WO2021243836A1 - Flame-retardant masterbatch, preparation method therefor, and application thereof - Google Patents

Abstract

The present invention relates to the field of polymer materials, and provides a flame-retardant masterbatch. A diphenyl phosphine oxide derivative having a specific structure and high thermal stability is used as a flame retardant and also has a melting point similar to that of a resin, so that the dispersity of the diphenyl phosphine oxide derivative in a polymer processing process is improved, and the effect of the flame retardant on melt fluidity is reduced; an antioxidant is used for preventing a polymer from becoming sticky, discolored, embrittled or broken due to decomposition; loading of the diphenyl phosphine oxide derivative and the antioxidant is achieved by means of a carrier resin, and meanwhile, the dispersity and the compatibility of the diphenyl phosphine oxide derivative and the antioxidant are improved. Results of the embodiments show that the flame-retardant masterbatch provided by the present invention shows good compatibility when being applied to resin products, and the flame-retardant effect can reach the V-0 level.

Description

Flame-retardant masterbatch and preparation method and application thereof

This application claims the priority of a Chinese patent application filed with the Chinese Patent Office, the application number is 2020104929794, and the invention title is "a flame-retardant masterbatch and its preparation method and application" on June 3, 2020, the entire content of which is incorporated by reference Incorporated in this application.

Technical field

The present invention relates to the field of polymer materials, in particular to a flame-retardant masterbatch and a preparation method and application thereof.

Background technique

Because of its good mechanical strength, insulation, corrosion resistance, plasticity and high elasticity, polymer materials can be used in different fields such as fibers, containers, films, coatings, engineering plastics, rubber, etc. However, most polymers All materials have a certain degree of flammability. With the improvement of fire safety requirements, higher and higher flame retardant and comprehensive performance requirements are put forward for polymer materials in electronic and electrical, automotive, textiles and other applications. Adding flame retardants to polymer materials is one of the effective methods to improve the flame retardancy of polymer materials.

At present, the commonly used polymer material flame retardants are mainly reactive flame retardants and additive flame retardants. The reactive flame retardant is added to the molecular chain of the resin as a third monomer reaction during the resin synthesis process. It is a permanent flame retardant modification method, but it has disadvantages such as high cost and easily affecting the degree of resin polymerization. Additive flame retardant means that with the addition of the flame retardant, it will not cause the flame retardant to react with the polymer matrix, but use the flame retardant properties of the flame retardant itself to improve the flame retardancy of the polymer material, because it has The advantages of flexible formula and good effect occupy a major position. However, due to the poor compatibility of the additive flame retardant with the matrix polymer, the flame retardant effect is not ideal.

Summary of the invention

The purpose of the present invention is to provide a flame-retardant masterbatch and a preparation method and application thereof. The flame-retardant masterbatch provided by the present invention shows good compatibility when applied to resin products, and has a good flame-retardant effect.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0～70 parts;

The diphenylphosphine oxide derivative has a chemical structure shown in formula I:

In the formula I, n is a positive integer, and R ₁ and R _{2 are} independently one of H, a C ₁ ～C ₆ alkyl group, and an aromatic group;

The melting point of the diphenylphosphine oxide derivative is 200°C to 340°C.

Preferably, the flame-retardant masterbatch includes the following components by weight: 20-60 parts of carrier resin, 20-70 parts of diphenyl phosphine oxide derivative, 3-8 parts of antioxidant, and 5 parts of synergistic flame retardant. ~60 servings.

Preferably, the diphenylphosphine oxide derivative has a chemical structure shown in formula II:

Preferably, the diphenylphosphine oxide derivative has a chemical structure shown in formula III:

Preferably, the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and At least one of bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

Preferably, the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and Two kinds of bis(2,4-dicumylphenyl) pentaerythritol diphosphite are compounded.

Preferably, the synergistic flame retardant is one of metal oxides, metal salts, natural minerals, carbon-based free radical initiators, and organic flame retardants containing at least one of the three elements of phosphorus, nitrogen and silicon. At least one.

Preferably, the metal oxide is at least one of titanium dioxide, zinc oxide and aluminum oxide.

Preferably, the natural mineral is at least one of montmorillonite, hydrotalcite and clay.

Preferably, the metal salt is at least one of zinc borate and zinc stannate.

Preferably, the carbon-based free radical initiator is at least one of 2,3-dimethyl-2,3-diphenylbutane and 2,3-dimethyl-2,3-dinaphthylbutane A sort of.

Preferably, the organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon is zinc diethylphosphinate, polysiloxane, cage silsesquioxane, and hexaphenoxy Cyclotriphosphazene, diphenyl sulfone phenylphosphonate, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, P-xylylene bis (9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), p-xylylene bis (diphenyl phosphine oxide), melamine cyanurate, At least one of melamine polyphosphate, melamine hydrobromide, tris(2,3-dibromopropyl) isocyanurate, aluminum diphenylphosphinate, and aluminum diethylphosphinate.

Preferably, the carrier resin is at least one of polyester, polyamide and polyolefin.

The present invention also provides a method for preparing the flame-retardant masterbatch according to the above technical scheme, which includes the following steps:

(1) Mix the carrier resin, diphenylphosphine oxide derivatives, antioxidants and synergistic flame retardants to obtain a mixture;

(2) The mixture obtained in the step (1) is granulated to obtain a flame-retardant masterbatch.

The present invention also provides the application of the flame-retardant masterbatch according to the above-mentioned technical solution or the flame-retardant masterbatch prepared by the preparation method according to the above-mentioned technical solution in resin products.

Preferably, when the resin product is a polyester fiber film, the synergistic flame retardant in the flame retardant masterbatch is polyphenyl diphenyl phosphonate, zinc diethyl phosphinate, and hexaphenoxy ring three. Phosphononitrile, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, caged silsesquioxane and montmorillonite At least one of.

Preferably, when the resin product is nylon fiber, the synergistic flame retardant in the flame retardant masterbatch is 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphine At least one of phenanthrene-10-oxide) ethane, titanium dioxide and clay.

Preferably, when the resin product is polypropylene fiber film, the synergistic flame retardant in the flame retardant masterbatch is tris (2,3-dibromopropyl) isocyanurate, 2,3-di Methyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-dinaphthylbutane and 1-benzene-1,2-bis(9,10-dihydro-9- At least one of oxy-10-phosphaphenanthrene-10-oxide) ethane.

Preferably, when the resin product is an injection molding material, the synergistic flame retardant in the flame retardant masterbatch is melamine cyanurate, melamine polyphosphate, melamine hydrobromide, aluminum diphenylphosphinate, and diphenylphosphinate. At least one of aluminum ethyl phosphinate, zinc oxide, zinc borate, and hydrotalcite.

Preferably, when the resin product is a cured sheet or a substrate, the synergistic flame retardant in the flame retardant masterbatch is p-xylylene bis (diphenyl phosphine oxide), 1-benzene-1,2-bis( 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10 -At least one of oxide), polysiloxane and cage silsesquioxane.

The present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0～70 parts; the diphenyl phosphine oxide derivative has the chemical structure shown in formula I:

In the formula I, n is a positive integer, and R ₁ and R _{2 are} independently one of H, C ₁ -C ₆ alkyl and aromatic groups; the melting point of the diphenyl phosphine oxide derivative is 200° C. ～340℃. The present invention uses the diphenyl phosphine oxide derivative with the structure of formula I, which has the characteristics of high phosphorus content and good flame retardancy, as the main flame retardant, and at the same time uses its appropriate melting point to improve its dispersibility in the polymer processing process And reduce the influence of flame retardants on melt fluidity; use antioxidants to prevent high molecular polymers from becoming sticky, discolored, brittle or broken due to decomposition; use resins as diphenyl phosphine oxide derivatives and antioxidants The carrier resin is used to realize the loading of p-diphenyl phosphine oxide derivatives and antioxidants, while improving the dispersibility and compatibility of diphenyl phosphine oxide derivatives and antioxidants; finally, the carrier resin, two The combination of phenyl phosphine oxide derivatives and antioxidants improves the flame retardant effect.

Attached drawings

Figure 1 is a TGA thermogravimetric loss analysis diagram of the phosphorus-containing flame retardant of structural formula II prepared in Example 1;

2 is a DSC melting point analysis chart of the phosphorus-containing flame retardant of structural formula II prepared in Example 1;

3 is a TGA thermogravimetric loss analysis diagram of the phosphorus-containing flame retardant of structural formula III prepared in Example 2;

4 is a DSC melting point analysis chart of the phosphorus-containing flame retardant of structural formula III prepared in Example 2.

detailed description

The present invention will be further described below in conjunction with embodiments and drawings.

The present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0～70 parts;

The diphenylphosphine oxide derivative has a chemical structure shown in formula I:

In the formula I, n is a positive integer, and R ₁ and R _{2 are} independently one of H, a C ₁ ～C ₆ alkyl group, and an aromatic group;

The melting point of the diphenylphosphine oxide derivative is 200°C to 340°C.

In the present invention, unless otherwise specified, the raw materials used are all conventional commercial products in the field.

In the present invention, unless otherwise specified, the operations performed are all at room temperature.

In terms of parts by weight, the flame-retardant masterbatch provided by the present invention includes 10 to 70 parts of carrier resin, preferably 20 to 60 parts, and more preferably 50 parts. In the embodiment of the present invention, the weight parts of the carrier resin may specifically be 60 parts, 40 parts, 20 parts or 50 parts. In the present invention, the amount of the carrier resin is controlled within the above range, and the good fluidity of the carrier resin during the melting process can be used to achieve the uniform dispersion effect of the components in the flame-retardant masterbatch and improve the flame-retardant masterbatch. The flame-retardant properties of the pellets can't evenly disperse other ingredients when the dosage is small, and excessive dosage will result in waste of raw materials.

In the present invention, the carrier resin is preferably at least one of polyester, polyamide and polyolefin, more preferably PET polyethylene terephthalate, PBT polybutylene terephthalate, PETG poly At least one of ethylene terephthalate-1,4-cyclohexanedimethanol, polypropylene, SEBS, and PA66 polyhexamethylene adipamide. In the embodiment of the present invention, the type of the carrier resin may specifically be PET, PA66, polypropylene or SEBS. In the present invention, the carrier resin serves as a carrier for the diphenyl phosphine oxide derivative and the antioxidant, and improves the dispersibility and compatibility of the diphenyl phosphine oxide derivative and the antioxidant.

Based on 10 to 70 parts by weight of the carrier resin, the flame-retardant masterbatch provided by the present invention includes 10 to 80 parts of diphenyl phosphine oxide derivatives, preferably 20 to 70 parts, more preferably 20 to 60 parts. In the embodiment of the present invention, the parts by weight of the diphenylphosphine oxide derivative may specifically be 40 parts, 30 parts, 60 parts or 12.5 parts. The use of the diphenylphosphine oxide derivative in the above-mentioned amount in the present invention can ensure the flame-retardant effect of the prepared flame-retardant masterbatch, and if the amount exceeds the above-mentioned amount range, the mechanical properties of the material will decrease.

In the present invention, the diphenylphosphine oxide derivative has a chemical structure shown in formula I:

In the formula I, n is a positive integer, preferably a positive integer from 1 to 5, more preferably 2 or 3; in the formula I, R ₁ and R _{2 are} independently H, C ₁ ～C ₆ alkyl And an aromatic group; preferably one of H and a C ₁ -C ₆ alkyl group, more preferably H.

In the present invention, when n is 2 or 3, and R ₁ and R ₂ are H, the diphenyl phosphine oxide derivative has the chemical structure shown in formula II:

In the present invention, when n is 2 or 3, and R ₁ and R ₂ are H, the diphenyl phosphine oxide derivative has the chemical structure shown in formula III:

In the present invention, the melting point of the diphenylphosphine oxide derivative is 200°C to 340°C, preferably 210°C to 330°C, more preferably 230 to 300°C, more preferably 250 to 280°C. In the embodiment of the present invention, the melting point of the diphenylphosphine oxide derivative may specifically be 272°C or 263°C. The present invention adopts the diphenyl phosphine oxide derivative with the above structure and melting point to solve the problems of uneven dispersion and hygroscopicity of conventional flame retardants, and the halogen-free flame retardant has high phosphorus content and good flame retardant effect. Good compatibility, with a higher melting point that is slightly lower than that of polyester and high-temperature nylon processing, it can be in a molten state in polymer materials, which further improves the compatibility of flame retardants in polymer materials.

The present invention has no special regulations on the synthesis method of the diphenyl phosphine oxide derivative, as long as the synthesis method well known to those skilled in the art is adopted. In the embodiment of the present invention, the method for synthesizing the diphenyl phosphine oxide derivative is preferably the polymerization reaction of diphenyl phosphine oxide and the corresponding chlorinated hydrocarbon under alkaline conditions, which is well known to those skilled in the art.

Based on 10-70 parts by weight of the carrier resin, the flame-retardant masterbatch provided by the present invention includes 1-10 parts of antioxidant, preferably 3-8 parts, more preferably 5 parts. In the present invention, if the amount of the antioxidant is too small, the antioxidant effect will not be achieved. If the amount of the antioxidant is too large, the antioxidant will directly interact with molecular oxygen to form free radicals, resulting in a pre-oxidation effect and accelerating the aging process. When the concentration is too high, The negative impact of this advanced oxidation effect will offset the stabilizing effect of antioxidants. In the present invention, the anti-oxidation effect is the best in the above-mentioned dosage range.

In the present invention, the antioxidant is preferably tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), tetra[β-(3,5-di-tert-butyl-4-hydroxybenzene) (Base) propionic acid] pentaerythritol ester (antioxidant 1010) and at least one of bis(2,4-dicumylphenyl) pentaerythritol diphosphite (antioxidant S9228), more preferably antioxidant 168, antioxidant There are two combinations of 1010 and antioxidant S9228, the most preferred is the combination of antioxidant 1010 and antioxidant S9228, or the combination of antioxidant 1010 and antioxidant 168.

In the present invention, there is no special regulation on the amount ratio of the antioxidant 168, antioxidant 1010 and antioxidant S9228, and the total amount only needs to meet the requirements of the flame-retardant masterbatch antioxidant provided by the present invention. In the embodiment of the present invention, the compound dosage of the antioxidant is specifically a 2:3 compound by weight ratio of 1010 and S9228; a 2:1 compound by weight ratio of 168 and 1010; or a weight ratio of 168 and 1010 1:1 compounding. In the present invention, the use of the above-mentioned compound antioxidant and the above-mentioned amount can more effectively prevent the high molecular polymer from becoming sticky, discolored, brittle or broken.

Based on 10 to 70 parts by weight of the carrier resin, the flame retardant masterbatch provided by the present invention includes 0 to 70 parts of a synergistic flame retardant, more preferably 5 to 60, and most preferably 10 to 50 parts. In the embodiment of the present invention, the weight parts of the synergistic flame retardant may specifically be 6 parts, 10 parts, 50 parts, 40 parts or 52.5 parts. The present invention has no special regulations on the addition of synergistic flame retardant. When the material requires higher flame retardant effect, synergistic flame retardant is added, but the amount of synergistic flame retardant cannot exceed the above range, otherwise it will cause the material The mechanical properties decrease.

In the present invention, the synergistic flame retardant is preferably a metal oxide, a metal salt, a natural mineral, a carbon-based free radical initiator, and an organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon At least one of the agents. In the present invention, the metal oxide is preferably at least one of titanium dioxide, zinc oxide and aluminum oxide. In the present invention, the natural mineral is preferably at least one of montmorillonite, hydrotalcite and clay. In the present invention, the metal salt is preferably at least one of zinc borate and zinc stannate. In the present invention, the carbon-based free radical initiator is preferably 2,3-dimethyl-2,3-diphenylbutane and 2,3-dimethyl-2,3-dinaphthylbutane At least one of them. In the present invention, the organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon is preferably zinc diethylphosphinate, polysiloxane, cage silsesquioxane, six Phenoxy cyclotriphosphazene, polyphenyl phosphonate diphenyl sulfone ester, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) Ethane, p-xylylene bis (9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), p-xylylene bis (diphenyl phosphine oxide), melamine cyanuride At least one of acid salt, melamine polyphosphate, melamine hydrobromide, tris(2,3-dibromopropyl) isocyanurate, aluminum diphenylphosphinate and aluminum diethylphosphinate kind. In the embodiment of the present invention, the type of the synergistic flame retardant can be specifically zinc diethylphosphinate, polysiloxane, titanium dioxide, aluminum diphenylphosphinate, melamine cyanurate, para Xylylene bis (diphenyl phosphine oxide), melamine hydrobromide, melamine cyanurate, or a synergist (2,3-dimethyl-2,3-diphenylbutane). In the present invention, the flame-retardant masterbatch made by selecting the above-mentioned synergistic flame retardant can exhibit a good flame-retardant synergistic effect when applied to resin products.

The flame-retardant masterbatch provided by the present invention uses the diphenyl phosphine oxide derivative with the structure of formula I, which has the characteristics of high phosphorus content and good flame retardancy, as the main flame retardant, and at the same time, uses its low melting point to improve its performance Dispersibility during polymer processing; using antioxidants to prevent polymer from becoming sticky, discolored, brittle or broken; using carrier resin to achieve the loading of p-diphenyl phosphine oxide derivatives and antioxidants, and at the same time improve the two The dispersibility and compatibility of phenyl phosphine oxide derivatives and antioxidants; finally, under the combined action of carrier resin, diphenyl phosphine oxide derivatives and antioxidants, the compatibility and resistance of flame retardants are improved. Burning effect.

The present invention also provides a method for preparing the flame-retardant masterbatch according to the above technical solution, which includes the following steps:

(1) Mix the carrier resin, diphenylphosphine oxide derivatives, antioxidants and synergistic flame retardants to obtain a mixture;

(2) The mixture obtained in the step (1) is granulated to obtain a flame-retardant masterbatch.

In the present invention, the carrier resin, the diphenyl phosphine oxide derivative, the antioxidant and the synergistic flame retardant are mixed to obtain the mixture. The present invention has no special regulations on the mixing operation, as long as the obtained dry raw materials are uniformly mixed.

In the present invention, the carrier resin, diphenyl phosphine oxide derivative, antioxidant and synergistic flame retardant are preferably mixed before the mixing of the carrier resin, diphenyl phosphine oxide derivative, antioxidant and synergistic flame retardant. Dry it. The present invention does not have special regulations on the drying method. The drying method well known to those skilled in the art can be used to remove the moisture absorbed by the above-mentioned materials during storage and some volatile substances, so as to prevent the resin from being volatile due to moisture or volatile The presence of substances causes the resin to decompose during processing, and at the same time avoid bubbles in the resin processing process.

After the mixture is obtained, the present invention granulates the mixture to obtain a flame-retardant masterbatch.

The present invention has no special regulations on the granulation method, and the granulation method well known to those skilled in the art can be used. In the present invention, the granulation device is preferably a component with a twin screw. In the present invention, the temperature of the twin screw is preferably 210 to 300°C, more preferably 210 to 275°C, and most preferably 220 to 270°C. In the embodiment of the present invention, the temperature of the twin screw may specifically be 270°C, 260°C, 200°C, or 220°C. The present invention adopts the above-mentioned temperature to prevent the carrier resin from being unable to be processed into a plastic state when the temperature is too low, and at the same time avoids the material sticking in the thread groove due to the high temperature due to the high temperature, and also avoids the decomposition of the raw material.

After the granulation is completed, in the present invention, the granulated product is preferably cooled and dried in sequence to obtain the flame-retardant masterbatch. The present invention has no special regulations on the cooling method, and the cooling method well known to those skilled in the art can be used. The present invention has no special regulations on the drying method, and the drying method well known to those skilled in the art can be used to remove the moisture absorbed by the masterbatch during the production process and the volatile substances that have not been volatilized. In the present invention, there is no special regulation on the drying temperature, and the drying temperature well known to those skilled in the art may be used. The purpose of drying the masterbatch in the present invention is to improve the stability of the masterbatch during storage.

The preparation method provided by the invention is easy to operate, low in cost, and very suitable for rapid and large-scale production.

The present invention also provides the flame-retardant masterbatch described in the above technical solution and the application of the flame-retardant masterbatch prepared by the preparation method described in the above technical solution in resin products.

In the present invention, when the resin product is a polyester fiber film, the synergistic flame retardant in the flame-retardant masterbatch is preferably polyphenyl diphenyl phosphonate, zinc diethyl phosphinate, and hexaphenoxy Cyclotriphosphazene, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, cage silsesquioxane and montan At least one of the soil removal. In the embodiment of the present invention, when the resin product is a polyester fiber film, the synergistic flame retardant in the flame retardant masterbatch may specifically be zinc diethylphosphinate. In the present invention, the flame retardant formula can maintain the better transparency and spinning performance of the fiber film, and give full play to the phosphorus-phosphorus synergistic effect and the phosphorus-silicon synergistic effect (the gas phase flame retardant mechanism and the solid phase flame retardant mechanism cooperate with each other). Different flame retardants participate in the combustion process of polyester at different temperatures when the polyester is decomposed. The synergistic formula system can improve the flame retardant efficiency and reduce the amount of flame retardant added. At the same time, the specific phosphorus-silicon-mineral synergistic effect Can improve the dripping performance of polyester.

In the present invention, when the resin product is nylon fiber, the synergistic flame retardant in the flame retardant masterbatch is preferably 1-benzene-1,2-bis(9,10-dihydro-9-oxy-10 -Phosphaphenanthrene-10-oxide) at least one of ethane, titanium dioxide and clay. In the embodiment of the present invention, when the resin product is nylon fiber, the synergistic flame retardant in the flame retardant masterbatch may specifically be titanium dioxide. In the present invention, the flame retardant formula can not only maintain the excellent spinnability of the fiber, but also exert the phosphorus and phosphorus synergy between the selected flame retardants, and the selected titanium dioxide and clay can be oxidized with diphenyl in a certain amount of addition. The synergistic effect of the phosphine derivative flame retardant can significantly promote the carbonization of nylon, further increase the oxygen index of the flame retardant nylon, and at the same time achieve the flame retardant effect of V-0.

In the present invention, when the resin product is a polypropylene fiber film, the synergistic flame retardant in the flame retardant masterbatch is preferably tris (2,3-dibromopropyl) isocyanurate, 2, 3-Dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-dinaphthylbutane and 1-benzene-1,2-bis(9,10-dihydro) -9-oxo-10-phosphaphenanthrene-10-oxide) at least one of ethane. In the embodiment of the present invention, when the resin product is nylon fiber, the synergistic flame retardant in the flame retardant masterbatch may specifically be 2,3-dimethyl-2,3-diphenylbutane. In the present invention, the flame retardant formula is a fusible flame retardant, which does not affect the spinning performance of polypropylene fiber. At the same time, it can exert the synergistic effect of phosphorus and bromine. The addition of a carbon-based free radical initiator can further accelerate the decomposition of polypropylene. The heat is dripping and the ratio of the three is optimized, so that the polypropylene can reach V-2 level when the flame retardant content is 1-2%, and the oxygen index is above 26%.

In the present invention, when the resin product is an injection molding material, the synergistic flame retardant in the flame retardant masterbatch is preferably melamine cyanurate, melamine polyphosphate, melamine hydrobromide, and diphenylphosphinic acid. At least one of aluminum, aluminum diethylphosphinate, zinc oxide, zinc borate, and hydrotalcite. In the embodiment of the present invention, when the resin product is an injection molding material, the synergistic flame retardant in the flame retardant masterbatch may specifically be aluminum diethylphosphinate. In the present invention, the flame retardant formula can fully utilize the synergistic mechanism between the gas phase flame retardant and solid phase flame retardant between phosphorus nitrogen flame retardant elements and the phosphorus-metal ion of metal oxides by introducing nitrogen-based flame retardants. Synergistically catalyze the formation of charcoal to achieve excellent flame retardant effect.

In the present invention, when the resin product is a cured sheet or a substrate, the synergistic flame retardant in the flame retardant masterbatch is p-xylylene bis (diphenyl phosphine oxide), 1-benzene-1,2- Bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene dimethyl bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) -10-oxide), at least one of polysiloxane and cage silsesquioxane. In the embodiment of the present invention, when the resin product is a cured sheet or a substrate, the synergistic flame retardant in the flame retardant masterbatch may specifically be polysiloxane. In the present invention, the synergistic formula system of selected organophosphorus-silicon flame-retardant elements added to the flame-retardant formula exerts the synergistic effects of phosphorous and phosphorous and silicon, and improves the flame retardant efficiency. Using polyolefin as the carrier resin can significantly improve the toughness of prepregs and substrates, and solve the problem of insufficient toughness; the flame retardant masterbatch derived from organic DPO has good compatibility with polymer resin materials, reducing inorganic flame retardancy The use amount of polar flame retardants such as chemical agents minimizes the influence of the flame retardant system on the electrical properties, so that the flame retardant polymer materials maintain better dielectric properties and lower water absorption.

The present invention does not have special regulations on the application process of flame-retardant masterbatch in resin products. According to the preparation process of resin products well known to those skilled in the art, the resin product preparation process needs to be added to improve its flame retardancy. The flame-retardant components of, can be directly replaced with the flame-retardant masterbatch prepared by the present invention.

In the present invention, the carrier resin of the flame-retardant masterbatch and the resin component selected in the preparation process of the resin-based product may be the same or different, and are preferably the same. When the same resin is selected, the problem of different processing parameters due to different resins can be further avoided, and the compatibility of the resin selected in the preparation process of the flame retardant masterbatch and resin products can be improved, thereby further improving the resistance of the material. Combustion performance. In the embodiment of the present invention, when the selected resin is polyphenylene ether resin, the preferred polyphenylene ether is poly-2,6-dimethyl-1,4-phenylene ether, modified polyphenylene ether terminated with epoxy structure One of phenyl ether and vinyl structure-terminated modified polyphenyl ether and a mixture of both, preferably the carrier added to the masterbatch is polypropylene, vinyl elastomer, styrene-butadiene copolymer , The flame retardant masterbatch of at least one of hydrogenated styrene-butadiene copolymer and maleic anhydride styrene-butadiene copolymer can solve the flame retardant performance of the material and can give the material better mechanical properties.

The flame-retardant masterbatch provided by the invention shows good compatibility when applied to resin products, and the flame-retardant effect can reach V-0 level.

The flame-retardant masterbatch provided by the present invention and its preparation method and application will be described in detail below with reference to the examples, but they should not be understood as limiting the protection scope of the present invention.

Raw materials and sources used in the examples:

Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), BASF; polyethylene terephthalate-1,4-cyclohexanedimethanol (PETG), Korea SK; Polypropylene PPH-T03 PetroChina Qingdao Refinery; PA6, BASF B3L; PA66, DuPont 101F NC010; PPA high temperature nylon, DuPont FE8200NC010; Polyphenylene ether S202A, Asahi Kasei; Methyl acrylate polyphenylene ether SA9000, Sabic; hexaphenoxy cyclotriphosphazene (HPCTP), polyphenyl diphenyl phosphonate, aluminum diphenyl phosphinate Qingdao Fuslin Chemical Technology Co., Ltd.; zinc diethyl phosphinate (ZDP ), Qingdao Opry New Material Co., Ltd.; Polysiloxane, Shandong Dongyue Organic Silicon New Material Co., Ltd.; Cage Silsesquioxane, Beijing Institute of Technology Flame Retardant Technology Co., Ltd.; Chopped Glass Fiber, T435TM, Taishan Glass Fiber Co., Ltd.; Chopped Basalt Fiber, BFCS-13-6, Zhejiang Jinshi Basalt Co., Ltd.; Modified Silsesquioxane (POSS), Beijing Institute of Technology Flame Retardant Material; Antioxidant Four [β-(3, 5 -Di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester (antioxidant 1010), bis(2,4-dicumylphenyl) pentaerythritol diphosphite (antioxidant S9228), Jiangsu Fu Biya Chemicals Co., Ltd.; Low-dielectric electronic fiber Bunanya Plastics; Anti-dripping agent (3300), Guangzhou Entropy Innovative Materials Co., Ltd.; SEBS, Baling Petrochemical; Solvent toluene and other conventional additives are commercially available.

Performance evaluation methods and implementation standards:

The vertical combustion test is tested in accordance with the GB/T2408-2008 method, the sample size (mm) (125±5)×(13.0±0.5)×(3.2/1.6±0.25); the oxygen index (LOI) test is in accordance with GB/T2406.1 -2008: Specimen size (mm)(80±5)×(6.5±0.5)×(3±0.25); tensile strength and elongation at break are tested according to GB/T1040-2006 method, type I, Tensile speed 500mm/min; dielectric constant (Dk), (1GHz) microwave induction analyzer measurement; drop weight impact test, ISO ImpactTester, install the sample as required, fix the drop weight at a height of 20mm, so that The free fall hits the material, and the clearer the cross cracks produced by the falling hammer hitting the material, the better the toughness of the material.

Example 1

Preparation of compound 1,2-bis(diphenylphosphinooxy)ethane (EDPO) with formula II structure

Put 200ml of toluene into a single-necked flask equipped with a stirrer, first add 22.6g of diphenylphosphoroxy DPO, then add an aqueous solution of 15g of NaOH, add 5.5g of dichloroethane, and react at 20°C for 2h. After the reaction is completed, it is filtered with suction, washed with water, and finally dried. Finally, 17.508 g of EDPO was obtained, with a yield of 81.3% and a phosphorus content of 14.2%.

The TGA test results of the prepared compound EDPO with the structure of formula II are shown in Figure 1. Its weight loss is 5% at 372.2°C, which has high thermal stability, and the final carbon residue is 3.97%; its DSC melting point test is shown in Figure 2, and its melting point is 272°C.

Preparation of flame-retardant masterbatch FRM-1

Use a blast oven to dry EDPO, PET, and antioxidants (1010 and S9228) at 150°C for 3.5 hours to fully dry the dried raw materials according to EDPO, 60, and antioxidants (1010). And S9228 weight ratio 2:3) a total of 5 parts by weight, put it into the high-speed mixer for full mixing for 10 minutes, pour out the evenly mixed mixture and put it into the extruder feeding hopper, the twin screw temperature is set to 270 ℃, processing, extrusion, cooling and granulation, the masterbatch is colorless, transparent, uniform particle size, no agglomerated powder, and finally dried at 130 ℃ to obtain white flame-retardant masterbatch FRM-1.

Example 2

Preparation of 1,4-bis(diphenylphosphinooxy)butane (BDPO) with the structure of formula III

Put 800ml of toluene into a single-neck flask equipped with a stirrer, first add 118g of diphenylphosphoroxy DPO, then add an aqueous solution of 70g of NaOH, add 35.5g of dichlorobutane, and react for 2h at a temperature of 20°C. After the reaction is completed, it is suction filtered, washed with water, and finally dried to finally obtain 115..8 g of BDPO product, with a yield of 91% and a phosphorus content of 13.5%.

The TGA test results of the prepared compound BDPO with the structure of formula III are shown in Figure 3. Its weight loss is 5% at 347°C, which has high thermal stability, and the final carbon residue is 1.2%; its DSC melting point test is shown in Figure 4, and its melting point is 263°C.

Preparation of flame-retardant masterbatch FRM-2

Use a blast oven to dry BDPO, PET and antioxidants (1010 and S9228) at 120°C for 3.5 hours to fully dry the dried raw materials according to BDPO, 60 parts of PET, and antioxidants (1010 And S9228, the weight ratio of the two is 2:3) A total of 5 parts by weight is put into the high-speed mixer for full mixing for 10 minutes, and the mixed material is poured out and put into the extruder feeding hopper, and the twin screw temperature is set to 260 ℃, processing, extrusion, cooling and granulation, the masterbatch is colorless, transparent, uniform particle size, no agglomerated powder, and finally dried at 130 ℃ to obtain white flame-retardant masterbatch FRM-2.

The raw materials EDPO and BDPO involved in Examples 3-29 were all obtained by the preparation method provided in Example 1 or 2.

Example 3

Preparation of flame-retardant masterbatch FRM-3

Use a blast oven to dry BDPO, zinc diethylphosphinate (ZDP), 5 parts of polysiloxane, PET and antioxidants (1010 and S9228) at 150℃ for 3.5h to fully dry the The raw materials are based on 30 parts of BDPO, 5 parts of zinc diethylphosphinate (ZDP), 5 parts of polysiloxane, 60 parts of PET, and 5 parts of antioxidant (1010 and S9228, the weight ratio of the two is 2:3). Put into the high-speed mixer to fully mix for 10 minutes, pour out the evenly mixed mixture into the extruder feeding hopper, set the twin-screw temperature to 260℃, carry out processing, extrusion, cooling and granulation, and masterbatch finished product It is colorless and transparent, with uniform particle size, and finally dried at 130°C to obtain white flame-retardant masterbatch FRM-3.

Example 4

Dry the flame-retardant masterbatch and mix it according to the weight ratio of the flame-retardant masterbatch FRM-2 and PET polyester chips at a ratio of 3:97. The mixed raw materials are fed into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 275℃, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, then dried, take it out and fill it in the mold, press it into a tablet at 270℃, and let it cool. After cutting the sample test.

Example 5

Dry the flame-retardant masterbatch and mix it according to the weight ratio of the flame-retardant masterbatch FRM-2 to the PET polyester chip at a ratio of 10:90, and feed the mixed raw materials into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 275℃, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in the mold, press and shape it on a flat plate vulcanizer at 270℃, and wait for it to cool down Cut sample test.

Example 6

The flame-retardant masterbatch is dried, and the weight ratio of the flame-retardant masterbatch FRM-1 to the PET polyester chip is 10:90. The mixed raw materials are fed into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 275℃, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in the mold, press and shape it on a flat plate vulcanizer at 270℃, and wait for it to cool down Cut sample test.

Example 7

Dry the flame-retardant masterbatch and mix it according to the weight ratio of the flame-retardant masterbatch FRM-3 and PET polyester chips at a ratio of 10:90, and feed the mixed raw materials into the screw extruder for melting and extrusion, the screw extruder is the highest The temperature was set to 275°C, after extrusion, it was cooled and pelletized, dried, taken out and filled in a mold, and pressed into a tablet at a 270°C flat vulcanizer. After cooling, the sample was cut and tested.

Example 8

Dry the flame-retardant masterbatch and mix it according to the weight ratio of the flame-retardant masterbatch FRM-2 and PBT polyester chips of 10:90, and feed the mixed raw materials into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 235℃, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dried, take it out and fill it in a mold, press and shape it on a flat vulcanizer at 240℃, and wait for it to cool down Cut sample test.

Example 9

The flame-retardant masterbatch is dried and mixed according to the weight ratio of the flame-retardant masterbatch FRM-2 and PETG chips at a ratio of 10:90. The mixed raw materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set Set the temperature to 230℃, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in a mold, press and shape it on a plate vulcanizer at 230℃, and cut the sample after cooling. test.

Example 10

Dry the raw materials and mix them evenly according to 35 parts of FRM-1 flame retardant masterbatch, 25 parts of BFCS-13-6 basalt fiber additive material, and 40 parts of PET polyester. The mixed raw materials are fed into the screw extruder to melt and extrude. The maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a tablet at 280°C on a plate vulcanizing machine. After cooling, the sample is cut for testing.

Example 11

Dry the raw materials, and mix them evenly according to 35 parts of FRM-1 flame retardant masterbatch, 25 parts of BFCS-13-6 basalt fiber additive material, 40 parts of PET polyester, and 0.5 parts of anti-dripping agent PTFE. The raw materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set to 280℃. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a vulcanizing machine at 280℃. After forming, let it cool down and cut samples for testing.

Example 12

Dry the raw materials and mix them evenly according to 35 parts of FRM-2 flame retardant masterbatch, 25 parts of T435TM chopped glass fiber additive material, and 40 parts of PET polyester. The mixed raw materials are fed into the screw extruder for melting and extrusion, The highest temperature of the machine is set to 280℃. After extrusion, it is cooled and pelletized, dried, taken out and filled in a mold, and pressed into a tablet at a 280℃ plate vulcanizing machine. After cooling, the sample is cut for testing.

Example 13

Dry the raw materials and mix them evenly according to 35 parts of FRM-3 flame retardant masterbatch, 25 parts of BFCS-13-6 basalt fiber additive material, and 40 parts of PET polyester. The mixed raw materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a tablet at 280°C on a plate vulcanizing machine. After cooling, the sample is cut for testing.

Example 14

Dry the raw materials, according to 35 parts of FRM-3 flame-retardant masterbatch, 25 parts of BFCS-13-6 basalt fiber additive material, 30 parts of PET polyester, and 10 parts of PETG resin. The maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a vulcanizing machine at 280°C. After cooling, Cut sample test.

The flame retardant properties of the materials in Examples 4-14 were tested, and the test results are shown in Table 1.

Table 1 Test results of flame retardant properties in Examples 4-14

It can be seen from Table 1 that when the flame-retardant masterbatch 1 and the flame-retardant masterbatch 2 prepared by the present invention are separately added to the polyester system, the pure PET exhibits a relatively good flame-retardant effect, and the oxygen index And vertical combustion has been improved to a certain extent, but there are still dripping and flame retardant grades that cannot reach 1.6mm V-0. When using the flame-retardant masterbatch 3 prepared by compounding the synergistic flame retardant with the diphenyl phosphine oxide derivative defined in the present invention, the prepared flame-retardant polyester reaches 1.6mm V-0 level, the LOI is increased to 34.5%, and the flame retardant The flame retardant effect of the reinforced polyester to 0.8mmV-0 is because the compound flame retardant system can give full play to the phosphorus-phosphorus synergistic effect and the phosphorus-silicon synergistic effect (the gas phase flame retardant mechanism and the solid phase flame retardant mechanism cooperate with each other). Different flame retardants participate in the combustion process of polyester at different temperatures when the polyester is decomposed, which can significantly improve the flame retardant efficiency and reduce the amount of flame retardant added. At the same time, the specific phosphorus-silicon synergy can solve the problem of easy dripping of polyester. The problem of falling.

Example 15

Preparation of flame-retardant masterbatch FRM-4

Use a blast oven to dry EDPO, PA66 carrier resin, titanium dioxide and antioxidants (1010 and S9228) at 85°C for 3.5 hours to fully dry the dried raw materials according to 60 parts EDPO and 40 parts PA66 carrier resin , 6 parts of titanium dioxide, 5 parts of antioxidant (1010 and S9228, the weight ratio of the two: 2:3) weight ratio into the high-speed mixer for full mixing for 10 minutes, pour out the uniform mixture into the extruder to feed The hopper and twin-screw temperature is set to 270℃, processed, extruded, cooled and pelletized. The finished masterbatch is white and translucent, with good dispersibility and no agglomerated powder. It is dried at 100℃ to obtain a white flame-retardant masterbatch. FRM-4.

Example 16

Preparation of flame-retardant masterbatch FRM-5

Use a blast oven to fully dry EDPO, aluminum diphenylphosphinate, melamine cyanurate, PA66 carrier resin, titanium dioxide and antioxidants (1010 and S9228) at 85°C for 3.5h, according to 20 parts EDPO, 40 parts of diphenyl aluminum phosphinate, 10 parts of melamine cyanurate, 40 parts of PA66 carrier resin, 5 parts of titanium dioxide, antioxidants (1010 and S9228, the weight ratio of the two: 2:3) total 5 parts The weight ratio is put into the high-speed mixer for full mixing for 10 minutes, and the evenly mixed mixture is poured into the extruder feeding hopper. The twin-screw temperature is set to 270°C for processing, extrusion, cooling and granulation. The finished masterbatch is in Dry at 100°C to obtain white translucent flame-retardant masterbatch FRM-5.

Example 17

Preparation of flame-retardant masterbatch FRM-6

Use a blast oven to fully dry EDPO, p-xylylene bis (diphenyl phosphine oxide), cage silsesquioxane, polypropylene carrier resin, and SEBS at 85°C for 3-4 hours. Parts EDPO, 40 parts p-xylylene bis (diphenyl phosphine oxide), 6 parts cage silsesquioxane, 15 parts polypropylene carrier resin, 5 parts SEBS carrier resin, 5 parts antioxidant (168 and The weight ratio of 1010 is 2:1). Put it into the high-speed mixer for full mixing for 10 minutes. Pour out the evenly mixed mixture and put it into the extruder feeding hopper. Set the twin screw temperature to 200°C for processing and extrusion. , Cooling and granulating, and drying the finished masterbatch at 80℃ to obtain translucent flame-retardant masterbatch FRM-6.

Example 18

Preparation of flame-retardant masterbatch FRM-7

Use a blast oven to treat EDPO, melamine hydrobromide, dicumin synergist (2,3-dimethyl-2,3-diphenylbutane), melamine cyanurate, polypropylene carrier resin, 1010 Antioxidant, 168 antioxidant were dried at 80℃ for 3.5h to fully dry, according to 12.5 parts of EDPO, 37.5 parts of melamine hydrobromide, 5 parts of dicumin synergist (2,3-dimethyl-2 ,3-Diphenylbutane), 10 parts of melamine cyanurate, 50 parts of polypropylene carrier resin, 2.5 parts of 1010 antioxidant, 2.5 parts of 168 antioxidant weight ratio into the high-speed mixer for full mixing In 10 minutes, pour out the evenly mixed mixture into the extruder feeding hopper, set the twin-screw temperature to 220°C, perform processing, extrusion, cooling and granulation, and dry the masterbatch product at 80°C to obtain a white translucent Flame-retardant masterbatch FRM-7.

Example 19

Take 100 parts of PPA resin, feed the raw materials into the screw extruder for melting and extruding. The maximum temperature of the screw extruder is set to 325°C. After extrusion, it is cooled and pelletized, dried, taken out and filled into the mold. ℃ flat vulcanizing machine compression molding, after cooling down, cut samples for testing.

Example 20

After the flame-retardant masterbatch is dried, it is mixed according to the weight ratio of the flame-retardant masterbatch FRM-4 and PA6 of 10:90, and the mixed raw materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set The temperature is 240°C, after extrusion, cooling and pelletizing, the flame-retardant PA6 resin composition is translucent, dried, taken out and filled into a mold, and pressed into a tablet at 240°C on a flat plate vulcanizer. After cooling, the sample is cut and tested.

Example 21

Mix according to the weight ratio of flame retardant masterbatch FRM-4 and PA66 of 20:80, feed the mixed raw materials into the screw extruder for melting and extruding. The maximum temperature of the screw extruder is set to 270℃, and then cooled after extrusion. Granulate, the flame-retardant PA66 resin composition is translucent, dry, take it out and fill it in a mold, press it into a tablet at 270°C on a flat-plate vulcanizer, and cut the sample after it cools.

Example 22

According to the flame-retardant masterbatch FRM-5 and PA66, the weight ratio is 20:80. The mixed raw materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set to 270℃, and it is cooled after extrusion. Granulate the powder without agglomeration, dry it, take it out and fill it in a mold, press it into a tablet at 270°C on a plate vulcanizing machine, and wait for it to cool before cutting samples for testing.

Example 23

According to the ratio of 20 parts of FRM-5 flame retardant masterbatch, 50 parts of PPA resin, and 30 parts of glass fiber T435TM, the mixed raw materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set to 320 ℃, after extrusion, cool and granulate, without agglomerated powder, dry, take it out and fill it in a mold, press and shape it on a plate vulcanizer at 320℃, and cut samples after cooling.

Example 24

According to the ratio of 20 parts of FRM-5 flame retardant masterbatch, 40 parts of PPA resin, 10 parts of PA66 resin, and 13-630 parts of fiber BFCS, the mixed raw materials are fed into the screw extruder to melt and extrude, and the screw is extruded. The maximum temperature of the machine is set to 320℃. After extrusion, it is cooled and granulated. There is no agglomerated powder, dried, taken out and filled in the mold, and pressed into a tablet at 320℃. After cooling, the sample is cut and tested.

Example 25

According to the ratio of 15 parts of FRM-6 flame-retardant masterbatch and 85 parts of PP resin, the mixed materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set to 220 ℃, and then cooled after extrusion. Granulate the powder without agglomeration, dry it, take it out and fill it in a mold, press it into a tablet at 220°C on a flat vulcanizing machine, and wait for it to cool before cutting samples for testing.

Example 26

Mix evenly according to the ratio of 4 parts of FRM-7 flame retardant masterbatch and 96 parts of PP resin. The mixed raw materials are fed into the screw extruder for melting and extrusion. The maximum temperature of the screw extruder is set to 220 ℃, and then cooled after extrusion. Granulate the powder without agglomeration, dry it, take it out and fill it in a mold, press it into a tablet at 220°C on a flat vulcanizing machine, and wait for it to cool before cutting samples for testing.

Example 27

According to the ratio of 10 parts of FRM-6 flame-retardant masterbatch, 70 parts of PPO (S202A) resin, and 20 parts of T435TM glass fiber, the mixed materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set The temperature is 250°C. After extrusion, it is cooled and granulated. There is no agglomerated powder. It is dried, taken out and filled in a mold. It is pressed into a tablet on a 250°C flat-plate vulcanizer. After cooling, the sample is cut and tested.

Example 28

100 parts of MPPO (SA9000) are fully dispersed and dissolved in 100 parts of toluene solvent, and then 3 parts of crosslinking accelerator DPC are added and mixed uniformly to obtain a toluene solution of polyphenylene ether resin composition, ie, resin varnish, with a concentration of 55%. The resin composition is adhered to the glass fiber cloth by impregnation or coating, and then heated and baked into a semi-cured state to obtain a semi-cured sheet. Take four prepregs and two copper foils prepared above, stack them in the order of copper foil, four prepregs, and copper foil, and then laminate them under vacuum conditions at 200°C for 1.5 hours to form a copper foil substrate. The physical properties of copper-containing substrates and copper-free substrates after etching are measured.

Example 29

Disperse and dissolve 80 parts of MPPO (SA9000) and 20 parts of flame-retardant masterbatch FRM-6 in 100 parts of toluene solvent, then add 3 parts of crosslinking accelerator DPC and mix uniformly to obtain flame-retardant modified polyphenylene ether resin The toluene solution of the composition is a resin varnish with a concentration of 55%. The resin composition is attached to the glass fiber cloth by impregnation or coating, and then heated and baked into a semi-cured state to obtain a prepreg. Take four prepregs and two copper foils prepared above, stack them in the order of copper foil, four prepregs, and copper foil, and then laminate them under vacuum conditions at 200°C for 1.5 hours to form a copper foil substrate. The physical properties of copper-containing substrates and copper-free substrates after etching are measured.

The flame retardant, mechanical and electrical properties of the materials in Examples 19-29 were tested, and the test results are shown in Table 2.

Table 2 Test results of flame retardant, mechanical and electrical properties of the materials in Examples 19-29

Remarks: —— indicates that the vertical flame retardant effect is very poor and almost has no flame retardancy, and the space indicates that the component has not been added or the performance has not been tested

It can be seen from Table 2 that the flame-retardant masterbatch prepared by the present invention has a good flame-retardant effect when added to pure PA6, PA66 and PPA. Among them, when PA6 and PA66 are added with flame retardant masterbatch 4 prepared by a combination of DPO derivative flame retardant and titanium dioxide, when 10% is added, the vertical combustion of PA6 reaches V-2 level, the oxygen index reaches 29.5%, and the oxygen index increases significantly. Adding 20% flame-retardant masterbatch, PA66 oxygen index reached more than 30%, and vertical combustion reached 3mm V-0 level, the flame-retardant masterbatch can be used in the melt spinning of flame-retardant nylon, excellent flame retardant effect can be spun Strong performance; when used in a glass fiber reinforced nylon system, the diphenyl phosphine oxide derivative defined by the present invention and the commonly used phosphorus nitrogen flame retardant and metal oxide prepared in a certain proportion of flame retardant masterbatch 5 can make poly The amide material achieves a 1.6mm V-0 flame retardant effect, and the oxygen index is further increased to more than 35%, while maintaining good mechanical properties and low water absorption. This is because the introduction of other specific phosphorus-based flame retardants and nitrogen-based flame retardants in the compound system can give full play to the synergistic mechanism between the gas phase flame retardant and solid phase flame retardant between the phosphorus nitrogen flame retardant elements, and the selected titanium dioxide In a certain amount of addition, the synergy with phosphorus-based flame retardants can significantly promote the formation of carbon from polyamides, further increase the oxygen index of flame-retardant polyamides, and at the same time achieve the flame retardant effect of V-0.

Add the flame-retardant masterbatch FRM-6 composed of the diphenyl phosphine oxide derivative defined by the present invention and polysiloxane to polypropylene, and add 15% polypropylene to reach the V-2 level, and the oxygen index is improved. Small and average flame retardant effect; when 4% phosphorous bromine initiator is added to compound FRM-7 masterbatch, polypropylene can reach V-2 level, and the oxygen index can be increased to 26.5%. This is because the diphenyl phosphine oxide derivatives defined in the present invention can also produce obvious phosphorus-bromine synergistic flame retardant effects with brominated flame retardants, and adding a small amount of carbon-based free radical initiators can further promote the decomposition of polypropylene Accelerate the drop of heat, so as to achieve an excellent flame retardant effect. The flame retardant system can be used in polypropylene molding compounds and polypropylene fiber films.

In Examples 27-29, the flame-retardant masterbatch 6 prepared by the present invention was added to ordinary polyphenylene ether, and the addition of 10% can make the glass fiber reinforced PPO reach the V-0 level and the oxygen index 36.9%. Because polyphenylene ether has extremely low dielectric constant, dielectric loss and water absorption, excellent heat resistance, good dimensional stability, and excellent adhesion to copper foil, it has a very large In the application space, the polyphenylene ether structure itself has certain flame retardancy, but due to the introduction of reactive groups such as vinyl and the reduction of molecular weight, the flame retardant performance is significantly reduced, vertical combustion is not graded, and the oxygen index drops to about 21%. After cross-linking and curing, there are problems such as insufficient toughness.

The flame-retardant masterbatch provided by the present invention is especially a resin varnish obtained from modified PPO with active group end caps, flame-retardant masterbatch, solvent, and crosslinking accelerator to make the resin composition adhere to the resin composition by impregnation or coating. Glass fiber cloth, heated and pressurized laminated board, add 20% flame retardant masterbatch, the vertical combustion is increased from no grade to V-0, and the oxygen index is increased from 21.3% to 29.8%, which has a good flame retardant effect. , And maintain a low dielectric constant similar to that of pure PPO without flame retardant. This is because of the synergistic formula system of specific organophosphorus silicon flame retardant elements added, and the organic DPO derived compound flame retardant master The particles have good thermal decomposition matching properties with the polymer resin material, fully exerting the synergistic effect of phosphorous and phosphorous and silicon, and improving the flame-retardant efficiency. The flame retardant masterbatch can reduce the use of polar flame retardants such as inorganic flame retardants, and minimize the influence of the flame retardant system on the dielectric properties and water absorption of the laminate, and the polyolefin carrier resin is non-polar The synergistic combination of resin and various influencing factors ultimately enables the flame-retardant PPO laminate to maintain better dielectric properties and lower water absorption. Through the drop-weight impact test, it is found that the cross cracks generated by the drop hammer impact of the sample after adding FRM-6 flame-retardant masterbatch are obviously clearer than those without the flame-retardant masterbatch. This is because the flame retardant in the flame-retardant masterbatch The agent and carrier resin have good compatibility with polyphenylene ether, and the added toughness polyolefin carrier resin can significantly improve the toughness of polyphenylene ether laminates and solve the problem of insufficient toughness of polyphenylene ether laminates . In the future, it can be widely used in the fields of printed circuit board film, high-speed and high-frequency copper clad laminate and other fiber cloth laminates, electronic and electrical, engineering plastics, etc., which have higher requirements for flame-retardant and dielectric properties.

The description of the above embodiments is only used to help understand the method and core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (20)

1. A flame retardant masterbatch, comprising the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and 0 to 0 parts of synergistic flame retardant 70 copies;

   The diphenylphosphine oxide derivative has a chemical structure shown in formula I:

   

   In the formula I, n is a positive integer, and R ₁ and R _{2 are} independently one of H, a C ₁ ～C ₆ alkyl group, and an aromatic group;

   The melting point of the diphenylphosphine oxide derivative is 200°C to 340°C.
2. The flame-retardant masterbatch according to claim 1, characterized in that it comprises the following components by weight: 20-60 parts of carrier resin, 20-70 parts of diphenyl phosphine oxide derivative, 3-8 parts of antioxidant And synergistic flame retardant 5-60 parts.
3. The flame-retardant masterbatch according to claim 1 or 2, wherein the diphenyl phosphine oxide derivative has a chemical structure represented by formula II:

   
4. The flame-retardant masterbatch according to claim 1 or 2, wherein the diphenyl phosphine oxide derivative has a chemical structure represented by formula III:

   
5. The flame-retardant masterbatch according to claim 1 or 2, wherein the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetra[β-(3,5-di-tert At least one of butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
6. The flame-retardant masterbatch according to claim 4, wherein the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetra[β-(3,5-di-tert-butyl) -4-Hydroxyphenyl) propionic acid] pentaerythritol ester and bis(2,4-dicumylphenyl) pentaerythritol diphosphite.
7. The flame-retardant masterbatch according to claim 1 or 2, wherein the synergistic flame retardant is a metal oxide, a metal salt, a natural mineral, a carbon-based free radical initiator, phosphorus, nitrogen and silicon At least one of the organic flame retardants of at least one of the three elements.
8. The flame-retardant masterbatch according to claim 7, wherein the metal oxide is at least one of titanium dioxide, zinc oxide and aluminum oxide.
9. The flame-retardant masterbatch according to claim 7, wherein the natural mineral is at least one of montmorillonite, hydrotalcite and clay.
10. The flame-retardant masterbatch according to claim 7, wherein the metal salt is at least one of zinc borate and zinc stannate.
11. The flame-retardant masterbatch according to claim 7, wherein the carbon-based free radical initiator is 2,3-dimethyl-2,3-diphenylbutane and 2,3-dimethyl At least one of -2,3-dinaphthylbutane.
12. The flame retardant masterbatch according to claim 7, wherein the organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon is zinc diethylphosphinate, polysiloxane , Cage silsesquioxane, hexaphenoxy cyclotriphosphazene, polyphenyl phosphonate diphenyl sulfone ester, 1-benzene-1,2-bis(9,10-dihydro-9-oxy-10 -Phosphaphenanthrene-10-oxide) ethane, p-xylylene bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), p-xylylene bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) Diphenyl phosphine oxide), melamine cyanurate, melamine polyphosphate, melamine hydrobromide, tris(2,3-dibromopropyl) isocyanurate, diphenyl aluminum phosphinate and two At least one of ethyl aluminum phosphinate.
13. The flame-retardant masterbatch according to claim 1 or 2, wherein the carrier resin is at least one of polyester, polyamide and polyolefin.
14. The preparation method of flame-retardant masterbatch according to any one of claims 1-13, comprising the following steps:

    (1) Mix the carrier resin, diphenylphosphine oxide derivatives, antioxidants and synergistic flame retardants to obtain a mixture;

    (2) The mixture obtained in the step (1) is granulated to obtain a flame-retardant masterbatch.
15. Application of the flame-retardant masterbatch according to any one of claims 1 to 13 or the flame-retardant masterbatch prepared according to the preparation method of claim 14 in resin products.
16. The application according to claim 15, characterized in that, when the resin product is a polyester fiber film, the synergistic flame retardant in the flame retardant masterbatch is polyphenyl phosphonate diphenyl sulfone ester, diethyl sulfonate Zinc phosphonate, hexaphenoxy cyclotriphosphazene, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, cage type At least one of silsesquioxane and montmorillonite.
17. The application according to claim 15, wherein when the resin product is nylon fiber, the synergistic flame retardant in the flame retardant masterbatch is 1-benzene-1,2-bis(9,10-two Hydrogen-9-oxo-10-phosphaphenanthrene-10-oxide) at least one of ethane, titanium dioxide and clay.
18. The application according to claim 15, wherein when the resin product is polypropylene fiber film, the synergistic flame retardant in the flame retardant masterbatch is tris(2,3-dibromopropyl) isotris Polycyanate ester, 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-dinaphthylbutane and 1-benzene-1,2-bis (9,10-Dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) at least one of ethane.
19. The application according to claim 15, wherein when the resin product is an injection molding material, the synergistic flame retardant in the flame retardant masterbatch is melamine cyanurate, melamine polyphosphate, and melamine hydrobromide , At least one of aluminum diphenylphosphinate, aluminum diethylphosphinate, zinc oxide, zinc borate and hydrotalcite.
20. The application according to claim 15, wherein when the resin product is a cured sheet or a substrate, the synergistic flame retardant in the flame retardant masterbatch is p-xylylene bis (diphenyl phosphine oxide), 1-Benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene bis(9,10-dihydro-9 -At least one of oxy-10-phosphaphenanthrene-10-oxide), polysiloxane and cage silsesquioxane.

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