A red phosphorus flame-retardant non-reinforced nylon / polyphenylene ether alloy material and a preparation method thereof

Abstract

The application discloses a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material and a preparation method thereof. The red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material is prepared from components including a nylon resin, a polyphenyl ether resin, a compatilizer, a red phosphorus flame-retardant master batch, a synergistic flame retardant and a lubricant. The application effectively solves the problem of the red phosphorus flame-retardant non-reinforced nylon material. Through compounding the red phosphorus flame-retardant master batch and the synergistic flame retardant, the total amount of the red phosphorus flame-retardant master batch and the synergistic flame retardant is controlled in a lower range under the premise of meeting the UL94 V-0 level requirement, so that the negative influence of the flame retardant on the mechanical properties and the processing properties of the nylon is reduced, the red phosphorus flame-retardant non-reinforced nylon material with excellent comprehensive performance and meeting the customer index requirement is obtained, and the product raw material cost is maximally controlled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of resin alloy materials, and particularly relates to a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material and a preparation method thereof. BACKGROUND

[0002] Nylon materials have good mechanical properties, low friction coefficient, excellent wear resistance, oil resistance and chemical resistance, and are easy to process and form, but need to add flame retardants to improve the flame retardant performance. Commonly used flame retardants include bromine, phosphorus and nitrogen. The bromine flame retardant has environmental problems, the nylon material added with the nitrogen flame retardant has unstable flame retardant effect and has a dripping phenomenon in the combustion process, and the red phosphorus master batch in the phosphorus flame retardant has better flame retardant effect and higher cost performance.

[0003] The red phosphorus flame-retardant glass fiber reinforced nylon with a glass fiber content of 30% can reach the UL94V-0 level in terms of flame retardant performance according to the recommended amount of the manufacturer and by adding the red phosphorus flame-retardant master batch alone. However, it is found in experiments that the non-reinforced nylon material added with the red phosphorus flame-retardant master batch alone is difficult to achieve the UL94V-0 level of flame retardant effect, and therefore, there is an urgent need to develop a red phosphorus flame-retardant non-reinforced nylon material capable of achieving the UL94V-0 level of flame retardant effect. SUMMARY

[0004] To solve the problems in the prior art, the present application provides a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material and a preparation method thereof. The present application selects and compounding the synergistic flame retardant, simultaneously uses an appropriate amount of polyphenyl ether resin, and adds the red phosphorus master batch together, so as to give the non-reinforced nylon material stable flame retardant effect and higher flame retardant grade.

[0005] One of the purposes of the present application is to provide a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material prepared from components including nylon resin, polyphenyl ether resin, compatibilizer, red phosphorus flame-retardant master batch, synergistic flame retardant and lubricant.

[0006] In a preferred embodiment of the present application,

[0007] Based on 100 parts by weight of the nylon resin,

[0008]

[0009] In a preferred embodiment of the present application,

[0010] The nylon resin is a conventional nylon resin in the prior art, preferably at least one of a nylon 66 resin and a nylon 6 resin; the relative viscosity of the nylon 66 resin is preferably 2.4-3.2, more preferably 2.6-2.8, and further preferably 2.6-2.7; and / or the relative viscosity of the nylon 6 resin is preferably 2.4-3.4, more preferably 2.7-2.9, and further preferably 2.7-2.8.

[0011] In a preferred embodiment of the present application,

[0012] The polyphenyl ether resin has an intrinsic viscosity of 0.35-0.6 dl / g, preferably 0.4-0.5 dl / g.

[0013] In a preferred embodiment of the present application,

[0014] The red phosphorus flame-retardant master batch is a conventional red phosphorus flame-retardant master batch in the prior art, preferably the red phosphorus content of the red phosphorus flame-retardant master batch is ≥40%, preferably 40-50%, and more preferably 40-45%; and / or the ignition point of the red phosphorus flame-retardant master batch is ≥320°C; further preferably the red phosphorus flame-retardant master batch is a red phosphorus flame-retardant master batch with a nylon carrier.

[0015] In a preferred embodiment of the present application,

[0016] The synergistic flame retardant is at least one of zinc borate, phosphate ester, and organic phosphite salt, preferably at least two of zinc borate, phosphate ester, and organic phosphite salt, and more preferably a combination of zinc borate and organic phosphite salt; preferably,

[0017] When the synergistic flame retardant is a combination of zinc borate and organic phosphite salt, the ratio of the two is 1:(1-1.5); and / or,

[0018] The phosphate ester is a polyaryl phosphate ester; the polyaryl phosphate ester is preferably PX-220; and / or,

[0019] The organic phosphite salt is at least one of the compounds shown in the following formula (I) and / or formula (II):

[0020]

[0021] In formula (I) and formula (II), R 1 and R 2 may be the same or different and are each independently linear or branched C1-C6-alkyl, aryl, or phenyl; R 3 is linear or branched C1-C 10 -alkylene, C6-C 10 -arylene, C6-C10 -alkylarylene or C6-C 10 -Arylalkylene; M is a calcium atom, magnesium atom, aluminum atom and / or zinc atom; m is 2 or 3, n is 1 or 3, x is 1 or 2; more preferably,

[0022] The organic phosphinates are calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, benzene-1,4-(dimethylphosphinate), magnesium dimethylphosphinate, and aluminum dimethylphosphinate. At least one of the following: zinc benzene-1,4-(dimethylphosphino)ate, calcium methylphenylphosphinoate, magnesium methylphenylphosphinoate, aluminum methylphenylphosphinoate, zinc methylphenylphosphinoate, calcium diphenylphosphinoate, magnesium diphenylphosphinoate, aluminum diphenylphosphinoate, and zinc diphenylphosphinoate; preferably at least one of the following: calcium dimethylphosphinoate, aluminum dimethylphosphinoate, zinc dimethylphosphinoate, calcium ethylmethylphosphinoate, aluminum ethylmethylphosphinoate, zinc ethylmethylphosphinoate, calcium diethylphosphinoate, aluminum diethylphosphinoate, and zinc diethylphosphinoate; more preferably at least one of the following: calcium dimethylphosphinoate, aluminum dimethylphosphinoate, zinc dimethylphosphinoate, calcium diethylphosphinoate, aluminum diethylphosphinoate, and zinc diethylphosphinoate; and most preferably aluminum diethylphosphinoate.

[0023] Organic phosphines used as synergistic flame retardants are commercially available, including Clariant's OP series, preferably OP1230, OP1311, OP1312 (aluminum diethylphosphinate), OP1314, OP1400, and more preferably OP1312.

[0024] In a preferred embodiment of the present invention,

[0025] The compatibilizer is a maleic anhydride-grafted compatibilizer, preferably at least one of maleic anhydride-grafted polyphenylene ether (PPO-g-MAH) and styrene-maleic anhydride graft copolymer (PS-g-MAH). Maleic anhydride-grafted compatibilizers have high polarity and reactivity; maleic anhydride can react with the amino and / or amine groups on the nylon molecular chain. Furthermore, the polyphenylene ether and / or styrene in the compatibilizer have excellent compatibility with the polyphenylene ether resin. Therefore, the interfacial adhesion between the nylon and polyphenylene ether resins in the formulation is increased, forming a stable structure.

[0026] In one preferred embodiment of the present application,

[0027] The lubricant is at least one of calcium stearate, montan wax and derivatives thereof. In addition to effectively reducing the friction between the materials and between the materials and the screw and the barrel, the lubricant can also act as a release agent to prevent the molded parts from sticking to the mold.

[0028] In one preferred embodiment of the present application,

[0029] The red phosphorus flame-retardant non-reinforced nylon / polyphenylene ether alloy material further comprises at least one of a toughening agent, an antioxidant, and a color master batch.

[0030] Based on 100 parts by weight of the nylon resin,

[0031] Toughening agent 12-24 parts by weight; preferably 16-24 parts by weight;

[0032] Antioxidant 0.2-0.6 parts by weight; preferably 0.2-0.4 parts by weight;

[0033] Color master batch 2-4 parts by weight; preferably 2-3 parts by weight.

[0034] The toughening agent is at least one of a maleic anhydride grafted toughening agent, preferably at least one of a maleic anhydride grafted polyolefin elastomer (preferably KT-916K) and a maleic anhydride grafted ethylene / octene copolymer (preferably 493D); and / or,

[0035] The antioxidant is at least one of the conventional antioxidants in the prior art, preferably at least one of a hindered phenol antioxidant 1098 (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine), a high molecular weight phosphite antioxidant S-9228 (bis[2,4-(diphenyl)tert-butylphenyl]pentaerythritol bisphosphite), and a hindered phenol antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester), more preferably a combination of the hindered phenol antioxidant 1098 and the high molecular weight phosphite antioxidant S-9228 or a combination of the hindered phenol antioxidant 1010 and the high molecular weight phosphite antioxidant S-9228; and / or,

[0036] The color master batch is at least one of a carbon black powder content of 30-50% and a carbon black master batch of a polyethylene or nylon carrier, preferably at least one of PE2718 and PA3803.

[0037] Other conventional components in the art can also be added in the present application, such as ultraviolet absorbers, preferably at least one of UV-360 (2,2'-methylenebis(4-tert-octyl-6-benzotriazol phenol)), UV-1577 (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol), and the like, in a conventional amount, which can be added by those skilled in the art according to the actual situation.

[0038] The second object of the present application is to provide a preparation method of the red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material of one of the objects of the present application, comprising the steps of mixing and melt-extruding and granulating the components including nylon resin, polyphenyl ether resin, compatibilizer, red phosphorus flame-retardant master batch, synergistic flame retardant, lubricant, and optionally toughening agent, antioxidant and color master batch.

[0039] In a preferred embodiment of the present application,

[0040] The extrusion conditions include: the extrusion temperature is 240-270 DEG C; and / or, the screw rotation speed is 220-280 rpm.

[0041] The present application can adopt the following specific technical solutions:

[0042] The components including nylon resin (the nylon resin is preferably dried at 100 DEG C for 4h in a forced air drying oven before use), polyphenyl ether resin, compatibilizer, red phosphorus flame-retardant master batch, synergistic flame retardant, lubricant, and optionally toughening agent, antioxidant and color master batch are weighed according to the proportion, mixed uniformly, added into the main feeding metering of the parallel twin-screw extruder, and then melt-blended and drawn to obtain the red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material. The prepared red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material is dried in a forced air drying oven (120 DEG C, 4h), molded into a national standard (GB) sample by an injection molding machine, placed in an environment of 23 DEG C, 50% RH for 24 hours, and then the related performance tests are carried out.

[0043] The injection molding process parameters include:

[0044] The injection temperature (DEG C) is: the rear section (230-250), the middle section (240-260), and the front section (250-270); and / or, the mold temperature (DEG C) is: 40-80; and / or, the injection pressure is: 40-60%.

[0045] The red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material in the present application can be used to produce railway communication cable sling buckles, and can also be used to produce household appliance and electronic and electrical related parts.

[0046] The present application has the following beneficial effects:

[0047] The application effectively solves the problem of red phosphorus flame-retardant non-reinforced nylon material. By compounding the red phosphorus flame-retardant master batch and the synergistic flame retardant, the total amount of the red phosphorus flame-retardant master batch and the synergistic flame retardant is controlled in a lower range on the premise of meeting the UL94 V-0 level requirement, so that the red phosphorus flame-retardant non-reinforced nylon material with excellent comprehensive performance and meeting the customer index requirement can be obtained, and the product raw material cost can be maximally controlled.

[0048] The application adds the synergistic flame retardant after compounding, and through the synergistic effect of the red phosphorus flame retardant and the polyphenyl ether resin, the developed non-reinforced nylon material reaches better flame-retardant performance than the expected effect. DETAILED DESCRIPTION

[0049] Hereinafter, the application will be specifically described in combination with specific examples, and it is necessary to point out that the following examples are only used for further illustration of the application, and cannot be understood as the limitation of the protection scope of the application, and some non-essential improvements and adjustments of the application by the person skilled in the art according to the content of the application still belong to the protection scope of the application.

[0050] The raw materials used in the examples and comparative examples of the application are all conventional commercially available raw materials, and part of the raw materials are as follows:

[0051] Nylon 66 (PA66): EPR27 (relative viscosity: 2.7), EPR24 (relative viscosity: 2.4), Pingdingshan Shenma Engineering Plastics Co., Ltd.;

[0052] Nylon 6 (PA6): YH800 (relative viscosity: 2.8), YH400 (relative viscosity: 2.4), Hunan Yuehua Chemical Co., Ltd.;

[0053] Polyphenyl ether (PPO): LXR040 (intrinsic viscosity: 0.4 dl / g), LXR045 (intrinsic viscosity: 0.45 dl / g), LXR050 (intrinsic viscosity: 0.5 dl / g), Lusstar Chemical New Material Co., Ltd. Ruicheng Branch;

[0054] Compatibilizer: KT-24 (maleic anhydride grafted polyphenyl ether), KT-5 (styrene and maleic anhydride grafted copolymer), Shenyang Ketong Plastic Co., Ltd.

[0055] Toughening agent: KT-916K (maleic anhydride grafted polyolefin elastomer), Shenyang Ketong Plastic Co., Ltd.; 493D (maleic anhydride grafted ethylene / octene copolymer), DuPont Company, USA;

[0056] Red phosphorus flame retardant: red phosphorus flame retardant master batch RPM440 (red phosphorus content 40%, ignition point ≥320℃), Zhonglan Morning Light Chemical Research and Design Institute Co., Ltd.;

[0057] Synergistic flame retardant: PX-220 (polyaryl phosphate), Zhejiang Wansheng Co., Ltd.; OP1312 (aluminum diethyl phosphinate), Clariant Chemicals (China) Co., Ltd.; Zinc borate (Kangda Flame Retardant Chemical Co., Ltd. in Yingkou);

[0058] Antioxidant: Hindered phenolic antioxidant 1098 (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine), Hindered phenolic antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester), Xibaida (Beijing) Chemical Materials Co., Ltd.; Phosphite antioxidant S-9228 (bis[2,4-(diphenyl)tert-butylphenyl]pentaerythritol bisphosphite, Dow Chemical Company, USA;

[0059] Lubricant: Calcium stearate, Tianjin Langhu Chemical Co., Ltd.; P12 (derivative of montan wax), Bruggemann Chemicals GmbH, Germany;

[0060] Carbon black master batch: PE2718 (polyethylene carrier, carbon black powder content 50%), PA3803 (nylon 6 carrier, carbon black powder content 30%), Cabot Corporation, USA;

[0061] Experimental equipment used in the present application:

[0062] A. Co-rotating twin-screw extruder: STS35, Kobe Long (Nanjing) Machinery Co., Ltd.;

[0063] B. Injection molding machine: EM80-SVP / 2, Zhen De Plastic Machinery Co., Ltd.;

[0064] C. Electronic universal testing machine: CMT6104, Mastech Industrial Systems (China) Co., Ltd.;

[0065] D. Pendulum impact testing machine: ZBC7151-B, Mastech Industrial Systems (China) Co., Ltd.;

[0066] E. Horizontal and vertical burning tester: ZZZ-RS-HL, Shenzhen Neutron Measurement and Control Instrument Co., Ltd.

[0067] Test items in the present application:

[0068] Bending strength: GB / T 9341-2008 (speed: 2 mm / min);

[0069] Simply supported beam notched impact strength (at room temperature and low temperature): GB / T 1043-2008;

[0070] Flame Retardant Performance: UL94 (Vertical Burning).

[0071] Example 1-2

[0072] 1) Dry the nylon resins (PA66) at 100℃ for 4h, after cooling, weigh the materials according to the sample formulation in Table 1, and mix uniformly in a high-speed mixer.

[0073] 2) Set the parallel twin-screw extruder screw speed to 280 rpm, and the extrusion temperature to 260, 265, 270, 270, 265, 260, 255, 255, 255, 255 (ten zones), die head (250). After the equipment is constant temperature for 30 minutes, put the mixed materials into the main feeding scale for metering, after melt blending, draw, water cooling, and granulation to obtain the red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material. After drying the sample at 120℃ for 4h, use an injection molding machine to form a national standard sample, after placing in a 23℃, 50% RH environment for 24 hours, perform relevant performance tests, and the test data are shown in Table 4.

[0074] The injection molding process parameters are as follows:

[0075] Injection temperature (℃): rear section (250), middle section (260), front section (270);

[0076] Mold temperature (℃): 80; injection pressure: 40%.

[0077] Example 3

[0078] 1) Dry the nylon resins (PA66 and PA6) at 100℃ for 4h, after cooling, weigh the materials according to the sample formulation in Table 1, and mix uniformly in a high-speed mixer.

[0079] 2) Set the parallel twin-screw extruder screw speed to 260 rpm, and the extrusion temperature to 260, 265, 270, 270, 265, 260, 255, 255, 255, 255 (ten zones), die head (250). After the equipment is constant temperature for 30 minutes, put the mixed materials into the main feeding scale for metering, after melt blending, draw, water cooling, and granulation to obtain the red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material. After drying the sample at 120℃ for 4h, use an injection molding machine to form a national standard sample, after placing in a 23℃, 50% RH environment for 24 hours, perform relevant performance tests, and the test data are shown in Table 4.

[0080] The injection molding process parameters are as follows:

[0081] Injection temperature (℃): rear section (240), middle section (255), front section (265);

[0082] Mold temperature (°C): 50; and / or, injection pressure: 45%.

[0083] Example 4

[0084] 1) The nylon resin (PA66 and PA6) was dried at 100°C for 4h, after cooling, the material was weighed according to the sample formula in Table 1, and mixed uniformly in a high-speed mixer.

[0085] 2) The parallel twin-screw extruder screw speed was set to 240 rpm, the extrusion temperature was set to 255, 260, 265, 265, 260, 255, 250, 250, 250, 250 (ten zones), die head (245), after the equipment was constant temperature for 30 minutes, the mixed material was put into the main feeding scale for metering, after melt blending, it was drawn, water-cooled, and pelletized to obtain a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material. After the sample was dried at 120°C for 4h, a standard sample was molded using an injection molding machine, and after being placed in an environment of 23°C, 50% RH for 24 hours, relevant performance tests were carried out, and the test data are shown in Table 4.

[0086] The injection molding process parameters are as follows:

[0087] Injection temperature (°C): rear section (240), middle section (250), front section (260);

[0088] Mold temperature (°C): 50; and / or, injection pressure: 50%.

[0089] Example 5

[0090] 1) The nylon resin (PA6) was dried at 100°C for 4h, after cooling, the material was weighed according to the sample formula in Table 1, and mixed uniformly in a high-speed mixer.

[0091] 2) The parallel twin-screw extruder screw speed was set to 220 rpm, the extrusion temperature was set to 250, 255, 260, 260, 255, 250, 245, 245, 245, 245 (ten zones), die head (240), after the equipment was constant temperature for 30 minutes, the mixed material was put into the main feeding scale for metering, after melt blending, it was drawn, water-cooled, and pelletized to obtain a red phosphorus flame-retardant non-reinforced nylon / polyphenyl ether alloy material. After the sample was dried at 120°C for 4h, a standard sample was molded using an injection molding machine, and after being placed in an environment of 23°C, 50% RH for 24 hours, relevant performance tests were carried out, and the test data are shown in Table 4.

[0092] The injection molding process parameters are as follows:

[0093] Injection temperature (°C): rear section (230), middle section (240), front section (250);

[0094] Mold temperature (°C): 40; Injection pressure: 60%.

[0095] Examples 6-10

[0096] Materials for Examples 6 and 7-10 were weighed according to the formulations in Tables 1 and 2, respectively, and samples were prepared using the method of Example 5. Test data are shown in Table 4.

[0097] Comparative Examples 1-8

[0098] Materials for Comparative Examples 1-8 were weighed according to the formulations in Table 3, and samples were prepared using the method of Example 5. Test data are shown in Table 4.

[0099] Table 1: Raw materials and dosages of each component in Examples 1-6

[0100] Raw material name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PA66 (EPR 27) 100 - 80 60 - - PA66 (EPR 24) - 100 - - - - PA6 (YH 800) - - 20 40 100 - PA6 (YH 400) - - - - - 100 PPO (LXR 050) - - 4 - - - PPO (LXR 045) - - - 8 5 5 PPO (LXR 040) 5 5 - - - - KT-24 3 3 - 5 3 3 KT-5 - - 3 - - - KT-916K - - 16 24 18 18 493D 18 18 - - - - RPM 440 15 15 16 18 15 15 1010 - - 0.2 - - - 1098 0.1 0.1 - 0.1 0.1 0.1 S-9228 0.1 0.1 0.2 0.1 0.1 0.1 Zinc borate 5 5 4 6 5 5 Calcium stearate - - 0.2 0.2 0.2 0.2 P12 0.4 0.4 - - - - PE 2718 2.5 2.5 2 - 2.5 2.5 PA 3803 - - - 3 - -

[0101] Table 2: Raw materials and dosages of each component in Examples 7-10

[0102] Raw material name Example 7 Example 8 Example 9 Example 10 PA6 (YH 800) 100 100 100 100 PPO (0.45 dl / g) 5 5 5 5 KT-24 3 3 3 3 KT-916K 18 18 18 18 RPM 440 15 15 15 15 Antioxidant 1098 0.1 0.1 0.1 0.1 Antioxidant S-9228 0.1 0.1 0.1 0.1 Zinc borate - - 2.5 2 OP 1312 5 - 2.5 3 PX-220 - 5 - - Calcium stearate 0.2 0.2 0.2 0.2 PE 2718 2.5 2.5 2.5 2.5

[0103] Table 3: Raw materials and dosage of each component in Comparative Examples 1-8

[0104]

[0105]

[0106] Table 4: Test data of Examples 1-10 and Comparative Examples 1-8 (National Standard)

[0107]

[0108] Note: In Comparative Example 1, the flame retardancy rating "HB" indicates that the vertical burning test method is not suitable.

[0109] The test data from Comparative Examples 1-6 show that the flame retardant effect of unreinforced nylon 6 obtained by adding a certain total amount of polyphenylene ether, red phosphorus flame retardant masterbatch, and zinc borate alone, or by compounding any two of the three components, is not ideal. Due to the phenomenon of excessive afterburning time or dripping ignition, the flame retardant performance can only reach a maximum of UL94V-2 (3.2mm). However, the flame retardant performance of Example 5, which adds the three components in the same total amount, can reach a UL94V-0 (3.2mm) rating, and the strength and toughness are more balanced. The experiments of Example 5 and Comparative Examples 1-6 demonstrate that in order to achieve a UL94V-0 flame retardant effect for red phosphorus flame-retardant unreinforced nylon 6 material, polyphenylene ether resin, red phosphorus flame retardant masterbatch, and the synergistic flame retardant zinc borate must be added simultaneously; none of them can be omitted.

[0110] From the test data of examples 7-10, it can be seen that, in addition to zinc borate, phosphoric acid ester (preferably PX-220) and organic phosphite (preferably OP1312) can also be used as synergistic flame retardants, and the flame retardant performance of non-reinforced nylon 6 material can also reach UL94 V-0 (3.2 mm) level; in addition, it is found through experiments that, by compounding zinc borate and organic phosphite (preferably OP1312), and then adding red phosphorus master batch and polyphenyl ether together, the flame retardant effect of non-reinforced nylon 6 material can be further improved, reaching 1.6 mm UL94 V-0 level, which may be due to the fact that, during the combustion process, the nylon sample added with the compounded synergistic flame retardant is more likely to form a stable coking layer on the surface, thereby better playing the role of heat insulation and reducing the entry of oxygen.

[0111] From the test data of examples 5 and comparative examples 7-8, it can also be seen that, although the compatibilizer is added in the red phosphorus flame-retardant non-reinforced nylon 6 material, the addition of polyphenyl ether still has an adverse effect on the toughness of the material, such as the simple beam room temperature and low temperature notched impact strength. With the increase of the content of polyphenyl ether in the sample, the simple beam notched impact strength value shows a gradually decreasing trend.

[0112] In addition, due to the poor flowability of polyphenyl ether resin caused by the molecular structure, excessive addition will inevitably affect the processing performance of the nylon material, making the surface of the molded part more prone to appear problems such as weld marks and scorching. At the same time, the market price of polyphenyl ether resin is slightly higher than that of nylon resin, and excessive addition will also significantly increase the raw material cost of the product, which is not conducive to market competition, therefore, the amount of polyphenyl ether resin is controlled in a small range in the present application.

Claims

1. A red phosphorus flame-retardant unreinforced nylon / polyphenylene ether alloy material, prepared from components including nylon resin, polyphenylene ether resin, compatibilizer, red phosphorus flame-retardant masterbatch, synergistic flame retardant, and lubricant; wherein the synergistic flame retardant is a combination of zinc borate and organic phosphinate; wherein the ratio of zinc borate to organic phosphinate is 1:(1-1.5); and wherein the organic phosphinate is at least one of the compounds shown in formula (I) and / or formula (II): In equations (I) and (II), R 1 and R 2 They can be the same or different, and can be independently linear or branched C1-C6-alkyl, aryl, or phenyl groups; R 3 C1-C is a linear or branched chain. 10 -alkylene, C6-C 10 -Asaryl, C6-C 10 -alkylarylene or C6-C 10 -Arylalkylene; M is a calcium atom, magnesium atom, aluminum atom and / or zinc atom; m is 2 or 3, n is 1 or 3, x is 1 or 2; Based on 100 parts by weight of nylon resin, 2-10 parts by weight of polyphenylene ether resin; Compatibilizer 1-10 parts by weight; 10-20 parts by weight of red phosphorus flame retardant masterbatch; 2-10 parts by weight of synergistic flame retardant; Lubricant 0.05-0.6 parts by weight.

2. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: Based on 100 parts by weight of nylon resin, 4-8 parts by weight of polyphenylene ether resin; 3-5 parts by weight of compatibilizer; 15-18 parts by weight of red phosphorus flame retardant masterbatch; Synergistic flame retardant 4-6 parts by weight; Lubricant 0.2-0.4 parts by weight.

3. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The nylon resin is at least one of nylon 66 resin and nylon 6 resin.

4. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The intrinsic viscosity of the polyphenylene ether resin is 0.35-0.6 dl / g.

5. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 4, characterized in that: The intrinsic viscosity of the polyphenylene ether resin is 0.4-0.5 dl / g.

6. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The red phosphorus flame retardant masterbatch has a red phosphorus content of ≥40%; and / or, the ignition point of the red phosphorus flame retardant masterbatch is ≥320℃.

7. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 6, characterized in that: The red phosphorus content of the red phosphorus flame retardant masterbatch is 40-50%.

8. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The organic phosphine salts are calcium dimethylphosphine, magnesium dimethylphosphine, aluminum dimethylphosphine, zinc dimethylphosphine, calcium ethylmethylphosphine, magnesium ethylmethylphosphine, aluminum ethylmethylphosphine, zinc ethylmethylphosphine, calcium diethylphosphine, magnesium diethylphosphine, aluminum diethylphosphine, zinc diethylphosphine, calcium diethylphosphine, magnesium diethylphosphine, aluminum diethylphosphine, zinc diethylphosphine, calcium methyl-n-propylphosphine, magnesium methyl-n-propylphosphine, aluminum methyl-n-propylphosphine, zinc methyl-n-propylphosphine, calcium dimethylphosphine, magnesium dimethylphosphine, aluminum dimethylphosphine, zinc dimethylphosphine, calcium dimethylphosphine, magnesium dimethylphosphine, aluminum dimethylphosphine, zinc dimethylphosphine, benzene-1,4-(dimethylphosphine), magnesium dimethylphosphine, aluminum dimethylphosphine, zinc dimethylphosphine, benzene-1,4-(dimethylphosphine), calcium dimethylphosphine, magnesium dimethylphosphine, aluminum dimethylphosphine, and so on. At least one of the following: zinc dimethylphosphine, calcium dimethylphosphine, magnesium dimethylphosphine, aluminum dimethylphosphine, zinc dimethylphosphine, calcium diphenylphosphine, magnesium diphenylphosphine, aluminum diphenylphosphine, and zinc diphenylphosphine.

9. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 1, characterized in that: The compatibilizer is a maleic anhydride-grafted compatibilizer; and / or... The lubricant is at least one of calcium stearate, lignite wax and its derivatives.

10. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in claim 9, characterized in that: The compatibilizer is at least one of maleic anhydride-grafted polyphenylene ether and styrene-maleic anhydride-grafted copolymer.

11. The red phosphorus flame-retardant unreinforced nylon / polyphenylene oxide alloy material as described in any one of claims 1-10, characterized in that: The red phosphorus flame-retardant unreinforced nylon / polyphenylene ether alloy material also contains at least one of a toughening agent, an antioxidant, and a color masterbatch.

12. A method for preparing a red phosphorus flame-retardant unreinforced nylon / polyphenylene ether alloy material as described in any one of claims 1-11, comprising the step of melting and extruding granulation of a mixture containing nylon resin, polyphenylene ether resin, compatibilizer, red phosphorus flame-retardant masterbatch, synergistic flame retardant, lubricant, and optionally toughening agent, antioxidant and color masterbatch.

13. The preparation method according to claim 12, characterized in that: The extrusion conditions include: an extrusion temperature of 240-270℃; and / or a screw speed of 220-280 rpm.

Images