Organophosphorus synergistic bromine-containing flame-retardant nylon material and preparation method thereof

Abstract

The application provides an organic phosphorus synergistic bromine flame-retardant nylon material and a preparation method thereof, and the organic phosphorus synergistic bromine flame-retardant nylon material comprises the following components in mass fractions: nylon resin 60-100 parts, halogenated polystyrene 10-30 parts, modified zinc borate 15-30 parts, flame retardant 5-15 parts, and auxiliary agent 0.1-5 parts; wherein the modified zinc borate is obtained by reacting zinc borate with a silane coupling agent containing a double bond, and then reacting with an allyl phosphate, vinyl POSS, maleic anhydride and a copolymer of styrene. The compatibility and combination effect of various components are optimized, the basic properties such as the strength and toughness of the nylon material are improved, the flame retardation is synergistically achieved from the gas phase and the condensed phase, the flame retardation performance of the composite material is ensured, the problems in the prior art are solved, and the further popularization of the flame-retardant nylon material has important significance.

Description

An organophosphorus synergistic brominated flame-retardant nylon material and its preparation method Technical Field

[0001] This invention relates to the field of polymer composite materials technology, and in particular to an organophosphorus synergistic bromine-based flame-retardant nylon material and its preparation method. Background Technology

[0002] With the widespread application of engineering plastics in the automotive, electronics, construction, and aerospace industries, the demand for flame-retardant materials is increasing. Nylon (PA), as an important thermoplastic engineering plastic, is widely used in many fields due to its excellent mechanical properties, chemical resistance, and processing performance. However, nylon has relatively low flame retardancy and is prone to causing fires, thus requiring flame-retardant modification to improve its safety.

[0003] Currently, the research and development trend of flame retardants is towards green and environmentally friendly products that are highly efficient and low in toxicity, while also optimizing flame retardant effects and material properties. Brominated flame-retardant nylon typically requires the addition of the inorganic flame retardant antimony trioxide. At high temperatures, the vaporization of antimony trioxide dilutes the oxygen concentration in the air, thereby achieving a synergistic flame-retardant effect.

[0004] However, influenced by multiple factors such as global supply chain tensions, tightening environmental policies in major producing countries, and surging demand from downstream new energy industries, the market price of antimony metal has recently experienced a rapid and dramatic rise. This price fluctuation in a key raw material has also had a significant impact on antimony trioxide, a traditional flame retardant synergist, causing its cost to soar. This, in turn, has increased the cost of flame-retardant nylon materials based on antimony trioxide, putting cost pressure on downstream applications such as the electronics and automotive industries. Against this backdrop, developing a novel flame-retardant nylon material that does not rely on antimony trioxide and possesses highly efficient flame retardancy, excellent comprehensive performance, and environmentally friendly properties has become a key research focus in this field.

[0005] In conclusion, there is an urgent need to provide a new technical solution to address the problems existing in current flame-retardant nylon products and meet the needs of the market and consumers. Summary of the Invention

[0006] Based on this, the present invention provides an organophosphorus synergistic brominated flame-retardant nylon material, which uses nylon resin in combination with different components such as halogenated polystyrene and modified zinc borate to optimize the compatibility and bonding effect between various components, improve the basic properties of nylon material such as strength and toughness, and achieve synergistic flame retardancy from both gas phase and condensed phase, ensuring the flame-retardant performance of the composite material, solving the problems existing in the prior art, and is of great significance for the further promotion of flame-retardant nylon materials.

[0007] One object of the present invention is to provide an organophosphorus synergistic brominated flame-retardant nylon material, wherein the organophosphorus synergistic brominated flame-retardant nylon material comprises the following components in parts by weight:

[0008] 60-100 parts of nylon resin

[0009] 10-30 parts of halogenated polystyrene

[0010] 15-30 parts of modified zinc borate

[0011] 5-15 parts flame retardant

[0012] Additives: 0.1-5 parts;

[0013] in,

[0014] The modified zinc borate is a product obtained by reacting zinc borate with a silane coupling agent containing double bonds, followed by copolymerization with allyl phosphate, vinyl POSS (vinyl cage polysilsesquioxane), maleic anhydride and styrene.

[0015] Furthermore, the nylon resin is selected from one or more of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 1010, nylon 1212 and nylon 610.

[0016] Furthermore, the halogenated polystyrene is brominated polystyrene.

[0017] Furthermore, the flame retardant includes organophosphorus flame retardants.

[0018] Furthermore, the additive is selected from one or more of toughening agents, antioxidants, lubricants, stabilizers, catalysts, initiators, and plasticizers.

[0019] This invention uses a compound of modified zinc borate, organophosphorus compounds, and brominated polystyrene. During combustion, the brominated polystyrene decomposes to produce hydrogen bromide and bromine free radicals that enter the gas phase. These free radicals react with and capture the H• and OH• free radicals that maintain the flame during the combustion reaction, thereby interrupting the chain reaction of combustion.

[0020] Organophosphorus compounds decompose to produce phosphoric acid, polyphosphoric acid, and other highly dehydrating substances. These substances react with the decomposition products of nylon and their own decomposition products, catalyzing the formation of a continuous carbon-rich layer on the material surface. This acts as a physical barrier, isolating heat and oxygen, preventing the escape of combustible gases, and protecting the internal substrate from further decomposition. Simultaneously, some phosphorus-containing substances enter the gas phase as PO• free radicals, which can also capture H• and OH• free radicals, assisting in gas-phase flame retardancy.

[0021] Zinc borate releases water of crystallization during the initial combustion phase, absorbing a large amount of heat and lowering the surface temperature of the material. Furthermore, its decomposition products (such as B2O3) react with substances like polyphosphoric acid produced by the decomposition of organophosphorus compounds, forming a borophosphate glassy layer that covers the char layer surface. This significantly enhances the density, strength, and thermal stability of the char layer and promotes its cross-linking reaction, making it less susceptible to being blown away by the flame. This invention also modifies zinc borate by introducing POSS and phosphate ester groups, thereby improving the material's heat resistance. It can also form a silica film layer at high temperatures, preventing the escape or dripping of small molecules generated by polymer decomposition and further enhancing its ability to block oxygen and heat transfer.

[0022] Therefore, the multiple components in this invention extinguish flames efficiently in the gas phase and establish a stable barrier in the condensed phase, thus achieving a synergistic effect in flame retardancy from multiple aspects. Compared with the use of a single flame retardant, the amount added is reduced and the flame retardant and fireproof effect is improved.

[0023] Another object of the present invention is to provide a method for preparing the above-mentioned organophosphorus synergistic brominated flame-retardant nylon material, wherein the method for preparing the organophosphorus synergistic brominated flame-retardant nylon material includes the following steps:

[0024] S1. Zinc borate and silane coupling agent are mixed and heated to obtain pretreated zinc borate.

[0025] S2. The pretreated zinc borate, allyl phosphate, vinyl POSS, maleic anhydride, styrene and initiator are mixed and heated under inert gas protection to obtain modified zinc borate.

[0026] S3. The modified zinc borate, nylon resin, halogenated polystyrene, flame retardant, and additives are fed into a twin-screw extruder and extruded and granulated to obtain an organophosphorus synergistic bromine-based flame-retardant nylon material.

[0027] Further, in step S1, the mass ratio of zinc borate to silane coupling agent is 1:(0.1-2).

[0028] Furthermore, in step S1, the temperature of the heating reaction is 50-100°C.

[0029] Further, in step S2, the mass ratio of the pretreated zinc borate, allyl phosphate, vinyl POSS, maleic anhydride and styrene is (1-4):(0.5-1):(0.5-1):(0.1-0.5):(1-2).

[0030] Furthermore, in step S2, the temperature of the heating reaction is 50-90°C.

[0031] The present invention has the following beneficial effects:

[0032] This invention discloses an organophosphorus synergistic brominated flame-retardant nylon material, composed of nylon, brominated polystyrene, modified zinc borate, and phosphate ester flame retardant. The modified zinc borate is a product of copolymerization of zinc borate with allyl phosphate, vinyl POSS, maleic anhydride, and styrene via a silane coupling agent to introduce double bonds. This introduces multiple groups such as phosphate ester, POSS, anhydride, and polystyrene into zinc borate, effectively enhancing its affinity with brominated polystyrene and the flame retardant. Simultaneously, the active anhydride enhances the bonding effect with nylon resin, acting as a compatibilizer and significantly improving the compatibility and bonding strength between different components. Furthermore, POSS itself enhances the mechanical properties of the composite material, and vinyl POSS, with its multiple active double bonds, enables the polymerization product to form a three-dimensional network structure during the reaction. After combining with nylon and other components, this structure provides excellent toughening, improving the toughness and strength of the composite material. More importantly, the zinc borate in this invention can function as an inorganic flame retardant, and the modified phosphate ester and POSS groups also have flame retardant functions. Therefore, it can more fully form a synergistic effect with brominated polystyrene and triphenyl phosphate flame retardant materials to achieve synergistic flame retardancy and achieve excellent flame retardant effect, thereby reducing the risk of fire and protecting life and property safety. This is of great significance for promoting green development in this field and improving the quality and safety of nylon products. Detailed Implementation

[0033] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0034] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0035] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention.

[0036] The nylon resin used in this embodiment of the invention is PA6, UBE NYLON® 1013B, with a relative viscosity of 2.3.

[0037] In the embodiments of this invention, the brominated polystyrene is PBS-64HW.

[0038] The vinyl POSS used in this embodiment of the invention was purchased from McLean.

[0039] Example 1

[0040] An organophosphorus synergistic brominated flame-retardant nylon material, wherein the organophosphorus synergistic brominated flame-retardant nylon material comprises the following components in parts by weight:

[0041] 75 parts of nylon resin

[0042] 15 parts of brominated polystyrene

[0043] 15 parts of modified zinc borate

[0044] 10 parts of triphenyl phosphate

[0045] Antioxidant 1010 1 part;

[0046] The preparation method of the above-mentioned organophosphorus synergistic brominated flame-retardant nylon material includes the following steps:

[0047] S1. Using a 90 wt% aqueous ethanol solution as a solvent, zinc borate and KH-570 (zinc borate:KH-570=2:1, m / m) were mixed and heated at 80℃ for 8 h. Then, the mixture was washed and dried to obtain pretreated zinc borate.

[0048] S2. Using toluene as a solvent, the pretreated zinc borate, allyl dimethyl phosphate, vinyl POSS, maleic anhydride, styrene, and azobisisobutyronitrile (pretreated zinc borate: allyl dimethyl phosphate: vinyl POSS: maleic anhydride: styrene: azobisisobutyronitrile = 2:1:0.8:0.2:2:0.1, m / m / m / m / m / m) are mixed and heated at 75°C for 12 hours under nitrogen protection. After removing the solvent and drying, modified zinc borate is obtained.

[0049] S3. According to the above-mentioned mass proportions, the modified zinc borate and other components such as nylon resin are put into a twin-screw extruder and extruded and granulated at 230-240°C to obtain organophosphorus synergistic bromine flame retardant nylon material.

[0050] Example 2

[0051] An organophosphorus synergistic brominated flame-retardant nylon material, wherein the organophosphorus synergistic brominated flame-retardant nylon material comprises the following components in parts by weight:

[0052] 85 parts of nylon resin

[0053] 17 parts of brominated polystyrene

[0054] 18 parts of modified zinc borate

[0055] 12 parts of triphenyl phosphate

[0056] Antioxidant 1010 1 part;

[0057] The preparation method of the above-mentioned organophosphorus synergistic brominated flame-retardant nylon material includes the following steps:

[0058] S1. Using a 90 wt% aqueous ethanol solution as a solvent, zinc borate and KH-570 (zinc borate:KH-570=2:1, m / m) were mixed and heated at 80℃ for 8 h. Then, the mixture was washed and dried to obtain pretreated zinc borate.

[0059] S2. Using toluene as a solvent, the pretreated zinc borate, allyl dimethyl phosphate, vinyl POSS, maleic anhydride, styrene, and azobisisobutyronitrile (pretreated zinc borate: allyl dimethyl phosphate: vinyl POSS: maleic anhydride: styrene: azobisisobutyronitrile = 2:1:0.8:0.2:2:0.1, m / m / m / m / m / m) are mixed and heated at 75°C for 12 hours under nitrogen protection. After removing the solvent and drying, modified zinc borate is obtained.

[0060] S3. According to the above-mentioned mass proportions, the modified zinc borate and other components such as nylon resin are put into a twin-screw extruder and extruded and granulated at 230-240°C to obtain organophosphorus synergistic bromine flame retardant nylon material.

[0061] Example 3

[0062] An organophosphorus synergistic brominated flame-retardant nylon material, wherein the organophosphorus synergistic brominated flame-retardant nylon material comprises the following components in parts by weight:

[0063] 100 parts of nylon resin

[0064] 20 parts of brominated polystyrene

[0065] 21 parts of modified zinc borate

[0066] 15 parts of triphenyl phosphate

[0067] Antioxidant 1010 1.5 parts;

[0068] The preparation method of the above-mentioned organophosphorus synergistic brominated flame-retardant nylon material includes the following steps:

[0069] S1. Using a 90 wt% aqueous ethanol solution as a solvent, zinc borate and KH-570 (zinc borate:KH-570=2:1, m / m) were mixed and heated at 80℃ for 8 h. Then, the mixture was washed and dried to obtain pretreated zinc borate.

[0070] S2. Using toluene as a solvent, the pretreated zinc borate, allyl dimethyl phosphate, vinyl POSS, maleic anhydride, styrene, and azobisisobutyronitrile (pretreated zinc borate: allyl dimethyl phosphate: vinyl POSS: maleic anhydride: styrene: azobisisobutyronitrile = 2:1:0.8:0.2:2:0.1, m / m / m / m / m / m) are mixed and heated at 75°C for 12 hours under nitrogen protection. After removing the solvent and drying, modified zinc borate is obtained.

[0071] S3. According to the above-mentioned mass proportions, the modified zinc borate and other components such as nylon resin are put into a twin-screw extruder and extruded and granulated at 230-240°C to obtain organophosphorus synergistic bromine flame retardant nylon material.

[0072] Comparative Example 1

[0073] A synergistic organophosphorus brominated flame-retardant nylon material is described. The difference between this comparative example and Example 1 is that step S2 is omitted, and pretreated zinc borate, triphenyl phosphate, vinyl POSS, maleic anhydride, and polystyrene (POLYREX® PG-33) in a mass ratio of 2:1:0.8:0.2:2 are mixed evenly to obtain modified zinc borate. Other components and preparation methods are the same.

[0074] Comparative Example 2

[0075] An organophosphorus synergistic brominated flame-retardant nylon material is described. The difference between this comparative example and Example 1 is that in step S2, vinyl POSS is replaced with an equal mass of styrene, while the other components and preparation methods are the same.

[0076] Test case

[0077] The performance of the organophosphorus synergistic brominated flame-retardant nylon materials prepared in Examples 1-3 and Comparative Examples 1-2 was tested.

[0078] Test method:

[0079] Tensile strength, notched impact strength and flame retardancy were determined in accordance with standards such as GB / T1040.2-2006, GB / T1843-2008 and UL-94.

[0080] The test results are shown in Table 1.

[0081] Table 1 Performance Test Results

[0082]

[0083] As shown in Table 1, the organophosphorus synergistic brominated flame-retardant nylon material prepared in the embodiments of the present invention exhibits good mechanical strength and excellent flame retardancy. However, in Comparative Example 1, replacing the modified zinc borate with a physical blend makes it difficult to improve the compatibility between components and also affects the integrity of the composite material. The components struggle to form a synergistic effect, resulting in a significant decrease in overall performance. Comparative Example 2, by replacing the POSS groups introduced into the modified zinc borate, makes it difficult to obtain an ideal network cross-linked structure and also fails to introduce siloxane components with heat resistance and flame retardant effects, leading to a reduction in both mechanical strength and flame retardancy. In summary, the organophosphorus synergistic brominated flame-retardant nylon material of the present invention overcomes the shortcomings of the prior art and has good application prospects.

[0084] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0085] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An organophosphorus synergistic brominated flame-retardant nylon material, characterized in that, The organophosphorus synergistic brominated flame-retardant nylon material comprises the following components in parts by weight: 60-100 parts nylon resin, 10-30 parts halogenated polystyrene, 15-30 parts modified zinc borate, 5-15 parts flame retardant, and 0.1-5 parts additives; wherein, the modified zinc borate is a product obtained by reacting zinc borate with a silane coupling agent containing double bonds, followed by copolymerization with allyl phosphate, vinyl POSS, maleic anhydride, and styrene; the halogenated polystyrene is brominated polystyrene; the flame retardant includes organophosphorus flame retardants; the organophosphorus synergistic... The preparation method of brominated flame-retardant nylon material includes the following steps: S1, mixing zinc borate and silane coupling agent and heating to obtain pretreated zinc borate; S2, mixing the pretreated zinc borate, allyl phosphate, vinyl POSS, maleic anhydride, styrene and initiator, and heating under inert gas protection to obtain modified zinc borate; S3, feeding the modified zinc borate, nylon resin, halogenated polystyrene, flame retardant and additives into a twin-screw extruder, and extruding and granulating to obtain organophosphorus synergistic brominated flame-retardant nylon material.

2. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, The nylon resin is selected from one or more of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 1010, nylon 1212 and nylon 610.

3. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, The additives are selected from one or more of toughening agents, lubricants, stabilizers, catalysts, initiators, and plasticizers.

4. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, In step S1, the mass ratio of zinc borate to silane coupling agent is 1:(0.1-2).

5. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, In step S1, the temperature of the heating reaction is 50-100℃.

6. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, In step S2, the mass ratio of the pretreated zinc borate, allyl phosphate, vinyl POSS, maleic anhydride and styrene is (1-4): (0.5-1): (0.5-1): (0.1-0.5): (1-2).

7. The organophosphorus synergistic brominated flame-retardant nylon material according to claim 1, characterized in that, In step S2, the temperature of the heating reaction is 50-90℃.

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