A toughened flame retardant, a flame-retardant impact-resistant resin composition, and a preparation method and application thereof

Abstract

This invention relates to a toughening flame retardant, a flame-retardant and impact-resistant resin composition, and their preparation method and application in the field of plastics processing. The toughening flame retardant is a modified polymer particle, comprising a core-shell structure consisting of a core of polymer A and a shell of polymer B; the modification is performed by halogenating agent C; polymer A is at least one of hydrogenated nitrile rubber and its derivatives; polymer B comprises a copolymer and its derivatives consisting of structural units X derived from maleic anhydride and structural units Y derived from monomer M; the toughening flame retardant is a single-component halogenated polymer particle with both flame-retardant and toughening functions, which can be used for toughening and flame-retardant modification of thermoplastic or thermosetting materials and / or alloys of the resin, improving the impact resistance and flame-retardant properties of the material.

Description

Technical Field

[0001] This invention relates to the field of plastics processing, and more specifically, to a toughening flame retardant, a flame retardant and impact-resistant resin composition, its preparation method and application. Background Technology

[0002] In recent years, with the continuous development of science and technology and the gradual improvement of people's quality of life, the demand for materials has been constantly increasing. Polymer materials, as one of the three major materials, have advantages such as light weight, low cost, and simple molding processes, and are widely used in various industries such as aerospace, automobile manufacturing, and food and beverage. Among them, plastics, as the most widely used category of polymer materials, are closely related to people's daily lives. However, the toughness and strength of plastic products are difficult to combine well in actual use, and the inherent flammability of plastic products limits their application in scenarios requiring impact resistance or flame retardancy.

[0003] From the perspective of materials science and engineering, strength and toughness are two particularly important but contradictory mechanical properties of plastics in structural materials. The simultaneous reinforcement and toughening of materials has always been one of the major unsolved problems in polymer materials science. Generally speaking, filling a plastic matrix with rigid particles can effectively improve the material's strength, stiffness, and dimensional stability, but at the same time, it can easily lead to increased brittleness. Furthermore, while glass fibers have achieved the goal of toughening and reinforcing plastics, processability has always been a challenge for the plastics processing industry. For example, using elastomers to toughen thermoplastics as toughening agents often results in a significant decrease in the material's stiffness and strength while increasing toughness. Adding rigid inorganic particles and elastomers can balance the contradiction between rigidity and toughness to a certain extent, but it is impossible to simultaneously obtain plastic materials with both high strength and high toughness.

[0004] Most polymer materials are organic, primarily composed of carbon and hydrogen, making them highly flammable and prone to fires and other safety incidents. Therefore, many countries have formulated and improved relevant laws, regulations, and industry standards to minimize and reduce these fires, and mandate that polymer materials in certain specific fields possess high flame-retardant properties. Currently, flame retardants used for polymer materials mainly include halogenated flame retardants, inorganic flame retardants, and intumescent flame retardants. Halogenated flame retardants have high flame-retardant efficiency for polymer materials, but their use poses serious safety and environmental hazards, thus their application in large quantities is increasingly limited. Inorganic flame retardants, such as magnesium hydroxide and aluminum hydroxide, while environmentally friendly, have low flame-retardant efficiency, requiring higher dosages to achieve a certain flame-retardant effect. Furthermore, these flame retardants have poor dispersibility, significantly impacting the mechanical properties of the substrate and making them unsuitable for solo application. Intumescent flame retardants possess advantages such as high flame retardant efficiency, low smoke, and low toxicity. By compounding small amounts of halogenated, phosphorus, and nitrogen-based flame retardants, their flame retardant efficiency can be synergistically improved, and this is widely recognized as one of the effective ways to achieve low-halogen or halogen-free flame retardants. Because flame retardants generally suffer from problems such as large addition amounts and poor dispersibility with the substrate, introducing flame retardant synergists can improve flame retardant efficiency and, to some extent, reduce the impact on material processability and mechanical properties caused by excessive addition of flame retardants.

[0005] Currently, researchers mainly improve the impact resistance and flame retardancy of materials by adding toughening agents and flame retardants separately. However, toughening agents are usually composed of flammable components, while the poor compatibility between flame retardants and the matrix can lead to a decrease in the mechanical properties of the material. It is particularly important to note that to achieve multifunctionality in polymer materials, it is often necessary to add large amounts of multi-component additives, and these additives may interact with each other, thus affecting the overall performance of the material. Therefore, developing more efficient single-component multifunctional additives has become one of the important approaches to achieving multifunctionality in polymer materials. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention proposes a toughening flame retardant. Specifically, it relates to a toughening flame retardant, a flame-retardant and impact-resistant resin composition, its preparation method, and its application.

[0007] The toughening and flame retardant has both good toughening effect and good flame retardancy. It can be used for toughening and flame retardant modification of at least one of thermoplastic or thermosetting materials such as polyolefins (e.g., polypropylene, polyethylene resin and its copolymers), polystyrene, polyoxymethylene, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene ether, polyphenylene sulfide, epoxy resin, unsaturated polyester, vinyl resin, etc., and / or at least one of alloys of the resins (e.g., PC / ABS, etc.), thereby improving the impact resistance and flame retardant properties of the materials.

[0008] One objective of this invention is to provide a toughening flame retardant. This toughening flame retardant features single-component multifunctional modification, combining excellent toughening and flame retardant effects. It can be used as a single-component multifunctional additive to efficiently achieve material multifunctionality while reducing the amount of additives required.

[0009] A second objective of this invention is to provide a method for preparing the toughening flame retardant, which is easy to implement and, in particular, can use readily available raw materials.

[0010] The toughening flame retardant can be applied to polymer materials. Specifically, it can be used in impact-resistant flame-retardant resin compositions containing the toughening flame retardant, which have both good impact resistance and good flame retardancy, and are particularly suitable for manufacturing compositions and products for use in densely populated places such as schools, hospitals and hotels, as well as in emerging fields such as smart home appliances and new energy vehicles.

[0011] An unexpected discovery was made: by grafting or physically coating maleic anhydride onto the surface of hydrogenated nitrile rubber via copolymerization with butadiene, divinylbenzene, isoprene, and / or dicyclopentadiene, or mixtures thereof, particles with a core-shell structure were obtained. Further halogenation of the particles with a halogenating agent resulted in the particle shell molecular chains simultaneously possessing halogen atoms and double bonds, yielding a single-component multifunctional additive with both excellent toughening and flame-retardant effects. These core-shell structured particles exhibit good dispersibility and compatibility in the resin matrix. Their surface retains some double bonds, allowing for cross-linking reactions with the resin matrix. The rubber phase and halogens effectively impart excellent flame-retardant and impact-resistant properties to the resin matrix, thus achieving the aforementioned objectives.

[0012] Therefore, in a first aspect, the present invention provides a toughening flame retardant, which is a highly efficient, multifunctional, single-component toughening flame retardant particle. The toughening flame retardant is a modified polymer particle, the polymer particle comprising a core-shell structure of a core composed of polymer A and a shell composed of polymer B; the modification is performed by modification with a halogenating agent C;

[0013] Preferably, the average particle size of the polymer particles can be 200–3,000,000 nm;

[0014] in,

[0015] The term "polymer particles" as used in this article refers to polymer particles with diameters ranging from nanometers to micrometers and shapes that are spherical or near-spherical.

[0016] The average particle size of the polymer particles can be 200–3,000,000 nm, for example, 200 nm, 250 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 750 nm, 850 nm, 950 nm, 1050 nm, 1150 nm, 1250 nm, 1350 nm, 1450 nm, 1550 nm, 1650 nm, 1750 nm, 1850 nm, 2000 nm, 2500 nm, 2750 nm, 3 000nm, 4000nm, 6000nm, 7000nm, 8000nm, 9000nm, 10000nm, 11000nm, 12000nm, 13000nm, 14000nm, 15000nm, 1600 0nm, 17000nm, 18000nm, 19000nm, 20000nm, 25000nm, 30000nm, 35000nm, 40000nm, 50000nm, 60000nm, 70000nm, 80 000nm, 90000nm, 100000nm, 200000nm, 300000nm, 400000nm, 600000nm, 800000nm, 1000000nm, 2000000nm, 3000000nm, or any value between the above or a range between any two of the above values ​​(e.g., 200–1500000nm, 200–600000nm, 200–200000nm, 400–150000nm, 450–100000nm). The average particle size is defined as the number-average particle size and is measured using a laser particle size analyzer. The ranges are: 000nm, 500–50000nm, 600–40000nm, 800–30000nm, 800–20000nm, 5000–300000nm, 8000–200000nm, 5000–150000nm, 6000–60000nm, 9000–2600000nm, 8000–2000000nm, 8000–1000000nm, 10000–800000nm, and 10000–600000nm.

[0017] Preferably, in the core-shell structure, the mass ratio between polymer A and polymer B can be in the range of (1:100) to (100:1), for example, specifically in the following ranges: (1:80) to (80:1), (1:60) to (60:1), (1:50) to (50:1), (1:40) to (40:1), (1:30) to (30:1), (1:20) to (20:1), (1:10) to (10:1), (1:8):(5:1), (1:6):(4:1), (1:4):(2:1), etc.

[0018] The toughening flame retardant is essentially a core-shell polymer particle consisting of a core of polymer A and a shell of polymer B. The shell and core are bonded together by physical or chemical interactions, and the polymer particle is modified by halogenating agent C.

[0019] The polymer A is at least one of hydrogenated nitrile butadiene rubber and its derivatives;

[0020] The polymer A may be at least one of hydrogenated nitrile butadiene rubber materials and their derivatives commonly used in the art. The polymer A may be at least one of hydrogenated nitrile butadiene rubber materials containing or not containing double bonds; the polymer A may contain or not contain halogens. The polymer A may be one or a mixture of hydrogenated nitrile butadiene rubber containing double bonds, hydrogenated nitrile butadiene rubber without double bonds, hydrogenated nitrile butadiene rubber that still contains double bonds after halogenation treatment, and / or hydrogenated nitrile butadiene rubber that does not contain double bonds after halogenation treatment.

[0021] In specific implementations, hydrogenated nitrile butadiene rubber (HNBR) can be selected from hydrogenated nitrile butadiene rubber commonly used in the art, with a hydrogenation rate of 50-99%; commercially available hydrogenated nitrile butadiene rubber commonly used in the art (such as hydrogenated nitrile butadiene rubber with a hydrogenation rate of 50-99% produced by companies such as Lanxess GmbH (Germany), Zeon Chemicals (Japan), and DSM (Netherlands)) or hydrogenated nitrile butadiene rubber prepared according to conventional methods in the art can be used.

[0022] In specific implementations, the hydrogenated nitrile butadiene rubber (HNBR) is a powdered rubber with a particle size ranging from 150 to 2,000,000 nm. Examples include 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 750 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, 2000 nm, 3000 nm, 4000 nm, 5000 nm, 6000 nm, and 750 nm. 000nm, 8000nm, 9000nm, 10000nm, 11000nm, 12000nm, 13000nm, 14000nm, 15000nm, 16000nm, 17000 nm, 18000nm, 19000nm, 20000nm, 25000nm, 30000nm, 35000nm, 40000nm, 45000nm, 50000nm, 55000n m, 60000nm, 70000nm, 80000nm, 90000nm, 100000nm, 200000nm, 300000nm, 400000nm, 500000nm, 600000nm, 800000nm, 1000000nm, 2000000nm, or any value between the above values, or a range between any two of the above values ​​(e.g., 150–500000nm, 150…). The ranges are ~200,000 nm, 300–150,000 nm, 300–100,000 nm, 200–40,000 nm, 400–30,000 nm, 500–20,000 nm, 5,000–50,000 nm, 6,000–2,500,000 nm, 8,000–2,000,000 nm, 8,000–1,000,000 nm, 8,000–800,000 nm, 8,000–600,000 nm, etc. The powdered rubber can be directly commercially available or obtained through conventional preparation methods in the art. Conventional preparation methods include, for example, mechanically pulverizing hydrogenated nitrile rubber; or spray drying hydrogenated nitrile rubber latex (with a conventional solid content, including but not limited to 40–60%). The preparation methods and processes described are known to those skilled in the art.

[0023] The polymer A, which forms the core structure, has a copolymer B of maleic anhydride and monomer M grafted or coated onto its surface to form a shell, and then a halogen is added to polymer B. The core and shell of this particle are tightly connected by chemical bonds or physical interactions, and the remaining double bonds and anhydride bonds in the shell can form chemical bonds with the resin matrix, thereby providing strong interfacial bonding and improving the impact resistance of the final product.

[0024] Preferably, polymer B, as the shell structure, is a copolymer of maleic anhydride and another monomer M. Polymer B comprises copolymers and their derivatives consisting of structural units X derived from maleic anhydride and structural units Y derived from monomer M; wherein monomer M is a monomer molecule containing multiple double bonds; specifically, monomer M may be selected from one or more of butadiene, divinylbenzene, isoprene, and / or dicyclopentadiene.

[0025] The total amount of monomer M, calculated as terminal olefins, is 10 to 1000 mol relative to 100 mol of the maleic anhydride, more preferably 20 to 800 mol.

[0026] The halogenating agent C may contain at least one substance that can successfully link halogens to the polymer molecular chain;

[0027] Preferably, the halogenating agent C can be selected from one or more of fluorine, chlorine, liquid bromine, elemental iodine, hydrofluoric acid, hydrogen chloride, hydrobromic acid and / or hydroiodic acid.

[0028] The double bond content of the toughening flame retardant can be 0.001–18.2 mmol / g, preferably 0.002–17 mmol / g; for example, 0.001 mmol / g, 0.002 mmol / g, 0.005 mmol / g, 0.01 mmol / g, 0.02 mmol / g, 0.03 mmol / g, 0.04 mmol / g, 0.05 mmol / g, 0.06 mmol / g, 0.07 mmol / g, 0.08 mmol / g, 0.09 mmol / g, 0.1 mmol / g, 0.2 mmol / g, 0.4 mmol / g, 0.6 mmol / g, 0.8 mmol / g, 1 mmol / g, 2 mmol / g, 3 mmol / g, 4 mmol / g, 5 mmol / g. l / g, 6 mmol / g, 7 mmol / g, 8 mmol / g, 9 mmol / g, 10 mmol / g, 12 mmol / g, 13 mmol / g, 14 mmol / g, 15 mmol / g, 16 mmol / g, 17 mmol / g, 18 mmol / g, or any value between the above or a range between any two of the above values ​​(e.g., 0.002–17 mmol / g, 0.002–15 mmol / g, 0.005–10 mmol / g, 0.005–8 mmol / g, 0.006–6 mmol / g, 0.008–4 mmol / g, 0.01–1 mmol / g, 0.01–0.8 mmol / g, 0.01–0.6 mmol / g, etc.). And / or,

[0029] The halogen content of the toughening flame retardant can be 0-35 wt%, for example, it can be 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, or any value between the above values ​​or a range between any two of the above values ​​(e.g., 2-30 wt%, 3-28 wt%, 4-25 wt%, 4-22 wt%, 5-20 wt%, 6-15 wt%, etc.).

[0030] In a second aspect, the present invention provides a method for preparing the toughened flame retardant. The method may include the following steps: copolymerizing components including maleic anhydride and the monomer M in the presence of an initiator to form a shell layer on the surface of polymer A particles, followed by halogenation with a halogenating agent to obtain the toughened flame retardant.

[0031] Specifically, the process may include the following steps: copolymerizing components including maleic anhydride and monomer M in the presence of an initiator, coating the components onto the surface of polymer particles A in the form of graft copolymerization or physical interaction, and halogenating the particles with a halogenating agent after the shell is formed to obtain the toughened flame retardant.

[0032] In practice, the following steps may be included:

[0033] (1) Disperse polymer A particles in an organic solvent, and in the presence of a first initiator, react maleic anhydride and a first monomer M by contacting them, and then introduce another monomer-containing solution to continue the reaction; wherein, the other monomer-containing solution contains an optional second monomer M and an optional second initiator;

[0034] (2) Add a halogenating agent to the product obtained in step (1) and continue the reaction to halogenate the polymer particles to obtain the toughening flame retardant.

[0035] in,

[0036] In step (1), the ratio of polymer A particles to the copolymer component is a conventional choice. However, in a preferred embodiment of the present invention, the total mass of maleic anhydride and monomer M relative to 100g of polymer A particles can be 1 to 10,000g, specifically 1g, 2g, 3g, 4g, 5g, 6g, 7g, 8g, 9g, 10g, 12g, 14g, 15g, 16g, 18g, 20g, 25g, 30g, 35g, 40g, 50g, 60g, 70g, 80g, 90g, 100g, 200g, 300g, 400g, 500g, 600g, 700g, 800g, 900g, 100g, 200g, 300g, 400g, 500g, 600g, 700g, 800g, 900g. g, 1000g, 1200g, 1400g, 1600g, 2000g, 3000g, 4000g, 5000g, 6000g, 7000g, 8000g, 9000g, 10000g or any value between the above values ​​or any range between any two of the above values ​​(e.g., 1-8000g, 5-6000g, 6-5000g, 8-4000g, 10-2000g, 10-1000g, 20-800g, 30-600g, 50-400g, 80-300g, 50-1000g, 60-2000g, 70-3000g, etc.).

[0037] In step (1),

[0038] The ratio of maleic anhydride to monomer M can be a conventional choice, but in a preferred embodiment of the present invention, the total amount of the first portion of monomer M and the second portion of monomer M, calculated based on terminal olefins, relative to 100 mol of the maleic anhydride is 10 to 1000 mol, preferably 20 to 800 mol; specifically, it can be 10 mol, 20 mol, 30 mol, 50 mol, 60 mol, 70 mol, 75 mol, 80 mol, 90 mol, 20 mol, 100 mol, 120 mol, 160 mol, 180 mol, 200 mol, or 240 mol. 260mol, 280mol, 300mol, 340mol, 360mol, 380mol, 400mol, 450mol, 500mol, 550mol, 600mol, 650mol, 700mol, 750mol, 800mol, 850mol, 900mol, 950mol, 1000mol or any value between the above values ​​or any range between any two of the above values ​​(for example, it can be a range of 30-700mol, 50-600mol, 60-500mol, 70-400mol, etc.).

[0039] In step (1), monomer M can be fed in one step (i.e., the amount of the second part of monomer M can be zero), or it can be fed in two parts (i.e., the first part of monomer M and the second part of monomer M). According to a more preferred embodiment of the present invention, the molar ratio between the second part of monomer M and the first part of monomer M is (0 to 100):100 (such as 0, 1:100, 2:100, 5:100, 8:100, 10:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 95:100, 100:100 or any value between the above values ​​or a range of values ​​between any two of the above values ​​(e.g., (2 to 95):100, (5 to 80):100, (8 to 70):100, etc.).

[0040] In the preparation method of the toughening flame retardant, the amount of organic solvent can be a conventional choice, as long as it provides a medium for the reaction in step (1). For example, relative to 100 mol of maleic anhydride, the amount of organic solvent can be 50-200 L. The specific amount can be adjusted according to actual needs.

[0041] In step (1), the organic solvent can be a solvent commonly used in various solution polymerization reactions. For example, the organic solvent includes organic acid alkyl esters, that is, the organic solvent can be selected from organic acid alkyl esters, or a mixture of organic acid alkyl esters and alkanes, or a mixture of organic acid alkyl esters and aromatic hydrocarbons; wherein, the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate; the alkanes include, but are not limited to: n-hexane and / or n-heptane. The aromatic hydrocarbons include, but are not limited to, at least one of benzene, toluene, and xylene.

[0042] In the preparation method of the toughening flame retardant, there are no special requirements for the amount of the initiator. Preferably, relative to 100 mol of maleic anhydride, the total amount of the first part initiator and the second part initiator can be 0.05-10 mol, more preferably 0.5-5 mol, and more preferably 0.8-1.5 mol. In step (1), the initiator can be added in one step (i.e., the amount of the second part initiator can be zero), or it can be added in two parts (i.e., the first part initiator and the second part initiator). According to a more preferred embodiment of the present invention, the molar ratio between the second initiator and the first initiator can be (0-100):100 (e.g., 0, 1:100, 5:100, 10:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values ​​or a range between any two of the above values, such as (0-90):100, (1-60):100, (10-45):100, etc.).

[0043] The initiator can be a reagent commonly used in the art for initiating polymerization reactions of maleic anhydride and olefins, and can be a thermally decomposable initiator. Preferably, the initiator can be selected from at least one of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, dicyclohexyl peroxide, azobisisobutyronitrile, and azobisisoheptanenitrile.

[0044] In step (1), polymer A, maleic anhydride, and monomer M react first upon contact. That is, polymer A, maleic anhydride, and monomer M do not react completely; only a portion undergoes polymerization in the presence of the initiator. The conditions for the reaction of polymer A, maleic anhydride, and monomer M can be conventional conditions, as long as the polymerization reaction is controlled to be only partially carried out. Preferably, the conditions for the reaction of maleic anhydride and monomer M include: an inert atmosphere, a temperature of 50–90°C (more preferably 60–70°C), a pressure (gauge pressure or relative pressure) of -0.3–1 MPa (more preferably 0–0.5 MPa), and a time of 0.5–4 h (more preferably 0.5–2 h).

[0045] In step (2),

[0046] The halogenating agent or a solution of the halogenating agent is added to the product obtained in step (1), and the mixture is stirred rapidly to carry out the reaction. The amount of the halogenating agent can be conventionally selected. Preferably, relative to 100 mol of monomer M, the amount of the halogenating agent can be in the range of 1 to 150 mol, and more preferably 5 to 120 mol. For example, it can be 1 mol, 2 mol, 5 mol, 8 mol, 10 mol, 20 mol, 30 mol, 50 mol, 60 mol, 70 mol, 75 mol, 80 mol, 90 mol, 100 mol, 110 mol, 120 mol or any value between the above values ​​or any range between any two of the above values ​​(for example, it can be in the range of 5 to 110 mol, 10 to 100 mol, 20 to 95 mol, 30 to 90 mol, 30 to 80 mol, etc.).

[0047] In step (2), the halogenation reaction can be carried out under conventional conditions. For example, the reaction conditions may include: a temperature of 0 to 100°C, preferably 2.5 to 90°C, more preferably 5 to 80°C, and even more preferably 30 to 80°C; a reaction time of 0.5 to 10 h, preferably 0.5 to 8 h, more preferably 0.5 to 6 h; and a stirring speed of 50 to 1000 rpm, preferably 50 to 500 rpm, more preferably 100 to 500 rpm.

[0048] In step (2), the product (suspension) obtained in step (1) can be post-treated (separated, washed, and dried) before the grafting reaction. The dried product is directly added to a halogenating agent or a halogenating agent solution for reaction. The washing can be done using a conventional washing solvent, such as at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether. The concentration of the halogenating agent solution can be 0.5–50 wt%, preferably 10–50 wt%.

[0049] The final product obtained in step (2) can be further separated to obtain toughened flame retardant granule products. For example, the separation process can be carried out as follows: centrifugation, water washing, organic solvent washing (the washing solvents mentioned above can be used, namely at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether and methyl tert-butyl ether), centrifugation, and drying (such as vacuum drying).

[0050] A third objective of this invention is to provide the application of the aforementioned toughening flame retardant or the product prepared by the aforementioned preparation method in flame-retardant and impact-resistant materials.

[0051] The fourth objective of this invention is to provide a composite additive, which may contain the toughening flame retardant described in the first objective of this invention or the product prepared by the preparation method described in the second objective of this invention;

[0052] Preferably, it may also contain at least one of aluminum hypophosphite flame retardants and flame retardant synergists;

[0053] in,

[0054] The weight ratio of the aluminum hypophosphite flame retardant to the toughening flame retardant is (0-50):1; preferably (0-30):1; more preferably (0-20):1; for example, it can be 0, 0.005:1, 0.01:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.6:1, 1.0:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10: 1, 12:1, 15:1, 18:1, 20:1, 24:1, 26:1, 28:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any value between the above or any two of the above values ​​(for example, it could be ((0.005~15):1, (0.01~12):1, (0.01~10):1, (0.01~5):1, (0.01~3):1, etc.).

[0055] The weight ratio of the flame retardant synergist to the toughening flame retardant is (0-50):1; preferably (0-20):1; more preferably (0-10):1; for example, it can be 0, 0.001:1, 0.002:1, 0.005:1, 0.006:1, 0.008:1, 0.01:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.6:1, 1.0:1, 2 The range is 1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 24:1, 26:1, 28:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any value between the above or any two of the above values ​​(e.g., (0.001-8):1, (0.005-5):1, (0.008-2):1, etc.).

[0056] Preferably, the aluminum hypophosphite flame retardant may be inorganic aluminum hypophosphite and / or alkyl aluminum hypophosphite; the alkyl aluminum hypophosphite may preferably be at least one of diethyl aluminum hypophosphite, dipropyl aluminum hypophosphite, and phenyl aluminum hypophosphite; the aluminum hypophosphite flame retardant is more preferably inorganic aluminum hypophosphite and / or diethyl aluminum hypophosphite.

[0057] The flame retardant synergist may be selected from at least one of 2,3-dimethyl-2,3-diphenylbutane (DMDPB, abbreviated as cyclohexane) and p-isopropylbenzene polymer (polycyclohexane).

[0058] The preparation method of the composite additive includes the following steps: preparing components including the toughening and flame retardant additive, optional aluminum hypophosphite flame retardant, and optional flame retardant synergist, and then mixing or not mixing these components.

[0059] The composite additive can be used by adding the components, including the toughening and flame retardant additive, optional aluminum hypophosphite flame retardant, and optional flame retardant synergist, together or separately to the matrix resin and mixing them.

[0060] A fifth objective of this invention is to provide a flame-retardant and impact-resistant resin composition, which may comprise the aforementioned toughening flame retardant and resin; specifically, it may comprise the toughening flame retardant described in one objective of this invention and / or the toughening flame retardant product prepared by the preparation method described in another objective of this invention, and further comprise resin. Preferably, the flame-retardant and impact-resistant resin composition may comprise the following components in parts by weight:

[0061] 100 parts resin;

[0062] The toughening flame retardant is used in quantities of 0.05 to 50 parts, preferably 0.1 to 30 parts, more preferably 0.1 to 20 parts, and more preferably 0.1 to 15 parts. For example, it can be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, or any value between the above values ​​or a range between any two of the above values ​​(for example, a range of 0.1 to 25, 0.5 to 20, 0.5 to 15, 0.5 to 12, etc.).

[0063] The flame-retardant and impact-resistant resin composition may also contain aluminum hypophosphite flame retardants and / or flame-retardant synergists.

[0064] Specifically,

[0065] The flame-retardant and impact-resistant resin composition may also contain aluminum hypophosphite flame retardants;

[0066] Based on 100 parts by weight of the resin, the amount of the aluminum hypophosphite flame retardant can be 0 to 2.0 parts, preferably 0.01 to 1.5 parts, and more preferably 0.1 to 0.8 parts; for example, it can be 0, 0.01, 0.02, 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2 or any value between the above values ​​or a range between any two of the above values ​​(for example, a range of 0.05 to 1.0, 0.08 to 0.8, 0 to 1, etc.).

[0067] Preferably, the aluminum hypophosphite flame retardant may be inorganic aluminum hypophosphite and / or alkyl aluminum hypophosphite; the alkyl aluminum hypophosphite is preferably at least one of diethyl aluminum hypophosphite, dipropyl aluminum hypophosphite, phenyl aluminum hypophosphite, etc.; the aluminum hypophosphite flame retardant is more preferably inorganic aluminum hypophosphite and / or diethyl aluminum hypophosphite.

[0068] The flame-retardant and impact-resistant resin composition may also contain flame-retardant synergists;

[0069] Based on 100 parts by weight of the resin, the amount of the flame retardant synergist can be 0 to 1.5 parts, preferably 0.01 to 1.2 parts, and more preferably 0.02 to 0.8 parts; for example, it can be 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5 or any value between the above values ​​or a range between any two of the above values ​​(for example, it can be a range of 0.01 to 1.0, 0.04 to 0.8, 0.05 to 0.5, 0.05 to 0.2, 0 to 0.5, etc.).

[0070] The flame retardant synergist may be selected from at least one of 2,3-dimethyl-2,3-diphenylbutane (DMDPB, abbreviated as cyclohexane) and p-isopropylbenzene polymer (polycyclohexane).

[0071] In specific implementations, the flame-retardant and impact-resistant resin composition may further include aluminum hypophosphite flame retardants and / or flame-retardant synergists; specifically, it may include the following components in parts by weight:

[0072] 100 parts resin;

[0073] The aluminum hypophosphite flame retardant is used in an amount of 0 to 2.0 parts, preferably 0.01 to 1.5 parts, and more preferably 0.1 to 0.8 parts;

[0074] The flame retardant synergist is 0-1.5 parts, preferably 0.01-1.2 parts, and more preferably 0.02-0.8 parts;

[0075] The toughening flame retardant is used in amounts of 0.05 to 50 parts, preferably 0.1 to 30 parts, more preferably 0.1 to 20 parts, and even more preferably 0.1 to 15 parts.

[0076] In practical applications, other functional additives may be added. For every 100 parts by weight of the thermoplastic resin, the amount of other functional additives can range from 0.1 to 100 parts by weight, and the specific amount can be adjusted as needed. These other functional additives may include at least one of antioxidants, light stabilizers, toughening agents, compatibilizers, pigments, dispersants, etc.

[0077] in,

[0078] The resin may be selected from at least one of thermoplastic resins or thermosetting resins and / or alloys of said resins; specifically, it may be at least one of polyolefins, polystyrene, polyoxymethylene, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene ether, polyphenylene sulfide, epoxy resin, unsaturated polyester, vinyl resin and / or at least one alloy of said resins (e.g., PC / ABS, etc.); the thermoplastic resin or thermosetting resin is preferably at least one of polyolefins, unsaturated polyesters, vinyl resins, polystyrene, nylon, etc.; the thermoplastic resin is preferably polyolefin; more specifically, the polyolefin may be selected from at least one of polyethylene, polypropylene, polyethylene resin and copolymers thereof.

[0079] The sixth objective of this invention is to provide a method for preparing the flame-retardant and impact-resistant resin composition, which may include the following steps: blending the components including the resin, the toughening flame retardant, an optional aluminum hypophosphite flame retardant, and an optional flame retardant synergist.

[0080] The preparation method may specifically include the following steps:

[0081] For thermoplastic resins:

[0082] a1. Mix the components, including the thermoplastic resin, the toughening flame retardant, optional aluminum hypophosphite flame retardant, and optional flame retardant synergist, until homogeneous; a high-speed mixer may be used.

[0083] b1. The premixed material from step (a1) is extruded and granulated, and then dried to obtain the flame-retardant and impact-resistant thermoplastic resin composition. Specifically, commonly used instruments and equipment in the art, such as a twin-screw extruder, can be used.

[0084] For thermosetting resins:

[0085] The flame-retardant and impact-resistant thermosetting resin composition is obtained by uniformly mixing the components, including the uncured resin, the toughening flame retardant, the optional aluminum phosphate flame retardant, and the optional flame retardant synergist.

[0086] Extensive experiments have shown that the toughening flame retardant described in this invention has good flowability and low moisture absorption. During the preparation of the flame-retardant and impact-resistant resin composition, the toughening flame retardant does not stick to the wall, is easy to feed, and the production operation is simple, requiring minimal production condition control. The resulting flame-retardant and impact-resistant thermoplastic resin composition exhibits good flame-retardant and impact-resistant effects. Furthermore, because the additives of this invention are generally non-polar, their water absorption rate is lower than that of conventional inorganic flame retardants, thus improving the water resistance of the samples prepared using this invention.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] (1) This invention provides a toughening flame retardant and its preparation method. Through structural design and formulation control, a single-component halogenated polymer particle with both flame retardant and toughening functions is prepared. Compared with the current method of adding flame retardant and toughening agent separately, this halogenated polymer particle is easily dispersed in thermoplastic resin and thermosetting resin before curing, effectively improving the efficiency of flame retardancy and toughening. In addition, the particles with residual double bonds on the surface can crosslink with some thermosetting resins (such as unsaturated polyester, vinyl resin, etc.), further improving the toughening efficiency of the material.

[0089] (2) This invention provides a low-addition-amount flame-retardant and impact-resistant resin composition and its preparation method. Through formulation control and the introduction of highly efficient, multifunctional, single-component toughening flame-retardant particles, the flame-retardant and impact-resistant effects of the resin can be improved, resulting in a resin composition with both flame-retardant and impact-resistant properties. Due to the improved flame-retardant and toughening efficiency of the additives, the reduced additive dosage, and the improved dispersion performance, the prepared resin composition exhibits excellent overall performance. It is suitable for products requiring both flame retardancy and toughness, such as at least one of plastics, fibers, films, fabrics, and injection-molded products, for example, injection-molded parts, and can be used in products such as home appliances, vehicles, electronic products, and machinery; it is also suitable for densely populated places such as hotels, hospitals, and schools, as well as for smart home appliances and new energy vehicles. Detailed Implementation

[0090] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0091] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0092] Source of raw materials

[0093] Polyethylene (PE): Grade 7042, Maoming Petrochemical;

[0094] Polypropylene (PP), Cangzhou Refining & Chemical GD-H-230;

[0095] Ethylene propylene diene monomer (EPDM) rubber: Grade 3112M, Shanghai Sinopec Mitsui;

[0096] Nylon 6: Brand name B3S, BASF;

[0097] PC: Polycarbonate, 7022IRF, China Petroleum & Chemical Corporation Beijing Yanshan Branch;

[0098] ABS: Polyacrylonitrile / butadiene / styrene copolymer, grade 3504, Shanghai Gaoqiao;

[0099] Vinyl resin: Grade 901, Shangwei;

[0100] Unsaturated polyester: Type 196, Jinan Baorui Resin Chemical Co., Ltd.;

[0101] Lianku, Guangzhou Xijia Chemical Co., Ltd.

[0102] Aluminum hypophosphite, Guangzhou Xijia Chemical Co., Ltd.

[0103] Maleic anhydride: Jiangsu Leien Environmental Protection Technology Co., Ltd.;

[0104] Compound antioxidant (antioxidant): Antioxidant 1010 (BASF), antioxidant 168 (BASF), and calcium stearate (Shandong Haona) are mixed evenly in a mass ratio of 2 / 2 / 1 to obtain the product;

[0105] Powdered hydrogenated nitrile butadiene rubber: Hydrogenated nitrile butadiene rubber latex with a solid content of 50% (produced by Qilu Petrochemical Co., Ltd.) is obtained by spray drying, with a hydrogenation rate of 91%, halogen content of 0, and an average particle size of about 10μm.

[0106] The performance testing method for the flame-retardant and impact-resistant resin composition of the present invention is performed according to the following standards:

[0107] Tensile strength: GB / T1040-2006

[0108] Flexural modulus: GB / T 9341-2008

[0109] Impact resistance: GB / T 1043.2-2018

[0110] Vertical combustion test standard number: GN / T 2408-2008

[0111] Limiting oxygen index test standard number: GB / T 2406.1-2008

[0112] Standard number for the glow wire flammability index test: GB / T5961.11-2006

[0113] 1. Preparation of toughening flame retardants

[0114] Example 1:

[0115] (1) Disperse 100g of powdered hydrogenated nitrile rubber particles in 1800mL of isoamyl acetate, then dissolve 100g of maleic anhydride and 2g of azobisisobutyronitrile in it to form solution one, and introduce a measured amount of butadiene (the molar ratio of maleic anhydride to butadiene is 1:1). Under a nitrogen atmosphere, react at 70℃ and 0.5MPa for 1 hour.

[0116] (2) Dissolve 50g of divinylbenzene in 200mL of isoamyl acetate to form solution two. Add solution two to the reaction system by a plunger pump and add it dropwise for 2 hours. After the addition is completed, continue to keep the reaction system warm for 3 hours.

[0117] (3) After the reaction, the pressure was released, and 120g of liquid bromine was added. The reaction was carried out at 80℃ for 3 hours. The system was allowed to stand and separate into layers. The heavy phase was centrifuged at 5000 rad / min for 20 minutes. The solid was washed with 4L of water and centrifuged at 5000 rad / min for 20 minutes. The solid was washed with 4L of ethanol and centrifuged at 5000 rad / min for 20 minutes. The solid was then vacuum dried to obtain the toughened flame retardant, namely the halogenated core-shell polymer particles #1. The average particle size of the obtained particles was approximately 14μm. The halogen content was determined to be 9.1wt% by EDS (energy dispersive spectroscopy) and the double bond content was determined to be 0.11mmol / g by iodometric titration.

[0118] Example 2:

[0119] The toughening flame retardant was prepared according to the method in Example 1, except that the system after the reaction in step (2) was centrifuged at 5000 rad / min for 30 minutes to obtain core-shell rubber particles, which were then washed and purified with n-hexane and vacuum dried. The dried core-shell rubber particles were then added to 500 g of bromine in an ethanol solution (20 wt%) and reacted at 80°C for 3 hours. The system after the reaction was centrifuged at 5000 rad / min for 20 minutes, the solid was washed with 4 L of water, centrifuged again at 5000 rad / min for 20 minutes, washed again with 4 L of ethanol, centrifuged again at 5000 rad / min for 20 minutes, and vacuum dried to obtain the flame retardant and toughening agent, namely, halogenated core-shell polymer particles #2. The average particle size of the obtained particles was approximately 14 μm, the halogen content was 8.6 wt% as determined by EDS, and the double bond content was 0.17 mmol / g as determined by iodometric titration.

[0120] Example 3:

[0121] The toughened flame retardant was prepared according to the method in Example 1, except that the reaction conditions in step (1) were changed to 70°C and 0.4 MPa for 2 hours; and in step (3), after adding 120 g of liquid bromine, the reaction conditions were changed to 60°C for 7 hours. The toughened flame retardant, namely halogenated core-shell polymer particles #3, was finally obtained. The average particle size of the obtained polymer particles was approximately 14 μm, the halogen content was 11.4 wt% as determined by EDS, and the double bond content was 0.03 mmol / g as determined by iodometric titration.

[0122] Example 4:

[0123] The toughening flame retardant was prepared according to the method in Example 1, except that solution 2 in step (2) was replaced with a solution of 0.5 g of azobisisobutyronitrile and 18 g of divinylbenzene dissolved in 200 mL of isoamyl acetate. The toughening flame retardant, namely halogenated core-shell polymer particles #4, was finally obtained. The average particle size of the obtained polymer particles was approximately 13 μm, the halogen content was 9.4 wt% as determined by EDS, and the double bond content was 0.24 mmol / g as determined by iodometric titration.

[0124] Example 5:

[0125] The toughening flame retardant was prepared according to the method of Example 1, except that the monomer introduced in step (1) was replaced with a measured amount of isoprene (the molar ratio of maleic anhydride to isoprene was 1:1); and the solution in step (2) was replaced with a solution formed by dissolving 11g of isoprene and 39g of divinylbenzene in 200mL of isoamyl acetate. The toughening flame retardant, namely halogenated core-shell polymer particles #5, was finally obtained. The average particle size of the obtained polymer particles was approximately 14μm, the halogen content was 8.7wt% as determined by EDS, and the double bond content was 0.19mmol / g as determined by iodometric titration.

[0126] Example 6:

[0127] The toughening flame retardant was prepared according to the method of Example 5, except that the amount of divinylbenzene in step (2) was changed to 10g, and halogenated core-shell polymer particles 6# were finally obtained. The average particle size of the obtained polymer particles was about 14μm, the halogen content was 9.7wt% by EDS test, and the double bond content was 0.23mmol / g by iodometric titration.

[0128] Example 7:

[0129] The toughening flame retardant was prepared according to the method of Example 1, except that divinylbenzene in step (2) was replaced with 36.0 g of isoprene, resulting in halogenated core-shell polymer particles #7. The average particle size of the obtained polymer particles was approximately 14 μm. The halogen content was determined to be 10.9 wt% by EDS and the double bond content was determined to be 0.36 mmol / g by iodometric titration.

[0130] 2. Preparation of flame-retardant and impact-resistant resin plastics

[0131] The formulations of the thermoplastic resin compositions used in the examples are shown in Table 1 (all amounts in Table 1 are parts by weight).

[0132] Example 8:

[0133] 100 parts by weight of polypropylene, 5 parts by weight of polymer granules #1, 0.2 parts by weight of aluminum hypophosphite, 0.1 parts by weight of flame retardant synergist DMDPB, and 0.25 parts by weight of antioxidant were placed in a low-speed mixer and thoroughly mixed. The mixture was then melt-blended through a twin-screw extruder at a temperature of 190℃~220℃ and a speed of 350rpm. The extruded granules were dried in a 90℃ constant temperature oven for 3 hours and then injected into standard specimens of specified sizes at an injection molding temperature of 200~220℃ for flame retardancy and impact testing.

[0134] Comparative Example 1:

[0135] The sample was prepared according to the method of Example 8, except that the formulation was changed to 100 parts by weight of polypropylene and 0.25 parts by weight of antioxidant. Flame retardancy and impact tests were then performed.

[0136] Comparative Example 2:

[0137] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "ordinary EPDM toughening agent 5 parts by weight". Flame retardancy and impact tests were then performed.

[0138] Example 9:

[0139] The sample was prepared according to the method of Example 8, except that "5 parts by weight of polymer particles 1#" in the formulation was replaced with "5 parts by weight of polymer particles 2#". Flame retardancy and impact tests were then performed.

[0140] Example 10:

[0141] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 3# 5 parts by weight". Then, flame retardancy and impact tests were performed.

[0142] Example 11:

[0143] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formula was replaced with "polymer particles 4# 8 parts by weight"; and the weight of aluminum hypophosphite was reduced from 0.2 to 0. Flame retardancy and impact tests were then performed.

[0144] Comparative Example 3:

[0145] The sample was prepared according to the method of Example 8, except that "5 parts by weight of polymer particles 1#" in the formulation was replaced with "8 parts by weight of EPDM rubber toughening agent"; and the weight of aluminum hypophosphite was reduced from 0.2 to 0. Flame retardancy and impact tests were then performed.

[0146] Example 12:

[0147] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 5# 5 parts by weight". Then, flame retardancy and impact tests were performed.

[0148] Example 13:

[0149] The sample was prepared according to the method of Example 8, except that "5 parts by weight of polymer particles 1#" in the formulation was replaced with "5 parts by weight of polymer particles 6#". Flame retardancy and impact tests were then performed.

[0150] Example 14:

[0151] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 7# 6 parts by weight". Flame retardancy and impact tests were then performed.

[0152] Example 15:

[0153] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 4# 5 parts by weight". Then, flame retardancy and impact tests were performed.

[0154] Example 16:

[0155] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 4# 5 parts by weight"; and the amount of flame retardant synergist was reduced to 0. Then flame retardant and impact tests were performed.

[0156] Example 17:

[0157] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formula was replaced with "polymer particles 4# 5 parts by weight"; and the amount of aluminum hypophosphite was reduced to 0. Then, flame retardancy and impact tests were performed.

[0158] Example 18:

[0159] The sample was prepared according to the method of Example 8, except that "polymer particles 1# 5 parts by weight" in the formulation was replaced with "polymer particles 4# 8 parts by weight". Then, flame retardancy and impact tests were performed.

[0160] Comparative Example 4:

[0161] The sample was prepared according to the method of Example 8, except that the weight percentage of polymer particles 1# in the formulation was reduced from 5 to 0, and the amount of aluminum hypophosphite was increased to 8. Flame retardancy and impact tests were then performed.

[0162] Comparative Example 5:

[0163] The sample was prepared according to the method of Example 8, except that the weight of polymer particles 1# in the formulation was reduced from 5 to 0; and the amount of aluminum hypophosphite was reduced to 0. Flame retardancy and impact tests were then performed.

[0164] Comparative Example 6:

[0165] The sample was prepared according to the method of Example 8, except that the weight percentage of polymer particles 1# in the formulation was reduced from 5 to 0. Flame retardancy and impact tests were then performed.

[0166] The formulations of Examples 8-18 and Comparative Examples 1-6 are shown in Table 1 (all amounts in Table 1 are parts by weight), and the properties of the prepared compositions are shown in Table 2.

[0167] Example 19:

[0168] 100 parts by weight of polyethylene, 10 parts by weight of polymer granules #1, and 0.25 parts by weight of antioxidant were placed in a low-speed mixer and thoroughly mixed. The mixture was then melt-blended through a twin-screw extruder at a temperature of 190℃~210℃ and a speed of 350rpm. The extruded granules were dried in a 90℃ constant temperature oven for 3 hours and then injected into samples at an injection molding temperature of 190~200℃ for flame retardancy and impact testing.

[0169] Comparative Example 7:

[0170] The sample was prepared according to the method of Example 19, except that polymer particles 1# were not added to the formulation. Flame retardancy and impact tests were then performed.

[0171] Example 20:

[0172] 100 parts by weight of nylon 6, 10 parts by weight of polymer granules #2, and 0.3 parts by weight of antioxidant were placed in a low-speed mixer and thoroughly mixed. The mixture was then melt-blended through a twin-screw extruder at a temperature of 220℃~240℃ and a speed of 350rpm. The extruded granules were dried in a 90℃ constant temperature oven for 3 hours and then injected into samples at an injection molding temperature of 230~240℃ for flame retardancy and impact testing.

[0173] Comparative Example 8:

[0174] The sample was prepared according to the method of Example 20, except that polymer particles #2 were not added to the formulation. Flame retardancy and impact tests were then performed.

[0175] Example 21:

[0176] 80 parts by weight of PC, 20 parts by weight of ABS, 10 parts by weight of polymer granules #4, and 0.3 parts by weight of antioxidant were placed in a low-speed mixer and thoroughly mixed. The mixture was then melt-blended through a twin-screw extruder at a temperature of 230℃~260℃ and a speed of 350rpm. The extruded granules were dried in a 90℃ constant temperature oven for 3 hours and then injected into samples at an injection molding temperature of 230~240℃ for flame retardancy and impact testing.

[0177] Comparative Example 9:

[0178] The sample was prepared according to the method of Example 21, except that polymer particles 4# were not added to the formulation. Flame retardancy and impact tests were then performed.

[0179] Example 22:

[0180] Mix 100 parts by weight of vinyl resin, 10 parts by weight of polymer granules #5, and 1 part of benzoyl peroxide thoroughly. Pour the mixture into a mold and gradually increase the temperature of the mold: 80℃ for 2 hours, 130℃ for 2 hours, and 160℃ for 2 hours. Then, wait for the mold to cool to approximately 100℃ and remove the material. Finally, allow the sample to cool to room temperature for flame retardancy and impact testing.

[0181] Comparative Example 10:

[0182] The sample was prepared according to the method of Example 22, except that polymer particles 5# were not added to the formulation. Flame retardancy and impact tests were then performed.

[0183] Example 23:

[0184] Mix 100 parts by weight of unsaturated polyester, 10 parts by weight of polymer granules #6, and 1 part of benzoyl peroxide thoroughly. Pour the mixture into a mold and gradually increase the temperature of the mold: 80℃ for 1 hour, 100℃ for 2 hours, and 130℃ for 2 hours. Then, wait for the mold to cool to approximately 100℃ and remove the material. Finally, allow the sample to cool to room temperature for flame retardancy and impact testing.

[0185] Comparative Example 11:

[0186] The sample was prepared according to the method of Example 23, except that polymer particles 6# were not added to the formulation. Flame retardancy and impact tests were then performed.

[0187] The formulations of the compositions used in Examples 19-23 and Comparative Examples 7-11 are shown in Table 3 (all amounts in Table 3 are parts by weight), and the properties of the prepared compositions are shown in Table 4.

[0188] Table 1: Formulations of the compositions of Examples 8-18 and Comparative Examples 1-6

[0189]

[0190] Table 2: Performance comparison of the compositions of Examples 8-18 and Comparative Examples 1-6

[0191]

[0192] As can be seen from the test results in Tables 1 and 2, PP resin is highly flammable and has poor impact resistance.

[0193] Examples 8-18 are flame-retardant and impact-resistant PP compositions containing toughening flame-retardant particles prepared using the present invention. As shown in Table 2, the thermoplastic resin compositions according to the present invention not only exhibit excellent impact resistance but also achieve a UL-94 test V-2 rating with low flame retardant addition, demonstrating good self-extinguishing properties. The compositions in Examples 8-18 passed the glow wire flammability index test at 750°C.

[0194] By comparing Example 11 with Comparative Examples 3, 4 and 5, and Example 8 with Comparative Example 2, it can be seen that, under the same amount of toughening flame retardant added, the composition using the toughening flame retardant of the present invention has superior overall impact resistance and flame retardant performance compared to compositions using individual toughening agents, individual flame retardants or combinations thereof in the prior art.

[0195] By comparing Examples 11 and 18 with Comparative Example 4 or Comparative Example 5, it can be seen that when the toughening flame retardant of the present invention is used in combination with aluminum hypophosphite flame retardant or flame retardant synergist, the flame retardant performance obtained is better than that obtained by using the same amount of single component through the synergistic effect between halogen and the two additives.

[0196] The comparison between Comparative Example 2 and Comparative Example 6 shows that the addition of existing toughening agents reduces the flame retardant properties of resin compositions containing flame retardants.

[0197] As can be seen from Comparative Example 1, PP resin itself is highly flammable and has poor impact resistance. Examples 8-18 are low-addition flame-retardant and impact-resistant plastic resin compositions prepared by the method of the present invention. As shown in Table 2, the prepared compositions not only have excellent impact resistance, but also achieve UL-94 test level V-2 with the addition of toughening flame retardants, exhibiting good self-extinguishing properties. They can pass the glow wire flammability index test at 750°C. Compared with pure PP, it not only has flame retardant and impact resistance, but also improves the tensile strength and flexural modulus of the composition, overcoming the technical difficulty of reduced overall material performance caused by poor dispersion of flame retardants and toughening agents in the matrix.

[0198] Table 3: Formulations of the compositions of Examples 19-23 and Comparative Examples 7-11

[0199]

[0200] Table 4: Performance comparison of compositions from Examples 19-23 and Comparative Examples 7-11

[0201]

[0202] As can be seen from Table 4, the toughening flame retardant particles of the present invention improve the flame retardancy and impact resistance of PE, PA6, PC / ABS, vinyl resin, and unsaturated polyester.

[0203] In summary, the single-component multifunctional toughening flame retardant particles of the present invention not only have high flame retardant and impact resistance efficiency, but also have good dispersibility in the substrate, overcoming the technical difficulty of reduced overall material performance caused by poor dispersibility of flame retardants and toughening agents in the substrate.

[0204] Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those skilled in the art. Furthermore, it should be understood that the aspects described in the invention, the parts of different embodiments, and the various features listed can be combined or interchanged in whole or in part. In the various embodiments described above, those embodiments referencing another embodiment can be appropriately combined with other embodiments, as will be understood by those skilled in the art. Moreover, those skilled in the art will understand that the foregoing description is merely illustrative and not intended to limit the invention.

Claims

1. A toughening flame retardant, comprising modified polymer particles, said polymer particles comprising a core-shell structure consisting of a core composed of polymer A and a shell composed of polymer B; said modification is performed by modification with halogenating agent C; The polymer A is at least one of hydrogenated nitrile butadiene rubber and its derivatives; The polymer B comprises a copolymer and its derivatives consisting of structural unit X derived from maleic anhydride and structural unit Y derived from monomer M; wherein monomer M is selected from one or more of butadiene, divinylbenzene, isoprene or dicyclopentadiene.

2. The toughening flame retardant according to claim 1, characterized in that: The average particle size of the polymer particles is 200~3,000,000 nm.

3. The toughening flame retardant according to claim 2, characterized in that: The average particle size of the polymer particles is 200~1,500,000 nm.

4. The toughening flame retardant according to claim 1, characterized in that: The mass ratio between polymer A and polymer B ranges from (1:100) to (100:1).

5. The toughening flame retardant according to claim 4, characterized in that: The mass ratio between polymer A and polymer B ranges from (1:80) to (80:1).

6. The toughening flame retardant according to claim 1, characterized in that: The halogenating agent C contains at least one substance that can link halogens to polymer molecular chains.

7. The toughening flame retardant according to claim 6, characterized in that: The halogenating agent C is selected from one or more of fluorine, chlorine, liquid bromine, elemental iodine, hydrofluoric acid, hydrogen chloride, hydrobromic acid, or hydroiodic acid.

8. The toughening flame retardant according to claim 1, characterized in that: The hydrogenated nitrile rubber is powdered hydrogenated nitrile rubber.

9. The toughening flame retardant according to claim 8, characterized in that: The hydrogenated nitrile butadiene rubber has a particle size of 150~2,000,000 nm.

10. The toughening flame retardant according to any one of claims 1 to 9, characterized in that: The toughening flame retardant has a double bond content of 0.001 ~ 18.2 mmol / g; and / or, The halogen content of the toughening flame retardant is 0~35wt%, and is not 0.

11. The toughening flame retardant according to claim 10, characterized in that: The toughening flame retardant has a double bond content of 0.002~17 mmol / g; and / or, The halogen content of the toughening flame retardant is 2-30 wt%.

12. The method for preparing the toughening flame retardant according to any one of claims 1 to 11, characterized in that... Includes the following steps: In the presence of an initiator, a shell is formed on the surface of polymer A by copolymerization of components including maleic anhydride and the monomer M, and then halogenated with a halogenating agent to obtain the toughened flame retardant.

13. The method for preparing the toughening flame retardant according to claim 12, characterized in that... Includes the following steps: (1) The polymer A is dispersed in an organic solvent, and maleic anhydride and the first monomer M are reacted in contact in the presence of the first initiator, and then another monomer-containing solution is introduced to continue the reaction; wherein the other monomer-containing solution contains optional second monomer M and optional second initiator. (2) Add a halogenating agent to the product obtained in step (1) and react to obtain the toughening flame retardant.

14. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (1), the total mass of the maleic anhydride and monomer M is 1 ~ 10000 g relative to 100 g of the polymer A.

15. The method for preparing the toughening flame retardant according to claim 14, characterized in that: In step (1), the total mass of the maleic anhydride and monomer M is 1 to 8000 g relative to 100 g of the polymer A.

16. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (1), The total amount of the first monomer M and the second monomer M, calculated as terminal olefins, relative to 100 mol of the maleic anhydride is 10~1000 mol; and / or, In step (1), The molar ratio between monomer M in the second part and monomer M in the first part is (0~100):

100.

17. The method for preparing the toughening flame retardant according to claim 16, characterized in that: In step (1), The total amount of the first monomer M and the second monomer M, based on terminal olefins, is 20 to 800 mol relative to 100 mol of the maleic anhydride.

18. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (1), The organic solvent includes alkyl esters of organic acids.

19. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (1), The organic solvent is selected from organic acid alkyl esters, or mixtures of organic acid alkyl esters and alkanes, or mixtures of organic acid alkyl esters and aromatic hydrocarbons.

20. The method for preparing the toughening flame retardant according to claim 19, characterized in that: The organic acid alkyl ester is selected from at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.

21. The method for preparing the toughening flame retardant according to claim 19, characterized in that: The alkane is selected from n-hexane and / or n-heptane.

22. The method for preparing the toughening flame retardant according to claim 19, characterized in that: The aromatic hydrocarbon is selected from at least one of benzene, toluene, and xylene.

23. The method for preparing the toughening flame retardant according to claim 13, characterized in that: The total amount of the first and second initiators relative to 100 mol of maleic anhydride is 0.05–10 mol; and / or, The molar ratio between the second initiator and the first initiator is (0~100):100; and / or, The initiator is a thermally decomposable initiator.

24. The method for preparing the toughening flame retardant according to claim 23, characterized in that: The total amount of the first and second initiators relative to 100 mol of maleic anhydride is 0.5 to 5 mol.

25. The method for preparing the toughening flame retardant according to claim 24, characterized in that: The total amount of the first and second initiators relative to 100 mol of maleic anhydride is 0.8 to 1.5 mol.

26. The method for preparing the toughening flame retardant according to claim 23, characterized in that: The initiator is selected from at least one of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide dicarbonate, dicyclohexyl peroxide dicarbonate, azobisisobutyronitrile, or azobisisoheptanenitrile.

27. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (1), the conditions for the reaction of maleic anhydride with monomer M include: Inert atmosphere, temperature 50~90℃; pressure 0~1 MPa; and / or, In step (2), The reaction conditions include: a temperature of 0~100℃ and a stirring speed of 50~1000rpm.

28. The method for preparing the toughening flame retardant according to claim 27, characterized in that: In step (1), the conditions for the reaction of maleic anhydride with monomer M include: Inert atmosphere, temperature 60~70℃; pressure 0~0.5 MPa.

29. The method for preparing the toughening flame retardant according to claim 27, characterized in that: In step (2), The reaction conditions include: a temperature of 2.5~90℃ and a stirring speed of 50~500rpm.

30. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (2), The halogenating agent or a solution of the halogenating agent is added to the product obtained in step (1), and the mixture is stirred to carry out the reaction.

31. The method for preparing the toughening flame retardant according to claim 30, characterized in that: In step (2), The amount of the halogenating agent used is in the range of 1 to 150 mol relative to 100 mol of monomer M.

32. The method for preparing the toughening flame retardant according to claim 31, characterized in that: In step (2), The amount of the halogenating agent used is 5 to 120 mol relative to 100 mol of monomer M.

33. The method for preparing the toughening flame retardant according to claim 13, characterized in that: In step (2), The product obtained in step (1) is post-treated before being reacted; the post-treatment includes separating, washing and drying the product obtained in step (1); the dried product is directly added to a halogenating agent or a halogenating agent solution for reaction.

34. The method for preparing the toughening flame retardant according to claim 33, characterized in that: In step (2), The concentration of the halogenating agent solution is 0.5~50wt%.

35. The method for preparing the toughening flame retardant according to claim 34, characterized in that: In step (2), The concentration of the halogenating agent solution is 10~50wt%.

36. The use of the toughening flame retardant according to any one of claims 1 to 11 or the product prepared by the preparation method according to any one of claims 12 to 35 in flame-retardant and impact-resistant materials.

37. A composite additive comprising the toughening flame retardant according to any one of claims 1 to 11 and / or a product prepared by the preparation method according to any one of claims 12 to 35.

38. The composite additive according to claim 37, characterized in that... It also contains at least one of aluminum hypophosphite flame retardants and flame retardant synergists.

39. The composite additive according to claim 38, characterized in that: The aluminum hypophosphite flame retardant is inorganic aluminum hypophosphite and / or alkyl aluminum hypophosphite.

40. The composite additive according to claim 39, characterized in that: The alkyl aluminum hypophosphite is selected from at least one of diethyl aluminum hypophosphite, dipropyl aluminum hypophosphite, and phenyl aluminum hypophosphite.

41. The composite additive according to claim 39, characterized in that: The aluminum hypophosphite flame retardant is selected from inorganic aluminum hypophosphite and / or diethyl aluminum hypophosphite.

42. The composite additive according to claim 38, characterized in that: The flame retardant synergist is selected from at least one of 2,3-dimethyl-2,3-diphenylbutane and p-isopropylbenzene polymer.

43. The composite additive according to claim 38, characterized in that: The weight ratio of the aluminum hypophosphite flame retardant to the toughening flame retardant is (0~50):

1.

44. The composite additive according to claim 43, characterized in that: The weight ratio of the aluminum hypophosphite flame retardant to the toughening flame retardant is (0~30):

1.

45. The composite additive according to claim 44, characterized in that: The weight ratio of the aluminum hypophosphite flame retardant to the toughening flame retardant is (0~20):

1.

46. ​​The composite additive according to claim 38, characterized in that: The weight ratio of the flame retardant synergist to the toughening flame retardant is (0~50):

1.

47. The composite additive according to claim 46, characterized in that: The weight ratio of the flame retardant synergist to the toughening flame retardant is (0~20):

1.

48. The composite additive according to claim 47, characterized in that: The weight ratio of the flame retardant synergist to the toughening flame retardant is (0~10):

1.

49. A flame-retardant and impact-resistant resin composition comprising the toughening flame retardant and resin as described in any one of claims 1 to 11.

50. The flame-retardant and impact-resistant resin composition according to claim 49, characterized in that: The resin composition comprises the following components in parts by weight: 100 parts resin; The toughening flame retardant is 0.05 to 50 parts.

51. The flame-retardant and impact-resistant resin composition according to claim 50, characterized in that: The resin composition comprises the following components in parts by weight: 100 parts resin; The toughening flame retardant is 0.1 to 30 parts.

52. The flame-retardant and impact-resistant resin composition according to claim 51, characterized in that: The resin composition comprises the following components in parts by weight: 100 parts resin; The toughening flame retardant is 0.1 to 20 parts.

53. The flame-retardant and impact-resistant resin composition according to claim 52, characterized in that: The resin composition comprises the following components in parts by weight: 100 parts resin; The toughening flame retardant is 0.1 to 15 parts.

54. The flame-retardant and impact-resistant resin composition according to claim 49, characterized in that: The resin is selected from at least one of thermoplastic resins, thermosetting resins, and / or alloys of the resins.

55. The flame-retardant and impact-resistant resin composition according to claim 54, characterized in that: The resin is selected from at least one of polyolefins, polystyrene, polyoxymethylene, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene ether, polyphenylene sulfide, epoxy resin, unsaturated polyester, vinyl resin and / or at least one alloy of the resins.

56. The flame-retardant and impact-resistant resin composition according to claim 54, characterized in that: The thermoplastic or thermosetting resin is selected from at least one of polyolefins, unsaturated polyesters, vinyl resins, polystyrene, and nylon.

57. The flame-retardant and impact-resistant resin composition according to claim 56, characterized in that: The thermoplastic resin is a polyolefin.

58. The flame-retardant and impact-resistant resin composition according to claim 57, characterized in that: The polyolefin is selected from at least one of polyethylene, polypropylene, and their copolymers.

59. The flame-retardant and impact-resistant resin composition according to claim 49, characterized in that... It also contains aluminum hypophosphite flame retardants and / or flame retardant synergists.

60. The flame-retardant and impact-resistant resin composition according to claim 59, characterized in that: The aluminum hypophosphite flame retardant is inorganic aluminum hypophosphite and / or alkyl aluminum hypophosphite.

61. The flame-retardant and impact-resistant resin composition according to claim 60, characterized in that: The alkyl aluminum hypophosphite is selected from at least one of diethyl aluminum hypophosphite, dipropyl aluminum hypophosphite, and phenyl aluminum hypophosphite.

62. The flame-retardant and impact-resistant resin composition according to claim 60, characterized in that: The aluminum hypophosphite flame retardant is selected from inorganic aluminum hypophosphite and / or diethyl aluminum hypophosphite.

63. The flame-retardant and impact-resistant resin composition according to claim 59, characterized in that: Based on 100 parts by weight of the resin, the amount of the aluminum hypophosphite flame retardant is 0 to 2.0 parts by weight.

64. The flame-retardant and impact-resistant resin composition according to claim 63, characterized in that: Based on 100 parts by weight of the resin, the amount of the aluminum hypophosphite flame retardant is 0.01 to 1.5 parts by weight.

65. The flame-retardant and impact-resistant resin composition according to claim 64, characterized in that: Based on 100 parts by weight of the resin, the amount of the aluminum hypophosphite flame retardant is 0.1 to 0.8 parts by weight.

66. The flame-retardant and impact-resistant resin composition according to claim 59, characterized in that: The flame retardant synergist is selected from at least one of 2,3-dimethyl-2,3-diphenylbutane and p-isopropylbenzene polymer.

67. The flame-retardant and impact-resistant resin composition according to claim 59, characterized in that: Based on 100 parts by weight of the resin, the amount of the flame retardant synergist is 0 to 1.5 parts by weight.

68. The flame-retardant and impact-resistant resin composition according to claim 67, characterized in that: Based on 100 parts by weight of the resin, the amount of the flame retardant synergist is 0.01 to 1.2 parts by weight.

69. The flame-retardant and impact-resistant resin composition according to claim 68, characterized in that: Based on 100 parts by weight of the resin, the amount of the flame retardant synergist is 0.02 to 0.8 parts by weight.

70. A method for preparing the flame-retardant and impact-resistant resin composition according to any one of claims 49 to 69, comprising the following steps: The components comprising the resin, the toughening flame retardant, optional aluminum hypophosphite flame retardant, and optional flame retardant synergist are blended.

71. The method for preparing the flame-retardant and impact-resistant resin composition according to claim 70, characterized in that... Includes the following steps: For thermoplastic resins: a1. Mix the components, including thermoplastic resin, the toughening flame retardant, optional aluminum phosphate flame retardant, and optional flame retardant synergist, evenly to obtain a premix. b1. Extrude and granulate the premixed material, and dry it to obtain a flame-retardant and impact-resistant thermoplastic resin composition. And / or, For thermosetting resins: The components, including the uncured resin, the toughening flame retardant, optional aluminum phosphate flame retardant, and optional flame retardant synergist, are mixed evenly to obtain a flame-retardant and impact-resistant thermosetting resin composition.

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