP_onsetThe values and the char yield at 700 ℃ were 242.7 ℃ and 0.1%, respectively. Initial decomposition temperature and T of PP/MPPR (75/25, w/w) samples compared to neat PP_maxThe values are increased by 5.3% and 106%, respectively, and the maximum thermal decomposition rate is reduced by about 40%. The above analytical results show thatT of all flame retardant PP samples after MPPR_onsetThe values are all obviously higher than pure PP, and the T of the material_maxThe value is increased along with the increase of the MPPR content, which shows that the addition of the flame retardant is beneficial to improving the thermal stability of the PP/MPPR flame-retardant composite material in the air, and further improving the flame retardant property of the PP/MPPR flame-retardant composite material.

Differential scanning calorimetry analysis was performed on the above application examples 1-3, application comparative example 1, and pure PP, and the results are shown in the following table:

obviously, the addition of MPPR changes the melting crystallization behavior of the flame-retardant PP material and the initial crystallization temperature (T) of the PP/MPPR flame-retardant composite material_onset-c) And crystallization peak temperature (T)_c) Is obviously higher than pure PP, and shows that MPPR has heterogeneous nucleation effect on PP crystals. Furthermore, as the MPPR content increases, the melting temperature (T) of the material_m) And degree of crystallinity (X)_c) With an increasing trend. This is probably because the MPPR plays a role as a nucleating agent in the crystallization process, and increasing the MPPR content means the enhancement of heterogeneous nucleation effect thereof, which enables the PP to be crystallized at a higher temperature, and at this time, the activity of the PP macromolecular chain is higher, and crystals with higher crystal perfection can be formed, thereby being beneficial to improving the crystallinity of the PP/MPPR composite material, but also possibly leading to the reduction of the impact property of the material, which is consistent with the subsequent mechanical property test result.

The application examples 1-3, the application comparative example 1 and pure PP are subjected to mechanical property test, and the results are as follows:

it can be seen that the mechanical properties of pure PP are the best, with a tensile strength of 32.0MPa and a notched impact strength of 3.15kJ/m². After the flame retardant is added, the mechanical properties of the PP material are reduced to different degrees.

Combining the analysis results of UL94, LOI, CONE, TGA, SEM and XPS, the MPPR flame retardant polypropyleneThe flame retardant mechanism of alkenes is summarized as follows: first, the acid source (PA) portion of the MPPR is thermally decomposed to produce phosphoric acid, which catalyzes the char-forming reaction in the char source (PER) portion and accelerates the carbonization of the polymer matrix. Meanwhile, MPPR is heated and decomposed to generate non-combustible gas NH₃And CO₂And the like. On one hand, the incombustible gas dilutes the concentration of the combustible gas and inhibits the combustion of materials; on the other hand, the escaped gas can expand the carbon layer to form an expanded carbon layer, so that the external oxygen and heat transmission is isolated, the further combustion of the polymer bottom layer substrate is prevented, and the flame retardant effect is realized. Therefore, the flame retardant MPPR has the flame retardant effects of both gas phase and condensed phase.

Application examples 4 to 5 and application comparative examples 2 to 4

The application examples 4-5 and the application comparative examples 2-4 are preparation methods of MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material by mixing the single-molecule intumescent flame retardant MPPR prepared in the synthesis example 1 with polypropylene and octavinyl oligomeric silsesquioxane, namely the preparation method of the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material mainly comprises the following steps:

uniformly mixing component raw materials mainly comprising a monomolecular intumescent flame retardant MPPR, polypropylene and octavinyl oligomeric silsesquioxane to obtain a mixture, adding the mixture into an internal mixer, carrying out internal mixing treatment for 5-10 min, and collecting the obtained internal mixing mixture; wherein the banburying treatment temperature is 180-200 ℃, and the screw rotating speed is 40-50 rpm;

and secondly, cooling the banburying mixture obtained in the step I, crushing and granulating to obtain the MPPR/POSS composite synergistic halogen-free flame-retardant polypropylene composite material.

In the preparation method, the unimolecular intumescent flame retardant MPPR, the polypropylene and the octavinyl oligomeric silsesquioxane (OV-POSS) are prepared from the following components in parts by weight in application examples 4-5 and application comparative examples 2-4:

	polypropylene	Single-molecule intumescent flame retardant MPPR	OV-POSS
				Comparative application example 2(PP1)	78	0	22
Comparative application example 3(PP2)	78	22	0
				Application example 4(PP3)	78	21	1
Application example 5(PP4)	78	20	2
				Comparative application example 4(PP5)	78	18	4

Thermogravimetric analysis was performed on the above application examples 4-5, application comparative examples 2-4, pure PP (PP0) and pure OV-POSS under a nitrogen atmosphere, and the results are shown in the following table:

it can be seen that pure PP rapidly decomposes between 410 ℃ and 480 ℃ in a nitrogen atmosphere at a temperature (T) corresponding to the maximum thermal decomposition rate_max) Occurs at 447.9 ℃. And the initial decomposition temperature (T) of all the PP composite materials added with the flame retardant_onset) Both are lower than pure PP due to early decomposition of the added flame retardant. Meanwhile, OV-POSS shows a one-step degradation process (230-300 ℃) in a nitrogen atmosphere, and the carbon residue rate of the OV-POSS is only 2.6%. Compared with pure PP and POSS, the carbon residue rate of the PP/POSS sample (PP1) reaches 2.9 percent and is higher than the theoretical calculated value of 0.64 percent, which indicates that POSS participates in the carbon forming reaction of PP molecular chains. In addition, the POSS is added at the temperature of 300-340 ℃ to promote the degradation of PP, which shows that inorganic SiO generated by POSS particles through thermal decomposition₂The particles participate in condensed phase carbon layer reactions in subsequent flame retardant systems, which will also be further verified in subsequent carbon layer SEM and EDS. T of PP/MPPR and PP/MPPR/POSS samples_maxThe value is higher than that of pure PP, because the expanded carbon layer formed by decomposing the flame retardant MPPR in the initial stage isolates the contact between the internal matrix material and external oxygen, and the degradation of the PP matrix is inhibited to a certain extent. When the temperature is increased to 700 ℃, pure PP is completely decomposed without any residual carbon, but the carbon residue rate of the flame-retardant PP composite material containing MPPR/POSS compound or MPPR is obviously increased, and especially for the flame-retardant system with the same load, the maximum carbon residue rate (10.1%) can be achieved at 700 ℃ by a flame-retardant PP sample (PP3) containing 1 wt% of POSS, which is higher than that of a flame-retardant PP sample without POSS (PP2, the carbon residue rate is 9.0%). This shows that the addition of 1 wt% POSS to the flame retardant PP composite material can significantly improve the char forming ability of the PP/MPPR flame retardant system condensed phase. Continuing to increase the substitution level (2 wt% or more) of the synergistic flame retardant POSS reduces the char yield of the system, thereby deteriorating the flame retardant properties of the material. This is mainly due to the following two reasons: on the one hand, the carbon forming capability of POSS is poorer than that of MPPR (maximum power point register), and the increase of the content of POSS means that the content of MPPR (maximum power point register) serving as a main flame retardant is correspondingly reduced, so that the relative reduction of MPPR (maximum power point register)The flame retardant property of the material is rarely influenced, so that the carbon residue rate of the flame retardant material is reduced; on the other hand, more POSS nano-particles are added and are easy to agglomerate, so that the dispersion of the MPPR (maximum power point regulator) as the main flame retardant in matrix resin and the carbonization reaction of the POSS participating in the PP macromolecular chain are influenced, and the carbonization capability and the carbon residue rate of the flame-retardant PP composite material are reduced.

Thermogravimetric analysis is carried out on the application examples 4-5, the application comparative examples 2-4, pure PP (PP0) and pure OV-POSS under an air atmosphere, and the results are shown in the following table:

it can be seen that the flame retardant PP samples have different degradation behavior under different carrier gas atmospheres (air versus nitrogen). Under air atmosphere, T of pure PP_onsetThe value is 259.3 ℃ and T_max325.5 ℃ and a char yield of 0.1% at 700 ℃ showed a one-step degradation process. The POSS particles show two-step degradation process (200-300 ℃ and 300-700 ℃) in air atmosphere, and T is_onsetValue sum T_maxThe values are 226.0 ℃ and 227.5 ℃ respectively. Compared with the thermal decomposition behavior under the nitrogen atmosphere, the carbon residue rate of the POSS is remarkably improved (from 2.6% to 53.7%), which fully indicates that ethylene groups in the POSS molecular structure are oxidized under the action of oxygen in the air atmosphere and participate in the formation of condensed phase carbon residue, and the carbon residue rate of the POSS in the thermogravimetric analysis of the air atmosphere is greatly improved. Meanwhile, the flame-retardant PP composite material is also shown in a two-step degradation process, namely 200-400 ℃ and 400-700 ℃. T of PP1 sample during first degradation step_onsetValue sum T_maxThe values are higher than those of pure PP and POSS, and the heat stability of the PP material can be effectively improved by adding POSS. In addition, the char yield of PP1 increased from 2.9% under nitrogen to 8.3% under air, indicating that the ability of POSS particles to participate in the promotion of coacervate phase char formation reactions was significantly enhanced under air conditions. Unlike nitrogen atmosphere, the initial decomposition temperature of PP3 and PP4 was significantly increased and the thermal decomposition rate was also significantly decreased compared to pure PP, indicating that the majority of PP was present under air atmosphere conditionsThe daughter strands are oxidized and participate in the char formation process. The weight loss in the second degradation process is caused by the re-oxidative degradation of the thermally unstable carbon residue formed in the first degradation process under the air atmosphere. In addition, it was found that the PP3 flame retardant material containing 1 wt% POSS in all samples had the lowest thermal decomposition rate and had the highest char yield of 9.9% at 700 ℃. This is attributable to the fact that the physical barrier formed by the expanded carbon layer produced in the first decomposition prevents further degradation of the internal matrix resin. Of note, with N₂As with the atmosphere, the addition of too many POSS particles (2 wt% or more) also reduces the ultimate char yield of the sample due to agglomeration.

The results of the vertical burning UL94 test and the limiting oxygen index test using the application examples 4-5, the application comparative examples 2-4 and pure PP (PP0) are shown in the following table:

the cone calorimetry tests of application example 4, application comparative example 3 and neat PP (PP0) were performed and the results are given in the following table:

the above table can be further analyzed for flame retardant performance of various PP composites by using the Fire Performance Index (FPI), where FPI is the ratio of ignition time (TTI) to PHRR, and the Fire Growth Rate (FGR), where PHRR to t_-PHRRThe ratio of (a) to (b). Generally, higher FPI values and lower FGR values indicate better flame retardancy. As shown in the above table, the fire performance indexes of pure PP (PP0) and sample of comparative application example 3(PP2) were 0.024sm²kW and 0.057sm²kW, the fire growth rate is 5.69kW/m²s and 1.66k W/m²And s. The sample of application example 4(PP3) had a higher FPI value (0.064 sm) than pure PP and PP2²kW) and lower FGR values (1.26 kW/m)²s) shows that the prepared PP/MPPR/POSS composite material has better flame retardant property. Smoke Release Rate (SPR)) And total smoke emission (TSP), with TSP peaks from 20.27m for PP2 and PP3 compared to pure PP²Respectively reduced to 19.17m²And 16.39m². In addition, the maximum smoke release rate (PSPR) value of PP3 was reduced to 0.049m²S (only 29% of pure PP). The result shows that the MPPR/POSS composite flame retardant has obvious improvement effect on the flame retardant property of PP and also has excellent smoke suppression function: in the combustion process, inorganic rigid silica particles generated by POSS decomposition cover the surface of the carbon layer, thereby effectively inhibiting the combustion of the material. Obviously, combustible gas formed by PP degradation and carbon particles are difficult to escape from the reinforced compact expanded carbon layer in the combustion process, so that the generation of smoke can be effectively reduced.

Differential scanning calorimetry was performed on the above application examples 4 to 5, application comparative examples 2 to 4, and pure PP (PP0), and the results are shown in the following table:

the mechanical property tests of the application examples 4-5, the application comparative examples 2-4 and the pure PP (PP0) are carried out, and the results are as follows:

after the cone calorimetric test, the samples prepared in the application example 4 and the application comparative example 3 are subjected to comparative analysis on the flame-retardant PP material carbon layer by EDS, and the results are as follows:

it is obvious that the content of each element in the carbon layer of different samples between the application example 4 and the application comparative example 3 is greatly changed, namely, when POSS (PP2) is not introduced, the content of the C element in the carbon layer is 47.4 percent, and after POSS (PP3) is added, the content of the C element is improved to 65.6 percent. The above results again strongly indicate that the addition of POSS nanoparticles obviously promotes the participation of PP macromolecular chains in the char formation reaction for forming the coacervate phase carbon layer, thereby improving the char yield of the PP flame retardant material and the coacervate phase carbon layer quality. Therefore, the quality of the condensed phase carbon layer can be obviously improved by utilizing the strong synergistic flame-retardant effect between the MPPR and the appropriate amount of POSS, and the flame-retardant property of the system is improved.